TW201601929A - Anti-reflection laminate and method for producing same - Google Patents

Abstract

To improve the mechanical durability of an anti-reflection laminate which comprises a fluorine-containing silicon compound layer on a magnesium fluoride layer. This anti-reflection laminate is provided with a transparent base and a multilayer part that is arranged on the transparent base. The multilayer part comprises, sequentially from the transparent base side, a magnesium fluoride layer and a fluorine-containing silicon compound layer. In addition, the multilayer part comprises, in a portion in the lamination direction, a first intermediate layer that has a ratio of the oxygen atom concentration (RO) [at%] to the magnesium atom concentration (RM) [at%], namely RO/RM of more than 0.2 but 1.5 or less.

Description

Antireflection laminate and method of manufacturing same Field of invention

The present invention relates to an antireflection laminate and a method of manufacturing the same.

Background of the invention

Touch panels are used in electronic devices such as smart phones and tablet PCs. Because people touch the surface of the touch panel with their fingers, they will adhere to dirt caused by fingerprints, sebum, sweat, and the like. When these dirt adheres, it is hard to fall off, and transparency and the aesthetics fall. The same problem is also pointed out in the cover glass, the optical element, the sanitary machine, the display case, and the cover glass disposed in front of the picture, which are disposed in front of the display.

In order to improve transparency and aesthetics, it is known to provide a fluorine-containing cerium compound layer as an antifouling layer on the surfaces. In addition to water repellency and oil repellency, the fluorine-containing cerium compound layer is also required to have mechanical durability such as scratch resistance and abrasion resistance at the time of use.

Further, in order to suppress reflection and to improve the visibility, it is known to provide an antireflection layer on the surface of the cover glass or the like. As the antireflection layer, a single layer body or a multilayer body having a magnesium fluoride layer as the outermost layer is known. It is also known that a fluorine-containing cerium compound layer is provided on the magnesium fluoride layer. In addition, in order to improve In the mechanical durability of the fluoroquinone compound layer, it is known that a ruthenium oxide layer as an adhesion layer is provided between the magnesium fluoride layer and the fluorine-containing ruthenium compound layer (see, for example, Patent Document 1).

However, when a fluorine-containing cerium compound layer is provided on the magnesium fluoride layer, there are the following problems. In applications requiring high mechanical durability, if a ruthenium oxide layer is provided only between the magnesium fluoride layer and the fluorine-containing ruthenium compound layer, the mechanical durability of the fluorine-containing ruthenium compound layer may not be sufficient. Further, in applications where high mechanical durability is not necessarily required, productivity improvement is prioritized, and a certain degree of mechanical durability can be obtained without providing a ruthenium oxide layer.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. Hei 7-104102

Summary of invention

An embodiment of the present invention has been made to solve the above problems, and an object thereof is to improve the mechanical durability of an antireflection laminate having a fluorine-containing cerium compound layer on a magnesium fluoride layer. Further, another object of the present invention is to provide an antireflection laminate which has excellent mechanical durability by having a ruthenium oxide layer between a magnesium fluoride layer and a fluorine-containing ruthenium compound layer.

The antireflection laminate of the present invention comprises a transparent substrate and a laminate portion disposed on the transparent substrate. The laminated portion has a magnesium fluoride layer and a fluorine-containing cerium compound layer in this order from the side of the transparent substrate. Further, the laminated portion has a first surface in a part of the lamination direction, and a ratio (R _O /R _M ) of the oxygen atom concentration R _O [at%] to the magnesium atom concentration R _M [at%] of the first surface is larger than 0.2 Below 1.5.

The method for producing an antireflection laminate of the present invention has a step of forming a magnesium fluoride layer, a step of performing an oxygen plasma treatment, and a step of forming a fluorine-containing cerium compound layer. The step of forming a magnesium fluoride layer is performed on a transparent substrate to form a magnesium fluoride layer. The step of performing the oxygen plasma treatment is to perform an oxygen plasma treatment on the surface of the magnesium fluoride layer. The step of forming a fluorine-containing cerium compound layer is performed on the magnesium fluoride layer to form a fluorine-containing cerium compound layer.

In the present specification, the "face" such as the first surface and the second surface having a predetermined atomic concentration in one of the lamination directions indicates that the layer has a "layer" which is parallel to the main surface of the laminated portion and has the same size as the main surface. Further, the "layer" has a thickness which can be measured by X-ray photoelectron analysis (XPS) or the like to the extent of atomic concentration.

According to the present invention, the mechanical durability can be improved in the antireflection laminate having the laminated portion having the magnesium fluoride layer and the fluorine-containing cerium compound layer.

10‧‧‧Anti-reflective laminate

11‧‧‧Transparent substrate

12‧‧‧Layered Department

13‧‧‧Magnesium fluoride layer

14‧‧‧Fluorine-containing compound layer

15‧‧‧Non-oxygenated layer

15a‧‧‧Non-oxygenated layer

16‧‧‧Oxygen layer

17‧‧‧1st

18‧‧‧Oxide layer

19‧‧‧2nd

20‧‧‧ Plasma Processing Unit (LIS)

21‧‧‧ slit opening

22‧‧‧Oxygen ion beam

23‧‧‧ permanent magnet

24‧‧‧Anode

25‧‧‧ cathode

26‧‧‧ gas supply port

27‧‧‧Discharge power supply

28‧‧‧ magnetic lines of force

31‧‧‧1st floor

32‧‧‧2nd floor

33‧‧‧3rd floor

Fig. 1 is a cross-sectional view showing a first embodiment of an antireflection laminate.

Fig. 2 is a plan view showing an example of a plasma processing apparatus (LIS).

Fig. 3 is a cross-sectional view showing an example of a plasma processing apparatus (LIS).

Fig. 4 is a cross-sectional view showing a second embodiment of the antireflection laminate.

Fig. 5 is a cross-sectional view showing a third embodiment of the antireflection laminate.

Form for implementing the invention

Hereinafter, embodiments for carrying out the invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and various modifications and substitutions may be made in the embodiments described below without departing from the scope of the invention.

Fig. 1 is a cross section showing a first embodiment of an antireflection laminate; Figure.

The anti-reflection laminate 10 has a transparent substrate 11 and a laminate portion 12 disposed on the transparent substrate 11. Further, the laminated portion 12 has the magnesium fluoride layer 13 and the fluorine-containing cerium compound layer 14 in this order from the transparent substrate 11 side. The fluorine-containing cerium compound layer 14 is disposed as the uppermost layer of the laminated portion 12.

(transparent substrate)

The transparent substrate 11 is not particularly limited as long as it is an antifouling property, and may be a glass, a resin, or a combination thereof (composite material, laminated material, or the like). Examples of the glass include soda lime glass, borosilicate glass, alkali-free glass, quartz glass, aluminosilicate glass, sapphire glass, and the like, and soda lime glass is suitably used. Examples of the resin include an acrylic resin such as polymethyl methacrylate, an aromatic polycarbonate resin such as a carbonate of bisphenol A, and an aromatic polyester such as polyethylene terephthalate (PET). Resin, etc., and PET is suitable for use.

The surface of the transparent substrate 11 may be subjected to acid treatment, alkali treatment, ultrasonic cleaning using ultrapure water or an organic solvent, etc., depending on the demand. For the acid treatment, for example, the use of diluted hydrofluoric acid, sulfuric acid, Treatment with hydrochloric acid, etc. The alkali treatment may be a treatment using an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution.

Further, a layer having various functions can be provided on the surface of the transparent substrate 11 by a vapor deposition method, a sputtering method, a wet method, or the like as needed. For example, in the case where the transparent substrate 11 is a soda lime glass plate, in order to improve the durability of the laminated portion 12 formed on the transparent substrate 11, a layer for suppressing elution of Na ions may be provided. Further, in order to increase the strength of the glass sheet, chemical strengthening can be performed.

The transparent substrate 11 may have a planar shape or a curved surface having a whole surface or a part of a curvature. Further, the transparent substrate 11 may have a thick plate shape having rigidity or a film shape having flexibility. The thickness of the transparent substrate 11 can be appropriately selected between 50 μm and 10 mm.

(magnesium fluoride layer)

The magnesium fluoride layer 13 has magnesium fluoride (MgF ₂ ) as a main component. Here, the magnesium fluoride layer having magnesium fluoride as a main component indicates that the content of magnesium fluoride in the layer exceeds 50% by mass. Hereinafter, "as a principal component" is used in the same definition. Examples of the atom contained in the magnesium fluoride layer other than the fluorine atom and the magnesium atom include an oxygen atom, a halogen atom, and a carbon atom. Hereinafter, a magnesium fluoride layer containing an oxygen atom is referred to as an oxygen-containing layer, and a magnesium fluoride layer containing no oxygen atom is referred to as a non-oxygen-containing layer. However, the absence of oxygen means that the oxygen content in the layer is approximately less than 5 at%. The non-oxygenated layer is preferably a layer composed only of magnesium fluoride. Further, the oxygen-containing layer is preferably a layer containing only a fluorine atom, a magnesium atom and an oxygen atom.

The magnesium fluoride layer 13 may have a single layer structure or a multilayer structure. In the case of a multilayer structure, the composition of the layers may be the same or different. In the case of a multilayer structure, it may be composed of a non-oxygen-containing layer and an oxygen-containing layer. The composition is an example. In the case of a multilayer structure, the layers constituting the magnesium fluoride layer 13 do not necessarily have to contain magnesium fluoride as a main component, as long as the entire multilayer structure constitutes a layer containing magnesium fluoride as a main component. However, it is preferred that each layer be a layer containing magnesium fluoride as a main component. The refractive index of the magnesium fluoride layer 13 is generally lower than that of the transparent substrate 11, and from this point of view, by selecting an appropriate thickness, it can function as an antireflection layer having excellent properties.

However, the antireflection layer is not limited to being composed only of the magnesium fluoride layer 13. As will be described later, the antireflection layer may contain a layer other than the magnesium fluoride layer 13. When the antireflection layer contains a layer other than the magnesium fluoride layer 13, the magnesium fluoride layer 13 is disposed on the uppermost layer of the antireflection layer.

When the antireflection layer is composed of the magnesium fluoride layer 13 alone, the thickness of the magnesium fluoride layer 13 is preferably 20 nm or more from the viewpoint of obtaining an antireflection effect, preferably 30 nm or more, more preferably 40 nm or more. Further, from the viewpoint of antireflection effect and productivity, the thickness of the magnesium fluoride layer 13 is preferably, for example, 120 nm or less, more preferably 110 nm or less, and still more preferably 105 nm or less. However, the thickness in this specification is the physical film thickness.

The magnesium fluoride layer 13 has a non-oxygen-containing layer 15 and an oxygen-containing layer 16 in this order from the transparent substrate 11 side. When the ratio of oxygen atoms contained in the oxygen-containing layer 16 is lower, the refractive index of the oxygen-containing layer 16 is closer to the refractive index of the non-oxygen-containing layer 15, and the effect on the anti-reflection effect is smaller. On the other hand, the oxygen atom concentration in the magnesium fluoride layer 13 is usually the highest on the side of the fluorine-containing cerium compound layer 14 side and gradually decreases toward the side surface of the transparent substrate 11. At this time, the boundary between the non-oxygen-containing layer 15 and the oxygen-containing layer 16 is not clear.

The laminated portion 12 has a first surface 17 in a portion of the lamination direction, and the ratio (R _O /R _M ) of the oxygen atom concentration R _O [at%] to the magnesium atom concentration R _M [at%] of the first surface 17 is greater than 0.2. And below 1.5. In general, the first surface 17 includes a layer of the main surface of the magnesium fluoride layer 13 on the side of the fluorine-containing cerium compound layer 14, that is, a layer including the main surface of the oxygen-containing layer 16 on the side of the fluorine-containing cerium compound layer 14.

When the ratio (R _O /R _M ) is 0.2 or less, since the oxygen atom concentration R _{O is} low, the mechanical durability of the fluorine-containing cerium compound layer 14 formed on the magnesium fluoride layer 13 is insufficient. From the viewpoint of mechanical durability, the ratio (R _O /R _M ) is preferably 0.3 or more, more preferably 0.5 or more, and still more preferably 1.0 or more. Further, when the ratio (R _O /R _M ) exceeds 1.5, since the oxygen atom concentration R _{O is} high, the surface refractive index of the oxygen-containing layer 16 rises, and the antireflection effect is lowered or the coloring is easily caused.

The surface of the magnesium fluoride layer 13, that is, the arithmetic mean roughness Ra (hereinafter also referred to as Ra) of the surface of the oxygen-containing layer 16 is preferably less than 1.3 nm. On the other hand, the arithmetic mean surface roughness Ra was measured in accordance with JIS B 0601:2001. When the arithmetic mean roughness Ra is less than 1.3 nm, the durability of the fluorine-containing cerium compound layer 14 formed on the magnesium fluoride layer 13 can be improved. From the viewpoint of durability, the arithmetic mean roughness Ra is preferably 1.0 nm or less, more preferably 0.8 nm or less, and still more preferably 0.6 nm or less.

In order to obtain the first surface in which the ratio (R _O /R _M ) is within the above range, oxygen atoms may be introduced into the surface of the magnesium fluoride layer by plasma irradiation as will be described later. At that time, the ratio (R _O /R _M ) of the surface of the magnesium fluoride layer after the plasma irradiation is increased, the Ra becomes smaller, and the mechanical durability is improved as compared with the plasma irradiation. At the same time, as described above, the refractive index rises, or damage due to plasma irradiation (hereinafter also referred to as irradiation damage) becomes large and becomes easy to color. Therefore, the arithmetic mean roughness Ra is preferably 0.2 nm or more. By setting this Ra, good mechanical durability can be achieved.

(fluorine-containing cerium compound layer)

The fluorine-containing cerium compound layer 14 is disposed on the uppermost layer of the anti-reflection layered body 10. Since the fluorine-containing cerium compound layer 14 has water repellency and oil repellency, it can function as an antifouling layer that suppresses contamination or the like. Moreover, since the slidability is also improved, the scratch resistance and the mechanical durability can be improved.

The thickness of the fluorine-containing cerium compound layer 14 is about the thickness of the monomolecular layer or is thicker. When the thickness of the monolayer is more than or equal to the thickness of the monolayer, water repellency and oil repellency can be obtained From the viewpoint of water repellency, oil repellency, and mechanical durability, it is preferably 3 nm or more, and more preferably 5 nm or more. Further, from the viewpoint of productivity and the transmittance or haze, it is preferably 30 nm or less, and more preferably 20 nm or less.

The fluorine-containing cerium compound layer 14 contains a fluorine-containing cerium compound as a main component. In order to impart various functions, the fluorine-containing cerium compound layer 14 may contain various optional components. The fluorine-containing cerium compound can be formed, for example, by a hydrolysis condensation reaction of a hydrolyzable fluorine-containing cerium compound. Hereinafter, the hydrolyzable fluorine-containing cerium compound is simply referred to as a hydrolyzable compound. The hydrolyzable compound has a hydrolyzable group or a hydrolyzable mercapto group to which an atom has been bonded to a deuterium atom, and has a fluorine-containing organic group bonded to the deuterium atom. Hereinafter, the hydrolyzable group or atomic number is referred to as a hydrolyzable group.

In the hydrolyzable compound, the hydrolyzable thiol group is hydrolyzed to a sterol group, and then the dehydration condensation is carried out between the molecules to form a decane bond represented by -Si-O-Si-, thereby generating fluorine矽 compound. Further, by allowing the fluorine-containing organic group to exist on the surface opposite to the surface on the side of the magnesium fluoride layer 13, the water repellency and the oil repellency can be exhibited.

The fluorine-containing cerium compound layer 14 may be formed using only a hydrolyzable compound, or may be formed by using any component other than the same. Examples of the optional component include a hydrolyzable hydrazine compound having no fluorine atom, a catalyst, and the like. Hereinafter, the hydrolyzable hydrazine compound having no fluorine atom is simply referred to as a non-fluorohydrolyzable compound. The hydrolyzable compound and the non-fluorohydrolyzable compound are not limited to those which are not hydrolyzed, and may be partially hydrolyzed.

The hydrolyzable compound preferably has one or more selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group, and a perfluoroalkyl group. Among these, a perfluoropolyether group is preferred. These groups are present as a fluorine-containing organic group bonded to a hydrazine atom of a hydrolyzable fluorenyl group by a linking group or directly. Further, the perfluoropolyether group means a divalent group having a structure in which a perfluoroalkylene group and an etheric oxygen atom are alternately bonded.

The number average molecular weight (Mn) of the hydrolyzable compound is preferably 2,000 or more and 10,000 or less, and more preferably 3,000 or more and 5,000 or less. When the number average molecular weight (Mn) is within the above range, water repellency, oil repellency, mechanical durability, and the like are all good. However, the number average molecular weight (Mn) can be determined by gel permeation chromatography.

The hydrolyzable compound is preferably a compound represented by the following general formulae (1) to (5), for example.

In the formula (1), R ^f1 is a linear perfluoroalkyl group having 1 to 16 carbon atoms, R ¹ is a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, and X ¹ is a hydrolyzable group or a halogen atom. m is 1 to 50, n is 0 to 2, and p is an integer from 1 to 10.

Examples of the alkyl group in the perfluoroalkyl group of R ^f1 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group and the like. Examples of the lower alkyl group of R ¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group and the like. Examples of the hydrolyzable group of X ¹ include an amine group, an alkoxy group, a decyloxy group, an alkenyloxy group, an isocyanate group and the like. Examples of the halogen atom of X ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The carbon number of R ^f1 is preferably from 1 to 4. R ¹ is preferably a methyl group. The hydrolyzable group of X ¹ is preferably an alkoxy group having 1 to 6 carbon atoms, and preferably a methoxy group or an ethoxy group. m is preferably an integer from 1 to 30. n is preferably an integer of 1 to 2. p is preferably an integer from 1 to 8.

C _q F _2q+1 CH ₂ CH ₂ Si(NH ₂ ) ₃ (2)

In the formula (2), q is an integer of 1 or more.

q is preferably an integer from 2 to 20. Examples of the compound represented by the formula (2) include n-trifluoro(1,1,2,2-tetrahydro)propyloxazane (n-CF ₃ CH ₂ CH ₂ Si(NH ₂ ) ₃ ). And n-hexafluoro(1,1,2,2-tetrahydro)pentyl decazane (nC ₃ F ₇ CH ₂ CH ₂ Si(NH ₂ ) ₃ ) or the like.

C _r F _2r+1 CH ₂ CH ₂ Si(OCH ₃ ) ₃ (3)

In the formula (3), r is an integer of 1 or more.

r is preferably an integer from 1 to 20. Examples of the compound represented by the formula (3) include 2-(perfluorooctyl)ethyltrimethoxydecane (nC ₈ F ₁₇ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ).

[Chemical 2]

In the formula (4), R ^f2 is represented by -(OC ₃ F ₆ ) _s -(OC ₂ F ₄ ) _t -(OCF ₂ ) _u - (s, t, and u are each independently an integer of 0 to 200) The divalent linear perfluoropolyether group, and each of R ² and R ³ is independently a hydrocarbon group having 1 to 8 carbon atoms. X ² and X ³ are independently a hydrolyzable group or a halogen atom, and a and b are independently 2 or 3, and c and f are independently an integer of 1 to 5, and d and e are independently an integer of 1 to 2.

Examples of the hydrocarbon group of one of R ² and R ³ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group. Examples of the hydrolyzable group of X ² and X ³ include an amine group, an alkoxy group, a decyloxy group, an alkenyloxy group, and an isocyanate group. Further, examples of the halogen atom of X ² and X ³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

s+t+u is preferably an integer of 20 to 300, and is preferably an integer of 25 to 100. In the case of R ² and R ³ , a methyl group, an ethyl group or a butyl group is preferred. The hydrolyzable group of X ² and X ³ is preferably an alkoxy group having 1 to 6 carbon atoms, and preferably a methoxy group or an ethoxy group. A and b are preferably 3 respectively. c and f are preferably integers of 1 to 2 alone.

F-(CF ₂ ) _v -(OC ₃ F ₆ ) _w -(OC ₂ F ₄ ) _y -(OCF ₂ ) _z (CH ₂ ) _h O(CH ₂ ) _i Si(X ⁴ ) _3-k (R ⁴ ) _k ...(5)

In the formula (5), X ⁴ is a hydrolyzable group, R ⁴ is a linear or branched hydrocarbon group having 1 to 22 carbon atoms, and v is an integer of 1 to 3, and w, y, and z are independently 0 to 200, respectively. An integer, h is 1 or 2, i is an integer from 2 to 20, and k is an integer from 0 to 2.

X ⁴ is preferably an alkoxy group having 1 to 6 carbon atoms, and preferably a methoxy group or an ethoxy group. R ⁴ is preferably an alkyl group having 1 to 10 carbon atoms. w+y+z is preferably an integer of 20 to 300, and an integer of 25 to 100 is preferred. i is preferably an integer from 2 to 10.

As the hydrolyzable compound, a commercially available product can be used. Such a commercially available product may, for example, be KP-801 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-130 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-178 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-185 (trade name, Shin-Etsu Chemical Co., Ltd.), X-71-186 (trade name, Shin-Etsu Chemical Co., Ltd.), X-71-190 (trade name, Shin-Etsu Chemical Co., Ltd.), OPTOOL (registered trademark) ) DSX (trade name, Daikin Industries Co., Ltd.), etc.

Next, a method of manufacturing the anti-reflection laminate 10 will be described.

The antireflection layered body 10 is produced by sequentially forming the magnesium fluoride layer 13 and the fluorine-containing cerium compound layer 14 on the transparent substrate 11.

The magnesium fluoride layer 13 can be produced, for example, by forming a non-oxygen-containing layer containing no oxygen, and then modifying a portion of the surface of the non-oxygen-containing layer to form an oxygen-containing oxygen-containing layer 16 containing oxygen. Further, the portion remaining in the non-oxygen-containing layer which is initially formed without being modified is the non-oxygen-containing layer 15 in the magnesium fluoride layer 13. In terms of the treatment method, oxygen plasma treatment is preferred. The oxygen plasma treatment is carried out by using a plasma containing oxygen ions which are produced using an introduction gas containing oxygen as a main component. The introduction gas preferably contains 95% by volume or more of oxygen. By performing the oxygen plasma treatment, the first surface 17 having a ratio (R _O /R _M ) of more than 0.2 and 1.5 or less can be formed.

The oxygen plasma treatment is preferably carried out so that the energy density is 10 kJ/m ² or more. Here, the energy density is the energy density of the surface to be treated. The energy density can be calculated from the input power of the plasma generating device and the irradiation time. From the viewpoint that the ratio (R _O /R _M ) of the surface to be processed which becomes the first surface increases and the mechanical durability of the antireflection layered body 10 becomes good, the energy density is preferably 15 kJ/m ² or more, and is 20 kJ. More preferably, it is /m ² or more, and more preferably 25 kJ/m ² or more. Further, from the viewpoint of suppressing the coloration of the magnesium fluoride layer 13 due to an increase in the ratio (R _O /R _M ) of the surface to be processed, the energy density is preferably 100 kJ/m ² or less, and is 85 kJ/m ² or less. Preferably, it is more preferably 75 kJ/m ² or less.

For oxygen plasma treatment, a linear ion source (LIS) or reactive ion etching (RIE) is suitable. In this case, it is preferable that the LIS is an oxygen ion beam which is directional to the surface to be treated.

The LIS has a simple structure consisting of an anode, a cathode, and a permanent magnet. It is an ion source that can be plasma generated and ion accelerated by a power source. The introduction gas for generating the plasma preferably contains oxygen as a main component. In the LIS, after the oxygen as the introduction gas is discharged into a plasma in a reduced-pressure gas atmosphere, oxygen ions in the plasma are emitted as a beam. With the LIS, a large area of the processed surface can be processed uniformly and at high speed.

2 and 3 are diagrams for explaining the structure of the LIS. Here, FIG. 2 is a plan view of the LIS. Figure 3 is a cross-sectional view taken along line A-A of Figure 2; 3, together with the LIS, the transparent substrate 11 having the non-oxygen-containing layer 15a as the material to be treated is shown, and the surface of the non-oxygen-containing layer 15a is treated by oxygen plasma to obtain the oxygen-containing layer 16 and the non-oxygenated layer. The appearance of the transparent substrate 11 of the layer 15.

As shown in FIG. 2, the LIS 20 has, for example, two linear slit openings 21. The oxygen ion beam 22 can be emitted from the slit opening portion 21. The transparent substrate 11 having the non-oxygen-containing layer 15a is disposed such that the non-oxygen-containing layer 15a and the slit opening portion 21 relative state. The transparent substrate 11 with the non-oxygen-containing layer 15a is transported in parallel with respect to the LIS 20, whereby the entire surface of the non-oxygen-containing layer 15a can be uniformly irradiated with the oxygen ion beam 22, and the surface layer of the non-oxygen-containing layer 15a can be changed. The oxygen-containing layer 16 is formed, and the remaining portion which has not been modified is the non-oxygen-containing layer 15.

As shown in FIG. 3, the LIS 20 has a permanent magnet 23 at the center and has both an anode 24 and a cathode 25. The anode 24 and the cathode 25 are arranged such that an electric field and a magnetic field are orthogonal to each other in the slit opening portion 21. The LIS 20 has a gas supply port 26 for supplying an introduction gas to the main surface side opposite to the main surface side having the slit opening portion 21.

In the LIS 20, oxygen as an introduction gas can be supplied to the anode 24 from the gas supply port 26 in a reduced pressure gas atmosphere. A discharge source 27 is connected to the anode 24 and the cathode 25. By applying a voltage to the anode 24 and the cathode 25, plasma and accelerated oxygen ions can be generated. Further, magnetic lines of force generated in the slit opening portion 21 are indicated by reference numeral 28 in FIG. The accelerated oxygen ions can be emitted from the slit opening portion 21 by the oxygen ion beam 22.

Here, when the material to be processed is conveyed at a constant speed, the energy density of the surface to be processed of the LIS can be approximated by the following equation.

Energy density (kJ/m ² ) = input power per unit length of LIS (W/m) / (transport speed (m/sec) × 10 ³ )

In addition, LIS can use commercially available products. Examples of such commercially available products include PPALS series PPALS 30, 56, and 81 (trade name, manufactured by General Plasma Inc.).

The fluorine-containing cerium compound layer 14 can be adhered to the surface of the magnesium fluoride layer 13 by the hydrolyzable fluorine-containing cerium compound (hydrolyzable compound), in particular, the oxygen-containing layer 16 The surface is formed by reacting it into a fluorine-containing cerium compound. When the fluorine-containing cerium compound layer 14 is formed, a hydrolyzable hydrazine compound (non-fluorohydrolyzable compound) having no fluorine atom may be used in combination.

The method of attaching the hydrolyzable compound to the surface of the magnesium fluoride layer 13 may be either a wet method or a dry method. Examples of the dry method include a vacuum deposition method, a reduced pressure chemical vapor method, and the like. In the dry method, a vacuum vapor deposition method is preferred from the viewpoint of suppressing unnecessary decomposition of the hydrolyzable compound and simplifying the structure of the film forming apparatus.

Examples of the vacuum vapor deposition method include a resistance heating method, an electron beam heating method, a high frequency induction heating method, a reactive vapor deposition method, a molecular beam epitaxy method, a hot wall vapor deposition method, an ion plating method, and a cluster ion. Beam method, etc. Among these, from the viewpoint of suppressing unnecessary decomposition of the hydrolyzable compound and simplifying the structure of the film forming apparatus, it is preferable to use a resistance heating method.

In the case of vacuum vapor deposition, the temperature of the transparent substrate 11 is preferably 150 ° C or less from the viewpoint of obtaining a sufficient film formation rate, preferably 100 ° C or less, more preferably 80 ° C or less, and most 60 ° C or less. good. Further, the temperature is usually 20 ° C or more.

The hydrolyzable compound is attached to the surface of the magnesium fluoride layer 13 and forms a metal oxyalkylene bond, or is attached to the surface of the magnesium fluoride layer 13 and forms a metal oxyalkylene bond, and is subjected to hydrolytic condensation reaction in the molecule. The oxime is bonded to form a fluorine-containing ruthenium compound. Thereby, the fluorine-containing cerium compound layer 14 can be formed on the magnesium fluoride layer 13.

Further, in order to promote the hydrolysis condensation reaction, the hydrolyzable compound may be subjected to heat treatment after being attached to the magnesium fluoride layer 13. On the heat treatment method In other words, a method using a hot plate, a constant temperature and humidity chamber, or the like can be mentioned. The heat treatment temperature is preferably 50 ° C or more and 200 ° C or less. Further, the heat treatment time is preferably 10 minutes or more and 60 minutes or less. The humidity of the heat treatment is preferably 40% RH or more and 95% RH or less.

Next, a second embodiment of the anti-reflection laminate 10 will be described.

Fig. 4 is a cross-sectional view showing a second embodiment of the anti-reflection layered body 10.

The anti-reflection laminate 10 may further have a ruthenium oxide layer between the magnesium fluoride layer 13 and the fluorine-containing ruthenium compound layer 14. 4 is a cross-sectional view showing the anti-reflection laminate 10 in which a ruthenium oxide layer 18 is provided between the magnesium fluoride layer 13 and the fluorine-containing yttrium compound layer 14 which are sequentially laminated on the transparent substrate 11. . By providing the yttrium oxide layer 18 between the magnesium fluoride layer 13 and the fluorine-containing yttrium compound layer 14, the mechanical durability of the anti-reflection laminate 10 can be further improved. The configuration other than the ruthenium oxide layer 18 is the same as that of the first embodiment.

(yttria layer)

The ruthenium oxide layer 18 has ruthenium oxide as a main component. The cerium oxide layer 18 can impart various functions depending on the demand, and therefore may contain additional components. One of the major faces of the yttrium oxide layer 18 is in contact with the oxygen-containing layer 16 of the magnesium fluoride layer 13. Further, the other main surface of the ruthenium oxide layer 18 is in contact with the fluorine-containing ruthenium compound layer 14. Examples of the additional component which the cerium oxide layer 18 can contain include a carbon atom and a nitrogen atom. These may be contained in the yttrium oxide layer 18 in an amount of approximately 3% by mass or less.

By providing such a ruthenium oxide layer 18, the adhesion between the layers on both sides of the ruthenium oxide layer 18 can be enhanced. Thereby, compared with the case where the yttrium oxide layer 18 is not inserted, the anti-reflection of the fluorine-containing yttrium compound layer 14 on the outermost surface can be greatly improved. The mechanical durability of the irrigated layer body 10. Therefore, in the case where mechanical durability is emphasized, the yttrium oxide layer 18 is preferably inserted.

When the ruthenium oxide layer 18 is provided, it is preferable that the laminated portion 12 has the second surface 19 in one of the lamination directions, the ruthenium atom concentration of the second surface 19 is 1 at%, and the oxygen atom concentration is 5 at% or more and 15 at% or less. In other words, when the concentration of germanium atoms or the like is measured in the lamination direction from one main surface of the laminated portion 12 (for example, the main surface opposite to the transparent substrate side) to the other main surface (for example, the main surface on the transparent substrate side) The oxygen atom concentration is preferably 5 at% or more and 15 at% or less on the surface of the layer in the direction in which the germanium atom concentration is 1 at%.

Usually, the second surface 19 is present in the vicinity of the junction between the magnesium fluoride layer 13 and the yttrium oxide layer 18. The second surface 19 can be obtained, for example, by forming a yttria layer 18 on the surface of the magnesium oxide layer 13 subjected to the oxygen plasma treatment, that is, on the surface of the oxygen-containing layer 16. The ruthenium oxide layer 18 can be suitably formed by, for example, a vacuum deposition method, a sputtering method, or the like using ruthenium oxide, ruthenium dioxide, or the like.

A magnesium fluoride layer composed only of magnesium fluoride (MgF ₂ ) is formed by ionic bonding of Mg ²⁺ and F ⁻ . No surface treatment is applied to such a magnesium fluoride layer, and only a layer of ruthenium oxide layer may not form a Mg-O-Si bond. Therefore, for example, if an antireflection laminate in which only a ruthenium oxide layer and a fluorine-containing ruthenium compound layer are laminated on a magnesium fluoride layer composed only of magnesium fluoride is formed and subjected to a sliding test, it is easy to be oxidized in the magnesium fluoride layer. The boundary surface of the enamel layer is peeled off, so that the mechanical durability is lowered. However, the antireflection layered body 10 of the embodiment has a first surface when oxygen atoms are introduced into the surface of the magnesium fluoride layer 13, and more preferably has a vicinity of the junction between the magnesium fluoride layer 13 and the yttrium oxide layer 18. On the second side 19, a chemical bond can be formed between the magnesium fluoride layer 13 and the yttrium oxide layer 18. As a result, the mechanical properties of the antireflection laminate 10 are excellent.

From the viewpoint of improving the mechanical durability of the antireflection laminate 10, the oxygen atom concentration of the second surface 19 (the niobium atom concentration is 1 at%) is preferably 7 at% or more, more preferably 10 at% or more. More than 12at% is especially good. Further, the above concentration can be obtained by forming the yttrium oxide layer 18 on the magnesium fluoride layer 13 in which the ratio (R _O /R _M ) of the surface layer portion has been adjusted within a predetermined range.

Further, the positions of the first surface 17 and the second surface 19 in the lamination direction of the laminated portion 12 may be the same or different, and it is generally preferable to use the same. That is, the ratio (R _O /R _M ) is more than 0.2 and preferably 1.5 or less in the surface where the germanium atom concentration is 1 at% and the oxygen atom concentration is 5 at% or more and 15 at% or less.

The thickness of the ruthenium oxide layer 18 is preferably 1.0 nm or more from the viewpoint of enhancing the effect of improving the adhesion, and is preferably 1.5 nm or more, more preferably 2.0 nm or more, and particularly preferably 3.0 nm or more. Moreover, the thickness of the ruthenium oxide layer 18 is preferably 10 nm or less, and preferably 8 nm or less from the viewpoint of not impairing the reflection characteristics and the productivity. Here, in the two main faces of the yttrium oxide layer 18, the position in the lamination direction of the main surface on the side of the magnesium fluoride layer 13 is not necessarily clear, so that the position at which the concentration of germanium atoms is 1 at% is inexpensive as the main side of the magnesium fluoride layer 13 side. The location of the face.

The arithmetic mean roughness Ra of the side surface of the fluorine-containing cerium compound layer 14 of the cerium oxide layer 18 is preferably less than 1.3 nm. When the arithmetic mean roughness Ra is less than 1.3 nm, the mechanical durability of the fluorine-containing cerium compound layer 14 formed on the yttrium oxide layer 18 can be improved. From the viewpoint of durability, the arithmetic mean roughness Ra is preferably 1.2 nm or less, more preferably 1.1 nm or less, and still more preferably 0.9 nm or less. Arithmetic average The roughness Ra is preferably 0.2 nm or more. Here, in general, the thickness of the yttrium oxide layer 18 is extremely thin with respect to the thickness of the magnesium fluoride layer 13, so that the arithmetic mean roughness Ra of the surface of the magnesium fluoride layer 13 is smaller, and the arithmetic mean of the surface of the yttrium oxide layer 18 is obtained. The smaller the roughness Ra is. Therefore, the arithmetic mean roughness Ra of the surface of the ruthenium oxide layer 18 can be adjusted by adjusting the arithmetic mean roughness Ra of the surface of the magnesium fluoride layer 13.

Next, a third embodiment of the anti-reflection layered body 10 will be described.

Fig. 5 is a cross-sectional view showing a third embodiment of the antireflection layered body 10.

The anti-reflection laminated body 10 has a first layer, a second layer, and a third layer from the side of the transparent substrate 11 between the transparent substrate 11 and the magnesium fluoride layer 13, and the first layer and the second layer are The third layers each have a predetermined refractive index, and the refractive indices between the layers have a predetermined relationship. 5 is a view showing a transparent substrate 11 and a first layer 31, a second layer 32, a third layer 33, a magnesium fluoride layer 13, a yttrium oxide layer 18, and a fluorine-containing yttrium compound layer 14 which are sequentially laminated thereon. A cross-sectional view of the anti-reflection laminate 10. The first layer 31 has a refractive index of 1.6 or more and less than 1.8. The second layer 32 has a refractive index of 2.2 or more and 2.5 or less. The third layer 33 has a refractive index of 2.0 or more and 2.3 or less. The refractive index of the second layer 32 is greater than the refractive index of the third layer 33. Further, the refractive index is a refractive index at a light having a wavelength of 550 nm.

The first layer 31, the second layer 32, and the third layer 33 function as an antireflection layer together with the magnesium fluoride layer 13. With the antireflection layer, the reflectance can be sufficiently lowered, the reflected color can be moderately colored, and the reflected color can be suppressed from changing with the incident angle of light. Moreover, even if the thickness of each layer is slightly changed, the change in the reflected color can be suppressed.

Moderate colorization and reflection suppression from reflection suppression and reflection color From the viewpoint of the change, the refractive index of the first layer 31 is preferably 1.65 or more, and more preferably 1.70 or more. Further, for the same reason, the refractive index of the first layer 31 is preferably 1.79 or less.

The constituent material of the first layer 31 is preferably a metal oxide. Examples of the metal oxide include cerium oxide, indium oxide, tin oxide, cerium oxide, titanium oxide, zirconium oxide, cerium oxide, cerium oxide, aluminum oxide, zinc oxide, and the like. The metal oxide may be contained alone or in combination of two or more. Further, the metal oxide may be a mixed oxide of two or more kinds of metals. The first layer 31 can be formed as appropriate by a vacuum deposition method, a sputtering method, or the like.

Further, the metal oxide does not necessarily mean only a metal oxide in which a metal atom and an oxygen atom are combined in a stoichiometric composition ratio, and a metal oxide having a composition ratio which is deviated from the non-stoichiometric composition ratio. According to the demand, for example, yttrium oxide can also be described as SiO _x . Therefore, in each metal oxide, when it is used alone, the composition is adjusted so as to achieve the refractive index required for the first layer. Further, the refractive index can be adjusted by making a mixture or a mixed oxide. The following is the same for the second and third layers.

The thickness of the first layer 31 is preferably 40 nm or more, more preferably 50 nm or more, and more preferably 60 nm or more from the viewpoints of suppressing reflection, moderate colorization of the reflected color, and suppression of change in reflected color. Further, for the same reason, the thickness of the first layer 31 is preferably 100 nm or less, more preferably 90 nm or less, and still more preferably 85 nm or less.

The refractive index of the second layer 32 is preferably 2.23 or more, more preferably 2.25 or more, and more preferably 2.30 or more from the viewpoints of suppressing reflection, moderate colorization of the reflected color, and suppression of change in reflected color. Also, for the same reason, the second The refractive index of the layer 32 is preferably 2.47 or less, more preferably 2.45 or less, and still more preferably 2.40 or less.

The constituent material of the second layer 32 is preferably a metal oxide. Examples of the metal oxide include cerium oxide, titanium oxide, and the like. The metal oxide may be contained alone or in combination of two or more. Further, the metal oxide may be a mixed oxide of two or more kinds of metals. Further, the metal oxide may also contain cerium oxide for adjusting the refractive index. The second layer 32 can be suitably formed by a vacuum deposition method, a sputtering method, or the like.

The thickness of the second layer 32 is preferably 30 nm or more, and preferably 35 nm or more, more preferably 40 nm or more, and more preferably 45 nm or more, from the viewpoints of suppressing reflection, moderate colorization of reflected color, and suppression of change in reflected color. . Further, for the same reason, the thickness of the second layer 32 is preferably 90 nm or less, more preferably 87 nm or less, still more preferably 85 nm or less, and particularly preferably 80 nm or less.

The refractive index of the third layer 33 is preferably 2.05 or more, and preferably 2.10 or more, from the viewpoints of suppressing reflection, moderate colorization of reflected color, and suppression of change in reflected color. Further, for the same reason, the refractive index of the third layer 33 is preferably 2.28 or less, and more preferably 2.25 or less.

The constituent material of the third layer 33 is preferably a metal oxide. Examples of the metal oxide include cerium oxide, indium oxide, tin oxide, cerium oxide, titanium oxide, zirconium oxide, cerium oxide, cerium oxide, aluminum oxide, zinc oxide, and the like. The metal oxide may be contained alone or in combination of two or more. When two or more kinds of metal oxides are contained, the refractive index is moderate, which is preferable. Further, the metal oxide may be a mixed oxide of two or more kinds of metals. The third layer 33 can be suitably formed by a vacuum deposition method, a sputtering method, or the like.

The thickness of the third layer 33 is preferably 30 nm or more, more preferably 33 nm or more, and more preferably 35 nm or more from the viewpoints of suppressing reflection, moderate colorization of reflected color, and suppression of change in reflected color. Further, for the same reason, the thickness of the third layer 33 is preferably 90 nm or less, more preferably 80 nm or less, and still more preferably 70 nm or less.

The thickness of the magnesium fluoride layer 13 used in combination with the first layer 31, the second layer 32, and the third layer 33 is 60 nm or more from the viewpoints of suppressing reflection, moderate colorization of reflected color, and suppression of change in reflected color. Preferably, it is preferably 70 nm or more, more preferably 75 nm or more. Further, for the same reason, the thickness of the magnesium fluoride layer 13 is preferably 120 nm or less, more preferably 110 nm or less, and still more preferably 105 nm or less.

In the anti-reflection laminated body 10 of the third embodiment, the surface reflectance of the surface of the fluorine-containing cerium compound layer 14 as the light incident surface (the stimulus value Y specified in JIS Z 8701) is preferably 0.2% or less. It is preferably 0.15% or less, more preferably 0.10% or less. According to the antireflection layered body 10 of the present embodiment, the apparent reflectance can be reduced to about 0.05% depending on the configuration of the antireflection layer.

The anti-reflection laminated body 10 of the third embodiment has a chromaticity value (a chromaticity coordinate defined in JIS Z 8701) when the side of the fluorine-containing cerium compound layer is used as a light incident surface and the incident angle is 5°. (x, y) is preferably 0.15 ≦ x ≦ 0.30, 0.15 ≦ y ≦ 0.30, and preferably 0.20 ≦ x ≦ 0.28, 0.20 ≦ y ≦ 0.30.

The anti-reflection laminated body 10 of the third embodiment has a reflection on the side of the fluorine-containing cerium compound layer as a light incident surface and an incident angle angle of 60°. The color chromaticity value is preferably 0.250 ≦ x ≦ 0.335, 0.250 ≦ y ≦ 0.335, and preferably 0.280 ≦ x ≦ 0.330, 0.280 ≦ y ≦ 0.330.

By having the above-described chromaticity value, it is possible to obtain a pale blue to white reflection color without excessive blue or red color, that is, the appearance of the anti-reflection laminate 10 is good.

The above description of the first to third embodiments of the antireflection laminate of the present invention will be described. Further, the antireflection laminate of the present invention is not limited to a magnesium fluoride layer or a fluorine-containing ruthenium compound layer provided on one of the main surfaces of the transparent substrate. The antireflection laminate of the present invention may be provided with a magnesium fluoride layer, a fluorine-containing ruthenium compound layer or the like on both main surfaces of the transparent substrate as needed.

The antireflection laminate of the present invention can be used, for example, in various electronic devices and structures.

As the electronic device, for example, a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), a cathode tube display (CRT), a surface conduction electron emission display (SED), or the like can be cited. The anti-reflection laminate can be used as a cover glass, a touch panel, or the like disposed in front of the displays. At this time, the anti-reflection laminate is disposed such that the transparent substrate side is on the display side.

As the structure, a display cabinet, a cover placed in front of the painting, and the like can be cited. The anti-reflection laminate can be used in part or in whole as a display cabinet, a cover disposed in front of the painting, and the like. However, the above application is only an example of the use of the antireflection laminate, and the use of the antireflection laminate is not limited thereto.

From the viewpoint of good mechanical durability of the fluorine-containing cerium compound layer disposed as the outermost layer and long-term maintenance of water repellency and oil repellency, anti-reverse The accretion layer is well suited for use as described above. Further, the antireflection laminate can appropriately adjust mechanical durability, productivity, and the like by the presence or absence of a ruthenium oxide layer. Therefore, it is suitable for various uses.

Example

Specific examples will be described below.

However, the invention is not limited by the embodiments.

(Examples 1 to 3)

A square soda lime glass substrate Dragontrail (trade name: manufactured by Asahi Glass Co., Ltd.) having a thickness of 1.1 mm and a length of 100 mm was prepared as a transparent substrate. A magnesium fluoride layer (MgF ₂ layer) composed only of MgF _{2 was} formed on one surface of the transparent substrate by vacuum deposition. Further, the MgF ₂ layer is composed only of a non-oxygen-containing layer substantially free of oxygen atoms.

Then, the surface of the MgF ₂ layer is subjected to an oxygen plasma treatment, and the surface layer portion of the MgF ₂ layer is modified to form an oxygen-containing layer to obtain a magnesium fluoride layer composed of a non-oxygen-containing layer and an oxygen-containing layer. Oxygen plasma treatment was carried out using LIS (PPALS81, manufactured by General Plasma Inc.). The input power of the LIS was Example 1: 300 W (energy density: 25 kJ/m ² ), Example 2: 600 W (energy density: 49 kJ/m ² ), and Example 3: 900 W (energy density: 74 kJ/m ² ). The magnesium fluoride layer after the oxygen plasma treatment had a refractive index of 1.38 and a thickness of 85 nm.

After the oxygen plasma treatment, the hydrolyzable compound was attached to the magnesium fluoride layer by a vacuum evaporation method. KY-185 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the hydrolyzable compound. Then, heat treatment was performed to form a fluorine-containing cerium compound layer having a thickness of 10 nm. The heat treatment conditions were set to be in an atmosphere and the heat treatment temperature was 90 ° C, and the heat treatment time was 60 minutes. Use this to make A test piece having a magnesium fluoride layer composed of a non-oxygen-containing layer and an oxygen-containing layer and a fluorine-containing cerium compound layer on the transparent substrate was obtained.

(Comparative Example 1)

A test piece was produced in the same manner as in Example 1 except that the oxygen plasma treatment was not performed.

Then, the surface composition of the fluorine-containing cerium compound layer side of the magnesium fluoride layer was measured by XPS (X-ray Photoelectron Spectroscopy) for each test piece, and the oxygen atom concentration R _O [at%] and magnesium were determined. The ratio of atomic concentration R _M [at%] (R _O /R _M ). Further, the XPS used was ULVAC-PHI, manufactured by Inc., trade name: Quantera SXM, and the measurement conditions are as follows.

(measurement conditions)

Pass Energy: 224eV

Energy step: 0.4eV/step

Beam diameter: φ 100μm

Sputtering ions: Ar ⁺

Accelerated voltage of sputtered ions: 2kV

Detection angle: 45° relative to the sample surface

Further, for each test piece, the arithmetic mean of the side surface of the fluorine-containing cerium compound layer of the magnesium fluoride layer was measured by an atomic force microscope (manufactured by Hitachi High-Tech Science Corporation, trade name: SPA400) in accordance with JIS B 0601:2001. Surface roughness Ra.

Further, a mechanical durability test of the fluorine-containing cerium compound layer was carried out for each test piece. In the mechanical durability test, a flat friction tester (manufactured by Daiei Scientific Seiki Co., Ltd., trade name: PA300A) was used as a test device, and an ethanol immersion cloth (BEMCOT) was used as the friction material, so that the pressure of the friction material was 1000 g/cm ² , The moving speed of the friction material was 107 mm/sec, and the number of reciprocating times was 30 times.

The water contact angle before and after the mechanical durability test was measured to evaluate the mechanical durability of the fluorine-containing cerium compound layer. Water contact angle line dropping 1 μ L of pure water and then by an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science) to be measured. When the water contact angle after the mechanical durability test was 80° or more, it was judged that the mechanical durability was good. However, the test conditions and judgment criteria here are suitable for test conditions and judgment criteria for applications such as display cabinets, cover glass disposed in front of paintings, and the like which do not require high mechanical durability.

Table 1 shows the ratio of the surface (first surface) of the magnesium fluoride layer (R _O /R _M ) (indicated by [O/Mg] in the table), the arithmetic mean surface roughness Ra, and the fluorine-containing cerium compound layer in mechanical durability. Water contact angle before and after the sex test. However, the ND in the table indicates the meaning of the detection limit (not detected: not detected).

[Table 1]

As is clear from Table 1, when the surface of the fluorine-containing cerium compound layer on the magnesium fluoride layer was subjected to the oxygen plasma treatment, the ratio (R _O /R _M ) was increased, and the arithmetic mean surface roughness Ra was decreased. When the ratio (R _O /R _M ) is more than 0.2 and the arithmetic mean surface roughness Ra is less than 1.3 nm, the mechanical durability of the antireflection laminate is improved. Further, the larger the ratio (R _O /R _M ) or the smaller the arithmetic mean surface roughness Ra, the more the mechanical durability of the antireflection laminate is improved.

(Examples 4 to 7)

A ruthenium oxide layer (SiO ₂ layer) as an adhesion layer is formed between the magnesium fluoride layer and the fluorine-containing ruthenium compound layer by sputtering, and the LIS is used for oxygen plasma treatment of the MgF ₂ layer. A test piece was produced in the same manner as in Example 1 except that the thickness of the SiO ₂ layer was set as follows. The input power of the LIS was Example 4: 300 W, Example 5: 600 W, and Example 6, 7: 900 W. The thickness of the SiO ₂ layer was Example 4 to 6: 5 nm, and Example 7: 2.5 nm.

(Comparative Example 2)

A test piece was produced in the same manner as in Example 4 except that the oxygen plasma treatment was not performed.

With respect to each test piece, the composition in the vicinity of the junction between the magnesium fluoride layer and the SiO ₂ layer was measured by XPS by the same apparatus and measurement conditions as described above, and the oxygen atom concentration at a position where the concentration of germanium atoms was 1 at% was determined. Further, the arithmetic mean surface roughness Ra of the surface of the fluorinated iridium compound layer side of the SiO ₂ layer was measured for each test piece.

Further, the mechanical durability test and the measurement of the water contact angle of the fluorine-containing cerium compound layer were carried out for each test piece. The mechanical durability test was carried out in the same manner as in Example 1 except that the friction material was changed to an unbleached gauze (a subsidiary white cloth for color durability test) and the number of reciprocations was changed to 50,000 times. When the water contact angle after the mechanical durability test was 80° or more, it was judged that the mechanical durability was good. However, the test conditions and the judgment criteria are suitable for test conditions and judgment criteria for applications requiring high mechanical durability such as touch panels.

Table 2 shows the oxygen atom concentration and ratio (R _O /R _M ) at the positions (surface, first surface, and second surface) where the concentration of germanium atoms is 1 at% (indicated by [O/Mg] in the table), SiO _{2 .} The arithmetic mean surface roughness Ra of the layer surface and the water contact angle of the fluorine-containing cerium compound layer before and after the mechanical durability test.

[Table 2]

As is clear from Table 2, when the SiO ₂ layer as the adhesion layer is formed between the magnesium fluoride layer and the fluorine-containing cerium compound layer, the mechanical durability of the anti-reflection laminate is greatly improved. In this case, a side having a germanium atom concentration of 1 at% and an oxygen atom concentration of 5 at% or more and 15 at% or less is present in the vicinity of the junction between the magnesium fluoride layer and the SiO ₂ layer. Further, when the thickness of the SiO ₂ layer is 2.5 nm or more, mechanical durability is good, and when it is 5 nm or more, mechanical durability is particularly preferable.

(Examples 8 to 10)

Between the transparent substrate and the magnesium fluoride layer, an InSiO _x layer (refractive index: 1.78, thickness: 70 nm) as a first layer and NbO as a second layer are sequentially formed from the transparent substrate side by a sputtering method. _{The x} layer (refractive index: 2.30, thickness: 60 nm) and the third layer of InCeO _x layer (refractive index: 2.20, thickness: 55 nm), and the LIS input power when the MgF ₂ layer is subjected to the oxygen plasma treatment is set as follows Test pieces were prepared in the same manner as in Example 4 except for the above. The input power of the LIS was Example 8: 300 W, Example 9: 600 W, and Example 10: 900 W. Further, the InSiO _x layer, the NbO _x layer, the InCeO _x layer, and the magnesium fluoride layer as a whole constitute antireflection.

(Comparative Example 3)

A test piece was produced in the same manner as in Example 8 except that the oxygen plasma treatment was not performed.

The test pieces of Examples 8 to 10 were subjected to a mechanical durability test of the fluorine-containing cerium compound layer and a measurement of the water contact angle. Mechanical durability test In the same manner as in Example 4, the friction material was set to an unbleached gauze (a subsidiary white cloth for color durability test), and the number of reciprocating times was set to 50,000 times. When the water contact angle after the mechanical durability test was 80° or more, it was judged that the mechanical durability was good.

Table 3 shows the water contact angle of the fluorine-containing cerium compound layer before and after the mechanical durability test.

As is clear from Table 3, even if there is another layer between the transparent substrate and the magnesium fluoride layer, the mechanical durability of the fluorine-containing cerium compound layer can be improved. Further, in the test pieces of Examples 8 to 10, the visual reflectance of the side of the fluorine-containing cerium compound layer side as the light incident surface was 0.05% or more and 0.10% or less. The chromaticity value of the reflection color when the incident angle angle is 5° is 0.20≦x≦0.28, 0.20≦y≦0.30, and the chromaticity value of the reflection color when the incident angle angle is 60° is 0.280≦x≦0.330, 0.280≦ Y≦0.330.

10‧‧‧Anti-reflective laminate

11‧‧‧Transparent substrate

12‧‧‧Layered Department

13‧‧‧Magnesium fluoride layer

14‧‧‧Fluorine-containing compound layer

15‧‧‧Non-oxygenated layer

16‧‧‧Oxygen layer

17‧‧‧1st

Claims (13)

An antireflection laminate comprising: a transparent substrate; and a laminate having a magnesium fluoride layer and a fluorine-containing ruthenium compound layer in this order from the transparent substrate side; and the laminate portion has a portion in the lamination direction In the first surface, the ratio (R _O /R _M ) of the oxygen atom concentration R _O [at%] of the first surface to the magnesium atom concentration R _M [at%] is more than 0.2 and not more than 1.5. The antireflection laminate according to claim 1, wherein the fluorine-containing ruthenium compound layer is a layer formed of a hydrolyzable fluorine-containing ruthenium compound having a perfluoropolyether group and having a number average molecular weight of 2,000 or more and 10000 or less. The antireflection laminate according to claim 1 or 2, wherein the arithmetic mean roughness Ra of the magnesium fluoride layer on the side surface of the fluorine-containing cerium compound layer is less than 1.3 nm. The antireflection laminate according to any one of claims 1 to 3, wherein the laminate portion has a ruthenium oxide layer between the magnesium fluoride layer and the fluorine-containing ruthenium compound layer. The antireflection laminate according to claim 4, wherein the laminated portion has a second surface, the germanium atom concentration of the second surface is 1 at%, and the oxygen atom concentration is 5 at% or more and 15 at% or less. The antireflection laminate according to claim 4 or 5, wherein the arithmetic mean roughness Ra of the ruthenium oxide layer on the side surface of the fluorine-containing ruthenium compound layer is smaller than 1.3nm. The antireflection laminate according to any one of claims 4 to 6, wherein the ruthenium oxide layer has a thickness of 2 nm or more and 10 nm or less. The antireflection laminate according to any one of claims 1 to 7, which has a refractive index of 1.6 or more and less than 1.8 from the side of the transparent substrate between the transparent substrate and the magnesium fluoride layer. The first layer, the second layer having a refractive index of 2.2 or more and 2.5 or less, and the third layer having a refractive index of 2.0 or more and 2.3 or less, and the refractive index of the second layer is larger than the refractive index of the third layer. In the antireflection laminate of claim 8, when the surface on the side of the fluorine-containing cerium compound layer is a light incident surface, the visual reflectance is 0.2% or less. An electronic machine having the antireflection laminate according to any one of claims 1 to 9. A structure having the antireflection laminate according to any one of claims 1 to 9. A method for producing an antireflection laminate, comprising the steps of: forming a magnesium fluoride layer on a transparent substrate; performing an oxygen plasma treatment on the surface of the magnesium fluoride layer; and forming a fluorine-containing layer on the magnesium fluoride layer矽 compound layer. The method for producing an anti-reflection laminate according to claim 12, which has a step of forming a ruthenium oxide layer on the magnesium fluoride layer after the step of performing the oxygen plasma treatment.