JP6105214B2 - Method for producing substrate having fine concavo-convex structure on surface - Google Patents

Description

  The present invention relates to a method for producing a substrate having a fine relief structure on the surface.

  Recent advances in photolithography technology have made it possible to form a fine structure (fine concavo-convex pattern) having a period of the wavelength level of light. In particular, members and products having fine uneven patterns with a period of 1 μm or less are widely useful in not only the semiconductor field but also the optical field.

  For example, a wire grid in which conductor wires such as metal are arranged in a lattice pattern with a specific period on a substrate has a period length that is considerably smaller than incident light (for example, a wavelength of visible light of 400 nm to 800 nm) (for example, If it is less than 1/2, the electric field vector component that oscillates in parallel to the conductor line is almost reflected and the vertical electric field vector component is almost transmitted. Can be used. Such a wire grid polarizing plate is desirable from the viewpoint of effective use of light because it can reflect and reuse light that does not pass through. In particular, if it can be applied to a polarizing plate used in a large-sized liquid crystal display device such as a television, it is very desirable from the viewpoint of energy saving.

  However, with the current photolithography technology, it is difficult to uniformly produce a fine concavo-convex structure having a large area and a period equal to or shorter than a wavelength. For example, even if the size of the fine uneven original plate obtained from a silicon-based material such as quartz is large, a wafer size of 12 inches in diameter is a general-purpose size. As a method for producing a wire grid polarizing plate at a low cost, a method is known in which a nano-imprint method is used to continuously produce a fine concavo-convex pattern from an original plate, and a metal thin wire is formed on the fine concavo-convex pattern by a vacuum deposition method or the like. It has been. However, since the conventional technology cannot obtain a fine uneven pattern having an area larger than that of the original plate, it cannot be used as a polarizing plate for a large liquid crystal display device. When producing a general-purpose master plate larger than 12 inches, a huge optical system and an advanced drive system for ensuring positional accuracy are newly required. From the viewpoint of production cost, The utility value is low.

  For this reason, several methods for producing a large-area original from a small original have been proposed. For example, a step-and-repeat method using a combination of a UV transfer method and an XY stage has been proposed (see Patent Document 1). In this step-and-repeat method, an original (mold) is positioned on an XY stage, resin filling into the mold and UV transfer of resin from the mold to the substrate are sequentially performed, and a large-area original is obtained by performing multiple transfers. To get.

  However, when the step-and-repeat method is applied to patterning of a large area, the resin protrudes from the mold end surface during filling of the resin between the mold and the substrate, and this protruding resin exists between adjacent patterns. , The accuracy of connecting patterns decreases.

  In general, in order to improve the productivity of the fine concavo-convex structure, a method of using a roll mold in which a mold having a fine concavo-convex structure on the surface is wound around a roll and continuously transferring to a substrate is used. (See Patent Document 2).

U.S. Pat. No. 7,077,992 JP 2008-290330 A

  However, since the roll mold of Patent Document 2 has at least one or more joints, the transferred concavo-convex structure base material has a portion where the concavo-convex pattern is interrupted, that is, a non-use area as a fine concavo-convex pattern. For this reason, the utilization efficiency of the transfer material may be reduced.

  The present invention has been made in view of the above points, and by reducing the unused area of the substrate to be transferred, it is possible to improve the utilization efficiency of the material to be transferred in the roll-to-roll continuous process. It aims at the manufacturing method of the base material which has an uneven structure on the surface.

The manufacturing method of the base material which has the fine concavo-convex structure on the surface of the present invention includes the first application step of applying the first resin composition on the base substrate, the first resin composition applied in the first application step, the stitching portions of the pattern, interrupted first transfer step of forming a first concave-convex pattern portion by transferring an uneven pattern of the roll mold having the pattern, wherein the first concave-convex pattern formed in the first transfer step In the first transfer step, only the second application step of selectively applying the second resin composition to the part where the part is interrupted and the periphery thereof, and the second resin composition applied in the second application step It is characterized by a second transfer step of transferring the uneven pattern of the used roll mold.

  According to such a configuration, the second resin composition is applied to the discontinuous portion of the first concave / convex pattern portion generated in correspondence with the discontinuous pattern of the pattern mold and its peripheral portion, and only the second resin composition is applied. In addition, by transferring the uneven pattern using the same pattern mold as in the first transfer step, a periodic fine structure is formed on substantially the entire surface of the substrate.

In the method for producing a substrate having the fine concavo-convex structure on the surface according to the present invention, a step difference between the first concavo-convex pattern portion and the first concavo-convex pattern portion is 2 μm or less, and the first concavo-convex pattern portion It is preferable that the roughness of the broken portion is 2 μm or less. Further, in the method for producing a substrate having the fine concavo-convex structure on the surface thereof according to the present invention, the substrate having the concavo-convex structure provided on the surface is joined in a roll shape by a microplasma welding method to form the roll mold, In the second application step, it is preferable to apply the second resin composition by a dispenser.

  According to the present invention, it is possible to improve the utilization efficiency of the transfer material in the continuous roll-to-roll process by reducing the unused area of the transfer substrate.

It is a schematic diagram which shows the manufacturing method of the roll mold which concerns on this Embodiment. It is a schematic diagram which shows the outline of the 1st application | coating process and 1st transfer process of the manufacturing method of the base material which has the fine concavo-convex structure of this Embodiment on the surface. It is a schematic diagram which shows the base material obtained at the 1st application | coating process and 1st transfer process of the manufacturing method of the base material which has the fine concavo-convex structure of this Embodiment on the surface. It is a schematic diagram which shows the outline of the 2nd application | coating process and 2nd transfer process of the manufacturing method of the base material which has the fine concavo-convex structure of this Embodiment on the surface. It is a schematic diagram which shows the base material which has the fine concavo-convex structure of this Embodiment on the surface.

Embodiments of the present invention will be described below.
When the present inventors produce a substrate having fine irregularities on the surface (hereinafter referred to as a fine irregular substrate) using a sheet-like material to be transferred produced by a roll-to-roll method, An attention was paid to the fact that a non-use area derived from a portion where the pattern was interrupted occurred, and this non-use area became a factor of reducing the yield of the fine uneven substrate. Then, the present inventors can reduce the unused area of the sheet-shaped transfer material by transferring the uneven pattern again to the portion where the uneven pattern of the fine uneven substrate is interrupted, and use of the sheet-shaped transfer material The inventors have found that the efficiency can be improved and have completed the present invention.

(Fine relief structure)
The fine concavo-convex structure according to the present invention refers to a structure having a concavo-convex period of 10 nm to 500 nm and a convex part height of 1000 nm or less.

(Fine uneven substrate)
The fine concavo-convex substrate according to the present embodiment is obtained by curing the resin composition using the roll mold according to the present embodiment. The fine concavo-convex base material obtained by using the roll mold 10 having a concavo-convex structure on the surface can be suitably used as a base material for a wire grid polarizing plate.

  Moreover, the fine concavo-convex base material obtained by using the roll mold according to the present embodiment having a fine concavo-convex structure on the surface can be suitably used as an optical element. In this case, as the fine structure, for example, a moth-eye structure in which a fine uneven pattern in which the period of the uneven structure is controlled to be equal to or less than the wavelength of visible light is formed on the surface can be used.

(Base material)
Examples of the base substrate material include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cycloolefin resin (COP), cross-linked polyethylene resin, polyvinyl chloride resin, polyarylate resin, polyphenylene ether resin, and modified polyphenylene ether resin. Amorphous thermoplastic resins such as polyetherimide resin, polyether sulfone resin, polysulfone resin, polyether ketone resin, polyethylene terephthalate (PET) resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin, polybutylene terephthalate Crystalline thermoplastic resins such as resin, aromatic polyester resin, polyacetal resin, polyamide resin, and ultraviolet (UV) curable such as acrylic, epoxy, and urethane Fat or thermosetting resins. Further, an ultraviolet curable resin or a thermosetting resin and an inorganic material, the above thermoplastic resin, or the like can be combined or used alone. Among these, the TAC film made of triacetyl cellulose resin and the COP and COC resin film made of cycloolefin resin can have low birefringence and high transmittance. It can be suitably used when used as a substrate.

(Resin composition)
The resin composition in the present embodiment refers to a resin composition containing a general ultraviolet curable resin such as acrylate or methacrylate or a thermosetting resin, and is more preferably an ultraviolet curable resin because of its superiority in a continuous process. In addition, other conventional additives such as flow regulators, leveling agents, organic and inorganic dyes and pigments, extenders, plasticizers, lubricants, reinforcing agents, as long as the original purpose is not impaired. Antioxidants, yellowing inhibitors, ultraviolet absorbers, bluing agents, anti-settling agents, antifoaming agents, antiwear agents, friction reducing agents, antistatic agents, antifogging agents, and the like can be included.

  Examples of the ultraviolet curable resin include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, isoamyl acrylate, n-lauryl acrylate, isomyristyl acrylate, stearyl. Acrylate, n-butoxyethyl acrylate, butoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, caprolactone acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, phenol Cyethyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, diethylaminoethyl acrylate, dimethyl Aminoethyl acrylate quaternized product, acrylic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl 2-hydroxyethylphthal Acid, neopentyl glycol acrylic acid benzoate, 2-acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl acrylate, 2-a Liloyloxyethyl acid phosphate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, PEG # 200 diacrylate, PEG # 400 diacrylate, PEG # 600 diacrylate, 1,4-butanediol diacrylate, neopentyl Glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate Acrylate, 1,10-decanediol diacrylate, glycerin diacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, bisphenol AEO adduct diacryl Rate, trifluoroethyl acrylate, tetrafluoropentyl acrylate, octafluoropentyl acrylate, perfluorooctyl ethyl acrylate, nonylphenol-EO adduct acrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylate benzoate, hydroxypivalic acid Neopentyl glycol diacrylate, tetrafurfuryl alcohol oligoacrylate, ethyl carbitol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, pentamethyl Piperidyl acrylate, tetramethylpiperidyl acrylate, Lactylphenol-EO modified acrylate, N-acryloyloxyethyl hexahydrophthalimide, isocyanuric acid-EO modified diacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, Isodecyl methacrylate, isoamyl methacrylate, n-lauryl methacrylate, isomyristyl methacrylate, stearyl methacrylate, n-butoxyethyl methacrylate, butoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, tripropylene glycol dimethacrylate, tetraethylene glycol di Tacrylate, caprolactone methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, 2-hydroxyethyl methacrylate, 4 -Hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, diethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate quaternized product, methacrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl Phthalic acid, 2-methacryloyloxyethyl 2-hydroxyethylphthalic acid, neopentyl glycol methacrylic acid benzoate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, glycidyl methacrylate, 2-methacryloyloxyethyl acid phosphate, Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, PEG # 200 dimethacrylate, PEG # 400 dimethacrylate, PEG # 600 dimethacrylate, 1,4-butanediol dimethacrylate, neopentylglycol dimethacrylate, 3- Methyl-1,5-pentanediol dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol dimethacrylate 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, bisphenol A-EO adduct Dimethacrylate, trifluoroethyl methacrylate, tetrafluoropentyl methacrylate, octafluoropentyl methacrylate, perfluorooctyl ethyl methacrylate, nonylphenol-EO adduct methacrylate, dimethylol tricyclodecane dimethacrylate, trimethylolpropane methacrylate benzoate, hydroxypivalin Acid neopentyl glycol dimethacrylate, tetrafurfuryl alcohol oligomethacrylate, ethyl Rubitol oligomethacrylate, 1,4-butanediol oligomethacrylate, 1,6-hexanediol oligomethacrylate, trimethylolpropane oligomethacrylate, pentaerythritol oligomethacrylate, pentamethylpiperidylmethacrylate, tetramethylpiperidylmethacrylate, paracumylphenol-EO modification Methacrylate, N-methacryloyloxyethyl hexahydrophthalimide, isocyanuric acid-EO modified dimethacrylate, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl } Benzene, 3-ethyl-3-{[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, 3-ethyl-3- (2-ethylhexyl) Roxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxy) methyloxetane, oxetanylsilsesquioxane, oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3 -Ethyloxetane-3-yl) methoxy] benzene and the like, but is not limited thereto.

(First application process)
There are no particular restrictions on the method of applying the resin composition to the substrate in the first application step. For example, the roll coater method, (micro) gravure coater method, air doctor coater method, blade coater method, knife coater method, rod Coater method, curtain (flow) coater method, kiss coater method, bead coater method, cast coater method, rotary screen method, dip coating method, slot orifice coater method, barcode method, spray coating method, extrusion coater, electrodeposition coating method, etc. The method is mentioned.

(Pattern mold with broken pattern)
A pattern mold having a discontinuous pattern refers to a mold having at least one region having no pattern, which is produced by joining molds having a pattern on the surface. Examples of the joining method include, but are not limited to, adhesion using an adhesive and welding.

(First transfer process)
The first transfer process is to apply the resin composition to the base material, and then contact the pattern mold, and then cure the resin composition by light irradiation or heating to produce an uneven structure of the mold on the surface of the base material. To do.

  The step between the portion where the first uneven pattern portion is broken and the peripheral portion is preferably 2 μm or less, and more preferably 1 μm or less. Further, the roughness of the portion where the first uneven pattern portion is interrupted is preferably 2 μm or less, and more preferably 1 μm or less.

(Second application process)
Regarding the second application step, it is necessary to selectively apply a resin to a portion where the first uneven pattern portion is interrupted instead of the entire surface application, and therefore, a partial application method using a dispenser, an inkjet, or the like is preferable.

  Moreover, also about the application quantity, it is preferable that the film thickness after hardening of a resin composition is 2 micrometers or less, and it is more preferable that it is 1 micrometer or less from a viewpoint of visibility.

  The resin composition used in the second coating step is preferably the same as the resin composition used in the first coating step.

(Second transfer process)
The second transfer step is the first unevenness in the first transfer step by applying the resin composition in the second application step and then contacting the pattern mold and then curing the resin composition by light irradiation or heating. This refers to producing a concavo-convex structure of a mold in a portion where the pattern is interrupted.

  At this time, the step between the uneven pattern and the first uneven pattern part produced in the portion where the first uneven pattern part is interrupted is preferably 2 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less from the viewpoint of visibility. .

  In order to make the level difference between the concave / convex pattern produced in the portion where the first concave / convex pattern part is interrupted and the first concave / convex pattern part 2 μm or less, the resin composition used for forming the first concave / convex pattern part, and the second fine pattern It is preferable that the resin composition used for forming the uneven pattern portion is the same resin composition. If the composition is the same, the wettability and adhesiveness are very good, and the step of the pattern joint at the joint after spreading by diffusion due to its own weight can be suppressed to 2 μm or less, and almost all pattern joints The level difference coincides with the height of the convex portion of the fine uneven pattern to be transferred.

(Roll mold manufacturing method)
Next, the manufacturing method of the roll mold which concerns on this Embodiment is demonstrated. 1A to 1D are schematic views showing a roll mold manufacturing method according to the present embodiment. As shown in FIG. 1A, the manufacturing method of the roll mold 10 according to the present embodiment is a cutting step of cutting out a rectangular base material 11 as shown in FIG. 1B from an original plate 12 provided with a concavo-convex structure pattern 12a. And a joining step of joining the pair of sides of the base material 11 to form the base material 11 in a cylindrical shape as shown in FIGS. 1C and 1D.

  In the cutting process, as the original plate 12 shown in FIG. 1A, for example, a Ni electroformed thin plate having a concavo-convex structure pattern 12a transferred from a master die by electroless Ni electroforming or the like is used. Next, as shown in FIG. 1B, a rectangular substrate 11 is cut out from the original plate 12. When the height of the concavo-convex structure to be transferred is 1 μm or less, Ni alloys such as Ni / B, Ni / P, and Ni / Co can be used instead of the Ni electroformed thin plate.

  In the joining step, as shown in FIG. 1C, the cut out rectangular base material 11 is bent and a pair of sides (11a and 11c in FIG. 1B) are joined by welding to form the base material 11 in a roll shape. As a welding method, for example, a laser welding method or a microplasma welding method can be used. In the case of using the microplasma welding method, the current value, the plasma gas, the shield gas, the electrode diameter, the nozzle diameter, the cap diameter, the torch angle, the arc length, the welding speed, and the like are finely adjusted, thereby making a pair of the base materials 11. Can be welded, and as shown in FIG. 1C and FIG. 1D, the joint side portion 10a can be formed. Next, as shown to FIG. 1C, the roll mold 10 is produced by processing the base material 11 which joined a pair of edge | sides 11a and 11c into a perfect circle shape.

  Here, the microplasma welding method refers to an arc that is further thinned by a thermal pinch effect through a narrow hole at the tip of the nozzle through a low-current (about 3 A) arc (non-migration type plasma arc) generated in a water-cooled nozzle. This is a welding method in which a column is generated and a small amount of H (hydrogen) is added to the shielding gas in order to reach the welding workpiece while the arc column remains thin, and the cooling pinch effect is maintained on the surface of the arc column by the dissociated heat. The arc column obtained by this welding method can be generated even at an extremely low current, and a stable arc can be obtained even at a minimum current of 0.1 A. If such a microplasma welding method is used, the base material 11 will not be melted down by the welding heat, and butt welding can be reliably performed. When stainless steel, heat-resistant corrosion-resistant alloy steel, or titanium steel is used as the base material 11, welding is possible even with a plate thickness of about 0.01 mm (10 μm).

(Manufacturing method of fine uneven substrate)
Next, the manufacturing method of the fine grooving | roughness base material using the roll mold 10 which concerns on the said embodiment is demonstrated. FIG. 2 is a schematic diagram showing an outline of the first application step and the first transfer step in the method for producing a fine uneven substrate according to the present embodiment. In the transfer apparatus 100 shown in FIG. 2, the uneven structure formed on the outer peripheral surface of the roll mold 10 is transferred to a transfer material to produce a fine uneven substrate.

As shown in FIG. 2, the transfer device 100 includes a feed roll 101 for feeding in succession a film-shaped base material F1 _a wound in a roll, and a take-up roll 102 for taking up the base material F1 _a I have. Between the feed roll 101 and the take-up roll 102, a coating from the upstream side in the transport direction of the base material F1 _a toward the downstream side, applying a resin J to be transferred to one side of the substrate F1 _a A roll 103 according to the above-described embodiment on the outer peripheral surface, and a shaping roll 104 that continuously transfers the concavo-convex structure to the photocurable resin J for transfer applied by the coating unit 103; A light source 105 for photocuring the photocurable resin having the concavo-convex structure transferred by the shaping roll 104 is provided via a plurality of transport rolls 106.

(First application process and transfer process)
Next, the first application process and the transfer process by the transfer apparatus 100 will be described. Feed roll 101 feeds the interleaf P wound through the (not shown) taken light transmissive substrate F1 _a. The base material F1 _a fed from the feed roll 101 is transported to the coating unit 103 via the plurality of transport rolls 106 while the interleaving paper P is transported via the roll 107, and on one side of the base material F1 _a . A photocurable resin (for example, an ultraviolet curable resin) is applied. Next, the substrate F1 _a, the outer peripheral surface of one side of the light curable resin is coated is forming roll 104, i.e., is conveyed in contact with the outer peripheral surface of the cylindrical mold 10, roll the photocurable resin The uneven structure provided on the surface of the mold 10 is pressed.

Then, with the concavo-convex structure on the surface of the roll mold 10 on forming roll 104 is pressed against the photocurable resin on the substrate F1 _a, and an exposure light source 105 to the outer peripheral surface of the roll mold 10 The photo-curing resin is photo-cured.

Next, after the base material F1 _a to which the concavo-convex structure has been transferred is attached onto the concavo-convex structure using the interleaf P conveyed through the roll 107 as a protective layer, the base material F1 _a is wound around the take-up roll 102, the wood F1 _b.

FIG. 3 is a schematic diagram showing the base material obtained in the first application step and the first transfer step of the method for manufacturing the base material having the fine concavo-convex structure on the surface according to the present embodiment. As shown in FIG. 3, the base material F1 _b has a portion 21 where the uneven pattern is interrupted.

(Second application process and second transfer process)
Next, the first application process and the transfer process by the transfer apparatus 100 will be described. FIG. 4 is a schematic diagram showing an outline of the second coating step and the second transfer step of the method for manufacturing a base material having the fine uneven structure on the surface according to the present embodiment. The base material F1 _b to which the concavo-convex structure is transferred is set on the feeding roll 101 as shown in FIG. The base material F1 _b fed from the feed roll 101 is a period until the interleaf P (not shown) is transported through the roll 107 and reaches the shaping roll 104 through the plurality of transport rolls 106. in the dispenser 108 (e.g., manufactured by Musashi engineering ML-5000XII and Iwashita engineering Ltd. ACCURA series), the light curing resin portion unevenness pattern of the substrate F1 _b is interrupted (e.g., ultraviolet curable resin) is applied. At this time, if the photocurable resin is periodically applied at a distance between the portions where the uneven patterns in the flow direction of the base material F1 _b are interrupted, the photocurable resin is selectively applied only to the portions where the uneven patterns are interrupted. can do. Next, the base material F1 _b is conveyed in the shaping roll 104 so as to come into contact with the outer peripheral surface of one surface coated with the photocurable resin, that is, the outer peripheral surface of the roll mold 10, and the roll mold is applied to the photocurable resin. The concavo-convex structure provided on the surface of 10 is pressed.

Then, with the concavo-convex structure of the roll mold 10 surface it is pressed against the photocurable resin on the substrate F1 _b, and exposure from the light source 105 to the outer peripheral surface of the roll mold 10, photocuring a photocurable resin To do.

Next, the base material F1 _b to which the concavo-convex structure has been transferred is pasted on the concavo-convex structure using the interleaf P conveyed through the roll 107 as a protective layer, and then wound on the take-up roll 102. It becomes material F2. The fine concavo-convex base material F2 is manufactured as described above.

  FIG. 5 is a schematic diagram showing the fine uneven substrate F2 of the present embodiment. As shown in FIG. 5, the concave / convex pattern 31 is formed on the fine concave / convex base material F <b> 2 by the second application process and the second transfer process.

(Wire grid polarizer)
The wire grid polarizing plate according to the present embodiment includes a fine uneven base material F2 obtained using the roll mold 10 according to the above embodiment, and a metal wire provided on the fine uneven base material F2. Prepare. This wire grid polarizing plate deposits a metal such as Al on a fine concavo-convex base material F2 having a concavo-convex structure of a grid structure manufactured using a roll mold 10, and removes unnecessary metal by etching to remove a metal wire. Manufactured by forming. In addition, you may provide the dielectric material layer which improves the adhesiveness between the fine uneven base material F2 and a metal wire between the fine uneven base material F2 and a metal wire as needed.

  As a method for forming the metal wire, for example, in consideration of productivity, optical characteristics, etc., an oblique deposition method is used in which deposition is performed from a direction inclined with respect to the surface of the concavo-convex structure forming surface of the fine concavo-convex substrate F2. Can do. By using the oblique deposition method, a wire grid polarizing plate can be manufactured by a roll-to-roll method with good production efficiency.

  The etching method is not particularly limited as long as it does not adversely affect the fine concavo-convex base material F2 and can selectively remove the conductor portion, but from the viewpoint of productivity, a method of immersing in an alkaline aqueous solution is preferable.

  In this way, from a fine concavo-convex pattern-shaped substrate that reduces the unused area by transferring the concavo-convex pattern to the portion where the concavo-convex pattern of the fine concavo-convex substrate is interrupted, or from a mold having the inverted concavo-convex pattern The wire grid polarizing plate obtained by linearly forming a reflective metal on a replicated large-area fine uneven pattern substrate has no light leakage during crossed Nicols, and the visibility of the overlapped portion is It can be used as a large area reflective polarizing plate.

  Examples and comparative examples performed for clarifying the effects of the present invention will be described below. In addition, this invention is not limited at all by these Examples and Comparative Examples.

  In the following Examples and Comparative Examples, a fine concavo-convex base material was produced, and a wire grid polarizing plate sheet was produced by depositing Al on the convex portions of the produced fine concavo-convex base material. Then, a substantially rectangular wire grid polarizer used for a liquid crystal display or the like is cut out from the produced wire grid polarizer sheet and placed on the backlight of the LCD so that the brightness and visibility of the overlapped portion (white brightness and black brightness) (Visibility of luminance) was evaluated (Example 1).

(Production of roll mold)
First, using a Ni electroforming mold having a fine uneven pattern of L / S with a pitch of 140 nm, the fine uneven pattern was thermally transferred to a cycloolefin resin plate (COP resin plate). Ni was sputtered on the surface of this resin plate as a conductive treatment, and then Ni was electroplated to produce a master plate (Ni electroformed plate) having a width of 210 mm × a length of 260 mm and a thickness of 0.2 mm. Next, the Ni electroformed plate was bent into a cylindrical shape, and both end portions were butt welded by microplasma welding to produce a cylindrical mold (roll stamper) having an inner diameter of 82.5 mm.

(Preparation of fine uneven substrate)
(First application process and transfer process)
The produced roll stamper was inserted on a rotating shaft whose outer diameter was 80 mm to 85 mm, and the rotating shaft was expanded to fix the roll stamper on the rotating shaft. The rotating shaft was processed so that the outer diameter when expanded was 82.5 mm and the roundness of the roll stamper after fixing was 15 μm. This was set as the shaping roll 104 of the transfer apparatus 100 shown in FIG. 2, and the grid-like convex portions were transferred by continuous UV transfer to produce a fine irregular base material. A TAC film with a film thickness of 80 μm (TD80UL-H: manufactured by FUJIFILM Corporation) is used as the base film F1, and acrylic UV curing is performed on one side by a gravure roll (coating part 103) with a # 225 oblique line and a pattern part width of 180 mm. A resin (refractive index of 1.52) was applied so as to have a width of 180 mm × application thickness of 2 μm to 3 μm. Using a UV lamp (light source 105) as a device for curing the acrylic ultraviolet curing resin, which was placed at the apex of the fixed roll stamper on the rotating shaft (when the base film F1 _a closest approach), 200 mW / cm Irradiated at an illuminance of ² . The produced film-like fine concavo-convex base material F1 _b was wound up in a roll shape by a winding roll 102.

Cut part of F1 _b produced by the first transfer step, contact-type film thickness meter, the sheet thickness using a laser microscope, measurement of the surface roughness, the step portion is concave-convex pattern portion and the uneven pattern was interrupted The roughness was 1.6 μm and the maximum was 1 μm.

(Production of photocurable resin)
Trimethylolpropane triacrylate (TMPTA) is 32% by mass as a monomer that is a trifunctional or higher acrylate compound, and N-vinyl-2-pyrrolidone (NVP) is 32% by mass as a monomer that is an N-vinyl compound. 33% by mass of 1,9-nonanediol diacrylate as another monomer and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Darocur TPO manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 1% by mass of silicon diacrylate was blended as a silicon compound containing an acrylic group by mass%, and foreign matter was filtered to prepare a photocurable resin (Composition 1).

(Second application process and second transfer process)
The fine uneven base material F1 _b obtained as described above is set on the feeding roll 101 of the transfer device 100 as shown in FIG. 4, and the portion where the uneven pattern is interrupted by the dispenser 108 of the transfer device 100 and its portion 0.002 cc of the acrylic ultraviolet curable resin was applied to the periphery. Since the acrylic ultraviolet curable resin is the same as the resin used in the first transfer step, it is possible to apply a thin coating with good wettability. Moreover, since the extending direction of the concave / convex pattern is the same as the extending direction of the long side of the portion where the concave / convex pattern is interrupted, it is possible to prevent the ultraviolet curable resin from leaking to the portion where the concave / convex pattern is transferred in the first transfer step. Can do. The coated base material was irradiated on the shaping roll 104 of the transfer apparatus 100 with a light source 105 at an illuminance of 200 mW / cm ² . The fine uneven base material F2 on the produced film was wound up into a roll shape by a winding roll 102.

  Then, when the level | step difference of the boundary part of a 1st transfer process and a 2nd transfer process was measured with the stylus type film thickness meter, it was 982 nm.

(Example 2)
(Preparation of fine uneven substrate)
In the same manner as in Example 1 in the first application step and the first transfer step, a fine uneven substrate F1 _b was obtained.

Then, the the second coating step and set a fine uneven substrate F1 _b to feed roll 101 of the transfer device 100 in the second transfer step, and diluted 10-fold with ethanol in the portion and its periphery is uneven pattern interrupted Acrylic ultraviolet curable resin was applied by 0.015 cc with a dispenser. Application of the acrylic UV curable resin compared to the case of application in Example 1 by volatilizing most of the ethanol of the acrylic UV curable resin diluted with ethanol until the shaping roll 104 is reached. The film thickness can be reduced. This was irradiated on the shaping roll 104 of the transfer apparatus 100 with a light source 105 at an illuminance of 200 mW / cm ² . The fine uneven base material F2 on the produced film was wound up into a roll shape by a winding roll 102.

  As in Example 1, the step at the boundary between the first transfer step and the second transfer step was measured with a stylus type film thickness meter and found to be 420 nm.

  A wire grid was prepared using the fine uneven base material F2 obtained in Example 1 and Example 2.

(Production of wire grid)
(Drying of uneven substrate)
In order to dry the water contained in the fine uneven substrate F2 obtained as described above, the roll-shaped fine uneven substrate F2 is transferred to a vacuum chamber provided with three 200W infrared heaters, The film of the fine uneven substrate F2 was run at 2 m / min while unwinding in a vacuum, and after heating, it was wound up into a roll. The degree of vacuum when the film running was stopped was 0.03 Pa, and the degree of vacuum during film running (drying) was 0.15 Pa. Moreover, in order to know the surface temperature of the TAC film of the fine uneven base material F2 after passing through the infrared heater, a thermo label was pasted on the TAC film in advance. The surface temperature of the TAC film after passing through the heater was between 60 ° C and 110 ° C.

(Formation of dielectric layer using sputtering method)
The fine uneven substrate F2 after drying was left in a vacuum tank of a dryer for 12 hours, and the temperature of the TAC film of the fine uneven substrate F2 was lowered to 23 ° C. Thereafter, the fine concavo-convex base material F2 was transferred to a vacuum chamber for forming a dielectric layer and forming a metal wire, and a dielectric layer and a metal wire were provided on the transfer surface of the lattice-shaped convex portion. Reactive AC magnetron sputtering was used to form the dielectric layer. Two silicon targets with a target size of 127 mm x 750 mm x 10 mmt are arranged in a roll shape under conditions of substrate to target distance 80 mm, argon gas flow rate 200 sccm, nitrogen gas flow rate 300 sccm, output 11 kW, frequency 37.5 kHz, travel speed 5 m / min. While unwinding the fine uneven base material F2, the film was transported to the take-up roll side by a film transport roll (main roller) to provide a silicon nitride layer as a dielectric layer. Thereafter, the fine uneven substrate F2 provided with the dielectric layer was wound up in a roll shape. The tension during sputtering was 30 N, the main roller temperature was 30 ° C., the background vacuum before starting sputtering was 0.005 Pa, and the vacuum during sputtering was 0.38 Pa. Silicon nitride was deposited on the Si chip under the same conditions, and the thickness of the silicon nitride layer was calculated using an ellipsometer. The thickness was 3 nm.

(Aluminum deposition)
After a silicon nitride layer is formed as a dielectric layer on the transfer surface of the grid-like convex portions of the fine concavo-convex base material F2 by a sputtering method, the film of the fine concavo-convex base material F2 is rotated in the direction opposite to that during sputtering of the silicon nitride layer. Then, a metal wire was formed by a resistance heating vapor deposition method, and the fine uneven substrate F2 on which the metal wire was formed was wound into a roll. In this example, aluminum (Al) was used as the metal.

  The oblique deposition method is used for the deposition of aluminum, and the angle formed by the normal deposition source on the substrate surface starts from 32 ° (θd) and ends at 15 ° (θs) in a plane perpendicular to the longitudinal direction of the lattice. A mask was placed on the surface. The opening width of the mask was 60 mm, and the distance between the center of the mask opening and the evaporation boat (deposition material) was 400 mm. The degree of vacuum before heating the vapor deposition boat was 0.005 Pa. The tension was 30 N, and the temperature of the main roller was 30 ° C. Pursuant to the above conditions, a purity of 99.9% or more on the heated boat while the film of the fine concavo-convex base material F2 having the lattice-shaped convex portion transferred at a film feed speed of 3.5 m / min is run on the heated boat. An aluminum wire having a diameter of 1.7 mm was fed at a feed rate of 200 mm / min to deposit aluminum. Then, the fine uneven base material F2 on which aluminum was vapor-deposited was wound up in a roll shape. About the obtained fine uneven base material F2, the film part of the late vapor deposition was cut out, and it was 130 nm when the film thickness of aluminum was converted from the emitted light intensity of the fluorescent X ray.

(Aluminum etching)
The film roll of the fine concavo-convex base material F2 to which the grid-like convex portions formed with the silicon nitride layer and the metal wire (aluminum) are transferred is 0.1 weight at a temperature of 23 ° C. while unwinding the film of the fine concavo-convex base material F2. It was run for 65 seconds in a% NaOH aqueous solution tank. Next, it was washed with water and air-dried to obtain the intended roll of wire grid polarizer.

(Visibility evaluation of white luminance and black luminance on the backlight)
A wire grid polarizing plate was disposed on the backlight instead of the PVA polarizing plate as the back polarizing plate of the LCD, and the front white luminance and black luminance were measured. They were 220 cd / m ² , 0.2 cd / m ² 230 cd / m ² , and 0.3 cd / m ² , respectively. In the white display and black display states, there was no change in the visibility of the wire grid at the boundary between the first transfer process and the second transfer process, and it was at a level that is practically acceptable.

  In addition, this invention is not limited to the said embodiment, It can change and implement variously. In the above-described embodiment, the size, shape, and the like illustrated in the accompanying drawings are not limited to this, and can be appropriately changed within a range in which the effect of the present invention is exhibited.

  The present invention is a production method capable of improving the yield of a fine concavo-convex substrate, for example, a wire grid polarizer used for a liquid crystal display, a polarizing beam splitter, an infrared communication device, a sensor, a medical-related inspection device, a display, etc. It can be suitably applied to the production of optical elements used as antireflection films for devices, solar cells, various types of lighting, copying machines, and the like.

DESCRIPTION OF SYMBOLS 10 Roll mold 10a Joining edge part 11 Base material 11a, 11b, 11c, 11d Opposite side 12 Original plate 101 Feeding roll 102 Winding roll 103 Coating part 104 Shaping roll 105 Light source 106 Conveying roll 107 Roll 108 Dispenser

Claims (3)

A first application step of applying the first resin composition on the base substrate;
The first resin composition applied in the first coating step, the joining portions of the pattern, Interrupted first transfer step of forming a first concave-convex pattern portion by transferring an uneven pattern of the roll mold having the pattern ,
A second application step of selectively applying the second resin composition to a portion where the first uneven pattern portion formed in the first transfer step is interrupted and its peripheral portion; and
A substrate having a fine concavo-convex structure on the surface, characterized by a second transfer step in which the concavo-convex pattern of the roll mold used in the first transfer step is transferred only to the second resin composition applied in the second application step. Manufacturing method.   The level difference of the part which said 1st uneven | corrugated pattern part and said 1st uneven | corrugated pattern part interrupted is 2 micrometers or less, and the roughness of the part which said 1st uneven | corrugated pattern part interrupted is 2 micrometers or less. The manufacturing method of the base material which has the fine concavo-convex structure on the surface. Bonding the base material provided with a concavo-convex structure on the surface in a roll shape by a microplasma welding method to form the roll mold,
The method for producing a substrate having a fine concavo-convex structure on the surface according to claim 1 or 2, wherein in the second application step, the second resin composition is applied by a dispenser.

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