JP2010254950A - Resin composition, antireflection film, display, and method for manufacturing antireflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a resin composition excellent in scratch resistance and antifouling properties, while suppressing the occurrence of appearance defects due to addition of a modified silicon-acrylate; an antireflection film and a display each using the resin composition; and a method for manufacturing the antireflection film. <P>SOLUTION: This antireflection film is equipped with a substrate and an antireflection layer. The antireflection layer is formed by curing a resin composition including: a first modified silicon compound having an acrylic or methacrylic group on at least one of both terminals thereof, and having a weight-average molecular weight of 8,000 or more; a second modified silicon compound having an acrylic or methacrylic group on a side chain thereof; a hollow or porous particle; and an ionizing radiation-curable resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition, an antireflection film, a display device, and a method for producing an antireflection film. In detail, it is related with the manufacturing method of the resin composition used for display apparatuses, such as a liquid crystal display device, an antireflection film, a display apparatus, and an antireflection film.

  The anti-reflection film is formed on the display surface side of CRT (Cathode Ray Tube) and liquid crystal display devices to prevent the reflection of external light and make the screen easier to see, and to improve the image quality by increasing the contrast. It is used to

  The antireflection film usually has a configuration comprising a transparent substrate serving as a base material / a resin layer for imparting hard coat properties / an antireflective layer having a low refractive index. In such an antireflection film, a high refractive index is required for the hard coat layer and a lower refractive index is required for the antireflection layer from the viewpoint of reflectivity.

  Recently, the antireflection layer is generally formed by wet coating. For example, a method is used in which a coating liquid containing a monomer containing a fluorine atom in its molecular structure is applied to the surface of a support, dried, and then cured by UV irradiation to form an antireflection layer. By incorporating the fluorinated functional group into the cured resin, effects such as improved scratch resistance and antifouling properties and improved appearance defects can be obtained. (For example, refer to Patent Document 1) However, there are concerns about environmental damage and harmfulness to the human body due to the inclusion of fluorine.

JP 2003-329804 A

  Therefore, a technique for adding hollow silica fine particles to a coating material instead of using a fluorine-based material has been proposed. However, if the addition amount of the hollow silica fine particles is increased to reduce the refractive index of the antireflection layer, there arises a problem that the scratch resistance and antifouling property are lowered. Thus, a technique has been proposed in which a modified silicon acrylate is added to a coating material to suppress a decrease in scratch resistance and antifouling property.

  In order to reduce the reflectance of the antireflection layer, a technique for further adding hollow silica fine particles to the coating material in addition to the fluorine-based material has been proposed. Even in this technique, it is considered that the deterioration of the scratch resistance and antifouling property is suppressed by adding a modified silicon acrylate to the coating material.

  However, the modified silicon acrylate has poor compatibility with the coating material (ultraviolet curable resin), and thus many appearance defects such as repellency and bright spots occur.

  Accordingly, an object of the present invention is to suppress the appearance defects due to the addition of modified silicon acrylate, and to have a resin composition having excellent scratch resistance and antifouling properties, an antireflection film, a display device and an antireflection using the same It is providing the manufacturing method of a film.

（Ｒａは、アルキル基、アクリル基またはメタクリル基である。Ｒｂは、アクリル基またはメタクリル基である。ｎは整数である。）

（Ｒｃ〜Ｒｄは、それぞれ独立して、アルキル基、アクリル基またはメタクリル基である。Ｒｅは、アクリル基またはメタクリル基である。ｎ、ｍは整数である。） In order to solve the above-mentioned problems,
The first invention is
A first modified silicon compound comprising at least one compound represented by formula (a) having a weight average molecular weight of 8000 or more;
A second modified silicon compound comprising at least one compound represented by formula (b);
Hollow or porous particles;
A resin composition containing an ionizing radiation curable resin.

(Ra is an alkyl group, an acryl group or a methacryl group. Rb is an acryl group or a methacryl group. N is an integer.)

(Rc to Rd are each independently an alkyl group, an acryl group or a methacryl group. Re is an acryl group or a methacryl group. N and m are integers.)

  In the first invention, preferably, the mass ratio of the first modified silicon compound and the second modified silicon compound (the mass of the first modified silicon compound / the mass of the second modified silicon compound) is 0.05. That's it.

  In the first invention, preferably, the weight average molecular weight of the first modified silicon compound is 8000 or more and 100,000 or less.

  In the first invention, the ionizing radiation curable resin is preferably an ultraviolet curable resin containing a monomer and / or oligomer having an acrylic group or a methacryl group.

  In the first invention, preferably, silsesquioxane having an acrylic group or a methacryl group is further contained, and the ionizing radiation curable resin contains a monomer and / or an oligomer having an acrylic group or a methacryl group.

（Ｒａは、アルキル基、アクリル基またはメタクリル基である。Ｒｂは、アクリル基またはメタクリル基である。ｎは整数である。）

（Ｒｃ〜Ｒｄは、それぞれ独立して、アルキル基、アクリル基またはメタクリル基である。Ｒｅは、アクリル基またはメタクリル基である。ｎ、ｍは整数である。） The second invention is
A method for producing an antireflection film in which an antireflection layer is formed on a substrate,
Antireflection layer,
A first modified silicon compound comprising at least one compound represented by formula (a) having a weight average molecular weight of 8000 or more, and a second modified silicon compound comprising at least one compound represented by formula (b) And applying a resin composition containing hollow particles or porous particles and an ionizing radiation curable resin to form a resin composition layer;
It is a manufacturing method of the anti-reflective film formed with the hardening process which irradiates ionizing radiation with a low oxygen concentration atmosphere with respect to a resin composition.

(Ra is an alkyl group, an acryl group or a methacryl group. Rb is an acryl group or a methacryl group. N is an integer.)

(Rc to Rd are each independently an alkyl group, an acryl group or a methacryl group. Re is an acryl group or a methacryl group. N and m are integers.)

  In the second invention, preferably, the low oxygen concentration atmosphere is 10000 ppm or less.

（Ｒａは、アルキル基、アクリル基またはメタクリル基である。Ｒｂは、アクリル基またはメタクリル基である。ｎは整数である。）

（Ｒｃ〜Ｒｄは、それぞれ独立して、アルキル基、アクリル基またはメタクリル基である。Ｒｅは、アクリル基またはメタクリル基である。ｎ、ｍは整数である。） The third invention is
A substrate and an antireflection layer;
Antireflection layer
A first modified silicon compound comprising at least one compound represented by formula (a) having a weight average molecular weight of 8000 or more, and a second modified silicon compound comprising at least one compound represented by formula (b) And an antireflection film that is formed by curing a resin composition containing hollow particles or porous particles and an ionizing radiation curable resin.

(Ra is an alkyl group, an acryl group or a methacryl group. Rb is an acryl group or a methacryl group. N is an integer.)

(Rc to Rd are each independently an alkyl group, an acryl group or a methacryl group. Re is an acryl group or a methacryl group. N and m are integers.)

（Ｒａは、アルキル基、アクリル基またはメタクリル基である。Ｒｂは、アクリル基またはメタクリル基である。ｎは整数である。）

（Ｒｃ〜Ｒｄは、それぞれ独立して、アルキル基、アクリル基またはメタクリル基である。Ｒｅは、アクリル基またはメタクリル基である。ｎ、ｍは整数である。） The fourth invention is:
A display for displaying an image;
An antireflection layer provided on the display surface side of the display unit,
Antireflection layer
A first modified silicon compound comprising at least one compound represented by formula (a) having a weight average molecular weight of 8000 or more, and a second modified silicon compound comprising at least one compound represented by formula (b) And a display device that is formed by curing a resin composition containing hollow particles or porous particles and an ionizing radiation curable resin.

(Ra is an alkyl group, an acryl group or a methacryl group. Rb is an acryl group or a methacryl group. N is an integer.)

(Rc to Rd are each independently an alkyl group, an acryl group or a methacryl group. Re is an acryl group or a methacryl group. N and m are integers.)

（Ｒａは、アルキル基、アクリル基またはメタクリル基である。Ｒｂは、アクリル基またはメタクリル基である。ｎは整数である。）

（Ｒｃ〜Ｒｄは、それぞれ独立して、アルキル基、アクリル基またはメタクリル基である。Ｒｅは、アクリル基またはメタクリル基である。ｎ、ｍは整数である。） The fifth invention is:
A display unit having a first surface for displaying an image;
A front surface member having a second surface facing the display surface and a third surface opposite to the second surface, and at least one surface of the first surface, the second surface, and the third surface And an antireflection layer provided on the
Antireflection layer
A first modified silicon compound comprising at least one compound represented by formula (a) having a weight average molecular weight of 8000 or more, and a second modified silicon compound comprising at least one compound represented by formula (b) And a display device that is formed by curing a resin composition containing hollow particles or porous particles and an ionizing radiation curable resin.

(Ra is an alkyl group, an acryl group or a methacryl group. Rb is an acryl group or a methacryl group. N is an integer.)

(Rc to Rd are each independently an alkyl group, an acryl group or a methacryl group. Re is an acryl group or a methacryl group. N and m are integers.)

  In the first to fifth inventions, the first modified silicon compound comprising at least one compound represented by the formula (a) having a weight average molecular weight of 8000 or more and at least one compound represented by the formula (b) By forming the antireflection layer using the resin composition containing the second modified silicon compound composed of seeds, it is possible to have excellent scratch resistance and antifouling properties and reduce appearance defects.

  In the first to fifth inventions, the first modified silicon compound represented by the formula (a) having a weight average molecular weight of 8000 or more can impart scratch resistance and antifouling property. The second modified silicon compound represented by the formula (b) improves the compatibility between the first modified silicon compound represented by the formula (a) and an ionizing radiation curable resin such as an ultraviolet curable resin. can do. Therefore, generation of repellency and bright spots can be suppressed.

  According to this invention, it has the effect that it has the outstanding abrasion resistance and antifouling property, and can reduce an external appearance fault.

It is a schematic sectional drawing which shows an example of a structure of the antireflection film by the 2nd Embodiment of this invention. It is a schematic sectional drawing which shows an example of a structure of the liquid crystal display device by 3rd Embodiment of this invention. It is a schematic sectional drawing which shows an example of a structure of the liquid crystal display device by 4th Embodiment of this invention.

Embodiments of the present invention will be described below with reference to the drawings.
The embodiments described below are specific examples of the present invention, and various technically preferable limitations are given. However, the scope of the present invention is particularly limited in the following description. Unless stated to the effect, the present invention is not limited to the embodiment. The description will be given in the following order.
1. 1st Embodiment (resin composition)
2. Second Embodiment (Antireflection Film)
3. Third embodiment (display device)
4). Fourth embodiment (display device)

1. First Embodiment A resin composition according to a first embodiment of the present invention will be described.

  The resin composition according to the first embodiment of the present invention is suitable, for example, for forming an antireflection layer on a hard coat layer provided on a transparent support. This resin composition has an ionizing radiation curable resin, a first modified silicon compound and a second modified silicon compound, and hollow silica fine particles.

[Ionizing radiation curable resin]
The ionizing radiation curable resin is a material that is cured by light or an electron beam. The ionizing radiation curable resin is not particularly limited, and can be appropriately selected from conventionally known ones. The ionizing radiation curable resin contains, for example, an ionizing radiation polymerizable monomer, an ionizing radiation polymerizable oligomer, an ionizing radiation polymerizable polymer, an ionizing radiation polymerization initiator, and the like. The ionizing radiation curable resin is, for example, a radical polymerization type ultraviolet curable resin having an acryl group or a methacryl group. The ultraviolet curable resin contains, for example, a monomer and / or oligomer having an acryl group or a methacryl group and a photopolymerization initiator. From the viewpoint of ease of production, an ultraviolet curable resin is most preferable. From the viewpoint of scratch resistance, the ultraviolet curable resin preferably contains 80% or more, and most preferably 90% or more, of a photopolymerizable polyfunctional monomer, a photopolymerizable oligomer, and a photopolymerizable polymer. As a polyfunctional monomer, for example, an ester of a polyhydric alcohol and (meth) acrylic acid, specifically, for example, ethylene glycol di (meth) acrylate, 1,4-dicyclohexanediacrylate, pentaerythritol tetra (meth) Acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, 1,2,3-cyclohexanetetramethacrylate and the like can be mentioned. Examples of the photopolymerizable oligomer and photopolymerizable polymer include urethane acrylate, polyol acrylate, polyester acrylate, and epoxy acrylate. From the viewpoint of a low refractive index, it preferably contains a fluorine-containing acrylic monomer, a fluorine-containing acrylic oligomer, and a fluorine-containing acrylic polymer.

[Modified silicon compound]
The first modified silicon compound is at least one modified silicon compound represented by the formula (a).

（Ｒａは、アルキル基（１≦炭素数≦１６）、アクリル基またはメタクリル基である。Ｒｂはアクリル基またはメタクリル基である。ｎは整数であり、例えば１００≦ｎ≦１５００、好ましくは１５０≦ｎ≦１３００である。）

(Ra is an alkyl group (1 ≦ carbon number ≦ 16), an acrylic group or a methacryl group. Rb is an acrylic group or a methacryl group. N is an integer, for example, 100 ≦ n ≦ 1500, preferably 150 ≦. n ≦ 1300.)

  The first modified silicon compound has an acrylic group or a methacryl group at one end, or has an acrylic group or a methacryl group at both ends. The weight average molecular weight of the first modified silicon compound is 8000 or more, for example, 8000 or more and 100,000 or less. When the weight average molecular weight is less than 8000, the effects of scratch resistance and antifouling tend to be reduced. In addition, a weight average molecular weight is measured by gel permeation chromatography (GPC: Gel Permeation Chromatography) analysis in carrier solvent: THF and polystyrene conversion.

  The second modified silicon compound is at least one modified silicon compound represented by the formula (b).

（Ｒｃ〜Ｒｄは、それぞれ独立して、アルキル基（１≦炭素数≦１６）、アクリル基またはメタクリル基である。Ｒｅはアクリル基またはメタクリル基である。ｎ、ｍは整数である。ｎは、例えば３≦ｎ≦１００、好ましくは９≦ｎ≦５０である。ｍ、例えばｍ≦１５０、好ましくはｍ≦１００である。）

(Rc to Rd are each independently an alkyl group (1 ≦ carbon number ≦ 16), an acrylic group or a methacryl group. Re is an acrylic group or a methacryl group. N and m are integers. For example, 3 ≦ n ≦ 100, preferably 9 ≦ n ≦ 50. M, for example, m ≦ 150, preferably m ≦ 100.

  The second modified silicon compound has an acryl group or a methacryl group in the side chain. It may or may not have an acrylic or methacrylic group at the end. The weight average molecular weight of the second modified silicon compound is not particularly limited, but is, for example, 1000 or more and 50000 or less.

  The content of the first modified silicon compound is, for example, not less than 0.1 wt% and not more than 3.0 wt%. If it is less than 0.1 wt%, functions such as scratch resistance and antifouling properties will be reduced, and if it exceeds 3.0 wt%, the functions of scratch resistance will be reduced. The content of the second modified silicon compound is, for example, 0.005 wt% or more and 2.97 wt% or less. If it is less than 0.005 wt%, appearance defects such as repellency and bright spots frequently occur, and if it exceeds 2.97 wt%, functions such as scratch resistance and antifouling properties are deteriorated.

  The mass ratio of the first modified silicon compound and the second modified silicon compound (the mass of the second modified silicon compound / the mass of the first modified silicon compound) is, for example, 0.05 to 0.99. When it is less than 0.05, appearance defects such as repellency and bright spots frequently occur, and when it exceeds 0.99, functions such as scratch resistance and antifouling properties are deteriorated.

The amount of the side chain functional group of the modified silicone compound is calculated from an integral curve of 1H-NMR (proton NMR) obtained by a nuclear magnetic resonance measuring apparatus (NMR). By 1H-NMR, the ratio of the integral curve of H bonded to silicon having a siloxane structure via C (for example, H of Si— (CH ₃ ) ₂ ) and the integral curve of C = CH ₂ of the functional group is obtained. . Since the chemical formula of the siloxane structure and the chemical formula of the functional group are known in advance, the ratio of the number of Si— (CH ₃ ) ₂ of the siloxane structure and the number of C═CH ₂ of the functional group is included in the measurement sample. The ratio (B / A) of the number A of siloxane structures having a — (CH ₃ ) ₂ bond and the number B of functional groups is known.
For example, paying attention to polydimethylsiloxane (chemical shift around Si—CH ₃ : 0 ppm), methacryl group (C = CH ₂ : chemical shift around 4 to 7 ppm), etc., present from the ratio of each obtained integral value The ratio can be calculated.

  The ionizing radiation curable resin preferably contains a fluorine-containing acrylic compound from the viewpoint of reducing the reflectance. In this case, the content of the fluorine-containing acrylic compound is preferably 10 wt% or more and 60 wt% or less with respect to the solid content of the resin composition. If it is less than 10 wt%, the reflectance tends to be extremely high. On the other hand, if it exceeds 60 wt%, a problem occurs in the coatability and an abnormality is likely to occur in the appearance after coating. Here, the acrylic compound is acrylate or methacrylate.

  The ionizing radiation curable resin preferably further contains an acrylic compound having three or more of at least one of an acrylic group and a methacryl group from the viewpoint of improving the antifouling property and scratch resistance. The surface tension of the acrylic compound is preferably 40 mN / m or more, more preferably 40 mN / m or more and 45 mN / m or less. The content of the acrylic compound with respect to the entire solid content of the resin composition is preferably 5 wt% or more and 18 wt% or less. When the number of at least one of the acryl group and the methacryl group is less than 3, the scratch resistance tends to be lowered. When the surface tension is less than 40 mN / m, the antifouling property and scratch resistance tend to be reduced, and when the surface tension exceeds 45 mN / m, the coating liquid tends to become cloudy. When the content of the acrylic compound is less than 5 wt%, the antifouling property and the scratch resistance tend to decrease, and when the content of the acrylic compound exceeds 18 wt%, the scratch resistance tends to decrease.

[Hollow silica fine particles]
The hollow silica fine particles are silica fine particles having a hollow inside. Moreover, the inside may be porous. When the gas is air having a refractive index of 1.0, the refractive index decreases in proportion to the occupation ratio of air in the fine particles as compared with the original refractive index of the fine particles. The refractive index of the hollow silica fine particles is, for example, 1.45 or less, but is not particularly limited. The average particle diameter of the hollow fine particles is, for example, 10 nm to 200 nm. As fine particles, porous silica fine particles may be used instead of the hollow silica fine particles. Further, as the fine particles, both hollow silica fine particles and porous silica fine particles may be used.

[Others]
You may add additives, such as a light stabilizer, a ultraviolet absorber, an antistatic agent, a flame retardant, and antioxidant, as needed. Further, if necessary, the ionizing radiation curable resin may be diluted with a solvent and used. In order to obtain excellent scratch resistance, an organic-inorganic hybrid material or the like may be used in combination.

For example, silsesquioxane can be used as the organic-inorganic hybrid material. Silsesquioxane is represented, for example, by a compositional formula [(RSiO _3/2 ) _n ] (R is an ultraviolet curable functional group, for example, an acryl group, a methacryl group, a vinyl group, etc.). Can be used. As the silsesquioxane, for example, a random structure, a complete cage structure, a ladder structure, or an incomplete cage structure can be used. Those having these structures can be used alone or in combination. The silsesquioxane preferably has at least one of an acrylic group and a methacrylic group as the organic functional group. By having such a functional group, it is bonded to an ultraviolet curable resin having an acryl group or a methacryl group, or a first or second modified silicon having an acryl group or a methacryl group, thereby forming a crosslinked structure or the like. Because it can be done. The content of silsesquioxane is preferably 6 wt% or more and 46 wt% or less, more preferably 12 wt% or more and 46 wt% or less. When it is 6 wt% or more, the scratch resistance of the antireflection layer 13 can be improved. When the content is 46 wt% or less, when the ionizing radiation curable resin containing an acrylate having a fluorine group is used, a decrease in the reflectance of the antireflection layer 13 can be suppressed. Moreover, it is preferable that silsesquioxane further has a perfluoroalkyl group from the point of the improvement of a reflective characteristic. In order to improve the scratch resistance, silsesquioxane nanofillers may be used. In this case, as the silsesquioxane, those having no functional group such as an acryl group or a methacryl group may be used.

  By using the resin composition according to the first embodiment of the present invention described above, an antireflection layer in an antireflection film described later can be formed. The antireflection film produced using this resin composition has excellent scratch resistance and antifouling properties, and can reduce appearance defects.

2. Second Embodiment An antireflection film according to a second embodiment of the present invention will be described.

  FIG. 1 shows an example of the configuration of an antireflection film according to the second embodiment of the present invention. As shown in FIG. 1, the antireflection film includes a base material 11, a hard coat layer 12 provided on the base material 11, and an antireflection layer 13 provided on the hard coat layer 12. Yes. In addition, the structure of an antireflection film is not limited to said structure. For example, a functional layer such as an antistatic layer, a high refractive index layer, an antiglare layer, or the like between at least one of the base material 11 and the hard coat layer 12 and between the hard coat layer 12 and the antireflection layer 13. It is good also as a structure which provided.

[Base material]
As a material of the base material 11, for example, a plastic film having transparency can be used. As a material for the transparent plastic film, for example, a known polymer film can be used. Specific examples of the known polymer film include triacetyl cellulose (TAC), polyester (TPEE), polyethylene terephthalate (PET), polyimide (PI), polyamide (PA), aramid, polyethylene (PE), poly Examples include acrylate (PAR), polyether sulfone, polysulfone, polypropylene (PP), diacetyl cellulose, polyvinyl chloride, acrylic resin (PMMA), polycarbonate (PC), epoxy resin, urea resin, urethane resin, and melamine resin. . The thickness of the substrate 11 is preferably 20 μm to 200 μm from the viewpoint of productivity, but is not particularly limited to this range.

[Hard coat layer]
The hard coat layer 12 improves the strength of the antireflection film. For example, a relatively hard material such as a melanin resin, an alkyd resin, an acrylic resin, a silicon resin, or a urethane resin is used. Silica gel, resin beads, and the like may be dispersed in the hard coat layer to scatter light and thereby impart antiglare properties. Fine particles made of a metal oxide or the like may be dispersed in the hard coat layer 12 to impart a high refractive index. In addition, a conductive material such as metal oxide fine particles, an antistatic resin, or a conductive polymer may be dispersed in the hard coat layer 12 to impart an antistatic function.

[Antireflection layer]
The antireflection layer 13 is a low refractive index layer having a refractive index lower than that of the hard coat layer 12. The antireflection film has an antireflection function by providing a layer having a different refractive index on the surface of the substrate 11 to reduce reflected light. Although details will be described later, the antireflection layer 13 can be formed using the resin composition according to the first embodiment.

[Method for producing antireflection film]
The antireflection film according to the second embodiment of the present invention can be manufactured, for example, as follows.

(Hard coat layer)
First, the hard coat layer 12 is formed on the substrate 11. The hard coat layer 12 can be formed by appropriately applying known techniques.

(Antireflection layer)
Next, an antireflection layer 13 is formed on the hard coat layer 12 as described below.

(Paint preparation)
First, the silica hollow fine particles, the ionizing radiation curable resin, the first modified silicon compound, the second silicon compound, and the solvent are mixed using a stirrer such as a disperser or a disperser such as a bead mill to prepare a paint. Moreover, you may make it add additives, such as a light stabilizer, a ultraviolet absorber, an antistatic agent, a flame retardant, and antioxidant, as needed.

  The solvent is not particularly limited, and various organic solvents, for example, alcohols such as isopropyl alcohol, methanol, ethanol, n-butanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, etc. Esters, aromatic hydrocarbons such as halogenated hydrocarbons, toluene, or xylene, or mixtures thereof can be used.

(Coating)
Next, the coating material prepared as described above is applied onto the hard coat layer 12. Examples of the coating method include a gravure coater, a bar coater, a die coater, a knife coater, a comma coater, a spray coater, and a curtain coater. In addition, the coating method is not limited to the said method, What kind of thing may be sufficient as long as predetermined thickness can be apply | coated uniformly.

(Dry)
Next, the paint applied on the hard coat layer 12 is dried. The drying conditions are not particularly limited, and may be natural drying or artificial drying that adjusts a drying temperature, a drying time, and the like.

(Curing)
Next, the resin composition dried on the hard coat layer 12 is cured by irradiation with ionizing radiation. Thereby, the antireflection layer 13 is formed.

  As the ionizing radiation, for example, an electron beam, an ultraviolet ray, a visible ray, a gamma ray, an electron beam or the like can be used, and an ultraviolet ray is preferable from the viewpoint of production equipment. As the ultraviolet ray source, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, or the like can be used. The integrated irradiation dose is preferably selected as appropriate in consideration of the curing characteristics of the resin, suppression of yellowing of the resin and the substrate 11, and the like. Moreover, the atmosphere of irradiation includes the atmosphere of inert gas, such as air, nitrogen, and argon, for example. The irradiation atmosphere is preferably a low oxygen concentration atmosphere having an oxygen concentration of 10,000 ppm or less, for example, from the viewpoint of suppressing reaction inhibition by oxygen.

  In the antireflection film according to the second embodiment of the present invention, the antireflection layer 13 is formed by using the resin composition according to the first embodiment, so that it has excellent scratch resistance and antifouling. The appearance defect can be reduced.

  The antireflection film according to the second embodiment of the present invention can be used by arranging it on the outermost surface of the display by providing an adhesive layer on one side. When the substrate is triacetyl cellulose, triacetyl cellulose is used as a protective film for protecting the polarizing layer of the polarizer. Therefore, the antireflection film according to the second embodiment of the present invention is used as it is as a protective film. be able to.

3. Third Embodiment A display device according to a third embodiment of the present invention will be described.
[Configuration of liquid crystal display device]
FIG. 2 shows an example of the configuration of a liquid crystal display device according to the third embodiment of the present invention. As shown in FIG. 2, the liquid crystal display device includes a backlight 3 that emits light, and a liquid crystal panel 2 that displays an image by temporally and spatially modulating the light emitted from the backlight 3. Polarizers 2a and 2b are provided on both surfaces of the liquid crystal panel 2, respectively. A polarizer 2b provided on the display surface side of the liquid crystal panel 2 is provided with an antireflection film 1 according to the second embodiment of the present invention.

  As the backlight 3, for example, a direct type backlight, an edge type backlight, or a flat light source type backlight can be used. The backlight 3 includes, for example, a light source, a reflecting plate, an optical film, and the like. Examples of the light source include a cold cathode fluorescent lamp (CCFL), a hot cathode fluorescent lamp (HCFL), an organic electroluminescence (OEL), and a light emitting diode (LED). ) Etc. are used.

  Examples of the liquid crystal panel 2 include a twisted nematic (TN) mode, a super twisted nematic (STN) mode, a vertically aligned (VA) mode, and a horizontal alignment (In-Plane Switching: IPS). Mode, Optically Compensated Birefringence (OCB) mode, Ferroelectric Liquid Crystal (FLC) mode, Polymer Dispersed Liquid Crystal (PDLC) mode, Phase Transition Guest Host (Phase) A display mode such as Change Guest Host (PCGH) mode can be used.

  For example, polarizers 2a and 2b are provided on both surfaces of the liquid crystal panel 2 so that their transmission axes are orthogonal to each other. The polarizers 2a and 2b allow only one of orthogonally polarized components of incident light to pass through and shield the other by absorption. Examples of the polarizers 2a and 2b include hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, ethylene / vinyl acetate copolymer partially saponified films, iodine, dichroic dyes, and the like. Those obtained by adsorbing the dichroic material and uniaxially stretching can be used.

4). Fourth Embodiment A display device according to a fourth embodiment of the present invention will be described.
[Configuration of liquid crystal display device]
FIG. 3 shows an example of the configuration of the liquid crystal display device according to the fourth embodiment of the present invention. The liquid crystal display device includes a liquid crystal panel 2 and a front member 4 disposed on the front side of the liquid crystal panel 2, and at least one of the liquid crystal panel 2 and the front member 4 includes an antireflection film 1. It differs from that of the embodiment. The liquid crystal panel 2 has a front surface (first surface) on which an image is displayed, and the front member 4 has a back surface (second surface) facing the front surface of the liquid crystal panel 2 and a side opposite to the back surface. And a front surface (third surface). The antireflection film 1 is provided on at least one of the front surface of the liquid crystal panel 2, the back surface of the front member 4, and the front surface of the front member 4. FIG. 3 shows an example in which the antireflection film 1 is provided on all surfaces of the front surface of the liquid crystal panel 2, the back surface of the front member 4, and the front surface of the front member 4. For example, an air layer is formed between the liquid crystal panel 2 and the front member 4. The same parts as those in the third embodiment described above are denoted by the same reference numerals and description thereof is omitted. In the present invention, the front surface refers to the surface on the side serving as the display surface, that is, the surface on the viewer side, and the back surface refers to the surface on the side opposite to the display surface.

  The front member 4 is a front panel or the like that is used for the purpose of providing mechanical, thermal, or weather resistance protection or design for the front surface (observer side) of the liquid crystal panel 2. The front member 4 has, for example, a sheet shape, a film shape, or a plate shape. Examples of the material of the front member 4 include glass, triacetyl cellulose (TAC), polyester (TPEE), polyethylene terephthalate (PET), polyimide (PI), polyamide (PA), aramid, polyethylene (PE), polyacrylate, Polyether sulfone, polysulfone, polypropylene (PP), diacetyl cellulose, polyvinyl chloride, acrylic resin (PMMA), polycarbonate (PC), and the like can be used, but the material is not particularly limited and is transparent. Any material having a property can be used.

  Specific embodiments of the present invention will be described in detail. However, the present invention is not limited to these examples. In the examples and comparative examples described below, the following modified silicon acrylate compounds A to H (hereinafter referred to as compounds A to H) were used for examination.

Compound A
Modified silicone acrylate compound (trade name 2426, manufactured by Shin-Etsu Silicone)
Weight average molecular weight: 15000
One end: Methacrylic group

Compound B
Modified silicone acrylate compound (trade name 164E manufactured by Shin-Etsu Silicone)
Weight average molecular weight: 12000
Both ends: Methacrylic group

Compound C
Modified silicone acrylate compound (trade name 164C, manufactured by Shin-Etsu Silicone)
Weight average molecular weight: 8000
Both ends: Methacrylic group

Compound D
Modified silicone acrylate compound (trade name 164B, manufactured by Shin-Etsu Silicone)
Weight average molecular weight: 5500
Both ends: Methacrylic group

Compound E
Modified silicone acrylate compound (trade name 1603, manufactured by Shin-Etsu Silicone)
Weight average molecular weight: 3000
Both ends: Acrylic group

Compound F
Modified silicone acrylate compound (trade name 164A manufactured by Shin-Etsu Silicone)
Weight average molecular weight: 2000
Both ends: Methacrylic group

Compound G
Modified silicone acrylate compound (trade name 2457 manufactured by Shin-Etsu Silicone)
Weight average molecular weight: 13000
Both ends: Acrylic group, side chain: Acrylic group

Compound H
Modified silicone acrylate compound (trade name 2459 manufactured by Shin-Etsu Silicone)
Weight average molecular weight: 25000
Side chain: Acrylic group

In addition, the said molecular weight is a weight average molecular weight calculated | required with the following measuring methods.
Analysis name: GPC analysis (gel permeation chromatography)
Analyzer: Shodex GPC SYSTEM21
Detector: RI detector Column temperature: 40 ° C
Carrier solvent: THF
Flow rate: 1 ml / min
Measurement method: 0.5% diluted as solid content of the measurement sample with THF, this solution is measured by column separation using an RI detector, and molecular weight distribution based on a calibration curve prepared with a standard polystyrene sample Measurements were made.

<Example 1>
As the substrate, a TAC film having a thickness of 80 μm was used. After forming a hard coat layer on this substrate, an antireflection layer was formed on the hard coat layer to obtain an antireflection film of Example 1.

[Formation of hard coat layer]
The hard coat layer was formed as follows.
Dipentaerythritol hexaacrylate, isocyanuric acid EO-modified diacrylate, dimethylol tricyclodecane diacrylate, antimony pentoxide, initiator (1-hydroxy-cyclohexyl-phenyl-ketone) are solidified in isopropyl alcohol as a solvent. The solution was dissolved so as to be 40% by weight to prepare a coating solution for the hard coat layer. In addition, solid content is substances other than the solvent in a coating liquid, and here is photopolymerizable prepolymers, such as dipentaerythritol hexaacrylate, antimony pentoxide, and an initiator. This hard coat layer coating solution is applied to the surface of a triacetylcellulose film (film thickness of 80 μm), which is a transparent substrate, by a gravure method so as to have a dry film thickness of 2 μm, and dried in an 80 ° C. oven for 1 minute and 30 seconds. It was. Then, it hardened by irradiating with a 160W high pressure mercury lamp for 3 seconds from the distance of 18 cm, and the hard-coat layer was formed.

[Formation of antireflection layer]
The antireflection layer was formed as follows.
A matrix was prepared by mixing 8 wt% of polyester acrylate oligomer, 35 wt% of pentaerythritol tetraacrylate, and 57 wt% of polyethylene glycol diacrylate. 60 wt% of hollow silica sol having an average particle diameter of 60 nm, 8 wt% of initiator (1-hydroxy-cyclohexyl-phenyl-ketone), 1.2 wt% of modified silicon acrylate compound B as a modified silicon acrylate compound, 30.5 wt% of this matrix Then, 0.3 wt% of the modified silicon acrylate compound G was added. This produced the low refractive index coating agent. Then, the coating solution which adjusted the solid content to 3.0 wt% using n-butanol as a solvent was obtained.

  This coating solution was applied onto the hard-coated layer subjected to the surface treatment using a small-diameter gravure method so as to have a dry film thickness of 100 nm, and dried in an oven set at 80 ° C. for 1 minute and 30 seconds. Thereafter, an antireflection layer was formed by irradiating a 160 W high pressure mercury lamp from a distance of 18 cm for 3 seconds in a nitrogen atmosphere with an oxygen concentration of 1000 ppm.

<Example 2>
An antireflection film was obtained in the same manner as in Example 1 except that 1.2 wt% of Compound B and 0.3 wt% of Compound H were added as the modified silicon acrylate compound.

<Example 3>
An antireflection film was obtained in the same manner as in Example 1 except that 1.2 wt% of compound A, 0.3 wt% of compound G, and 0.3 wt% of compound H were added as the modified silicon acrylate compound.

<Example 4>
An antireflection film was obtained in the same manner as in Example 1 except that 1.2 wt% of Compound C and 0.3 wt% of Compound G were added as the modified silicon acrylate compound.

<Example 5>
An antireflection film was obtained in the same manner as in Example 1 except that 1.2 wt% of Compound B and 0.1 wt% of Compound G were added as the modified silicon acrylate compound.

<Example 6>
An antireflection film was obtained in the same manner as in Example 1 except that 3.0 wt% of Compound B, 0.3 wt% of Compound G, and 0.3 wt% of Compound H were added as the modified silicon acrylate compound.

<Example 7>
In the antireflection layer forming step, an antireflection film was obtained in the same manner as in Example 1 except that the oxygen concentration in the nitrogen atmosphere was 10000 ppm.

<Comparative Example 1>
No modified silicon acrylate compound was added. In the formation process of the antireflection layer, the oxygen concentration in the nitrogen atmosphere was set to 50000 ppm. Except for the above, an antireflection film was obtained in the same manner as in Example 1.

<Comparative example 2>
An antireflection film was obtained in the same manner as in Example 1 except that 1.5 wt% of Compound A was added as a modified silicon acrylate compound.

<Comparative Example 3>
An antireflection film was obtained in the same manner as in Example 1 except that 1.2 wt% of Compound A was added as a modified silicon acrylate compound.

<Comparative example 4>
An antireflection film was obtained in the same manner as in Example 1 except that 1.0 wt% of compound A was added as a modified silicon acrylate compound.

<Comparative Example 5>
An antireflection film was obtained in the same manner as in Example 1 except that 1.5 wt% of Compound B was added as a modified silicon acrylate compound.

<Comparative Example 6>
An antireflection film was obtained in the same manner as in Example 1 except that 1.2 wt% of Compound B was added as a modified silicon acrylate compound.

<Comparative Example 7>
An antireflection film was obtained in the same manner as in Example 1, except that 1.0 wt% of Compound B was added as a modified silicon acrylate compound.

<Comparative Example 8>
An antireflection film was obtained in the same manner as in Example 1, except that 1.2 wt% of Compound B and 0.3 wt% of Compound E were added as the modified silicon acrylate compound.

<Comparative Example 9>
An antireflection film was obtained in the same manner as in Example 1 except that 1.2 wt% of compound B and 0.3 wt% of compound D were added as the modified silicon acrylate compound.

<Comparative Example 10>
An antireflection film was obtained in the same manner as in Example 1 except that 1.2 wt% of Compound E was added as a modified silicon acrylate compound.

<Comparative Example 11>
An antireflection film was obtained in the same manner as in Example 1 except that 1.5 wt% of Compound H was added as a modified silicon acrylate compound.

<Comparative Example 12>
An antireflection film was obtained in the same manner as in Example 1 except that 1.2 wt% of Compound H was added as a modified silicon acrylate compound.

<Comparative Example 13>
An antireflection film was obtained in the same manner as in Example 1 except that 1.0 wt% of Compound H was added as a modified silicon acrylate compound.

<Comparative example 14>
An antireflection film was obtained in the same manner as in Example 1 except that 0.3 wt% of the compound D, 1.2 wt% of the compound G, and 1.0 wt% of the compound H were added as the modified silicon acrylate compound.

<Comparative Example 15>
As modified silicon acrylate compounds, 1.2 wt% of compound B and 0.3 wt% of compound G were added. In the formation process of the antireflection layer, the oxygen concentration in the nitrogen atmosphere was set to 50000 ppm. Except for the above, an antireflection film was obtained in the same manner as in Example 1.

[Characteristic evaluation]
The manufactured Examples 1 to 7 and Comparative Examples 1 to 15 were used as samples, and the following characteristics evaluation was performed for each.

[SW: Steel wool scratch resistance test]
A rubbing test was performed using a rubbing tester under the following conditions.
Evaluation environmental condition 23 ° C, 55% RH
Rubbing material: Steel wool was wound around the rubbing tip of a tester in contact with the sample, and the band was fixed so as not to move.
Movement distance (one way): 5 cm, rubbing speed: 10 cm / sec, load: 400 g / cm ² , tip contact area: 1 cm × 1 cm, number of rubbing: 10 reciprocations Apply the back side oily black ink of the sample after rubbing, with reflected light By visually observing, scratches on the rubbing portion were evaluated according to the following criteria.
A: No scratch.
○: Several weak scratches can be confirmed. ×: Strong scratches can be confirmed.

[Anti-fouling]
Using magic ink (ZEBRA Co., Ltd., Mackie extra fine: oily), a 1 cm diameter circle was drawn on the sample and painted, and whether or not the ink repelled was visually observed. Further, after 30 seconds, rubbing with Bencot M-3 (Asahi Kasei Co., Ltd.), it was visually observed whether the ink was wiped off.
The antifouling property was evaluated according to the following criteria.
A: The ink repels and can be wiped off.
○: The ink does not repel but can be wiped off.
X: The ink cannot be wiped off.

[Chemical resistance]
The state of the sample after being immersed in a 1% aqueous sodium hydroxide solution for 30 minutes was visually observed and evaluated according to the following criteria.
A: No trace is left.
○: Some marks remain.
X: The film is peeled off.

[Repel]
Black tape (Nichiban Co., Ltd. VT-50) was attached to the back surface of a 10 cm × 10 cm sample, and the number of repels was confirmed by visual observation.

  The measurement results are shown in Table 1.

  In Examples 1 to 7, the modified silicon compound represented by the formula (a) having a functional group (methacrylic group or acrylic group) only at the terminal and a functional group (methacrylic group or acrylic group) in the side chain. Both the modified silicon compound represented by the formula (b) are used. For this reason, good characteristics were obtained in all evaluations.

  From Comparative Example 1 to Comparative Example 9, it can be seen that the modified silicon compound represented by the formula (a) having a functional group only at the terminal does not provide good characteristics even when used alone or in combination. It was. Further, it was found that the modified silicon compound represented by the formula (a) having a functional group only at the terminal cannot obtain good characteristics even when the molecular weight is changed or the addition amount is changed.

  From Comparative Example 10, it can be seen that even with the modified silicon compound represented by the formula (a) having a functional group only at the terminal, repelling does not occur if the molecular weight is low, but the scratch resistance and antifouling property are not good. It was.

  From Comparative Example 11 to Comparative Example 13, it was found that the modified silicon compound represented by the formula (b) having a functional group in the side chain alone was not good in scratch resistance.

  From Comparative Example 14, when the weight average molecular weight is smaller than 8000, the modified silicon compound represented by the formula (a) may be used in combination with the modified silicon compound represented by the formula (b) having a functional group in the side chain. It was found that the scratch resistance was not good.

  From Comparative Example 15, it was found that when the oxygen concentration was high in the antireflection layer forming step, the scratch resistance and alkali resistance were not good.

<Example 8>
First, as in Example 1, a TAC film having a thickness of 80 μm was prepared. Next, a hard coat layer was formed on the TAC film in the same manner as in Example 1.

An antireflection layer was formed as follows.
First, a low refractive index coating agent having the following composition was prepared.
Acrylic oligomer having fluorine group 60.5wt%
(Product name AR110, manufactured by Daikin Industries, Ltd.)
Hollow silica sol with an average particle size of 60 nm 35 wt%
1-hydroxy-cyclohexyl-phenyl-ketone (initiator) 3 wt%
Modified silicon acrylate compound B 1.2 wt%
(Product name 164E, manufactured by Shin-Etsu Silicon)
Modified silicon acrylate compound G 0.3wt%
(Product name 2457 manufactured by Shin-Etsu Silicon)

  Next, the low refractive index coating agent was dissolved in n-butanol as a solvent at a solid content of 1.25 wt% to obtain a coating solution. Next, using a small diameter gravure method, the coating solution was applied on the hard coat layer so as to have a dry film thickness of 120 nm. Next, after drying the coating solution in an oven at a temperature of 80 ° C. for 1 minute 30 seconds, a 160 W high-pressure mercury lamp is irradiated for 3 seconds from a distance of 18 cm in a nitrogen atmosphere having an oxygen concentration of 1000 ppm, thereby providing an antireflection layer. Formed. Thus, an antireflection film was obtained.

<Example 9>
An antireflection film was obtained in the same manner as in Example 8 except that a low refractive index coating agent having the following composition was used.
Acrylate oligomer having a fluorine group 59.5 wt%
(Product name AR110, manufactured by Daikin Industries, Ltd.)
Acrylic modified silsesquioxane 1wt%
(Product name ACSQ manufactured by Toa Gosei Co., Ltd.)
Hollow silica sol with an average particle size of 60 nm 35 wt%
1-hydroxy-cyclohexyl-phenyl-ketone (initiator) 3 wt%
Modified silicon acrylate compound B 1.2 wt%
(Product name 164E, manufactured by Shin-Etsu Silicon)
Modified silicon acrylate compound G 0.3wt%
(Product name 2457 manufactured by Shin-Etsu Silicon)

<Example 10>
An antireflection film was obtained in the same manner as in Example 9 except that 57.5 wt% of the acrylate oligomer having a fluorine group and 3 wt% of acryl-modified silsesquioxane were used.

<Example 11>
An antireflection film was obtained in the same manner as in Example 9, except that the acrylate oligomer having a fluorine group was 54.5 wt% and the acrylic modified silsesquioxane was 6 wt%.

<Example 12>
An antireflection film was obtained in the same manner as in Example 9 except that 48.5 wt% of the acrylate oligomer having a fluorine group and 12 wt% of the acrylic modified silsesquioxane were used.

<Example 13>
An antireflection film was obtained in the same manner as in Example 9 except that 42.5 wt% of the acrylate oligomer having a fluorine group and 18 wt% of the acrylic-modified silsesquioxane were used.

<Example 14>
An antireflection film was obtained in the same manner as in Example 9 except that 36.5 wt% of the acrylate oligomer having a fluorine group and 24 wt% of the acrylic modified silsesquioxane were used.

<Example 15>
An antireflection film was obtained in the same manner as in Example 9 except that 30.5 wt% of the acrylate oligomer having a fluorine group and 30 wt% of the acrylic-modified silsesquioxane were used.

<Example 16>
An antireflection film was obtained in the same manner as in Example 9 except that 14.9 wt% of the acrylate oligomer having a fluorine group and 45.6 wt% of the acryl-modified silsesquioxane were used.

<Example 17>
An antireflection film was obtained in the same manner as in Example 9 except that the acrylate oligomer having a fluorine group was 0 wt% and the acrylic modified silsesquioxane was 60.5 wt%.

<Example 18>
An antireflection film was obtained in the same manner as in Example 11 except that 6 wt% of pentaerythritol triacrylate was used instead of 6 wt% of the acrylic-modified silsesquioxane.

<Example 19>
An antireflection film was obtained in the same manner as in Example 11 except that 6 wt% of dipentaerythritol hexaacrylate was used in place of 6 wt% of the acrylic-modified silsesquioxane.

<Example 20>
An antireflection film was obtained in the same manner as in Example 11 except that 6 wt% of polyurethane acrylate oligomer was used instead of 6 wt% of acrylic-modified silsesquioxane.

<Example 21>
An antireflection film was obtained in the same manner as in Example 12 except that 12 wt% of pentaerythritol triacrylate was used instead of 12 wt% of the acrylic-modified silsesquioxane.

<Example 22>
An antireflection film was obtained in the same manner as in Example 12 except that 12 wt% of dipentaerythritol hexaacrylate was used instead of 12 wt% of the acrylic-modified silsesquioxane.

<Example 23>
An antireflection film was obtained in the same manner as in Example 12 except that 12 wt% of the polyurethane acrylate oligomer was used instead of 12 wt% of the acrylic-modified silsesquioxane.

<Example 24>
An antireflection film was obtained in the same manner as in Example 14 except that 24 wt% of pentaerythritol triacrylate was used instead of 24 wt% of the acrylic-modified silsesquioxane.

<Example 25>
An antireflection film was obtained in the same manner as in Example 14 except that 24 wt% of dipentaerythritol hexaacrylate was used instead of 24 wt% of the acrylic-modified silsesquioxane.

<Example 26>
An antireflection film was obtained in the same manner as in Example 14 except that 24 wt% of the polyurethane acrylate oligomer was used instead of 24 wt% of the acrylic-modified silsesquioxane.

<Example 27>
An antireflection film was obtained in the same manner as in Example 18 except that 10.5 wt% of the acrylate oligomer having a fluorine group and 50 wt% of pentaerythritol triacrylate were used.

<Example 28>
An antireflection film was obtained in the same manner as in Example 19 except that 10.5 wt% of the acrylate oligomer having a fluorine group and 50 wt% of dipentaerythritol hexaacrylate were used.

<Example 29>
An antireflection film was obtained in the same manner as in Example 20, except that the acrylate oligomer having a fluorine group was 10.5 wt% and the polyurethane acrylate oligomer was 50 wt%.

<Example 30>
An antireflection film was obtained in the same manner as in Example 8, except that 60.5 wt% of acrylate oligomer having the following composition was used instead of 60.5 wt% of the acrylate oligomer having a fluorine group.
Polyester acrylate oligomer 8wt%
Pentaerythritol tetraacrylate 35wt%
Polyethylene glycol diacrylate 57wt%

(Example 31)
An antireflection film was obtained in the same manner as in Example 16 except that 14.9 wt% of the acrylate oligomer having a fluorine group and 45.6% of phenyl-modified silsesquioxane (Ph—SQ) were used.

(Example 32)
An antireflection film was obtained in the same manner as in Example 16 except that 14.9 wt% of the acrylate oligomer having a fluorine group and 45.6% of methyl-modified silsesquioxane (Me-SQ) were used.

[Characteristic evaluation]
The produced Examples 8 to 30 were used as samples, and the following characteristic evaluation was performed for each.

[SW: Steel wool scratch resistance test]
A rubbing test was performed using a rubbing tester under the following conditions.
Evaluation environmental condition 23 ° C, 55% RH
Rubbing material: Steel wool was wound around the rubbing tip of a tester in contact with the sample, and the band was fixed so as not to move.
Moving distance (one way): 5 cm, rubbing speed: 10 cm / sec, load: 400 g / cm ² , 800 g / cm ² , 1 kg / cm ² , tip contact area: 1 cm × 1 cm, number of rubbing: 10 samples rubbed An oily black ink was applied to the back side of the film and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
A: No scratch.
○: 5 or less scratches can be confirmed.
X: 6 or more scratches can be confirmed.

[Anti-fouling]
Using magic ink (ZEBRA Co., Ltd., Mackie extra fine: oily), a 1 cm diameter circle was drawn on the sample and painted, and whether or not the ink repelled was visually observed. Further, after 30 seconds, rubbing with Bencot M-3 (Asahi Kasei Co., Ltd.), it was visually observed whether the ink was wiped off.
The antifouling property was evaluated according to the following criteria.
A: The ink repels and can be wiped off.
○: The ink does not repel but can be wiped off.
X: The ink cannot be wiped off.

[Chemical resistance]
The state of the sample after being immersed in a 1% aqueous sodium hydroxide solution for 30 minutes was visually observed and evaluated according to the following criteria.
A: No trace is left.
○: Some marks remain.
X: The film is peeled off.

[Repel]
A black tape (Nichiban Co., Ltd. VT-50) was attached to the back surface of a 10 cm × 10 cm sample, the number of repels was confirmed by visual observation, and evaluation was performed according to the following criteria.
○: No repelling ×: Repelling

[Reflectance]
First, the reflectance R was measured as follows.
Black tape is applied to the back side of the coating, and the minimum reflectance of the coating surface is measured with a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, product name: U-4100) at an incident angle of 12 ° with a wavelength of 370 nm to 790 nm. did. Here, the application back surface means a surface opposite to the side on which the hard coat layer and the antireflection layer of the transparent substrate are laminated. The application surface refers to the surface on the side where the antireflection layer of the antireflection film is formed.
Next, the minimum reflectance R _min among the measured reflectances R was evaluated according to the following criteria.
A: R _min ≦ 1%
○: 1% <R _min ≦ 2.0%
×: 2.0%> R _min

Table 2 shows the structures of the antireflection films of Examples 8 to 30.

Table 3 shows the evaluation results of the antireflection films of Examples 8 to 30.

From Tables 2 and 3, the following was found.
From Examples 8 to 17, the scratch resistance can be further improved by adding acrylic-modified silsesquioxane. Further, when the amount of the acrylic-modified silsesquioxane added is increased, the scratch resistance is improved, but when the amount added is excessive, the function of the antireflection layer tends to be lowered. Considering these points, the amount of the acrylic-modified silsesquioxane added is preferably 6 wt% or more and 46 wt% or less, more preferably 12 wt% or more and 46 wt% or less.

From Examples 18 to 29, as the amount of the substitute material for the acrylic-modified silsesquioxane is increased, the scratch resistance is improved, but the reflection property tends to be lowered. This is considered to be due to the following reason. In other words, to obtain the same level of scratch resistance as acrylic-modified silsesquioxane using an acrylic-modified silsesquioxane substitute material, more substitute materials must be added than acrylic-modified silsesquioxane. Goodbye. If a large amount of the substitute material is added in this way, the amount of the acrylate oligomer having a fluorine group is reduced, resulting in a decrease in reflection characteristics.
From Example 30, when a three-component acrylate is used instead of the acrylate oligomer having a fluorine group, scratch resistance is obtained, but the reflectance tends to decrease.

In Example 31, since phenyl-modified silsesquioxane is used as the silsesquioxane, the scratch resistance is reduced. In Example 32, since methyl-modified silsesquioxane is used as the polysilsesquioxane, the scratch resistance is reduced.
In Examples 8 to 32, although compound B and compound G are used, there is a sample in which the scratch resistance is lowered, in order to reduce reflectance, a fluorine-containing acrylate is used in combination. It is because it is doing.

(Example 33)
First, as in Example 1, a TAC film having a thickness of 80 μm was prepared. Next, a hard coat layer was formed on the TAC film in the same manner as in Example 1.

An antireflection layer was formed as follows.
First, a low refractive index coating agent having the following composition was prepared.
Acrylate oligomer having fluorine group 18.5wt%
(Product name AR110, manufactured by Daikin Industries, Ltd.)
Acrylic modified silsesquioxane 17wt%
(Product name ACSQ manufactured by Toa Gosei Co., Ltd.)
Hollow silica sol with an average particle size of 60 nm 50 wt%
(JGC Catalysts & Chemicals Co., Ltd., trade name through rear 4320)
Pentaerythritol triacrylate 10wt%
α-hydroxyketone (initiator) 2wt%
(Product name Irgacure 127 manufactured by Ciba Specialty Chemicals)
Modified silicon acrylate compound B 2wt%
(Product name 164E manufactured by Shin-Etsu Silicone)
Modified silicon acrylate compound G 0.5 wt%
(Product name 2457 manufactured by Shin-Etsu Silicone)

  Next, the low refractive index coating agent was dissolved in n-butanol as a solvent to obtain a coating solution having a solid content of 1.25 wt%. Next, using a small diameter gravure method, the coating solution was applied on the hard coat layer so as to have a dry film thickness of 120 nm. Next, after drying the coating solution in an oven at a temperature of 80 ° C. for 1 minute 30 seconds, a 160 W high-pressure mercury lamp is irradiated for 3 seconds from a distance of 18 cm in a nitrogen atmosphere having an oxygen concentration of 1000 ppm, thereby providing an antireflection layer. Formed. Thus, an antireflection film was obtained.

(Example 34)
An antireflection film was obtained in the same manner as in Example 33 except that 10 wt% of trimethylolpropane triacrylate was used instead of 10 wt% of pentaerythritol triacrylate.

(Example 35)
An antireflection film was obtained in the same manner as in Example 33 except that 10 wt% of ethoxylated (3) trimethylolpropane triacrylate was used instead of 10 wt% of pentaerythritol triacrylate.

(Example 36)
An antireflection film was obtained in the same manner as in Example 33 except that 10 wt% of ethoxylated (6) trimethylolpropane triacrylate was used instead of 10 wt% of pentaerythritol triacrylate.

(Example 37)
An antireflection film was obtained in the same manner as in Example 33 except that 10 wt% of ethoxylated (9) trimethylolpropane triacrylate was used instead of 10 wt% of pentaerythritol triacrylate.

(Example 38)
An antireflection film was obtained in the same manner as in Example 33 except that 10 wt% of ethoxylated (15) trimethylolpropane triacrylate was used instead of 10 wt% of pentaerythritol triacrylate.

(Example 39)
An antireflection film was obtained in the same manner as in Example 33 except that 10 wt% of ethoxylated (20) trimethylolpropane triacrylate was used instead of 10 wt% of pentaerythritol triacrylate.

(Example 40)
An antireflection film was obtained in the same manner as in Example 39 except that 12.5 wt% of ethoxylated (20) trimethylolpropane triacrylate and 14.5 wt% of acryl-modified silsesquioxane were used.

(Example 41)
An antireflection film was obtained in the same manner as in Example 39 except that 15 wt% of ethoxylated (20) trimethylolpropane triacrylate and 12 wt% of acryl-modified silsesquioxane were used.

(Example 42)
An antireflection film was obtained in the same manner as in Example 39 except that 18 wt% of ethoxylated (20) trimethylolpropane triacrylate and 9 wt% of acryl-modified silsesquioxane were used.

(Example 43)
An antireflection film was obtained in the same manner as in Example 39 except that 20 wt% of ethoxylated (20) trimethylolpropane triacrylate and 7 wt% of acryl-modified silsesquioxane were used.

(Example 44)
An antireflection film was obtained in the same manner as in Example 39 except that 5 wt% of ethoxylated (20) trimethylolpropane triacrylate and 22 wt% of acryl-modified silsesquioxane were used.

(Example 45)
An antireflection film was obtained in the same manner as in Example 39 except that 3 wt% of ethoxylated (20) trimethylolpropane triacrylate and 24 wt% of acryl-modified silsesquioxane were used.

(Example 46)
An antireflection film was obtained in the same manner as in Example 33 except that 10 wt% of methoxypolyethylene glycol (550) monoacrylate was used instead of 10 wt% of pentaerythritol triacrylate.

(Example 47)
An antireflection film was obtained in the same manner as in Example 33 except that 10 wt% of polyethylene glycol (600) diacrylate was used instead of 10 wt% of pentaerythritol triacrylate.

(Example 48)
An antireflection film was obtained in the same manner as in Example 33 except that 10 wt% of ethoxylated pentaerythritol tetraacrylate was used instead of 10 wt% of pentaerythritol triacrylate.

(Example 49)
An antireflection film was obtained in the same manner as in Example 33 except that 10 wt% of trimethylolpropane trimethacrylate was used instead of 10 wt% of pentaerythritol triacrylate.

(Example 50)
An antireflection film was obtained in the same manner as in Example 33 except that 10 wt% of pentaerythritol tetraacrylate was used instead of 10 wt% of pentaerythritol triacrylate.

[Characteristic evaluation]
The produced Examples 33 to 50 were used as samples, and the following characteristic evaluation was performed for each.

[Friction resistance test (dynamic friction coefficient)]
Frictional resistance tester: HEIDON-14D (Shinto Kagaku Co., Ltd.) was used, a film surface slipperiness test was performed at a load of 200 g (contact area with respect to the film 3 cm × 3 cm), and a dynamic friction coefficient was measured. Evaluation environmental conditions 23 ° C. 55% RH, moving distance (one way): 8 cm, moving speed: 10 cm / min, material sliding on film surface: dynamic coefficient of friction was measured using Bencott M-3 (Asahi Kasei Corporation). .

[SW: Steel wool scratch resistance test]
Using a rubbing tester: AB-301 (Tester Sangyo Co., Ltd.), a rubbing test was conducted under the following conditions.
Evaluation environmental condition 23 ° C, 55% RH
Rubbing material: Steel wool was wound around the rubbing tip of a tester in contact with the sample, and the band was fixed so as not to move. # 0000 was used as the roughness of the steel wool.
Moving distance (one way): 5 cm, rubbing speed: 10 cm / sec, load: 400 g / cm ² , 600 g / cm ² , 800 g / cm ² , 1 kg / cm ² , tip contact area: 1 cm × 1 cm, rubbing frequency: 10 An oily black ink was applied to the back side of the sample that had been rubbed back and forth, and visually observed with reflected light to determine whether or not the rubbed part was scratched. And the maximum value of the load which did not have a damage | wound in a scraping part was calculated | required.

Moreover, using the maximum value of the load with no scratch on the rubbing portion, the steel wool (SW) scratch resistance was evaluated based on the following criteria.
A: The maximum value of the load with no scratch on the rubbed part is 1000 g / cm ² or more. ○: The maximum value of the load with no scratch on the rubbed part is 800 g / cm ^2.
(Triangle | delta): The maximum value of the load which was not damaged at the rubbing part is 600 g / cm < ² >.
X: The maximum value of the load with no scratch on the rubbed portion is 400 g / cm ² or less.

[Anti-fouling]
Using magic ink (ZEBRA Co., Ltd., Mackie extra fine: oily), a 1 cm diameter circle was drawn on the sample and painted, and whether or not the ink repelled was visually observed. Further, after 30 seconds, rubbing with Bencott M-3 (Asahi Kasei Co., Ltd.), it was visually observed whether the ink could be wiped off. And this wiping property test was repeatedly performed.
The antifouling property was evaluated according to the following criteria.
A: The ink repels and can be wiped off, and can be easily wiped off repeatedly.
○: The ink repels and can be wiped off, but it is difficult to wipe it off repeatedly.
Δ: Ink does not repel but can be wiped off.
X: The ink cannot be wiped off.

Moreover, based on the wiping possibility number in the above-mentioned wiping property test, the wiping property was evaluated according to the level as shown below.
Level 1: Number of wiping possible is 3 times or less Level 2: Number of wiping possible is 4 times or more and 10 times or less Level 3: Number of wiping possible times is 11 times or more and 15 times or less Level 4: Number of possible wiping times is 16 times or more and 20 or less Level 5 : The number of wiping times is 20 times or more and 30 times or less Level 6: The number of wiping times is 31 times or more

[Reflectance]
First, the reflectance R was measured as follows.
Black tape is applied to the back side of the coating, and the minimum reflectance of the coating surface is measured with a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, product name: U-4100) at an incident angle of 12 ° with a wavelength of 370 nm to 790 nm. did. Here, the application back surface means a surface opposite to the side on which the hard coat layer and the antireflection layer of the transparent substrate are laminated. The application surface refers to the surface on the side where the antireflection layer of the antireflection film is formed.
Next, the minimum reflectance R _min among the measured reflectances R was evaluated according to the following criteria.
A: R _min ≦ 1%
○: 1% <R _min ≦ 2.0%
×: 2.0%> R _min

[surface tension]
The surface tension of the acrylates used in Examples 33 to 50 described above (in Table 4, (1) to (12) acrylates) was measured using a platinum plate method. As a measuring device, an automatic surface tension meter (manufactured by Kyowa Interface Science Co., Ltd., trade name: CBVP-A3) was used. The measurement temperature was set to 25 ° C.

Table 4 shows the structures of the antireflection films of Examples 33 to 50.

Table 5 shows the evaluation results of the antireflection films of Examples 33 to 50.

However, in Table 4, types (1) to (12) of acrylates are as follows.
(1) Pentaerythritol triacrylate (manufactured by Sartomer, trade name: SR444)
(2) Trimethylolpropane triacrylate (Sartomer, trade name: SR315S)
(3) Ethoxylation (3) Trimethylolpropane triacrylate (manufactured by Sartomer, trade name: SR454)
(4) Ethoxylation (6) Trimethylolpropane triacrylate (manufactured by Sartomer, trade name: SR444)
(5) Ethoxylation (9) Trimethylolpropane triacrylate (Sartomer, trade name: SR502)
(6) Ethoxylation (15) Trimethylolpropane triacrylate (Sartomer, trade name: SR9035)
(7) Ethoxylation (20) Trimethylolpropane triacrylate (Sartomer, trade name: SR415)
(8) Methoxypolyethylene glycol (550) monoacrylate (manufactured by Sartomer, trade name: CD553)
(9) Polyethylene glycol (600) diacrylate (Sartomer, trade name: SR610)
(10) Ethoxylated pentaerythritol tetraacrylate (manufactured by Sartomer, trade name: SR494)
(11) Trimethylolpropane trimethacrylate (manufactured by Sartomer, trade name: SR350)
(12) Pentaerythritol tetraacrylate (manufactured by Sartomer, trade name: SR295)

Tables 4 and 5 revealed the following.
From Examples 33 to 36, it can be seen that when the surface tension is less than 40 mN / m, the antifouling property and the scratch resistance tend to decrease.
From Examples 37 to 42 and Example 44, the surface tension of acrylate B is 40 mN / m or more, the number of functional groups of acrylate B is 3, and the amount of acrylate B added is 5 wt% or more and 18 wt% or less. It can be seen that the antifouling property and the scratch resistance tend to be improved.
From Example 43, it can be seen that when the amount of acrylate B added exceeds 18 wt%, the scratch resistance tends to decrease.
From Example 45, it can be seen that when the amount of acrylate B added is less than 5 wt%, the antifouling property and scratch resistance tend to decrease.
From Examples 46 and 47, it can be seen that when acrylate B having less than trifunctionality is used, the scratch resistance tends to decrease.
From Example 48, it is understood that when acrylate B having a surface tension of less than 40 mN / m is used, even when a tetrafunctional acrylate is used, the scratch resistance tends to decrease.
From Example 49, it can be seen that even when acrylate B having a methacryl group is used, if the surface tension is less than 40 mN / m, the antifouling property and the scratch resistance tend to be lowered.
From Example 50, it can be seen that, when it is desired to use tetrafunctional acrylate B, as in Examples 37 to 42 and Example 44 described above, the antifouling property and scratch resistance tend to decrease.
In Examples 33 to 50, although compound B and compound G are used, there is a sample in which the scratch resistance is lowered, in order to reduce reflectance, a fluorine-containing acrylate is used in combination. It is because it is doing.

  As described above, in consideration of antifouling property and scratch resistance, the surface tension is 40 mN / m or more, an acrylic compound having a trifunctional or higher functional acrylic group or a methacrylic group is used, and the addition amount of the acrylic compound is 5 wt% or more. It is preferable to set it to 18 wt% or less.

  The present invention is not limited to the above-described embodiments and examples of the present invention, and various modifications and applications can be made without departing from the gist of the present invention.

  For example, the numerical values, shapes, materials, configurations, and the like given in the above-described embodiments and examples are merely examples, and different numerical values, shapes, materials, configurations, and the like may be used as necessary.

  Moreover, although the above-mentioned embodiment demonstrated the antireflection film of the structure of a base material / hard coat layer / antireflection layer, the structure of an antireflection film is not limited to this. For example, the hard coat layer may be omitted. The antireflection layer may have a multilayer structure in which a low refractive index layer and a high refractive index layer are appropriately laminated, and the low refractive index layer may be formed using the resin composition according to the first embodiment.

  Further, in the above-described embodiment, the antireflection film provided on the display surface of the liquid crystal display has been described as an example where the present invention is applied. However, the present invention is not limited to this, and a CRT (Cathode Ray Tube ) On the display surface of various display devices such as display, plasma display (PDP), electro luminescence (EL) display, surface-conduction electron-emitter display (SED) It is applicable to the antireflection film used.

DESCRIPTION OF SYMBOLS 1 ... Antireflection film 2a, 2b ... Polarizer 2 ... Liquid crystal panel 3 ... Backlight 4 ... Front member 11 ... Base material 12 ... Hard-coat layer 13 ... Antireflection layer

Claims (12)

A first modified silicon compound comprising at least one compound represented by formula (a) having a weight average molecular weight of 8000 or more;
A second modified silicon compound comprising at least one compound represented by formula (b);
Hollow or porous particles;
A resin composition comprising an ionizing radiation curable resin.

(Ra is an alkyl group, an acryl group or a methacryl group. Rb is an acryl group or a methacryl group. N is an integer.)

(Rc to Rd are each independently an alkyl group, an acryl group or a methacryl group. Re is an acryl group or a methacryl group. N and m are integers.)   2. The mass ratio of the first modified silicon compound and the second modified silicon compound (the mass of the first modified silicon compound / the mass of the second modified silicon compound) is 0.05 or more. Resin composition.   The resin composition according to claim 1, wherein the first modified silicon compound has a weight average molecular weight of 8000 or more and 100,000 or less.   2. The resin composition according to claim 1, wherein the ionizing radiation curable resin is an ultraviolet curable resin containing a monomer and / or oligomer having an acrylic group or a methacryl group. Further containing a silsesquioxane having an acrylic or methacrylic group,
The resin composition according to claim 1, wherein the ionizing radiation curable resin includes a monomer and / or an oligomer having an acrylic group or a methacryl group. The ionizing radiation curable resin contains an acrylic compound having three or more of at least one of an acrylic group and a methacryl group,
The acrylic compound has a surface tension of 40 mN / m or more,
The resin composition according to claim 1, wherein the content of the acrylic compound with respect to the entire solid content is 5 wt% or more and 18 wt% or less.   The resin composition according to claim 1, wherein the ionizing radiation curable resin contains a fluorine-containing ionizing radiation curable resin. A method for producing an antireflection film in which an antireflection layer is formed on a substrate,
The antireflection layer,
A first modified silicon compound comprising at least one compound represented by formula (a) having a weight average molecular weight of 8000 or more, and a second modified silicon compound comprising at least one compound represented by formula (b) And applying a resin composition containing hollow particles or porous particles and an ionizing radiation curable resin to form a resin composition layer;
The manufacturing method of the anti-reflective film formed with the hardening process which irradiates ionizing radiation with a low oxygen concentration atmosphere with respect to the said resin composition.

(Ra is an alkyl group, an acryl group or a methacryl group. Rb is an acryl group or a methacryl group. N is an integer.)

(Rc to Rd are each independently an alkyl group, an acryl group or a methacryl group. Re is an acryl group or a methacryl group. N and m are integers.) The method for producing an antireflection film according to claim 8, wherein the low oxygen concentration atmosphere is 10,000 ppm or less. A substrate and an antireflection layer;
The antireflection layer is
A first modified silicon compound comprising at least one compound represented by formula (a) having a weight average molecular weight of 8000 or more, and a second modified silicon compound comprising at least one compound represented by formula (b) And an antireflection film formed by curing a resin composition comprising hollow particles or porous particles and an ionizing radiation curable resin.

(Ra is an alkyl group, an acryl group or a methacryl group. Rb is an acryl group or a methacryl group. N is an integer.)

(Rc to Rd are each independently an alkyl group, an acryl group or a methacryl group. Re is an acryl group or a methacryl group. N and m are integers.) A display for displaying an image;
An antireflection layer provided on the display surface side of the display unit,
The antireflection layer is
A first modified silicon compound comprising at least one compound represented by formula (a) having a weight average molecular weight of 8000 or more, and a second modified silicon compound comprising at least one compound represented by formula (b) And a display device that is formed by curing a resin composition including hollow particles or porous particles and an ionizing radiation curable resin.

(Ra is an alkyl group, an acryl group or a methacryl group. Rb is an acryl group or a methacryl group. N is an integer.)

(Rc to Rd are each independently an alkyl group, an acryl group or a methacryl group. Re is an acryl group or a methacryl group. N and m are integers.) A display unit having a first surface for displaying an image;
A front member having a second surface opposite to the first surface, and a third surface opposite to the second surface; the first surface, the second surface, and the third surface; An antireflection layer provided on at least one of the surfaces of
The antireflection layer is
A first modified silicon compound comprising at least one compound represented by formula (a) having a weight average molecular weight of 8000 or more, and a second modified silicon compound comprising at least one compound represented by formula (b) And a display device that is formed by curing a resin composition including hollow particles or porous particles and an ionizing radiation curable resin.

(Ra is an alkyl group, an acryl group or a methacryl group. Rb is an acryl group or a methacryl group. N is an integer.)

(Rc to Rd are each independently an alkyl group, an acryl group or a methacryl group. Re is an acryl group or a methacryl group. N and m are integers.)

Images