JP2016020049A - Fingerprint resistant antireflection film for insert molding and resin molded article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fingerprint resistance antireflection film for insert molding excellent in antireflection property and fingerprint resistance while having a hard coat layer.SOLUTION: A hard coat layer, a high refractive index layer and a low refractive index layer are laminated in this order on a single face of a thermoplastic transparent substrate film. A refractive index of the high refractive index layer is 1.50 to 1.65, and a film thickness thereof is 130 to 180 nm. The refractive index of the low refractive index layer is 1.36 to 1.42 and the film thickness thereof is 70 to 100 nm. The low refractive index preferably contains an antifouling agent, and the hard coat layer preferably contains acrylic modification unsaturated dicarboxylic acid (anhydride) grafted polyolefin.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a film suitable for insert molding, and relates to a film excellent in antireflection and fingerprint resistance, and a resin molded product including the film on the surface.

  When designing automobile parts, mobile phones, etc., a film for surface protection and decoration is installed in the mold in advance, and the film is applied to the surface of the resin molded product at the same time as injection molding by heat fusion. Insert molding is used. As such a film, for example, Patent Document 1 discloses a hard coat film for insert molding in which a hard coat layer is laminated on a thermoplastic transparent substrate film. In this hard coat film, the base film is made of an acrylic resin containing a rubber component, and the hard coat layer is made of an ionizing radiation curable resin. Thereby, it has sufficient surface hardness and it is supposed that a crack, whitening, and a wrinkle do not arise in a hard-coat layer also in insert molding in the shape of a deep drawing.

JP 2012-81628 A

  However, in recent years, with the widespread use of touch panels, there is an increasing need for antireflection and fingerprint resistance in this type of insert molding hard coat film. However, the insert molding film of Patent Document 1 does not provide performance for these requirements.

  Accordingly, an object of the present invention is to provide a fingerprint-resistant antireflection film that is an insert-molding film and has a hard coat layer and is excellent in antireflection and fingerprint resistance.

  The present invention is a fingerprint-resistant antireflection film for insert molding in which a hard coat layer, a high refractive index layer, and a low refractive index layer are laminated in this order on one surface of a thermoplastic transparent substrate film. The refractive index of the high refractive index layer is 1.50 to 1.65, the film thickness is 130 to 180 nm, the refractive index of the low refractive index layer is 1.36 to 1.42, and the film thickness is 70 to 100 nm. It is characterized by being.

  It is also preferable that the low refractive index layer contains an antifouling agent.

  The hard coat layer is preferably formed by curing a composition containing an acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin.

  The fingerprint-resistant antireflection film for insert molding is integrated on the surface of the resin molded product by thermally fusing the thermoplastic transparent substrate film at the time of insert molding.

  In the present invention, “XX to XX” indicating a numerical range means “XX or more and XX or less” unless otherwise specified.

  According to the present invention, in the film for insert molding provided with a hard coat layer, on the hard coat layer, a high refractive index layer and a low refractive index layer are further in this order in a predetermined refractive index and relative relationship of film thickness. They are stacked so that Thereby, the visibility reflectance before the sebum dirt such as fingerprints adheres is 2.0% or less and the reflection saturation is less than 6.0, and sufficient antireflection can be achieved. At the same time, ΔE before and after the fingerprint attachment becomes 7.0 or less, and even if the fingerprint is attached, it is difficult to see (not noticeable) and the fingerprint resistance is improved.

  Moreover, antifouling property can also be provided by making the low refractive index layer contain an antifouling agent. Thereby, fingerprints are hardly attached in the first place, and even if they are attached, the fingerprints can be easily wiped off, and more excellent fingerprint resistance can be obtained.

  Further, when the hard coat layer contains an acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin, the moldability is further improved. Specifically, it is possible to follow a mold having a more complicated shape, and it is possible to accurately apply a film to the resin molded product having a more complicated shape by insert molding.

<Anti-fingerprint anti-reflective film>
The anti-fingerprint anti-reflection film of this embodiment is a film suitable for insert molding, and is provided on one side of a thermoplastic transparent base film with a hard coat layer and a high refractive index layer from the thermoplastic transparent base film side. And a low refractive index layer are laminated in this order. Below, the component of the anti-fingerprint antireflection film suitable for this insert molding will be described in order.

[Thermoplastic transparent substrate film]
As the thermoplastic transparent substrate film, a film made of a polycarbonate resin and / or a polymethyl methacrylate resin can be used. In particular, a film having a two-layer structure of a polycarbonate layer and a polymethyl methacrylate layer is preferable. In this case, it is desirable to laminate a hard coat layer on the polymethyl methacrylate layer. This is because the composition for forming a hard coat layer described later can be wet-coated on the thermoplastic transparent substrate film. In addition, when an acrylic resin (cured product of a monomer having an acrylic group) is included as a binder component of the hard coat layer, the refractive indexes of the hard coat layer and the polymethyl methacrylate layer are close to each other. If so, interference unevenness of reflected light is less likely to occur. In addition, since the materials of the methyl methacrylate layer and the hard coat layer are similar, the adhesion between the thermoplastic transparent substrate film and the hard coat layer is also improved. On the other hand, since the polycarbonate layer has a higher glass transition point (Tg) than the polymethylmethacrylate layer, ink flow hardly occurs during insert molding by decorative printing on the polycarbonate layer. The film thickness and refractive index of the thermoplastic transparent substrate film are not particularly limited as long as they are within a conventionally known general range in this type of insert molding film. Specifically, the film thickness of the thermoplastic transparent substrate film is usually 30 to 300 μm, preferably 125 to 200 μm. Moreover, the refractive index of a thermoplastic transparent base film is 1.49-1.59 normally.

[Hard coat layer]
The hard coat layer is formed by curing the composition for forming a hard coat layer. The hard coat layer has required strength and hardness, and is a layer that is laminated to improve the surface hardness of the resin molded product. The thickness of the hard coat layer after drying and curing is preferably 1 to 20 μm. A film thickness of less than 1 μm is not preferable because sufficient surface hardness cannot be obtained. A film thickness greater than 20 μm is not preferable because problems such as a decrease in flexibility occur. In addition, although the refractive index of a hard-coat layer is not specifically limited as long as the material mentioned later is used, as a refractive index of such a material, it is about 1.49-1.54.

<Composition for forming hard coat layer>
As the composition for forming a hard coat layer, a conventionally known composition can be used without limitation in this type of insert molding film, and typically, an ultraviolet curable resin (B) and A photopolymerization initiator (C).

  Examples of the ultraviolet curable resin (B) include urethane (meth) acrylate (oligomer), epoxy (meth) acrylate (oligomer), polyester (meth) acrylate (oligomer), polyether (meth) acrylate (oligomer), ( 1 type (s) or 2 or more types chosen from the group which consists of a meth) acrylate (oligomer) etc. can be used.

  The photopolymerization initiator (C) is used as a polymerization initiator when the hard coat layer forming composition is cured by ultraviolet rays (UV) to form a coating film. As a photoinitiator (C), if a polymerization is started by ultraviolet irradiation, it will not specifically limit, A well-known compound can be used. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, acetophenone polymerization initiators such as 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy 1,2 -Benzoin polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4' -Benzophenone polymerization initiators such as tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothio Xanthone, such thioxanthone type polymerization initiators such as 2,4-diethyl thioxanthone, and the like. These photopolymerization initiators (C) may be used alone or in combination of two or more.

  When the composition for forming a hard coat layer has a basic composition comprising an ultraviolet curable resin (B) and a photopolymerization initiator (C), the ultraviolet curable resin (B) and the photopolymerization initiator (C) With respect to the total of 100 parts by mass, the component (B) may be 90 to 99 parts by mass, and the component (C) may be 1 to 10 parts by mass. If the photopolymerization initiator (C) is less than this range, the polymerization is insufficient and the adhesion cannot be exhibited. On the other hand, if it exceeds this range, it will only increase unnecessarily, which is not preferable.

  In addition to the above components (B) and (C), the hard coat layer forming composition preferably also contains an acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A). Thereby, the adhesiveness of a thermoplastic transparent base film and a hard-coat layer can be improved.

  Acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is composed of a structural unit derived from polyolefin, a structural unit derived from unsaturated dicarboxylic acid (anhydride), and a structural unit derived from acrylic. It can be obtained from a polyolefin component, an unsaturated dicarboxylic acid (anhydride) component, and an acrylic component. In addition, each of these components (polyolefin component, unsaturated dicarboxylic acid (anhydride) component, acrylic component) described below may be one type or two or more types.

  Examples of the polyolefin component constituting the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) include, for example, one or more α-olefins having 4 to 12 carbon atoms and propylene as essential constituent units. Preferred is a copolymer. Here, examples of the α-olefin having 4 to 12 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and the like. 1-butene, 1-pentene, 1-decene and 4-methyl-1-pentene are preferred, and 1-butene is most preferred. The proportion of these α-olefins having 4 to 12 carbon atoms in the polyolefin component is preferably 15 to 70 mol%. However, in a copolymer having a structural unit of an α-olefin having 4 to 12 carbon atoms and an olefin other than propylene, for example, when ethylene is also a structural unit (for example, propylene / 1-butene / ethylene copolymer). In this case, the proportion of ethylene in the polyolefin component is preferably 1 mol% or less, more preferably 0.5 mol% or less, and 0.1 mol% or less. Further preferred.

  The polyolefin component constituting the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is a heat-degraded polyolefin from a polymer polyolefin, that is, a low-molecular polyolefin obtained by thermally decomposing a polymer polyolefin at a high temperature. Preferably there is. Thermally degrading polyolefins from high molecular weight polyolefins are those in which relatively many double bonds exist uniformly at the ends and in the molecule, and are easy to graft unsaturated dicarboxylic acids (anhydrides). It is possible to improve the later-described unsaturated dicarboxylic acid (anhydride) addition rate, which is considered difficult to increase, to a relatively high range described later. As a method for obtaining a thermally degraded polyolefin, for example, a polymer polyolefin having a number average molecular weight of 15,000 to 150,000 is 180 to 300 ° C. in the presence of an organic peroxide, and 300 to 450 ° C. in the absence of an organic peroxide. Then, it may be heated for 0.5 to 1 hour. A method of heating in the absence of an organic peroxide is preferred.

  Examples of the unsaturated dicarboxylic acid (anhydride) component constituting the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and cyclohexene dicarboxylic acid. Unsaturated dicarboxylic acids such as acid, cycloheptene dicarboxylic acid and aconitic acid; unsaturated dicarboxylic anhydrides such as maleic anhydride, citraconic anhydride and itaconic anhydride; And an esterified product of 5 with an alkyl alcohol.

  As an acrylic component constituting the acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A), for example, an acrylic having an active hydrogen such as a hydroxyl group-containing (meth) acrylate such as 4-hydroxybutyl (meth) acrylate Examples thereof include acrylic components containing isocyanate groups such as 2-acryloylethyl isocyanate, and (meth) acrylic acid esters such as methyl (meth) acrylate can also be used as the acrylic component. . In the present specification, “(meth) acrylate” refers to acrylate and methacrylate.

  The method for obtaining the acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) from the polyolefin component, the unsaturated dicarboxylic acid (anhydride) component, and the acrylic component is not particularly limited. It can be obtained by grafting an unsaturated dicarboxylic acid (anhydride) component and then reacting the acrylic component. In addition, what is necessary is just to set suitably about the reaction conditions etc. in the said method according to the method of normal organic synthesis. For example, when the (meth) acrylic acid ester is used as the acrylic component when the acrylic component is reacted, an organic peroxide having a hydrogen abstraction ability such as dicumyl peroxide may be used.

  In the case where an acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is also added to the hard coat layer forming composition in addition to the ultraviolet curable resin (B) and the photopolymerization initiator (C), acrylic The component (A) is 9 to 45 parts by mass with respect to a total of 100 parts by mass of the modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A), the ultraviolet curable resin (B) and the photopolymerization initiator (C). The component (B) may be 45 to 90 parts by mass, and the component (C) may be 1 to 10 parts by mass. When the amount of component (A) is less than this range, the effect due to this cannot be obtained accurately. On the other hand, when the amount is larger than this range, the relative proportion of the component (B) serving as the base material becomes low, so that the surface hardness is lowered.

  In the hard coat layer forming composition, conventionally known additives such as a surface preparation agent, a leveling agent, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, an antistatic agent, and an antifoaming agent, as necessary, You may contain in the range which does not impair the effect of this invention.

  The diluent solvent used for the preparation of the hard coat layer forming composition is not particularly limited as long as it is used for adjusting the viscosity of the hard coat layer forming composition and is non-polymerizable. With such a diluting solvent, the composition for forming a hard coat layer can be easily applied on the thermoplastic transparent substrate film.

  Examples of the diluent solvent include toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, Examples include diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, heptane, octane, decane, dodecane, propylene glycol monomethyl ether, and 3-methoxybutanol.

  After the composition for forming a hard coat layer is applied on a thermoplastic transparent substrate film, the hard coat layer can be laminated on the thermoplastic transparent substrate film by curing by irradiating with ultraviolet rays. As a method of applying the hard coat layer forming composition on the thermoplastic transparent substrate film, a roll coating method, a spin coating method, a dip coating method, a brush coating method, a spray coating method, a bar coating method, a knife coating method, Any known method such as a die coating method, a gravure coating method, a curtain flow coating method, a reverse coating method, a kiss coating method, or a comma coating method may be employed. At the time of application, in order to improve adhesion, it is also preferable to pre-treat the surface of the thermoplastic transparent substrate film in advance such as corona discharge treatment.

As the ultraviolet ray source used for the ultraviolet ray irradiation, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, an electron beam accelerator, a radioactive element or the like is used. It is preferable that the irradiation amount of an ultraviolet-ray is 50-5000 mJ / cm < ² > as an integrated light quantity in ultraviolet wavelength 365nm. When the irradiation amount is less than 50 mJ / cm ² , curing of the hard coat layer forming composition becomes insufficient, which is not preferable. On the other hand, when it exceeds 5000 mJ / cm ² , the ultraviolet curable resin (B) tends to be colored, which is not preferable.

(High refractive index layer)
Next, the high refractive index layer will be described. The high refractive index layer is a layer having a refractive index higher than that of the low refractive index layer described later, and has an antireflection effect and fingerprint resistance (fingerprint It is a layer that exhibits an effect of making it difficult to see, and constitutes an antireflection layer and an anti-fingerprint layer together with a low refractive index layer. The refractive index of the high refractive index layer is 1.50 to 1.65. When the refractive index of the high refractive index layer is less than 1.50, the refractive index difference with the low refractive index layer is too small, and reflection at the interface between the high refractive index layer and the low refractive index layer becomes weak, thus preventing reflection. Performance and fingerprint resistance may not be fully exhibited. On the other hand, when the refractive index of the high refractive index layer exceeds 1.65, reflection at the interface between the high refractive index layer and the low refractive index layer becomes strong and coloring of reflected light becomes strong. The film thickness of the high refractive index layer is 130 to 180 nm. When the film thickness of the high refractive index layer is less than 130 or exceeds 180 nm, the interference balance with the low refractive index layer is lost, and the reflectance, reflection saturation C, and reflection color difference ΔE when sebum dirt adheres are reduced. As a result, an increase in anti-reflection property and fingerprint resistance cannot be obtained.

<Composition for forming high refractive index layer>
The high refractive index layer is formed by applying a coating liquid composed of a composition for forming a high refractive index layer on the hard coat layer and then curing it by ultraviolet irradiation. The coating method, curing conditions, and dilution solvent for viscosity adjustment may be the same as those for the hard coat layer. As a material constituting the composition for forming a high refractive index layer, metal oxide fine particles and an ultraviolet curable resin can be arbitrarily used within the range of the refractive index of the high refractive index layer.

  The metal oxide fine particles are blended for positively increasing the refractive index. Examples of the metal oxide fine particles include fine particles of zinc oxide, titanium oxide, cerium oxide, aluminum oxide, silane oxide, antimony oxide, zirconium oxide, tin oxide, silicon oxide, ITO, and the like. In particular, tin oxide, antimony oxide, and ITO are preferable from the viewpoint of conductivity and antistatic ability, and titanium oxide, cerium oxide, zinc oxide, and zirconium oxide are preferable from the viewpoint of high refractive index. The average particle diameter of the metal oxide fine particles preferably does not greatly exceed the thickness of the high refractive index layer, and is particularly preferably 0.15 μm or less. When the average particle diameter of the metal oxide fine particles greatly exceeds the thickness of the high refractive index layer, the optical performance of the high refractive index layer tends to deteriorate, such as light scattering. As the ultraviolet curable resin, the same type of resin as that used in the hard coat layer can be used.

  The refractive index of the high refractive index layer can be set by appropriately adjusting the blending ratio of the ultraviolet curable resin as the base resin and the metal oxide fine particles. Content of metal oxide microparticles | fine-particles is adjusted to 90 mass parts or less with respect to a total of 100 mass parts with ultraviolet curable resin. When the content of the metal oxide fine particles exceeds 90 parts by mass, the relative amount of the ultraviolet curable resin in the coating film is decreased, and the coating film becomes brittle.

  Further, the high refractive index layer forming composition contains a photopolymerization initiator in order to cure the high refractive index layer forming composition with ultraviolet rays to form a coating film. As the photopolymerization initiator, the same photopolymerization initiator as that used in the hard coat layer can be used. The photopolymerization initiator is contained in an amount of 1.0 to 10.0% by mass in the composition for forming a high refractive index layer. When the content of the photopolymerization initiator is less than 1.0% by mass, the high refractive index layer is not sufficiently cured. On the other hand, when the content exceeds 10.0% by mass, the photopolymerization initiator is unnecessarily increased, which is not preferable. The conditions for ultraviolet irradiation may be the same as those for the hard coat layer.

  In the composition for forming a high refractive index layer, conventionally known additives such as a surface conditioner, a leveling agent, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, an antistatic agent, and an antifoaming agent are added as necessary. May be contained within a range not impairing the effects of the present invention.

(Low refractive index layer)
Next, the low refractive index layer will be described. The low refractive index layer is a layer having a lower refractive index than the high refractive index layer, and has an antireflection effect and fingerprint resistance (fingerprints are difficult to see due to a significant refractive index and relative film thickness relationship with the high refractive index layer. The anti-reflection layer and the anti-fingerprint layer together with the high refractive index layer. The refractive index of the low refractive index layer is in the range of 1.36 to 1.42. If the refractive index is less than 1.36, it is difficult to form a sufficiently hard layer. If the refractive index exceeds 1.42, the difference in refractive index from the high refractive index layer is too small. Reflection at the interface between the high refractive index layer and the low refractive index layer becomes weak, and the antireflection performance and fingerprint resistance may not be sufficiently exhibited.

  The film thickness of the low refractive index layer is 70 to 100 nm. When the film thickness of the low refractive index layer is less than 70 nm or exceeds 100 nm, the interference balance with the high refractive index layer is lost, and the reflectance, reflection chroma C, and reflection color difference ΔE when sebum dirt adheres increase. As a result, sufficient antireflection and fingerprint resistance cannot be obtained.

<Composition for forming low refractive index layer>
The low refractive index layer is formed by applying a coating liquid composed of a composition for forming a low refractive index layer on the high refractive index layer and then curing it by ultraviolet irradiation. The application method, curing conditions, and dilution solvent for viscosity adjustment may be the same as those for the hard coat layer and the high refractive index layer. The composition for forming a low refractive index layer contains an ultraviolet curable resin, hollow silica fine particles, and a photopolymerization initiator.

  The ultraviolet curable resin for forming the low refractive index layer is not particularly limited as long as it is a polyfunctional (meth) acrylate. As a resin for forming a low refractive index layer in this type of film, in general, a reactive silicon compound such as γ-acryloxypropyltrimethoxysilane in addition to polyfunctional (meth) acrylate is used as a starting material. However, from the viewpoint of achieving both productivity and hardness, a composition containing an ultraviolet curable polyfunctional (meth) acrylate as a main component is preferable.

  The polyfunctional (meth) acrylate is not particularly limited, and examples thereof include dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, (Meth) acryl derivatives of polyfunctional alcohols such as 1,6-hexanediol di (meth) acrylate and 1,6-bis (3- (meth) acryloyloxy-2-hydroxypropyloxy) hexane, polyethylene glycol di ( And (meth) acrylate and polyurethane (meth) acrylate.

  The polyfunctional (meth) acrylate may be a fluorine-containing monomer. A fluorine-containing monomer having a structure in which a fluorine atom is introduced into a molecule as a methylene fluoride group or a fluorinated methine group is a monomer in which almost all of the fluorine atoms are introduced into the molecule as a methylene fluoride group or a fluorinated methine group As long as it is a polyfunctional monomer, all known monomers can be used. That is, it may be any of two or more (polyfunctional) monomers, or a mixture thereof. These fluorine-containing compounds can increase the strength and hardness of the cured film, and can improve the scratch resistance and wear resistance of the surface of the cured film. Among the fluorine-containing compounds, fluorine-containing polyfunctional (meth) acrylates are preferable because a crosslinked structure can be formed and the strength and hardness of the cured film are high.

The hollow silica fine particles are fine particles in which silica (silicon dioxide, SiO ₂ ) is formed in a substantially spherical shape and has a hollow portion in the outer shell. The average particle diameter is 10 to 100 nm, the thickness of the outer shell is about 1 to 60 nm, the porosity of the hollow portion is 40 to 45%, and the refractive index is a low refractive index of 1.20 to 1.29. Since the hollow portion contains air having a refractive index of 1.0, the cured film formed by curing the polyfunctional (meth) acrylate can be reduced in refractive index and reflectance, and silica. The scratch resistance and abrasion resistance of the cured film can be improved by inorganic fine particles called fine particles. When the void ratio of the hollow portion is less than 40%, the amount of air in the hollow portion is reduced, and it becomes impossible to reduce the refractive index and reflectivity of the cured film. On the other hand, when the void ratio of the hollow portion exceeds 45%, it is necessary to make the outer shell thin in order to increase the void ratio, which makes it difficult to manufacture.

  The hollow silica fine particles are preferably modified with a silane coupling agent as necessary. Thereby, the outstanding effect which is not in the conventional general (non-modified) silica fine particles or hollow silica fine particles, that is, the effect of excellent compatibility with the polyfunctional (meth) acrylate can be exhibited. Therefore, when the modified hollow silica fine particles are mixed with polyfunctional (meth) acrylate, aggregation of the modified hollow silica fine particles can be suppressed, and a cured film having no transparency and excellent transparency can be obtained. Furthermore, in the cured film, the polymerizable double bond of the silane coupling agent and the polymerizable double bond of the polyfunctional (meth) acrylate are copolymerized (chemically bonded) to form a strong cured film. Scratch resistance and wear resistance can be dramatically improved.

In this case, in order to enhance the effect of modification, the hollow silica fine particles are more preferably modified with a silane coupling agent having a polymerizable double bond represented by the following chemical formula (1).
Z-R1-Si (OR2) ₃ (1)
[In formula, Z is a (meth) acryloyloxy group, R1 is a C1-C4 alkylene group, R2 is a hydrogen atom, a methyl group, or an ethyl group. ]

The modified hollow silica fine particles will be further described. The modified hollow silica fine particles are produced by surface-treating the surface of the hollow silica fine particles having an average particle diameter of 5 to 100 nm and a specific surface area of 50 to 1000 m ² / g with a silane coupling agent. The Specifically, an organosilyl group (monoorganosilyl group, diorganosilyl group, or triorganosilyl group) is bonded to the surface of the hollow silica fine particle by a hydrolysis reaction between the silanol group on the surface of the hollow silica fine particle and the silane coupling agent. In addition, the surface has an organic group directly bonded to a large number of silicon atoms.

  The refractive index of the low refractive index layer can be set by appropriately adjusting the blending ratio of the ultraviolet curable resin as the base resin and the hollow silica fine particles. Specifically, the content of the hollow silica fine particles is preferably 30 to 80 parts by mass with respect to a total of 100 parts by mass with the ultraviolet curable resin. When this content is less than 30 parts by mass, the content of the hollow silica fine particles is small, and the resulting cured film cannot be reduced in refractive index and reflectance. On the other hand, when the amount exceeds 80 parts by mass, excess hollow silica fine particles cannot react with the ultraviolet curable resin, and the hollow silica fine particles remain, and on the contrary, the cured film surface lacks scratch resistance and wear resistance. When the modified hollow silica fine particles are used, the (meth) acryloyloxy group contained in the silane coupling agent of the modified hollow silica fine particles and the polymerizable double bond of polyfunctional (meth) acrylate are copolymerized and bonded. As a result, the function of the modified hollow silica fine particles and the function of the polyfunctional (meth) acrylate are expressed synergistically and continuously.

  As the photopolymerization initiator, the same type as the polymerization initiator used in the hard coat layer and the high refractive index layer can be used. The content of the photopolymerization initiator is preferably 0.1 to 20% by mass in the composition for forming a low refractive index layer. When the content of the photopolymerization initiator is less than 0.1% by mass, the polymerization curing of the coating solution for the low refractive index layer becomes insufficient, and when it exceeds 20% by mass, the refractive index of the cured film after polymerization curing. Is not preferable because of an increase. The conditions for ultraviolet irradiation may be the same as those for the hard coat layer and the high refractive index layer.

(Anti-fouling agent)
Note that the low refractive index layer can be imparted with antifouling properties (an effect of making fingerprints difficult to attach and easy to wipe) to improve fingerprint resistance. As the antifouling agent, a known polysiloxane or fluorine antifouling agent is preferably added as appropriate. Preferred examples of the polysiloxane compound include, for example, polyether-modified polydimethylsiloxane having an acrylic group, polyether-modified dimethylsiloxane, polyester-modified dimethylsiloxane having an acrylic group, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, And aralkyl-modified polymethylalkylsiloxane.

  On the other hand, the fluorine-based compound used as an antifouling agent preferably has a substituent that contributes to bond formation or compatibility with the low refractive index layer. The substituents may be the same or different, and a plurality of substituents may be present. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited.

  In the composition for forming a low refractive index layer, conventionally known additives such as a surface conditioner, a leveling agent, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, an antistatic agent, and an antifoaming agent are optionally added. May be contained within a range not impairing the effects of the present invention.

《Resin molding using anti-fingerprint anti-reflective film》
The resin molded product of this embodiment is obtained by molding a resin by an insert molding fusion method and simultaneously integrating a fingerprint-resistant antireflection film on the surface of the resin molded product. For example, by holding a fingerprint-resistant antireflection film in a cavity in an injection mold and injecting molten resin into the mold, a resin molded product with a fingerprint-resistant antireflection film integrated on the surface is obtained. Can be obtained.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the scope of these examples. The refractive index of each layer obtained by curing the composition for forming a hard coat layer, the composition for forming a high refractive index layer, and the composition for forming a low refractive index layer prepared in each production example was measured as follows. did.

[Refractive index of each layer]
(1) A composition for forming each layer (coating solution) on an acrylic resin plate ("Delagrass A", manufactured by Asahi Kasei Chemicals Co., Ltd.) having a refractive index of 1.49 by a dip coater (manufactured by Sugiyama Motoiri Scientific Co., Ltd.) ), And the thickness of the layer was adjusted so that the optical film thickness was about 550 nm.
(2) After drying the solvent, each coating solution was cured by irradiating 400 mJ of ultraviolet rays using a 120 W high-pressure mercury lamp in a nitrogen atmosphere by an ultraviolet irradiation device (manufactured by Iwasaki Electric Co., Ltd.) as necessary.
(3) The back surface of the acrylic resin plate is roughened with sandpaper, and the one painted with black paint is measured with a spectrophotometer ("U-Best V560", manufactured by JASCO Corporation) at 5 ° at a light wavelength of 400 to 650 nm. The −5 ° regular reflectance was measured, and the minimum or maximum value of the reflectance was read.
(4) The refractive index was calculated from the extreme value of the reflectance using the following formula.

[Composition for forming hard coat layer]
The following raw materials were used as the hard coat layer forming composition, and the respective raw materials were mixed in the composition described in Table 1 below to prepare a hard coat layer forming composition HC1. Each raw material of the composition for forming a hard coat layer is as follows.
Acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (a): hydroxyl group-containing methacrylate-modified maleic anhydride-grafted polyolefin synthesized in Production Example 1 UV curable resin (b):
(B-1); “EBECRYL8402” manufactured by Daicel-Cytec Corporation
(B-2); “KAYARAD DPCA-20” manufactured by Nippon Kayaku Co., Ltd.
(B-3); “Light acrylate 1.9ND-A” manufactured by Kyoeisha Chemical Co., Ltd.
Photopolymerization initiator (c): “IRGACURE184 (I-184)” manufactured by Ciba Specialty Chemicals Co., Ltd.

[Production Example 1: Synthesis of acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin]
Polymer polyolefin (copolymer of propylene and 1-butene: “Tafmer XR110T” manufactured by Mitsui Chemicals, Inc.) is placed in a reaction vessel equipped with a stirrer and a thermometer, heated to 360 ° C. and melted, under a nitrogen stream Was heated for 80 minutes to obtain a low molecular polyolefin by thermal degradation.

  Next, 160 parts of the low molecular polyolefin was put into a reaction vessel equipped with a stirrer, a thermometer and a cooling tube, heated to 180 ° C. under a nitrogen stream and melted, and then 25 parts of maleic anhydride and 1- 20 parts of dodecene was added and mixed uniformly. Next, a solution prepared by dissolving 1 part of dicumyl peroxide in 20 parts of xylene prepared in advance was added dropwise over 2 hours while maintaining 180 ° C. After the addition, the solution was further stirred at 180 ° C for 2 hours to graft maleic anhydride. The reaction was carried out. Thereafter, xylene and 1-dodecene were distilled off under reduced pressure to obtain maleic anhydride grafted polyolefin.

Next, 450 parts of the maleic anhydride-grafted polyolefin was put into a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, heated to 105 ° C. under a nitrogen stream, and toluene 300 while maintaining the temperature. The portion was gradually added dropwise with stirring. Then, the hydroxyl group-containing methacrylate (manufactured by Daicel Chemical Industries' PLACCEL _{FM4: CH 2 = C (CH} 3) COO (CH 2) 2 O [CO (CH 2) 5 O] n H ") were added 135 parts of stirring The reaction was carried out at the same temperature for 3 hours, followed by cooling to obtain a hydroxyl group-containing methacrylate-modified maleic anhydride grafted polyolefin solution. The solid content concentration of the obtained solution was 66.1%.

(Preparation of composition H-1 for forming a high refractive index layer)
Zinc antimonate fine particle dispersion (manufactured by Nissan Chemical Industries, Ltd., Celnax CX-603M-F2) in terms of solid content is 70 parts by mass, urethane acrylate (molecular weight 1400, viscosity at 60 ° C. is 2500 to 4500 Pa · s, Japan Synthetic Chemical Industry Co., Ltd., purple light UV7600B) 25 parts by mass, photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd., Irgacure 184) 5 parts by mass, and isopropyl alcohol 500 parts by mass are mixed together, and high refraction. A composition for forming a rate layer (a zinc-antimonate-containing fine particle curable coating solution) was obtained. The refractive index of H-1 was 1.58.

(Preparation of composition H-2 for forming a high refractive index layer)
37 parts by mass of fine titanium oxide particles, 58 parts by mass of urethane acrylate (molecular weight 1400, viscosity at 60 ° C. is 2500 to 4500 Pa · s, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Purple UV7600B), photopolymerization initiator (Ciba Specialty Chemicals) 5 parts by mass of Irgacure 184 manufactured by Co., Ltd. and 500 parts by mass of isopropyl alcohol were mixed to obtain a composition for forming a high refractive index layer (containing zinc antimonate fine particle curable coating solution). The refractive index of H-2 was 1.65.

(Preparation of high refractive index layer-forming composition H-3)
95 parts by mass of urethane acrylate (molecular weight: 1400, viscosity at 60 ° C .: 2500-4500 Pa · s, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Purple UV7600B), photopolymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., Irgacure 184) 5 parts by mass and 500 parts by mass of isopropyl alcohol were mixed to obtain a composition for forming a high refractive index layer (zinc antimonate-containing fine particle curable coating solution). The refractive index of H-3 was 1.50.

(Preparation of composition H-4 for forming a high refractive index layer)
40 parts by mass of fine titanium oxide particles, 55 parts by mass of urethane acrylate (molecular weight 1400, viscosity at 2500C of 2500 to 4500 Pa · s, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., purple light UV7600B), photopolymerization initiator (Ciba Specialty Chemicals) 5 parts by mass of Irgacure 184 manufactured by Co., Ltd. and 500 parts by mass of isopropyl alcohol were mixed to obtain a composition for forming a high refractive index layer (containing zinc antimonate fine particle curable coating solution). The refractive index of H-4 was 1.66.

(Preparation of High Refractive Index Layer Composition H-5)
10 parts by mass of hollow silica fine particles having a particle size of 60 nm, 85 parts by mass of urethane acrylate (molecular weight 1400, viscosity at 60 ° C. is 2500 to 4500 Pa · s, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., purple light UV7600B), photopolymerization initiator ( 5 parts by mass of Ciba Specialty Chemicals Co., Ltd., Irgacure 184) and 500 parts by mass of isopropyl alcohol were mixed to obtain a composition for forming a high refractive index layer (zinc antimonate-containing fine particle curable coating solution). . The refractive index of H-5 was 1.49.

(Preparation of composition L-1 for low refractive index layer)
40 parts by mass of hollow silica fine particles having a particle size of 60 nm, 60 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “DPHA”), photopolymerization initiator (manufactured by Ciba Specialty Chemicals) , Irgacure 907) 5 parts by mass, silicon additive (BIC Chemie Japan Co., Ltd., BYKUV-3570) 8 parts by mass, silicon additive (Shin-Etsu Chemical Co., Ltd., TIC2457) 5 parts by mass, alumina additive ( Big Chemie Japan Co., Ltd. product, NANOBYKUV-3601) 0.5 parts by mass and isopropyl alcohol 2000 parts by mass were mixed to obtain a composition for low refractive index layer (silica-containing curable coating solution). The refractive index of L-1 was 1.39.

(Preparation of composition L-2 for low refractive index layer)
30 parts by mass of hollow silica fine particles having a particle size of 60 nm, 70 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “DPHA”), photopolymerization initiator (manufactured by Ciba Specialty Chemicals) , Irgacure 907) 5 parts by mass, silicon additive (BIC Chemie Japan Co., Ltd., BYKUV-3570) 8 parts by mass, silicon additive (Shin-Etsu Chemical Co., Ltd., TIC2457) 5 parts by mass, alumina additive ( Big Chemie Japan Co., Ltd. product, NANOBYKUV-3601) 0.5 parts by mass and isopropyl alcohol 2000 parts by mass were mixed to obtain a composition for low refractive index layer (silica-containing curable coating solution). The refractive index of L-2 was 1.42.

(Preparation of composition L-3 for low refractive index layer)
60 parts by mass of hollow silica fine particles having a particle size of 60 nm, 40 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “DPHA”), photopolymerization initiator (manufactured by Ciba Specialty Chemicals) , Irgacure 907) 5 parts by mass, silicon additive (BIC Chemie Japan Co., Ltd., BYKUV-3570) 8 parts by mass, silicon additive (Shin-Etsu Chemical Co., Ltd., TIC2457) 5 parts by mass, alumina additive ( Big Chemie Japan Co., Ltd. product, NANOBYKUV-3601) 0.5 parts by mass and isopropyl alcohol 2000 parts by mass were mixed to obtain a composition for low refractive index layer (silica-containing curable coating solution). The refractive index of L-3 was 1.36.

(Preparation of composition L-4 for low refractive index layer)
65 parts by mass of hollow silica fine particles having a particle size of 60 nm, 35 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “DPHA”), photopolymerization initiator (manufactured by Ciba Specialty Chemicals) , Irgacure 907) 5 parts by mass, silicon additive (BIC Chemie Japan Co., Ltd., BYKUV-3570) 8 parts by mass, silicon additive (Shin-Etsu Chemical Co., Ltd., TIC2457) 5 parts by mass, alumina additive ( Big Chemie Japan Co., Ltd. product, NANOBYKUV-3601) 0.5 parts by mass and isopropyl alcohol 2000 parts by mass were mixed to obtain a composition for low refractive index layer (silica-containing curable coating solution). The refractive index of L-4 was 1.43.

(Preparation of composition L-5 for low refractive index layer)
25 parts by mass of hollow silica fine particles having a particle size of 60 nm, 75 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “DPHA”), photopolymerization initiator (manufactured by Ciba Specialty Chemicals) , Irgacure 907) 5 parts by mass, silicon additive (BIC Chemie Japan Co., Ltd., BYKUV-3570) 8 parts by mass, silicon additive (Shin-Etsu Chemical Co., Ltd., TIC2457) 5 parts by mass, alumina additive ( 0.5 parts by mass (NANOBYKUV-3601) manufactured by Big Chemie Japan Co., Ltd. and 2000 parts by mass of isopropyl alcohol were mixed to obtain a composition for a low refractive index layer (silica-containing curable coating solution). The refractive index of L-5 was 1.35.

(Preparation of composition L-6 for low refractive index layer)
55 parts by mass of hollow silica fine particles with a particle size of 60 nm, 45 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “DPHA”), photopolymerization initiator (manufactured by Ciba Specialty Chemicals) , Irgacure 907) 5 parts by mass, silicon additive (by BYKUV Japan, BYKUV-3570) 8 parts by mass, fluorine-containing acrylic compound (Shin-Etsu Chemical Co., Ltd., KY1203) 10 parts by mass, alumina additive (BIC Chemie Japan Co., Ltd. product, NANOBYKUV-3601) 0.5 mass part and isopropyl alcohol 2000 mass part were mixed, and the composition (silica-containing curable coating liquid) for low refractive index layers was obtained. The refractive index of L-6 was 1.39.

<Example 1-1>
Film (PC / PMMA) having a two-layer structure of a polycarbonate layer having a thickness of 188 μm and a polymethyl methacrylate layer: on the PMMA layer of “C001” manufactured by Sumitomo Chemical Co., Ltd. (HC-1 ) Was applied with a roll coater such that the dry film thickness was 7 μm, and dried at 80 ° C. for 2 minutes. Then, ultraviolet rays were irradiated with a 120 W high-pressure mercury lamp (manufactured by Nippon Batteries Co., Ltd.) under a nitrogen atmosphere (integrated light amount 300 mJ / cm ² ), and the hard coat layer forming composition was cured to form a hard coat layer.

Next, the high refractive index layer-forming composition H-1 was applied on the hard coat layer so that the thickness upon drying was 150 nm, and then an ultraviolet irradiation device (made by Eye Graphics, A high refractive index layer was formed by irradiating 300 mJ / cm ² of ultraviolet rays using a 120 W high pressure mercury lamp) and curing the composition for forming a high refractive index layer.

Finally, the low refractive index layer composition L-1 was applied onto the high refractive index layer so that the thickness upon drying was 90 nm, and then an ultraviolet irradiation device (made by Eye Graphics Co., Ltd.) in a nitrogen atmosphere. , 120 W high pressure mercury lamp) was used to irradiate 300 mJ / cm ² of ultraviolet rays to cure the low refractive index layer composition to form a low refractive index layer, thereby producing a fingerprint-resistant antireflection film for insert molding.

  Subsequently, the obtained anti-fingerprint antireflection film was held in the cavity in the injection mold so that the polycarbonate layer side of the thermoplastic transparent substrate film was in contact with the molten resin, and was melted at a temperature of about 360 ° C. A polycarbonate resin (for molded product main body) was injected into the mold at a pressure of 29400 kPa and allowed to cool to obtain a resin molded product. That is, a resin-molded article having a fingerprint-resistant antireflection film on its surface was produced by fusing the anti-fingerprint anti-reflection film by an insert molding fusing method that fuses simultaneously with molding.

<Example 1-2>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the film thickness of the low refractive index layer was changed to 70 nm.

<Example 1-3>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the thickness of the low refractive index layer was 80 nm.

<Example 1-4>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the film thickness of the low refractive index layer was 100 nm.

<Example 1-5>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-2 except that the thickness of the high refractive index layer was 130 nm.

<Example 1-6>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-4, except that the thickness of the high refractive index layer was 180 nm.

<Example 1-7>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the composition for low refractive index layer L-2 was used.

<Example 1-8>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the composition for low refractive index layer L-3 was used.

<Example 1-9>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the composition for high refractive index layer H-2 was used.

<Example 1-10>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the composition for high refractive index layer H-3 was used.

<Example 1-11>
Except for using a polycarbonate film (PC): “C008” manufactured by Sumitomo Chemical Co., Ltd. as the thermoplastic transparent substrate film, the anti-fingerprint antireflection film for insert molding and the resin molding are the same as in Example 1-1. An article was made.

<Example 1-12>
Polymethylmethacrylate film (PMMA) for thermoplastic transparent substrate film: Fingerprint-resistant antireflection film for insert molding and resin in the same manner as in Example 1-1 except that “S014G” manufactured by Sumitomo Chemical Co., Ltd. is used. A molded product was produced.

<Example 2-1>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the composition for low refractive index layer L-6 was used.

<Example 3-1>
A fingerprint-resistant antireflective film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the hard coat layer forming composition HC-2 was used.

<Example 3-2>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-2 except that the hard coat layer forming composition HC-2 was used.

<Example 3-3>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-3 except that the hard coat layer forming composition HC-2 was used.

<Example 3-4>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-4 except that the hard coat layer forming composition HC-2 was used.

<Example 3-5>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-5 except that the hard coat layer forming composition HC-2 was used.

<Example 3-6>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-6 except that the hard coat layer forming composition HC-2 was used.

<Example 3-7>
A fingerprint-resistant antireflective film for insert molding and a resin molded product were produced in the same manner as in Example 1-7, except that the hard coat layer forming composition HC-2 was used.

<Example 3-8>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-8, except that the composition for forming a hard coat layer HC-2 was used.

<Example 3-9>
A fingerprint-resistant antireflective film for insert molding and a resin molded product were produced in the same manner as in Example 1-9, except that the hard coat layer forming composition HC-2 was used.

<Example 3-10>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-10 except that the hard coat layer forming composition HC-2 was used.

<Example 3-11>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-11 except that the composition HC-2 for forming a hard coat layer was used.

<Example 3-12>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-12 except that the hard coat layer forming composition HC-2 was used.

<Example 3-13>
A fingerprint-resistant antireflective film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the hard coat layer forming composition HC-3 was used.

<Example 3-14>
A fingerprint-resistant antireflective film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the hard coat layer forming composition HC-4 was used.

<Example 2-2>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 2-1, except that the hard coat layer forming composition HC-2 was used.

<Comparative Example 1-1>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the film thickness of the low refractive index layer was changed to 60 nm.

<Comparative Example 1-2>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the thickness of the low refractive index layer was 110 nm.

<Comparative Example 1-3>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the film thickness of the high refractive index layer was 120 nm.

<Comparative Example 1-4>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the film thickness of the high refractive index layer was 190 nm.

<Comparative Example 1-5>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the composition for low refractive index layer L-4 was used.

<Comparative Example 1-6>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the composition for low refractive index layer L-5 was used.

<Comparative Example 1-7>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that the composition for high refractive index layer H-4 was used.

<Comparative Example 1-8>
The same method as in Example 1-1 except that the high refractive index layer composition H-5 was used. A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced.

<Comparative Example 1-9>
A fingerprint-resistant antireflection film for insert molding and a resin molded product were produced in the same manner as in Example 1-1 except that PET was used for the transparent substrate film.

<Comparative Example 1-10>
A fingerprint-resistant antireflective film for insert molding and a resin molded product were produced in the same manner as in Comparative Example 1-1 except that the hard coat layer forming composition HC-2 was used.

<Comparative Example 1-11>
A fingerprint-resistant antireflective film for insert molding and a resin molded product were produced in the same manner as in Comparative Example 1-4 except that the hard coat layer-forming composition HC-2 was used.

  Various physical properties of the produced anti-fingerprint antireflection film for insert molding were evaluated by the following methods. The result is shown to Tables 2-4 with the structure of each Example and a comparative example. In Tables 2 to 4, “L layer” is the low refractive index layer, “L composition” is the type of the low refractive index layer forming composition, “H layer” is the high refractive index layer, “H composition” "Product" means the type of the composition for forming a high refractive index layer, "HC layer" means the hard coat layer, and "HC composition" means the kind of composition for forming the hard coat layer.

[Visibility reflectance]
In order to remove the back surface reflection of the measurement surface, a back surface roughened with sandpaper and painted with a black paint was measured with a spectrophotometer (trade name: FE3000, manufactured by Otsuka Electronics Co., Ltd.), with a light wavelength of 380 nm to 780 nm. A -5 ° specular reflection spectrum was measured. Using the obtained spectral reflectance of 380 nm to 780 nm and the relative spectral distribution of the CIE standard illuminant D65, the tristimulus value Y of the object color due to reflection in the XYZ color system assumed in JIS Z8701 is obtained as the luminous reflectance. (%).

[Reflection saturation C]
The color space CIE1976L * a * b * color system defined in JISZ8729 is calculated using the spectral reflectance of light having a wavelength of 380 to 780 nm measured with the luminous reflectance and the relative spectral distribution of CIE standard illuminant D65. Then, Cab * = {(a *) 2+ (b *) 2} 1/2 was calculated from the obtained a * and b * values.

[Reflection color difference ΔE]
The color space CIE1976L * a * b * color system defined in JISZ8729 is calculated using the spectral reflectance of light having a wavelength of 380 to 780 nm measured with the luminous reflectance and the relative spectral distribution of CIE standard illuminant D65. ΔE * a * b * = {(ΔL *) 2+ (Δa *) 2+ (Δb *) 2} 1/2 defined in JIS Z8730 was calculated.

[Antireflection]
The case where the visibility reflectance was 2.0% or less was marked with ◯, and the case where the reflectance was higher than 2.0% was marked with ×.

[Fingerprint appearance]
Fingerprints were attached to the anti-fingerprint anti-reflective film for insert molding, and changes in appearance before and after the components were attached were evaluated. Use a glass plate (FL2.0 manufactured by Nippon Sheet Glass Co., Ltd.) as a comparison object, where the fingerprint is less visible than when the fingerprint is attached to the glass plate. Was marked with x.

[Fingerprint wiping properties]
A fingerprint similar to the fingerprint appearance test was adhered to the test piece, and the fingerprint was wiped off by rubbing 30 times with 500 gf / cm ² load using a flannel cloth (white flannel / gold ingot grade). After that, the case where the fingerprint was not seen was marked with ◯, and the case where the fingerprint was seen was marked with X.

[Moldability]
About each obtained resin molded product, the cross-cutting tape test was done based on JISD0202-1998. Judgment is, among the 100 squares, the case where no peeling occurred (0 square), ◎, the case where peeling hardly occurred (1-5 squares), and the case where peeling occurred (6 squares or more) as x. did.

  In Examples 1-1 to 1-12, a sufficient antireflection function was obtained, the fingerprint was difficult to see, the fingerprint wiping property was good, and the moldability was also good. Moreover, in Examples 3-1 to 3-14 in which the hard coat layer contains an acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin, the adhesiveness was improved and the moldability was excellent. Furthermore, in Examples 2-1 to 2-2, due to the effect of the antifouling agent, fingerprints are harder to see than the anti-reflective films for insert molding of Examples 1 and 3 series, and the fingerprints can be wiped off. It was excellent.

On the other hand, in Comparative Examples 1-1, 1-5, and 1-10, the fingerprint was difficult to see and the fingerprint wiping property was good, but the reflectance was high. In Comparative Examples 1-2, 1-3, and 1-7, the saturation was high, and the fingerprint was colored and became conspicuous. In Comparative Examples 1-4, 1-6, 1-8, and 1-11, ΔE was high, and the fingerprint was visible even after the fingerprint wiping test. In Comparative Example 1-9, the moldability was insufficient because PET was used for the transparent substrate.

Claims (4)

On one side of the thermoplastic transparent substrate film, a hard coat layer, a high refractive index layer, and a low refractive index layer are laminated in this order,
The high refractive index layer has a refractive index of 1.50 to 1.65, a film thickness of 130 to 180 nm,
A fingerprint-resistant antireflection film for insert molding, wherein the low refractive index layer has a refractive index of 1.36 to 1.42 and a film thickness of 70 to 100 nm.   The fingerprint-resistant antireflection film for insert molding according to claim 1, wherein an antifouling agent is contained in the low refractive index layer.   The fingerprint resistance for insert molding according to any one of claims 1 and 2, wherein the hard coat layer is formed by curing a composition containing an acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin. Antireflection film. A resin molded product comprising the fingerprint-resistant antireflection film for insert molding according to any one of claims 1 to 3 on a surface.