JP6516415B2 - Film body having a fine uneven structure on the surface, structure having the film body on the surface, and polymerizable composition for forming the film body - Google Patents

Description

  The present invention provides a film having a microrelief structure on the surface to be used by being provided on the surface of a substrate, a structure having the film on the surface thereof, and a polymerizing material used for forming the film. It relates to a composition.

  A surface layer is provided on the surface of a screen of a flat panel display (FPD) such as a liquid crystal display device or a plasma display to prevent reflection and secure visibility. What is generally referred to as a dry method on the surface layer, that is, one in which a dielectric multilayer film is formed by a vapor phase process and low reflectance is realized by an optical interference effect, generally referred to as a wet method That is, there is a low refractive index material coated on a substrate film. Moreover, although these are techniques which are completely different in principle, there are some which reduce light reflection by providing a fine concavo-convex structure in the surface (for example, patent documents 1-5). In addition, the fine concavo-convex structure of the surface is also called moth eye (registered trademark) structure.

  The surface layer having such an antireflective function is not limited to the screen of the display, but is the screen of the operation panel of an apparatus such as an MFP (Multi Function Printer) or the like, a screen of a mobile phone, a tablet type portable terminal, a smart phone, etc. It is also provided on the surface of the show window.

Japanese Patent Application Laid-Open No. 50-070040 Unexamined-Japanese-Patent No. 2003-215314 Japanese Patent Application Publication No. 2003-240903 Japanese Patent Application Laid-Open No. 2004-059820 JP, 2005-092099, A WO 95/15572 pamphlet Patent No. 4368415 specification

  However, for the surface layer having a fine uneven structure on the surface, good antireflection properties can be obtained, but on the other hand, mechanical strength such as surface scratch resistance and substrate adhesion is insufficient and it is easy to wear, There are problems such as easy scratching and peeling.

  Patent Documents 1 to 5 disclose a surface layer having good antireflection property and good light transmittance, using a general material for forming a polymer film, which has good antireflection properties. There is. However, in these cases, no study has been made from the viewpoint of making the scratch resistance of the surface having a fine concavo-convex structure practical. Therefore, it does not have practicality in the abrasion resistance of the surface.

  The present invention has been made in view of the above problems, and in addition to good antireflection property and light transmittance, a film having a fine asperity structure on the surface, having good scratch resistance and substrate adhesion. It is an object of the present invention to provide a body, a structure having the membrane on its surface, and a polymerizable composition used for forming the membrane.

  As a result of intensive investigations to solve the above problems, the inventor of the present invention polymerizes and forms a (meth) acrylic polymerizable composition, and sets the crosslink density of the polymerizable composition within a certain range. Led to a film body having a fine uneven structure on the surface, having good scratch resistance and substrate adhesion, in addition to good light reflection resistance and light transparency. .

In order to solve the above-mentioned subject, a film body which has a fine concavo-convex structure in the surface concerning one mode of the present invention is a film body which can reduce reflection of light by the fine concavo-convex structure in the surface, The polymerizable composition comprises a polymerizable composition polymerized by irradiation, and the polymerizable composition contains a polyfunctional (meth) acrylate and a polyfunctional urethane (meth) acrylate each having an alkylene glycol chain, and is contained in the polymerizable composition. The crosslink density is characterized by being 3.30 × 10 ⁻³ mol / cm ³ or more and 5.70 × 10 ⁻³ mol / cm ³ or less. In addition, "(meth) acrylate" means "acrylate" or "methacrylate".

  According to one aspect of the present invention, there is provided a film having fine asperity structure on the surface, which has good scratch resistance and adhesion to a substrate in addition to good light reflection preventing property and light transmitting property. The structure having a film on the surface and the polymerizable composition used to form the film can be provided.

It is a cross-sectional schematic diagram of the anti-reflective film which concerns on embodiment of this invention, and a structure which has this. It is a schematic diagram which shows one manufacturing process of the structure which concerns on embodiment of this invention, and shows the process of apply | coating a polymeric composition to a base film. It is a schematic diagram which shows one manufacturing process of the structure which concerns on embodiment of this invention, and shows the process of forming a fine concavo-convex structure in the coating film of the polymeric composition apply | coated to a base film.

  Hereinafter, embodiments of the present invention will be described in detail. In the present embodiment, an antireflective film mainly used for preventing reflection of light is illustrated as a film having a fine uneven structure on the surface, but it is also used as a transmittance improving film, a surface protective layer, etc. it can. Moreover, the description of "A and / or B" in the present specification means "A or B or both".

  FIG. 1 is a schematic cross-sectional view of an antireflective film according to the present embodiment and a structure having the same. As shown in FIG. 1, the antireflective film 2 is provided on a base material 3 to be subjected to antireflective processing, and the antireflective film 2 and the base material 3 constitute a structure 10.

  The material of the substrate 3 is not particularly limited as long as it can support the antireflective film 2, and can be determined in consideration of the application. When the antireflective film 2 is applied to a display member, the substrate 3 is preferably a transparent substrate, that is, one that transmits light. Examples of the material constituting the transparent substrate include synthetic polymers such as methyl methacrylate (co) polymer, polycarbonate, styrene (co) polymer, methyl methacrylate-styrene copolymer, cellulose diacetate, cellulose triacetate (Abbreviated as TAC), semi-synthetic polymers such as cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polylactic acid, polyamide, polyimide, polyether sulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl Examples include acetals, polyether ketones, polyurethanes, composites of these polymers (composites of polymethyl methacrylate and polylactic acid, composites of polymethyl methacrylate and polyvinyl chloride, etc.), and glass.

  The substrate 3 may be opaque. With respect to the opaque base material 3, it becomes the surface antireflective effect of an opaque body. For example, in the case of a black base, a jet black appearance is obtained, and in the case of a colored base, a high color purity appearance is obtained, whereby an article with high designability is obtained. The shape of the substrate 3 is not particularly limited, and examples thereof include films, sheets, injection molded products, melt molded products such as press molded products, and the like.

  As a shape of the base material 3, although the thin thing of sheet form or a film form is illustrated in FIG. 1, three-dimensional shapes, such as flat form and a molding, may be sufficient. In order to provide the antireflective film 2 on a three-dimensionally shaped substrate, the antireflective film 2 is directly attached to the substrate using an adhesive or the like, or the antireflective film 2 is provided on the sheet-like substrate 3 The antireflective film may be attached to a three-dimensionally shaped base material using an adhesive or the like.

  As a manufacturing method of the base material 3, you may use what was manufactured by injection molding, extrusion molding, cast molding, etc. whichever manufacturing method. Furthermore, the surface of the substrate 3 may be coated or corona-treated for the purpose of improving the properties such as adhesion, antistatic property, abrasion resistance, weather resistance and the like.

  As a target article which provides the anti-reflective film 2 and performs an anti-reflective process, a display apparatus and a translucent member are mentioned. As a member that can be subjected to the antireflective treatment (the antireflective film 2 is directly attached, or the antireflective film having the antireflective film 2 formed on the sheet-like base material 3 attached), particularly liquid crystal display The front plate which constitutes the outermost surface of the device, a polarizing plate, a retardation plate, a light reflecting sheet, a prism sheet, a polarized light reflecting sheet, a protective plate made of acrylic or the like, a hard coat layer disposed on the polarizing plate surface . In addition to the optical element such as a lens, the anti-reflection film 2 may be applied to a show window, a window glass, a printed material, a photograph, a painted article, a lighting device, a housing, and the like.

  As shown in FIG. 1, the surface of the antireflective film 2 has a fine concavo-convex structure 1 called a moth-eye structure in which a plurality of fine convex portions are arranged. The shape per protrusion is tapered toward the tip, and the distance between the peaks of the protrusions is equal to or less than the visible light wavelength.

And the anti-reflective film 2 is formed from the polymeric composition which superposes | polymerizes by active energy ray irradiation. The polymerizable composition used to form the antireflective film 2 is polymerized by active energy ray irradiation, and contains at least a polyfunctional (meth) acrylate and a polyfunctional urethane (meth) acrylate each having an alkylene glycol chain. And the crosslink density in the polymerizable composition is 3.30 × 10 ⁻³ mol / cm ³ or more and 5.70 × 10 ⁻³ mol / cm ³ or less.

  By using a polymerizable composition containing at least a polyfunctional (meth) acrylate and a polyfunctional urethane (meth) acrylate each having an alkylene glycol chain, which is polymerized by active energy ray irradiation, good curability can be obtained. There is no problem in the distance between apexes of the fine uneven structure, and good light reflection preventing property is realized, and the light transmittance is also high.

And when the crosslink density in the polymerizable composition is 3.30 × 10 ⁻³ mol / cm ³ or more and 5.70 × 10 ⁻³ mol / cm ³ or less, good scratch resistance can be obtained. At the same time, the adhesion to the substrate is also good. When the crosslink density is less than 3.30 × 10 ⁻³ mol / cm ³ , it is too soft to be easily scratched, and the substrate adhesion is also reduced. On the other hand, if the crosslink density exceeds 5.70 × 10 ⁻³ mol / cm ³ , it is too hard, and the projections of the fine concavo-convex structure may be broken, for example, to be easily scratched, and the adhesion to the substrate may also be reduced.

  In the following, the polymerizable composition according to the present embodiment is referred to as a polymerizable composition X in order to be distinguished from the other polymerizable compositions.

  Such an antireflective film 2 has good scratch resistance and substrate adhesion in addition to good light antireflectivity and light transparency, and is used as a surface layer for the outermost surface of FPD, etc. By doing this, it is possible to greatly contribute to the improvement of the visibility and durability such as FPD.

  Moreover, in the polymerizable composition X, it is more preferable to satisfy the following conditions (i) to (iii).

  (I) It is preferable to make the sum total of content of the polyfunctional (meth) acrylate and the polyfunctional urethane (meth) acrylate which have an alkylene glycol chain, respectively as 65 mass% or more. According to this, abrasion resistance can be made higher. In this case, more preferably 70% by mass or more.

  (Ii) In the polymerizable composition X, the weight average molecular weight of multifunctional urethane (meth) acrylate having an alkylene glycol chain [hereinafter referred to as Mw. The measurement is performed by gel permeation chromatography (hereinafter abbreviated as GPC) method. It is preferable to set it as 1,000-4,000. According to this, the abrasion resistance can be further enhanced, and the transferability of the fine concavo-convex structure 1 in the manufacturing process can be enhanced. In this case, more preferably, the Mw is 1,000 to 3,000.

  (Iii) In the polymerizable composition X, when polyfunctional (meth) acrylate and polyfunctional urethane (meth) acrylate each having an alkylene glycol chain are used as the first component and the second component, as the third component, It further contains at least one of multifunctional (meth) acrylate, multifunctional urethane (meth) acrylate, monofunctional (meth) acrylate and monofunctional urethane (meth) acrylate, each having no alkylene glycol chain It is also good. In that case, it is preferable that at least one of the first to third components have a pentaerythritol skeleton. According to this, the adhesion to various substrates and the abrasion resistance can be further enhanced.

  Hereinafter, the manufacturing method of the polymeric composition X which comprises the anti-reflective film 2, and the structure 10 is demonstrated in detail.

[Polymerizable Composition X]
As described above, the polymerizable composition X contains at least a polyfunctional (meth) acrylate containing an alkylene glycol chain and a polyfunctional urethane (meth) acrylate containing an alkylene glycol chain.

  Examples of polyfunctional (meth) acrylates having an alkylene glycol chain include the following (1) and (2).

(1) Di (meth) acrylate having an alkylene glycol chain (1-1) Polyoxyalkylene (alkylene is C2 to 4) [molecular weight 106 or more and number average molecular weight [abbreviated as Mn hereinafter. The measurement is performed by gel permeation chromatography (hereinafter abbreviated as GPC) method. Or less], each di (meth) acrylate of polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and the like.
(1-2) Di (meth) acrylate of alkylene oxide (AO) adduct of dihydric phenol compound; dihydric phenol compound [C 6-18, eg, monocyclic phenol (catechol, resorcinol, hydroquinone etc.), condensed polycyclic phenol (Dihydroxynaphthalene etc.), AO adduct of bisphenol compounds (bisphenol A, -F and -S etc.) [Di (meth) acrylate of EO 4 molar adduct of resorcinol, di (meth) acrylate of dihydroxynaphthalene PO 4 molar adduct Acrylate, bisphenol A, -F, and -S, EO 2 mol, and PO 4 mol each adduct, etc.] each di (meth) acrylate etc.
(1-3) Di (meth) acrylate of aliphatic dihydric alcohol (C2-30) AO adduct; AO addition of aliphatic dihydric alcohol [C2-30, such as neopentyl glycol and 1,6-hexanediol] Di (meth) acrylates and the like of [EO 20 mole adduct of neopentyl glycol, EO 16 mole adduct of 1, 6 hexanediol, etc.] and the like.
(1-4) Di (meth) acrylate of alicyclic group-containing dihydric alcohol (C6 to 30) AO adduct; di (meth) acrylate of EO 20 mole adduct of dimethylol tricyclodecane, EO 26 mole addition of cyclohexane dimethanol Di (meth) acrylates and di (meth) acrylates of EO 22 molar adducts of hydrogenated bisphenol A, and the like.

(2) Poly (trivalent to hexavalent or higher) (meth) acrylate (2-1) having an alkylene glycol chain, poly (trivalent to hexavalent or higher) alcohol AO adduct of C3 to 40 (Meth) acrylate; each tri (meth) acrylate of EO 36 mole adduct of trimethylolpropane (hereinafter abbreviated as TMP), each tri (meth) acrylate of EO 30 mole as glycerin (hereinafter abbreviated as GR), and each PO 3-mole adduct Tri (meth) acrylate and tetra (meth) acrylate of EO 24 molar adduct of pentaerythritol (abbreviated below as PE), penta (meth) acrylate and hexa (meth) acrylate of EO 48 molar adduct of dipentaerythritol (abbreviated below as DPE) ) Acrylate etc.

  As polyfunctional urethane (meth) acrylate which has an alkylene glycol chain, the following are mentioned, for example.

(3) Multifunctional urethane (meth) acrylate having an alkylene glycol chain A urethane (meth) acrylate having a molecular weight of 400 or more and an Mn of 5,000 or less having a plurality of urethane bonds and two or more acryloyl groups. The following two can be mentioned.

  Poly (difunctional to trifunctional or higher) isocyanate, polyvalent (divalent to hexavalent or higher) polyol, method obtained by urethane reaction with hydroxyl group-containing (meth) acrylate, or poly (difunctional to trifunctional) Or higher) after esterification reaction of isocyanate and polyvalent (divalent to hexavalent or higher) polyol is previously obtained by urethanization reaction, after esterification of (meth) acrylic acid and / or carboxyl group-containing (meth) acrylate How to get by.

  As the polyisocyanate, C 6 to 33 (excluding carbon of NCO group), for example aliphatic polyisocyanate [hexamethylene diisocyanate (HDI) etc.], aromatic (fatty) polyisocyanate [2,4- and / or 2, 6 -Tolylene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), etc., alicyclic polyisocyanate [isophorone diisocyanate (IPDI), 4,4'-methylene bis (cyclohexyl isocyanate), etc. ] Is mentioned. The polyol has a molecular weight of 62 or more and Mn 3,000 or less, such as ethylene glycol, 1,4-butanediol (hereinafter referred to as EG and 1,4-BD, respectively), NPG, polyether polyol, polycaprolactone polyol, polyester polyol, Polycarbonate polyol, PTMG and the like can be mentioned. Examples of the hydroxyl group-containing (meth) acrylate include C5 to 30, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, PE tri (meth) acrylate, DPE penta (meth) acrylate and the like. As a specific example of a carboxyl group-containing (meth) acrylate, 2-acryloyloxyethyl phthalic acid etc. are mentioned.

  Further, as described above, the polymerizable composition X may contain, as the third component, polyfunctional (meth) acrylate and / or polyfunctional urethane (meth) acrylate having no alkylene glycol chain.

  As polyfunctional (meth) acrylate and / or polyfunctional urethane (meth) acrylate which does not have an alkylene glycol chain, for example, polyfunctional (meth) acrylate which does not perform AO addition in the above (1) to (3) and / or Multifunctional urethane (meth) acrylates and the following (4) to (7) can be mentioned.

(4) Polyester (meth) acrylate A plurality of polyvalent (divalent to tetravalent) carboxylic acids, polyvalent (divalent to octavalent or higher) alcohols, and a plurality of esters obtained by esterification of an acryloyl group-containing compound Polyester acrylate having a molecular weight of 150 or more and an Mn of 4,000 or less having an ester bond and 5 or more acryloyl groups; as polyvalent carboxylic acids, for example, aliphatic [C3 to 20, such as malonic acid, maleic acid (anhydride), adipin Acid, sebacic acid, succinic acid, a reaction product of acid anhydride (such as a reaction product of dipentaerythritol and maleic anhydride), alicyclic [C5 to 30, for example, cyclohexanedicarboxylic acid, tetrahydro (anhydride) phthalic acid, methyl Tetrahydro (talic anhydride) and aromatic polyvalent carboxylic acid [C8-30, such as isophthalic acid Acid, terephthalic acid, phthalic acid (anhydride), trimellitic acid (anhydride), pyromellitic acid (anhydride)] and the like can be mentioned.

(5) Epoxy (meth) acrylate Epoxy (meth) acrylate having a molecular weight of 400 or more and Mn of 5,000 or less obtained by the reaction of polyvalent (divalent to tetravalent) epoxide and (meth) acrylic acid.

(6) Butadiene polymer having (meth) acryloyl group in main chain and / or side chain Polybutadiene poly (meth) acrylate (Mn 500 to 500,000) and the like.

  (7) Siloxane polymer having (meth) acryloyl group in main chain and / or side chain of dimethylpolysiloxane; dimethylpolysiloxane poly (meth) acrylate (Mn 300 to 20,000) and the like.

  Also, as monofunctional (meth) acrylate having no alkylene glycol chain, a reaction of aliphatic, alicyclic, heterocyclic and araliphatic monohydric alcohol with (meth) acrylic acid or (meth) acrylic acid chloride (Meth) acrylates obtained by treatment are listed, and two or more may be used in combination.

  Examples of the aliphatic monohydric alcohol (meth) acrylate (B1) include octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate.

  The (meth) acrylate (B2) of the alicyclic monohydric alcohol includes cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and the like. Examples of the (meth) acrylate (B3) of the heterocyclic monohydric alcohol include tetrahydrofurfuryl (meth) acrylate, (meth) acryloyl morpholine and the like.

  Examples of (meth) acrylates of aromatic aliphatic monohydric alcohols (B4) include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, mono (meth) acrylate of o-, m- or p-phenylphenol, 3, Mono (meth) acrylate of 3'-diphenyl-4,4'-dihydroxybiphenyl and the like can be mentioned.

  As a monofunctional urethane (meth) acrylate having no alkylene glycol chain, a compound obtained by the urethanization reaction of a monofunctional isocyanate and a hydroxyl group-containing (meth) acrylate, a compound obtained by the urethanization reaction of a monofunctional isocyanate and a divalent polyol And a compound obtained by the esterification reaction of (meth) acrylic acid and / or a carboxyl group-containing (meth) acrylate with a compound having one hydroxyl group in one molecule.

  As monofunctional isocyanate, methyl isocyanate, ethyl isocyanate, propyl isocyanate, "Additive TI" manufactured by Sumika Bayer Urethane Co., Ltd. and the like can be mentioned.

  As the hydroxyl group-containing (meth) acrylate, divalent polyol and carboxyl group-containing (meth) acrylate, those mentioned above can be mentioned.

  Further, in the polymerizable composition X, the polyfunctional (meth) acrylate and / or the polyfunctional urethane (meth) acrylate not having an alkylene glycol chain which may be contained is not particularly limited, but as described above, pentacene Those having an erythritol skeleton are preferable, and more preferable examples include pentaerythritol tri (meth) acrylate, dipentaerythritol poly (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

  Furthermore, in the polymerizable composition X, for example, a polymerization initiator, a filler, an additive, an active energy ray cationic curable resin, and the like can be contained, if necessary, as long as the effects of the present invention are not inhibited.

[Polymerization initiator]
As a polymerization initiator, a photoinitiator, a thermal polymerization initiator, and these mixtures are mentioned, for example.

  When a photopolymerization initiator is contained, it can be cured also by the below-mentioned active energy ray (ultraviolet ray etc.) other than an electron beam, and when a thermal polymerization initiator is contained, it is cured also by heat other than an electron beam be able to. When the polymerization initiator is not contained, it can be cured by an electron beam.

The UV irradiation dose (mJ / cm ² ) in the case of UV curing is usually 10 to 10,000, preferably 100 to 5, from the viewpoint of the curability of the composition and the flexibility of the cured product (cured film), It is 000. In the case of curing by heat, heating is preferably performed in an oven at 50 to 200 ° C. for 1 minute to 20 hours, preferably for 5 minutes to 10 hours in an oven at 80 to 180 ° C. from the viewpoint of the curability of the composition and the heat resistance of the substrate. It is preferable to process.

  As the photopolymerization initiator, benzoin compounds [C14 to 18, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether]; acetophenone compounds [C8 to 18, such as acetophenone, 2, 2-diethoxy- 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2 -Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one]; anthraquinone compound [C14-19, for example, 2-ethyl anthraquinone, 2-t-butyl ant Quinone, 2-chloroanthraquinone, 2-amyl anthraquinone]; thioxanthone compound [C13-17, such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone]; ketal compound [C16-17, such as acetophenone dimethyl ketal] Benzophenone compound [C13-21, such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone]; phosphine oxy compound [C22-28, eg 2,4, 2 , 6-trimethyl benzoyl diphenyl phosphine oxide, bis- (2, 6 dimethoxy benzoyl)-2, 4, 4- trimethyl pentyl phosphine oxide, bis (2, 4, 6- tri Chirubenzoiru) - phenyl phosphine oxide], and mixtures thereof.

  Among the above-mentioned photopolymerization initiators, acetophenone compounds and phosphine oxide compounds are preferable from the viewpoint of light resistance that the cured product after irradiation with active energy rays is unlikely to yellow, more preferably 1-hydroxycyclohexyl phenyl ketone, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and bis- (2,6-dimethoxybenzoyl) -2, Particularly preferred is 4,4-trimethylpentyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone.

  As a thermal polymerization initiator, peroxides [C4-24, such as t-butyl hydroperoxide, t-butyl peroxybenzoate, benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide]; azo compounds [C8-14, For example, 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis-2,4-dimethyl valeronitrile, 1,1-azobis-1-cyclohexane And carboxonitrile, and mixtures thereof.

  Among the above-mentioned thermal polymerization initiators, preferred are t-butyl peroxybenzoate and methyl ethyl ketone peroxide from the viewpoint of the stability and reactivity of the polymerizable composition X.

  The amount of the polymerization initiator used is usually 20% or less based on the total weight of the radically polymerizable composition in the polymerizable composition X, and the active energy ray curability of the polymerizable composition X and the light resistance of the coating film Preferably it is 0.1 to 20%, More preferably, it is 0.3 to 15%.

[Filler]
As the filler, for example, inorganic filler {carbon black, silica (for example, finely divided silicic acid, hydrous silicic acid, diatom and colloidal silica), silicate (for example, finely divided magnesium silicate, talc, soap stone, stearite, silica) Calcium acid, magnesium aluminosilicate and sodium aluminosilicate), carbonates [eg precipitated (active, dry, heavy or light) calcium carbonate and magnesium carbonate], clays (eg kaolinic clays, sericitic clays, vorophyllite) Clays, montmorillonite clays, bentonites and acid clays), sulfates [eg aluminum sulfate (eg sulfuric acid band and satin white), barium sulfate (eg barite powder, precipitated barium sulfate and lithopone), magnesium sulfate and potassium sulfate Calcium (such as anhydrous gypsum and hemihydrate gypsum)], lead white, mica powder, zinc oxide, alumina, zirconium oxide, titanium oxide, activated calcium fluoride, cement, lime, calcium sulfite, molybdenum disulfide, Asbestos, glass fibers, lock fibers, microballoons, etc.}, organic fillers (eg, styrene beads, melamine beads, acrylic beads, acrylic-styrene beads, polycarbonate beads, etc .; composite systems, for example, JP-A-10-330409 And organic-inorganic composite beads disclosed in JP-A-2004-307644.

  Among these, from the viewpoint of the transparency of the cured product, preferred are silica, silicates, and organic fillers, and more preferred are silica and organic fillers. The filler may be used in combination of two or more. The shape of the filler is not particularly limited, and may be, for example, an irregular shape, a hollow shape, a porous shape, a petal shape, an aggregate shape, a granulated shape, or a spherical shape.

  The amount of the filler to be used is usually 30% or less based on the total weight of the polymerizable composition X, preferably 0.5 to 20%, more preferably 0. from the viewpoint of mechanical properties and flexibility of the cured product. 7 to 10%.

〔Additive〕
Additives include, for example, dispersants, antifoaming agents, leveling agents, silane coupling agents, thixotropy-imparting agents (thickeners), slip agents, releasability-imparting agents, antistatic agents, antioxidants, and ultraviolet light absorption Agents.

  The amount of the entire additive used is usually 30% or less, preferably 0.005 to 15%, based on the total weight of the polymerizable composition X.

(Dispersant)
Examples of the dispersant include organic dispersants [polymer dispersant (Mn 2,000 to 500,000) and low molecular dispersant (molecular weight 100 or more and Mn 2,000 or less)] and inorganic dispersant.

  Among organic dispersants, polymer dispersants include, for example, formalin condensates of naphthalene sulfonates [eg alkali metal (eg Na and K) and ammonium salts], polystyrene sulfonates (same as above), polyacrylics Acid salts (same as above), polycarboxylates (same as above), carboxymethylcellulose (Mn 1,000 to 10,000) and polyvinyl alcohol (Mn 1,000 to 100,000).

Among the organic dispersants, examples of low molecular weight dispersants include the following (a) to (h) and the like.
(A) Polyoxyalkylene type Aliphatic alcohol (C4-30), [alkyl (C1-30)] phenol, aliphatic (C4-30) amine and aliphatic (C4-30) amide AO (C2-4) 1 to 30 molar adducts; as aliphatic alcohols, for example n-, i-, sec- and t-butanol, octanol and dodecanol, as alkylphenols, for example methylphenol and nonylphenol, as aliphatic amines, for example laurylamine and Examples of methyl stearyl amine and aliphatic amide include stearic acid amide.
(B) Polyalcohol type: Monoester compound of C4-30 fatty acid (for example, lauric acid and stearic acid) and polyvalent (divalent to hexavalent or higher) alcohol (for example, GR, PE, sorbit and sorbitan).
(C) Carboxylate-type Alkali metal (same as above) salts of C4-30 fatty acids (as above).
(D) Sulfate ester type C4-30 aliphatic alcohol (same as above) and sulfate ester alkali metal (same as above) salt of AO (C2-4) 1-30 molar adduct of aliphatic alcohol etc.
(E) Sulfonate type Alkali metal sulfonate (same as above) salt of [alkyl (C1-30)] phenol (same as above).

(F) Phosphoric acid ester type C4-30 aliphatic alcohol (same as above) and mono- or diphosphate ester salt of 1-30 molar adduct of aliphatic alcohol with AO (C2-4) (eg alkali metal The same as salts) and quaternary ammonium salts).
(G) Primary to tertiary amine salt type C4 to 30 aliphatic amines [primary (eg lauryl etc.), secondary (eg dibutylamine) and tertiary (eg dimethyl stearylamine)] hydrochloride, triethanolamine And inorganic acid (eg hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid) salts of monoesters of C4-30 fatty acids (same as above).
(H) Quaternary ammonium salt type C4-30 quaternary ammonium (for example, butyl trimethyl ammonium, diethyl lauryl methyl ammonium and dimethyl distearyl ammonium), inorganic acids (same as above) and the like.

  Inorganic dispersants include alkali metal (same as above) salts of polyphosphoric acid and phosphoric acid-based dispersants (such as phosphoric acid, monoalkyl phosphate esters and dialkyl phosphate esters, etc.).

  The amount of the dispersant to be used is generally 10% or less, preferably 0.1 to 5%, based on the total weight of the polymerizable composition X.

(Defoamer)
As an antifoamer, for example, lower alcohol (C1-6) antifoam (eg methanol and butanol), higher alcohol (C8-18) antifoam (eg octyl alcohol and hexadecyl alcohol), fatty acid (C10-20) Antifoaming agents (eg oleic acid and stearic acid), fatty acid esters (C11-30) antifoaming agents (eg glycerol monolaurate), phosphoric acid ester antifoaming agents (eg tributyl phosphate), metallic soap antifoaming agents (eg stear) Calcium phosphate and aluminum stearate), polyether antifoams [eg PEG (Mn 200 to 10,000) and PPG (Mn 200 to 10,000)], silicone antifoams etc (eg dimethyl silicone oil, alkyl modified silicone oil and fluoro) Silicon Oil) and mineral oil (such as silica powder as dispersed in mineral oil) defoaming agent.

  The amount of the antifoaming agent used is usually 3% or less, preferably 0.01 to 2%, based on the total weight of the polymerizable composition X.

(Leveling agent)
As the leveling agent, for example, PEG type nonionic surfactant (for example, 1 to 40 molar adduct of nonylphenol EO and 1 to 40 molar adduct of stearic acid EO), polyhydric alcohol type nonionic surfactant (for example, sorbitan palmitic acid monobasic) Esters, sorbitan stearic acid monoester and sorbitan stearic acid triester), fluorosurfactants (eg 1 to 50 molar adducts of perfluoroalkyl EO, perfluoroalkyl carboxylate and perfluoroalkyl betaine), modified silicone oils [poly Ether-modified silicone oil and (meth) acrylate-modified silicone oil etc.] can be mentioned.

  The amount of leveling agent used is usually 3% or less, preferably 0.01 to 2%, based on the total weight of the polymerizable composition X.

(Silane coupling agent)
As a silane coupling agent, for example, an amino type silane coupling agent (for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane and γ-phenylaminoflopyrtrimethoxysilane), a ureido type silane coupling agent (for example For example, ureidopropyltriethoxysilane), vinyl-based silane coupling agents [eg, vinylethoxysilane, vinylmethoxysilane and vinyltris (β-methoxyethoxy) silane], methacrylate-based silane coupling agents (eg, γ-methacryloxypropyltrimethoxysilane) And γ-methacryloxypropylmethyldimethoxysilane), epoxy-based silane coupling agents (eg, γ-glycidoxypropyltrimethoxysilane), isocyanate-based silane coupling (Eg γ-isocyanatopropyltriethoxysilane), polymeric silane coupling agents (eg polyethoxydimethylsiloxane and polyethoxydimethylsiloxane), cationic silane coupling agents [eg N- (N-benzyl-β-aminoethyl) Γ-aminopropyltrimethoxysilane hydrochloride] can be mentioned.

  The amount of the silane coupling agent used is usually 10% or less, preferably 0.5 to 7%, based on the total weight of the polymerizable composition X.

(Thixotropic agent)
Thixotropy-imparting agents (thickeners) include, for example, inorganic systems (eg bentonite, organically treated bentonite and very fine surface treated calcium carbonate) and organic systems (eg hydrogenated castor oil wax, calcium stearate, aluminum oleate and polymerized linseed) Oil).

  The amount of the thixotropic agent to be used is generally 20% or less, preferably 0.5 to 10%, based on the total weight of the polymerizable composition X.

(Slip agent)
Slip agents include, for example, higher fatty acid esters (eg, butyl stearate), higher fatty acid amides (eg, ethylene bis stearic acid amide and oleic acid amide), metallic soaps (eg, calcium stearate and aluminum oleate), high molecular weight hydrocarbons (eg, Paraffin waxes), polyolefin waxes (e.g. polyethylene waxes, polypropylene waxes and polyethylene waxes containing carboxyl groups) and silicones (e.g. dimethyl silicone oils, alkyl-modified silicone oils and fluorosilicone oils).

  The amount of the slip agent to be used is generally 5% or less, preferably 0.01 to 2%, based on the total weight of the polymerizable composition X.

(Release agent)
The releasing agent may be, for example, a fluorine-containing compound, a silicone compound, a phosphoric acid ester compound, a compound having a long chain alkyl group, a solid wax (polyalkylene wax, amide wax, Teflon powder (Teflon is a registered trademark), etc. And the like, and the like.

  The amount of release agent to be used is generally 5% or less, preferably 0.01 to 2%, based on the total weight of the polymerizable composition X.

(Antistatic agent)
Examples of the antistatic agent include ionic liquids, cationic antistatic agents other than ionic liquids, anionic antistatic agents, and nonionic antistatic agents.

  The ionic liquid has a melting point below room temperature, and at least one of the cations or anions constituting the ionic liquid is an organic ion, and has an initial conductivity of 1 to 200 ms / cm (preferably 10 to 200 ms / cm) It is a certain normal temperature molten salt, For example, the normal temperature molten salt of patent document 6 is mentioned.

  As a cation which comprises an ionic liquid, an amidinium cation, a guanidinium cation, and a tertiary ammonium cation are mentioned, for example.

  As an amidinium cation, for example, imidazolinium cation [1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium , 1,3-dimethyl-2,4-diethylimidazolinium, etc.]; imidazolium cation [1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1, 2,3-Trimethylimidazolium, etc.]; Tetrahydropyrimidinium cation [1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6 -Tetrahydropyrimidinium, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2 , 3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium etc .; and dihydropyrimidinium cation [1,3-dimethyl-1,4- or -1,6-dihydropyrimidinium 1,2,3-Trimethyl-1,4- or -1,6-dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4- or -1,6-dihydropyrimidinium, etc. ] Is mentioned.

  As the guanidinium cation, for example, guanidinium cation having an imidazolinium skeleton [2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolinium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, etc.]; guanidinium cation having an imidazolium skeleton [2-dimethylamino] Amino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-dimethylamino-1-methyl -3,4-diethylimidazolium etc.]; tetrahydropyrimido Guanidinium cation having a lithium skeleton [2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4 , 5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium etc.]; and guanidinium having a dihydropyrimidinium skeleton The cation [2-dimethylamino-1,3,4-trimethyl-1,4- or -1,6-dihydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4- or -1, 6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4- or -1,6-dihydropyrimidinium Etc.], and the like.

  Examples of tertiary ammonium cations include methyl dilauryl ammonium.

  The above amidinium cation, guanidinium cation and tertiary ammonium cation may be used alone or in combination of two or more. Among these, an amidinium cation is preferable from the viewpoint of initial conductivity, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

  In terms of ionicity, examples of the organic acid and / or inorganic acid constituting the anion include the following.

  Examples of the organic acid include carboxylic acid, sulfuric acid ester, higher alkyl ether sulfuric acid ester, sulfonic acid and phosphoric acid ester.

  Inorganic acids include, for example, super strong acids (eg borofluoric acid, tetraboronic acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid Be

The organic acid and the inorganic acid may be used alone or in combination of two or more. Among the above organic acids and inorganic acids, preferred from the viewpoint of the initial conductivity of the ionic liquid are conjugate bases of super strong acids, super strong acids, whose Hammett acidity function (-H ₀ ) of the constituting anion is 12 to 100. Acids and mixtures thereof that form anions other than the conjugated bases of

  As anions other than the conjugate base of super strong acid, for example, halogen (eg, fluorine, chlorine and bromine) ion, alkyl [carbon number (abbreviated as C hereinafter) 1 to 12] benzenesulfonic acid (eg, p-toluenesulfonic acid) ion and Poly (n = 1 to 25) fluoroalkanesulfonic acid (e.g. undecafluoropentanesulfonic acid) ion can be mentioned.

  Super strong acids include those derived from protic acids and combinations of protic acids and Lewis acids, and mixtures thereof.

  As a protonic acid as a super strong acid, for example, bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane (C1) To 30) sulfonic acid (eg methanesulfonic acid, dodecanesulfonic acid), poly (n = 1-30) fluoroalkane (C1 to 30) sulfonic acid (eg trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropane sulfone) Acids, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboronic acid. Among these, borofluoric acid, trifluoromethanesulfonic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferable from the viewpoint of easiness of synthesis.

  Protic acids used in combination with Lewis acids include, for example, hydrogen halide (eg hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid And pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof. Among these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity.

  The Lewis acid includes, for example, boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride and mixtures thereof. Among these, boron trifluoride and phosphorus pentafluoride are preferred in view of the initial conductivity of the ionic liquid.

  The combination of a protic acid and a Lewis acid is optional, but as a superstrong acid consisting of these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride There may be mentioned sulfonic acid, tetraboronic acid, hexafluorophosphoric acid, chlorofluoroboric acid, hexafluoroarsenic acid and mixtures thereof.

  Among the above-mentioned anions, preferred from the viewpoint of the initial conductivity of the ionic liquid are conjugated bases of superstrong acids (superstrong acids consisting of protic acids and superstrong acids consisting of a combination of protic acids and Lewis acids), more preferred It is a conjugated base of a super strong acid consisting of a protic acid and a protic acid, and a super strong acid consisting of boron trifluoride and / or phosphorus pentafluoride.

  Among the ionic liquids composed of the above cations and anions, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoride is preferable from the viewpoint of initial conductivity. Boronates, more preferably 1-ethyl-3-methylimidazolium tetrafluoride borates.

  Examples of the cationic antistatic agent include amidinium salts other than ionic liquids, guanidinium salts and quaternary ammonium salts. Anions constituting the salt include conjugate bases of weak acids, strong acids and super strong acids. Among the cationic antistatic agents, preferred from the viewpoint of antistaticity are amidinium salts and guanidinium salts of conjugate bases of super strong acids.

  As an anionic antistatic agent, sulfonic acid [C10 or more and Mn 1,000 or less, such as lauryl sulfonic acid, polyethylene sulfonic acid] salt, sulfuric acid ester [C10 to 25 such as lauryl alcohol sulfuric ester, EO 3 molar adduct of lauryl alcohol Sulfuric acid ester salts, phosphoric acid ester [C10 to 25 such as octyl alcohol phosphoric acid ester, lauryl alcohol EO molar adduct phosphoric acid ester] salts and the like can be mentioned. As a cation which comprises this salt, an alkali metal (Na, K etc.) ion is mentioned. Among these, sulfonates are preferred from the viewpoint of antistaticity.

  As a non-ionic antistatic agent, EO adducts of higher alcohols (C8-24, for example, oleyl alcohol, lauryl alcohol and stearyl alcohol), PEG fatty acid esters, polyhydric (2-3 or more) alcohols [GR, PE And fatty acid esters of sorbitol (hereinafter abbreviated as SO), sorbitan, etc.] and the like, and fatty acid esters of polyhydric alcohols are preferable from the viewpoint of antistaticity.

  The amount of the antistatic agent used is usually 20% or less based on the total weight of the polymerizable composition X, antistatic property, improvement of fingerprint wiping performance by reducing the contact angle, water resistance of the film, and Preferably it is 0.5-15% from a light transmittance viewpoint of hardened | cured material.

(Antioxidant)
As an antioxidant, hindered phenols [eg, triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 3,5-di-t -Butyl-4-hydroxybenzylphosphonate diethyl ester] and amine systems such as n-butylamine, triethylamine and diethylaminomethyl methacrylate.

  The amount of the antioxidant used is usually 3% or less, preferably 0.005 to 2%, based on the total weight of the polymerizable composition X.

(UV absorber)
Examples of UV absorbers include benzotriazole-based compounds such as 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- ( 3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole and 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole], triazines [eg 2- (4,6-Diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol], benzophenone series (eg 2-hydroxy-4-n-octyloxybenzophenone) and oxalic acid Acid anilides such as 2-ethoxy-2'-ethyl oxalic acid bisanilide can be mentioned.

  The amount of the UV absorber to be used is generally 3% or less, preferably 0.005 to 2%, based on the total weight of the polymerizable composition X.

[Active energy ray cation curable resin]
Examples of the active energy ray cation curable resin include monofunctional alicyclic epoxy resin, bifunctional alicyclic epoxy resin, polyfunctional (trivalent to trivalent or higher) alicyclic epoxy resin, and a mixture thereof. Be

  Monofunctional cycloaliphatic epoxy resins: C5-15, such as cyclohexane oxide, cyclopentaoxide, alpha-pinene oxide, 3,4-epoxyvinylcyclohexane.

  Difunctional cycloaliphatic epoxy resin; C 8-30, eg 2- (3,4-epoxy) cyclohexyl-5,5-spiro- (3,4-epoxy) cyclohexane-m-dioxane, 3,4-epoxycyclohexylmethyl -3,4-Epoxycyclohexanecarboxylate, 3,4-Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, vinylcyclohexanedioxide, bis (3,4-epoxycyclohexylmethyl) Adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, exo-exo bis (2,3-epoxycyclopentyl) ether, endo-exo bis (2,3-epoxycyclopentyl) ether, 2,2-bis 4- (2,3-epoxy Propoxy) cyclohexyl) propane, 2,6-bis (2,3-epoxypropoxycyclohexyl-p-dioxane), 2,6-bis (2,3-epoxypropoxy) norbornene, limonene dioxide, 2,2-bis ( 3,4-Epoxycyclohexyl) propane, dicyclopentadiene dioxide, 1,2-epoxy-6- (2,3-epoxypropoxy) hexahydro-4,7-methanoindane, p- (2,3-epoxy) cyclopentylphenyl -2,3-epoxypropyl ether, 1- (2,3-epoxypropoxy) phenyl-5,6-epoxyhexahydro-4,7-methanoindane, o- (2,3-epoxy) cyclopentylphenyl-2,3 -Epoxypropyl ether), 1,2-bis [5- (1,2-epoxy) 4,7 hexahydroisochromeno meth Noin Dano cyclohexyl] ethane, cyclopentenyl phenyl glycidyl ether.

  Multifunctional (trivalent to trivalent or higher) cycloaliphatic epoxy resin; C 40 or more and Mn 20,000 or less, for example, ε-caprolactone (1 to 10 moles) adduct of 3,4-epoxycyclohexanemethanol and polyvalent ( Trivalent to 20-valent or higher) Esterified products of alcohols (GR, TMP, PE, DPE, hexapentaerythritol) and the like.

  Among them, preferred is a bifunctional alicyclic epoxy resin from the viewpoint of the curability and the hardness of the cured product. The amount of the active energy ray cationic curable resin to be used is usually 40% or less based on the total weight of the polymerizable composition X, preferably 0.5 to 40% from the viewpoint of curability and toughness, and low shrinkage, and further Preferably it is 1 to 25%.

  When the active energy ray cationic curable resin is contained, it is preferable to use a photoacid generator in combination from the viewpoint of curability. As the photoacid generator, for example, allylsulfonium salt [triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate Etc], allyliodonium salt [diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate etc.], sulfonic acid ester [o-nitrobenzyl tosylate, p-nitrobenzyl dimethoxyanthracene sulfonic acid, tosylate acetophenone etc], ferrocene [(2,4-Cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (I ) Hexafluorophosphate, etc.] and the like.

  Among the photoacid generators, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate and diphenyliodonium hexafluorophosphate are preferred from the viewpoint of the stability and reactivity of the composition of the present invention, and more preferred is p- (Phenylthio) phenyl diphenyl sulfonium hexafluorophosphate.

  The amount of the photoacid generator used is usually 10% or less based on the total weight of the composition of the present invention, preferably 0.1 to 5% from the viewpoint of the active energy ray curability of the composition and the light resistance of the coating More preferably, it is 0.3 to 3%.

[Production method]
The structure 10 applies the polymerizable composition X to the substrate 3 to form a coated film, and if necessary, dries the coated film, transfers the fine uneven structure 1 to the surface of the coated film, and activates the activation energy. It can obtain by irradiating and hardening a coating film (refer FIG. 1). The polymerizable composition X is applied to at least a part of at least one side of the substrate 3. As an apparatus for applying the polymerizable composition X to the substrate 3, various apparatuses, for example, a coating machine [die coater, bar coater, gravure coater, roll coater (size press roll coater, gate roll coater, etc.), air knife] Coater, spin coater, blade coater, etc.] can be used. The thickness of the coating film is usually 0.5 to 250 μm, preferably 1 to 100 μm from the viewpoints of abrasion resistance, solvent resistance, contamination resistance and drying property, and curability, as a film thickness after drying.

  More specifically, as a method of manufacturing the structure 10, for example, a known method described in Patent Document 7 can be mentioned. In this case, a mold having an inverted structure of the fine concavo-convex structure 1 in which the width between the apexes of adjacent convex portions is equal to or less than the visible light wavelength is pressed against the surface of the coating film to be the antireflective film 2 After curing the coating film with the above, the mold is released.

  In this case, a coating film to be the anti-reflection film 2 is disposed between the mold and the substrate 3 on which the inverted structure of the fine concavo-convex structure 1 is formed, and the coating film is cured by irradiation with active energy rays. A method of transferring the concavo-convex shape of the mold to the coating film surface and thereafter peeling the mold, transferring the concavo-convex shape of the mold to the coating film to be the antireflective film 2 and peeling the mold Methods of irradiating an energy beam to cure the coating film may be mentioned. Among these, the former is preferable from the viewpoint of the transferability of the fine concavo-convex structure 1 and the degree of freedom of the surface composition. The former is particularly suitable when using a belt-like or roll-like mold capable of continuous production, and is a method excellent in productivity.

  The method of forming the inverted structure of the fine concavo-convex structure 1 in the mold is not particularly limited, and examples thereof include electron beam lithography, laser light interference, and the like. For example, a suitable photoresist film is coated on a suitable support substrate, exposed to light such as an ultraviolet laser, an electron beam, X-ray, etc., and developed to obtain a mold in which a reverse structure of a fine uneven structure is formed. There is a method of using the mold as it is as a stamper. Alternatively, the inverted structure of the fine concavo-convex structure 1 may be formed on the support substrate by selectively etching the support substrate by dry etching via the photoresist layer to remove the resist layer.

  Alternatively, anodized porous alumina may be used as a mold. For example, a pore structure of 20 to 200 nm may be formed by anodizing aluminum with oxalic acid, sulfuric acid, phosphoric acid or the like as an electrolytic solution at a predetermined voltage, and this may be used as a stamper. According to this method, after high-purity aluminum is anodized for a long time at a constant voltage, the oxide film is once removed and again anodization can form pores with very high regularity in a self-organizing manner. Furthermore, in the second step of anodizing, by combining the anodizing treatment and the hole diameter enlargement treatment, it is possible to form an inverted structure of the fine uneven structure 1 whose cross section is not rectangular but triangular or bell-shaped. In addition, it is also possible to sharpen the angle of the deepest portion of the pore by appropriately adjusting the time and conditions of the anodizing treatment and the hole diameter enlargement treatment.

  Furthermore, a replica mold may be produced from a mold having the fine concavo-convex structure 1 by electroforming or the like, and this may be used as a stamper.

  The shapes of the mold 22 and the stamper are not particularly limited, and may be, for example, flat, belt, or roll. In particular, when the belt-like shape or the roll-like shape is used, the fine uneven structure 1 can be transferred continuously, and the productivity can be further enhanced.

  Hereinafter, the manufacturing method of the structure 10 is concretely demonstrated using FIG. 2, FIG. Here, a manufacturing method for continuously transferring the fine concavo-convex structure 1 to the coating film of the polymerizable composition X will be exemplified. FIG. 2 shows one manufacturing process of the structure 10 according to the embodiment of the present invention, and is a schematic view showing a process of applying the polymerizable composition X to the base film 3 ′ which is the base 3. FIG. 3 shows one manufacturing process of the structure 10 according to the embodiment of the present invention, and the coating film 2 'of the polymerizable composition X applied to the base film 3' which is the base 3 is fine It is a schematic diagram which shows the process to which the uneven structure 1 is transcribe | transferred.

  As shown in FIG. 2, the base film 3 ′ is hung on the coating roll 21 and is conveyed by the rotation of the coating roll 21. The lip tip of the die coater 20 is disposed on the outer peripheral surface of the coating roll 21 so as to face each other. The polymerizable composition X is provided from the lip tip of the die coater 20, and is applied onto the base film 3 'to form a coated film 2'.

  The polymerizable composition X can also be used diluted with an organic solvent when applied to the substrate 3. Examples of the organic solvent include alcohols (C1-10, such as methanol, ethanol, n- and i-propanol, n-, sec- and t-butanol, benzyl alcohol, octanol), ketones (C3-8, such as acetone, Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, dibutyl ketone, cyclohexanone), ester or ether ester (C4 to 10, such as ethyl acetate, butyl acetate, ethyl lactate), γ-butyrolactone, ethylene glycol monomethyl acetate, propylene glycol monomethyl acetate, etc. Ether [C 4 to 10, eg EG monomethyl ether (methyl cellolob), EG monoethyl ether (ethyl cellolob), diethylene glycol monobutyl ether Cellosolve), propylene glycol monomethyl ether], aromatic hydrocarbon (C6-10, for example, benzene, toluene, xylene), amide (C3-10, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone), halogenated hydrocarbon ( C1-2, for example, methylene dichloride, ethylene dichloride), petroleum solvents (petroleum ether, petroleum naphtha, etc.). These may be used alone or in combination of two or more.

  The amount of the organic solvent used is usually 200% or less based on the total weight of the composition of the present invention before the addition of the organic solvent, preferably 5 to 100% from the viewpoint of ease of handling and coating stability Preferably it is 10 to 80%. In addition, when the organic solvent is used for the purpose of dilution etc., the process of drying coating film 2 'is provided.

  Next, as shown in FIG. 3, the base film 3 ′ on which the coating film 2 ′ is formed is passed between the nip roll 24 and the roll-shaped mold 22, and the outer peripheral surface of the mold 22 is Press the coating film 2 'side. The base film 3 ′ on which the coating film 2 ′ is formed is conveyed to a position where the peeling roll 25 faces with the coating film 2 ′ side pressed against the outer peripheral surface of the mold 22.

  On the outer peripheral surface of the mold 22, a reverse structure 23 of the fine concavo-convex structure 1 is formed. When the coating film 2 ′ side is pressed against the outer peripheral surface of the mold 22, the reversal structure 23 is transferred to the coating film 2 ′, and the fine concavo-convex structure 1 is formed.

  Further, on the side of the mold 22 that rotates in the state where the coating film 2 ′ is supported on the outer peripheral surface, an irradiation unit 26 that irradiates active energy rays is disposed. The irradiation part 26 irradiates the active energy ray which hardens the polymeric composition X with respect to coating film 2 'which is carry | supported and conveyed. The coating film 2 ′ is polymerized and cured by being irradiated with active energy rays.

  The base film 3 ′ on which the coating film 2 ′ is cured is then peeled from the mold 22 by passing between the mold 22 and the peeling roll 25. Thereby, the structure 10 which has the anti-reflective film 2 to which the fine concavo-convex structure 1 was transferred is obtained.

The method for curing the polymerizable composition X by irradiation with active energy rays can be determined in consideration of the type of monomers in the polymerizable composition X, and the like. For example, electron beam, ultraviolet light, visible light, plasma, infrared light The method of irradiating etc. is mentioned and the method of irradiating an ultraviolet-ray among them is preferable. As a method of irradiating an ultraviolet-ray, the method of using a high pressure mercury lamp, a metal halide lamp, a fusion lamp, etc. are mentioned, for example. The irradiation amount of the ultraviolet light may be determined according to the absorption wavelength and the content of the polymerization initiator. Usually, 400 to 4000 mJ / cm ² is preferable, and 400 to 3000 mJ / cm ² is more preferable. When the accumulated light amount is 400 mJ / cm ² or more, the resin composition can be sufficiently cured to suppress the decrease in abrasion resistance due to insufficient curing. Also. When the integrated light amount is 4000 mJ / cm ² or less, it is easy to prevent the coloring of the surface layer and the deterioration of the base material. The irradiation intensity is preferably suppressed to an output that does not cause deterioration or the like of the base material.

  When the substrate 3 is a molded product having a shape other than the above-described film or sheet (hereinafter, may be referred to as a three-dimensional shape), the polymerizable composition X may be applied directly to the mold. That is, the polymerizable composition X is applied to the surface of the mold on which the inverted structure of the fine concavo-convex structure 1 is formed, and this is irradiated with an active energy ray to be cured to form only the antireflective film 2 alone. . After curing, the antireflective film 2 is peeled off from the mold and attached to a separately formed three-dimensional base material.

  In addition, for example, after semi-curing the polymerizable composition X, the mold is pressed against the surface on which the inverted structure of the fine concavo-convex structure 1 is formed, the fine concavo-convex structure 1 is transferred, and then the active energy ray is polymerized. It may be a method of irradiating the polymer composition X and curing it completely. As a method of semi-curing the polymerizable composition X, it can be determined in consideration of the composition of the polymerizable composition X and the like, and examples thereof include a heating method and the like.

[Summary]
A film having a fine concavo-convex structure on the surface according to aspect 1 of the present invention is a film capable of reducing light reflection by the fine concavo-convex structure on the surface, and from a polymerizable composition polymerized by active energy ray irradiation. The polymerizable composition contains a polyfunctional (meth) acrylate and a polyfunctional urethane (meth) acrylate each having an alkylene glycol chain, and the crosslink density in the polymerizable composition is 3.30 × 10 ^{−. 3} mol / cm ³ or more and 5.70 × 10 ⁻³ mol / cm ³ or less.

  According to this, since the polymerizable composition contains the polyfunctional (meth) acrylate and the polyfunctional urethane (meth) acrylate each having an alkylene glycol chain, the light transmitting property is excellent and the fine asperity on the surface is obtained. Formation of the structure is also easy, and good light reflection prevention can be realized.

Furthermore, since the crosslinking density in the polymerizable composition is 3.30 × 10 ⁻³ mol / cm ³ or more and 5.70 × 10 ⁻³ mol / cm ³ or less, the scratch resistance of the surface having a micro uneven structure is And adhesion to a substrate can be made practical and good.

  Thereby, it is possible to provide a film having a fine uneven structure on the surface, which has good scratch resistance and substrate adhesion, in addition to good light reflection prevention and light transmission performance.

  The film body having a fine concavo-convex structure on the surface according to aspect 2 of the present invention is further characterized in that the polyfunctional (meth) acrylate and the polyfunctional urethane (meth) acrylate each having an alkylene glycol chain in the polymerizable composition. It is preferable that the sum total of content of these is 65 mass% or more. According to this, abrasion resistance can be made higher.

  It is preferable that the film body which has a fine concavo-convex structure in the surface which concerns on aspect 3 of this invention is a weight average molecular weight 1000-4000 of the said polyfunctional urethane (meth) acrylate which has an alkylene glycol chain. According to this, the abrasion resistance can be further enhanced, and the transferability of the fine concavo-convex structure 1 in the manufacturing process can be enhanced.

  The film body having a fine concavo-convex structure on the surface according to aspect 4 of the present invention comprises the multifunctional (meth) acrylate and the polyfunctional urethane (meth) acrylate each having an alkylene glycol chain, and a first component and a second component In the above case, the polymerizable composition may contain, as a third component, a polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate, a monofunctional (meth) acrylate and a monofunctional urethane, each having no alkylene glycol chain. It further contains at least one of (meth) acrylates, and at least one of the first component, the second component, and the third component has a pentaerythritol skeleton. According to this, the adhesion to various substrates and the abrasion resistance can be further enhanced.

  The film body having the fine uneven structure on the surface according to the fifth aspect of the present invention is used for anti-reflection of light and / or transmission improvement of light.

  A structure according to aspect 6 of the present invention comprises a base material and a film body having a microrelief structure on the surface of the present invention provided on the surface of the base material.

The polymerizable composition according to aspect 7 of the present invention is a polymerizable composition for forming a film having a fine concavo-convex structure on the surface, which is polymerized by active energy ray irradiation and each of which is a polyfunctional having an alkylene glycol chain. (Meth) acrylate and polyfunctional urethane (Meth) acrylate, and when polymerized, the crosslink density in the polymerizable composition is 3.30 × 10 ⁻³ mol / cm ³ or more and 5.70 × 10 ⁻³ mol / Cm ³ or less.

  By using such a polymerizable composition, a film having a microrelief structure on the surface according to Embodiment 1 of the present invention can be easily obtained.

  The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto as long as the gist thereof is not exceeded.

  In Examples and Comparative Examples, three types of multifunctional (meth) acrylates and four types of multifunctional urethane (meth) acrylates shown in Table 1 were used as appropriate. For the formation of the antireflective film in the structures of Comparative Examples 1 to 3 and the polymerizable compositions X (1) to (10) used for forming the antireflective film in the structures of Examples 1 to 10 in Table 1. The composition of the comparative polymerizable compositions (1) to (3) used is shown. Further, in Table 1, the photopolymerization initiator, the solvent, and the silicone compounded to each polymerizable composition used for the formation of the antireflective film in the structures of Examples 1 to 10 and Comparative Examples 1 to 3 are shown. Also show the oil (if necessary). The numbers in Table 1 indicate parts by weight, and the total amount of multifunctional (meth) acrylate and multifunctional urethane (meth) acrylate is 100 parts by weight.

  "UA-7100" in Table 1 is a multifunctional urethane acrylate [trade name "NK oligo UA-7100, manufactured by Shin-Nakamura Chemical Co., Ltd.", and "X22-1602" is a reactive silicone oil [trade name " X-22-1602 ", manufactured by Shin-Etsu Chemical Co., Ltd.]. Also, "KF-353" is a non-reactive silicone oil [trade name "KF-353", manufactured by Shin-Etsu Chemical Co., Ltd.], "cation BB" is dodecyltrimethyl ammonium chloride [trade name "Nissan cation BB", NOF Corporation].

  Moreover, compounds (1) to (3) of polyfunctional urethane (meth) acrylates in Table 1 were synthesized as follows.

Preparation Example 1: Synthesis of Compound (1)
In a glass autoclave, 34 g of water (25% to glycerin) was introduced as a solvent. After 136.5 g (1.50 mol) of glycerin was charged and nitrogen substitution was performed, the temperature was raised to 95 ° C., and 0.63 g (0.25 mol% per alcohol functional group) of potassium hydroxide was added thereto.

  Nitrogen substitution was performed again, and 1188.0 g (27.0 mol) of EO (ethylene oxide) was continuously introduced over 720 minutes while maintaining the reaction pressure at 75 to 95 ° C. and a reaction pressure of 0.25 MPa or less. Thereafter, it was aged for 300 minutes to obtain a crude polyether (1). To the obtained crude polyether (1), alkaline adsorbent treatment [1.8% of water is added to the crude polyether and mixed for 30 minutes at 85 to 90 ° C., followed by Kyoward 600 (Kyowa Chemical Co., Ltd. as an adsorbent 0.5% of the crude polyether) and mixed at the same temperature for 30 minutes, and then the adsorbent is removed by filtration. The same applies to each of the following examples] and dehydration (dehydration is carried out until the water content becomes 0.1% or less at 130 ° C. under a reduced pressure of -0.1 MPa. The same applies to each of the following examples), and polyether (1) Got). As a result of analysis, the hydroxyl value of polyether (1) was 190.7. The hydroxyl value was measured in accordance with JIS K-1557 (the same applies hereinafter).

  Next, 500 g of the obtained polyether (1) was charged into a reaction vessel set with a stirring rod and a thermometer, and heated to 110 ° C. under a nitrogen stream, and then 132.0 g of IPDI was charged, 110 ° C. The reaction was carried out for 10 hours to obtain polyether polyurethane (1). The hydroxyl value of polyether polyurethane (1) was 50.5.

  300 g of the obtained polyether polyurethane (1), 25 g of acrylic acid, 1 g of sulfuric acid, 0.2 of hydroquinone and 300 g of toluene were charged, and the mixture was heated under reflux at 110 ° C. for 15 hours to cause esterification reaction. 10.9 g of produced water was obtained. Then, the reaction mixture was cooled, 500 g of toluene was added, and the mixture was neutralized and washed with a 15% aqueous NaOH solution. After liquid separation, the aqueous layer is removed and washed with 300 ml of 15% aqueous NaCl solution three times, 0.2 g of p-methoxyphenol is then added to the toluene layer, and the toluene is distilled off under reduced pressure to give 275 g of compound (1). I got

Production Example 2: Synthesis of Compound (2)
The glycerin in Preparation Example 1 is 69.1 g (0.75 mol) and 102.0 g (0.75 mol) of pentaerythritol, EO is 3834.6 g (87.2 mol) of EO and 1035.3 g of PO (propylene oxide). The reaction was carried out in the same manner as in Production Example 1 except that the amount was changed to (17.9 mol), to obtain polyether (2). The hydroxyl value of the obtained polyether (2) was 58.6.

  Next, the polyether (2) obtained in the same manner as in Production Example 1 was reacted except that 37.7 g of IPDI in Production Example 1 was added, to obtain polyether polyurethane (2). The hydroxyl value of the polyether polyurethane (2) was 39.5. Furthermore, in the same manner as in Production Example 1 except that the amount of acrylic acid in Production Example 1 was changed to 17 g, 257 g of Compound (2) was obtained from the obtained polyether polyurethane (2).

Preparation Example 3: Synthesis of Compound (3)
The same procedure as in Preparation Example 1 was repeated, except that the glycerin in Preparation Example 1 was changed to 138.2 g (1.50 mol) of glycerin, and EO was changed to 5100.5 g (115.9 mol) in EO and 584.6 g (10.1 mol) of PO. The reaction was carried out to obtain polyether (3). The hydroxyl value of the obtained polyether (3) was 43.4.

  Next, polyether (3) was reacted in the same manner as in Production Example 1 except that 30.0 g of IPDI in Production Example 1 was added, to obtain polyether polyurethane (3). The hydroxyl value of the polyether polyurethane (3) was 26.1. Furthermore, in the same manner as in Production Example 1 except that acrylic acid in Production Example 1 was changed to 13 g, 255 g of compound (3) was obtained from the obtained polyether polyurethane (3).

  The structures of Examples 1 to 10 are produced as follows using polymerizable compositions X (1) to (10), and similarly, compared using comparative polymerizable compositions (1) to (3). The structures of Examples 1 to 3 were produced as follows. Moreover, the metal mold | die used for preparation of each structure of Examples 1-10 and Comparative Examples 1-3 was produced as follows.

<Production Example 4: Production of Mold>
First, a 10 cm square glass substrate was prepared, and aluminum (Al) as a material of a mold was applied on the glass substrate to a film thickness of 1.0 μm by a sputtering method. Next, by repeating the process of anodizing aluminum and performing etching immediately thereafter, an anode having a large number of minute holes in which the distance between the bottom points of adjacent holes (recesses) is equal to or less than the visible light wavelength An oxide layer was formed. Specifically, the mold was manufactured by a flow (5 anodic oxidations and 4 etchings) in which anodic oxidation, etching, anodic oxidation, etching, anodic oxidation, etching, anodic oxidation, etching and anodic oxidation are sequentially performed. According to the repeated process of such anodic oxidation and etching, the shape of the minute hole to be formed becomes a shape (tapered shape) which is tapered toward the inside of the mold.

  The mold substrate is not limited to glass, and metal materials such as SUS, Ni, etc., polypropylene, polymethylpentene, cyclic olefin polymers (product name "Zeonor" (typically norbornene resin etc.) It may be a resin material such as polyolefin resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate or triacetyl cellulose under the product name "Arton" (product of JSR Corporation). Further, instead of a substrate on which aluminum is deposited, a bulk substrate of aluminum may be used. The shape of the mold may be flat or roll (cylindrical). The conditions for anodic oxidation were 0.6 wt% of oxalic acid, a liquid temperature of 5 ° C., and an applied voltage of 80 V. Anodizing time was 15 seconds. The conditions for etching were 1 mol / l of phosphoric acid and a liquid temperature of 30 ° C. and 25 minutes, respectively. The mold height by SEM observation was 231 nm.

<Production of Structure of Example 1>
The polymerizable composition X (1) was coated on a TAC film (thickness 40 μm), the solvent was dried at a temperature of 80 ° C. for 1 minute in a normal air drier to form a resin layer, and then the gold prepared in Production Example 4 It stuck, paying attention so that air bubbles did not enter on the surface of a model. Next, ultraviolet (UV) light is irradiated to the TAC film side at ² J / cm ² to cure the resin layer, and thereafter, the laminated film of the cured resin layer and the TAC film is peeled off. 1 structure was obtained. The resulting structure was digital micrometer (TH-104 manufactured by Tester Sangyo Co., Ltd.) and found to be 52 μm.

  Further, as a specific method of forming (replicating) the fine irregularities on the substrate using the mold, in addition to the 2P method (photopolymerization method), for example, a heat press method (emboss method), injection molding Various methods such as a method, a replication method such as a sol-gel method, a lamination method of a finely textured sheet, and a transfer method of a finely textured layer may be appropriately selected according to the application of the antireflective article and the material of the substrate.

  The structure of Example 1 was used as it is as a sample for the measurement of the transmittance | permeability. In addition, the structure of Example 1 is attached to a TAC film side on a black acrylic board (Acrolite EX 502 made by Mitsubishi Rayon) using a double-sided adhesive film, and the curability, reflectance, water contact angle, surface scratch resistance It was used as a sample for measuring contamination resistance and adhesion to substrate.

<Preparation of the structure of Examples 2 to 10>
The structures of Examples 2 to 10 and the various measurement samples are the same as in Example 1 except that the polymerizable composition X (1) is changed to the polymerizable compositions X (2) to (10). Made.

<Preparation of the structure of Comparative Examples 1 to 3>
In Example 1, the structures of Comparative Examples 1 to 3 and the various measurement samples are prepared in the same manner except that the polymerizable composition X (1) is changed to the comparative polymerizable compositions (1) to (3). Made.

  The physical properties were measured and evaluated for each of the structures and samples requiring measurement of Examples 1 to 10 and Comparative Examples 1 to 3 prepared as described above by the following measurement method. The results are shown in Table 2.

(Evaluation of curability)
The surface having a fine uneven structure in the structure was palpated with a fingertip and evaluated according to the degree of tackiness. Evaluation criteria are as follows.
Good: There is no tackiness at all.
Evil: I have some tackiness.

(Measurement of reflectance)
Using a Shimadzu Corporation spectrophotometer UV-3100PC, a sample in which the structure is attached to a black acrylic plate is measured at a regular reflectance of 5 °.

(Measurement of transmittance)
According to JIS K7361, using a haze / transmittance meter HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd., the surface having a fine concavo-convex structure is measured toward the light source.

(Evaluation of surface scratch resistance)
Using a steel wool # 0000 of 25 mm in a reciprocating abrasion tester (HEIDON Tribo gear TYPE 30), a sample in which the structure is attached to a black acrylic sheet, a load of 200 g or 400 g, a wear distance of 10 mm, a speed of 10 mm / sec, After 10 cycles of abrasion, visually judge the flaw under the fluorescent light. Evaluation criteria are as follows.
5: no scratch.
4: There are several scratches.
3: There is a half scratch of a 25 mm cylinder.
2: There are 2/3 scratches of a 25 mm cylinder.
There is a scratch on the entire surface of a 1: 25 mm cylinder.

(Evaluation of substrate adhesion)
Based on JIS K 5600, 100 square grids of 1 mm square are placed on the surface side of the sample in which the structure is pasted on a black acrylic plate and having 100 μm grids of 1 mm square, and used 5 times using industrial 24 mm Sellotape (registered trademark) made by Nichiban. Peeling was performed, the number of remaining squares was counted, and determination was made according to the following criteria.
3: All 100 squares are left.
2: 50 to 99 squares are left.
1: The remaining squares are less than 49 squares.

Comparative Examples 1 and 2 are examples in which the crosslink density in the polymerizable composition is larger than 5.70 × 10 ⁻³ mol / cm ³ . It is considered that the antireflective film 2 is too hard due to the high crosslinking density, and the projections of the fine uneven structure are easily broken. On the other hand, Comparative Example 3 is an example in which the crosslink density in the combined composition is smaller than 3.30 × 10 ⁻³ mol / cm ³ . It is considered that the antireflective film 2 is soft and easily scratched because the crosslink density is low.

  In addition, as shown in Table 2, a combination of polyfunctional (meth) acrylate and polyfunctional urethane (meth) acrylate is used as the polymerizable composition X forming the antireflective film or as the comparative polymerizable composition. . Therefore, in any of the structures of Examples 1 to 10 and Comparative Examples 1 to 3, the curability is good, there is no problem in the distance between apexes, and the reflectance and the transmittance are low.

  The present invention uses a specific (meth) acrylic polymerizable composition, and has anti-reflection performance, light transmission performance, high adhesion to various substrates, high removability for human fingerprint stains, high scratch resistance It can be used for an antireflective film having a fine uneven structure on the surface, a permeability improving film, a surface protective layer, and the like. For example, optical devices such as light guide plates, polarizing plates, protective plates and anti-reflection plates, and various touch panels including such optical devices, liquid crystal displays, display devices such as electrochromic displays and electrophoretic displays, etc. It can be used. In addition, it can be used also for the surface layer which gives good visibility to lenses, show windows and the like.

1 Fine uneven structure 2 Antireflective film (film having fine uneven structure on the surface)
2 'coated film 3 base material 3' base film 10 structure 20 die coater 21 coating roll 22 mold 23 inversion structure 24 nip roll 25 peeling roll 26 irradiation part

Claims (6)

A film body capable of reducing the reflection of light by a fine uneven structure on the surface,
It comprises a polymerizable composition polymerized by active energy ray irradiation,
The polymerizable composition contains a polyfunctional (meth) acrylate and a polyfunctional urethane (meth) acrylate each having an alkylene glycol chain,
The sum of the values of the polymerization of the respective compositions that contained in the composition functional groups × wt% ÷ 100 ÷ molecular weight state, and are 3.30 × 10 ^-3 or more 5.70 × 10 ^-3 or less,
The total content of the polyfunctional (meth) acrylate and the polyfunctional urethane (meth) acrylate in the polymerizable composition each having an alkylene glycol chain is 65 mass based on the mass of the entire polymerizable composition A film having a micro uneven structure on the surface characterized by being at least% . The film body having a microrelief structure on the surface according to claim 1, wherein the weight average molecular weight of the polyfunctional urethane (meth) acrylate having an alkylene glycol chain is 1000 to 4000. When said polyfunctional (meth) acrylate and said polyfunctional urethane (meth) acrylate each having an alkylene glycol chain are used as the first component and the second component,
The polymerizable composition contains, as a third component, a polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate, a monofunctional (meth) acrylate and a monofunctional urethane (meth) acrylate each having no alkylene glycol chain. Further containing at least one of
The film having a micro uneven structure on the surface according to claim 1 or 2 , wherein at least one of the first component, the second component and the third component has a pentaerythritol skeleton. body. The film body having a micro uneven structure on the surface according to any one of claims 1 to 3 , which is used for anti-reflection of light and / or transmission improvement of light. A substrate,
The film body provided with the fine concavo-convex structure in the surface in any one of Claims 1-4 provided in the surface of this base material. A polymerizable composition for forming a film having a fine uneven structure on its surface,
Polymerized by active energy radiation,
Each containing a multifunctional (meth) acrylate having an alkylene glycol chain and a multifunctional urethane (meth) acrylate,
The sum of the value of the number of functional groups × weight% × 100 molecular weight of each composition contained in the polymerizable composition is 3.30 × 10 ⁻³ or more and 5.70 × 10 ⁻³ or less ,
The total content of the polyfunctional (meth) acrylate and the polyfunctional urethane (meth) acrylate in the polymerizable composition each having an alkylene glycol chain is 65 mass based on the mass of the entire polymerizable composition % Or more .

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