JP6270840B2 - Method for producing photocurable resin film - Google Patents

Description

The present invention relates to a method for producing a photocurable resin film.
This application claims priority based on Japanese Patent Application No. 2013-132686 for which it applied to Japan on June 25, 2013, and uses the content here.

  Conventionally, the photocurable resin film has a laminated film constituted by sandwiching a liquid photocurable resin composition between a pair of base film, and the photocurable resin composition is cured by ultraviolet irradiation. (For example, refer to Patent Document 1).

  As an apparatus for producing a film made of a curable resin, there is an apparatus using a hot air heating furnace, an oven, or the like that heats the film to cure the resin (see, for example, Patent Document 2).

JP 2006-306081 A JP 2009-197102 A

After photocuring the above-mentioned photocurable resin composition, when heating the photocurable resin film for further curing, a manufacturing apparatus using a hot air heating furnace or the like can be used. The manufacturing apparatus has a problem in terms of production efficiency because it takes a long time to cure the resin composition.
If the heating temperature is raised, the problem of production efficiency can be improved, but in that case, there is a concern about deformation and thermal decomposition of the film.

The present invention has been made in view of the above-described circumstances, and when heating the photocurable resin composition of the photocurable resin film to further advance the curing, the production efficiency is not lowered and the film It aims at providing the manufacturing method of the photocurable resin film which can prevent a deformation | transformation and thermal decomposition of this.

One embodiment of the present invention relates to the following [1] to [7].
[1] Obtained by irradiating a belt-shaped laminated film formed by sandwiching a photocurable resin layer made of a liquid photocurable resin composition with a pair of base films to cure the photocurable resin layer It has a heating furnace that heats a photocurable resin film to increase the hardness of the photocurable resin layer, and the heating furnace irradiates far-infrared rays on the photocurable resin film. The manufacturing apparatus of the photocurable resin film which has a 1 or several far-infrared irradiation means which heats.
[2] The photocurable property according to [1], wherein the far-infrared irradiation unit includes a flat-plate far-infrared heater installed so as to face the photocurable resin film introduced into the heating furnace. Resin film production equipment.
[3] It further has a transfer means for transferring the photocurable resin film in its longitudinal direction, and the far-infrared irradiation means irradiates the far-infrared ray on the photocurable resin film transferred by the transfer means. The apparatus for producing a photocurable resin film according to [1] or [2].
[4] Any of the above [1] to [3], wherein the plurality of far-infrared irradiation means can be arranged side by side along the transfer direction of the photocurable resin film and can set the irradiation amount of the far-infrared rays independently of each other. The manufacturing apparatus of the photocurable resin film as described in any one.
[5] The light according to any one of [1] to [4], wherein at least one side edge of the photocurable resin film is configured by laminating only the pair of substrate films. Production equipment for curable resin film.
[6] The apparatus for producing a photocurable resin film according to any one of [1] to [5], wherein the photocurable resin composition is a polyvalent allyl ester resin.

[7] Obtained by irradiating a belt-shaped laminated film formed by sandwiching a photocurable resin layer made of a liquid photocurable resin composition with a pair of base films to cure the photocurable resin layer A photocurable resin film is introduced into a heating furnace having far-infrared irradiation means, and the photocurable resin film is heated by irradiating the photocurable resin film with far-infrared rays by the far-infrared irradiation means. A method for producing a resin film.
The light is, for example, ultraviolet rays.

According to the aspect of the present invention, since a heating furnace having a far-infrared irradiation means is used, it is intended for a photocurable resin film having a laminated structure in which a photocurable resin layer is sandwiched between substrate films. The heating efficiency with respect to the photocurable resin layer can be improved, and the hardness of the photocurable resin layer can be increased.
Since there is no need to increase the heating temperature, film deformation and thermal decomposition can be suppressed.

It is the schematic which shows the heating furnace of the manufacturing apparatus of the photocurable resin film which concerns on one Embodiment of this invention. It is the cross-sectional schematic which looked at the heating furnace from the transfer direction of the photocurable resin film. It is the schematic which shows the whole manufacturing apparatus of a photocurable resin film. It is a top view of the far-infrared heater used for a heating furnace, and a side view of a far-infrared heater. It is a perspective view which shows a heat generating body. It is a schematic perspective view which shows an example of a photocurable resin film. It is a graph which shows the test result about the temperature of the photocurable resin film in a heating furnace.

Hereinafter, an embodiment of the present invention will be described with reference to FIGS.
FIG. 6 shows an example of a photocurable resin film. The photocurable resin film 1 shown here is a film-like photocurable resin layer 2 made of a liquid photocurable resin composition. It is a belt-like body sandwiched between the material films 3 and 4.

In the photocurable resin film 1, the width dimension of the pair of substrate films 3 and 4 is set to be larger than the width dimension of the photocurable resin layer 2, and between the side edges of the substrate films 3 and 4. The photocurable resin layer 2 is not formed. That is, both side edge portions of the photocurable resin film 1 are ear portions 5 in which only a pair of base films 3 and 4 are laminated together.
In addition, the photocurable resin film 1 may be configured by laminating only a pair of base films 3 and 4 only on one side edge.

  The photocurable resin composition in the present embodiment is not particularly limited as long as the curing reaction (polymerization reaction) proceeds by active energy rays such as light (ultraviolet light and visible light) and an electron beam. The photocurable resin composition is preferably prepared by blending a polymerizable resin component with a photopolymerizable initiator. In addition, as a photocurable resin composition in this embodiment, the compound which has two or more photopolymerizable carbon-carbon double bonds is preferable. Examples of the photocurable resin composition include (1) polyvalent allyl ester resin, (2) polyvalent vinyl ester resin, (3) polyfunctional urethane (meth) acrylate resin, and (4) cage-type siloxane- (meta ) Acrylate resin composition.

(1) The polyvalent allyl ester resin is a composition containing a polyvalent allyl ester compound and a photopolymerization initiator. The polyvalent allyl ester compound is produced by a transesterification reaction between an allyl ester monomer of a polyvalent carboxylic acid and a C 2-20 polyhydric alcohol having 2 to 6 hydroxyl groups.
Specific examples of the allyl ester monomer of polyvalent carboxylic acid include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, diallyl 1,2-cyclohexanedicarboxylate, 1,3-cyclohexanedicarboxylic acid Examples include diallyl acid, diallyl 1,4-cyclohexanedicarboxylate, diallyl endomethylenetetrahydrophthalate, diallyl methyltetrahydrophthalate, diallyl adipate, diallyl succinate, diallyl maleate, and the like. These allyl ester monomers can be used in combination of two or more as required, and are not limited to the specific examples described above.

Among specific examples of the polyhydric alcohol having 2 to 20 carbon atoms, the divalent alcohol includes ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neo Pentyl glycol, hexamethylene glycol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, Examples include bisphenol-A ethylene oxide adduct, bisphenol-A propylene oxide adduct, 2,2- [4- (2-hydroxyethoxy) -3,5-dibromophenyl] propane, and the like.
Specific examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, dipentalysitol and the like. A mixture of two or more of these polyhydric alcohols may be used. Moreover, it is not limited to the above-mentioned specific example.

Furthermore, the polyvalent allyl ester compound is radically polymerizable and can be polymerized by heat, ultraviolet rays, electron beams or the like. It can also be copolymerized with other radically polymerizable compounds.
The radical polymerizable compound to be copolymerized with the polyvalent allyl ester compound is not particularly limited as long as it is a compound copolymerizable with the polyvalent allyl ester compound. Specific examples thereof include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, allyl benzoate, allyl α-naphthoate, allyl β-naphthoate, allyl 2-phenylbenzoate, allyl 3-phenylbenzoate, 4-phenylbenzoic acid. Allyl, allyl o-chlorobenzoate, allyl m-chlorobenzoate, allyl p-chlorobenzoate, allyl o-bromobenzoate, allyl m-bromobenzoate, allyl p-bromobenzoate, 2,6-dichlorobenzoate Allyl acid, allyl 2,4-dichlorobenzoate, allyl 2,4,6-tribromobenzoate, diallyl 1,4-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,2-cyclohexanedicarboxylate, 1-cyclohexene-1,2-dicarboxylic acid di Allyl, 3-methyl-1,2-cyclohexanedicarboxylic acid diallyl, 4-methyl-1,2-cyclohexanedicarboxylic acid diallyl, endic acid diallyl, chlorendic acid diallyl, 3,6-methylene-1,2-cyclohexanedicarboxylic acid Allyl esters such as diallyl, triallyl trimelliate, tetraallyl pyromellitic acid, diallyl diphenate, diallyl succinate, diallyl adipate, dibenzyl malate, dibenzyl fumarate, diphenyl malate, diphenyl fumarate, dibutyl maleate Maleic acid diesters / fumaric acid diesters, such as rate, dibutyl fumarate, dimethoxyethyl fumarate, dimethoxyethyl fumarate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate , I-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, isobornyl (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene diglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra ( ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tri (Meth) acrylic esters such as cyclodecanedimethanol di (meth) acrylate, dicyclopentenyl (meth) acrylate, ethoxylated cyclohexanedimethanol dimethacrylate, adamantyl (meth) acrylate; styrene, α-methylstyrene, methoxystyrene , Aromatic vinyl compounds such as divinylbenzene; aliphatic carboxyl such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl stearate, vinyl caproate Vinyl ester; cycloaliphatic carboxylic acid vinyl ester and other alicyclic vinyl esters; benzoic acid vinyl ester and t-butyl benzoic acid vinyl ester and other aromatic vinyl esters, diallyl carbonate, diethylene glycol bisallyl carbonate, trade name CR manufactured by PPG -39 Allyl carbonate compounds such as polyethylene glycol bis (allyl) carbonate resin represented by 39, allyl (meth) acrylate having a different polymerizable double bond in the molecule, vinyl (meth) acrylate and maleic acid Compounds such as diallyl, nitrogen-containing polyfunctional allyl compounds such as triallyl isocyanurate and triallyl cyanurate, unsaturated polyester resin, vinyl ester resin, urethane acrylate, epoxy acrylate and other oligoacrylates, etc. And the like.

  However, these radically polymerizable compounds are merely examples and are not limited to the above. These radically polymerizable compounds may be used in combination of two or more in order to obtain the desired physical properties.

  (2) As polyvalent vinyl ester resin, what substituted the allyl group of the said polyvalent allyl ester by the vinyl group is mentioned.

  (3) The polyfunctional urethane (meth) acrylate resin is obtained by reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound using a catalyst such as dibutyltin dilaurate as necessary. Can be mentioned. Examples of polyisocyanate compounds include isophorone diisocyanate, tricyclodecane diisocyanate, norbornene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Examples include isocyanate compounds. Specific examples of the hydroxyl group-containing (meth) acrylate compound include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3- ( Examples include meth) acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol tri (meth) acrylate.

  (4) As a cage-type siloxane- (meth) acrylate resin composition, the resin composition described in JP 2010-195986 A can be mentioned.

  On the other hand, each of the base films 3 and 4 is a film made of a light transmissive resin that can transmit ultraviolet rays. Specific examples of the material for the base films 3 and 4 include polyethylene terephthalate (PET), polypropylene, and polyethylene. In addition, the material of the base film 3 and the base film 4 may be the same or different. Furthermore, you may have a function which transfers a hard-coat layer and an antireflection layer to the hardened | cured material film of the photocurable resin of this invention.

  As shown in FIG. 3, the photocurable resin film manufacturing apparatus 10 according to this embodiment sandwiches a photocurable resin layer 2 made of a liquid photocurable resin composition between a pair of substrate films 3 and 4. The first processing part 6 to be a strip-like photocurable resin film 1 and the second processing part 7 (heating part) for heating the photocurable resin film 1 to increase the hardness of the photocurable resin layer 2 are provided. ing.

The first processing unit 6 irradiates the laminated film with ultraviolet rays while transferring the laminated film in the longitudinal direction thereof, and includes two substrate rolls 11 and 12, a coating unit 13, a laminate unit 14, and ultraviolet irradiation. A part 15 and a take-up roll 16 are provided. The base roll 11 supplies the base film 3, and the base roll 12 supplies the base film 4.

The coating unit 13 coats a liquid photocurable resin composition on the base film 3 (one base film 3) fed out from the one base roll 11, and the photocurable resin composition A film-like photocurable resin layer 2 (see FIG. 6) is formed.
The coating unit 13 is driven and rotated by a motor (not shown) to transfer one base film 3 in the longitudinal direction, and one base film 3 wound around the outer peripheral surface of the backup roll 21. The slit die 22 for coating the photocurable resin composition is provided on the top.

The laminating unit 14 includes a photocurable resin layer formed by one base film 3 that has passed through the coating unit 13 and a base film 4 (the other base film 4) that is fed out from the other base roll 12. 2 is sandwiched to obtain a laminated film (see FIG. 6). The laminate part 14 is constituted by a pair of rolls 14 a and 14 b that sandwich the base films 3 and 4 and the photocurable resin layer 2.

The ultraviolet irradiation unit 15 irradiates the laminated film to be transferred with ultraviolet rays R <b> 1 to cure the photocurable resin layer 2 to obtain the photocurable resin film 1. The ultraviolet irradiation unit 15 is disposed downstream of the laminating unit 14 in the transport direction of the laminated film . Specific examples of the ultraviolet irradiation unit 15 include lamps using arc discharge (metal halide lamp, xenon lamp, mercury lamp, etc.), lamps using glow discharge (neon lamp, etc.), and the like.

  The winding roll 16 is driven and rotated by a motor (not shown) or the like and winds the photocurable resin film 1 after passing through the ultraviolet irradiation unit 15.

As shown in FIG. 1 and FIG. 2, the second processing unit 7 irradiates the photocurable resin film 1 with far infrared rays while transferring the photocurable resin film 1 in the longitudinal direction thereof. The photocurable resin layer 2 is further cured by heating 1.
The 2nd process part 7 is the supply roll 31 which supplies the photocurable resin film 1, the heating furnace 32 which heats the photocurable resin film 1, and the winding roll 33 which winds up the photocurable resin film 1 (refer FIG. 3). ).

  The heating furnace 32 is a continuous heating furnace, and includes a furnace main body 34 into which the photocurable resin film 1 is introduced, one or a plurality of transfer rollers 35 that transfer the photocurable resin film 1 in the furnace main body 34, and 1 or a plurality of far infrared heaters 36 (far infrared irradiation means) for heating the photocurable resin film 1 in the furnace body 34.

4A and 4B are diagrams showing the far-infrared heater 36, in which FIG. 4A is a plan view of the far-infrared heater, and FIG. 4B is a side view of the far-infrared heater. As shown in this figure, the far-infrared heater 36 is formed in a flat plate shape, for example.
The far-infrared heater 36 includes a rectangular thin metal plate 37 made of aluminum alloy, stainless steel, or the like, and a heating element 39 that is inserted into a through hole 38 that penetrates between both end surfaces 37a and 37a in the longitudinal direction of the thin metal plate 37. .

A far-infrared radiation layer 40 is formed on the outer surface of the metal thin plate 37.
As the material of the far-infrared radiation layer 40, a far-infrared radiation material such as silica (SiO ₂ ), zirconium oxide (ZrO ₂ ), tin oxide (SnO ₂ ), titanium oxide (TiO ₂ ), alumina (Al ₂ O ₃ ) , Beryllia (BeO ₂ ), cordierite (2MgO · 2Al ₂ O ₃ · 5SiO ₂ ) and other II-IV group metal oxide ceramics, iron oxide (Fe ₂ O ₃ ), chromium oxide (Cr ₂ O ₃ ), II-VIII group metal oxide ceramics such as nickel oxide (NiO) and cobalt oxide (CoO), non-oxide ceramics such as silicon carbide (SiC), and mixtures thereof are preferably used.
For the far-infrared radiation layer 40, it is preferable to use a material in which a powder mainly composed of a far-infrared radiation material is bound by a binder such as synthetic resin or glass.
The thickness of the far infrared radiation layer 40 is, for example, 10 to 100 μm. The far-infrared radiation layer 40 can be formed by a dipping method or the like.

As shown in FIG. 5, the heating element 39 has a structure in which a spiral resistance heating element 42 having an outer diameter smaller than the inner diameter dimension is accommodated in a bottomed cylindrical metal cartridge 41.
Ends 42a and 42b of the resistance heating element 42 are connected to a power source (external energy source) (not shown).

  When the heating element 39 generates heat by energizing the resistance heating element 42 and the metal thin plate 37 reaches a high temperature, the far-infrared radiation layer 40 is heated. As a result, the far-infrared radiation layer 40 emits far-infrared rays. Far-infrared rays are electromagnetic waves having a wavelength of, for example, 4 to 1000 μm.

  In the illustrated example, the heating element 39 is inserted into the through holes 38a and 38c close to the side edges 37b and 37b among the three through holes 38 (38a, 38b and 38c). Air for temperature adjustment can be introduced into the central through hole 38b.

As shown in FIG. 1, the far-infrared heater 36 is provided at a position facing the photocurable resin film 1 transferred in the furnace body 34.
Specifically, in the furnace body 34, an upper surface side heater 43 composed of one or more far infrared heaters 36 arranged horizontally and a lower surface side heater 44 composed of one or more far infrared heaters 36 arranged horizontally. And a transfer space 45 in which the photocurable resin film 1 is transferred is secured between them.

In the example shown in FIG. 1, the upper surface side heater 43 includes one or a plurality of heater blocks. The upper surface side heater 43 in the illustrated example has four heater blocks 43A to 43D. The heater blocks 43A to 43D are arranged in this order from the inlet 34a to the outlet 34b.
The heater blocks 43A to 43D have, for example, the same length dimension and area. Therefore, the heater block 43 </ b> A constitutes about a quarter of the length of the upper surface side heater 43, and the other heater blocks 43 </ b> B to 43 </ b> D are also approximately about the length direction of the upper surface side heater 43. It constitutes a quarter part.
Each of the heater blocks 43A to 43D includes one or a plurality of far infrared heaters 36.
In the illustrated example, the heater blocks 43 </ b> A to 43 </ b> D each include a plurality of heater units 46. The heater unit 46 includes one or more far infrared heaters 36.

The lower surface side heater 44 includes one or a plurality of heater blocks. The lower surface side heater 44 in the illustrated example has four heater blocks 44A to 44D. The heater blocks 44A to 44D are arranged in this order from the inlet 34a to the outlet 34b.
The heater blocks 44A to 44D have the same length and area. Therefore, the heater block 44 </ b> A constitutes about a quarter of the length of the lower surface side heater 44, and the heater blocks 44 </ b> B to 44 </ b> D also each have about 4 minutes of the length direction of the lower surface side heater 44. 1 part.
Each of the heater blocks 44 </ b> A to 44 </ b> D includes one or a plurality of far infrared heaters 36.
In the illustrated example, the heater blocks 44 </ b> A to 44 </ b> D each include a plurality of heater units 47. The heater unit 47 includes one or a plurality of far infrared heaters 36.

The heater blocks 43 </ b> A to 43 </ b> D and the heater blocks 44 </ b> A to 44 </ b> D are preferably capable of independently setting the far-infrared irradiation amount by adjusting the power supplied to the heating element 39 of the far-infrared heater 36.
Moreover, it is preferable that the far-infrared heater 36 which comprises each heater block can set the irradiation amount of a far-infrared radiation each independently.
For this reason, the heating temperature of the upper surface side heater 43 and the lower surface side heater 44 can be set independently for each region in the transfer direction D1. For example, the heating temperature can be set independently for each of the heater blocks 43A to 44D or for each of the heater units 46 and 47. When the heater units 46 and 47 are composed of a plurality of far infrared heaters 36, the heating temperature can be set independently for each far infrared heater 36.

  The far-infrared heater 36 can be installed so that the through hole 38 is perpendicular to the transfer direction D1 (up and down direction in FIG. 4) of the photocurable resin film 1.

As illustrated in FIG. 2, the transfer roller 35 has a function of feeding and moving the photocurable resin film 1. The transfer roller 35 has a shaft portion 35a and a transfer portion 35b having an outer diameter larger than that of the shaft portion 35a, and rotates around the shaft portion 35a so that the photocurable resin film placed on the transfer portion 35b. 1 can be transferred.
The transfer roller 35 is installed horizontally with the shaft portion 35a oriented vertically to the transfer direction of the photocurable resin film 1 (direction perpendicular to the paper surface of FIG. 2).
As shown in FIG. 1, the plurality of transfer rollers 35 can be provided at intervals in the transfer direction of the photocurable resin film 1 (right direction in FIG. 1).

  The winding roll 33 is driven and rotated by a motor or the like (not shown) to wind the photocurable resin film 1. The winding roll 33 constitutes a transfer means for transferring the photocurable resin film 1 in the longitudinal direction.

Next, an example of the manufacturing method of the photocurable resin film using the manufacturing apparatus 10 comprised as mentioned above is demonstrated.
As shown in FIG. 3, a liquid photocurable resin composition is applied to one surface of one base film 3 in the coating portion 13 of the first processing portion 6 (coating step).
Next, in the laminating section 14, the photocurable resin layer 2 is sandwiched between the one base film 3 that has passed through the coating section 13 and the other base film 4 that has been fed out from the other base roll 12. It is set as the film 1 (lamination process).

Next, the laminated film 1 transferred by the ultraviolet irradiation unit 15 is irradiated with ultraviolet R1 to advance the polymerization reaction of the photocurable resin layer 2 to cure the photocurable resin layer 2, and the photocurable resin film. 1 is obtained (ultraviolet irradiation process).
At this time, the photocurable resin layer 2 may be in a semi-cured state in which the polymerization reaction does not proceed completely and an unreacted product remains. It is preferable that the photocurable resin layer 2 is in any one of gel-like to solid (eg, gel-like to semi-solid).

  The photocurable resin film 1 that has undergone the ultraviolet irradiation process is wound around a winding roll 16. The winding roll 16 is used as the supply roll 31 as it is.

  As shown in FIG. 1, the photocurable resin film 1 is introduced from the supply roll 31 to the furnace body 34. The photocurable resin film 1 is transferred by the transfer roller 35 through the transfer space 45 between the upper surface side heater 43 and the lower surface side heater 44 from the inlet 34a toward the outlet 34b along the horizontal plane.

  At this time, the heating element 39 is heated by energizing the resistance heating element 42 of the far infrared heater 36 that constitutes the upper surface heater 43 and the lower surface heater 44, the metal thin plate 37 is heated to a high temperature, and the far infrared radiation layer 40 is heated. . As a result, the far-infrared radiation layer 40 emits far-infrared rays (see FIG. 4).

Far-infrared rays from the far-infrared heater 36 are radiated to the facing photocurable resin film 1. By far infrared rays, the polymerization reaction of the photocurable resin layer 2 further proceeds and the hardness of the photocurable resin layer 2 is increased (thermosetting step).
Thereby, the photocurable resin film 1 in which the hardness of the photocurable resin layer 2 is increased is obtained.

  The inside of the heating furnace 32 may be an air atmosphere or a nitrogen gas atmosphere. When the nitrogen gas atmosphere is used, a situation in which the polymerization reaction of the photocurable resin layer 2 becomes insufficient due to consumption of the polymerization initiator in the photocurable resin layer 2 by contact with air can be avoided.

FIG. 7 is a graph showing the measurement results of the temperature in the heating furnace 32 in the thermosetting process. The horizontal axis represents the temperature change during the transfer process of the photocurable resin film 1 and represents the position in the transfer direction in the heating furnace 32. The vertical axis represents temperature.
A solid line shows the temperature change of the photocurable resin film 1 (Test 1). A broken line shows the temperature change of the base film 3 when only the base film 3 is introduced into the heating furnace 32 in place of the photocurable resin film 1 (Test 2).
A two-dot chain line indicates a set temperature of the upper surface heater 43 and the lower surface heater 44.

As shown in FIG. 7, in the heating furnace 32, the temperature of the photocurable resin film 1 in the transfer direction in the heating furnace 32 is set by setting the temperature for each of the heater blocks 43 </ b> A to 44 </ b> D (specifically, for each heater unit 47). The distribution can be adjusted.
In the illustrated example, the temperature distribution has a peak at a substantially central position in the length direction of the heating furnace 32 (Test 1).
Moreover, it can be seen from comparison between Test 1 and Test 2 that the temperature of the photocurable resin film 1 is higher due to the reaction heat of the polymerization reaction of the photocurable resin layer 2.
The far-infrared irradiation amount of the far-infrared heater 36 is preferably determined in consideration of the reaction heat of the polymerization reaction of the photocurable resin layer 2.

The maximum temperature of the photocurable resin film 1 is preferably 165 to 180 ° C (preferably 170 to 175 ° C).
Thereby, the thermal deformation and thermal decomposition of the base films 3 and 4 can be avoided, and the polymerization reaction in the photocurable resin layer 2 can be sufficiently advanced.

In order to advance the polymerization reaction in the photocurable resin layer 2 with certainty, it is preferable to avoid a sudden temperature rise or a sudden temperature drop. For this reason, as shown in Test 1 in FIG. 7, by slowly setting the temperature rise and drop, the polymerization reaction is reliably advanced, and a high-hardness photocurable resin film 1 can be obtained.
Further, if the high temperature state is maintained for a long time, the adhesion between the base films 3 and 4 and the photocurable resin layer 2 becomes excessively strong, and it is easy to peel off the base films 3 and 4 in a later step. However, as shown in Test 1 of FIG. 7, such a situation can be prevented by setting a short time for the high temperature state.

Since the manufacturing apparatus 10 includes the far-infrared heater 36, the photocurable resin film 1 can be heated by far-infrared rays.
The photocurable resin film 1 has a laminated structure in which the photocurable resin layer 2 is sandwiched between a pair of base films 3 and 4, so that the heating efficiency to the photocurable resin layer 2 tends to be low. Since it reaches the deep part of the photocurable resin film 1 and heats it, the heating efficiency can be increased.
For this reason, the production efficiency of the photocurable resin film 1 can be increased. Moreover, heat loss can be reduced and energy consumption can be suppressed.

Moreover, since the photocurable resin film 1 can be reliably heated to the inside by far-infrared rays, overheating is less likely to occur compared to a method of heating by heat conduction using air as a medium (such as a hot air heating method), and the substrate film 3, 4 deformation and thermal decomposition can be prevented.
When the base films 3 and 4 are peeled off from the photocurable resin layer 2 due to deformation of the base films 3 and 4 due to excessive heating, the polymerization initiator in the photocurable resin layer 2 is consumed by contact with air. The polymerization reaction of the photocurable resin layer 2 may be insufficient, but the manufacturing apparatus 10 can prevent such a situation, so that the polymerization reaction of the photocurable resin layer 2 can be sufficiently advanced. it can.
Moreover, in the manufacturing apparatus 10, since heating efficiency can be improved, a required heating time can be shortened. Further, the length of the heating furnace 32 in the transfer direction D1 can be shortened.

The manufacturing apparatus 10 that employs heating by far infrared rays does not need to consider the adverse effect on the transfer of the photocurable resin film 1 due to the airflow in the heating furnace 32, and can be transferred normally, compared to the hot air heating type and the like. It is.
In addition, since the internal structure can be simplified by adopting the far infrared heater 36, the manufacturing apparatus 10 can be downsized, which is advantageous in reducing the installation space of the apparatus.

Since the manufacturing apparatus 10 employs the far-infrared heater 36, it is easier to set the temperature in the heating furnace 32 than a hot air heating type or the like. For example, since the temperature can be set for each region in the transfer direction D1 in the heating furnace 32, heating according to the characteristics of the photocurable resin film 1 is possible.
For example, as shown in Test 1 of FIG. 7, the polymerization reaction in the photocurable resin layer 2 can be surely advanced by setting the temperature rise and drop gently. In particular, if the temperature drop is abrupt, the progress of the polymerization reaction tends to be insufficient. However, by slowing the gradient of the temperature drop, the polymerization reaction is reliably advanced and the hardness of the photocurable resin layer 2 is increased. Can do.

Further, since the far-infrared heater 36 is employed, unlike the hot air heating type or the like, dust generation does not occur and adverse effects of dust can be prevented.
Furthermore, the temperature in the width direction of the photocurable resin film 1 in the heating furnace 32 can be made uniform, and the characteristics of the photocurable resin film 1 can be made uniform in the width direction.

Although the details of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention.
Both side edge portions of the photocurable resin film 1 in FIG. 6 are configured by laminating only a pair of base films 3 and 4, but the photocurable resin layer 2 is paired with a pair of bases as in the other portions. It may be configured to be sandwiched between the material films 3 and 4.
The hardness index includes JIS K6253 and JIS K7215.

DESCRIPTION OF SYMBOLS 1 Photocurable resin film 2 Photocurable resin layer 3, 4 Base film 5 Ear part 7 2nd process part 10 Manufacturing apparatus 32 Heating furnace 33 Winding roll (transfer means)
36 far infrared heater (far infrared irradiation means)

Claims (5)

The photocurable resin layer is formed by irradiating light to a belt-like laminated film formed by sandwiching a photocurable resin layer made of a liquid photocurable resin composition between a pair of light transmissive base films capable of transmitting ultraviolet rays. Introducing a photocurable resin film obtained by curing in a gel-like to semi-cured state into a heating furnace having a plurality of far-infrared irradiation means installed side by side along the transfer direction of the photocurable resin film ,
Wherein the plurality of far-infrared irradiation means, in the heating furnace, the temperature was raised to the transport direction of the photocurable resin film, and then so that the temperature distribution of cooling, is set irradiation amount of far-infrared independently The manufacturing method of the photocurable resin film which irradiates far infrared rays from both surfaces of the said photocurable resin film, and heats the said photocurable resin film. The far-infrared irradiation means has a far-infrared irradiation amount set in the heating furnace such that a temperature distribution having a peak at a substantially central position in a length direction of the heating furnace is set in the heating furnace. The manufacturing method of the photocurable resin film of description. 3. The photocurable resin film according to claim 1, wherein the far infrared irradiation means includes a flat far infrared heater installed so as to face the photocurable resin film introduced into the heating furnace. Manufacturing method . The at least one side edge part of the said photocurable resin film of the photocurable resin film of any one of Claims 1-3 comprised by laminating | stacking only a pair of said base film. Manufacturing method . The said photocurable resin composition is polyvalent allyl ester resin, The manufacturing method of the photocurable resin film of any one of Claims 1-4.

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