JP2009241351A - Film for insert molding, insert-molded article and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film for insert molding which has low reflectivity and small wavelength dependency of the reflectivity, to provide an insert-molded article in which the original color of a decorative layer and a colored substrate is sufficiently reproduced and which has high designing properties, and to provide a method of manufacturing the same. <P>SOLUTION: The film for insert molding 10 has fine recessed-projected structure on the surface thereof. In the film for insert molding 10, the fine recessed-projected structure has a plurality of projected portions and the average interval between the projected portions is ≤400 nm. The insert-molded article has a substrate comprising a resin material and the film for insert molding 10 whose surface opposite to a side where the fine recessed-projected structure is formed is in contact with the substrate. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an insert-molding film, an insert-molded product, and a manufacturing method thereof.

  As a method for imparting design properties to a molded product, an insert molding method (including an in-mold molding method) is well known. According to the insert molding method, for example, an insert molded product in which a base material made of a resin material and an insert molding film having a decorative layer are laminated, a colored base material made of a resin material and a transparent insert molding film A laminated insert molded product or the like is obtained.

  However, in the insert molded product, the transparent film main body constituting the insert molding film exists on the front surface of the decorative layer or the colored base material. Therefore, the reflection is caused by light reflection on the surface of the film main body. There is a problem that the decorative layer and the colored base material are generally whitish or the hue is changed, and the original colors of the decorative layer and the colored base material cannot be reproduced, and the design properties are deteriorated. For example, even if an insert molded product is designed to have a jet black design, the brightness increases due to the reflection of a fluorescent lamp or the like, and it is difficult to show the jet black.

As a low reflection insert molding film, an insert molding film in which a low reflection layer formed by alternately laminating a high refractive index metal compound thin film and a low refractive index metal compound thin film has been proposed ( Patent Document 1).
However, the low reflection layer cannot be said to have a sufficiently low reflectivity and has a wavelength dependency of the reflectivity, so that the hue of the reflected light is changed, and the original color of the decorative layer or the colored substrate is changed. There is a problem that cannot be reproduced sufficiently.
JP 09-099453 A

  The present invention relates to an insert molding film having a low reflectivity and a low wavelength dependency of the reflectivity, an insert molded product having a high design property in which the original colors of the decorative layer and the colored base material are sufficiently reproduced, and production thereof Provide a method.

The insert molding film of the present invention is a film for insert molding having a fine concavo-convex structure on the surface, wherein the fine concavo-convex structure has a plurality of convex portions, and an average interval between the convex portions is 400 nm or less. It is characterized by that.
The fine concavo-convex structure is preferably formed by transferring the fine concavo-convex structure on the surface of anodized alumina because a film for insert molding can be produced seamlessly with a large area.

  The insert-molded article of the present invention has a base material made of a resin material and an insert-molding film of the present invention in which the surface opposite to the side on which the fine concavo-convex structure is formed contacts the base material. And

  The method for producing an insert-molded product according to the present invention includes a step of placing a film for insert molding according to the present invention in a mold, injecting a molten resin material into the mold, and solidifying the resin material to form a base made of the resin material. An insert-molded article having a material and an insert-molding film having a surface opposite to the side on which the fine concavo-convex structure is formed is in contact with the base material is obtained.

The insert molding film of the present invention has a low reflectivity and a low wavelength dependency of the reflectivity.
The insert-molded product of the present invention has a sufficiently high design, since the original colors of the decorative layer and the colored substrate are sufficiently reproduced.
According to the method for producing an insert-molded product of the present invention, the original colors of the decorative layer and the colored base material are sufficiently reproduced, and an insert-molded product having a high design property can be obtained.

  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.

<Film for insert molding>
FIG. 1 is a cross-sectional view showing an example of an insert molding film of the present invention. The insert molding film 10 includes a film body 12 and a cured resin film 14 having a fine concavo-convex structure (not shown) formed on the surface of the film body 12.

(Film body)
The film body 12 is a film or sheet that can transmit light. Examples of the material for the film body 12 include acrylic resins, polycarbonates, styrene resins, polyesters, cellulose resins (such as triacetyl cellulose), polyolefins, and alicyclic polyolefins, and are excellent in transparency and weather resistance. From the point of view, an acrylic resin is preferable.

  As the acrylic resin, JP-A-8-323934, JP-A-11-147237, JP-A-2002-80678, and JP-A-2002-80678 are known in that they have scratch resistance, pencil hardness, heat resistance, and chemical resistance. The acrylic resins described in JP 2002-80679 A and JP 2005-97351 A are preferable. Moreover, the thing of Unexamined-Japanese-Patent No. 2005-163003 and Unexamined-Japanese-Patent No. 2005-139416 is preferable at the point of the shaping | molding whitening resistance at the time of performing insert molding (in-mold shaping | molding).

  The film body 12 is made of known additives (stabilizers, antioxidants, lubricants, processing aids, plasticizers, impact agents, fillers, antibacterial agents, antifungal agents, mold release agents, antistatic agents, ultraviolet absorption Agents, light stabilizers, heat stabilizers, flame retardants, etc.).

10-500 micrometers is preferable, as for the thickness of the film main body 12, 30-300 micrometers is more preferable, and 50-200 micrometers is especially preferable. If the thickness of the film body 12 is 500 μm or less, rigidity suitable for insert molding (in-mold molding) can be obtained, and the film can be manufactured stably. If the thickness of the film main body 12 is 10 μm or more, a sense of depth can be more sufficiently imparted to the insert-molded product together with the protection of the base material.
The film body 12 may be a laminated film or a laminated sheet.

  As a manufacturing method of the film main body 12, well-known methods, such as a melt-extrusion method (melt casting method, T-die method, inflation method), a calendar method, are mentioned, The T-die method is preferable from the point of economical efficiency. Moreover, when manufacturing the film main body 12 by a T-die method, from the point which improves surface smoothness, the method of forming into a film by pinching | interposing to several rolls (metal roll etc.) or belts (metal belt etc.) is used. Is preferred.

(Cured resin film)
The cured resin film 14 is a film made of a cured product of an active energy ray-curable resin composition described later, and has a fine uneven structure on the surface.
The fine concavo-convex structure has a plurality of convex portions made of a cured product of the active energy ray-curable resin composition.

  As the fine concavo-convex structure, 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 is preferable. It is known that the moth-eye structure in which the distance between the protrusions is less than or equal to the wavelength of visible light can be an effective anti-reflection measure by continuously increasing the refractive index from the refractive index of air to the refractive index of the material. ing.

The average interval between the convex portions is not more than the wavelength of visible light, that is, not more than 400 nm. When the convex portions are formed using a mold of anodized alumina, which will be described later, the average distance between the convex portions is about 100 nm, and is preferably 200 nm or less, and particularly preferably 150 nm or less.
The average interval between the convex portions is preferably 20 nm or more from the viewpoint of easy formation of the convex portions.
The average interval between the convex portions is obtained by measuring 50 intervals between adjacent convex portions (distance from the center of the convex portion to the center of the adjacent convex portion) by electron microscope observation, and averaging these values. .

As for the height of a convex part, when an average space | interval is 100 nm, 80-500 nm is preferable, 120-400 nm is more preferable, 150-300 nm is especially preferable. When the height of the convex portion is 80 nm or more, the reflectance is sufficiently low and the wavelength dependence of the reflectance is small. If the height of a convex part is 500 nm or less, the scratch resistance of a convex part will become favorable.
The height of the convex portion is a value obtained by measuring the distance between the topmost portion of the convex portion and the bottommost portion of the concave portion existing between the convex portions when observed with an electron microscope at a magnification of 30000 times.

  The aspect ratio of the convex portion (height of the convex portion / average interval between the convex portions) is preferably 0.8 to 5.0, more preferably 1.2 to 4.0, and 1.5 to 3.0. Particularly preferred. If the aspect ratio of the convex portion is 1.0 or more, the reflectance is sufficiently low. If the aspect ratio of the convex portion is 5.0 or less, the scratch resistance of the convex portion is good.

  The shape of the convex part is a shape in which the convex sectional area in the direction perpendicular to the height direction continuously increases in the depth direction from the outermost surface, that is, the sectional shape in the height direction of the convex part is a triangle, trapezoid, A shape such as a bell shape is preferred.

The thickness of the cured resin film 14 is preferably 1 to 50 μm.
The difference between the refractive index of the cured resin film 14 and the refractive index of the film body 12 is preferably 0.2 or less, more preferably 0.1 or less, and particularly preferably 0.05 or less. If the refractive index difference is 0.2 or less, reflection at the interface between the cured resin film 14 and the film body 12 is suppressed.

  When the surface has a fine concavo-convex 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 that

  When the material of the cured resin film 14 is hydrophobic, the water contact angle on the surface of the fine uneven structure is preferably 90 ° or more, more preferably 110 ° or more, and particularly preferably 120 ° 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 14 is hydrophilic, the water contact angle on the surface of the fine concavo-convex 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 attached 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 the deformation of the fine concavo-convex structure due to water absorption of the cured resin film 14 and the accompanying increase in reflectance.

(Other layers)
The insert molding film of the present invention may have other layers such as a thermoplastic resin layer, a decorative layer, and an adhesive layer.

A thermoplastic resin layer is a layer used as a base material at the time of forming a decoration layer, for example.
Examples of the material for the thermoplastic resin layer include acrylic resins, polycarbonates, styrene resins, polyesters, cellulose resins (such as triacetyl cellulose), polyolefins, and alicyclic polyolefins.

  The decorative layer is preferably present on the surface of the film body 12 on the side opposite to the cured resin film 14, and when it has a thermoplastic resin layer, it is present between the film body 12 and the thermoplastic resin layer. Is preferred. As a decoration layer, the printing layer formed by the printing method and the vapor deposition layer formed by the vapor deposition method are mentioned.

The printed layer is a pattern, pattern, character, or the like in the insert molded product. Examples of the printed pattern include wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, and solid surface.
Examples of the method for forming the printing layer include an offset printing method, a gravure rotary printing method, a screen printing method, a roll coating method, a spray coating method, and a flexographic printing method.
The thickness of the printing layer is usually about 0.5 to 30 μm.

  The vapor deposition layer is formed of a metal (aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, or the like), an alloy thereof, or a compound thereof. Examples of the method for forming the vapor deposition layer include vacuum vapor deposition, sputtering, ion plating, and plating.

The adhesive layer is preferably formed on the outermost layer of the insert molding film on the side opposite to the cured resin film 14.
Examples of the material for the adhesive layer include acrylic resins, urethane resins, and epoxy resins.
The difference between the refractive index of the adhesive layer and the adjacent layer, i.e., the decorative layer or the refractive index of the film body 12, is preferably 0.2 or less, more preferably 0.1 or less, and particularly preferably 0.05 or less. If the refractive index difference is 0.2 or less, reflection at the interface between the adhesive layer and the adjacent layer can be suppressed.
The thickness of the adhesive layer is usually about 1 to 5 μm.

<Method for producing film for insert molding>
The insert molding film 10 is manufactured as follows using, for example, a manufacturing apparatus shown in FIG.

  The active energy ray-curable resin composition is transferred from the tank 24 between the roll-shaped mold 22 having a fine concavo-convex structure (not shown) on the surface and the strip-shaped film body 12 that moves along the surface of the roll-shaped mold 22. Supply.

  The film main body 12 and the active energy ray curable resin composition are nipped between the roll-shaped 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 is squeezed into the film. While being uniformly distributed between the main body 12 and the roll-shaped mold 22, it is filled in the concave portions of the fine concavo-convex structure of the roll-shaped mold 22.

The active energy ray curable resin composition is irradiated with the active energy ray curable resin composition through the film body 12 from the active energy ray irradiating device 30 installed below the roll-shaped mold 22 to cure the active energy ray curable resin composition. Thus, the cured resin film 14 to which the fine uneven structure on the surface of the roll mold 22 is transferred is formed.
The film 10 for insert molding is obtained by peeling the film body 12 having the cured resin film 14 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 .

(Roll mold)
The roll-shaped mold 22 has a fine uneven structure on the surface. The fine uneven structure has a plurality of recesses.
Examples of the roll-shaped mold include a mold produced by electron beam drawing, a mold produced by a laser beam interference method, a mold having an anodized alumina on the surface, and the like. From the viewpoint of easy production, a mold having anodized alumina on the surface is preferable.

  Anodized alumina is a porous oxide film (alumite) of aluminum and has a plurality of pores (concave portions) on the surface.

A mold having an anodized alumina on the surface can be produced, for example, through the following steps (a) to (e).
(A) A step of forming an oxide film by anodizing roll-shaped 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 the roll-shaped aluminum again in the electrolytic solution to form an oxide film having pores at the pore generation points.
(D) A step of enlarging the diameter of the pores.
(E) A step of repeatedly performing the steps (c) and (d).

(A) Process:
As shown in FIG. 3, when the aluminum 34 is anodized, an oxide film 38 having pores 36 is formed.
The purity of aluminum is preferably 99% or more, more preferably 99.5% or more, and particularly preferably 99.8% or more. When the purity of aluminum is low, when anodized, an uneven structure having a size to scatter visible light may be formed due to segregation of impurities, or the regularity of pores obtained by anodization may be lowered.
Examples of the electrolytic solution include sulfuric acid, oxalic acid, and phosphoric acid.

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

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

(B) Process:
As shown in FIG. 3, 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.

(C) Process:
As shown in FIG. 3, 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.

(D) Process:
As shown in FIG. 3, a process of expanding the diameter of the pores 36 (hereinafter referred to as a pore diameter expansion 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.

(E) Process:
As shown in FIG. 3, when the anodic oxidation in the step (c) and the pore diameter expansion 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 is formed, and a mold (roll mold 22) having an anodized alumina 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 14 manufactured using anodized alumina having such pores is insufficient. is there.

  The surface of the anodized alumina may be treated with a release agent so that separation from the cured resin film 14 is easy. Examples of the treatment method include a method of coating a silicone resin or a fluorine-containing polymer, a method of depositing a fluorine-containing compound, a method of coating a fluorine-containing silane coupling agent or a fluorine-containing silicone-based silane coupling agent, and the like.

Examples of the shape of the pore 36 include a substantially conical shape, a pyramid shape, a cylindrical shape, and the like, and a cross-sectional area of the pore in a direction perpendicular to the depth direction, such as a cone shape and a pyramid shape, is a depth from the outermost surface. A shape that continuously decreases in the direction is preferred.
The average interval between the pores 36 is not more than the wavelength of visible light, that is, not more than 400 nm. The average interval between the pores 36 is preferably 20 nm or more.
The average distance between the pores 36 was measured by measuring the distance between adjacent pores 36 (distance from the center of the pore 36 to the center of the adjacent pore 36) by electron microscope observation, and averaging these values. It is what.

When the average interval is 100 nm, the depth of the pores 36 is preferably 80 to 500 nm, more preferably 120 to 400 nm, and particularly preferably 150 to 300 nm.
The depth of the pore 36 is a value obtained by measuring the distance between the bottom of the pore 36 and the top of the convex portion existing between the pores 36 when observed with an electron microscope at a magnification of 30000. It is.
The aspect ratio of the pores 36 (depth of pores / average interval between pores) is preferably 0.8 to 5.0, more preferably 1.2 to 4.0, and 1.5 to 3.0. Is particularly preferred.
The surface of the cured resin film 14 formed by transferring the pores 36 as shown in FIG. 3 has a so-called moth-eye structure.

(Active energy ray-curable resin composition)
The active energy ray-curable resin composition contains a polymerizable compound and a polymerization initiator.
Examples of the polymerizable compound include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.
The active energy ray-curable 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 ¹¹ _x Si (OR ¹² ) _y (1).
^However, R ^{11, R 12} 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 ²¹ O [Si (OR ²³ ) (OR ²⁴ ) O] _z R ²² (2).
^However, R 21 ^{to R 24} each represent an alkyl group having 1 to 5 carbon atoms, z is an integer of 3 to 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, 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 Acetophenone such as phenyl) -butanone; benzoin ether such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)- Acylphosphine oxides such as 2,4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; methylbenzoylformate, 1,7-bisacridinylheptane, 9-phenyl Examples include acridine. These may be used alone or in combination of two or more.

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

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

  The active energy ray-curable resin composition may contain an antistatic agent, a release agent, an additive such as a fluorine compound for improving the antifouling property, 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 fine uneven structure of the cured resin film 14 to 90 ° or more, a fluorine-containing compound or a silicone compound is used as an active energy ray-curable resin composition capable of forming a hydrophobic material. It is preferable to use the composition containing.

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 41)}} C (O) O- (CH 2) m - (CF 2) n -X ··· (4).
However, ^R41 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, and n 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 ⁵¹ _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, and 3-trifluoroacetoxypropyl group. It is done.

R ⁵¹ represents an alkyl group having 1 to 10 carbon atoms. Examples of R ⁵¹ 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, R ⁵² C (O) O (wherein R ⁵² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) and the like.
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 ⁵² 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, 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 61) p - ···}} (6).
^{However, R 61} represents an alkylene group having 2 to 4 carbon atoms, p is an integer of 2 or more. Examples of R ⁶¹ 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 ⁶¹ ) or may be composed of two or more oxyalkylene units (OR ⁶¹ ). The arrangement of two or more oxyalkylene units (OR ⁶¹ ) 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) acrylates such as X-22-1602 (manufactured by Shin-Etsu Chemical Co., Ltd.).

(Hydrophilic material)
In order to make the water contact angle of the surface of the fine concavo-convex structure of the cured resin film 14 25 ° or less, the active energy ray-curable resin composition capable of forming a hydrophilic material contains at least a hydrophilic monomer. Is preferably used. Moreover, it is more preferable to contain a cross-linkable polyfunctional monomer from the viewpoint of scratch resistance and imparting water resistance. In addition, the same (namely, hydrophilic polyfunctional monomer) may be sufficient as the polyfunctional monomer which can be bridge | crosslinked with a hydrophilic monomer. Furthermore, the active energy ray-curable resin composition may contain other monomers.

As the active energy ray-curable resin composition capable of forming a hydrophilic material, it is more preferable to use a composition containing the following polymerizable compound.
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.

As tetrafunctional or higher polyfunctional (meth) acrylate, 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 hydrophilic monofunctional monomer include monofunctional (meth) acrylate having a polyethylene glycol chain in the ester group such as M-20G, M-90G, M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.), hydroxyalkyl (meth) acrylate, etc. And cationic monomers such as monofunctional (meth) acrylates having a hydroxyl group in the ester group, monofunctional acrylamides, methacrylamidopropyltrimethylammonium methyl sulfate, and methacryloyloxyethyltrimethylammonium methyl sulfate.
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 substrate 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.

  In the insert molding film 10 described above, the surface has a fine uneven structure having a plurality of convex portions, and the average interval between the convex portions is 400 nm or less, so the reflectance on the surface is low, In addition, the wavelength dependence of reflectance is small.

  In addition, the film for insert molding of this invention is not limited to the film 10 for insert molding of the example of illustration. For example, in the insert molding film 10, the fine concavo-convex structure is formed on the surface of the cured resin film 14 of the insert molding film 10, but directly formed on the surface of the film body 12 without providing the cured resin film 14. May be. However, the cured resin of the insert molding film 10 from the point that the fine uneven structure can be efficiently formed using the roll-shaped mold 22 and the insert molding film 10 can be reattached when the fine uneven structure is damaged. A fine uneven structure is preferably formed on the surface of the film 14.

<Insert molded product>
The insert-molded article of the present invention has a base material made of a resin material and an insert-molding film of the present invention in which the surface opposite to the side on which the fine concavo-convex structure is formed contacts the base material.
The substrate may be colored with a colorant (pigment, dye, etc.), and the surface may be printed, painted, or the like.

  Examples of the resin material include olefin resins (polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, olefin thermoplastic elastomer, etc.), styrene resins, ABS resins ( (Acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), acrylic resin, urethane resin, unsaturated polyester resin, epoxy resin, polyphenylene oxide / polystyrene resin, polycarbonate, polyacetal, polycarbonate modified Polyphenylene ether, polyethylene terephthalate, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyetherimide, polyimide, liquid crystal polyester, Riariru heat-resistant resin, various composite resin, various modified resins.

  The resin material may contain a colorant (pigment, dye, etc.). In addition, resin materials are known additives (stabilizers, antioxidants, lubricants, processing aids, plasticizers, impact agents, foaming agents, fillers, antibacterial agents, antifungal agents, mold release agents, antistatic agents. Agents, ultraviolet absorbers, light stabilizers, heat stabilizers, flame retardants, etc.).

The insert-molded article of the present invention is useful as an inner / outer member, an optical product inner member, an optical lens, an electric product member, a packaging container, a miscellaneous product, and the like.
Interior / exterior components include automotive interior components (instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards, etc.), automotive exterior components (weather strips, bumpers, bumpers, etc.) Guards, side mud guards, body panels, spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts, etc.), automobiles Other examples include members for interior and exterior of various vehicles (trains, aircraft, ships, etc.).
Optical product internal members include optical product (camera etc.) lens barrels, projection display devices such as front projectors and rear projectors, multi-vision systems equipped with a plurality of these projection display devices, digital still cameras, video cameras, etc. Examples include all optical devices that require removal of unnecessary light, such as imaging devices, optical pickup devices, and optical fiber communication systems.
Examples of the optical lens include resin lenses such as a pickup lens, a camera lens, and a spectacle lens.
Examples of the electrical product member include a housing, a button, and a switch.
Examples of the packaging container include a bottle, a cosmetic container, and an accessory case.
The miscellaneous goods include prizes and accessories.

  In the insert molded product of the present invention described above, since the insert molding film of the present invention is provided on the surface, the original colors of the decorative layer and the colored substrate are sufficiently reproduced, and the design property is high.

<Method of manufacturing insert molded product>
The insert molding product manufacturing method of the present invention is a base material made of a resin material by placing a film for insert molding of the present invention in a mold and then injecting and solidifying a molten resin material into the mold. And a method of obtaining an insert molded product having an insert molding film in which the surface opposite to the side on which the fine concavo-convex structure is formed is in contact with the substrate.

Specifically, the following method is mentioned.
(I) If necessary, the film for insert molding is formed into a predetermined shape in advance by vacuum forming or the like, and after removing unnecessary portions, the film is placed in a mold, and a molten resin material is placed in the mold. A method of injecting, solidifying, and integrating the film for insert molding and the substrate.
(II) An insert molding film is placed in the mold, and after molding into a predetermined shape by vacuum molding in the mold, the molten resin material is injected into the same mold, solidified, and insert molding A method of integrating a film for use with a substrate (so-called in-mold method).

Hereinafter, the method (I) will be described with reference to FIG.
(I) The insert molding film 10 is attached to a flat portion in the mold 42.
(Ii) The mold 42 and the mold 52 provided with a plurality of resin gates 50 on the injection machine 48 side are closed, and the resin material 54 heated and melted from the resin gate 50 is injected into the mold.
(Iii) The mold 42 and the mold 52 are opened to obtain an insert molded product 56.

  In the manufacturing method of the insert molded article of the present invention described above, since the insert molding film of the present invention is used, the original colors of the decorative layer and the colored substrate are sufficiently reproduced, and the design property is A high insert molded product can be obtained.

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

(Pores of anodized alumina)
A part of the anodized alumina is shaved, platinum is vapor-deposited on the cross section for 1 minute, and the cross section is subjected to an acceleration voltage of 3.00 kV using a field emission scanning electron microscope (JSM-7400F, manufactured by JEOL Ltd.). Observed and measured 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 was vapor-deposited on the fracture surface of the cured resin film for 10 minutes, and the cross-section was observed in the same manner as the anodized alumina, and the interval between the convex portions and the height of the convex portions were measured. Each measurement was performed for 50 points, and the average value was obtained.

(Weighted average reflectance)
For the insert molded product, the relative reflectance of the surface of the cured resin film side was measured in the range of an incident angle of 5 ° and a wavelength of 380 to 780 nm using a spectrophotometer (manufactured by Hitachi, Ltd., U-4000). Calculated in conformity.

(Water contact angle)
Using a contact angle measuring device (manufactured by Kruss, DSA10-Mk2), 1.6 μL of water was dropped on the surface of the fine concavo-convex structure of the cured resin film, and after 10 seconds of dropping, the water contact angle was 1 second apart. 10 points were measured, and the average value was obtained. Furthermore, the same operation was performed 3 times by changing the position where water was dropped, and the average value of 4 times in total was further averaged.

(Creativity)
The appearance of the surface on the insert molding film side of the insert molded product under the light of a fluorescent lamp was visually evaluated as follows.
○: Reflection of the fluorescent lamp is slight, and the black color of the colored substrate looks jet black.
(Triangle | delta): There is reflection of a fluorescent lamp, and the black of a coloring base material is not so much as jet black.
X: Reflection of a fluorescent lamp is intense, and the black color of the colored substrate is not jet black.

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

(C) Process:
The roll was anodized in 0.3 M oxalic acid aqueous solution for 20 seconds under the conditions of a direct current of 40 V and a temperature of 16 ° C.
(D) Process:
The roll on which the oxide film was formed was immersed in 5 mass% phosphoric acid at 32 ° C. for 8 minutes to carry out pore diameter expansion treatment.

(E) Process:
The step (c) and the step (d) are repeated 5 times in total to obtain a roll-shaped mold a having anodized alumina having substantially conical pores with an average period of 100 nm and a depth of 220 nm formed on the surface. It was.
The roll-shaped mold a was immersed in a 0.1% by weight diluted solution of OPTOOL DSX (manufactured by Daikin Chemicals Sales Co., Ltd.) and air-dried overnight to subject the oxide film surface to a fluorination treatment.

[Preparation of active energy ray-curable resin composition]
Each component was mixed in the ratio shown in Table 1 and Table 2, and active energy ray-curable resin compositions A and B were prepared.

Abbreviations in the table are as follows.
DPHA: dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., Aronix M400),
M260: polyethylene glycol diacrylate n = 13-14 (Toagosei Co., Ltd., Aronix M260),
HEA: 2-hydroxyethyl acrylate,
Ir184: 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals).

Abbreviations in the table are as follows.
TAS: trimethylolethane, acrylic acid, succinic anhydride condensed ester,
C6DA: 1,6-hexanediol diacrylate,
X-22-1602: radical polymerizable silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)
Ir184: 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals).

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

[Example 1]
An insert molding film was manufactured using the manufacturing apparatus shown in FIG.
As the roll mold 22, the roll mold a was used.
The active energy ray curable resin composition A was used as the active energy ray curable resin composition.
As the film body 12, the acrylic resin film was used.
The active energy ray-curable resin composition A was cured by irradiating the coating film of the active energy ray-curable resin composition A with ultraviolet rays having an integrated light amount of 3200 mJ / cm ² from the film body 12 side.
About the obtained film for insert molding, the average space | interval between convex parts, the height of a convex part, a weighted average reflectance, and the water contact angle were measured. The results are shown in Table 3.

Using the obtained film for insert molding, in-mold molding was performed by an in-mold molding apparatus (all rounder 270M, manufactured by Aburg Co.).
As a resin material for the base material, polymethyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., Acrypet VH) colored by adding 1% by mass of carbon black was used.
The design property was evaluated about the obtained insert molded product. The results are shown in Table 3.

[Example 2]
A film for insert molding and an insert molded product were obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition B was used. About the film for insert molding, the average space | interval between convex parts, the height of a convex part, a weighted average reflectance, and the water contact angle were measured. The results are shown in Table 3. Moreover, the design property was evaluated about the insert molded product. The results are shown in Table 3.

  The film for insert molding of the present invention is useful for the production of insert molded products such as automobile interior members and optical product inner members.

It is sectional drawing which shows an example of the film for insert molding of this invention. It is a block diagram which shows an example of the manufacturing apparatus of the film for insert molding of this invention. It is sectional drawing which shows the manufacturing process of the mold which has an anodized alumina on the surface. It is sectional drawing which shows the manufacturing process of the insert molded product of this invention.

Explanation of symbols

10 Insert Molding Film 56 Insert Molded Product

Claims (4)

An insert molding film having a fine uneven structure on the surface,
The film for insert molding, wherein the fine concavo-convex structure has a plurality of convex portions, and an average interval between the convex portions is 400 nm or less.   The film for insert molding according to claim 1, wherein the fine concavo-convex structure is formed by transferring the fine concavo-convex structure on the surface of anodized alumina. A base material made of a resin material;
An insert-molded article comprising: the insert-molding film according to claim 1 or 2, wherein a surface opposite to the side on which the fine concavo-convex structure is formed is in contact with the base material.   After the film for insert molding according to claim 1 or 2 is disposed in a mold, a molten resin material is injected into the mold and solidified to form a substrate made of the resin material, and the fine unevenness A method for producing an insert-molded product, wherein an insert-molded product having an insert-molded film whose surface opposite to the side on which the structure is formed contacts the substrate is obtained.

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