JP3360106B2 - Deflection color filter materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deflecting color filter material in which the transmittance of light of a specific wavelength changes depending on the incident angle of light, a deflecting color filter using the material (a dichroic color filter). ) And its manufacturing method.

[0002]

2. Description of the Related Art A color filter extracts only a necessary wavelength from light emitted from a light source by absorbing or transmitting only light of a specific wavelength, and is used for a color display or the like. , And is attracting attention as an indispensable element in the field of optoelectronics such as optical information processing, and is currently being actively researched and developed.

Heretofore, as a color filter, a glass material in which ions such as metals and dielectrics or colloids are dispersed has been known to exhibit high characteristics. However, with inorganic compound filters such as glass, it is difficult to exhibit the polarization dependence that the transmittance varies depending on the viewing angle, so in an element that requires viewing angle dependence such as a three-dimensional display. However, this is not always the appropriate material. Therefore, recently, attention has been focused on organic compounds that easily cause anisotropy in light absorption, and the development of dyes for polarizing color filters has been vigorously pursued.

[0004] Among organic compounds, rhodamine and methylene blue have been developed as optical dyes, but these dyes are difficult to produce large-area crystals for use as color filter materials. Even if a crystal is produced, it is not easy to take a crystal structure in which an absorption band exhibiting strong light absorption brings anisotropy. Even if it is attempted to form a film, it is not easy to prepare a homogeneous optical thin film without light scattering by itself, and it is usually necessary to form a film by dispersing it in a matrix such as a polymer. For this reason, it becomes difficult to control the molecular orientation in the solid. Furthermore, due to lack of sufficient thermal stability,
It has the drawback that it is fragile against strong light such as laser light and has a short service life.

[0005] As a crystal structure control technique in which an absorption band showing strong light absorption of an organic compound has anisotropy, that is, a molecular orientation control technique, an organic monomolecular film developed on a water surface is scooped up on a solid substrate. The Langmuir-Blodgett method that accumulates it is well known. By using this method, the orientation of molecules can be easily controlled. However, since it is necessary to form a monolayer on the water surface, there is a restriction in the molecular design that a long alkyl chain must be attached to the molecule, and the monolayer is skimmed one by one. Since it must be done, it takes a lot of trouble to manufacture, and when a thick film required to adjust the light transmittance is created, the quality of the optical thin film deteriorates and many defects that cause light scattering It has disadvantages such as easy occurrence.

[0006] From the above problems, organometallic complexes have been highly expected as dyes for new color filters which can have viewing angle anisotropy at present. Organometallic complexes have various kinds of interactions with compounds, such as metal-metal interaction, metal-organic ligand interaction, ligand-ligand interaction, and can have strong absorption due to them. It is known. It is also known that certain types have extremely high thermal stability due to a strong coordination bond between a metal and a ligand, and high durability can be obtained. More recently,
Attention has also been focused on optical functional materials such as nonlinear optical materials and the like, as conductive materials and magnetic materials, and their potential is high and demand is expected to increase in the future.

At present, among organic metal complexes, metal phthalocyanine is known as a dye having high durability and capable of easily forming a large-area, high-quality thin film. This compound can exhibit several colors by changing the central metal, and it is also possible to control the molecular orientation by controlling the film forming conditions in the vacuum evaporation method. However, it is difficult to change to the central metal to achieve full color, and the anisotropy due to the molecular orientation of the strong absorption band for controlling the transmittance is not very noticeable.
These compounds are not necessarily advantageous for providing viewing angle dependence, and further have the drawbacks that these compounds are not easy to synthesize, expensive and not easily available.

On the other hand, several types of planar organometallic complexes are known compounds, and their conductivity and nonlinear optical properties have been studied so far. In addition, since various colors can be exhibited by changing the central metal and the ligand, application as a pigment or the like has been attempted. However, it is generally known that these compounds can control the molecular orientation in the film only when using a cleavage plane of an alkali halide or the like in which the lattice constant of the crystal coincides with the substrate under the normal conditions during film formation. There is no example in which a film is formed with anisotropy on an amorphous glass substrate having no lattice plane, and there is no known possibility of using the film as a deflection color filter material. When making a color filter, the use of a hygroscopic substance such as an alkali halide for the supporting substrate has a major drawback that durability cannot be ensured. There is a demand for coating and forming a dye on a glass substrate made of quartz or the like which has excellent stability in the atmosphere.

[0009]

In practical use of a deflecting color filter, the ratio of the transmittance of vertically incident light to the transmittance of horizontally incident light is large, it can be applied to extraction of various absorption wavelength bands, and scattered light can be used. That it can be a transparent thin film material without any defects, that it is stable in the atmosphere and thermally stable, that it has stability not to be damaged by incident light, that it is easy to obtain and handle, etc. It is an object of the present invention to provide a polarizing color filter material, a polarizing color filter, and a method for manufacturing the same, which comprise an organometallic complex dye satisfying the above conditions.

[0010]

Means for Solving the Problems The present inventors have found that an organometallic complex compound having a planar structure can have a crystal structure in which planar molecules are overlapped in a solid, and that an interaction occurs between the overlapped molecules. Focusing on the fact that light absorption occurs based on this, if a strong light absorption band based on this intermolecular interaction can be oriented so as to be completely anisotropic in a solid thin film, a deflection color filter material will be manufactured. The present inventors have made predictions that they can be made, and have made intensive studies on the orientation controllability of various organometallic complexes, and as a result, have accomplished the present invention.

That is, according to the present invention, the following general formula (1)
And a material for a deflection color filter comprising a planar organometallic complex represented by the formula:

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ are a substituent A having a carbon atom as a bonding atom, a substituent B having a hetero atom as a bonding atom,
And when R ₁ and R ₂ are the substituents A and / or B, R ₁ and R ₂ may be mutually connected to form a ring; _{When 3} and R ₄ are the aforementioned substituents A and / or B, those R ₃ and R ₄ may be mutually connected to form a ring, and M represents copper, nickel, palladium and platinum. According to the present invention, there is provided a deflection color filter formed by forming a thin film of the above-mentioned material on a substrate. Further, according to the present invention, the aforementioned material is placed on a substrate at -100 ° C.
A method for manufacturing a deflection color filter is provided, wherein a thin film of the material is formed by vacuum deposition at the following temperature. Furthermore, according to the present invention, there is provided a polarizing color filter formed by laminating two or more thin films of the above materials on a substrate. Still further, according to the present invention, the material is vacuum-deposited on a substrate at a temperature of -100 ° C or less to form a thin film of the material, and further, one or more thin films of the material are stacked thereon. A method for producing a polarizing filter is provided.

In the deflecting color filter of the present invention, a plane type organometallic complex having a strong light absorption band in a visible light region has its transition moment of absorption oriented perpendicular to the substrate surface, thereby being incident perpendicularly to the substrate surface. Is high, but the transmittance of light horizontally incident on the substrate surface is significantly reduced. At this time, the existence of different crystal structures in the film makes the transmittance of the film dependent on the viewing angle. By changing the wavelength range where appears, and by using different materials at this time,
By changing the wavelength range in which the transmittance of the film exhibits the dependency on the incident angle, and by laminating at least one kind of film exhibiting the dependency of the transmittance on the incident angle in different wavelength ranges, the transmittance in an arbitrary wavelength range is obtained. Is characterized in that the transmittance and the reflectance are controlled to arbitrary magnitudes by expressing the incident angle dependency of the above, and further controlling the film thickness to be laminated.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The substituent A having a carbon atom as a bonding atom includes an aliphatic group, an aromatic group, an acyl group and the like. Its carbon atoms are from 1 to 23, preferably from 1 to 14
It is. In this case, the aliphatic group includes an alkyl group and a cycloalkyl group. Examples of the alkyl group include those having 1 to 23, preferably 1 to 8, and more preferably 1 to 3 carbon atoms, such as methyl, ethyl, propyl and hexyl. Examples of the cycloalkyl group include those having 3 to 23, preferably 6 to 14 carbon atoms, such as cyclohexyl and cyclooctyl. The aromatic group includes an aryl group and an aralkyl group. Examples of the aryl group include those having 6 to 23, preferably 6 to 14 carbon atoms, such as phenyl, tolyl, and naphthyl. The aralkyl group has 7 to 23 carbon atoms, preferably 7 to 1 carbon atom.
And the like, for example, benzyl, phenethyl, naphthylmethyl and the like.

The acyl group is represented by the following general formula (2)
Are represented.

Embedded image R ₅ CO— (2) In the above formula, R ₅ represents an aliphatic group or an aromatic group. Its carbon number is 1 to 22, preferably 1 to 14. In this case, the aliphatic group includes an alkyl group and a cycloalkyl group. The alkyl group has 1 to 2 carbon atoms.
2, preferably 1 to 3. Examples of the cycloalkyl group include those having 3 to 22, preferably 6 to 14 carbon atoms. The aromatic group includes an aryl group and an aralkyl group. The aryl group has 6 to 22 carbon atoms, preferably 6 to 22 carbon atoms.
14. As an aralkyl group,
Those having 7 to 22, preferably 7 to 11 carbon atoms are mentioned.

A substituent B wherein the bonding atom is a hetero atom;
In each of the hetero atoms, oxygen, nitrogen, sulfur,
Phosphorus and silicon are included. The total number of atoms constituting the substituent B is 2 to 22, preferably 2 to 13. Examples of the substituent having an oxygen atom as a bonding atom include those having a total number of atoms constituting the main chain of 2 to 21, preferably 2 to 13, such as the following. (1) —OR _{6 In the} above formula, R ₆ represents hydrogen, an aliphatic group or an aromatic group.
In this case, specific examples of the aliphatic group and the aromatic group include the same as those described above. (2)-(OA) n-H In the above formula, A represents a lower alkylene group having 1 to 4, preferably 2 to 3 carbon atoms such as methylene, ethylene, propylene and butylene. n shows the number of 2-4, preferably 2-3.

Examples of the substituent having a nitrogen atom as a bonding atom include those having a total number of atoms of 3 to 22, preferably 3 to 9, constituting the main chain, for example, the following: (1) —NH—R _{7 In the} above formula, R ₇ represents hydrogen, an aliphatic group or an aromatic group.
In this case, specific examples of the aliphatic group and the aromatic group include the same as those described above. (2)-(NHA) m-NR ₈ R _{9 In the} above formula, A represents a lower alkylene group having 1 to 4, preferably 2 to 3 carbon atoms, and m represents a number of 1 to 4, preferably 2 to 3 Is shown. R ₈ and R ₉ represent hydrogen, an aliphatic group or an aromatic group. In this case, specific examples of the aliphatic group and the aromatic group include the same as described above.

Examples of the substituent having a sulfur atom as a bonding atom include those having 2 to 21, preferably 2 to 8, atoms constituting the main chain, such as the following. (1) —SR _{10 In the} above formula, R ₁₀ represents hydrogen, an aliphatic group or an aromatic group.
In this case, specific examples of the aliphatic group and the aromatic group include the same as described above. (2)-(SA) n-H In the above formula, A represents a lower alkylene group having 1 to 4, preferably 2 to 3 carbon atoms. n shows the number of 2-4, preferably 2-3.

Examples of the substituent having a phosphorus atom as a bonding atom include those having a total number of atoms constituting the main chain of 2 to 22, preferably 2 to 13, such as the following. (1) —PO ₄ R ₁₁ R _{12 In the} above formula, R ₁₁ and R ₁₂ represent hydrogen, an aliphatic group or an aromatic group. In this case, specific examples of the aliphatic group and the aromatic group include the same as described above. By way of example of substituents that the phosphorus atom and the bond _{atoms, -PO 4 (CH 3) 2} , -P
O ₄ (C ₆ H ₅ ) ₂ and —PO ₄ (CH ₃ C ₆ H ₄ ) ₂ .

Examples of the substituent having a silicon atom as a bonding atom include those having the total number of atoms constituting the main chain of 4 to 19, preferably 4 to 13, such as the following. (1) —SiR ₁₃ R ₁₄ R _{15 In the} above formula, R ₁₃ , R ₁₄ , R
₁₅ represents hydrogen, an aliphatic group or an aromatic group. In this case, specific examples of the aliphatic group and the aromatic group include the same as described above. Specific examples of the substituent for the silicon atom and bonded _{atoms, -SiH 3, -Si (CH 3} ) 3, -Si
H ₂ C ₂ H _5, include -SiH ₂ C ₆ H ₅ and the like.

The halogen group includes chlorine, bromine, iodine and fluorine.

When R ₁ and R ₂ represent the substituent A and / or the substituent B, R ₁ and R ₂ may be mutually connected to form a ring. The ring in this case can be a 4- to 8-membered ring, preferably a 5- to 6-membered ring.

When R ₃ and R ₄ represent the substituent A and / or the substituent B, the R ₃ and R ₄ may be mutually connected to form a ring. The ring in this case can be a 4- to 8-membered ring, preferably a 5- to 6-membered ring.

The method for synthesizing the planar organometallic complex of the present invention is not particularly limited, and any method generally used for producing an organometallic complex may be used. As a typical method for producing a complex that is generally preferably used, a method is known in which a compound serving as a ligand is reacted with a solvent (such as an alcohol) -soluble metal compound in a solvent solution of an alcohol or the like. In the present invention, the intended planar organometallic complex of the present invention can be obtained by using this method.

In the present invention, as the ligand compound, a glyoxime derivative represented by the following general formulas (3) and (4) is used. General formula (3):

Embedded image General formula (4):

Embedded image In the above formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meaning as described above. Further, the compound of the general formula (3) and the compound of the general formula (4) may be the same or different.

The solvent-soluble metal compound used in the present invention includes metal halides (chloride, bromide, iodide, etc.), organic acid salts (acetate, etc.), and organic complex salts (acetylacetonate, etc.). . Generally, metal chlorides are used. Metal species M that provides the complex of the general formula (1)
A transition metal that forms a complex with the glyoxime derivative is used, but copper (Cu), nickel (Ni), palladium (Pd), and platinum (Pt) are preferably used.

When the ligand compound and the metal compound are reacted to form an organometallic complex, two or more metal compounds having different metal species can be used as the metal compound. In this case, a mixture of organometallic complexes having different metal species can be obtained.

In the present invention, in order to obtain a deflected color filter, the transition moment of the strong light absorption band of the compound of the general formula (1) appearing in the visible to near-infrared light region is oriented perpendicular to the substrate surface. The temperature of the substrate is cooled to −100 ° C. or lower so that the viewing angle dependence of the transmittance is exhibited, and the complex compound is vacuum-deposited. At this time, in order to more effectively control the orientation, it is desirable that the substrate temperature be lower. The lower limit temperature is about -250 ° C. Generally, it is preferred to use liquid nitrogen temperature. In this case, as the complex compound, a mixed crystal of a complex compound having a different metal species M in the complex compound of the general formula (1) can also be used.

In the present invention, the vacuum deposition rate of the complex compound is controlled in order to change the wavelength range in which the viewing angle dependence of the transmittance is exhibited, whereby polymorphs of the same complex compound are mixed in the same thin film. Then, the sum of the light absorption rates of the respective polymorphs can be used. For example, in the case of platinum diphenylglyoxime, the absorption peak wavelength is 550 nm when the deposition rate expressed by the generated film growth rate is 2 nm or more per minute.
When the deposition rate is 0.1 nm or less per minute, a blue phase polymorph that has an absorption peak wavelength around 700 nm is formed, and the deposition rate is 0.1 mm / min.
At 1 to 2 nm, each polymorph is mixed, and the proportion of each polymorph changes in proportion to the deposition rate, thereby changing the absorption wavelength range. At this time, the deposition rate to be changed is slightly different depending on the complex compound to be deposited,
In each case, the rate of polymorphism can be controlled by changing the deposition rate in the range of 0.01 to 3 nm per minute.

In the present invention, two or more thin films of the complex compound represented by the general formula (1) may be laminated in order to change the wavelength range in which the transmittance depends on the incident angle. At this time, the number and order of lamination are not particularly limited.

In the present invention, the thickness of the thin film of the complex compound on the substrate is 10 to 100,000 nm, preferably 10 to 10000 nm.
000 nm. The thickness of each thin film in the case of laminating the second or more layers is 10 to 100,000 nm, preferably 10 to 1000 nm, but the magnitude of the light transmittance and the reflectance at an arbitrary wavelength is adjusted. In order to do so, the thickness of the thin film is appropriately adjusted.

In the present invention, when the first layer is deposited, the substrate temperature is cooled to -100 ° C. or lower. However, when the second layer or more is laminated, the substrate temperature at that time is not particularly limited. Generally, the temperature used simply is room temperature of about 20 to 30 ° C., but −100 ° C. is required to precipitate a different crystal structure.
It may be cooled below.

The substrate on which the planar organometallic complex of the present invention is deposited is not particularly limited, and any substrate may be used. In general, a glass substrate such as quartz is preferably used as a substrate for producing a color filter, but a transparent plastic substrate such as an ITO transparent electrode, an aluminum-deposited transparent electrode, a gold-deposited transparent electrode, or an acrylic plate may also be used. Can be done.

In the present invention, the degree of vacuum of the container, the evaporation source, and the distance between the evaporation source and the substrate during vacuum evaporation are not particularly limited. Generally, the degree of vacuum used simply is 10 ^-7 to 1
It is on the order of 0 ^-5 Torr, but it is desirable to have a higher vacuum.

The complex compound of the present invention has a linear column structure in which molecules having a planar structure in the solid state are stacked, and the electron orbital of the central metal overlaps between adjacent molecules in the complex, and the complex is based on the interaction. Shows strong light absorption. Since this light absorption has its absorption transition moment only in the direction parallel to the straight-chain column, if the orientation control in which the straight-chain columns are all oriented in the same direction in the thin film is performed, the light is incident in the parallel direction to the straight-chain column. Although it does not absorb light at all, it absorbs vertically incident light, which results in anisotropy, that is, viewing angle dependence of transmittance.

The complex compound of the present invention has a linear column structure in which molecules having a planar structure in a solid state are stacked.
At that time, there are a plurality of ways of stacking molecules, and as a result, various polymorphs having different crystal forms exist. Since the interaction force of molecules differs between polymorphs, the absorption energy of light, that is, the absorption wavelength also differs. By utilizing the difference in the absorption wavelength of the polymorph and mixing it in the same thin film, it becomes possible to control the transmittance wavelength distribution. Since the appearance of the polymorph varies depending on the crystallization conditions when the complex compound crystallizes in a solid state, the existence probability varies depending on the vapor deposition conditions. Further, the way of stacking the molecules of the complex compound of the present invention differs depending on the type of the compound. For this reason, since the interaction force of molecules differs between compounds, the absorption energy of light, that is, the absorption wavelength also differs. By utilizing the difference between the absorption wavelengths of the different compounds and mixing them in the same thin film or in different thin films, it becomes possible to control the transmittance wavelength distribution. By combining at least two or more compounds having absorption at a wavelength at which light is to be absorbed, it becomes possible to transmit only an arbitrary wavelength.

[0036]

The planar organometallic complex according to the present invention comprises:
The ligand compound (glyoxime derivative) as the raw material is inexpensive and easy to handle, and is easily produced by reacting with a metal chloride or metal acetylacetonate compound in an alcohol solution. can do. Further, the complex compound can be easily purified by a sublimation method or a recrystallization method using a nitrobenzene, orthodichlorobenzene, dimethylformamide solution or the like.

According to the present invention, it has not been possible on an amorphous substrate surface on which a crystal lattice plane or the like has not been formed.
It is possible to control the orientation of the metal complex in the thin film, thereby making it possible to express the viewing angle dependence of the transmittance.

The thin film of the planar organometallic complex according to the present invention can significantly reduce the transmittance of horizontally incident light even when the transmittance of vertically incident light is close to 100%.

When the planar organometallic complex according to the present invention is formed on a substrate, different crystal forms can be mixed in the film by appropriately adjusting the deposition rate, whereby the transmittance depends on the viewing angle. It is possible to arbitrarily adjust the wavelength range in which the property is exhibited.

The planar organometallic complex according to the present invention comprises:
The compound has a one-dimensional chain structure in which metal atoms are arranged in a straight line, and has extremely high crystallinity. Further, by appropriately selecting the substituent, the distance between metal atoms can be appropriately changed,
The absorption maximum wavelength can be arbitrarily shifted by introducing a different center metal. Therefore, by appropriately combining at least one or more of these, by laminating, it is possible to arbitrarily adjust the wavelength range in which the incident angle dependence of the transmittance at an arbitrary wavelength is expressed, and the wavelength band to be filtered is adjusted. Selection can be made easily.

Since the complex compound according to the present invention can be made into a thin film by a vacuum evaporation method, it is easy to produce a film whose thickness is freely controlled. Thus, the transmittance of the color filter can be arbitrarily adjusted depending on the film thickness. Further, the produced thin film is homogeneous, has little light scattering property, and is extremely stable even in the atmosphere.

[0042]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Reference Example 1 Diphenylglyoxime (in the above formula (1),
(R _{1 to} R ₄ : phenyl group) 0.12 g was dissolved in 50 ml of ethanol in a 100 ml beaker. Here 5
0.20 g of potassium tetrachloroplatinate (II) dissolved in 100 ml of pure water was added, and the reaction temperature was set to 4 on a hot plate.
The mixture was stirred for 8 hours while controlling at 0-50 ° C. As the reaction proceeded, a fine brownish granular precipitate formed. After completion of the stirring, the reaction solution was returned to room temperature, and the deposited precipitate was filtered. The precipitate was washed with ethanol and pure water, and then dried in a desiccator under reduced pressure. The obtained product was recrystallized from a dimethylformamide solution to obtain 0.16 g of red-purple needle-like crystals of platinum diphenylglyoximat.

Reference Example 2 In Reference Example 1, instead of diphenylglyoxime,
Dimethylglyoxime (in the general formula (1), R
_An experiment was carried out in the same manner except that _{1 to} R ₄ : methyl group) was used, and platinum dimethylglyoximat (dark blue, needle-like crystals)
I got

Reference Example 3 In Reference Example 1, instead of diphenylglyoxime,
Using dimethylglyoxime, tetrachloroplatinic acid (I
I) An experiment was conducted in the same manner except that nickel (II) acetyl acetate was used instead of potassium to obtain nickel dimethylglyoximat (dark red, needle-like crystals).

Reference Example 4 In Reference Example 1, instead of diphenylglyoxime,
Using dimethylglyoxime, tetrachloroplatinic acid (I
I) Palladium dimethylglyoximat (yellow, needle-like crystals) was obtained in the same manner as described above except that palladium (II) chloride was used instead of potassium.

Example 1 The complex compound obtained in Reference Example 1 was placed on a glass evaporation heater (quartz crucible: φ20 × H45 mm) to obtain an evaporation sample. Synthetic quartz (ES grade; area 15 x 30 mm,
Thickness: 1.0 mm)) is fixed above the evaporation boat,
The pressure was reduced to 3 × 10 ⁻⁷ Torr. Thereafter, the substrate was cooled to −175 ° C., and vacuum deposition was performed at a rate of 0.2 nm per minute to a thickness of about 160 nm. The viewing angle dependence of the transmittance of the film thus prepared was measured with an ultraviolet-visible spectrophotometer. FIG. 1 and Table 1 show the viewing angle dependence of the transmittance of the platinum-diphenylglyoximato-deposited thin film at this time. Centering on a wavelength of 700 nm, 50
In the wavelength range of 0 to 900 nm, the viewing angle dependence of the transmittance appears. A peak at around 550 nm where the transmittance is reduced is seen, which is due to the presence of the red phase polymorph present in about 10% of the whole.

[0048]

[Table 1]

Example 2 The complex compound obtained in Reference Example 1 was placed on a glass evaporation heater (quartz crucible: φ20 × H45 mm) to obtain an evaporation sample. Synthetic quartz (ES grade; area 15 x 30 mm,
Thickness: 1.0 mm)) is fixed above the evaporation boat,
The degree of vacuum was reduced to 7 × 10 ⁻⁷ Torr. Thereafter, the substrate was cooled to −175 ° C., and vacuum deposition was performed at a rate of 2.1 nm per minute to a thickness of about 100 nm. The viewing angle dependence of the transmittance of the film thus prepared was measured with an ultraviolet-visible spectrophotometer. At this time, the viewing angle dependence of the transmittance of the platinum diphenylglyoximato evaporated thin film is shown.
2 and Table 2. With a wavelength of 550 nm as the center, 450
In the wavelength range from to 700 nm, the viewing angle dependence of the transmittance appears. It is shown that the wavelength distribution where the viewing angle dependency of the transmittance appears differs from that of Example 1 even though the same compound as in Example 1 is used.

[0050]

[Table 2]

Example 3 The platinum diphenylglyoximato obtained in Reference Example 1 was applied to a glass deposition heater (quartz crucible: φ20 × H45m).
m) to obtain an evaporation sample. Synthetic quartz (ES grade;
(Area 15 × 30 mm, thickness: 1.0 mm) was fixed above the evaporation boat, and the degree of vacuum was reduced to 4 × 10 ⁻⁷ Torr. Thereafter, the substrate is cooled to -175 ° C.
Vacuum deposition was performed at a speed of nm to a thickness of about 80 nm. Thereafter, the substrate temperature was set at 25 ° C., and the platinum dimethylglyoximat obtained in Reference Example 2 was vacuum-deposited on the platinum diphenylglyoximato thin film at a rate of 1.5 nm per minute to a thickness of about 140 nm. About the membrane created in this way,
The dependence of the transmittance on the incident angle was measured with an ultraviolet-visible spectrophotometer. FIG. 3 and Table 3 show the incident angle dependence of the transmittance of the laminated deposited thin film at this time. The incident angle dependence of the transmittance appears in the wavelength range of 500 to 900 nm centering on the wavelength of 620 nm.

[0052]

[Table 3]

Example 4 The platinum diphenylglyoximato obtained in Reference Example 1 was applied to a glass deposition heater (quartz crucible: φ20 × H45m).
m) to obtain an evaporation sample. Synthetic quartz (ES grade;
(Area 15 × 30 mm, thickness: 1.0 mm)) was fixed above the evaporation boat, and the degree of vacuum was reduced to 3 × 10 ⁻⁷ Torr. Thereafter, the substrate was cooled to −175 ° C., and vacuum evaporation was performed at a rate of 6 nm per minute to a thickness of about 60 nm.
Thereafter, the substrate temperature was set to 22 ° C., and the nickel dimethylglyoximat obtained in Reference Example 3 was placed on the platinum diphenylglyoximato thin film at a rate of 0.5 nm per minute for about 130 nm.
Vacuum deposited to a thickness of. With respect to the film thus formed, the dependence of the transmittance on the incident angle was measured with an ultraviolet-visible spectrophotometer. FIG. 4 and Table 4 show the dependency of the transmittance of the laminated thin film on the incident angle at this time. The incident angle dependence of the transmittance appears in the wavelength range of 450 to 650 nm centering on the wavelength of 540 nm. It is shown that the wavelength distribution at which the incident angle dependence of the transmittance appears differs from that of the first embodiment.

[0054]

[Table 4]

Example 5 The platinum diphenylglyoximat obtained in Reference Example 1 was applied to a glass deposition heater (quartz crucible: φ20 × H45m).
m) to obtain an evaporation sample. Synthetic quartz (ES grade;
(Area 15 × 30 mm, thickness: 1.0 mm)) was fixed above the evaporation boat, and the degree of vacuum was reduced to 3 × 10 ⁻⁷ Torr. Thereafter, the substrate was cooled to −175 ° C., and vacuum evaporation was performed at a rate of 5.5 nm per minute to a thickness of about 60 nm. Thereafter, the substrate temperature was set to 22 ° C., and the palladium dimethylglyoximate obtained in Reference Example 4 was applied on the platinum diphenylglyoximato thin film at a rate of 1.0 nm / min for about 15 minutes.
Vacuum deposited to a thickness of 0 nm. With respect to the film thus formed, the dependence of the transmittance on the incident angle was measured with an ultraviolet-visible spectrophotometer. FIG. 5 and Table 5 show the dependency of the transmittance of the laminated thin film on the incident angle at this time. Wavelength 460
The incident angle dependence of the transmittance appears in the wavelength range of 400 to 600 nm centering on nm.

[0056]

[Table 5]

Example 6 A glass deposition heater (quartz crucible: φ20 × H45m) was prepared using the platinum diphenylglyoximat obtained in Reference Example 1
m) to obtain an evaporation sample. Synthetic quartz (ES grade;
(Area 15 × 30 mm, thickness: 1.0 mm)) was fixed above the evaporation boat, and the degree of vacuum was reduced to 3 × 10 ⁻⁷ Torr. Thereafter, the substrate was cooled to −175 ° C., and vacuum evaporation was performed at a rate of 7 nm per minute to a thickness of about 60 nm.
Thereafter, the substrate temperature was set to 24 ° C., and the platinum dimethylglyoximato obtained in Reference Example 2 was vacuum-deposited on the platinum diphenylglyoximato thin film at a rate of 0.4 nm per minute to a thickness of about 100 nm. Subsequently, the palladium dimethylglyoximate obtained in Reference Example 4 was added at 0.3 nm / min.
Vacuum deposited at a speed of about 100 nm to a thickness of about 100 nm. Further, the nickel dimethylglyoximato obtained in Reference Example 3 was vacuum-deposited thereon at a rate of 0.3 nm per minute to a thickness of about 100 nm. With respect to the film thus formed, the dependence of the transmittance on the incident angle was measured with an ultraviolet-visible spectrophotometer. FIG. 6 and Table 6 show the incident angle dependence of the transmittance of the laminated thin film at this time. In a wide wavelength range from 350 to 850 nm, the incident angle dependence of the transmittance appears.

[0058]

[Table 6]

[Brief description of the drawings]

FIG. 1 shows a substrate temperature of -175 ° C. and a sample deposition rate of 0.
The figure which shows the transmittance | permeability spectrum of the platinum diphenylglyoximato thin film which made 2 nm / min and vacuum-evaporated on the quartz substrate. The solid line shows the transmittance distribution when the substrate surface is irradiated with incident light perpendicularly. The broken line indicates the transmittance distribution when the incident light is irradiated from an angle inclined by 60 degrees from the perpendicular to the substrate surface.
A large viewing angle dependence appears in the transmittance near 700 nm.

FIG. 2 shows a substrate temperature of -175 ° C. and a sample deposition rate of 2.
The figure which shows the transmittance | permeability spectrum of the platinum diphenylglyoximato thin film which made 1 nm / min and was vacuum-deposited on the quartz substrate. The solid line shows the transmittance distribution when the substrate surface is irradiated with incident light perpendicularly. The broken line indicates the transmittance distribution when the incident light is irradiated from an angle inclined by 60 degrees from the perpendicular to the substrate surface.
A large viewing angle dependence appears in the transmittance near 550 nm.

FIG. 3 is a view showing a transmittance spectrum of a film in which a platinum diphenylglyoximato thin film is vacuum-deposited on a quartz substrate at a substrate temperature of −175 ° C., and a platinum dimethylglyoximat thin film is further laminated thereon. The solid line shows the transmittance distribution when the substrate surface is irradiated with incident light perpendicularly. The dashed line indicates an angle of 20 degrees from the perpendicular to the substrate surface, and the dashed line indicates 40 degrees from the perpendicular to the substrate surface.
The two-dot chain line indicates the transmittance distribution when the incident light is irradiated from an angle inclined 60 degrees from the perpendicular to the substrate surface, and the dotted line indicates the transmittance distribution when the incident light is irradiated from the angle inclined 70 degrees from the perpendicular to the substrate surface. 7
A large incident angle dependence appears in the transmittance near 00 nm.

FIG. 4 is a diagram showing a transmittance spectrum of a film in which a platinum diphenylglyoximato thin film is vacuum-deposited on a quartz substrate at a substrate temperature of −175 ° C., and a nickel dimethylglyoximato thin film is further laminated thereon. The solid line shows the transmittance distribution when the substrate surface is irradiated with incident light perpendicularly. The alternate long and short dash line is an angle inclined by 20 degrees from the perpendicular to the substrate surface, the broken line is an angle inclined by 40 degrees from the perpendicular to the substrate surface, and the alternate long and two short dashes line is 6 degrees from the perpendicular to the substrate surface.
From the angle inclined at 0 °, the dotted line indicates the transmittance distribution when the incident light is irradiated at an angle inclined at 70 ° from the perpendicular to the substrate surface. A large incident angle dependence appears in the transmittance near 550 nm.

FIG. 5 is a diagram showing a transmittance spectrum of a film in which a platinum diphenylglyoximato thin film is vacuum-deposited on a quartz substrate at a substrate temperature of −175 ° C., and a palladium dimethylglyoximat thin film is further laminated thereon. The solid line shows the transmittance distribution when the substrate surface is irradiated with incident light perpendicularly. The alternate long and short dash line is from an angle inclined by 20 degrees from the perpendicular to the substrate surface, the broken line is from an angle inclined by 40 degrees from the perpendicular to the substrate surface, the two-dot chain line is from an angle inclined by 60 degrees from the perpendicular to the substrate surface, and the dotted line is the angle from the perpendicular to the substrate surface. It is a transmittance distribution when incident light is irradiated from an angle inclined by 70 degrees from a perpendicular. A large incident angle dependence appears in the transmittance near 450 nm.

FIG. 6 A platinum diphenylglyoximato thin film is vacuum-deposited on a quartz substrate at a substrate temperature of -175 ° C., and a platinum dimethylglyoximat thin film, a palladium dimethylglyoximat thin film, and a nickel dimethylglyoximat thin film are further formed thereon. The figure which shows the transmittance | permeability spectrum of the film | membrane which laminated | stacked sequentially. The solid line shows the transmittance distribution when the substrate surface is irradiated with incident light perpendicularly. The broken line is the transmittance distribution when the incident light is irradiated from an angle inclined by 70 degrees from the perpendicular of the substrate surface. 350 to 85
In a wide wavelength range of 0 nm, the transmittance has a large incident angle dependence.

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C07F 15/00 C07F 15/00 F (72) Inventor Takanori Tano 1-1-1 Higashi, Tsukuba, Ibaraki Pref. Inventor Hiroshi Ushijima 1-1-1, Higashi, Tsukuba-shi, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Kenji Osasa 1-1-1, Higashi, Higashi, Tsukuba-shi, Ibaraki Pref. Document JP-A-4-8771 (JP, A) JP-A-4-23868 (JP, A) JP-A-9-230134 (JP, A) JP-A-64-93556 (JP, A) 62970 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G02B 5/20

Claims (6)

(57) [Claims] 1. A polarizing color filter material comprising a planar organometallic complex represented by the following general formula (1). Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ are a substituent A having a carbon atom as a bonding atom, a substituent B having a hetero atom as a bonding atom,
And when R ₁ and R ₂ are the substituents A and / or B, R ₁ and R ₂ may be mutually connected to form a ring; _{When 3} and R ₄ are the aforementioned substituents A and / or B, those R ₃ and R ₄ may be mutually connected to form a ring, and M represents copper, nickel, palladium and platinum. Indicates a metal selected from the list) 2. A deflecting color filter comprising a thin film of the material according to claim 1 formed on a substrate. 3. A method for manufacturing a deflecting color filter, comprising forming a thin film of the material of claim 1 on a substrate by vacuum vapor deposition at a temperature of -100 ° C. or less. 4. The method according to claim 3, wherein the vacuum deposition rate of the material is 0.01 to 3 nm, expressed as a film growth rate per minute. 5. A polarizing color filter comprising two or more thin films of the material according to claim 1 laminated on a substrate. 6. The method according to claim 1, wherein the material according to claim 1 is vacuum-deposited on a substrate at a temperature of -100 ° C. or less to form a thin film of the material, and further, at least one kind of the material according to claim 1 is laminated thereon. A method for producing a polarizing color filter, comprising: