JP2011245767A - Laminate, and article having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart an antistatic property to a film having a fine uneven structure, a laminate of the same, and an article having the same.SOLUTION: The laminate includes a film having the fine uneven structure formed on one surface and an adhesive agent layer laminated on the other surface of the film, and the laminate is stuck on a transparent base plate via the adhesive agent layer wherein the adhesive agent layer contains an antistatic agent.

Description

  The present invention relates to a laminate and an article having the same.

  A member used for a front plate of an image display device or the like is required to have an antireflection function that hardly reflects sunlight rays, illumination light, and the like.

  In recent years, it has been known that an article having a fine concavo-convex structure with a period equal to or shorter than the wavelength of visible light on the surface exhibits an antireflection effect, a lotus effect and the like. In particular, it is known that a fine concavo-convex structure called a moth-eye structure is an effective antireflection means by continuously increasing the refractive index from the refractive index of air to the refractive index of the material of the article. .

  An article having a fine concavo-convex structure on its surface can be obtained, for example, by sticking a film having a fine concavo-convex structure on its surface to the article main body so that the surface on which the fine concavo-convex structure is not formed is in contact. Adhesives such as transparent adhesives and double-sided adhesive tapes are often used for attaching the film and the article body. Alternatively, a pressure-sensitive adhesive layer may be provided on the surface where the fine uneven structure of the film is not formed, and the film may be attached to the article body via the pressure-sensitive adhesive layer.

  As a film having a fine concavo-convex structure on the surface, for example, Patent Document 1 discloses an antireflection article having a fine concavo-convex structure formed on the surface by a transfer method using anodized alumina as a stamper.

JP 2009-109572 A

  By the way, when a roll-shaped continuous stamper is used and a film having a fine concavo-convex structure on the surface is produced by a roll-to-roll transfer method, the film is charged when the film is conveyed by a roll, and the trace of the discharge May remain on the surface of the fine relief structure.

  In addition, the surface of the fine concavo-convex structure may be treated with water-repellent treatment, but when the surface of the fine concavo-convex structure is processed by wet coating, the wettability of the coating liquid deteriorates due to film charging. There is a fear.

  In addition, a film having a fine concavo-convex structure on the surface is generally provided with a protective film and a release film on both sides after production, but when the release film is peeled off, dust is deposited on the film due to the release charge. There is a risk of adhesion. Moreover, when adhesive processing is performed on the surface opposite to the surface having the fine concavo-convex structure of the film and a release film is installed, dust may adhere to the adhesive or the fine concavo-convex structure when the film is peeled off.

  This invention is made | formed in view of the said situation, and it aims at providing antistatic property to the film which has a fine uneven structure, its laminated body, and the article | item which has this.

  The laminate of the present invention comprises a film having a fine concavo-convex structure formed on one surface and an adhesive layer laminated on the other surface of the film, and an antistatic property-imparting agent is added to the adhesive layer. Therefore, it has an antistatic property.

The laminate of the present invention is characterized in that the pressure-sensitive adhesive layer has a surface resistance value of 1.0 × 10 ⁸ Ω / cm ² or more and less than 1.0 × 10 ¹⁵ Ω / cm ² .

  Moreover, the article of the present invention is characterized by having a transparent substrate and the above-mentioned laminate adhered to the transparent substrate via an adhesive layer.

  According to the present invention, a film having a fine uneven structure formed on one surface and an adhesive layer laminated on the other surface of the film are attached to a transparent substrate via the adhesive layer. The laminate is characterized in that the pressure-sensitive adhesive layer contains an antistatic property-imparting agent, and an article having the laminate is obtained.

It is sectional drawing which shows an example of the articles | goods of this invention. It is sectional drawing which shows an example of the film with which the laminated body of this invention is equipped. It is a block diagram which shows an example of the manufacturing apparatus of the film with which the laminated body of this invention is equipped. It is sectional drawing which shows the manufacturing process of the mold which has an anodized alumina on the surface.

  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.

  FIG. 1 is a cross-sectional view showing an example of the article of the present invention. The article 10 of this example has a transparent substrate 12 and a laminate 14 of the present invention attached on the transparent substrate 12.

<Transparent substrate>
Although it does not restrict | limit especially as the transparent substrate 12, As a raw material of the transparent substrate 12, inorganic glass, acrylic resin, polycarbonate, a styrene resin, polyester, cellulose resin (triacetyl cellulose etc.), polyolefin, alicyclic polyolefin, etc. Is mentioned.

<Laminated body>
The laminate 14 of the present invention includes a film 16 having a fine concavo-convex structure (not shown) formed on one surface, and an adhesive layer 18 laminated on the other surface of the film 16. The laminate 14 is stuck on the transparent substrate 12 via the pressure-sensitive adhesive layer 18.

(Adhesive layer)
The pressure-sensitive adhesive layer 18 is not particularly limited as long as the pressure-sensitive adhesive force and transparency when adhered to a transparent substrate are ensured. For example, as an adhesive, there are an acrylic adhesive and a rubber adhesive. The pressure-sensitive adhesive layer 18 contains an antistatic agent.

(Antistatic agent)
The antistatic agent is not particularly limited as long as it has compatibility with the pressure-sensitive adhesive, can ensure transparency, and does not cause a decrease in pressure-sensitive adhesive force. As the antistatic agent, either a low molecular antistatic agent or a high molecular antistatic agent may be used.

  For example, examples of the low-molecular antistatic agent include nonionic surfactants, anionic surfactants, cationic surfactants, and zwitterionic surfactants.

  Examples of the polymer antistatic agent include nonionic polymer type, anionic polymer type, and cationic polymer type.

  The thickness of the pressure-sensitive adhesive layer 18 is preferably 5 to 100 μm, and more preferably 10 to 50 μm. If the thickness is less than 5 μm, sufficient adhesion and adhesion to the adherend may not be obtained. On the other hand, if the thickness is greater than 100 μm, the amount of residual solvent contained in the adhesive increases, which may cause foaming.

  The amount of the antistatic agent mixed in the pressure-sensitive adhesive layer 18 is preferably 0.01 to 10.0 parts by mass, more preferably 0.5 to 4.0 parts by mass.

(the film)
The film 16 shown in FIG. 1 has a film body 16a and a cured resin film 16b formed on the surface of the film body 16a.

  The film body 16a is a film having optical transparency. Examples of the material for the film body 16a include acrylic resins, polycarbonates, styrene resins, polyesters, cellulose resins (such as triacetyl cellulose), polyolefins, and alicyclic polyolefins.

  The cured resin film 16b is a light-transmitting film made of a cured product of an active energy ray-curable resin composition described later, and has a plurality of convex portions 19 on the surface, for example, as shown in FIG.

  The protrusion 19 is preferably formed by transferring a plurality of pores (recesses) on the surface of anodized alumina.

  The plurality of convex portions 19 preferably form a so-called moth-eye structure in which a plurality of protrusions (convex portions) having a substantially conical shape or a pyramid shape are arranged at intervals equal to or shorter than the wavelength of visible light. It is known that the moth-eye structure becomes an effective antireflection means by continuously increasing the refractive index from the refractive index of air to the refractive index of the material.

  The average period between the convex portions 19 is preferably not more than the wavelength of visible light, that is, not more than 400 nm, more preferably not more than 200 nm, and particularly preferably not more than 150 nm. Here, the average period between the convex portions 19 means that the cross section of the cured resin film 16b is observed with an electron microscope, and the interval P between the adjacent convex portions 19 (from the center of the convex portion 19 to the center of the adjacent convex portion 19). ) Is measured at 50 points, and these values are averaged.

  In addition, when the convex part 19 is formed using the mold of the anodic oxidation alumina mentioned later, the average period between the convex parts 19 becomes about 100 nm, and is preferable.

  H is preferably 100 to 500 nm, and more preferably 130 to 400 nm. When the height of the convex portion 19 is 100 nm or more, the reflectance is sufficiently low and the wavelength dependence of the reflectance is small. If the height of the convex part 19 is 500 nm or less, the mechanical strength of the convex part 19 will become favorable.

  H and W can be measured by observing the cross section of the cured resin film 16b with an electron microscope.

  W is a width in the same plane (hereinafter referred to as a reference plane) as the bottom of the concave portion formed around the convex portion 19.

  H is the height from the reference surface to the top of the convex portion 19.

  H / W is the manufacturing condition of the mold having anodized alumina on the surface, the viscosity of the active energy ray-curable resin composition filled in the pores (recesses) of the mold (see JP 2008-197216 A) It can adjust by selecting etc. suitably.

  When the surface has a moth-eye structure, if the surface is made of a hydrophobic material, super water repellency can be obtained by the lotus effect, and if the surface is made of a hydrophilic material, super hydrophilicity can be obtained. It is known.

  When the material of the cured resin film 16b is hydrophobic, the water contact angle on the surface of the moth-eye structure is preferably 90 ° or more, more preferably 100 ° or more, and particularly preferably 110 ° or more. If the water contact angle is 90 ° or more, water stains are less likely to adhere, so that sufficient antifouling properties are exhibited. Moreover, since water does not adhere easily, anti-icing can be expected.

  When the material of the cured resin film 16b is hydrophilic, the water contact angle of the surface of the moth-eye structure is preferably 25 ° or less, more preferably 23 ° or less, and particularly preferably 21 ° or less. If the water contact angle is 25 ° or less, the dirt adhering to the surface is washed away with water and oil dirt is less likely to adhere, so that sufficient antifouling properties are exhibited. The water contact angle is preferably 3 ° or more from the viewpoint of suppressing deformation of the moth-eye structure due to water absorption of the cured resin film 16b and the accompanying increase in reflectance.

(Film production method)
The film 16 is manufactured as follows using, for example, a manufacturing apparatus shown in FIG.

  Between the surface of the roll-shaped mold 22 having a reverse microstructure composed of a plurality of concave portions (not shown) corresponding to the plurality of convex portions 19 on the surface, and the strip-shaped film main body 16a moving along the surface of the mold 22 Then, the active energy ray-curable resin composition 21 is supplied from the tank 24.

  The film main body 16a and the active energy ray curable resin composition 21 are nipped between the mold 22 and the nip roll 28 whose nip pressure is adjusted by the pneumatic cylinder 26, and the active energy ray curable resin composition 21 is removed from the film. The main body 16a and the mold 22 are uniformly distributed, and at the same time, the concave portions of the mold 22 are filled.

  The active energy ray curable resin composition 21 is sandwiched between the mold 22 and the film body 16a, and the active energy ray irradiation device 30 installed below the mold 22 is used to activate the film body 16a from the film body 16a side. By irradiating the energy ray curable resin composition 21 with active energy rays and curing the active energy ray curable resin composition 21, a cured resin film 16b to which a plurality of recesses on the surface of the mold 22 is transferred is formed. .

  The film 16 is obtained by peeling the film body 16 a having the cured resin film 16 b formed on the surface by the peeling roll 32.

The active energy ray irradiation device 30 is preferably a high-pressure mercury lamp, a metal halide lamp, or the like. In this case, the amount of light irradiation energy is preferably 100 to 10,000 mJ / cm ² . In addition, an active energy ray means visible light, an ultraviolet-ray, an electron beam, plasma, a heat ray (infrared rays etc.).

(mold)
The mold 22 has a reversal structure (hereinafter referred to as a reversal fine concavo-convex structure) corresponding to the fine concavo-convex structure on the surface of the finally obtained film on the surface of the mold body.

  Examples of the material for the mold main body include metals (including those having an oxide film formed on the surface), quartz, glass, resin, ceramics, and the like. Examples of the shape of the mold body include a roll shape, a circular tube shape, a flat plate shape, and a sheet shape.

  Examples of the mold production method include the following methods (X) and (Y). The method (X) is preferable because the mold can have a large area and can be easily produced.

    (X) A method of forming anodized alumina having a plurality of pores (concave portions) on the surface of a mold body made of aluminum.

    (Y) A method of directly forming a fine concavo-convex structure on the surface of a mold body by lithography, electron beam drawing, laser light interference, or the like.

  As the method (X), a method having the following steps (a) to (e) is preferable.

      (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).

Step (a):
As shown in FIG. 4, when the aluminum 34 is anodized, an oxide film 38 having pores 36 is formed. Examples of the electrolytic solution include oxalic acid and sulfuric 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.

Step (b):
As shown in FIG. 4, the regularity of the pores can be improved by once removing the oxide film 38 and using it as the pore generation point 40 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 the oxide film and removed. Examples of such a solution include a chromic acid / phosphoric acid mixed solution.

Step (c):
As shown in FIG. 4, when the aluminum 34 from which the oxide film has been removed is anodized again, an oxide film 38 having cylindrical pores 36 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.

Step (d):
As shown in FIG. 4, a process for expanding the diameter of the pores 36 (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 the oxide film. 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.

Step (e):
As shown in FIG. 4, when the anodic oxidation in the step (c) and the pore diameter enlargement process in the step (d) are repeated, the pores 36 have a shape in which the diameter continuously decreases in the depth direction from the opening. An anodized alumina (a porous oxide film of aluminum (alumite)) is formed, and a mold 22 having an inverted fine uneven structure on the surface 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 reflectance of the cured resin film produced using the anodized alumina having such pores is insufficient. .

  Examples of the shape of the pores 36 include a substantially conical shape and a pyramid shape.

  The average period between the pores 36 is not more than the wavelength of visible light, that is, not more than 400 nm. The average period between the pores 36 is preferably 25 nm or more.

  The depth of the pores 36 is preferably 100 to 500 nm, and more preferably 150 to 400 nm.

  The surface of the cured resin film 16b formed by transferring the pores 36 as shown in FIG. 4 has a so-called moth-eye structure.

  The surface of the mold 22 may be treated with a release agent so as to facilitate separation from the cured resin film. Examples of the release agent include silicone resins, fluororesins, and fluorine compounds.

(Active energy ray-curable resin composition)
The active energy ray-curable resin composition contains a polymerizable compound and a polymerization initiator.

  As an active energy ray curable resin composition, when an acrylic film is used as a film body, an acrylic monomer is a main component because the difference between the refractive index of the film body and the refractive index of the cured resin film is sufficiently small. Are preferred.

  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 resin composition may contain a non-reactive polymer and 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.

  Examples of non-reactive polymers include acrylic resins, styrene resins, polyurethanes, cellulose resins, polyvinyl butyral, polyesters, thermoplastic elastomers, and the like.

  Examples of the active energy ray sol-gel reactive composition include alkoxysilane compounds and alkyl silicate compounds.

  As an alkoxysilane compound, the compound of following formula (1) is mentioned.

R ¹ _x Si (OR ² ) _y (1)
^However, R 1, ^{R 2} each represent an alkyl group having 1 to 10 carbon atoms, x, y represents an integer satisfying the relation of x + y = 4.

  Examples of the alkoxysilane compound include tetramethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-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 ³ O [Si (OR ⁵ ) (OR ⁶ ) O] _z R ⁴ (2)
However, R < ³ > -R < ⁶ > 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 utilizing 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, and 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, benzoyl Examples include diethoxyphosphine oxide. 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. The polymerization initiator may be used in combination.

  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 resin film may be colored or the mechanical strength may be lowered.

  The active energy ray-curable resin 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. .

(Hydrophobic material)
In order to set the water contact angle of the surface of the moth-eye structure of the cured resin film to 90 ° or more, the composition containing a fluorine-containing compound or a silicone compound as an active energy ray-curable resin composition capable of forming a hydrophobic material It is preferable to use a product.

Fluorine-containing compounds:
As the fluorine-containing compound, a compound having a fluoroalkyl group represented by the following formula (3) is preferable.

_{- (CF 2) n -X ···} (3)
However, X represents a fluorine atom or a hydrogen atom, n represents an integer greater than or equal to 1, 1-20 are preferable, 3-10 are more preferable, and 4-8 are especially preferable.

  Examples of the fluorine-containing compound include a fluorine-containing monomer, a fluorine-containing silane coupling agent, a fluorine-containing surfactant, and a fluorine-containing polymer.

  Examples of the fluorine-containing monomer include a fluoroalkyl group-substituted vinyl monomer and a fluoroalkyl group-substituted ring-opening polymerizable monomer.

  Examples of the fluoroalkyl group-substituted vinyl monomer include fluoroalkyl group-substituted (meth) acrylates, fluoroalkyl group-substituted (meth) acrylamides, fluoroalkyl group-substituted vinyl ethers, and fluoroalkyl group-substituted styrenes.

  Examples of the fluoroalkyl group-substituted ring-opening polymerizable monomer include fluoroalkyl group-substituted epoxy compounds, fluoroalkyl group-substituted oxetane compounds, and fluoroalkyl group-substituted oxazoline compounds.

  As the fluorine-containing monomer, a fluoroalkyl group-substituted (meth) acrylate is preferable, and a compound of the following formula (4) is particularly preferable.

^{_{CH 2 = C (R 7)}} C (O) O- (CH 2) m - (CF 2) p -X ··· (4)
However, R ⁷ represents a hydrogen atom or a methyl group, X represents a hydrogen atom or a fluorine atom, m represents an integer of 1 to 6, preferably 1 to 3, more preferably 1 or 2, p Represents an integer of 1 to 20, preferably 3 to 10, and more preferably 4 to 8.

  As the fluorine-containing silane coupling agent, a fluoroalkyl group-substituted silane coupling agent is preferable, and a compound of the following formula (5) is particularly preferable.

(R ^f ) _a R ⁸ _b SiY _c (5)
R ^f represents a C1-C20 fluorine-substituted alkyl group which may contain one or more ether bonds or ester bonds. Examples of R ^f include 3,3,3-trifluoropropyl group, tridecafluoro-1,1,2,2-tetrahydrooctyl group, 3-trifluoromethoxypropyl group, 3-trifluoroacetoxypropyl group and the like. It is done.

R ⁸ represents an alkyl group having 1 to 10 carbon atoms. Examples of R ² include a methyl group, an ethyl group, and a cyclohexyl group.

  Y represents a hydroxyl group or a hydrolyzable group.

Examples of the hydrolyzable group include an alkoxy group, a halogen atom, and R ⁹ C (O) O (wherein R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).

  Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, Examples include octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, and the like.

  Examples of the halogen atom include Cl, Br, I and the like.

Examples of R ⁹ C (O) O include CH ₃ C (O) O, C ₂ H ₅ C (O) O, and the like.

  a, b, and c are integers satisfying a + b + c = 4 and satisfying a ≧ 1, c ≧ 1, and preferably a = 1, b = 0, and c = 3.

  Fluorine-containing silane coupling agents include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriacetoxysilane, dimethyl-3,3,3-trifluoropropylmethoxysilane, tri Examples include decafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane.

  Examples of the fluorine-containing surfactant include a fluoroalkyl group-containing anionic surfactant and a fluoroalkyl group-containing cationic surfactant.

Examples of the fluoroalkyl group-containing anionic surfactant include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C ₆ -C ₁₁ ) oxy. ] -1-alkyl _(C 3 _{~C 4)} sulfonate, sodium 3- [omega - fluoroalkanoyl _{(C 6 ~C} 8) -N- ethylamino] -1-sodium sulfonic acid, fluoroalkyl _{(C 11} ~ C ₂₀ ) carboxylic acid or a metal salt thereof, perfluoroalkyl carboxylic acid (C _{7 to} C ₁₃ ) or a metal salt thereof, perfluoroalkyl (C _{4 to} C ₁₂ ) sulfonic acid or a metal salt thereof, perfluorooctane sulfonic acid diethanolamine N-propyl-N- (2-hydroxy Chill) perfluorooctane sulfonamide, perfluoroalkyl _(C 6 _{-C 10)} sulfonamide propyl trimethyl ammonium salts, perfluoroalkyl _{(C 6} -C 10)-N-ethylsulfonyl glycine salts, monoperfluoroalkyl _{(C 6} -C ₁₆₎ ethyl phosphoric acid ester, and the like.

Examples of the fluoroalkyl group-containing cationic surfactant include aliphatic quaternary compounds such as fluoroalkyl group-containing aliphatic primary, secondary or tertiary amine acids, and perfluoroalkyl (C ₆ -C ₁₀ ) sulfonamidopropyltrimethylammonium salts. Examples thereof include ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.

  Fluorine-containing polymers include polymers of fluoroalkyl group-containing monomers, copolymers of fluoroalkyl group-containing monomers and poly (oxyalkylene) group-containing monomers, and copolymers of fluoroalkyl group-containing monomers and crosslinking reactive group-containing monomers. A polymer etc. are mentioned. The fluorine-containing polymer may be a copolymer with another copolymerizable monomer.

  As the fluorine-containing polymer, a copolymer of a fluoroalkyl group-containing monomer and a poly (oxyalkylene) group-containing monomer is preferable.

  As the poly (oxyalkylene) group, a group represented by the following formula (6) is preferable.

− (OR ¹⁰ ) _q − (6)
^{However, R 10} represents an alkylene group having 2 to 4 carbon atoms, q represents an integer of 2 or more.
Examples of R ¹⁰ include —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) —, and the like.

The poly (oxyalkylene) group may be composed of the same oxyalkylene unit (OR ¹⁰ ), or may be composed of two or more oxyalkylene units (OR ¹⁰ ). The arrangement of two or more oxyalkylene units (OR ¹⁰ ) may be a block or random.

Silicone compounds:
Examples of the silicone compound include (meth) acrylic acid-modified silicone, silicone resin, silicone silane coupling agent and the like.

  Examples of the (meth) acrylic acid-modified silicone include silicone (di) (meth) acrylate.

(Hydrophilic material)
In order to set the water contact angle of the surface of the moth-eye structure of the cured resin film to 25 ° or less, an active energy ray-curable resin composition that can form a hydrophilic material is a composition containing the following polymerizable compound: It is preferable to use it.

10 to 50% by mass of a tetrafunctional or higher polyfunctional (meth) acrylate,
30-80% by weight of bifunctional or higher hydrophilic (meth) acrylate,
A polymerizable compound comprising a total of 100% by mass of 0 to 20% by mass of a monofunctional monomer.

  Examples of tetrafunctional or higher polyfunctional (meth) acrylates include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, succinic acid / trimethylolethane / acrylic acid molar mixture 1: 2: 4 condensation reaction mixture, urethane acrylates (manufactured by Daicel-Cytec: EBECRYL220, EBECRYL1290K, EBECRYL1290K, EBECRYL5129, EBECRYL8210, EBECRYL 8301, KRM 8200), polyether acrylates (manufactured by Daicel-Cytec: EBEC) YL81), modified epoxy acrylates (manufactured by Daicel-Cytec: EBECRYL3416), polyester acrylates (manufactured by Daicel-Cytech: EBECRYL450, EBECRYL657, EBECRYL800, EBECRYL810, EBECRYL8111, EBECRYL81L, EBECRYL81L It is done. These may be used alone or in combination of two or more.

  The polyfunctional (meth) acrylate having 4 or more functional groups is more preferably a polyfunctional (meth) acrylate having 5 or more functional groups.

  The proportion of the tetrafunctional or higher polyfunctional (meth) acrylate is preferably 10 to 50% by mass, more preferably 20 to 50% by mass, and particularly preferably 30 to 50% by mass from the viewpoint of water resistance and chemical resistance. If the ratio of the tetrafunctional or higher polyfunctional (meth) acrylate is 10% by mass or more, the elastic modulus is increased and the scratch resistance is improved. If the ratio of the tetrafunctional or higher polyfunctional (meth) acrylate is 50% by mass or less, small cracks are hardly formed on the surface, and the appearance is hardly deteriorated.

  Long-chain polyethylene such as Aronix M-240, Aronix M260 (manufactured by Toagosei Co., Ltd.), NK ester AT-20E, NK ester ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.) Examples thereof include polyfunctional acrylates having glycol and polyethylene glycol dimethacrylate. These may be used alone or in combination of two or more.

  In the polyethylene glycol dimethacrylate, the total of the average repeating units of the polyethylene glycol chain present in one molecule is preferably 6 to 40, more preferably 9 to 30, and particularly preferably 12 to 20. If the average repeating unit of the polyethylene glycol chain is 6 or more, the hydrophilicity is sufficient and the antifouling property is improved. When the average repeating unit of the polyethylene glycol chain is 40 or less, the compatibility with a polyfunctional (meth) acrylate having 4 or more functionalities is improved, and the active energy ray-curable resin composition is hardly separated.

  30-80 mass% is preferable and, as for the ratio of bifunctional or more hydrophilic (meth) acrylate, 40-70 mass% is more preferable. When the ratio of the bifunctional or higher hydrophilic (meth) acrylate is 30% by mass or more, the hydrophilicity is sufficient and the antifouling property is improved. When the proportion of the bifunctional or higher hydrophilic (meth) acrylate is 80% by mass or less, the elastic modulus is increased and the scratch resistance is improved.

  As the monofunctional monomer, a hydrophilic monofunctional monomer is preferable.

  Examples of the aqueous monofunctional monomer include monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group such as M-20G, M-90G, and M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.) and hydroxyalkyl (meth) acrylates. Examples thereof include cationic monomers such as monofunctional (meth) acrylates having a hydroxyl group in the ester group, monofunctional acrylamides, methacrylamidopropyltrimethylammonium methylsulfate, and methacryloyloxyethyltrimethylammonium methylsulfate.

  Moreover, as a monofunctional monomer, you may use viscosity modifiers, such as acryloyl morpholine and vinyl pyrrolidone, adhesive improvement agents, such as acryloyl isocyanate which improves the adhesiveness to a base material, etc.

  The proportion of the monofunctional monomer is preferably 0 to 20% by mass, and more preferably 5 to 15% by mass. By using a monofunctional monomer, the adhesion between the member and the cured resin is improved. When the proportion of the monofunctional monomer is 20% by mass or less, antifouling property or scratch resistance is sufficient without a shortage of tetrafunctional or higher polyfunctional (meth) acrylate or bifunctional or higher hydrophilic (meth) acrylate. Expressed in

  The monofunctional monomer may be blended in the active energy ray-curable resin composition in an amount of 0 to 35 parts by mass as a polymer having a low polymerization degree obtained by (co) polymerizing one type or two or more types. As a polymer having a low degree of polymerization, 40/60 of monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group such as M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.) and methacrylamide propyltrimethylammonium methyl sulfate. Copolymer oligomer (MRC Unitech Co., Ltd., MG polymer) and the like can be mentioned.

(Laminate manufacturing method)
The laminate 14 of the present invention is formed by applying and drying a pressure-sensitive adhesive coating liquid constituting the pressure-sensitive adhesive layer 18 to a predetermined thickness on a release film, and the pressure-sensitive adhesive layer 18 has a fine uneven structure of the film 16. It is obtained by transferring to the surface on the side where it is not formed.

  In addition, the laminate 14 is obtained by applying and drying the pressure-sensitive adhesive layer 18 to a predetermined thickness on the surface of the film 16 where the fine uneven structure is not formed. It can also be manufactured by bonding a release film after forming.

  As the release film, a sheet in which a release agent layer is formed by coating a release agent such as a fluororesin, a silicone resin, or a long chain alkyl group-containing carbamate on the surface of a release sheet substrate such as a resin film is used. .

  As the release film substrate, a resin film such as a polyester such as polyethylene terephthalate, a polyolefin such as polyethylene, polypropylene, or polybutadiene can be used. Although the thickness of the base material for peeling films changes somewhat with materials to be used, it is about 10-100 micrometers normally.

  In order to form an adhesive layer on a release film, an adhesive coating solution is prepared, and the usual gravure coating method, bar coating method, spray coating method, spin coating method, roll coating method are performed. The coating liquid can be applied using a die coating method, a knife coating method, an air knife coating method, a hot melt coating method, a curtain coating method, or the like. After applying the adhesive coating solution, in order to prevent the solvent and low-boiling components from remaining, the adhesive layer is developed by heating and drying at a temperature of about 60 to 150 ° C. for about 30 seconds to 5 minutes. Is formed.

  The obtained laminated body 14 may be stuck on the transparent substrate 12 through the pressure-sensitive adhesive layer 18 as it is, or may be temporarily wound around a roll or the like and stored. When storing, it is stored with the release film or the like laminated on the exposed pressure-sensitive adhesive layer 18.

  The laminate 14 is coated on the film 16 by applying and drying the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 18 on the surface of the film 16 where the fine concavo-convex structure is not formed. It can also be obtained by laminating the agent layer 18. A pressure-sensitive adhesive layer is formed in advance by applying a pressure-sensitive adhesive to a release film, etc., and laminating by bonding the pressure-sensitive adhesive layer on the release paper and the surface on the side where the fine uneven structure of the film is not formed. The body may be manufactured. If it is such a method, storage and conveyance of a laminated body are easy.

  Since the laminate of the present invention described above has good adhesion to the transparent substrate and has antistatic performance, the adhesion to the transparent substrate is good and the workability during production of the laminate is also good. It is possible to achieve improvement in antistatic properties when peeling the release film.

  Moreover, since the laminated body of this invention is provided with the film by which the fine uneven structure was formed in the surface, it can exhibit the outstanding antireflection function.

  In addition, the laminated body of this invention is not limited to the laminated body 14 of the example of illustration. For example, in the laminate 14, the plurality of convex portions 19 are formed on the surface of the cured resin film 16 b of the film 16, but are directly formed on the surface of the film body 16 a without providing the cured resin film 16 b. Also good. However, a plurality of protrusions 19 are formed on the surface of the cured resin film 16b of the film 16 as shown in FIG. 2 because the plurality of protrusions 19 can be efficiently formed using the roll-shaped mold 22. Is preferred.

<Production method>
The article of the present invention is obtained by sticking the above-described laminate of the present invention onto a transparent substrate via the adhesive layer of the laminate.

  When a release film or the like is laminated on the pressure-sensitive adhesive layer of the laminate, the release film is peeled from the laminate to expose the surface of the pressure-sensitive adhesive layer and adhered onto the transparent substrate.

  The article of the present invention can be suitably used as a member of an image display device or the like that requires an antireflection function. If the member of this invention is used, since a sunlight ray, illumination light, etc. are hard to reflect, visibility can be maintained.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

(Pores of anodized alumina)
Part of the anodized alumina is shaved, platinum is deposited on the cross section for 1 minute, and the cross section is subjected to acceleration voltage: 3.00 kV using a field emission scanning electron microscope (JSM-7400F, manufactured by JEOL Ltd.). Observed and measured pore spacing and pore depth. Each measurement was performed for 50 points, and the average value was obtained.

(Convex part of cured resin film)
Platinum is vapor-deposited on the fracture surface of the cured resin film for 5 minutes, and the cross-section is observed using a field emission scanning electron microscope (JSM-7400F, JSM-7400F) under an acceleration voltage of 3.00 kV. The average interval between the parts and the height of the convex part were measured. Each measurement was performed for 5 points, and the average value was obtained.

(Refractive index)
The refractive indexes of the film body and the cured resin film were measured using an Abbe refractometer (NAR-2, manufactured by Atago Co., Ltd.).

(Transmittance)
The total light transmittance of the film main body before film roughening and the film was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd.) according to JIS K7361-1.

(Dynamic viscoelasticity)
In accordance with JIS K7244-4, the loss factor tan δ was measured under the condition of a measurement frequency of 0.1 Hz.

(Film reflectivity)
Using a spectrophotometer (manufactured by Hitachi, Ltd., U-4000), the relative reflectance of the surface of the cured resin film was measured in the range of incident angle: 5 ° and wavelength of 380 to 780 nm. Visibility according to JIS R3106 The reflectance was calculated.

(Adhesiveness)
A pressure-sensitive adhesive tape (product name 31B, manufactured by Nitto Denko Co., Ltd.) is pasted on the surface opposite to the pressure-sensitive adhesive layer of the laminates produced in Examples and Comparative Examples, and cut into a size of 25 mm × 250 mm to be used for pressure-sensitive adhesive evaluation. It was. The surface of the pressure-sensitive adhesive layer exposed by peeling the release film from the pressure-sensitive adhesive sheet was attached to an acrylic plate (Mitsubishi Rayon Co., Ltd., product name: Acrylite L # 001, 70 mm × 150 mm size). Thereafter, after being left for 24 hours in an environment of 23 ° C. and a relative humidity of 50%, a peeling speed of 300 mm / in accordance with JIS Z0237 is used in the same environment using a tensile tester (Orientec Co., Ltd., device name: Tensilon). The value (N / 25 mm) measured under the condition of minute and peeling angle of 180 ° was defined as the adhesive strength.

(Antistatic property)
The antistatic performance evaluation of the pressure-sensitive adhesive layer of the laminates produced in the examples and comparative examples was performed using a surface resistivity meter (manufactured by Toa Electric Industry Co., Ltd., device name: ULTRA MEGOHMMETER MODEL SM-10E). This was done by measuring. The measurement was performed under constant temperature and humidity conditions of room temperature 22 ° C. and humidity 55%.

(Manufacturing method of mold a)
After applying a blanket polishing treatment to an aluminum ingot having a diameter of 200 mm and a length of 350 mm cut from a 99.99% pure aluminum ingot, a rubbing treatment was applied to the aluminum ingot in a perchloric acid / ethanol mixed solution (volume Ratio: 1/4) was electropolished and mirror finished.

Step (a):
The aluminum prototype was anodized in a 0.3 M oxalic acid aqueous solution under the conditions of DC: 40 V and temperature: 16 ° C. for 30 minutes.

Step (b):
The aluminum original mold on which the oxide film having a thickness of 3 μm was formed was immersed in a 6% by mass phosphoric acid / 1.8% by mass chromic acid mixed aqueous solution to remove the oxide film.

Step (c):
The aluminum prototype was anodized in a 0.3 M oxalic acid aqueous solution for 30 seconds under the conditions of DC: 40 V and temperature: 16 ° C.

Step (d):
The aluminum prototype on which the oxide film was formed was immersed in a 5% by mass phosphoric acid aqueous solution at 30 ° C. for 8 minutes to carry out pore size expansion treatment.

Step (e):
The step (c) and the step (d) are repeated 5 times in total, and a roll-shaped mold a having anodized alumina having substantially conical pores with an average period of 100 nm and a depth of 200 nm formed on the surface is obtained. Obtained.

  The mold a was dipped in a 0.1% by mass diluted solution of OPTOOL DSX (manufactured by Daikin Chemicals Sales) for 10 minutes at room temperature and pulled up. The mold a treated with a release agent was obtained by air drying overnight.

(Preparation of active energy ray-curable resin composition)
An active energy ray-curable resin composition A (Table 1) having the following composition was prepared.

活性エネルギー線硬化性樹脂組成物Ａを硬化させてなる厚さ５μｍの硬化樹脂膜は、透明であり、屈折率は１．５１であった。

The cured resin film having a thickness of 5 μm obtained by curing the active energy ray-curable resin composition A was transparent and had a refractive index of 1.51.

[Example 1]
The film was manufactured using the manufacturing apparatus shown in FIG.

  As the roll-shaped mold 22, the mold a was used.

  As the active energy ray curable resin composition 21, the active energy ray curable resin composition A was used.

  As the film main body 16a, a polyester film which is easily bonded on both sides was used.

The coating film of the active energy ray-curable resin composition A is irradiated from the film body 16a side with an ultraviolet ray having an integrated light amount of 1000 mJ / cm ² to cure the active energy ray-curable resin composition A, and the cured resin film 16b. Formed.

  The average period between the convex parts of the obtained film 16 was 100 nm, and the height of the convex parts was 200 nm. When the visibility reflectance and the total light transmittance of the film 16 were measured, the visibility reflectance was 0.09% and the total light transmittance was 95.5%.

  100 of acrylic acid ester copolymer (weight average molecular weight: 700,000) obtained by copolymerizing butyl acrylate (BA) and methyl acrylate (MA) at BA / MA = 95/5 (mass ratio). Part by mass, 1.0 part by mass of an aluminum chelate cross-linking agent (Soken Chemical Co., Ltd., product name: M5A), 1.0 part by mass of an anionic antistatic agent (Kao Corporation, Electro Stripper ME) were mixed, and then Diluted with methyl ethyl ketone to prepare a pressure-sensitive adhesive coating solution having a nonvolatile content concentration of 20% by mass.

  Using a knife coater, this adhesive coating solution was applied to the release agent-treated surface of a release film (manufactured by Lintec Corporation, product name: SP-PET 381031C, thickness: 38 μm) so that the thickness after drying was 25 μm. Dry at 60 ° C. for 60 seconds. Next, the pressure-sensitive adhesive layer was bonded to the surface opposite to the cured resin film 16b of the obtained film 16 (the surface on the film body 16a side) and transferred to prepare a laminate with a release film. About the obtained laminated body, adhesiveness and antistatic property were evaluated. The results are shown in Table 2.

  In addition, the laminate with the release film did not generate static electricity when the film was conveyed on a roll, and exhibited excellent wettability even when wet coating was further applied to the fine uneven surface of the laminate.

[Comparative Example 1]
100 of acrylic acid ester copolymer (weight average molecular weight: 700,000) obtained by copolymerizing butyl acrylate (BA) and methyl acrylate (MA) at BA / MA = 95/5 (mass ratio). A pressure-sensitive adhesive coating solution having a nonvolatile content concentration of 25% by mass was prepared by mixing 1.2 parts by mass of an aluminum chelate crosslinking agent (Soken Chemical Co., Ltd., product name: M5A) and then diluting with methyl ethyl ketone. Except for the above, a laminate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2.

  In addition, the laminate with the release film generated static electricity when the film was conveyed on a roll, and static discharge traces remained on the film surface. Even when wet coating was further applied to the fine uneven surface of the laminate, the coating liquid repelled and uniform coating could not be achieved.

表２から明らかなように、実施例１では、透明基板に対する粘着力に優れており、且つ帯電防止性能を有している。

As is clear from Table 2, Example 1 has excellent adhesion to the transparent substrate and has antistatic performance.

  On the other hand, in Comparative Example 1, traces were made on the surface of the fine concavo-convex structure due to the generation of static electricity. In addition, workability in wet coating deteriorated.

10 Article 12 Transparent substrate 14 Laminate 16 Film 18 Adhesive layer

Claims (3)

A laminate comprising a film having a fine concavo-convex structure formed on one surface and a pressure-sensitive adhesive layer laminated on the other surface of the film, and is attached to a transparent substrate via the pressure-sensitive adhesive layer. ,
The pressure-sensitive adhesive layer contains an antistatic property imparting agent. The laminate according to claim 1, wherein the pressure-sensitive adhesive layer has a surface resistance value of 1.0 × 10 ⁸ Ω / cm ² or more and less than 1.0 × 10 ¹⁵ Ω / cm ² .   An article comprising: a transparent substrate; and the laminate according to claim 1 attached to the transparent substrate via an adhesive layer.

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