JP2013129198A - Formed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a formed body having a cured film with salients formed irregularly in arrangement on a surface of the cured film and being spaced apart averagely by 100 nm or more from each other, and to provide a method of manufacturing the formed body simply.SOLUTION: In a formed body having salients formed on a surface, the salients are two or more aggregated protrusions formed on the surface of the formed body and composed of a hardened matter of an active energy ray-curable resin composition, the average interval of the protrusions is ≤400 nm, and the average interval of the salients is ≤400 nm.

Description

  The present invention relates to a molded body having a cured film having fine convex portions formed on the surface.

  In recent years, a material having a surface with a fine concavo-convex structure having a period equal to or shorter than the wavelength of light exhibits functionality such as an antireflection function, a Lotus effect, and the like. In particular, a fine concavo-convex structure called the Moth-Eye structure in which protrusions such as a substantially conical shape, a triangular pyramid shape, and a quadrangular pyramid shape are arranged is effective by continuously increasing from the refractive index of air to the refractive index of the material. It is known to become a means for preventing reflection.

The following method is known as a method for forming a fine relief structure on the material surface.
(1) A method of producing a mold using an electron beam lithography method and transferring an inverted structure of the mold.
(2) A method in which a mold having a reversal structure corresponding to a fine concavo-convex structure is produced by laser beam interferometry, and the reversal structure of the mold is transferred (Patent Document 1).
(3) Anodized alumina having pores on the surface (hereinafter simply referred to as anodized alumina) obtained by anodizing aluminum is used as a mold, and the pores of the mold are transferred to form protrusions. Method (Patent Document 2).

  According to the methods (1) and (2), it is possible to produce molds with different periods, heights and shapes, but it is not only difficult to increase the area, but also fine irregularities obtained by transfer. Since the regularity of the structure is high, an interference color is generated, which causes an appearance problem in applications such as an antireflection film.

  In the method (3), the surface of the material is industrially more productive than other methods because the area of the mold can be increased, the size can be increased, and a seamless roll-shaped mold can be easily produced. In this method, a fine uneven structure can be formed. Further, since the pores are formed in a self-organized manner, there is no long-range regularity, and no interference color is generated on the transfer surface.

  Anodized alumina uses oxalic acid as an electrolytic solution, and when anodized aluminum is formed at a formation voltage of 40 V, highly regular pores with a period of about 100 nm are formed on the surface, and sulfuric acid is used as an electrolytic solution. When aluminum is anodized at 25 V, it is known that highly regular pores with a period of about 63 nm are formed on the surface (Non-patent Document 1).

  However, when aluminum is anodized by a combination other than the combination of the electrolytic solution and the formation voltage, not only the regularity of the pores but also the straightness of the pores or the pores branch. Anodized alumina that has pores with periods other than about 100 nm and about 63 nm and can be used as a mold for a molded article used for optical applications such as antireflection, could not be obtained in practice. For this reason, it has not been possible to obtain a molded article having protrusions with a period other than about 100 nm or 63 nm, particularly a molded article having protrusions with a period greater than 100 nm.

  Prior to the anodic oxidation of aluminum, a substrate having protrusions produced by electron beam lithography or the like is pressed against the aluminum surface to form fine dents, and the pits are used as pore generation points for anodic oxidation, so that the period is increased. A method of forming pores other than about 100 nm and about 63 nm has been proposed (Patent Document 3).

However, in this method, since it is necessary to produce a substrate having protrusions by electron beam lithography or the like, it cannot cope with an increase in area as in a mold. Even if a mold obtained in a small area is used as a mold, the fine concavo-convex structure obtained by transfer has very high regularity, produces interference colors, and has problems in application to antireflection films and the like. there were.
Therefore, as described above, it is difficult to form a non-regular protrusion structure with a period of 100 nm or more by the conventionally known methods (1) to (3).

JP 2001-264520 A JP 2005-156695 A JP-A-10-121292

Masuda, “Preparation of highly ordered anodic porous alumina and its application to nanofabrication”, Applied Physics, 2000, Vol. 69, No. 5, p. 558

  Therefore, the objective of this invention is providing the molded object which has the cured film in which the convex part which has an average space | interval of 100 nm or more and has an arrangement | sequence regularity was formed in the surface.

The molded body of the present invention is a molded body having convex portions formed on the surface thereof, wherein the convex portions are formed by assembling two or more of the following projections, and the average interval between the convex portions is 400 nm or less. It is characterized by being.
(Projection)
A plurality of protrusions made of a cured product of the active energy ray-curable resin composition formed on the surface of the molded body, and an average interval between the protrusions is 400 nm or less.

The molded body of the present invention is preferably an antireflection member in which the cured film on which the convex portions are formed is an antireflection film.
The molded article of the present invention is preferably a member that improves the light extraction efficiency of electroluminescence or a light emitting diode.

  The molded article of the present invention has a cured film having an average interval of 100 nm or more and having a convex portion having no regular arrangement on the surface, which can be used for optical applications such as antireflection.

2 is a scanning electron micrograph of the cross section of the molded product obtained in Example 1. FIG. It is sectional drawing which shows a part of manufacturing process of an anodized alumina. It is sectional drawing which shows an example of the manufacturing method of the molded object of this invention. It is sectional drawing which shows the other example of the manufacturing method of the molded object of this invention.

  In this specification, (meth) acrylate means an acrylate or a methacrylate. Moreover, an active energy ray means visible light, an ultraviolet-ray, an electron beam, plasma, a heat ray (infrared rays etc.), etc.

<Molded body>
The molded body of the present invention is a molded body having a cured film on the surface of which convex portions (aggregates) formed by aggregation of two or more protrusions are formed as shown in FIG. The convex portion may be formed on a part of the surface of the molded body or may be formed on the entire surface.

  The protrusions are a plurality of protrusions made of a cured product of the active energy ray-curable resin composition, and the average interval between the protrusions is 400 nm or less. When the protrusions are formed using an anodized alumina mold, the average distance between the protrusions is at most about 100 nm, and is preferably 200 nm or less, and particularly preferably 150 nm or less.

  Assuming that the aspect ratio (height / cycle) of the protrusion is independent without forming a convex portion, 1.1 or more is preferable, 1.3 to 7 is more preferable, and 1.5 to 5 is Particularly preferred. When the aspect ratio of the protrusions is less than 1.1, the ratio of protrusions (hereinafter referred to as single protrusions) that are present alone without forming convex portions increases even if the elastic modulus of the protrusions is low. When the aspect ratio of the protrusion exceeds 7, the releasability from the mold is remarkably lowered.

  The ratio of the single protrusions is preferably 40% or less, more preferably less than 20%, and particularly preferably less than 10%, out of the total (100%) of the protrusions forming the convex portion (aggregate) and the single protrusions. When the proportion of the single protrusion is more than 40%, it becomes difficult to develop the performance (specifically, the light extraction performance due to -1st order diffraction from the total reflection interface) obtained with a molded product having a wide interval between the convex portions.

  The ratio of the protrusions forming the protrusions is preferably 60% or more, more preferably more than 80%, out of the total (100%) of the protrusions forming the protrusions (aggregates) and the single protrusions, 90% More than% is particularly preferred. When the ratio of the protrusions forming the protrusions is less than 60%, the performance obtained with a molded body having a wide interval between the protrusions (specifically, light extraction performance by -1st order diffraction from the total reflection interface) It becomes difficult to express.

  The number of protrusions forming the convex portion is two or more, more preferably 2 to 10, and most preferably 2 to 7. As the number of protrusions forming the convex portion increases, the interval between the convex portions increases. All the convex portions may not be an aggregate of the same number of protrusions, but the distribution should be as narrow as possible. Further, the protrusions forming the convex portion may be fused or not fused.

  When the molded body of the present invention is used as an antireflection member, the shape of the convex portion is a shape in which the convex sectional area in the direction orthogonal to the height direction continuously increases from the outermost surface in the depth direction, that is, the convex portion. The cross-sectional shape in the height direction is preferably a triangle, trapezoid, bell shape or the like.

The average interval between the convex portions is 400 nm or less, preferably 350 nm or less, and more preferably 300 nm or less. When the average interval between the convex portions exceeds 400 nm, the visible light is scattered, which is not suitable for optical use such as an antireflection member.
The average interval between the convex portions is preferably 100 nm or more, more preferably 130 nm or more, and particularly preferably 150 nm or less. When the average interval between the convex portions is less than 100 nm, the performance (specifically, the light extraction performance by the first-order diffraction from the total reflection interface) that is obtained with a molded article having a wide interval between the convex portions is difficult to be exhibited. Become.
The average interval between the convex portions is obtained by measuring 50 intervals between adjacent convex portions (distance from the center of the convex portion to the center of the adjacent convex portion) by electron microscope observation, and averaging these values. .

The height of the convex part is preferably ½ to 4 times the base of the convex part. When the height of the convex portion is less than ½ times the bottom of the convex portion, the antireflection effect is low. When the height of the convex portion exceeds four times the bottom of the convex portion, mechanical strength such as scratch resistance becomes weak.
The arrangement of the convex portions has no regularity. That is, the set of protrusions is generated randomly. If there is regularity, an interference color is generated, which causes a problem in appearance in an application where it is used on the outermost surface such as an antireflection film.

The cured film may be provided on the surface of the transparent substrate. Examples of the transparent substrate include the transparent substrate.
The difference between the refractive index of the cured film and the refractive index of the transparent substrate is preferably 0.2 or less, more preferably 0.1 or less, and particularly preferably 0.05 or less. When the refractive index difference exceeds 0.2, reflection at the interface between the cured film and the transparent substrate increases, and when used as an antireflection member, reflection at the interface between the cured film and air is caused by the Moth-Eye structure. Even if it is kept low, the reflectivity of the antireflection member as a whole does not become sufficiently low.

The molded article of the present invention includes an antireflection film, an antireflection film, an antireflection article, an optical waveguide, a relief hologram, a lens, a polarization separation element, a light extraction efficiency improving film, a half-wave plate, a low-pass filter, a crystal device, and the sun. Optical articles such as batteries; application development as cell culture sheets, super-water-repellent films, super-hydrophilic films, etc. can be expected, especially for use as anti-reflective members (anti-reflective films, anti-reflective films, anti-reflective articles) Is suitable.
Examples of the antireflection member include an image display device (liquid crystal display device, plasma display panel, electroluminescence display, cathode tube display device, etc.), automobile meter cover, lens, show window, glasses, half-wave plate, Examples thereof include an antireflection film, an antireflection film, and an antireflection sheet provided on the surface of a low-pass filter.
When used in an image display device, an antireflection film may be applied on the outermost surface, or an antireflection film may be formed directly on the material forming the outermost surface, and the antireflection film is formed on the front plate of the image display device. A film may be provided.

<Method 1 for producing molded article>
The method for producing a molded product of the present invention is a method for producing a molded product having a cured film having a convex portion formed on the surface, and includes a method having the following steps as an example.
(I) A step of bringing the active energy ray-curable resin composition into contact with the surface of the mold having pores on the surface.
(Ii) In the state where the active energy ray-curable resin composition is in contact with the surface of the mold, the active energy ray-curable resin composition is irradiated with active energy rays to cure the active energy ray-curable resin composition. And forming a cured film having protrusions corresponding to the pores.
(Iii) By separating the cured film and the mold at a temperature at which the elastic modulus of the smooth cured film of the active energy ray-curable resin composition is less than 1 GPa, the protrusions on the surface of the cured film are 2 The process of forming the convex part formed by gathering two or more.

(I) Process:
The mold is not particularly limited, and examples include molds produced by electron beam drawing, those produced by laser beam interferometry, anodized alumina, etc., which can increase the area, and make roll molds easy. From a certain point, anodized alumina is preferable.

(Anodized alumina)
Anodized alumina is a porous oxide film (alumite) of aluminum.

Anodized alumina can be produced, for example, through the following steps (a) to (e).
(A) A step of forming an oxide film by anodizing aluminum in an electrolytic solution under a constant voltage.
(B) A step of removing the oxide film and forming pore generation points for anodic oxidation.
(C) A step of anodizing aluminum again in an electrolytic solution to form an oxide film having pores at the pore generation points.
(D) A step of enlarging the diameter of the pores.
(E) A step of repeatedly performing the steps (c) and (d).

(A) Process:
The purity of aluminum is preferably 99% or more, more preferably 99.5% or more, and particularly preferably 99.8% or more. When the purity of aluminum is low, when anodized, an uneven structure having a size to scatter visible light may be formed due to segregation of impurities, or the regularity of pores obtained by anodization may be lowered.
Examples of the electrolytic solution include sulfuric acid and oxalic acid.

When using oxalic acid as electrolyte:
The concentration of oxalic acid is preferably 0.7 M or less. When the concentration of oxalic acid exceeds 0.7M, the current value becomes too high, and the surface of the oxide film may become rough.
When the formation voltage is 30 to 60 V, anodized alumina having highly regular pores with a period of 100 nm can be obtained. Regardless of whether the formation voltage is higher or lower than this range, the regularity tends to decrease.
The temperature of the electrolytic solution is preferably 60 ° C. or lower, and more preferably 45 ° C. or lower. When the temperature of the electrolytic solution exceeds 60 ° C., a so-called “burn” phenomenon occurs, and the pores may be broken, or the surface may melt and the regularity of the pores may be disturbed.

When using sulfuric acid as the electrolyte:
The concentration of sulfuric acid is preferably 0.7M or less. If the concentration of sulfuric acid exceeds 0.7M, the current value may become too high to maintain a constant voltage.
When the formation voltage is 25 to 30 V, anodized alumina having highly regular pores with a period of 63 nm can be obtained. The regularity tends to decrease whether the formation voltage is higher or lower than this range.
The temperature of the electrolytic solution is preferably 30 ° C. or lower, and more preferably 20 ° C. or lower. When the temperature of the electrolytic solution exceeds 30 ° C., a so-called “burn” phenomenon occurs, and the pores may be broken or the surface may melt and the regularity of the pores may be disturbed.

(B) Process:
The regularity of the pores can be improved by once removing the oxide film and using this as the pore generation point for anodic oxidation.

  Examples of the method for removing the oxide film include a method in which aluminum is not dissolved but is dissolved in a solution that selectively dissolves alumina and removed. Examples of such a solution include a chromic acid / phosphoric acid mixed solution.

(C) Process:
As shown in FIG. 2, when the aluminum 12 from which the oxide film has been removed is anodized again, an oxide film 16 having cylindrical pores 14 is formed.
Anodization may be performed under the same conditions as in step (a). Deeper pores can be obtained as the anodic oxidation time is lengthened.

(D) Process:
As shown in FIG. 2, a process for expanding the diameter of the pores 14 (hereinafter referred to as a pore diameter expanding process) is performed. The pore diameter expansion treatment is a treatment for expanding the diameter of the pores obtained by anodic oxidation by immersing in a solution dissolving alumina. Examples of such a solution include a phosphoric acid aqueous solution of about 5% by mass.
The longer the pore diameter expansion processing time, the larger the pore diameter.

(E) Process:
As shown in FIG. 2, when the anodic oxidation in the step (c) and the pore diameter expansion process in the step (d) are repeated, the pores 14 have a shape in which the diameter continuously decreases in the depth direction from the opening. Anodized alumina (mold 10) is obtained.
The total number of repetitions is preferably 3 times or more, and more preferably 5 times or more. When the number of repetitions is 2 times or less, the diameter of the pores decreases discontinuously. Therefore, the effect of reducing the reflectivity of a cured film (antireflection film) manufactured using anodized alumina having such pores is obtained. Inferior.

The surface of the anodized alumina may be treated with a release agent so as to facilitate separation from the cured film. Examples of the treatment method include a method of coating a silicone polymer or a fluorine polymer, a method of depositing a fluorine compound, a method of coating a fluorine silane coupling agent or a fluorine silicone silane coupling agent, and the like.
Examples of the shape of the anodized alumina include a flat plate shape, a columnar shape, and a cylindrical shape. Examples of the columnar or cylindrical mold include a mold made of columnar or cylindrical aluminum, or a mold having an aluminum layer on the surface of a columnar or cylindrical support.

Examples of the shape of the mold pore include a cone shape, a pyramid shape, and a cylindrical shape. When the molded body of the present invention is used as an antireflection member, the shape is perpendicular to the depth direction, such as a cone shape or a pyramid shape. A shape in which the cross-sectional area of the pores in the direction to be continuously decreased from the outermost surface in the depth direction is preferable.
The surface of the cured film manufactured using the mold 10 having the pores 14 as shown in FIG. 2 has a so-called Moth-Eye structure, which is an effective antireflection means.

The depth of the mold pores is preferably 60 nm or more, and more preferably 100 nm or more. When the depth of the pores is 90 nm or more, the reflectance of the obtained cured film (antireflection film) is sufficiently low.
The aspect ratio (depth / period) of the pores of the mold is preferably 1.1 or more, more preferably 1.3 to 7, and particularly preferably 1.5 to 5. When the aspect ratio of the pores is less than 1.1, the ratio of single protrusions increases even if the elastic modulus of the protrusions is low. When the aspect ratio of the pores exceeds 7, the releasability from the mold is significantly lowered.

(Active energy ray-curable resin composition)
The active energy ray curable composition contains a polymerizable compound and a polymerization initiator.
Examples of the polymerizable compound include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.
The active energy ray-curable composition may contain a non-reactive polymer, an active energy ray sol-gel reactive composition.

Examples of the monomer having a radical polymerizable bond include a monofunctional monomer and a polyfunctional monomer.
Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, Phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl ( )) (Meth) acrylate derivatives such as acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate; (meth) acrylic acid, (meth) acrylonitrile; styrene, α -Styrene derivatives such as methylstyrene; (meth) acrylamide derivatives such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and the like. These may be used alone or in combination of two or more.

  Polyfunctional monomers include ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, polybutylene glycol di (Meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (3- ( Ta) acryloxy-2-hydroxypropoxy) phenyl) propane, 1,2-bis (3- (meth) acryloxy-2-hydroxypropoxy) ethane, 1,4-bis (3- (meth) acryloxy-2-hydroxypropoxy) ) Butane, dimethylol tricyclodecane di (meth) acrylate, ethylene oxide adduct di (meth) acrylate of bisphenol A, propylene oxide adduct di (meth) acrylate of bisphenol A, neopentyl glycol di (meth) hydroxypivalate Bifunctional monomers such as acrylate, divinylbenzene, and methylenebisacrylamide; pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide Functional tri (meth) acrylate, trimethylolpropane propylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate and other trifunctional monomers; succinic acid / trimethylolethane / acrylic acid 4 or more functional monomers such as dipentaerystol hexa (meth) acrylate, dipentaerystol penta (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethanetetra (meth) acrylate; bifunctional or more Urethane acrylates, bifunctional or higher functional polyester acrylates, and the like. These may be used alone or in combination of two or more.

  Examples of the monomer having a cationic polymerizable bond include monomers having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like, and a monomer having an epoxy group is particularly preferable.

  Examples of the oligomer or reactive polymer include unsaturated polyesters such as a condensate of unsaturated dicarboxylic acid and polyhydric alcohol; polyester (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, epoxy (meth) Examples thereof include acrylates, urethane (meth) acrylates, cationic polymerization type epoxy compounds, homopolymers of the above-described monomers having a radical polymerizable bond in the side chain, and copolymerized polymers.

Non-reactive polymers include acrylic resins, styrene resins, polyurethane resins, cellulose resins, polyvinyl butyral resins, polyester resins, thermoplastic elastomers, and the like.
Examples of the active energy ray sol-gel reactive composition include alkoxysilane compounds and alkylsilicate compounds.

As an alkoxysilane compound, the compound of following formula (1) is mentioned.
R _x Si (OR ′) _y (1).
However, R and R ′ each represent an alkyl group having 1 to 10 carbon atoms, and x and y represent integers satisfying the relationship of x + y = 4.

  Examples of the alkoxysilane compound include tetramethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyltriethoxysilane, Examples include methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, trimethylpropoxysilane, and trimethylbutoxysilane.

Examples of the alkyl silicate compound include a compound of the following formula (2).
R ¹ O [Si (OR ³ ) (OR ⁴ ) O] _z R ² (2).
However, R < ¹ > -R < ⁴ > represents a C1-C5 alkyl group, respectively, and z represents the integer of 3-20.

  Examples of the alkyl silicate compound include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, n-pentyl silicate, acetyl silicate and the like.

  When using a photocuring reaction, examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxy. Acetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropane- Carbonyl compounds such as 1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoic acid Diethoxy phosphine oxide, and the like. These may be used alone or in combination of two or more.

  When using an electron beam curing reaction, examples of the polymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t- Thioxanthone such as butylanthraquinone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl Dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholy Phenyl) -butanone and other acetophenones; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)- Acylphosphine oxides such as 2,4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; methylbenzoylformate, 1,7-bisacridinylheptane, 9-phenyl Examples include acridine. These may be used alone or in combination of two or more.

  When utilizing a thermosetting reaction, examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, organic peroxides such as t-butylperoxybenzoate and lauroyl peroxide; azo compounds such as azobisisobutyronitrile; N, N-dimethylaniline, N, N-dimethyl-p- Examples thereof include a redox polymerization initiator combined with an amine such as toluidine.

  As for the quantity of a polymerization initiator, 0.1-10 mass parts is preferable with respect to 100 mass parts of polymeric compounds. When the amount of the polymerization initiator is less than 0.1 parts by mass, the polymerization is difficult to proceed. When the amount of the polymerization initiator exceeds 10 parts by mass, the cured film may be colored or the mechanical strength may be lowered.

  The active energy ray-curable composition may contain an antistatic agent, a release agent, an additive such as a fluorine compound for improving antifouling properties, fine particles, and a small amount of a solvent, if necessary.

Examples of the method of bringing the active energy ray-curable resin composition into contact with the surface of the mold include the following methods (I) to (III).
(I) A method of supplying an active energy ray-curable resin composition 20 between a mold 10 and a transparent substrate 24 and rolling with a nip roll or the like as shown in FIG.
(II) A method of applying the active energy ray-curable resin composition 20 to the surface of the mold 10 as shown in FIG. After applying the active energy ray-curable resin composition 20 to the surface of the mold 10, the coating film of the active energy ray-curable resin composition 20 may be covered with the transparent substrate 24.
(III) A method of pressing the mold 10 against the coating film of the active energy ray curable resin composition 20 after applying the active energy ray curable resin composition 20 on the transparent substrate 24 as shown in FIG.

Examples of the coating method include a roller coating method, a bar coating method, and an air knife coating method.
As the transparent substrate 24, a substrate capable of transmitting active energy rays, such as acrylic resin, polycarbonate, polystyrene resin, polyester, cellulose resin (such as triacetyl cellulose), polyolefin, alicyclic polyolefin, crystal, glass Etc.
Examples of the shape of the transparent substrate 24 include melt molded products such as films, sheets, injection molded products, and press molded products.
On the surface of the transparent substrate 24, a layer for improving adhesion and a hard coat layer may be formed.

(Ii) Process:
Irradiation of the active energy ray is performed using, for example, a high-pressure mercury lamp, a metal halide lamp, etc., and the active energy ray-curable resin composition 20 is in contact with the surface of the mold 10 (pores formed on the surface of the mold 10). In a state in which the active energy ray-curable resin composition 20 is filled.
The amount of light irradiation energy is preferably 100 to 10,000 mJ / cm ² .

(Iii) Process:
The temperature at which the cured film and the mold are separated is preferably a temperature at which the elastic modulus of the smooth cured film of the active energy ray-curable resin composition is less than 1 GPa, and more preferably 0 to 100 ° C. The smooth cured film means a smooth cured film obtained by curing an active energy ray-curable resin composition that does not have protrusions and protrusions on the surface. The elastic modulus of the smooth cured film can be measured with, for example, an ultra-micro hardness meter manufactured by Fischer Instruments.

  The elastic modulus of the smooth cured film at the temperature when separating the cured film and the mold is preferably less than 1 GPa, more preferably 0.01 GPa to 0.8 GPa, and most preferably 0.08 GPa to 0.6 GPa. If the elastic modulus of the smooth cured film is 0.01 GPa or more, the cured film has sufficient friction resistance and the like. If the elastic modulus of the smooth cured film is less than 1 GPa, when the cured film and the mold are separated, two or more protrusions on the surface of the cured film are aggregated to form a convex portion.

  In the manufacturing method of the molded body of the present invention described above, the cured film and the mold are separated at a temperature at which the elastic modulus of the smooth cured film is less than 1 GPa. As a result, a molded body having a cured film having a convex portion formed on the surface having convex portions having an average interval of 100 nm or more and having no regular arrangement is formed. It is done.

<Method 2 for producing molded body>
It is the method which has the following process as an example of the other manufacturing method of the molded object of this invention.
(Iv) A step of bringing the active energy ray-curable resin composition into contact with the surface of a mold having pores having an aspect ratio (depth / cycle) of 3.1 or more on the surface.
(V) In the state where the active energy ray-curable resin composition is in contact with the surface of the mold, the active energy ray-curable resin composition is irradiated with active energy rays to cure the active energy ray-curable resin composition. And forming a cured film having protrusions corresponding to the pores.
(Vi) By separating the cured film and the mold at a temperature at which the elastic modulus of the smooth cured film of the active energy ray-curable resin composition is 1 GPa or more, 2 protrusions on the surface of the cured film are formed. The process of forming the convex part formed by gathering two or more.

(Iv) Process:
Except for the aspect ratio of the pores of the mold, it is the same as the above-described step (i).
The aspect ratio (depth / cycle) of the pores of the mold is 3.1 or more, more preferably 3.1 to 7, and particularly preferably 3.1 to 5. When the aspect ratio of the pores is less than 1.1, the ratio of single protrusions increases even if the elastic modulus of the protrusions is low. When the aspect ratio of the pores exceeds 7, the releasability from the mold is significantly lowered.

(V) Process:
This is the same as step (ii) described above.

(Vi) Process:
Except for the elastic modulus of the smooth cured film, it is the same as the above-mentioned step (iii).
The elastic modulus of the smooth cured film at the temperature when separating the cured film and the mold is preferably 1 GPa or more, more preferably 1 GPa to 8 GPa, and most preferably 1 GPa to 5 GPa. If the elastic modulus of the smooth cured film is too high, the cured film may crack when peeled from the mold. If the elastic modulus of the smooth cured film is 1 GPa or more and the aspect ratio is 3.1 or more, when the cured film and the mold are separated, two or more protrusions on the surface of the cured film are aggregated to form a convex portion. Is done.

  In the method for producing a molded body of the present invention described above, if the aspect ratio of the pores of the mold is 3.1 or more, even if the elastic modulus of the smooth cured film is 1 GPa or more, the protrusions on the surface of the cured film are Convex portions formed by aggregation of two or more are formed, and as a result, a molded body having a cured film having an average interval of 100 nm to 400 nm and having convex portions having no regularity formed on the surface can be easily obtained. .

Examples of the present invention are shown below. However, the present invention is not limited to these.
Various measurements and evaluations in the examples were performed according to the following methods.

(Pores of anodized alumina)
A part of the anodized alumina is shaved, platinum is vapor-deposited on the cross section for 1 minute, and the cross section is subjected to an acceleration voltage of 3.00 kV using a field emission scanning electron microscope (JSM-7400F, manufactured by JEOL Ltd.). Observed and measured the period of the pores and the depth of the pores.

(Convex part of cured film)
Platinum was vapor-deposited on the fracture surface of the molded body for 10 minutes, and the cross-section was observed in the same manner as in anodized alumina, and the average interval between the convex portions (or single projections) and the height of the convex portions (or single projections) were measured. Each measurement was performed for 50 points, and the average value was obtained.

(Weighted average reflectance)
After the back surface of the transparent base material is roughened, the molded body coated with matte black is used with a spectrophotometer (manufactured by Hitachi, Ltd., U-4000), with an incident angle of 5 ° and a wavelength range of 380 to 780 nm. The reflectance was measured and calculated according to JIS R3106.

(Elastic modulus of smooth cured film)
About the cured film having no projection on the surface, obtained by filling the active energy ray-curable resin composition between the aluminum mirror plate and the film and irradiating the film side with ultraviolet rays of a predetermined integrated light amount, The measurement was performed at 20 ° C. under the following conditions using an ultrafine hardness meter (Fischer Instruments HM2000, manufactured by Fischer Instruments). The integrated amount of ultraviolet light to be irradiated was the same as the integrated amount of ultraviolet light during mold transfer.
Loading speed: 1 mN / 10 seconds,
Holding time: 10 seconds,
Load unloading speed: 1 mN / 10 seconds,
Indenter: Vickers.

(Light extraction efficiency improvement rate)
The film of the present invention was attached to the outermost surface of the organic EL display device with a double-sided optical tape having a refractive index of 1.47, and the entire surface was driven at a voltage of 5 V, and the luminance was measured.

[Mold production]
An aluminum rolled plate having a purity of 99.99% was electropolished in a perchloric acid / ethanol mixed solution (1/4 volume ratio).
(A) Process:
The aluminum plate was anodized in a 0.5 M oxalic acid aqueous solution for 6 hours under the conditions of a direct current of 40 V and a temperature of 16 ° C.
(B) Process:
The aluminum plate on which the oxide film was formed was immersed in a 6% by mass phosphoric acid / 1.8% by mass chromic acid mixed aqueous solution for 6 hours to remove the oxide film.

(C) Process:
The aluminum plate was subjected to anodization in a 0.3 M oxalic acid aqueous solution under the conditions of a direct current of 40 V and a temperature of 16 ° C. for the time shown in Table 1.
(D) Process:
The aluminum plate on which the oxide film was formed was immersed in 5% by mass phosphoric acid at 32 ° C. for the time shown in Table 1 to carry out pore diameter expansion treatment.

(E) Process:
The steps (c) and (d) were repeated 5 times in total to obtain anodized alumina a to e having substantially conical pores having the period and depth shown in Table 1.
Anodized alumina was immersed in a 0.1% by weight diluted solution of OPTOOL DSX (manufactured by Daikin Chemicals Sales Co., Ltd.) and air-dried overnight to subject the oxide film surface to fluorination treatment.

[Adjustment of active energy ray-curable resin composition]
Each component was mixed in the ratio shown in Table 2 and Table 3, and active energy ray-curable resin composition AF was prepared.

[Production of film]
75 parts by mass of a rubber-containing multistage polymer obtained by polymerizing methyl methacrylate, butyl acrylate, methyl acrylate, 1,3-butadiene and allyl methacrylate, and 25 parts by mass of an acrylic resin (BR80 manufactured by Mitsubishi Rayon Co., Ltd.) The part was melt-extruded in advance and then formed into a 200 μm thick acrylic resin film.

[Example 1]
(I) Process:
A few drops of the active energy ray-curable resin composition A are dropped on the surface of the anodized alumina b, and a polyethylene terephthalate film (A4300, manufactured by Toyobo Co., Ltd.) (hereinafter referred to as a PET film) is placed on the entire surface of the anodized alumina b. I spread it with a roller to spread.
(Ii) Process:
The curable resin composition A was cured by irradiating the coating film of the active energy ray-curable resin composition A with ultraviolet rays having an integrated light amount of 3200 mJ / cm ² from the PET film side.

(Iii) Process:
The cured film and the anodized alumina b were separated at 20 ° C. to obtain a molded body composed of a cured film having a convex portion formed on the surface and a PET film. Table 4 shows the elastic modulus of the smooth cured film, the ratio of the single protrusion, the structure of the protrusions, the average interval between the protrusions, the height of the protrusions, and the reflectance.

[Example 2]
Except having used active energy ray hardening resin composition B, it carried out similarly to Example 1, and obtained the molding which consists of a cured film by which the convex part was formed in the surface, and PET film. Table 4 shows the elastic modulus of the smooth cured film, the ratio of the single protrusion, the structure of the protrusions, the average interval between the protrusions, the height of the protrusions, and the reflectance.

Example 3
Except having used active energy ray hardening resin composition C, it carried out similarly to Example 1, and obtained the molding which consists of a cured film by which the convex part was formed on the surface, and PET film. Table 4 shows the elastic modulus of the smooth cured film, the ratio of the single protrusion, the structure of the protrusions, the average interval between the protrusions, the height of the protrusions, and the reflectance.

Example 4
Except having used anodized alumina a, it carried out similarly to Example 1, and obtained the molded object which consists of a cured film with which the convex part was formed in the surface, and PET film. Table 4 shows the elastic modulus of the smooth cured film, the ratio of the single protrusion, the structure of the protrusions, the average interval between the protrusions, the height of the protrusions, and the reflectance.

Example 5
Except for using the anodized alumina c and the active energy ray-curable resin composition C, a molded body composed of a cured film having a convex portion formed on the surface and a PET film was obtained in the same manner as in Example 1. Table 4 shows the elastic modulus of the smooth cured film, the ratio of the single protrusion, the structure of the protrusions, the average interval between the protrusions, the height of the protrusions, and the reflectance.

Example 6
Except for using the anodized alumina d and the active energy ray-curable resin composition D, a molded body composed of a cured film having a convex portion formed on the surface and a PET film was obtained in the same manner as in Example 1. Table 4 shows the elastic modulus of the smooth cured film, the ratio of the single protrusion, the structure of the protrusions, the average interval between the protrusions, the height of the protrusions, and the reflectance.

Example 7
Except for using the anodized alumina e and the active energy ray-curable resin composition E, a molded body composed of a cured film having a convex portion formed on the surface and a PET film was obtained in the same manner as in Example 1. Table 4 shows the elastic modulus of the smooth cured film, the ratio of the single protrusion, the structure of the protrusions, the average interval between the protrusions, the height of the protrusions, and the reflectance.

Example 8
Except having used active energy ray hardening resin composition F, it carried out similarly to Example 7, and obtained the molding which consists of a cured film by which the convex part was formed on the surface, and PET film. Table 4 shows the elastic modulus of the smooth cured film, the ratio of the single protrusion, the structure of the protrusions, the average interval between the protrusions, the height of the protrusions, and the reflectance.

Example 9
Instead of the PET film, an acrylic resin film was used, and a cured film having a convex portion formed on the surface and the acrylic resin film were used in the same manner as in Example 1 except that the cumulative amount of ultraviolet light was 400 mJ / cm ^2. A molded body was obtained. Table 4 shows the elastic modulus of the smooth cured film, the ratio of the single protrusions, the structure of the protrusions, the average interval between the protrusions, the height of the protrusions, the reflectance, and the light extraction efficiency improvement rate.

Example 10
Instead of the PET film, an acrylic resin film was used, and a cured film having a convex portion formed on the surface and an acrylic resin film were used in the same manner as in Example 2 except that the cumulative amount of ultraviolet light was 400 mJ / cm ^2. A molded body was obtained. Table 4 shows the elastic modulus of the smooth cured film, the ratio of the single protrusion, the structure of the protrusions, the average interval between the protrusions, the height of the protrusions, and the reflectance.

[Comparative Example 1]
The active energy ray-curable resin composition E was used, and a cured film having a single protrusion formed on the surface and a PET film were formed in the same manner as in Example 1 except that the cumulative amount of ultraviolet light was 400 mJ / cm ^2. A molded body was obtained. Table 5 shows the elastic modulus of the smooth cured film, the ratio of the single protrusions, the average interval between the single protrusions, the height of the single protrusions, and the reflectance.

[Comparative Example 2]
Except for using anodized alumina c, a molded body made of a cured film having a single protrusion formed on the surface and a PET film was obtained in the same manner as in Comparative Example 1. Table 5 shows the elastic modulus of the smooth cured film, the ratio of the single protrusions, the average interval between the single protrusions, the height of the single protrusions, and the reflectance.

Example 11
Except for using anodized alumina d, a molded body composed of a cured film having a single protrusion formed on the surface and a PET film was obtained in the same manner as in Comparative Example 1. Table 5 shows the elastic modulus of the smooth cured film, the ratio of the single protrusions, the average interval between the single protrusions, the height of the single protrusions, and the reflectance.

[Comparative Example 4]
Except having used active energy ray hardening resin composition F, it carried out similarly to Example 11, and obtained the molding which consists of a cured film and PET film in which the single processus | protrusion was formed in the surface. Table 5 shows the elastic modulus of the smooth cured film, the ratio of the single protrusions, the average interval between the single protrusions, the height of the single protrusions, and the reflectance.

[Comparative Example 5]
A molded body comprising a cured film having a single protrusion formed on the surface and an acrylic resin film was obtained in the same manner as in Comparative Example 1 except that an acrylic resin film was used instead of the PET film. Table 5 shows the elastic modulus of the smooth cured film, the ratio of the single protrusions, the average interval between the single protrusions, the height of the single protrusions, the reflectance, and the light extraction efficiency improvement rate.

  The molded article produced by the production method of the present invention is an antireflection film, an antireflection film, an antireflection article, an optical waveguide, a relief hologram, a lens, an automobile meter cover, a polarization separation element, and an organic electroluminescence light extraction efficiency improving film. , Half-wave plates, low-pass filters, crystal devices, and other optical articles; cell culture sheets, super-water-repellent films, super-hydrophilic films, etc. Suitable for use as a preventive article.

10 Mold 14 Pore 20 Active energy ray-curable resin composition

Claims (3)

A molded body having convex portions formed on the surface,
The convex portion is formed by aggregating two or more of the following protrusions,
The molded object whose average space | interval of the said convex part is 400 nm or less.
(Projection)
A plurality of protrusions made of a cured product of the active energy ray-curable resin composition formed on the surface of the molded body, and an average interval between the protrusions is 400 nm or less.   The molded body according to claim 1, wherein the cured film on which the convex portions are formed is an antireflection member in which an antireflection film is used.   The molded article according to claim 1, which is a member for improving light extraction efficiency of electroluminescence or a light emitting diode.