JP2015152691A - Anti-glare anti-reflection film for insert molding and resin molded product produced using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-glare anti-reflection film for insert molding having superior stain resistance and to provide a molded product obtained by fusion-bonding the same.SOLUTION: The anti-glare anti-reflection film for insert molding is provided that includes an anti-glare hard coat layer formed on a thermoplastic transparent base material film, and a low refractive index layer formed as an outermost layer on the side of the anti-glare hard coat layer, of the thermoplastic transparent base material film. The low refractive index layer is formed by curing a low refractive index layer-forming resin composition containing; (a) a fluorine-containing ultraviolet curable resin; (b) a polyether-modified polydimethylsiloxane having an acrylic group, or a polyester-modified polydimethylsiloxane having an acrylic group; (c) an ultraviolet curable resin that can be copolymerized with (a) and (b); (d) hollow silica microparticles; and (e) a photopolymerization initiator, each of the (a) to (d) being contained in a predetermined concentration.

Description

  The present invention relates to an antiglare antireflection film suitable for insert molding, and relates to an antiglare antireflection film excellent in antifouling properties.

  In the design of automobile parts and mobile phones, a part of insert molding is used in which a decorative film subjected to hard coat processing or printing is applied to a molded product by a thermal fusion method. With the widespread use of car navigation and mobile phones, the opportunity to use insert molding for cover of these displays is increasing, and insert molding films that can prevent reflection of external light on the display surface in order to improve visibility It was sought after.

  Currently, an antiglare antireflection film that meets such requirements is provided. For example, in Patent Document 1, a hard coat layer and an antireflection layer are sequentially laminated on one side of a base film such as a polycarbonate film. It has become.

JP 2013-139105 A

  However, as car navigation systems and mobile phones equipped with capacitive touch panels with multi-touch functions have become more popular in recent years, the trend in performance requirements for decorative films used in insert molding has changed, and the demand for antireflection functions has changed. In addition to this, there is a new need that has not existed in the past to suppress the adhesion of fingerprints to the touch panel surface. However, the conventional antiglare antireflection film is specialized in the antireflection function, and since no measures are taken on the adhesion of fingerprints, it cannot meet the needs to suppress the adhesion of fingerprints.

  Therefore, an object of the present invention is to provide an antiglare antireflection film for insert molding, which is excellent in antifouling property.

  The present invention has an antiglare hard coat layer on one surface of a thermoplastic transparent substrate film, and the outermost antiglare hard coat layer of the thermoplastic transparent substrate film is provided on the one surface side. An anti-glare antireflection film for insert molding comprising a low refractive index layer as a surface layer, wherein the low refractive index layer comprises: (a) 5.0 to 15.0% by mass of a fluorine-containing ultraviolet curable resin, (b) Polyether-modified polydimethylsiloxane having an acrylic group or polyester-modified polydimethylsiloxane having an acrylic group of 2.0 to 8.0% by mass, UV curable resin 9 copolymerizable with (c) (a) and (b) 9 0.070.0% by mass, (d) 22.0-83.0% by mass of hollow silica fine particles, (e) a resin composition for a low refractive index layer comprising 1.0-10.0% by mass of a photopolymerization initiator Thing (however, (a) (b) (c) Total d) (e) is 100% by weight.) To cure the result, the mass% of (b), characterized in that less than weight percent (a).

  At this time, metal oxide fine particles and an ultraviolet curable resin are contained between the antiglare hard coat layer and the low refractive index layer, and the refractive index of the low refractive index layer is 1.6 to 2 higher than that of the low refractive index layer. It is preferable to provide a high refractive index layer having a refractive index of .1.

  The antiglare hard coat layer is obtained by curing a composition for an antiglare hard coat layer containing light-transmitting organic fine particles in a binder, and the binder is an acrylic-modified unsaturated dicarboxylic acid (anhydride). It is also preferred to include a grafted polyolefin.

  Furthermore, it is also preferable that the thermoplastic transparent substrate film has a two-layer structure of a polycarbonate layer and a polymethyl methacrylate layer, and the antiglare hard coat layer is formed on the polymethyl methacrylate layer.

  The anti-glare antireflection film for insert molding is integrated with the surface of the resin molded product by heat-sealing the thermoplastic transparent film during 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, an antiglare hard coat layer on a thermoplastic transparent substrate film, and further, a low refractive index layer obtained by curing a resin composition for a low refractive index layer appropriately set as the outermost layer. By forming it, it is possible to provide an antiglare antireflection film suitable for insert molding, which is difficult to attach a fingerprint and has excellent fingerprint wiping property even when the fingerprint is attached.

  Furthermore, if a high refractive index layer with a specific refractive index is provided between the antiglare hard coat layer and the low refractive index layer, the visibility is better and the fingerprint is less likely to adhere. However, it is possible to provide an antiglare and antireflection film suitable for insert molding having excellent fingerprint wiping properties.

  In addition, when the antiglare hard coat layer contains an acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin, it can be made to follow a more complex shaped mold, and a more complex shaped resin molded product Can be insert molded.

  In addition, when the thermoplastic transparent substrate film has a two-layer structure of a polycarbonate layer and a polymethyl methacrylate layer, and the antiglare hard coat layer is formed on the polymethyl methacrylate layer, a resin is formed during insert molding. The polycarbonate layer to be fused has a glass transition point (Tg) higher than that of the polymethylmethacrylate layer. Therefore, after decorative printing on the polycarbonate layer, the ink flow occurs when insert molding is performed using this antiglare antireflection film. Is less likely to occur.

《Anti-glare anti-reflection film》
The antiglare antireflection film suitable for insert molding of the present embodiment has an antiglare hard coat layer laminated on one surface of a thermoplastic transparent substrate film, and is the outermost layer on the antiglare hard coat layer side. As shown, the low refractive index layer is laminated. Further, a high refractive index layer can be provided between the antiglare hard coat layer and the low refractive index layer.

  Below, the component of the glare-proof antireflection film suitable for this insert molding is demonstrated in order.

[Thermoplastic transparent substrate film]
As the thermoplastic transparent substrate film, a film made of a polycarbonate resin 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 an antiglare hard coat layer on the polymethyl methacrylate layer. If it does so, the composition for glare-proof hard-coat layer formation can be wet-coated favorably. In addition, when an acrylic resin (cured product of a monomer having an acrylic group) is included as a binder component of the antiglare hard coat layer, interference of reflected light is caused because the refractive indexes of the antiglare hard coat layer and the polymethyl methacrylate layer are close to each other. Unevenness is unlikely to occur. In addition, since the materials of the methyl methacrylate layer and the antiglare hard coat layer are similar, the adhesion between the methyl methacrylate layer and the antiglare hard coat layer is excellent. On the other hand, the polycarbonate layer has a higher glass transition point (Tg) than the polymethylmethacrylate layer, so that the ink flow hardly occurs during insert molding by decorative printing on the polycarbonate layer. The film thickness of the thermoplastic transparent substrate film is usually 30 to 300 μm, preferably 125 to 200 μm. Moreover, it is preferable that the refractive index of a thermoplastic transparent base film is 1.49-1.59.

[Anti-glare hard coat layer]
The antiglare hard coat layer has irregularities on its surface, and light is reflected and diffused on the irregularities (surface diffusibility), and has a function capable of exhibiting antiglare properties. This anti-glare hard coat layer is formed by curing a composition for forming an anti-glare hard coat layer containing a translucent organic fine particle (D) in a binder, and has a required strength and hardness as a hard coat layer. Have. The film thickness after drying and curing of the antiglare hard coat layer 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.

<Binder>
The binder preferably contains at least one or more of acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A), ultraviolet curable resin (B), and photopolymerization initiator (C). It will be. By containing the acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) together with the photopolymerization initiator (C), it is possible to exhibit excellent adhesion to the thermoplastic transparent substrate film, By containing at least one ultraviolet curable resin (B), appropriate fluidity can be imparted.

  The 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, a copolymer having one or more α-olefins having 4 to 12 carbon atoms and propylene as essential constituent units. A polymer is preferably mentioned. 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 the 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 the case of coalescence), 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. Is more preferable.

  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. It is preferable that 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.

  The number average molecular weight of the polyolefin component constituting the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is preferably 500 to 40000, more preferably 1500 to 30000.

  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. Unsaturated dicarboxylic acids such as dicarboxylic acid, cycloheptene dicarboxylic acid, and aconitic acid; unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, and the unsaturated dicarboxylic acid anhydride and carbon number 1 And esterified products with alkyl alcohols of ˜5.

  The acrylic component constituting the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) has active hydrogen such as a hydroxyl group-containing (meth) acrylate such as 4-hydroxybutyl (meth) acrylate. Examples include acrylic components and acrylic components containing an isocyanate group such as 2-acryloylethyl isocyanate, and (meth) acrylic esters such as methyl (meth) acrylate may also be used as the acrylic component. it can. 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 to the acrylic component and then reacting it. In addition, what is necessary is just to set suitably about the reaction conditions etc. in each 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.

  It is important that the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) has a melting point of 92 to 112 ° C. As a result, excellent adhesion is exhibited even at high temperatures, and the mold can be opened immediately without cooling at a high mold temperature without causing peeling of the coating film. Preferably, the melting point of the acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is 95-110 ° C. If the melting point of the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is less than 92 ° C, the adhesiveness at high temperature becomes insufficient, and the mold opens immediately without cooling at a high mold temperature. Then, peeling will occur in the coating film. On the other hand, when the melting point of the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) exceeds 112 ° C., the resulting coating film tends to be turbid. In addition, the water resistance of the resulting antiglare hard coat layer is lowered, and moisture easily penetrates into the antiglare hard coat layer, so that the adhesion with the thermoplastic transparent substrate film is lowered and delamination occurs. There is a fear. The melting point is measured by differential scanning calorimetry (DSC).

  The acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) has a proportion of structural units derived from the unsaturated dicarboxylic acid (anhydride) in the structure (that is, unsaturated dicarboxylic acid (anhydride)). It is important that the addition ratio is 5 to 15% by mass. Thereby, compatibility with the ultraviolet curable resin (component B to be described later) generally having high polarity is improved, and as a result, a coating film without turbidity can be obtained. Preferably, the addition rate of the unsaturated dicarboxylic acid (anhydride) in the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is 6 to 13% by mass. When the addition ratio of the unsaturated dicarboxylic acid (anhydride) in the acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is less than 5% by mass, the resulting coating film becomes turbid and water resistance is also improved. Will be reduced. On the other hand, when the addition ratio of the unsaturated dicarboxylic acid (anhydride) in the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) exceeds 15% by mass, the water resistance is lowered. The addition rate of the unsaturated dicarboxylic acid (anhydride) in the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) may be calculated from the peak ratio of the carbonyl group in infrared analysis (IR), for example. .

  The number average molecular weight of the acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A) is not particularly limited, but is preferably, for example, 600 to 50100, and more preferably 1600 to 30100. If the number average molecular weight is too small, the physical properties of the coating film tend to decrease. There is a risk of damage.

  Specific examples of the ultraviolet curable resin (B) include, for example, urethane (meth) acrylate (oligomer), epoxy (meth) acrylate (oligomer), polyester (meth) acrylate (oligomer), polyether (meth) acrylate ( Oligomer), (meth) acrylate (oligomer) and the like.

The ultraviolet curable resin (B) can be obtained by a conventionally known method.
The ultraviolet curable resin (B) preferably has a weight average molecular weight of 100 to 50,000. When the weight average molecular weight is less than 100, the physical properties of the coating film tend to be lowered. On the other hand, when it exceeds 50000, the fluidity tends to be lowered and the workability during coating may be impaired.

  The photopolymerization initiator (C) is used as a polymerization initiator when a coating film is formed by curing the resin composition for an antiglare hard coat layer with an active energy ray such as ultraviolet rays (UV). The photopolymerization initiator (C) is not particularly limited as long as it initiates polymerization by irradiation with active energy rays, and a 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.

  The blending ratio of the photopolymerization initiator (C) is (C) / [(A) + (B)] = 0.1 / 100 to 10/100 (mass ratio). When the photopolymerization initiator (C) is less than the above range, the polymerization becomes insufficient and the adhesion cannot be exhibited. On the other hand, if it is more than the above range, it will only increase unnecessarily, which is not preferable.

<Translucent organic fine particles (D)>
The translucent organic fine particles (D) are for exhibiting a light diffusing function in the antiglare hard coat layer, an antiglare function by forming irregularities on the surface, and the like. The translucent organic fine particles (D) are formed from a resin obtained by polymerizing at least one monomer selected from, for example, vinyl chloride, (meth) acrylic monomer, styrene, and ethylene. As such translucent resin fine particles, a (meth) acrylic resin, a styrene-acrylic monomer copolymer resin (referred to as a styrene-acrylic copolymer resin) or a cross-linked product thereof is used because the refractive index can be easily adjusted. Preferably it is formed. In the case of a styrene-acrylic copolymer resin, it is more preferable in that the refractive index can be arbitrarily adjusted by changing the copolymer composition of both monomers. Here, in addition to styrene-acrylic copolymer resin or (meth) acrylic resin (refractive index 1.49), vinyl chloride resin, polystyrene resin (refractive index 1.54), polyethylene resin, melamine resin (refractive index 1.57). ), The translucent organic fine particles (D) can be formed from a resin containing a polycarbonate resin or the like.

  The translucent organic fine particles (D) are preferably monodispersed with a uniform particle diameter in order to uniformly diffuse or scatter light in the antiglare hard coat layer and on the surface thereof. The average particle diameter of the light-transmitting organic fine particles (D) is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 1 to 10 μm in order to sufficiently exhibit its function. When this average particle diameter is less than 0.1 μm, the antiglare property on the surface of the antiglare hard coat layer tends to be insufficient. On the other hand, when it exceeds 20 μm, the haze value of the antiglare hard coat layer becomes too high, and the transparency tends to be impaired. Here, the average particle diameter is a value calculated from a particle number distribution obtained by measuring the distribution by a Coulter counter method, converting the measured distribution into a particle number distribution. The Coulter counter method is a particle size measurement method using electric resistance, and is a method of measuring an average particle diameter by measuring a change in electric resistance between two electrodes that occurs when particles pass through pores. .

  The ratio Y / X of the average particle diameter (Y) of the translucent organic fine particles (D) to the film thickness (X) of the antiglare hard coat layer is preferably 0.3 to 1.5, 0.5 -1.5 is more preferable. When this ratio Y / X is less than 0.3, the amount of translucent organic fine particles (D) added to form desired irregularities on the surface of the antiglare hard coat layer increases, and the haze value increases. Therefore, the image definition tends to decrease. On the other hand, when it exceeds 1.5, the unevenness on the surface of the antiglare hard coat layer becomes too large, so that the haze value becomes large, the image sharpness deteriorates, and the glare becomes undesirably strong.

  The content of the translucent organic fine particles (D) is usually 1 to 70 parts by mass, preferably 2 to 60 parts by mass, more preferably 3 to 50 parts by mass, and most preferably 10 to 40 parts by mass with respect to 100 parts by mass of the binder. Part by mass. When the content of the light-transmitting organic fine particles (D) is less than 1 part by mass, the function of the light-transmitting organic fine particles (D) cannot be sufficiently exhibited, and satisfactory antiglare properties cannot be obtained. . On the other hand, when the amount is more than 70 parts by mass, the haze value of the antiglare hard coat layer becomes too high, and when the antiglare antireflection film is placed on the display surface or the like, whitening or the like occurs and image recognizability is reduced. descend.

  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 are added to the resin composition for the antiglare hard coat layer as necessary. You may contain the thing in the range which does not impair the effect of this invention.

  The dilution solvent used for the preparation of the resin composition for the binder or the antiglare hard coat layer is used for adjusting the viscosity of the binder or the resin composition for the antiglare hard coat layer, and is non-polymerizable. If there is no particular limitation. With such a dilution solvent, the resin composition for an antiglare hard coat layer can be easily applied onto 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.

  Furthermore, in order to make the surface of the antiglare hard coat layer have no defects and a uniform coating surface, it is preferable to use a non-swelling solvent of the translucent organic fine particles (D). The non-swelling solvent means a solvent that does not swell the translucent organic fine particles (D). As this non-swellable solvent, an alcohol solvent is preferable, and the amount added is preferably 10 to 60% by mass in the total amount of the solvent. When this addition amount is less than 10% by mass, it becomes difficult to form a uniform antiglare hard coat layer. On the other hand, when it exceeds 60 mass%, the dispersibility of translucent organic fine particles (D) deteriorates, and it becomes difficult to form a uniform anti-glare hard coat layer.

  After applying the above resin composition for an antiglare hard coat layer on a thermoplastic transparent substrate film, it is cured by irradiating an active energy ray to harden the antiglare hard coat on the thermoplastic transparent substrate film. Layers can be stacked. As a method for applying the antiglare hard coat layer resin 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 Any known method such as a coating method, 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 the adhesion, it is preferable to perform a pretreatment such as a corona discharge treatment on the surface of the thermoplastic transparent substrate film in advance.

As an active energy ray source used for irradiation of active energy rays, 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 active energy 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 antiglare hard coat layer 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.

(Low refractive index layer)
The refractive index of the low refractive index layer is required to be set lower than the refractive index of the anti-glare hard coat layer and, if a high refractive index layer is present, the refractive index of the high refractive index layer. Is preferably 1.33-1.46. When the refractive index is less than 1.33, the amount of fine particles to be blended in order to reduce the refractive index contained in the coating film increases, and it is difficult to form a sufficiently hard layer. On the other hand, when the refractive index exceeds 1.46, it is difficult to obtain sufficient antireflection performance. The low refractive index layer is preferably 0.05 to 0.25 μm. The low refractive index layer is made of a cured product obtained by curing the resin composition for the low refractive index layer with ultraviolet rays, and the composition thereof will be described below.

<Resin composition for low refractive index layer>
The resin composition for a low refractive index layer comprises (a) 5.0 to 15.0% by mass of a fluorine-containing ultraviolet curable resin, (b) a polyether-modified polydimethylsiloxane having an acrylic group or a polyester-modified poly having an acrylic group. 2.0 to 8.0% by mass of dimethylsiloxane, 9.0 to 70.0% by mass of ultraviolet curable resin copolymerizable with (c) (a) and (b), (d) 22.0 hollow silica fine particles -83.0% by mass, (e) 1.0 to 10.0% by mass of a photopolymerization initiator, and (b) is less in mass% than (a), and (a) (b ) (C) (d) (e) is 100% by mass.

  (A) The fluorine-containing ultraviolet curable resin is for exhibiting an antifouling function, and can weaken the adhesion of fingerprints attached when the surface of the low refractive index layer is touched. Examples of fluorine-containing ultraviolet curable resins include (meth) acrylates containing C2-C7 perfluoroalkyl chains. Specifically, those represented by the following chemical formula (1) or the following chemical formula (2) The thing shown in is mentioned.

（ 式中、ｎ は０ 〜 １ ０ ０ の整数である。また、Ｘ はＨ 又はＦ である。）

(In the formula, n is an integer of 0 to 1 0 0. X is H or F.)

（ 式中、Ｘ はパーフルオロアルキル基又はパーフルオロポリエーテルを表す。）

(Wherein X represents a perfluoroalkyl group or a perfluoropolyether)

  The fluorine-containing ultraviolet curable resin is contained in an amount of 5.0 to 15.0% by mass in the hard coat resin composition. If the content is less than 5.0% by mass, the adhesion of fingerprints attached when the surface of the low refractive index layer is touched cannot be weakened. On the other hand, if it exceeds 15.0% by mass, the wiping property of the fingerprint is deteriorated.

  (B) The polyether-modified polydimethylsiloxane having an acrylic group or the polyester-modified polydimethylsiloxane having an acrylic group is for improving the wiping property of fingerprints attached to the surface of the low refractive index layer.

The basic skeleton (polydiorganosiloxane) of a polyether-modified polydimethylsiloxane having an acrylic group or a polyester-modified polydimethylsiloxane having an acrylic group is represented by the following general formula (3), and a polymerizable reactive group is contained in one molecule. Are compounds having at least 2, preferably 2-8.

  A and B in the general formula (3) are linear or branched organic groups, an alkyl chain (C1-30), a perfluoroalkyl chain (C1-10), an arylalkyl chain, Aliphatic to aromatic (poly) ester chains (partial molecular weight of the organic chain 100 to 3000), aliphatic to aromatic (poly) ether chains (partial molecular weight of the organic chain 100 to 3000) and aliphatic Or at least one skeleton selected from the group consisting of aromatic (poly) urethane chains (partial molecular weight of the organic chain 100 to 3000), and a polymerizable reactive group is introduced into the organic group In the molecule, A and B may be the same or different, and A or B may be the same or different. However, the number of polymerizable reactive groups introduced into A and B is a compound having two, preferably 2 to 8, per molecule. Furthermore, it is more preferable that the polymerizable reactive group is introduced into B for the convenience of synthesis. C in the general formula (3) represents the length of the polysiloxane skeleton in the form of c + 1, and is preferably an integer of 3 to 250, more preferably 6 to 100.

  As the polymerizable reactive group, at least an acrylic group is introduced. The acryl group to be introduced is preferably an acryloyloxy group in terms of excellent reactivity. In addition to the acryloyloxy group, a (meth) acryloyloxy group, an α-fluoroacryloyloxy group, and the like can also be introduced. As a bonding method between the polymerizable reactive group and the polysiloxane skeleton, a conventionally known bonding method, for example, (poly) ether type, (poly) ester type, (poly) ester type and (poly) urethane type are combined. All of the bonding methods such as a bonding method combining a (poly) ether type and a (poly) urethane type, a bonding method combining a (poly) ester type and a (poly) ether type, and the like can be employed.

  For example, in the case of a bonding method combining a polyester type and a polyurethane type, the structure of the polydiorganosiloxane molecule has a basic skeleton as shown in the following general formula (4) and extends from the polysiloxane site. A polymerizable reactive group is bonded to the ends of three or more side chains of the chain.

  X in the general formula (4) is an integer of 3 to 250, preferably an integer of 6 to 100, and Y and Z are integers satisfying that Y + Z is 3 or more, preferably 4 to 20, m and n are both integers of 1-10. m and n may be the same or different, but the same is preferable in that a polyether-modified polydimethylsiloxane having an acrylic group or a polyester-modified polydimethylsiloxane having an acrylic group can be easily prepared.

  R1 in the general formula (4) is a linear alkyl group (1 to 30 carbon atoms), a perfluoroalkyl group (1 to 10 carbon atoms), an arylalkyl group, a polyester group (partial molecular weight of the side chain) 200 to 2000, and bonded to the Si atom via an alkyl chain), a polyether group (partial molecular weight of the side chain is 200 to 2000, and bonded to the Si atom via an alkyl chain) One of them). R1 may be the same or different in the molecule, but it is more preferable that they are the same because preparation of a polyether-modified polydimethylsiloxane having an acrylic group or a polyester-modified polydimethylsiloxane having an acrylic group is simple. Further, from the viewpoint of compatibility with the resin at the time of use, it is most general and preferable that R1 is a methyl group.

  R2 in the general formula (4) is a linear or branched chain having 3 to 30 carbon atoms, preferably 3 to 15 carbon atoms, and has at least two urethane bonds on the chain. It is bonded to the siloxane skeleton and R3 (provided that R3 is bonded so that three or more are contained in one molecule of polydiorganosiloxane). In the molecule, R2 may be the same or different, but the same is more preferable because the preparation of the polyether-modified polydimethylsiloxane having an acrylic group or the polyester-modified polydimethylsiloxane having an acrylic group is simple.

  R3 in the general formula (4) is a portion having a polyester skeleton, preferably a polyester skeleton containing three or more ester bonds, and has a polymerizable reactive group as described above, preferably a (meth) acryloyl group at the terminal. Are combined. R3 in the molecule may be the same or different, but the same is more preferable because the preparation of the polyether-modified polydimethylsiloxane having an acrylic group or the polyester-modified polydimethylsiloxane having an acrylic group is simple. Further, from the viewpoint of compatibility with the resin at the time of use, it is most general and preferable that R3 has a polycaprolactone skeleton composed of 3 or more caprolactones.

  R4 in the general formula (4) is any one of hydrogen, fluorine and methyl group, and R4 may be the same or different in the molecule, but the polyether-modified polydimethylsiloxane or acrylic group having an acrylic group is The same is more preferable because the preparation of the polyester-modified polydimethylsiloxane is simple.

  Next, some more specific examples in the case of using the bonding method combining the polyester type and the polyurethane type as described above will be described together with an example of the manufacturing method. However, the following examples of the production method do not mean that the polyether-modified polydimethylsiloxane having an acrylic group or the polyester-modified polydimethylsiloxane having an acrylic group is limited to the following examples.

  For example, by ring-opening polymerization of ε-caprolactone using polydimethylsiloxane represented by average formula (5) obtained by a conventionally known method, triisocyanate represented by general formula (6), and ethylene glycol monomethacrylate. Using the prepared polymerizable reactive group-containing polyester represented by the general formula (7) in a molar ratio of 1: 2: 4, a polycrystal represented by the average formula (8) is obtained by a conventionally known urethane bond forming reaction. A dimethylsiloxane compound is obtained. At this time, after adding polydimethylsiloxane (5) to triisocyanate (6) and forming urethane bonds at both ends of polydimethylsiloxane (5), urethane with polymerizable reactive group-containing polyester (7) By forming a bond, a by-product [for example, a by-product composed only of polydimethylsiloxane (5) and triisocyanate (6), or a polymerizable reactive group-containing polyester (7) and triisocyanate (6) only. The desired polydimethylsiloxane (8) can be obtained in a high yield by suppressing the production of by-products and the like].

  Here, d in the average formulas (5) and (8) is an integer of 15 to 20, e is an integer of 1 to 5, f in the general formula (6) is an integer of 4 to 8, and the general formula (7) And g in average formula (8) is an integer of 3-5. In the average formulas (5) and (8), Me represents a methyl group.

  In addition, for example, polydimethylsiloxane represented by the average formula (9) obtained by a conventionally known method, diisocyanate represented by the general formula (10), and ε-caprolactone using pentaerythritol triacrylate By using a polymerizable reactive group-containing polyester represented by the general formula (11) prepared by ring-opening polymerization in a molar ratio of 1: 2: 2, an average formula (12) is obtained by a conventionally known urethane bond forming reaction. The polydimethylsiloxane compound represented by these is obtained. At this time, after adding polydimethylsiloxane (9) to diisocyanate (10) and forming urethane bonds at both ends of polydimethylsiloxane (9), urethane bonds with polymerizable reactive group-containing polyester (11) By forming a by-product [for example, a by-product consisting of only polydimethylsiloxane (9) and diisocyanate (10), or a by-product consisting only of polymerizable reactive group-containing polyester (11) and diisocyanate (10) Etc.] and the desired polydimethylsiloxane (12) can be obtained in high yield.

  Here, h in the average formula (9) is an integer of 25 to 35, i is an integer of 1 to 5, j in the general formula (10) is an integer of 5 to 10, and k in the general formula (11). Is an integer of 3-5. In the average formula (12), h is 29, i is 5, j is 6, and k is 5.

  Further, for example, the above two examples are combined to react polydimethylsiloxane represented by the average formula (9), triisocyanate (6), and polymerizable reactive group-containing polyester (11) at a molar ratio of 1: 2: 4. Thus, polydimethylsiloxane having 12 acryloyloxy groups can be obtained.

  In addition to this, polydimethylsiloxane is synthesized by a method in which a polyester portion having a polymerizable reactive group and a polyurethane portion are bonded and then introduced into a siloxane skeleton, or a method in which a polymerizable reactive group is finally introduced. It is also possible. Usually, the compound represented by General formula (3) can be used individually or in combination of 2 or more types.

  In addition, an organopolysiloxane having one polymerizable reactive group per molecule, for example, a polysiloxane having one end (meth) acryloyloxy-modified polydimethylsiloxane, a perfluoroalkyl group and a (meth) acryloyloxy group at one end, A polydiorganosiloxane having the specific structure (polyether-modified polydimethylsiloxane having an acrylic group or polyester-modified polydimethylsiloxane having an acrylic group) can also be used in combination.

  The polyether-modified polydimethylsiloxane having an acrylic group or the polyester-modified polydimethylsiloxane having an acrylic group is contained in an amount of 2.0 to 8.0% by mass in the resin composition for hard coat. When the content is less than 2.0% by mass, the wiping property of fingerprints attached to the surface of the antiglare hard coat layer is not improved. On the other hand, if it exceeds 8.0% by mass, it is not possible to weaken the adhesiveness of fingerprints attached when the antiglare hard coat layer surface is touched.

  (C) The ultraviolet curable resin copolymerizable with (a) and (b) can impart hardness to the low refractive index layer. Examples of the ultraviolet curable resin copolymerizable with (a) and (b) include urethane (meth) acrylate (oligomer), epoxy (meth) acrylate (oligomer), polyester (meth) acrylate (oligomer), and polyether. (Meth) acrylate (oligomer), (meth) acrylate (oligomer), etc. are mentioned. The ultraviolet curable resin copolymerizable with (a) and (b) is contained in an amount of 9.0 to 70.0% by mass in the resin composition for the low refractive index layer. When the content is less than 9.0% by mass, the low refractive index layer is insufficient in hardness or the transmittance is lowered. On the other hand, when it exceeds 70.0 mass%, the wiping property of fingerprints is not improved.

  (D) The hollow silica fine particles are blended to actively lower the refractive index. The refractive index of the hollow silica fine particles varies depending on the production method, but is preferably 1.25 to 1.40. The hollow silica fine particles are not particularly limited as long as the refractive index is lowered, and known hollow silica fine particles can be used. Specific examples include acrylic modified hollow silica fine particle through rear NAU manufactured by JGC Catalysts & Chemicals. The hollow silica fine particles are contained in an amount of 22.0 to 83.0% by mass in the low refractive index layer resin composition. When the content of the silica fine particles is less than 22.0% by mass, the refractive index of the low refractive index layer cannot be in the above range. On the other hand, when the content of the silica fine particles is more than 83.0% by mass, the coating film strength becomes weak. Further, the size of the hollow silica fine particles is preferably 0.1 μm or less. When the particle diameter of the hollow silica fine particles is larger than 0.1 μm, it is not preferable because light scattering occurs and the haze value tends to increase and whiten. In the present specification, the particle diameter is a value obtained by measuring an average particle diameter by a dynamic light scattering method using a particle size distribution measuring apparatus (manufactured by Otsuka Electronics Co., Ltd., PAR-III). is there.

  (E) The photopolymerization initiator is used as a polymerization initiator when a coating film is formed by curing the resin composition for a low refractive index layer with active energy rays such as ultraviolet rays (UV). The photopolymerization initiator is not particularly limited as long as it initiates polymerization upon irradiation with active energy rays, and known compounds can be used. For example, acetophenone-based polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin, 2,2-dimethoxy 1,2-diphenylethane-1 Benzoin-based polymerization initiators such as -one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4'-tetra (t- Examples thereof include benzophenone polymerization initiators such as (butylperoxycarbonyl) benzophenone, and thioxanthone polymerization initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone. 1.0-10.0 mass% of photoinitiators are contained in the resin composition for low refractive index layers. When the content of the photopolymerization initiator is less than 1.0% by mass, curing of the antiglare hard coat layer is insufficient. On the other hand, when the content exceeds 10.0% by mass, the photopolymerization initiator is unnecessarily increased, 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 for improving the antireflection effect due to a significant refractive index difference from the above-described low refractive index layer. The refractive index of the high refractive index layer is set higher than that of the antiglare hard coat layer and the low refractive index layer, and the refractive index of the high refractive index layer is 1.6 to 2.1. When this refractive index is smaller than 1.6, the antireflection performance cannot be improved. On the other hand, it is difficult to form a high refractive index layer having a refractive index exceeding 2.1. The film thickness after drying and curing of the high refractive index layer is preferably 0.05 to 0.25 μm. Outside the above range, the effect of preventing reflection due to light interference becomes insufficient. Furthermore, the high refractive index layer is made of a cured product obtained by curing a resin composition for a high refractive index layer obtained by mixing metal oxide fine particles and an ultraviolet curable resin with ultraviolet rays or the like.

<Resin composition for high refractive index layer>
As a material constituting the resin composition for 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, 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 is larger than 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, for example, an ultraviolet curable resin having a refractive index of 1.6 to 1.8 which is polymerized and cured can be used. Examples of such ultraviolet curable resins include urethane (meth) acrylate (oligomer), epoxy (meth) acrylate (oligomer), polyester (meth) acrylate (oligomer), polyether (meth) acrylate (oligomer), ( And (meth) acrylate (oligomer).

  In the high refractive index layer, 30 to 90 parts by mass of metal oxide fine particles are contained, and 10 to 70 parts by mass are contained. If the content of the metal oxide fine particles is less than 30 parts by mass, the refractive index of the high refractive index layer is out of the above range, which is not preferable. When the content of the metal oxide fine particles exceeds 90 parts by mass, the relative amount of the metal oxide fine particles with respect to the coating film increases and the coating film becomes brittle. On the other hand, if the content of the ultraviolet curable resin is less than 10 parts by mass, the relative amount of the ultraviolet curable resin with respect to the coating film is small and the coating film becomes brittle. On the other hand, when the content of the ultraviolet curable resin exceeds 70 parts by mass, the refractive index of the high refractive index layer falls outside the above range, which is not preferable.

  Further, the high refractive index layer resin composition contains a photopolymerization initiator to form a coating film by curing the high refractive index layer resin composition with active energy rays such as ultraviolet rays (UV). It is. The photopolymerization initiator is not particularly limited as long as it initiates polymerization upon irradiation with active energy rays, and known compounds can be used. For example, acetophenone-based polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin, 2,2-dimethoxy 1,2-diphenylethane-1 Benzoin-based polymerization initiators such as -one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4'-tetra (t- Examples thereof include benzophenone polymerization initiators such as (butylperoxycarbonyl) benzophenone, and thioxanthone polymerization initiators such as 2-chlorothioxanthone and 2,4-diethylthioxanthone. 1.0-10.0 mass% of photoinitiators are contained in the resin composition for high refractive index layers. 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.

  In the resin composition for 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.

[Formation of antiglare hard coat layer, high refractive index layer and low refractive index layer]
The antiglare hard coat layer, the high refractive index layer and the low refractive index layer are coated with the resin composition for each layer on the thermoplastic transparent substrate film, and then cured by irradiation with active energy rays, thereby making the thermoplastic transparent substrate. It is formed for each layer in order from the layer on the film side. The coating method of the resin composition for the antiglare hard coat layer, the resin composition for the high refractive index layer, and the resin composition for the low refractive index layer is not particularly limited. For example, a roll coating method, a spin coating method, a dip coating method, Any known method such as a spray coating method, a bar coating method, a knife coating method, a die coating method, an ink jet method, or a gravure coating method can be adopted. The type of active energy ray is not particularly limited, but it is preferable to use ultraviolet rays from the viewpoint of convenience and the like. In addition, in order to improve the adhesiveness of the antiglare hard coat layer to the thermoplastic transparent substrate film, the surface of the thermoplastic transparent substrate film can be pretreated such as corona discharge treatment. From the viewpoint of coatability, the resin composition for each layer is preferably diluted with a solvent for coating. The solvent is not particularly limited as long as it is a known one that has been conventionally used for coating liquids for forming each layer. For example, alcohol-based, ketone-based, and ester-based solvents can be appropriately selected.

<< Resin molding using anti-glare anti-reflection film >>
The molded product of the present embodiment is obtained by molding a resin by an insert molding fusion method and simultaneously integrating an antiglare reflective film on the surface of the molded product. For example, an antiglare antireflection film is held in a cavity in an injection mold, and a molten resin is injected into the mold to obtain a molded product in which an antiglare antireflection film is integrated on the surface. be able to.

  Hereinafter, the embodiment 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.

[Thermoplastic transparent substrate film]
In each Example and Comparative Example, the following were used as the thermoplastic transparent substrate film.
Polycarbonate film (PC)
“C000” manufactured by Sumitomo Chemical Co., Ltd. 188 μm
Polymethylmethacrylate film (PMMA)
“S014G” manufactured by Sumitomo Chemical Co., Ltd., 188 μm
Film (PC / PMMA) consisting of a two-layer structure of a polycarbonate layer and a polymethyl methacrylate layer
“C001” manufactured by Sumitomo Chemical Co., Ltd. 200 μm

[Resin composition for antiglare hard coat layer]
As the resin composition for the antiglare hard coat layer, the following raw materials were used, and the respective raw materials were mixed in the composition described in Table 1 below, and the antiglare hard coat layer resin compositions HC1-1 and HC1- 2 was prepared. In addition, the compounding quantity of each material has described the mass% of solid content. The raw materials for the resin composition for the antiglare hard coat layer are as follows.
<Acrylic modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A)>
Hydroxyl group-containing methacrylate-modified maleic anhydride grafted polyolefin (A1) synthesized in Production Example 1 below
<Ultraviolet curable resin (B)>
"EBECRYL8402" manufactured by Daicel-Cytec
“KAYARAD DPCA-20” manufactured by Nippon Kayaku Co., Ltd.
“Light acrylate 1.9ND-A” manufactured by Kyoeisha Chemical Co., Ltd.
<Photopolymerization initiator (C)>
“IRGACURE 184 (I-184)” manufactured by Ciba Specialty Chemicals Co., Ltd.
<Translucent organic fine particles (D)>
Fine particles of cross-linked acrylic-styrene copolymer resin [manufactured by Sekisui Plastics Co., Ltd., SSX1055QXE, monodispersed fine particles with uniform particle size, average particle size (a) is 5.0 μm] 30 parts by mass <leveling agent (E) >
Big Chemie Japan Co., Ltd. “BYK-333”

<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 (a1) by thermal degradation.

  Next, 160 parts of the low-molecular polyolefin (a1) is placed in a reaction vessel equipped with a stirrer, a thermometer, and a cooling pipe, heated to 180 ° C. under a nitrogen stream and melted, and then 25 parts of maleic anhydride. And 20 parts of 1-dodecene were 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 a maleic anhydride grafted polyolefin (aa1).

Next, 450 parts of the maleic anhydride-grafted polyolefin (aa1) is placed in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, and the temperature is raised to 105 ° C. under a nitrogen stream to maintain the temperature. While stirring, 300 parts of toluene 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 mixture was reacted at the same temperature for 3 hours and then cooled to obtain a solution of the hydroxyl group-containing methacrylate-modified maleic anhydride grafted polyolefin (A1). The solid content concentration of the obtained solution was 66.1%.

  About each obtained resin composition for anti-glare hard-coat layers, the composition refractive index after hardening was confirmed. The composition refractive index after curing is measured by the following method, and the results are also shown in Table 1 above.

<Composition refractive index after curing>
(1) On the PET film [trade name “A4100”, manufactured by Toyobo Co., Ltd.], the thickness of each layer is such that the coating liquid for each layer is 100 to 500 nm in thickness after drying and curing by a bar coater. Was adjusted and applied. After drying, the film was cured by irradiating with 400 mJ of ultraviolet light using a 120 W high-pressure mercury lamp in a nitrogen atmosphere with an ultraviolet irradiation device (manufactured by Iwasaki Electric Co., Ltd.) to prepare a film for refractive index measurement.
(2) The reflection spectrum was measured with a reflection spectral film thickness meter [“FE-3000”, manufactured by Otsuka Electronics Co., Ltd.] after roughening the back surface of the produced film with sandpaper and painting with black paint.
(3) From the reflectance read from the reflection spectrum, the constant of the wavelength dispersion formula (Formula 1) of n-Cauchy shown below was obtained, and the refractive index at the wavelength of 589 nm was obtained.
N (λ) = a / λ ⁴ + b / λ ² + c (Formula 1)
a, b, c: chromatic dispersion constant

[Resin composition for high refractive index layer]
As the high refractive index layer resin composition, the following raw materials were used, and the respective raw materials were mixed in the composition described in Table 2 below to prepare high refractive index layer resin compositions H1-1 to H1-4. . In addition, the compounding quantity of each material has described the mass% of solid content. The raw materials for the high refractive index layer resin composition are as follows.
<Metal oxide fine particles>
“ZRMEK25% -F47” (zirconium oxide fine particle dispersion) manufactured by CI Kasei Co., Ltd.
"RTTMIBK15WT% -N24" manufactured by CI Kasei Co., Ltd. (Titanium oxide fine particle dispersion)
<UV curable resin>
"Shikou UV-7600B" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
<Photopolymerization initiator>
“IRGACURE907 (I-907), IRGACURE184 (I-184)” manufactured by Ciba Specialty Chemicals Co., Ltd.

[Resin composition for low refractive index layer]
As the resin composition for the low refractive index layer, the following raw materials are used, and each raw material has the composition described in Tables 3 and 4 below, and (a) a fluorine-containing resin and (b) a polyether-modified polydimethylsiloxane or Low refractive index by mixing polyester-modified polydimethylsiloxane, (c) UV curable resin copolymerizable with (a) and (b), (d) hollow silica fine particles, and (e) photopolymerization initiator. Rate layer resin compositions L1-1 to L1-15 and L2-1 to L2-12 were prepared. In addition, the compounding quantity of each material has described the mass% of solid content. The raw materials for the resin composition for the low refractive index layer are as follows.
<(A) Fluorine-containing resin>
Fluorine-containing UV curable resin “OPTOOL DAC-HP” manufactured by Daikin Industries, Ltd.
Fluorine-containing UV curable resin DIC Corporation “MegaFac RS-75”
"Megafac F-558" made by DIC Corporation, a non-UV curable resin containing fluorine
<(B) Polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane>
Polyether-modified polydimethylsiloxane having an acrylic group "BYK-UV 3500" manufactured by Big Chemie Japan Co., Ltd.
Polyether-modified polydimethylsiloxane having an acrylic group "BYK-UV 3530" manufactured by Big Chemie Japan Co., Ltd.
Polyester-modified polydimethylsiloxane having an acrylic group "BYK-UV 3570" manufactured by Big Chemie Japan Co., Ltd.
Polyether-modified polydimethylsiloxane having no acrylic group "BYK331" manufactured by Big Chemie Japan Co., Ltd.
<(C) UV curable resin copolymerizable with (a) and (b)>
Dipentaerythritol hexaacrylate “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.
Urethane acrylate having 6 acrylic groups in one molecule "Shikou UV-7600B" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
<(D) Hollow silica fine particles>
“Acrylic modified hollow silica fine particles through rear NAU” manufactured by JGC Catalysts & Chemicals Co., Ltd.
<(E) Photopolymerization initiator>
“IRGACURE907 (I-907), IRGACURE184 (I-184)” manufactured by Ciba Specialty Chemicals Co., Ltd.

(Example 1-1)
An anti-glare hard material obtained by mixing a resin composition for hard coat (HC1-1) and a solvent (methyl isobutyl ketone) in a ratio of 1: 1 on one surface of a polymethyl methacrylate film “S014G, 188 μm” manufactured by Sumitomo Chemical Co., Ltd. The coating solution for the coating layer was applied with a bar coater so that the film thickness after curing was 10 μm, and was cured by irradiating with 400 mJ ultraviolet rays with a 120 W high-pressure mercury lamp to form an antiglare hard coat layer.

  Next, a coating solution for a low refractive index layer prepared by mixing a resin composition for low refractive index layer (L1-1) and a solvent (methyl isobutyl ketone) at a ratio of 1: 5 on this antiglare hard coat layer. An anti-glare antireflection film (F1-1) is applied by applying a UV coating of 400 mJ with a 120 W high-pressure mercury lamp in a nitrogen atmosphere and curing it with a bar coater so that the film thickness after curing is 0.1 μm. ) Was produced.

  About the obtained anti-glare antireflection film, fingerprint wiping property, scratch resistance, minimum reflectance, haze, transmitted image definition, reflected image line brightness, and anti-glare property were measured by the following methods. The results are shown in Table 5 below.

(Examples 1-2 to 1-15)
In the same manner as in Example 1-1, except that the thermoplastic transparent substrate film, the resin composition for hard coat, and the resin composition for low refractive index layer were combined with the materials and layers described in Table 5 below, Dazzle antireflection films (F1-2 to F1-15) were produced. About the obtained anti-glare antireflection film, fingerprint wiping property, scratch resistance, minimum reflectance, haze, image clarity, and anti-glare property were measured by the following methods. The results are shown in Table 5 below. When “PC / PMMA” was used as the thermoplastic transparent substrate film, various layers were formed on the polymethyl methacrylate layer (PMMA layer).

<Fingerprint wiping>
Artificial finger oil solution (1 g of urea, 4.6 g of lactic acid, 8 g of sodium pyrophosphate, 7 g of sodium chloride, 20 mL of ethanol diluted to 1 L with distilled water) 1 drop of antiglare antireflection film surface (low refractive index layer surface) Dripping into. Then, use Nippon Paper Crecia Co., Ltd. Kimwipe to blend in the artificial finger oil. Then, after carrying out 5 reciprocating wiping using Toray Co., Ltd. Toraysee, the surface trace was observed visually and evaluated in the following three steps.
○: When there is no trace of artificial finger oil △: When some trace of artificial finger oil remains *: When trace of artificial finger oil remains

<Abrasion resistance>
The surface after anti-glare antireflection film surface was subjected to 10 reciprocating frictions with a stroke width of 25mm and a speed of 30mm / sec by applying a load of 250gf to # 0000 steel wool and evaluated with the following ○ and ×. did. The steel wool was gathered to about 10 mmφ, and was cut and rubbed so as to have a uniform surface.
○: 0 to 10 scratches ×: 11 or more scratches

<Minimum reflectance>
In order to prevent back reflection of the antiglare antireflection film, the back surface was roughened with sandpaper and painted with a black paint, and a spectrophotometer [trade name: U-best 560, manufactured by JASCO Corporation] 5 ° and −5 ° specular reflection spectra at wavelengths of 380 nm to 780 nm were measured. The minimum reflectance (%) was read from the obtained reflection spectrum.

<Haze value>
A haze meter (Nippon Denshoku Industries Co., Ltd., NDH2000) was used, and the haze value (%) as an optical characteristic was measured.

<Transparent image clarity and reflected image clarity>
A value of image definition (transmission image definition) through an optical comb having a width of 1 mm using an image definition measuring device based on JIS K 7105-1981 (image clarity measuring device manufactured by Suga Test Instruments Co., Ltd., ICM-1T). (Degree) (%) and the value of image sharpness (reflection image sharpness) (%) measured by 45 ° reflection. The criteria for determination of the measurement results are as follows.
Transmission image definition: "100% to 90% ... no antiglare property", "less than 90% 15% or more ... good antiglare effect", "less than 15% less than 0% ... prevention The dazzling effect is too strong. ''
Reflected image sharpness: "100% to 80% ... no antiglare property", "less than 80%, 5% or more ... good antiglare effect", "less than 5%, less than 0% ... prevention The dazzling effect is too strong. ''

<Anti-glare property>
When reflecting the fluorescent lamp light so that the fluorescent lamp distance is 3 m and the incident angle is 10 ° on the AGAR-treated surface, evaluate how much the contour of the fluorescent lamp reflected regularly at 10 ° is blurred according to the following evaluation criteria. did. As the fluorescent lamp, FHF32EXNH manufactured by Panasonic Corporation was used.
○: The contour is so blurred that it cannot be confirmed. ×: The contour is not blurred.

(Example 2-1)
An anti-glare hard material obtained by mixing a resin composition for hard coat (HC1-1) and a solvent (methyl isobutyl ketone) in a ratio of 1: 1 on one surface of a polymethyl methacrylate film “S014G, 188 μm” manufactured by Sumitomo Chemical Co., Ltd. The coating solution for the coating layer was applied with a bar coater so that the film thickness after curing was 10 μm, and was cured by irradiating with 400 mJ ultraviolet rays with a 120 W high-pressure mercury lamp to form an antiglare hard coat layer.

  Next, a coating solution for a high refractive index layer obtained by mixing a resin composition for high refractive index layer (H-1) and a solvent (methyl isobutyl ketone) at a ratio of 1: 5 on this antiglare hard coat layer. A high refractive index layer was formed by coating with a bar coater such that the film thickness after curing was 0.1 μm, and irradiating with a 120 W high-pressure mercury lamp in a nitrogen atmosphere by irradiating with 400 mJ ultraviolet rays.

  Finally, a low-refractive-index layer coating solution prepared by mixing the low-refractive-index layer resin composition (L1-1) and the solvent (methyl isobutyl ketone) in a ratio of 1: 5 on this high-refractive index layer is a bar coater. The antiglare antireflection film (F2-1) is applied by applying an ultraviolet ray of 400 mJ with a 120 W high-pressure mercury lamp in a nitrogen atmosphere and curing the film so that the film thickness after curing is 0.1 μm. Produced.

  About the obtained anti-glare antireflection film, fingerprint wiping property, scratch resistance, minimum reflectance, haze, transmitted image definition, reflected image definition, and anti-glare property were measured by the above methods. The results are shown in Table 6 below.

(Examples 2-2 to 2-16)
Except that the thermoplastic transparent substrate film, the resin composition for hard coat, the resin composition for high refractive index layer, and the resin composition for low refractive index layer were combined with the materials and each layer described in Table 6 below, Examples In the same manner as in 2-1, antiglare antireflection films (F2-2 to F2-16) were produced. About the obtained anti-glare antireflection film, fingerprint wiping property, scratch resistance, minimum reflectance, haze, transmitted image definition, reflected image definition, and anti-glare property were measured by the above methods. The results are shown in Table 6 below. When “PC / PMMA” was used as the thermoplastic transparent substrate film, various layers were formed on the polymethyl methacrylate layer (PMMA layer).

(Examples 3-1 to 3-15), (Examples 4-1 to 4-16)
Fusion of antiglare antireflection film to molded article: The antiglare antireflection film obtained in Examples 1-1 to 1-15 and Examples 2-1 to 2-16 was used as a thermoplastic transparent substrate film. The polycarbonate resin held in the cavity in the injection mold so as to be in contact with the molten polycarbonate resin and melted at a temperature of about 360 ° C. is injected into the mold at a pressure of 29400 kPa, and allowed to cool. A resin molded product having a flat plate portion and curved surface portions having a radius R = 0.5 mm at both ends thereof was obtained. That is, a resin molded product having an antiglare antireflection film on its surface was obtained by fusing the antiglare antireflection film by an insert molding fusion method in which it was fused simultaneously with molding.

  With respect to the obtained resin molded product, fingerprint wiping property, scratch resistance, minimum reflectance, haze, transmitted image definition, reflected image line brightness, and antiglare property were measured by the above methods at the flat plate portion. Moreover, the following method evaluated the presence or absence of the crack in the curved surface shape used as the curvature radius R = 0.5mm. The results are shown in Tables 7 and 8 below.

<Presence or absence of cracks in the curved surface shape of the molded product>
The curved surface portion of the molded product was visually confirmed to check for cracks and other cracks.
○: No cracks such as cracks, ×: No cracks such as cracks.

(Comparative Example 1-1 to Comparative Example 1-13)
In the same manner as in Example 1-1, except that the thermoplastic transparent substrate film, the resin composition for hard coat, and the resin composition for low refractive index layer were combined with the materials and layers described in Table 9 below, Dazzle antireflection films (F3-1 to F3-13) were produced. About the obtained anti-glare antireflection film, fingerprint wiping property, scratch resistance, minimum reflectance, haze, image definition, and anti-glare property were measured by the above methods. The results are shown in Table 9 below.

(Comparative Examples 2-1 to 2-12)
Except that the thermoplastic transparent substrate film, the resin composition for hard coat, the resin composition for high refractive index layer, and the resin composition for low refractive index layer were combined with the materials described in Table 8 and each layer, Examples In the same manner as in 2-1, antiglare antireflection films (F2-1 to F2-12) were produced. About the obtained anti-glare antireflection film, fingerprint wiping property, scratch resistance, minimum reflectance, haze, transmitted image definition, and reflected image definition anti-glare property were measured by the above methods. The results are shown in Table 10 below.

(Comparative Examples 3-1 to 3-13), (Comparative Examples 4-1 to 4-12)
Fusion of antiglare antireflection film to molded article: The antiglare antireflection film is in contact with a polycarbonate resin in which a thermoplastic transparent base film is melted (having a curved shape with a radius of curvature R = 0.5 mm). ) The polycarbonate resin held in the cavity in the injection mold and melted at a temperature of about 360 ° C. is injected into the mold at a pressure of 29400 kPa (having a curved shape with a curvature radius R = 0.5 mm). And allowed to cool. That is, the antiglare antireflection film was integrated on the molded product by fusing the antiglare antireflection film by an insert molding fusion method in which fusion was performed simultaneously with molding.

  About the fusion-molded product of the obtained antiglare antireflection film, fingerprint wiping property, scratch resistance, minimum reflectance, haze, image sharpness, antiglare property, curved surface shape with radius of curvature R = 0.5 mm The presence or absence of cracks was measured by the same method as in Example 3-1. The results are shown in Tables 11 and 12 below.

  From the results of Examples 1-1 to 1-15 shown in Table 5, (a) fluorine-containing resin, (b) polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane, (c) (a) and (b By providing the outermost layer with a low refractive index layer obtained by curing a resin composition for a low refractive index layer comprising (d) a hollow silica fine particle and (e) a photopolymerization initiator. It was revealed that fingerprint wiping property can be imparted to the antiglare antireflection film. Here, when compared with the results of Comparative Example 1-11 shown in Table 9, when (a) the fluorine-containing resin is not an ultraviolet curable resin, no scratch resistance is obtained, and (a) the fluorine-containing resin contains fluorine. It became clear that it was an ultraviolet curable resin. In addition, from the result of Comparative Example 1-3, in order to develop fingerprint wiping properties, not only (a) fluorine-containing ultraviolet curable resin, but also (b) polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane In addition, referring to the results of Comparative Example 1-12, when the polyether-modified polydimethylsiloxane or the polyester-modified polydimethylsiloxane has an acrylic group, fingerprint wiping can be obtained. It became clear. And from the comparison with Comparative Examples 1-1 to 1-6, 1-10, the concentration of each component in the resin composition for the low refractive index layer is (a) fluorine-containing ultraviolet curable resin 5.0 to 15 0.0 mass%, (b) polyether-modified polydimethylsiloxane having an acrylic group or polyester-modified polydimethylsiloxane having an acrylic group, 2.0 to 8.0 mass%, and (c) (a) and (b) Polymerizable ultraviolet curable resin 9.0 to 70.0 mass%, (d) hollow silica fine particles 22.0 to 83.0 mass%, (e) photopolymerization initiator 1.0 to 10.0 mass% ( However, it became clear that the total of (a), (b), (c), (d), and (e) was 100% by mass). In addition, referring to the results of Comparative Examples 1-7 to 1-9, it is clear that fingerprint wiping can be obtained when the density of (a) is larger than the density of (b) in this density range. It became. Examples 2-1 to 2-16 (Table 6) and Comparative Examples 2-1 to 2-12 (Table 10) in which a high refractive index layer was formed between the low refractive index layer and the antiglare hard coat layer The same thing is clear from the comparison of.

  Examples 1-1 to 1-15 shown in Table 5 and 3-1 to 3-15 shown in Table 7 and Examples 2-1 to 2-16 shown in Table 6 and Table 8 In contrast to Examples 4-1 to 16, insert molding was performed using an antiglare antireflection film in which the low refractive index layer having the above composition was cured on the outermost layer to form a low refractive index layer. When the antiglare antireflection film was integrated with the surface of the product, it was confirmed that each characteristic possessed by the antiglare antireflection film alone was also exhibited on the surface of the molded product. Here, comparing the results of Comparative Example 3-13, the resin composition for an antiglare hard coat layer contains an acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin (A), so that the scratch resistance is increased. It can be seen that molding can be performed along a more complicated mold shape by insert molding while securing the above.

  Moreover, in the results of Examples 2-1 to 2-16 shown in Table 6, when focusing on the minimum reflectance, the composition refractive index after curing of the high refractive index layer resin composition forming the high refractive index layer In Example 2-16 using H1-4 (Table 2) having a refractive index of 1.52, the minimum reflectance is not reduced as compared with Example 1-2 in which the high refractive index layer is not formed. On the other hand, in Examples 2-1 to 15 using H1-1,2,3 in which the refractive index of the composition after curing of the resin composition for a high refractive index layer is 1.6 to 2.1, it is high. By forming the refractive index layer, a significant reduction in the minimum reflectance was recognized. Thereby, it is more reflective by providing a high refractive index layer having a refractive index of 1.6 to 2.1 higher than the refractive index of the low refractive index layer between the antiglare hard coat layer and the low refractive index layer. It became clear that it can be set as the anti-glare antireflection film with a smaller rate.

Claims (5)

It has an antiglare hard coat layer on one surface of the thermoplastic transparent substrate film, and is low as the outermost layer on one surface side of the thermoplastic transparent substrate film provided with the antiglare hard coat layer. An antiglare antireflection film for insert molding comprising a refractive index layer,
The low refractive index layer is
(A) Fluorine-containing ultraviolet curable resin 5.0 to 15.0 mass%,
(B) Polyether-modified polydimethylsiloxane having an acrylic group or polyester-modified polydimethylsiloxane having an acrylic group, 2.0 to 8.0% by mass,
(C) 9.0 to 70.0% by mass of an ultraviolet curable resin copolymerizable with (a) and (b),
(D) 22.0-83.0 mass% of hollow silica fine particles,
(E) Photoinitiator 1.0-10.0 mass%
A resin composition for a low refractive index layer (however, the total of (a), (b), (c), (d), and (e) is 100% by mass), and the mass of (b) % Is less than the mass% of (a), an antiglare antireflection film for insert molding.   Between the anti-glare hard coat layer and the low refractive index layer, it contains metal oxide fine particles and an ultraviolet curable resin, and has a refractive index of 1.6 to 2.1 higher than the refractive index of the low refractive index layer. The antiglare antireflection film for insert molding according to claim 1, further comprising a high refractive index layer having a refractive index. The antiglare hard coat layer is obtained by curing a composition for an antiglare hard coat layer containing translucent organic fine particles in a binder,
The anti-glare antireflection film for insert molding according to claim 1 or 2, wherein the binder contains an acrylic-modified unsaturated dicarboxylic acid (anhydride) grafted polyolefin.   2. The thermoplastic transparent substrate film has a two-layer structure of a polycarbonate layer and a polymethyl methacrylate layer, and the antiglare hard coat layer is formed on the polymethyl methacrylate layer. The anti-glare antireflection film for insert molding according to any one of claims 1 to 3.   A resin molded product comprising the antiglare antireflection film for insert molding according to any one of claims 1 to 4 on a surface.