JPS585701A - Optical parts provided with antireflection film - Google Patents

Abstract

PURPOSE:To obtain optical parts provided with antireflection films which have a high effect of preventing reflection of a visible light region and the color reflected whereby is of an amber color system by providing four layers wherein the refractive indices of the respective layers are specified respectively in specific ranges on a transmparent substrate. CONSTITUTION:The 1st layer 20 of which the refractive index n1 is 1.63<=n1 <=1.65, the 2nd layer 30 of which the refractive index n2 is 1.955<=n2<=1.985, the 3rd layer 40 of which the refractive index n3 is 2.01<=n3<=2.03, and the 4th layer 50 of which the refractive index n4 is 1.46<=n4<=1.49 are formed on a transparent substrate successively from the transparent substrate side. Plastic materials used for lenses of spectacles, cameras, etc., instruments, apparatus, etc., for example, acryl resins, polycarbonate, etc. are used for said substrate 10. Aluminum oxide, etc. are used for the 1st layer 20, zirconium oxide, etc. for the 2nd layer 30, zirconium oxide, etc. for the 3rd layer and silicon oxide, etc. for the 4th layer 50.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a transparent substrate such as glass or plastic.
The present invention relates to an anti-reflection film having an amber reflective color with a strong C+6C color.

Lens l1lT such as Mene lens and iI Me2 lens.

RuihiroVarious types of transparent covers - INOII transparent articles, especially optical parts that require high transmittance, reduce the reflection of incident light on one surface and increase the light transmittance. This is well known. As an anti-reflection film for optical parts made of glass, a MgFg film formed by a vacuum evaporation method is known as a typical film, and is also in practical use.

To improve the adhesion of the I[+& film], such a Mgν layer is vacuum-deposited! Optical parts must be heated to temperatures between 01c and 400°C. Therefore, when forming an optical component made of plastic with low heat resistance (Mgν), sufficient heating is not possible, resulting in insufficient adhesion and hardness. Therefore, the antireflection performance of optical components made of IIK plastics cannot be put to practical use, and there are limitations in terms of materials, Il method, etc. due to the poor heat resistance of the plastic substrate and the fact that there are many plastics with low refractive index. For example, in a low refractive index material, a silicon oxide film (GTO, film) is bonded to plastic, but the refractive index of the silicon oxide film is t46.
~t4? Since its refractive index is close to that of a normal plastic lens substrate, it cannot function as an antireflection film in a single layer state and cannot be used. When obtaining an antireflection film using a silicon oxide film, two layers are used.

One or more multilayer coatings are required.

As an anti-reflection film for plastic lenses,
In the case of a glass lens, there is a single-layer MgF1 anti-reflection film and a two-layer anti-reflection film that has the same color range from reddish-purple to masonda B, and a 5-layer anti-reflection film that has a nine-green reflective light to further improve its properties. Antireflection films having a layered structure are known. For example, as a five-layer antireflection layer of this type, OR-black!
Ahos layer 2 having an optical thickness of λO on the surface of the lens 10
, ZrO with optical film thickness of λO
An antireflection layer is known in which an 8101 layer 4 and an 8101 layer 4 having an optical thickness of λ are sequentially formed.

In this case, λ is the design wavelength, λ-446n
wm~S 70 nmz is often adopted.

However, this 4-layer O-reflection coating that has green reflected light reflects the green light that has the highest O sensitivity for 2 people, so it is difficult to reduce the single AIC+ reflectance to (17- or less). It had the following drawback.

On the other hand, the antireflection film having amber-colored O reflected light is
! Because it suppresses the reflection of greenish light, which is highly sensitive, it is known to have improved transparency and is preferable compared to antireflection films that reflect greenish light, and has been put to practical use in glass eyeglass lenses. In terms of lenses.

When coating with an antireflection film, there are limits to the combinations of film material and refractive index because the plastic substrate cannot be heated to a temperature above 100°C, so antireflection with amber-colored reflected light is still preferred. The situation is that no membrane has been obtained.

In view of the above, the present invention provides a material suitable for plastic optical parts that has an amber reflective color tone, has high antireflection performance and high transparency, and has high mechanical strength and chemical stability. It was invented as a result of research with the aim of providing an antireflection film having a film structure, and its gist is that # refractive index -
is L41≦q≦t! SO 1st layer & refractive index -zttss≦
b≦ttssO second layer, refractive index −#2.01≦q≦lO
! ! 0#l; I layer, refractive heavy state 4 is t44≦−≦t4? O
Fourth? The anti-reflection film has an amber-white color and an amber-white color, which is characterized by the formation of a four-layer coating.

The present invention will be explained in more detail below with reference to one drawing. FIG. 2 shows a cross-sectional view of a nine-part optical component provided with an antireflection film according to one embodiment of the present invention. 1-01111 and the refractive index - is L41
The first layer consisting of ≦-≦twiO film, sO is this first layer 2
・The good refractive index formed on the top is ttss≦−≦LtIII
The iridescent layer 40 is formed on the second layer 30 and has a refractive index of 101≦-≦toso, and 50 is the c+ layer formed on the S layer 40 with a refractive index of 101≦−≦toso. t44≦−≦
t4? f) Showing the fourth layer.

In the present invention, the transparent 16 substrate has high transparency;
It has excellent scratch resistance, abrasion resistance, chemical stability, -1 stability, and optical properties, and is used for lenses, cameras, and other various applications such as I@1 needle instruments and devices. A plastic material with characteristics used for cover transparent plates, various materials, and other various optical members, Pleage allyl resin (also known as ox-it carbonate) )% polymethyl metatarylate, polycarbonate, polystyrene, etc. are used. Of course, it is also possible to use various other plastic materials having the above 1e411 properties as well as the J-lase substrate. Among them, one light source has a refractive index of t4t・~ts@・ for a transparent substrate! It is most suitable for polyallyl diglycol carbonate known as KO1-19.

The first layer 20 in the present invention is 1.6 M≦−≦tisO
Although an optical film having a refractive index of - can be used, it is possible to obtain such a range of refractive index as the film, and the refractive index can be easily controlled.

An aluminium oxide film containing 70% or more of aluminum oxide (lxtom) or aluminum oxide (mujsos), which has excellent chemical and physical durability and is easy to form, is optimal. . Also, the first layer O film thickness is optical film thickness -4
Te(1/4-3/121)λ・≦-4<(1/4
+ V1! 8) It is best to set it in the range of λ.
)) The dominant wavelength λ for anti-reflection is (14? 5 pw)
a ~ as Is S pm. λ・ is the same below.

Also, number one! The layer SO is ttss≦−≦t!・SO refraction rate -
Among them, the 470 film can be used because it can obtain a decoy with such a refractive index, is easy to control the refractive index, and has excellent chemical and physical durability. , Zirconium oxide (Zr01), which is easier to form a film, or Zirconium oxide (!ro1)1r701! A low refractive index zirconium oxide film containing the above is optimal. In addition, the second layer O film thickness is 55/128λ・≦−～≦ with an optical film thickness of −4.
N7/1! It is preferable to use the 8λ·O range.

Comude n@Fi, ttss6; ng≦ttss o range.

Furthermore, for the third layer 40, an optical film having a refractive index of 2.01≦−≦Lo so may be used, and among others, the film can obtain such a refractive index range.

Moreover, zirconium oxide (
zrow) or zirconium oxide (ZrO2) 709
A high refractive index zirconium oxide film containing one or more is optimal.

Also, the first layer O film thickness is -4 optical film thickness! S/12
@λ・≦−4≦2! /1!・λ・ OIi is preferably set, where ζ is −d101≦4≦10sol.

The second layer sO and the first layer 40 are optimally composed of a low refractive index zirconium oxide film and a high refractive index zirconium oxide film. The refractive index of the second layer and the first layer zirconium oxide film can be adjusted by adjusting the degree of vacuum and the deposition rate during vacuum deposition. A high refractive index can be achieved by lowering the refractive index, that is, by performing evaporation with Yuri in an atmosphere with a large amount of residual gas in a vacuum.On the other hand, a high refractive index can be achieved by lowering the deposition source temperature
This is possible by increasing the evaporation temperature.

Also, does the fourth layer S@ satisfy t46≦−≦t4? An optical film having a refractive index of
Such a refractive index O range is obtained, and the refractive index &)11
1114 Pest bird, chemical.

Silicon oxide (1ids) or silicon oxide (sio, ), which has excellent physical durability and is easy to form a film.
A silicon oxide film containing 7.- or more is optimal.

In addition, the fourth layer O film thickness is (1/4) with the optical film thickness - and 4.
-1/128)λ・≦m4a4≦(1/4 + l/
1211) is preferably in the range of 1·, where - is 'L44≦a*≦t4to@s.

This fourth layer consists of one light O amber colored yarn reflective spun l [the most important factor affecting the O cross emissivity, and the fourth layer OI
If the refractive index is low, the reflectance will be low, but if the refractive index is 1.4
4) When the temperature decreases, the silicon oxide film becomes porous, mechanical and chemical durability decreases, which is undesirable, and the refractive index decreases.
4? If it becomes too high, the reflectance increases and the performance as an antireflection film deteriorates, which is not preferable.

Adjustment of the refractive index of the first layer and the fourth layer described above.

Adjustment of the refractive index O of the zirconium oxide of the third and fourth layers is carried out by changing the same IIK and vapor deposition conditions.

IIIK above, the refractive index and film thickness of each of the first to fourth layers should be selected within a specific range. It is possible to provide an antireflection film in which the reflected light is amber-colored.

Note that the anti-reflection film having an amber reflective color according to the present invention has severe restrictions on the refractive index and film thickness of each layer, but it is important to correctly control the film thickness of the second layer and the third layer. >, it is possible to obtain an antireflection film having an amber reflective color and a low reflectance. In particular, the
The film thickness control O accuracy is (1/128) J., and the easy layer O
The thickness of the film is (2/128)λ・f)IifK
Caution is required.

1 and 111 show that the aluminum monooxide (MUATOs) film, the zirconium oxide film (grow) film, the silicon oxide (ALTG) film and the tI film are formed on the surface of the plastic lens with a green color. In the anti-reflection film having O-type reflective color, the second layer O-zirco oxide film is composed of two wavelengths, but one rounded one achieves an amber reflective color, which is a complementary color to green. In the invention, such a zirconium oxide film is used in the low refractive index portion and the high refractive index portion! It is divided into layers, and the film thickness structure is shifted from the normal gutter wavelength.

In the present invention, one of the characteristics of the two anti-reflection films is the difference in the main liquid length. Green - edge one yellow-green area) O approx.**・pm-1!17mm
The optical film thickness is assumed to be 9*t*is, and the anti-reflection film is '-
It can be made into an amber reflective color.

In addition, in the first development @, we improved the adhesion strength of the above-mentioned four-layer anti-reflection film to the plastic transparent substrate II surface, and compensated for the weak scratch resistance and abrasion resistance of the plastic transparent substrate OSS. Plastic transparent base 10 and first layer like 2nd S@t)! This can be done by interposing the underput 46 between O and fllsllIK. As for this undercoat.

The most suitable material is selected from among organic and inorganic substances that are effective in improving adhesion, scratch resistance, and abrasion resistance. It has excellent scratch resistance, abrasion resistance, and chemical durability of 411.

Furthermore, silicon oxide (atom) film is easy to coat.

An undercoat consisting of an oxide film containing silicon oxide (snow) or more is particularly preferable, and the film thickness of such an undercoat is LSpwa ~ 2 pwa.
D@@ is preferable to q#, undercoat O film thickness is 2
``Voice!'' When it becomes large, the stress generated in this layer becomes large.
If the strength of the plastic transparent substrate decreases, or peeling or cracking occurs, it is undesirable.
sto glasses lens Kl 6 pym or more 0810.
When a film is formed, eyeglass lenses Ome l1lO] PDA!
I will complete the LL grade 091 exam and cheat. On the other hand, lLsp
If the value is too small, the effect of improving the scratch resistance and abrasion resistance of the plastic ivy transparent substrate will be lost, and the amplitude of ripples in the spectral reflection characteristics will be large, which will have a negative effect on the reflective fat stop. So it's not desirable.

In addition, as the difference between the refractive index and O of the under-cut silicon oxide (sio) or the glass transparent substrate based on it increases, the lag s-0 increases.1. 4! It is preferable to set it as i-t S5.

Teeth, plastic ivy Transparent substrate and undercoat to improve adhesion to O.Other O
Alternatively, the plastic transparent substrate may be subjected to a chemical conversion treatment.

In the present invention, as described above, improvements in weather resistance, hard f1 adhesion, etc. in each of the 1st to 40th layers are made within the range of the refractive index of each layer.

and other components such as MgO, OaO, TLOhte'101 in small amounts within the range where the desired properties can be obtained.
tmu 40g, 1iio1. 810
, ZnO, Ga1O1°S, o1&o・0■ can be added to form a 1L or composite film.

The cs*m1P1 of the present invention will be explained below.

Implementation IP11 Wash the polyallyl carbonate lens substrate (trade name, 0R-19 lens) and place it in a vacuum deposition tank.
The vapor deposition tank was evacuated to 1×10''ITorr and the lens base was heated to about 1.0°C while the following 0IIA deposition was performed in sequence.First, IN deposition vacuum degree i 5
The first layer was deposited at a deposition rate of -161 aluminum oxide (muhog) l[. Next, the vacuum level was readjusted to SX10-1〒orr K, and zirconium oxide fS film was deposited on the alumium oxide film.
A second layer consisting of 5youO low refractive index zirconium oxide (ZrO) film was formed by evaporation at a deposition rate of 0, and then the low refractive index oxide was A fifth layer of high refractive index zirconium oxide (ZrO) with a thickness of 755 μm is deposited on the zirconium film at a deposition rate of zirconium oxide tsX/-・C. ″
After being readjusted to be easily 〒orr, silicon oxide was deposited on the high refractive index zirconium oxide film at a deposition rate of 20 m/-.O, and a fourth layer of saponified silicon was formed.

The refractive index of each layer deposited in II was measured by the Apelles method.

Refractive index of the first layer aluminum oxide film F11.6'5
The refractive index of the second layer, a low refractive index zirconium oxide film, is t955, and the refractive index of the third layer, a high refractive index zirconium oxide film, is 2-01).

The refractive index of the fourth layer of silicon oxide film is 1.4.

In addition, the reflection color tone of this anti-reflection film exhibits a reddish amber color, and the results of the t-measurement of the reflection characteristics of this anti-reflection film are as follows:
It is shown in curve a of m5 and is repeated in nine ways.

Moreover, when the reflected color tone of this anti-reflection film is shown in the 011 coordinates,
It is shown by point 0 in FIG. 6, and it is recognized that it is located in the diagonally shaded area Pf) indicating the amber-colored line spacing.

amga 2 Place a cleanly washed polyallyl carbonate lens substrate (trade name: 0R-1?Lens) into a vacuum deposition tank.
The inside of the vapor deposition tank is 1×10″i! orr Exhaust circle. Next, while heating the lens substrate to about 1.-0, the following vapor deposition process is carried out. First, the vacuum of the vapor deposition tank is reduced.
[tsXlm - After adjusting K, WJK aluminum oxide was deposited on the lens base surface at a deposition rate of Sm/-.0.

Form a first layer consisting of a 77.mu.
After readjusting the Torr pc, zirconium oxide was deposited on the aluminum oxide film at a deposition rate of 54 oiO low refractive index zirconium oxide (!ro).
b) forming a second layer consisting of a membrane;

Next, the degree of vacuum t! ! X 1 @-' Torr I
After readjusting the IC, high refractive index zirconium oxide (!rob) was deposited on the low refractive index zirconium oxide film at a deposition rate of 701IAt).
An S-th layer consisting of a film was formed. Next, the evaporation tank 0 vacuum [1
After readjusting the 1X10'' ink color, apply silicon oxide to the above-mentioned high-grade zirconium oxide film! Deposited at a deposition rate of Om/-・O,・bo'h.

A fourth layer of silicon oxide was formed.

Ko041! The refractive index t of each layer was made constant by the Abeles method.

The refractive index of the first layer O (aluminum oxide lll0[g-fold book is t44) and the second layer O low refractive index zirconium oxide film is t! 45], and the refractive index of the first layer high refractive index zirconium oxide film was 2.02.

The refractive index of the silicon oxide film of the fourth layer is t47, and the reflection color tone of the H-O anti-reflection film is amber, and the O-reflection characteristics of the H-O reflection blocking film are kept constant. Oran line b (
Be a good example.

In addition, when the reflective color tone of the ζO reflective lipostatic membrane is shown on the 0-1 coordinate,
It is indicated by the 49110th point 1, and it is recognized that it is located within the shaded area r indicating the amber color range.

Example S A cleanly washed polyacyl carnate lens substrate (trade name, 0R-s9 lens) was set in a vacuum deposition tank,
The inside of the vapor deposition tank was evacuated using a stage.Then, the lens substrate was heated to about 1111 m1, and the following vapor depositions were carried out in sequence.
! ×1·-STorr After adjusting the pc, Niumium was evaporated onto the lens substrate surface 1lKII compound 7 at a deposition rate of black/-··O.

The first layer consisting of go@mO aluminum oxide (40m) film was formed.Then, the degree of vacuum was reduced to 4×1...
After readjusting K, a 6sS/-aO smoke layer of zirconium oxide is deposited on the above aluminum oxide ix9^ film, and sm
o'ho @ refractive index oxide di refractive index gym oxide (!rot) I
Form a second layer consisting of I, followed by 4X1 in the same vacuum
Zirconium oxide is evaporated onto the low refractive index zirconium oxide film at a deposition rate of 817-.
After forming the S-th layer consisting of a zirconium oxide film with a high refractive index and adjusting the vacuum degree of the vapor deposition tank to 4X1@''4Teorr K, 20 μm/s of silicon oxide was formed on the high refractive index zirconium oxide film.
-・Deposited at aOO deposition rate,・! A fourth layer of 5X silicon oxide was formed.

It is a good idea to determine the refractive index of each layer that is vapor-deposited using the Apelles method.

The refractive index of the first layer O-aluminum oxide film is t4B),
The second layer low refractive index zirconium oxide film 01lA has a refractive index of t
! 85, the refractive index of the third layer high refractive index zirconium oxide film is taS.

The fourth layer silicon oxide film had a refractive index of t411. The reflection color tone of this anti-reflection film is amber, and the results of measuring the reflection characteristics of this anti-reflection film are as follows: No. 11101
11! Thank you for showing IaK.

Moreover, when the reflected color tone of the ζO antireflection film is shown in the axm column, it is shown as point OO in FIG. 6, and it is recognized that it is located within the hatched area P indicating the amber color range.

Implementation fi4: Set the cleaned polyallyl carbonate lens substrate (trade name, (3R-59 lens) in a vacuum evaporation tank, and evacuate the evaporation tank at 90°C. The following vapor deposition was performed in sequence while heating the lens substrate to approximately 100°C.First, the vacuum &
After adjusting the temperature to 2 x 10-1 err K, 1=umium oxide was vapor-deposited on the surface of the lens substrate at a deposition rate of 3 μm/a·oOO.

A first layer consisting of an aluminum oxide (JmOs) film was formed using a vacuum gf4X10-1 teror.
After readjusting rK, Ks on the above aluminum oxide film
! A second layer consisting of a 5ioXo low refractive index zirconium oxide (KrO@) film was formed by depositing zirconium oxide at a deposition rate of st/-·a (D).

Subsequently, under the same vacuum fO4xto-ste◎rr pc, zir oxide: I
A first layer consisting of a high refractive index zirconium oxide (Zr01) film is formed by evaporating at a deposition rate of aumt8m/-.AlD.
After the K is readjusted, silicon oxide is deposited on the high refractive index zirconium oxide film at a deposition rate of zoX/-(10,II) to form a fourth layer of ?10XO silicon oxide.

The refractive index of each layer was measured by the Apelles method.

The first layer of aluminum oxide (=Lamb film O refractive index is t6s),
The second layer low refractive index zirconium oxide film Oj1 has a refractive index of tt
ss>, and the refractive index of the fifth layer O high refractive index Zirpnium oxide film is 2.0s and Tob.

The refractive index of the fs4 silicon oxide film was 1.44.

In addition, the reflection color tone of this anti-reflection film is amber, and the results of determining the reflection characteristics t-im of this anti-reflection film are as shown in the first line of the chain diagram.

Also, when the reflected color tone of this anti-reflection film is shown in the OXX coordinates, it is shown as the OD point in FIG. 6, and it is recognized that it is located in the diagonally shaded area r indicating the amber color range.

The vacuum evaporation method was used to form each layer in the above embodiments, but the method for forming such a film is not limited to this, but may include sputtering, chemical vapor deposition, ion plate tinder method, etc. It is of course possible to use various types of; - Tainder methods as well.

IIK above, according to the present invention, the first to fourth layers O refractive index,
It is recognized that by setting the optical film thickness within the predetermined range as described above, a high antireflection effect can be obtained in the visible range due to the interference effect, and an amber-like reflective color tone can be obtained. This is particularly suitable for use as a lens exclusively for mega lenses, as it has both anti-reflection performance and anti-friction properties.

Moreover, the materials constituting the antireflection film of the present invention include silicon oxide (atom), zirconium oxide (XrOboro), and
, aluminum oxide (muhos) - If a film containing these as the main components is used, these will have high mechanical strength,
It also has high chemical stability.

Because it has excellent durability, plastic ivy lens O is used for #.
Ideal as an anti-reflection film.

[Brief explanation of the drawing]

Figure 1 shows cross sections Ia and 1Ml of an optical component on which a single-layer antireflection film having a conventional O-green reflective color is formed.
@l is the optical component O which can be formed with the present invention 04-layer anti-reflection film O
Cross section, 1st 4th. lli! 6111 is a spectral reflection characteristic diagram of a good optical component formed with O-type 04-layer anti-reflection coating of the present invention.
1 is a C-work 1 coordinate diagram showing the reflection color tone of an optical component on which the 044-layer antireflection film of the present invention is formed. 1.: Transparent substrate, 20: First layer, 10: Second layer, 40:
2nd layer, zO: 4th layer, 40:7nf/Seki, Guh Sai2TfA Δ6 ″f3 SekiL rogyoku (su) f4 rA

Claims (5)

[Claims] (1) On a transparent substrate, a first layer with a refractive index of - t45≦-≦tist from the side of the transparent substrate, m refractive index wstts
s≦b≦tysso second layer, refractive index - is lO1≦b≦1
O3O 1st≦b≦refraction index - is t44≦-≦t4? tD 4th
? An optical component provided with an anti-reflection film having a four-layer amber color thread, 0 gray color, and a tD structure. (2) Amber colored thread 0 according to claim 1, characterized in that the refractive index n of the transparent substrate forming the anti-reflection film (4 layers) satisfies t490≦n,≦ts;as. The anti-reflection film with gray color is installed by Ryoto Gaku Parts. (3) The main liquid length λ of the anti-reflection film consisting of 4 layers is *49S
pm≦20≦a m S S pm A is a mourning optical component according to claim 1. (4) Anti-reflection film consisting of 4 layers O first layer optical film 2.≦
An optical component according to claim 4, characterized in that -4≦1''2'lλ. (5) The first layer of the anti-reflection film consisting of four layers is t45≦−≦
The second layer of the aluminum oxide film having a refractive index of t450 is t955≦−≦t! A low refractive index zirconium oxide film having an easy SO refractive index -, the first layer having an oso refractive index of 2.01≦-≦*oso refractive index n. A high refractive index dillium oxide film with a fourth layer of 144
≦-≦'L4tt) Patent claim 01, characterized in that it is a silicon oxide film having a refractive index of 114! Enclosed in paragraph 1 O
An optical component provided with an anti-reflection film having a reflected color of ay<--colored thread. ~! -pat) Undercoat film of silicon oxide film, optical film thickness -4 is (1/4-S/12B)λ・≦-4≦(
1/4 + 5ha28) J, the first layer consisting of an aluminum oxide film, the optical thickness -4 is 557128λ≦-
〜≦17/1215λ・0 The first made of dienconium oxide film with low refractive index! layer, optical film thickness -4 is 25/12-λ@≦
k 4a ≦2”F/128λ@0”a II refractive index 5th layer made of zirconium oxide film, optical film thickness n4 (1
4 is (1/4-3/128)λ・≦n4a4≦(1/
4 + S/12・)λ・O silicon oxide film formed by sequentially forming a fourth layer.
g1 An optical component provided with an antireflection film having an amber reflective color as described in No. 1.