JP2019152836A - Low reflection member, and display device and article using the same - Google Patents

Abstract

To provide a low reflection member that is superior in antireflection properties and has writing suitability with a pen, and can maintain contamination removal properties by a simple method for a long period.SOLUTION: The present invention relates to a low reflection member having a low refractive index layer, including an inorganic compound, on a transparent plastic film, and the low reflection member has a release layer on the plane, on the opposite side from a light-transmissive base material, of the low refractive index layer, and is characterized in that the release layer is positioned on an outermost surface of the low reflection member, and the low reflection member has a reflection factor of 2.0% or smaller on the surface on the release layer side. <It is conditioned> that a surface of a sample on a release layer side is painted out by writing with an oily marking pen. Water is dripped with a syringe 60 seconds after the writing so that at least the region written with the oily marking pen on the surface of the sample on the release layer side is all covered with the water. When the sample is tilted at 45° from a horizontal plane 10 seconds after the dripping of the water is completed, the writing ink flows together with the water.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a low reflection member, a display device using the same, and an article.

In a display device such as a liquid crystal display device, an organic EL display device, a micro LED display device, a showcase, etc., in order to improve the visibility of a visual object (for example, an image in a display device; various articles in a showcase) The surface may be subjected to antireflection treatment.
As such an antireflection treatment, there is a means for forming a low refractive index layer containing a material having a low reflectance such as silica on the surface of a display device or the like (Patent Document 1).

  On the other hand, in a display device, a showcase or the like, the surface may be subjected to antifouling treatment. Examples of the antifouling treatment include means for forming an antifouling layer containing a water repellent and oil repellent material such as a fluorine-based resin on the surface of a display device or the like (Patent Document 2).

JP 2017-161893 JP 2011-225499 A

  Although the low refractive index layer of Patent Document 1 is excellent in antireflection properties, there is a problem in that it is inferior in soil removability when soiling occurs. In addition, the low refractive index layer composed of the low refractive index inorganic particles and the binder resin contains a large amount of low refractive index inorganic particles in order to lower the refractive index, and thus has a problem that the scratch resistance is not sufficient.

The antifouling layer of Patent Document 2 repels water and oil and has a predetermined antifouling property. However, the antifouling layer having excellent water repellency and oil repellency as disclosed in Patent Document 2 moves so that the water and oil that repels roll on the surface of the antifouling layer when wiping off the water and oil. Could not be easily removed. In addition, the antifouling layer made of a fluorine-based resin as in Patent Document 2 is inferior in scratch resistance, and the antifouling property tends to be insufficient.
Further, the antifouling layer excellent in water repellency and oil repellency as disclosed in Patent Document 2 repels water-based ink and oil-based ink, and thus has a problem that information cannot be written with a pen. 2. Description of the Related Art In recent years, applications that capture information written on a whiteboard or projection screen on a personal computer screen and applications that share information written on the surface of a tablet terminal with participants in a conference have been proposed. In order to cope with these applications, it is required to satisfy both the writing property with the pen and the removability of the pen, but the antifouling layer of Patent Document 2 cannot cope with it.

  In addition, the self-cleaning function of a titanium oxide photocatalyst is mentioned as a technique for removing dirt easily. However, since titanium oxide has a high refractive index, it is not suitable for antireflection, light transmission and low haze. In addition, titanium oxide has a problem that the plastic film and the binder resin are deteriorated with time due to photocatalytic activity. Further, the self-cleaning function by the titanium oxide photocatalyst needs to be activated by irradiating the titanium oxide photocatalyst with ultraviolet rays in order to develop the function, and the irradiation time of the ultraviolet rays needs about 10 minutes. Therefore, it cannot be said that the dirt can be easily removed in a short time.

  The present invention has been made in view of such circumstances, has excellent anti-reflection properties, has writing ability with a pen, and is capable of maintaining dirt removability with a simple method over a long period of time. It is an object to provide a reflective member and a display device and an article using the low reflective member.

In order to solve the above problems, the present invention provides the following [1] to [3].
[1] A low reflection member having a low refractive index layer containing an inorganic compound on a transparent plastic film, and having a release layer on the surface of the low refractive index layer opposite to the light transmissive substrate. The release layer is located on the outermost surface of the low reflection member, the reflectance of the surface of the low reflection member on the release layer side is 2.0% or less, and the following conditions 1 to 3 are satisfied: A low reflection member that fills.
<Condition 1>
Sample A is prepared by cutting the low reflection member into a size of 5.0 cm × 5.0 cm. An area of 1.0 cm × 1.0 cm in the center of the surface of the release layer side of sample A is oily in “3.b) Types of ink classification” in JIS S6037: 2006, and “4. Quality” and Write and paint with an oil-based marking pen that satisfies the conditions of “5. Material and structure”. After 60 seconds from writing, when the area written with the oil-based marking pen on the surface of the release layer was rubbed 5 times with a load of 500 g / cm ² using a No. 300 cotton cloth, the ink surface of the release layer Remain.
<Condition 2>
As in Condition 1, the surface of the release layer side of Sample A is written and painted with an oil-based marking pen. After 60 seconds have passed since writing, water is dropped with a dropper so that at least the entire area written with the oil-based marking pen on the surface of the release layer side of Sample A is covered with water. After 10 seconds from the completion of the dripping of water, when the sample A is inclined 45 ° from the horizontal plane, the written ink flows together with the water.
<Condition 3>
Sample B is obtained by subjecting the surface of the release layer of sample A to 1000 reciprocating friction using a No. 300 cotton flannel cloth at a load of 500 g / cm ² . When the same operation as in Condition 2 was performed except that sample A was changed to sample B, 10 seconds after the completion of the dripping of water, and when sample B was tilted 45 ° from the horizontal plane, writing was made. Ink flows with water.
[2] A display device having the low reflection member according to [1].
[3] An article in which the release layer of the low reflection member according to [1] is disposed so as to face the surface.

  According to the present invention, there are provided a low-reflection member, a display device, and an article that have excellent antireflection properties, have pen-writing ability with a pen, and can maintain dirt removability with a simple method over a long period of time. Can do.

It is sectional drawing which shows one Embodiment of the low reflection member of this invention. It is sectional drawing which shows other embodiment of the low reflection member of this invention. It is sectional drawing which shows one Embodiment of the display apparatus of this invention. It is a photograph which shows the state in which the ink written on the surface of the mold release layer came up from the mold release layer after dripping water, and the state in which the written ink flowed with water.

[Low reflection member]
The low reflective member of the present invention is a low reflective member having a low refractive index layer containing an inorganic compound on a transparent plastic film, on the surface opposite to the light transmissive substrate of the low refractive index layer. Having a release layer, the release layer is located on the outermost surface of the low reflection member, the reflectance of the surface of the low reflection member on the release layer side is 2.0% or less, and The conditions 1 to 3 are satisfied.
<Condition 1>
Sample A is prepared by cutting the low reflection member into a size of 5.0 cm × 5.0 cm. An area of 1.0 cm × 1.0 cm in the center of the surface of the release layer side of sample A is oily in “3.b) Types of ink classification” in JIS S6037: 2006, and “4. Quality” and Write and paint with an oil-based marking pen that satisfies the conditions of “5. Material and structure”. After 60 seconds from writing, when the area written with the oil-based marking pen on the surface of the release layer was rubbed 5 times with a load of 500 g / cm ² using a No. 300 cotton cloth, the ink surface of the release layer Remain.
<Condition 2>
As in Condition 1, the surface of the release layer side of Sample A is written and painted with an oil-based marking pen. After 60 seconds have passed since writing, water is dropped with a dropper so that at least the entire area written with the oil-based marking pen on the surface of the release layer side of Sample A is covered with water. After 10 seconds from the completion of the dripping of water, when the sample A is inclined 45 ° from the horizontal plane, the written ink flows together with the water.
<Condition 3>
Sample B is obtained by subjecting the surface of the release layer of sample A to 1000 reciprocating friction using a No. 300 cotton flannel cloth at a load of 500 g / cm ² . When the same operation as in Condition 2 was performed except that sample A was changed to sample B, 10 seconds after the completion of the dripping of water, and when sample B was tilted 45 ° from the horizontal plane, writing was made. Ink flows with water.

1 and 2 are sectional views showing an embodiment of the low reflection member of the present invention.
1 and 2 includes a hard coat layer 20, a low refractive index layer 30, and a release layer 40 in this order on a transparent plastic film 10. Further, the low reflection member 100 of FIG. 2 has a hard coat layer 20, a low refractive index layer 30, and a release layer 40 on both surfaces of the transparent plastic film 10.
In addition, the low reflection member of this invention is not limited to embodiment of FIG.1 and FIG.2. For example, the hard coat layer 20 may not be provided between the transparent plastic film 10 and the low refractive index layer 30. Further, the low refractive index layer 30 and the release layer 40 do not need to be formed on the entire surface of the transparent plastic film 10, and these layers may be provided on at least a part of the transparent plastic film 10. Moreover, the low reflection member may have other layers, such as the high refractive index layer mentioned later.

<Reflectance>
The low reflection member of the present invention requires that the reflectance on the surface on the release layer side is 2.0% or less.
When the reflectance exceeds 2.0%, the antireflection performance becomes insufficient, and the visibility of a visual object (for example, an image on a display device and various articles on a showcase) cannot be improved.
The reflectance of the surface on the release layer side of the low reflection member is preferably 1.5% or less, and more preferably 1.0% or less.
Note that lowering the reflectance of the low-reflection member is also preferable because the light transmittance of the low-reflection member can be increased.

In this specification, the reflectance means the luminous reflectance Y value of the CIE 1931 standard color system, which means an average value measured at 10 points.
Moreover, in this specification, the reflectance of the surface of the release layer side of the low reflection member is a sample in which a black plate is bonded to the opposite side of the reflectance measurement surface of the low reflection member via a transparent adhesive layer. And measurement is performed by making light incident at an incident angle of 5 ° from the release layer side of the sample. The light source for measuring the reflectance is preferably D65.
The difference in refractive index between the member (for example, a transparent plastic film) in contact with the sample transparent adhesive layer and the transparent adhesive layer is preferably within 0.15, and more preferably within 0.10. The black plate preferably has a total light transmittance of JIS K7361-1: 1997 of 1% or less, and more preferably 0%. The difference in refractive index between the resin constituting the black plate and the transparent adhesive layer is preferably within 0.15, and more preferably within 0.10.

  In order to easily make the reflectance of the surface on the release layer side to be 2.0% or less, it is preferable to set the thickness and the refractive index of the release layer in the ranges described later.

The low reflection member of the present invention is required to satisfy the following condition 1.
<Condition 1>
Sample A is prepared by cutting the low reflection member into a size of 5.0 cm × 5.0 cm. An area of 1.0 cm × 1.0 cm in the center of the surface of the release layer side of sample A is oily in “3.b) Types of ink classification” in JIS S6037: 2006, and “4. Quality” and Write and paint with an oil-based marking pen that satisfies the conditions of “5. Material and structure”. After 60 seconds from writing, when the area written with the oil-based marking pen on the surface of the release layer was rubbed 5 times with a load of 500 g / cm ² using a No. 300 cotton cloth, the ink surface of the release layer Remain.

Satisfying condition 1 indicates that the oil can be written with the oil-based marking pen on the surface of the release layer side of the low reflection member, and the ink is sufficiently adhered.
Moreover, satisfying Condition 1 and satisfying Condition 2 described later indicate that the ink of the oil-based marking pen can be removed by a simple operation of dripping water while the ink is sufficiently adhered.

In condition 1, “when the area written with the oil-based marking pen on the surface of the release layer is rubbed 5 times with a load of 500 g / cm ² using a No. 300 cotton cloth, the ink remains on the surface of the release layer. "" Does not mean that 100% of the ink remains. For example, when the total amount of ink components written on the release layer is 100 parts by mass, the amount of ink transferred to the flannel side after 5 reciprocating frictions with the flanked region is 1 part by mass or less. Assume that Condition 1 is satisfied.
The oil marking pen that satisfies the conditions of “4. Quality” and “5. Material and structure” used in the conditions 1 to 3 is “JIS S6037: 2006“ 3.b) Type by ink classification ”is oily. As an example, an ink color “black” of a trade name “Mckey Extra Fine” manufactured by Zebra Corporation may be used.

  In the conditions 1, 3 and 4, it is preferable to use a flannel cloth having a size of 3.0 cm × 3.0 cm by folding a cloth of 12.0 cm × 12.0 cm once in each direction.

  In order to easily satisfy the condition 1, the release layer is formed from the material described later, the thickness of the release layer is set in the range described later, and the adhesion between the low refractive index layer and the release layer is improved. It is preferable to do.

The low reflection member of the present invention is required to satisfy the following condition 2.
<Condition 2>
As in Condition 1, the surface of the release layer side of Sample A is written and painted with an oil-based marking pen. After 60 seconds have passed since writing, water is dropped with a dropper so that at least the entire area written with the oil-based marking pen on the surface of the release layer side of Sample A is covered with water. After 10 seconds from the completion of the dripping of water, when the sample A is inclined 45 ° from the horizontal plane, the written ink flows together with the water.

Fig.4 (a) is a photograph which shows the state after progress for 10 seconds after dripping water to the area | region written with the oil-based marking pen. When the ink is completely separated from the surface of the release layer as shown in FIG. 4A, the ink flows together with water by tilting the low reflection member. FIG. 4B is a photograph showing a state where the written ink flows together with water by tilting the low reflection member. The red frames in FIGS. 4A and 4B are written on paper placed under the low reflection member as a mark of 1.0 cm × 1.0 cm. 4A and 4B, a resin plate (2 mm × 100 mm × 100 mm) having a smooth surface is disposed below the paper, and the low reflection member is the resin plate (2 mm × 100 mm × 100 mm). It is fixed on all sides. Moreover, the ruler installed in place of the scales in FIGS. 4A and 4B is fixed on the low reflection member. In FIG. 4B, the low reflection member was tilted by grasping the resin plate.
Depending on the speed at which the low reflection member is tilted, the ink may flow from the original part, but may remain in a part of the sample that has moved slightly from the original part. However, in this case, the moved ink can be easily removed by washing with water or lightly wiping with a wet cloth.
Thus, satisfying Condition 2 means that the dirt attached to the surface of the low reflection member can be removed by an extremely simple operation of dripping water, waiting for a short time, and tilting the writing member. .
In addition, in condition 2 and conditions 3 and 4 to be described later, it is preferable that the dropped water is ion-exchanged water. Moreover, it is preferable that 1 ml or more of water is dropped on a writing area of 1.0 cm × 1.0 cm.

2. Description of the Related Art In recent years, an application for capturing information written on a whiteboard or a projection screen on a personal computer screen and an application for sharing information written on the surface of a tablet-type display device with participants in a conference have been proposed. In order to deal with these applications, it is required to achieve both writing performance with a pen and removability of the pen. Satisfying Condition 1 and Condition 2 is preferable in terms of being able to deal with these applications.
Further, in the showcase and the show window, in order to show information such as products to customers and the like, a performance capable of being written and erased with a pen is also required. In particular, it is preferable to have writing properties and erasability with an oil-based marking pen that are excellent in ink fixing properties, easy to perform conspicuous writing with high concentration. Satisfying condition 1 and condition 2 is preferable also in satisfying the performance.
Satisfying condition 2 means that various oil-based stains (fingerprint component, cosmetic component, paint, exhaust gas component, animal excrement) can be easily removed with water. Therefore, a portable information terminal (especially a portable information terminal with a touch panel function) that is often touched by a hand, a showcase, a surface of a show window and a window, and a show window used facing outdoors It is useful to apply the low reflection member of the present invention on the surface of the window.

Condition 2 is that it is preferable that the written ink flows together with the water when the sample A is tilted 45 ° from the horizontal plane after 5 seconds have elapsed from the completion of the dripping of water.
In order to easily satisfy the condition 2, it is preferable to form the release layer from a material described later, and to set the thickness of the release layer in a range described later.

In addition, the self-cleaning function of a titanium oxide photocatalyst is mentioned as a technique for removing dirt easily. However, since titanium oxide has a high refractive index, it is not suitable for antireflection, light transmission and low haze. In addition, titanium oxide has a problem that a plastic film and a binder resin are deteriorated with time due to photocatalytic activity. Further, the self-cleaning function by the titanium oxide photocatalyst needs to be activated by irradiating the titanium oxide photocatalyst with ultraviolet rays in order to develop the function, and the irradiation time of the ultraviolet rays needs about 10 minutes. Therefore, it cannot be said that dirt can be easily removed in a short time.
Moreover, a means for removing dirt adhered to the outermost layer by forming a coating film made of a water-soluble material on the low refractive index layer and dissolving the coating film with water is also conceivable. However, this means can remove the dirt only once. Further, with this means, after removing the dirt once, the low refractive index layer is exposed and the low refractive index layer is easily damaged, so that the antireflection property is gradually lowered.

The low reflection member of the present invention is required to satisfy the following condition 3.
<Condition 3>
Sample B is obtained by subjecting the surface of the release layer of sample A to 1000 reciprocating friction using a No. 300 cotton flannel cloth at a load of 500 g / cm ² . When the same operation as in Condition 2 was performed except that sample A was changed to sample B, 10 seconds after the completion of the dripping of water, and when sample B was tilted 45 ° from the horizontal plane, writing was made. Ink flows with water.

  Condition 3 indicates that the characteristics of Condition 2 are maintained even if the surface of the release layer is rubbed many times with flannel cloth. In other words, satisfying the condition 3 means that the dirt removal property by a simple method can be maintained for a long time.

Many recent display devices are equipped with a touch panel function as standard. And since a display device equipped with a touch panel function is easily contaminated with sebum on the surface, it is wiped off many times every day. Further, in the showcase, the show window, and the window, the surface is cleaned on a daily basis in order to improve the visibility.
Therefore, satisfying Condition 3 is preferable in that it is suitable for a display device equipped with a touch panel function, a showcase, a show window, and a window.
In the present specification, “showcase” means a box whose inside can be visually recognized in a normal state, and includes a refrigerator and a freezer.

Condition 3 is that it is preferable that the written ink flows together with the water when the sample A is tilted 45 ° from the horizontal plane after 5 seconds have elapsed from the completion of the dripping of water.
In order to easily satisfy the condition 3, it is preferable to increase the scratch resistance of the surface of the low reflection member (release layer surface).
Since the transparent plastic film is oleophilic, the adhesion between the transparent plastic film and the release layer is usually insufficient. Even if a release layer is formed on the transparent plastic film, the release layer is scratch resistant. Are often inferior. In the present invention, a low refractive index layer is interposed between the transparent plastic film and the release layer, and the surface of the low refractive index layer is subjected to the treatment described later, whereby the low refractive index layer and the release layer are separated. As a result, the condition 3 is easily satisfied by improving the scratch resistance of the surface of the low reflective member (release layer surface).

The low reflection member of the present invention preferably further satisfies the following condition 4.
<Condition 4>
Sample C was obtained by subjecting the surface of the release layer of Sample A to 5000 reciprocating friction using a No. 300 cotton cloth with a load of 500 g / cm ² . When the same operation as in Condition 2 was performed except that sample A was changed to sample C, 10 seconds after the completion of the dripping of water, the sample C was written when tilted 45 ° from the horizontal plane. Ink flows with water.

  Condition 4 is that it is preferable that the written ink flows together with the water when the sample A is tilted 45 ° from the horizontal plane after 5 seconds have elapsed from the completion of the dripping of water.

<Transparent plastic film>
Transparent plastic film is polyester, triacetyl cellulose (TAC), cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyether sulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone , Polymethyl methacrylate, polycarbonate, polyurethane, and amorphous olefin (Cyclo-Olefin-Polymer: COP).
Among these transparent plastic films, from the viewpoint of mechanical strength and dimensional stability, a polyester film that has been stretched, particularly biaxially stretched, is preferred. Among the polyester films, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are preferable.

The thickness of the transparent plastic film is preferably 5 to 500 μm, and more preferably 10 to 200 μm.
The transparent plastic film preferably has a total light transmittance of JIS K7361-1: 1997 of 80% or more, more preferably 90% or more, and further preferably 95% or more.

  From the viewpoint of improving the adhesion with the layer formed on the film, the transparent plastic film is subjected to an easy adhesion treatment such as a physical or chemical surface treatment such as an oxidation method or an uneven method on one or both sides. It may be. From the same viewpoint, it is also preferable to form an easy adhesion layer on the transparent plastic film.

<Low refractive index layer>
The low refractive index layer can be broadly classified into those formed by a wet method and those formed by a dry method.
As a wet method, a method of forming by a sol-gel method using a metal alkoxide, a method of forming by applying a low refractive index resin such as a fluororesin, and a binder resin composition containing low refractive index inorganic particles A method of applying and forming a coating solution for forming a low refractive index layer may be mentioned.
Examples of the dry method include a method in which a material having a desired refractive index is selected from low-refractive index inorganic particles described later, and the material is formed by physical vapor deposition or chemical vapor deposition using the material.
The wet method is excellent in terms of production efficiency. Moreover, the low refractive index layer formed by the wet method is suitable in that it is excellent in the coating suitability of the release layer. Furthermore, the low refractive index layer formed by the wet method is preferable in that it can easily improve the adhesion with the layer immediately below (for example, a transparent plastic film, a hard coat layer, or a high refractive index layer).
Further, among the wet methods, a method of forming using a low refractive index inorganic particle as an inorganic compound and a low refractive index layer forming coating solution containing a binder resin composition is preferable. That is, the low refractive index layer preferably contains low refractive index inorganic particles as an inorganic compound and a binder resin.

  The average primary particle diameter of the low refractive index inorganic particles is preferably 5 to 200 nm, more preferably 10 to 150 nm. When the low refractive index inorganic particles are hollow particles, the average primary particle diameter is preferably 5 to 200 nm, more preferably 30 to 150 nm, and further preferably 40 to 110 nm. When the average primary particle diameter is in the above range, the thickness of the low refractive index layer can be easily made uniform.

The average primary particle diameter of the low refractive index inorganic particles and the high refractive index particles described later can be calculated by the following operations (1) to (3).
(1) The cross section of a low reflection member is imaged with TEM or STEM. The acceleration voltage of TEM or STEM is preferably 10 kv to 30 kV, and the magnification is preferably 50,000 to 300,000 times.
(2) Ten arbitrary primary particles are extracted from the observation image, and the particle diameter of each primary particle is calculated. The particle diameter is measured as a distance between straight lines in a combination of two straight lines that maximizes the distance between the two straight lines when the cross section of the primary particle is sandwiched between two parallel straight lines.
(3) The same operation is performed five times on the observation image of another screen of the same sample, and the value obtained from the total number of 50 particles is taken as the average particle diameter of the primary particles.

Examples of the low refractive index inorganic particles include silica and magnesium fluoride.
The low refractive index inorganic particles preferably have voids from the viewpoint of reducing the reflectance. Since the inorganic particles having voids have fine voids inside and air is contained in the voids, the refractive index is low. Examples of the inorganic particles having voids include porous inorganic particles and hollow inorganic particles. Among these, hollow inorganic particles are preferable. Among the hollow inorganic particles, hollow silica is preferable.

The hollow inorganic particles refer to particles having an outer shell layer made of an inorganic compound, the inside of the particles surrounded by the outer shell layer being hollow, and containing air inside the particles.
The shape of the hollow inorganic particles may be any of a spherical shape, a chain shape, a needle shape, a plate shape, a piece shape, a rod shape, a fiber shape, etc., such as a spherical shape, a spheroid shape, and a polyhedral shape that can approximate a sphere. . Among these, a true spherical shape and a substantially spherical shape are preferable, and a spheroid shape or a true spherical shape is more preferable.

While the hollow inorganic particles can lower the refractive index, they tend to be inferior in water resistance and scratch resistance compared to other low refractive index inorganic particles. In particular, when hollow particles having a large particle size with an increased air ratio are used, the water resistance and scratch resistance of the low refractive index layer are likely to be lowered.
However, the low reflective member of the present invention has a weak point (water resistance and scratch resistance) of the hollow inorganic particles due to the release layer located on the low refractive index layer even when the low refractive index layer contains hollow inorganic particles. Can be compensated). Further, in the case where the low refractive index layer contains hollow inorganic particles, the adhesion of the low refractive index layer and the release layer is improved by performing the treatment described later on the surface of the low refractive index layer, so that the hollow inorganic particles It is preferable in that the weak point (decrease in water resistance and scratch resistance) can be compensated more.

  The low-refractive index inorganic particles may be surface-treated, but from the viewpoint of improving the adhesion between the low-refractive index layer and the release layer, those having no surface treatment are preferable.

The content of the low refractive index inorganic particles is preferably 20 to 250 parts by mass, more preferably 30 to 230 parts by mass, and still more preferably 40 to 200 parts by mass with respect to 100 parts by mass of the binder resin of the low refractive index layer.
By setting the content of the low refractive index inorganic particles to 20 parts by mass or more, it is possible to improve the antireflection property and to easily improve the adhesion between the low refractive index layer and the release layer. Moreover, by making content of a low refractive index inorganic particle into 250 mass parts or less, the fall of the coating strength of a low refractive index layer can be suppressed, and it can be made easy to suppress the fall of the abrasion resistance of a low reflection member by extension.
Further, the low refractive index inorganic particles can be used in combination with hollow inorganic particles and other low refractive index inorganic particles. In this case, the ratio of the hollow inorganic particles to the total amount of the low refractive index inorganic particles contained in the low refractive index layer is preferably 50% by mass or more, more preferably 60% by mass or more and 95% by mass or less, and 70% by mass or more and 90% by mass. % Or less is more preferable.

  The binder resin of the low refractive index layer preferably includes a cured product of a curable resin composition such as a thermosetting resin composition or an ionizing radiation curable resin composition, from the viewpoint of improving the scratch resistance. More preferably, it contains a cured product of the ionizing radiation curable resin composition.

The binder resin of the low refractive index layer preferably does not substantially contain a fluorine component from the viewpoints of adhesion to the release layer and suitability for application of the release layer coating solution.
“Substantially not contained” means that the fluorine atom content of the fluorine component is 1% by mass or less, preferably 0.1% by mass or less, more preferably 0. 0% by mass, based on the total amount of the binder resin in the low refractive index layer. It is 01 mass% or less, More preferably, it is 0 mass%.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as necessary.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as “ionizing radiation curable compound”). Examples of the ionizing radiation curable functional group include an ethylenically unsaturated bond group such as a (meth) acryloyl group, a vinyl group, and an allyl group, an epoxy group, and an oxetanyl group. As the ionizing radiation curable compound, a compound having an ethylenically unsaturated bond group is preferable, a compound having two or more ethylenic unsaturated bond groups is more preferable, and among them, having two or more ethylenically unsaturated bond groups, Polyfunctional (meth) acrylate compounds are more preferred. As the polyfunctional (meth) acrylate compound, any of a monomer and an oligomer can be used.
The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.
In this specification, (meth) acrylate means acrylate or methacrylate, (meth) acrylic acid means acrylic acid or methacrylic acid, and (meth) acryloyl group means acryloyl group or methacryloyl group. means.

Among the polyfunctional (meth) acrylate compounds, bifunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, 1,6-hexane. Examples thereof include diol diacrylate.
Examples of the tri- or higher functional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Examples include pentaerythritol tetra (meth) acrylate and isocyanuric acid-modified tri (meth) acrylate.
The (meth) acrylate-based monomer may be modified by partially modifying the molecular skeleton, and is modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, or the like. Can also be used.

Moreover, examples of the polyfunctional (meth) acrylate oligomer include acrylate polymers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
Urethane (meth) acrylate is obtained by reaction of polyhydric alcohol and organic diisocyanate with hydroxy (meth) acrylate, for example.
A preferable epoxy (meth) acrylate is a (meth) acrylate obtained by reacting (meth) acrylic acid with a tri- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like. (Meth) acrylates obtained by reacting the above aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins and the like with polybasic acids and (meth) acrylic acid, and bifunctional or higher functional aromatic epoxy resins, It is a (meth) acrylate obtained by reacting an alicyclic epoxy resin, an aliphatic epoxy resin or the like with a phenol and (meth) acrylic acid.
The ionizing radiation curable compounds can be used alone or in combination of two or more.

When the ionizing radiation curable compound is an ultraviolet curable compound, the ionizing radiation curable composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthones, and the like.
The photopolymerization accelerator can reduce polymerization inhibition by air during curing and increase the curing speed. For example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc. One or more selected may be mentioned.

When the low refractive index layer contains low refractive index inorganic particles as an inorganic compound and a binder resin, the low refractive index is low on at least a part of the surface of the low refractive index layer (the surface on the release layer side of the low refractive index layer). It is preferable that the inorganic particles are exposed. Since the low refractive index inorganic particles are exposed from the surface of the low refractive index layer, the adhesion between the low refractive index layer and the release layer can be easily improved.
In order to expose the low refractive index inorganic particles from the surface of the low refractive index layer, the surface of the low refractive index layer is subjected to corona discharge treatment after the low refractive index layer is formed, or the surface of the low refractive index layer is saponified. It is preferable to process. When the low refractive index layer including the low refractive index inorganic particles and the binder resin is formed, the surface of the low refractive index inorganic particles is covered with the binder resin. Here, the thickness of the binder resin covering the surface of the low refractive index inorganic particles may be thick or thin depending on the location. Then, the portion of the surface of the low refractive index inorganic particles that is thinly covered with the binder resin is subjected to the above-described corona discharge treatment or saponification treatment, so that the thin binder resin is removed and the low refractive inorganic particles are exposed. .

The low refractive index layer preferably contains a silane coupling agent from the viewpoint of further improving the adhesion with the release layer and maintaining the stain removability for a longer period.
Silane coupling agents include: alkoxysilanes such as tetraethoxysilane and methyltriethoxysilane; vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Silane coupling agents containing (meth) acryloyl groups such as propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltriethoxysilane; epoxy silane coupling agents; amino silane couplings Agents and the like. Among these, a silane coupling agent containing a (meth) acryloyl group is preferable from the viewpoint of scratch resistance.

  The content of the silane coupling agent is preferably 5 to 60% by mass, more preferably 7 to 45% by mass, and still more preferably 10 to 30% by mass of the total solid content of the low refractive index layer.

The thickness of the low refractive index layer is preferably 70 to 120 nm, more preferably 80 to 110 nm, and still more preferably 85 to 105 nm.
The thickness of the low refractive index layer can be calculated, for example, by measuring the thickness of 20 locations from a cross-sectional image taken using a scanning transmission electron microscope (STEM) and calculating the average value of the 20 locations. The thicknesses of the release layer, hard coat layer, and high refractive index layer described later can be calculated in the same manner.

The refractive index of the low refractive index layer is preferably 1.26 to 1.37, more preferably 1.28 to 1.35, and even more preferably 1.30 to 1.33.
In this specification, the refractive index can be calculated, for example, by fitting a reflection spectrum measured by a reflection photometer and a reflection spectrum calculated from an optical model of a multilayer thin film using a Fresnel coefficient.

<Release layer>
The release layer is formed on the side opposite to the transparent plastic film of the low refractive index layer.
The release layer is required not to swell or dissolve when water is dropped under conditions 2 to 4.

The release layer is preferably a cured product of a release layer forming composition containing an organic solvent-dispersed silica sol.
The organic solvent-dispersed silica sol is a colloidal solution in which colloidal silica having a particle size of nano-order is dispersed in an organic solvent. A cured product of the release layer forming composition containing the organic solvent-dispersed silica sol can be obtained by applying the release layer forming composition containing the organic solvent-dispersed silica sol and dehydrating and condensing the silica sol by heating or the like. Examples of the organic solvent for the organic solvent-dispersed silica sol include alcohols, glycols, esters, ketones, ethers, saturated hydrocarbons, and unsaturated hydrocarbons.
The particle diameter of the silica sol is preferably 1 to 20 nm from the viewpoint of setting the release layer thickness within the range described below.

  Specific examples of the organic solvent-dispersed silica sol include trade names IPA-ST (particle size: about 12 nm), IPA-ST-UP (particle size: about 9 to 15 nm), MIBK-ST (particle size: about 12 nm) manufactured by Nissan Chemical Industries, Ltd. 12 nm), PMA-ST (particle size of about 12 nm) and PGM-ST (particle size of about 12 nm), MIBK-SD (particle size of about 12 nm); trade name PL-1-IPA (10-15 nm, manufactured by Fuso Chemical Industry Co., Ltd.) ), PL-1-TOL (10 to 15 nm), PL-1-PGME (10 to 15 nm), PL-1-MEK (10 to 15 nm); trade name “Suriria” manufactured by JGC Catalysts & Chemicals.

Moreover, it is preferable that a mold release layer is a hardened | cured material of the mold release layer forming composition containing the modified material of organic solvent dispersion | distribution silica sol. Examples of the modified organic solvent-dispersed silica sol include those obtained by reacting silanol of silica sol with a silane coupling agent represented by the following formula (I).
While the cured product of the composition containing the modified product (a product obtained by reacting silanol of silica sol with a silane coupling agent represented by the following formula (I)) has a high level of hydrophilicity, Since the presence of the group has writing ability with an oil-based marking pen, Condition 1 can be easily satisfied. Further, the cured product of the composition containing the modified product has a high level of hydrophilicity, and water enters between the dirt adhering to the release layer and the surface of the release layer. The attached object can be lifted and condition 2 can be easily satisfied. In addition, the cured product of the composition containing the modified product is excellent in adhesion to the low refractive index layer, and can improve the scratch resistance of the low reflective member, so that Condition 3 can be easily satisfied. Furthermore, since the cured product of the composition containing the modified product has a low refractive index of about 1.4, the reflectance can be easily lowered.
In addition, the cured product of the composition containing the modified product has hydrophilicity so that it can be written with an aqueous marking pen, and when the water is dropped, the ink of the attached aqueous marking pen may emerge. It can be done.
The above-described actions are as follows: “having minute hydrophilic domains and hydrophobic domains on the surface of the cured product of the composition containing the modified product” and “coordination energy of water to the hydrophilic domains> hydrophobic domains and pen components This is considered to be caused by the fact that the relationship of binding force is established. The reason why the release layer does not peel when water is dropped is considered to be because the modified product and the inorganic compound in the low refractive index layer are chemically bonded.

_{^{(W) 3-k (R}} ) k Si-R 1 - (X-R 2) m -N + (R 3) (R 4) -R 5 -Y (I)
[In formula (I), W represents an alkoxy group having 1 to 3 carbon atoms, R represents an alkyl group having 1 to 3 carbon atoms, k represents 0 or 1, and R ¹ represents 1 to 5 carbon atoms. Represents an alkylene group, X represents —NHCOO—, —NHCONH— or —S—, m represents 0 or 1, and R ² may have an ether bond, an ester bond or an amide bond, and has 1 to 10 carbon atoms. Represents an alkylene group or —CH ₂ CH ₂ N ⁺ (CH ₃ ) {(CH ₂ ) _n Y)} CH ₂ CH ₂ OCH ₂ CH ₂ —, and R ³ and R ⁴ may be the same or different. represents ~ 3 alkyl group, ^{R 5} represents a methylene group, an ethylene group, a propylene group or a methylene-phenylene group, Y is -COO ^- or -SO ₃ ^- represents an. ]

Examples of R (the alkyl group having 1 to 3 carbon atoms) of the above formula (I) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and among these, a methyl group is preferable.
Examples of R ¹ (the alkylene group having 1 to 5 carbon atoms) in the above formula (I) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group. Among these, a trimethylene group is preferable.
The ^{R 2} of the formula (I), an ethylene group, trimethylene group, ethylene oxyethylene groups and _{^{-CH 2 CH 2 N + (CH}} 3) {(CH 2) n Y)} CH 2 CH 2 OCH 2 CH 2 -Is preferred.
Examples of the alkyl group having 1 to 3 carbon atoms of R ³ and R ^{4 in} the above formula (I) include a methyl group and an ethyl group, and among these, a methyl group is preferable.

Specific examples of the silane coupling agent of the above formula (I) include the following compounds.
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOOCH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 COO -
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 COO -
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 OCH 2 CH 2 N + (CH 3) 2 CH 2 COO -
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 N + (CH 3) (CH 2 COO -) CH 2 CH 2 OCH 2 CH 2 N + (CH 3) 2 CH 2 COO -
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCONHCH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCONHCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 COO -
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ COOCH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ COO ⁻
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ C ₆ H ₄ COO ⁻
(C ₂ H ₅ O) ₂ Si (CH ₃ ) CH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ⁻
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 -
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 -
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 CH 2 CH 2 N + (CH 3) 2 CCH 2 CH 2 CH 2 SO 3 -
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 OCH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 -
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 N + (CH 3) (SO 3 -) CH 2 CH 2 OCH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO ₃ ⁻
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCONHCH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 -
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCONHCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 -
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ⁻
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ COOCH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ⁻
_{(C 2 H 5 O) 2} Si (CH 3) CH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 -

  The silane coupling agent of the formula (I) can be obtained by reacting a dialkylamino group-containing silicon compound (for example, a dimethylamino group-containing silicon compound) with a haloacetic acid compound, a sultone ring compound or a lactone ring compound.

The temperature at which the silane coupling agent of formula (I) is added is not limited, but is preferably between about 20 ° C. and the boiling point of the solvent.
The reaction temperature is not limited, but is preferably between about 20 ° C. and the boiling point of the solvent.
Although the reaction time is not limited, it is preferably 10 minutes to 48 hours, more preferably 6 hours to 24 hours.

  Solvents used in the reaction for obtaining the silane coupling agent of formula (I) include ester solvents: methyl acetate, ethyl acetate, butyl acetate and the like, alcohol solvents: methanol, ethanol, isopropanol, n-butanol, tert- Butanol, pentanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether and 1,4-butanediol, etc. Ether solvents: diethyl ether, tetrahydrofuran, dioxane, etc. Ketone solvents: aprotic solvents such as acetone and methyl ethyl ketone : Dimethyl sulfoxide, N, N-dimethylformamide, etc. Aromatic hydrocarbon solvents: Toluene, xylene, etc., and mixed solvents thereof.

The reaction temperature for obtaining the silane coupling agent of formula (I) is preferably the boiling point or higher of the solvent used, and the reaction may be carried out under pressure in order to obtain a temperature higher than the boiling point.
The reaction time is usually 6 hours to 36 hours, preferably 8 hours to 36 hours, more preferably 8 hours to 24 hours.

A commercially available product can be used as it is as the dimethylamino group-containing silicon compound which is a raw material of the silane coupling agent of the formula (I).
Alternatively, commercially available dimethylamino group-containing alcohols (eg: 2-dimethylaminoethanol, 3-dimethylaminopropanol, 4-dimethylaminobutanol, 2-dimethylaminoethoxyethanol and N, N, N′-trimethyl-N ′-( 2-hydroxyethyl) -bis (2-aminoethyl ether or the like) is reacted with a silane coupling agent having an isocyanate group (for example, 3-isocyanatopropyltriethoxysilane or the like) or a compound having an —NHCOO— group or a commercially available product. Silane coupling agent (for example, 3-isocyanatopropyltriethoxysilane) having an isocyanate group in a dimethylamino group-containing amine (for example, N, N-dimethylethylenediamine, N, N-dimethyl-1,3-propanediamine, etc.) React Compounds having a HCONH- group to obtained can be used.
Further, dimethylallylamine, 2- (dimethylamino) ethyl acrylate, 2- (dimethylamino) ethyl methacrylate, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide and the like A thioether group-containing silicon compound (for example, 3-mercaptopropyltrimethoxy, 3-mercaptopropylmethyldimethoxysilane, etc.) can be reacted with thioether group-containing silicon compound to obtain a thioether group-containing silicon compound.

Solvents for reacting silica sol silanol with the silane coupling agent of formula (I) are alcohol solvents: methanol, ethanol, isopropanol, n-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol. And 1,4-butanediol, ether solvents: diethyl ether, tetrahydrofuran and dioxane, ketone solvents: acetone and methyl ethyl ketone, aprotic solvents: dimethyl sulfoxide, N, N-dimethylformamide, water, etc. And a mixed solvent thereof.
Among these, alcohol solvents and water are preferable, and these solvents can be used alone or in combination of two or more.

  The amount of the raw material silica sol with respect to 100 parts by mass of the solvent is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight.

The amount of the silane coupling agent of the formula (I) relative to the silica sol is preferably 0.1 to 10.0 mmol, more preferably 0.5 to 5.5 mmol, relative to 1 g of the silica sol.
By making it 0.1 mmol or more, it is easy to improve the hydrophilicity of the cured product, and by making it 10.0 mmol or less, self-condensation between silane coupling agents is suppressed, and with the lack of silanol groups in silica sol Thus, it can be suppressed that the hardness of the cured product is insufficient and the scratch resistance of the release layer is lowered.

The above-mentioned modified organic solvent-dispersed silica sol (the product obtained by reacting silanol of silica sol with the silane coupling agent of formula (I)) is modified with a functional group represented by the following formula (II). .
^{_{(-O-) 3-k (R}} ) k Si-R 1 - (X-R 2) m -N + (R 3) (R 4) -R 5 -Y (II)
The embodiment of each symbol (k, R, Y, etc.) in the formula (II) is the same as the embodiment of each symbol in the above formula (I).

Examples of the modified organic solvent-dispersed silica sol include those obtained by reacting silanol of silica sol with a silane coupling agent containing a (meth) acryloyl group.
Examples of the silane coupling agent containing such a (meth) acryloyl group include 3-methacryloxypropyltriemethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxy. Examples thereof include propyltriethoxysilane.

The release layer forming composition containing the modified product of the organic solvent-dispersed silica sol may further contain other curing components such as a normal organic solvent-dispersed silica sol and a curable resin composition.
The curable resin composition contained in the release layer forming composition may be the same as the curable resin composition exemplified for the low refractive index layer. By including the curable resin composition in the release layer forming composition, the adhesion with the low refractive index layer can be further enhanced.
The content of the curable resin composition is 5 to 30 parts by mass with respect to 100 parts by mass of the active ingredient of the silica sol, from the viewpoint of the balance between the hydrophilicity of the release layer and the adhesion with the low refractive index layer. Is preferred.

The release layer forming composition can be cured, for example, by applying and drying on a low refractive index layer and then dehydrating and condensing silica sol. The dehydration condensation of the silica sol proceeds even by heat treatment, but it is preferable to use a catalyst such as a base and an acid in order to promote the dehydration condensation. The catalyst may be added to the release layer forming composition, or the release layer may be exposed to a catalyst atmosphere after the release layer is formed.
The temperature conditions for the dehydration condensation of the silica sol are not particularly limited, and may be appropriately determined in the range of 20 to 250 ° C.
Moreover, when a mold release layer forming composition contains a curable resin composition, hardening of a silica sol and hardening of a curable resin composition may be performed simultaneously, and any one may be performed first.

The thickness of the release layer is preferably 1 to 25 nm, more preferably 3 to 20 nm, and still more preferably 5 to 15 nm.
By setting the thickness of the release layer to 1 nm or more, the scratch resistance of the release layer can be easily improved. Moreover, the fall of antireflection performance can be suppressed by the thickness of a mold release layer being 25 nm or less. Furthermore, by setting the thickness of the release layer to 25 nm or less, the molecules constituting the release layer are arranged in an orderly manner and have a high degree of hydrophilicity, and it is considered that Condition 2 is easily satisfied.

The refractive index of the release layer is preferably 1.49 or less, and more preferably 1.46 or less. As described above, if the thickness of the release layer is reduced, it is possible to suppress a decrease in the antireflection performance based on the low refractive index layer or the like, but by setting the refractive index of the release layer to 1.49 or less. Further, it is possible to further suppress a decrease in antireflection performance.
Note that the lower limit of the refractive index of the release layer is about 1.30.

<Hard coat layer>
A hard coat layer may be provided between the transparent plastic film and the low refractive index layer in order to enhance the scratch resistance. In addition, when it has the high refractive index layer mentioned later on the transparent plastic film side of a low refractive index layer, it is preferable to form a hard-coat layer between a transparent plastic film and a high refractive index layer.

The hard coat layer preferably contains a cured product of a curable resin composition such as a thermosetting resin composition or an ionizing radiation curable resin composition, and from the viewpoint of improving scratch resistance, an ionizing radiation curable resin. More preferably, it contains a cured product of the composition.
The thermosetting resin composition and ionizing radiation curable resin composition of the hard coat layer may be the same as the thermosetting resin composition and ionizing radiation curable resin composition of the low refractive index layer described above. it can.

  The thickness of the hard coat layer is preferably 0.1 to 100 μm, more preferably 0.5 to 20 μm, and still more preferably 1 to 10 μm. By setting the thickness of the hard coat layer in the above range, it is possible to easily suppress the occurrence of curling while improving the scratch resistance.

The refractive index of the hard coat layer is preferably adjusted in the range of 1.45 to 1.70.
When the low refractive index layer has a high refractive index layer in contact with the transparent plastic film side, the refractive index of the hard coat layer is preferably lower than the refractive index of the high refractive index layer, 1.50 to 1.65. More preferably, it is more preferably 1.55 to 1.60. If the refractive index of the hard coat layer is within such a range, the hard coat layer has a role as a middle refractive index layer, and the hard coat layer (medium refractive index layer), the high refractive index layer, and the low refractive index layer. Since the interference action by the three layers becomes possible, the reflectance can be further reduced.

Examples of means for imparting a role as a medium refractive index layer to the hard coat layer include a means for blending a resin having a high refractive index in the hard coat layer coating liquid and a means for blending particles having a high refractive index.
Examples of the resin having a high refractive index include those obtained by introducing a sulfur-containing group, an aromatic ring, or the like into the thermosetting resin or ionizing radiation-curable compound described above. Examples of the high refractive index particles include those similar to the high refractive index particles used in the high refractive index layer described later.

<High refractive index layer>
The low reflective member of the present invention preferably has a high refractive index layer in contact with the transparent plastic film side of the low refractive index layer from the viewpoint of lowering the reflectance.
The high refractive index layer can be formed from, for example, a high refractive index layer coating solution containing high refractive index particles and a binder resin composition.

Examples of the high refractive index particles include antimony pentoxide, zinc oxide, titanium oxide, cerium oxide, tin-doped indium oxide, antimony-doped tin oxide, yttrium oxide, and zirconium oxide.
The average particle diameter of the primary particles of the high refractive index particles is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 7 to 50 nm.

  The content of the high refractive index particles is preferably 50 to 1000 parts by mass, and 100 to 750 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of increasing the refractive index of the coating and balancing the coating strength. More preferably, it is 200 to 500 parts by mass.

  Examples of the binder resin for the high refractive index layer include a cured product of a curable resin composition. As a curable resin composition, the thing similar to what was illustrated by the low-refractive-index layer can be used, and an ionizing radiation curable resin composition is suitable.

The refractive index of the high refractive index layer is preferably from 1.55 to 1.85, more preferably from 1.56 to 1.75.
Further, the thickness of the high refractive index layer is preferably 200 nm or less, and more preferably 50 to 180 nm.

<Other layers>
The low reflection member of the present invention may have other layers.
For example, an adhesive layer, an antistatic layer, a printing layer, and the like may be provided on the surface of the transparent plastic film opposite to the side having the low refractive index layer and the release layer.

<Other physical properties>
From the viewpoint of improving the visibility of the visual object, it is preferable that the haze of JISK7136: 2000 is less than 2.0% and 1.5% or less at the portion having low light transmittance of the low reflection member. Is more preferable, and it is further more preferable that it is 1.0% or less.
In addition, the location which has a light transmittance, for example, a printing layer was formed in the surface on the opposite side to the side which has a low refractive index layer and a release layer of a transparent plastic film, and the light transmittance fell. This is intended to exclude a place (a place where the total light transmittance is 50% or less).

  The surface on the release layer side of the low reflection member preferably has an arithmetic average roughness Ra (JIS B0601: 1994) with a cutoff value of 0.08 mm of 0.02 μm or less, more preferably 0.01 μm or less. preferable.

<Size, shape, etc.>
The low reflection member may be a single wafer or a roll.
Further, the size of the sheet is not particularly limited, but generally the size is about 2 to 500 inches diagonally. The roll width and length are not particularly limited, but generally the width is about 500 to 3000 mm and the length is about 500 to 5000 m.
Further, the shape of the single wafer is not particularly limited, and may be, for example, a polygon (triangle, quadrangle, pentagon, etc.), a circle, or a random irregular shape.

<Application>
The low reflection member of the present invention described above is arranged on the surface of a display device, an instrument panel, a clock, a showcase, a show window, etc., for example, thereby providing a visual object (for example, a display element in the display device; an instrument panel). , Instrument such as speedometer, tachometer, fuel gauge, water temperature meter and distance meter; dial, long hand, short hand and second hand, etc. for analog watches; various items in showcases and show windows); The visibility of the object can be improved, the writing ability with a pen is good, and the dirt removal property by a simple method can be maintained for a long time.

[Display device]
The display device of the present invention has the above-described low reflection member of the present invention.
More specifically, the display device of the present invention is a display device having a display element and a low reflection member disposed on the outermost surface on the light emitting surface side of the display element. The low reflection member of the present invention is arranged such that the surface having the release layer faces the side opposite to the display element. In addition, when it has a low refractive index layer and a mold release layer on both surfaces of a transparent plastic film and either side satisfy | fills conditions 1-3, the low reflection member on a display element may be which direction.

Examples of the display element include a liquid crystal display element, an EL display element, a plasma display element, and a micro LED display element.
Examples of the liquid crystal display element include a TN method, an STN method, a TSTN method, an IPS method, a VA method, a multi-domain method, and an OCB method. Moreover, the in-cell touchscreen liquid crystal element which incorporates a touchscreen function in any of these systems is also mentioned.

Further, the display device of the present invention may have a touch panel function.
Examples of the touch panel include a resistive film type, a capacitance type, an electromagnetic induction type, an infrared type, and an ultrasonic type.
The low reflection member can be installed on the front surface of the display element in the following order, for example.
(A) Display element / surface protective plate / low reflective member (b) display element / low reflective member (c) touch panel having display element / low reflective member on the surface

[Goods]
The article of the present invention is formed by arranging the release layer of the low reflection member of the present invention described above so as to face the surface.

  Articles include instrument panels, watches, showcases, show windows and windows. That is, the article of the present invention includes an instrument panel, a watch, a showcase, a show window, and a window in which the release layer of the low reflection member is arranged to face the surface.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not limited to the form as described in an Example.

1. Evaluation and Measurement The following measurements and evaluations were performed on the low reflection members obtained in Examples and Comparative Examples. The results are shown in Table 1.
1-1. Reflectivity (luminous reflectance Y value)
A black plate (Kuraray) is placed on the transparent plastic film side of the low reflection member of Example and Comparative Example via a transparent adhesive layer having a thickness of 25 μm (manufactured by Panac Corporation, trade name: Panaclean PD-S1, refractive index 1.49). A sample (5 cm × 5 cm) in which a product, product name: COMOGLASS DFA2CG 502K (black), total light transmittance 0%, thickness 2 mm, refractive index 1.49) was bonded together was produced.
When the vertical direction with respect to the surface of the low reflection member is set to 0 degree, light is incident on the sample from a direction of 5 degrees, and the reflectance of the sample (luminous reflectance Y based on the regular reflection light of the incident light). Value).
The reflectance is measured by using a spectral reflectance measuring device (manufactured by Shimadzu Corporation, trade name: MPC3100), measuring a 5 ° regular reflectance in a wavelength range of 380 to 780 nm, and then the brightness that humans perceive with eyes. A value indicating luminous reflectance calculated by software for conversion (built-in MPC3100) was obtained as reflectance. The reflectance at 10 locations for each sample was measured, and the average value was taken as the reflectance of each sample.

1-2. Confirmation of Conditions 1 to 3 After cutting the low-reflective members of Examples and Comparative Examples to a size of 5.0 cm × 5.0 cm, a transparent adhesive layer having a thickness of 25 μm (product of Panac Corporation, product) Name: Panaclean PD-S1) and a 2 mm thick transparent glass plate (5.0 cm × 5.0 cm) were prepared. It was confirmed whether the conditions 1-3 were satisfy | filled using the produced sample. Those satisfying each condition were designated as “A”, and those not satisfying each condition were designated as “C”. When conditions 1 were not satisfied, conditions 2 and 3 were not evaluated.
In addition, the atmosphere at the time of performing conditions 1-3 was made into temperature 23 degreeC +/- 5 degreeC, and humidity 40-65%. Moreover, before implementing conditions 1-3, each sample was left to stand in the said atmosphere for 10 minutes or more.
Further, “JIS S6037: 2006“ 3.b) Type of ink classification ”used in conditions 1 to 3 is oily, and an oil-based marking pen that satisfies the conditions of“ 4. Quality ”and“ 5. Material and structure ” "" Was written on the thin book side (thick side of the line) as the ink color "black" of the trade name "Mackey extra fine" manufactured by Zebra.
In conditions 1 and 3, reciprocal friction was performed at a speed of 30 mm one way and 1 second per reciprocation using a Gakushin type friction tester in accordance with JIS L0849: 2013.
Moreover, in conditions 2 and 3, water used ion-exchange water, and the dripping amount of the water dripped at the writing area | region was 1 ml.

1-3. Steel wool resistance (SW resistance)
After pressing # 0000 steel wool to the surface of the release layer side of the sample prepared in 1-2 above and rubbing it 10 times with a load of 500 g / cm ² , a black plate was placed on the back of the sample, and the fluorescent lamp It was visually evaluated whether or not scratches were visible from the release layer side under illumination. The case where the scratches were not visible was designated as “A”, and the case where the scratches were visible was designated as “C”. Furthermore, regarding a sample with an evaluation A at a load of 500 g / cm ² , when the same evaluation was performed at a load of 700 g / cm ² , a sample in which no scratch was visually recognized was designated as “AA”.

2. Preparation of coating solution The following coating solution was prepared.
<Coating liquid for hard coat layer>
-Urethane acrylate (trade name "UX5005", manufactured by Nippon Kayaku Co., Ltd., 9 functional) 50 parts by mass-25 parts by mass of pentaerythritol triacrylate-Acrylate monomer (trade name "R684", manufactured by Nippon Kayaku Co., Ltd., bifunctional) 25 Mass parts / photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) 4 parts by mass / leveling agent (trade name “Megafac F477”, manufactured by DIC) 0.2 parts by mass / methyl ethyl ketone 125 parts by mass / propylene 25 parts by mass of glycol monomethyl ether acetate

<Coating liquid for low refractive index layer>
・ Propylene oxide modified pentaerythritol tetraacrylate (trade name “ATM-4P”, manufactured by Shin-Nakamura Chemical Co., Ltd., solid content 100%) 75 parts by mass ・ Pentaerythritol triacrylate 25 parts by mass ・ Dispersion liquid containing hollow silica fine particles (solid Min 20%, average primary particle diameter 60 nm) 800 parts by mass-reactive silica fine particle-containing dispersion (trade name “MIBK-SD”, manufactured by Nissan Chemical Industries, solid content 30%, average primary particle diameter 12 nm) 83 parts by mass Photopolymerization initiator (trade name “Irgacure 127”, manufactured by BASF) 7 parts by mass 9300 parts by mass of methyl isobutyl ketone Propylene glycol monomethyl ether acetate 1100 parts by mass

<Release layer coating solution 1>
-5 parts by mass of a solution containing the following modified organic solvent-dispersed silica sol (solid content: about 0.08% by mass)
・ Ion-exchanged water 45 parts by mass ・ Isopropyl alcohol 5 parts by mass

<Solution containing modified organic solvent-dispersed silica sol>
40 ml of dehydrated ethyl acetate, 4.39 g of 1,2-oxathiolane 2,2-dioxide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.26 g of N, N-dimethyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) And stirred at room temperature for 24 hours. The resulting white precipitate was filtered to obtain 8.5 g of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine.
Next, 4.0 g of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine and an organic solvent-dispersed silica sol (Nissan Chemical Industries, IPA-ST (solid content 30% )) 13.2 g was dissolved in a solvent (a mixed solvent of ethanol 80 ml and water 140 ml) and heated to reflux overnight. After cooling, 520 mg of lithium hydroxide monohydrate (manufactured by Nacalai Tesque) was dissolved in a small amount of water and added to the reaction solution for neutralization. The resulting reaction solution was modified with a (—O—) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ — group by adding water to 500 g. 500 g of a solution containing a modified organic solvent-dispersed silica sol was obtained (solid content: about 1.6% by mass).

<Release layer coating solution 2>
-4 parts by mass of a solution containing the modified organic solvent-dispersed silica sol (solid content: about 0.064 parts by mass)
_{· Si 5 O 4 (OC 2} H 5) 12 ( trade name "Ethyl Silicate 40", manufactured by Colcoat Co., Ltd.) 0.02 parts by weight (solid basis)
-0.002 part by mass of 3-methacryloxypropyltrimethoxysilane-45 parts by mass of ion-exchanged water-5 parts by mass of isopropyl alcohol

<Coating solution for antifouling layer>
-Urethane acrylate (trade name "UV1700B", manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 98 parts by weight-Fluorine-based antifouling agent (trade name "Megafac RS75", manufactured by DIC) 2 parts by weight-Polymerization initiator (trade name ""Irgacure184" (manufactured by BASF) 4 parts by weight • 2000 parts by weight methyl isobutyl ketone • 200 parts by weight propylene glycol monomethyl ether acetate

3. Production of Low Reflective Member [Example 1]
On a polyethylene terephthalate film (refractive index of 1.65) having a thickness of 100 μm, the hard coat layer coating liquid having the above formulation was applied, dried (70 ° C., 1 minute) and irradiated with ultraviolet rays (100 mJ / cm ² ), and a thickness of 10 μm was applied. A hard coat layer was formed. Next, the low-refractive-index layer coating solution having the above-mentioned formulation is applied onto the hard coat layer, dried (90 ° C., 1 minute) and irradiated with ultraviolet rays (200 mJ / cm ² ), and has a thickness of 90 nm and a refractive index of 1.35. A refractive index layer was formed.
Next, after the surface of the low refractive index layer is subjected to corona discharge treatment, the release layer coating liquid 1 having the above formulation is applied, dried (100 ° C., 1 minute), and further heat treated at 110 ° C. for 15 minutes to cure the silica sol ( The release layer was formed by dehydration condensation, and the low reflection member of Example 1 was obtained. The theoretical thickness of the release layer based on the coating amount is 10 nm.
In addition, it was 1.43 when the coating liquid 1 for mold release layers was formed with the thickness which can measure a refractive index, and the refractive index was measured.

[Example 2]
A low reflection member of Example 2 was obtained in the same manner as Example 1 except that the thickness of the release layer was changed to 15 nm.

[Example 3]
A low reflection member of Example 3 was obtained in the same manner as in Example 1 except that the thickness of the release layer was changed to 7 nm.

[Example 4]
The “hollow silica fine particle-containing dispersion (solid content 20%, average primary particle size 60 nm)” of the coating solution for low refractive index layer is referred to as “hollow silica fine particle-containing dispersion (solid content 20%, average primary particle size 75 nm). The low reflection member of Example 4 was obtained in the same manner as in Example 1 except that it was changed to "."

[Example 5]
The “hollow silica fine particle-containing dispersion (solid content 20%, average primary particle size 60 nm)” of the coating solution for low refractive index layer is referred to as “hollow silica fine particle-containing dispersion (solid content 20%, average primary particle size 50 nm). The low reflection member of Example 5 was obtained in the same manner as in Example 1 except that it was changed to "."

[Example 6]
The “hollow silica fine particle-containing dispersion (solid content 20%, average primary particle size 60 nm)” of the coating solution for low refractive index layer is referred to as “hollow silica fine particle-containing dispersion (solid content 20%, average primary particle size 100 nm). The low reflection member of Example 6 was obtained in the same manner as in Example 1 except that it was changed to “.”

[Example 7]
A low reflection member of Example 7 was obtained in the same manner as Example 1 except that a high refractive index layer (refractive index 1.65, thickness 165 nm) was formed between the hard coat layer and the low refractive index layer. .
The high refractive index layer was formed by applying the following coating solution for high refractive index layer, drying (90 ° C., 1 minute) and ultraviolet irradiation (200 mJ / cm ² ).
<Coating liquid for high refractive index layer>
・ Pentaerythritol triacrylate (trade name PET30, manufactured by Nippon Kayaku Co., Ltd., solid content: 100%) 100 parts by mass-antimony pentoxide-containing dispersion (trade name “V-4564”, manufactured by JGC Catalysts & Chemicals, solid content: 40% 1100 parts by mass / fluorine leveling agent (trade name “Megafac F568”, manufactured by DIC, solid content 5%) 300 parts by mass / photopolymerization initiator (trade name “Irgacure 127”, BASF) 8 parts by mass)

[Example 8]
A low reflective member of Example 8 was obtained in the same manner as in Example 1 except that the low refractive index layer coating solution was changed to the low refractive index layer coating solution of Example 8 below.
<The coating liquid for low refractive index layers of Example 8>
-Silane coupling agent 1 (tetraethoxysilane) 25 parts by mass-Silane coupling agent 2 (3-methacryloxypropyltriemethoxysilane) 25 parts by mass-Pentaerythritol triacrylate 50 parts by mass-Hollow silica fine particle-containing dispersion ( Solid content 20%, average primary particle diameter 60 nm) 800 parts by mass, photopolymerization initiator (trade name “Irgacure 127”, manufactured by BASF) 7 parts by mass, methyl isobutyl ketone 9300 parts by mass, IPA 1100 parts by mass

[Example 9]
In the same manner as in Example 1, a hard coat layer and a low refractive index layer were formed on a polyethylene terephthalate film (refractive index: 1.65).
Next, after the surface of the low refractive index layer is subjected to corona discharge treatment, the release layer coating liquid 2 having the above formulation is applied, dried (100 ° C., 1 minute), and heat-treated at 110 ° C. for 15 minutes to cure the silica sol ( After dehydration condensation, ultraviolet irradiation (200 mJ / cm ² ) was performed to obtain a low reflection member of Example 9. The theoretical thickness of the release layer based on the coating amount is 10 nm.
In addition, it was 1.43 when the coating liquid 2 for mold release layers was formed in the thickness which can measure a refractive index, and the refractive index was measured.

[Comparative Example 1]
A low reflection member of Comparative Example 1 was obtained in the same manner as in Example 1 except that the release layer was not formed on the low refractive index layer.

[Comparative Example 2]
A release layer is not formed on the low refractive index layer, but the antifouling layer coating solution of the above formulation is applied to the low refractive index layer, dried and irradiated with ultraviolet rays, and has a thickness of 10 nm and a refractive index of 1.50. A low reflection member of Comparative Example 2 was obtained in the same manner as in Example 1 except that the layer was formed.

[Comparative Example 3]
A low reflective member of Comparative Example 3 was obtained in the same manner as in Example 1 except that the low refractive index layer was not formed on the hard coat layer and the release layer was formed directly on the hard coat layer.

As is clear from Table 1, the low-reflection members of Examples 1 to 9 can suppress reflection and improve the visibility of a visual object, have writing ability with a pen, and are simple. It can be confirmed that the soil removability by a simple method can be maintained for a long time.
Although not evaluated in the table, the low reflection member of Example 8 satisfies the condition 4 of the specification and can maintain the soil removal property for an extremely long time.

10: Transparent plastic film 20: Hard coat layer 30: Low refractive index layer 40: Release layer 100: Low reflection member 200: Display element 300: Display device

Claims (9)

A low reflection member having a low refractive index layer containing an inorganic compound on a transparent plastic film, wherein the low refractive index layer has a release layer on the surface opposite to the light transmissive substrate, The release layer is located on the outermost surface of the low reflection member, the reflectance of the release layer side surface of the low reflection member is 2.0% or less, and satisfies the following conditions 1 to 3. Reflective member.
<Condition 1>
Sample A is prepared by cutting the low reflection member into a size of 5.0 cm × 5.0 cm. An area of 1.0 cm × 1.0 cm in the center of the surface of the release layer side of sample A is oily in “3.b) Types of ink classification” in JIS S6037: 2006, and “4. Quality” and Write and paint with an oil-based marking pen that satisfies the conditions of “5. Material and structure”. After 60 seconds from writing, when the area written with the oil-based marking pen on the surface of the release layer was rubbed 5 times with a load of 500 g / cm ² using a No. 300 cotton cloth, the ink surface of the release layer Remain.
<Condition 2>
As in Condition 1, the surface of the release layer side of Sample A is written and painted with an oil-based marking pen. After 60 seconds have passed since writing, water is dropped with a dropper so that at least the entire area written with the oil-based marking pen on the surface of the release layer side of Sample A is covered with water. After 10 seconds from the completion of the dripping of water, when the sample A is inclined 45 ° from the horizontal plane, the written ink flows together with the water.
<Condition 3>
Sample B is obtained by subjecting the surface of the release layer of sample A to 1000 reciprocating friction using a No. 300 cotton flannel cloth at a load of 500 g / cm ² . When the same operation as in Condition 2 was performed except that sample A was changed to sample B, 10 seconds after the completion of the dripping of water, and when sample B was tilted 45 ° from the horizontal plane, writing was made. Ink flows with water.   The low reflective member according to claim 1, wherein the low refractive index layer includes low refractive index inorganic particles as the inorganic compound and a binder resin.   The low reflective member according to claim 2, wherein the low refractive index inorganic particles are hollow inorganic particles.   The low reflection member according to any one of claims 1 to 3, wherein the release layer has a thickness of 1 to 25 nm.   The low reflective member according to any one of claims 1 to 4, wherein the low refractive index layer and the release layer are provided on both sides of the transparent plastic film.   The low reflective member according to any one of claims 1 to 5, further comprising a hard coat layer between the transparent plastic film and the low refractive index layer.   The display apparatus which has the low reflection member of any one of Claims 1-6.   The display device according to claim 7, which is provided with a touch panel function.   The article | item formed by arrange | positioning so that the mold release layer of the low reflection member of any one of Claims 1-6 may face the surface.