JPH06294909A - Dye and sheet for optical cut filter - Google Patents

Abstract

PURPOSE:To obtain such a material that can be easily worked and satisfies requests for products of small lot and various kinds by using specified dyes having flat transmittance in a visible region and excellent transparency and good heat resistance and light resistance. CONSTITUTION:The dyes are at least six kinds of dyes selected among yellow dyes expressed by formula I, pyridone azo yellow dyes expressed by formula II, and anthraquinone yellow dyes expressed by formula III. In formula I, X1, X2 and X3 are independently hydrogen atoms, alkyl groups, or halogen atoms. In formula II, R1 is a hydrogen atom or alkyl group, R2 is a hydrogen atom, alkyl group which may have substituents, cycloalkyl grlup, allyl group, or phenyl group which may have substituents, and Ar is a phenyl group which may have substituents. In formula III, R3, R4, R5, R3', R4', R5' are same or different hydrogen atoms, halogen atoms, alkyl groups, alkoxycarbonyl groups, or acyloxy groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an optical cut filter,
In particular, the present invention relates to a dye and sheet for a neutral density filter, which is important for controlling the amount of visible light.

[0002]

BACKGROUND OF THE INVENTION ND is an important part of a camera (including a video camera).
There is a (neutral density) filter, which is used for so-called adjustment of the amount of visible light. For example,
When the visible light is extremely strong, the ND filter is used to adjust the light amount to an appropriate amount, and a stable visible image can be obtained by the exposure with the appropriate light amount.

These ND filters are required to have various physical and chemical characteristics shown below. (1) Cut the visible part (400 to 700 nm) flat. (2) It is necessary to have filters that cut at arbitrary transmittances according to the characteristics of various models. Therefore, cut filters having various transmittances in small quantities and in a wide variety of products can be easily and inexpensively manufactured. (3) It has excellent heat resistance and light resistance. (4) Excellent transparency.

However, many of the known optical cut filters (hereinafter abbreviated as cut filters) cannot be said to sufficiently satisfy the above-mentioned required characteristics, and improvements are desired. In particular, glass is often used as the material of the cut filter at present, and it is difficult to process it because it requires complicated technology, and it is difficult to deal with various cut filters of a large variety of small lots, and the cost is high. There are various problems such as the above, and there is a demand for a cut filter that is easy to process and that can meet the demands of small quantities and a large variety of products.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve various problems of the above-mentioned cut filter. As a result, they have found a dye having a very flat visible portion transmittance and excellent transparency, and further having good heat resistance and light resistance. Further, they have found that a low-cost cut filter sheet that can be easily processed by the dye and various resins and can meet the demand of a large number of small quantities can be produced, and thus the present invention has been completed. That is, the present invention is represented by the general formula (1)

[0006]

[Chemical 15]

[In the formula, X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom, an alkyl group or a halogen atom. ]
A yellow dye represented by the general formula (2)

[0008]

[Chemical 16]

[In the formula, R ₁ represents a hydrogen atom or an alkyl group, and R ₂ represents a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an allyl group or a substituent. Represents a phenyl group, and Ar represents a phenyl group which may have a substituent. ] Pyridoneazo yellow dye represented by the general formula (3)

[0010]

[Chemical 17]

[Wherein R ₃ , R ₄ , R ₅ , R ₃ ', R ₄ ',
R ₅ 'is the same or independently, a hydrogen atom, a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, unsubstituted or substituted aryl group, aralkyl group, alkoxy group,
An alkoxyalkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group or an acyloxy group is shown. ] Anthraquinone yellow dye represented by the general formula (4)
(Chemical formula 18)

[0012]

[Chemical 18] [In the formula, the aromatic rings A, B and C may have a substituent. ] A quinophthalone yellow dye represented by the general formula (5)

[0013]

[Chemical 19]

[In the formula, the aromatic ring D may have a substituent. ] A perylene red dye represented by the general formula (6)

[0015]

[Chemical 20]

[Wherein X ₄ is a hydrogen atom, a halogen atom,
The alkoxy group or phenoxy group which may have a substituent is shown. ] Anthraquinone red dye represented by
General formula (7) (Chemical formula 21)

[0017]

[Chemical 21]

[In the formula, R ₆ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group, and Ring E represents an aromatic ring which may have a substituent or a cyclohexyl group. ] Anthraquinone red dye represented by the general formula (8)

[0019]

[Chemical formula 22]

[In the formula, the aromatic ring F may have a substituent. ] Anthraquinone blue dye represented by the general formula (9)

[0021]

[Chemical formula 23]

[In the formula, X represents a hydrogen atom or a halogen atom,
n shows the integer of 1-4. ] Anthraquinone red dye represented by the general formula (10)

[0023]

[Chemical formula 24]

[Wherein R ₇ , R ₈ , R ₉ , R ₇ ′, R ₈ ′,
R ₉ 'is the same or independently a hydrogen atom, a halogen atom,
An alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an alkoxyalkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an acyloxy group are shown. ] Anthraquinone green dye represented by the general formula (11)

[0025]

[Chemical 25]

[In the formula, R ₁₀ and R ₁₁ are the same or independently of each other, a hydrogen atom, an alkyl group which may be linear or branched, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group or an alkoxyalkyl. And a ring G represents an aromatic ring or a cyclohexyl group. ] Anthraquinone blue dye represented by the general formula (12)

[0027]

[Chemical formula 26]

[In the formula, X ₆ and X ₇ represent an oxygen atom or an NH group, and R ₁₂ represents a hydrogen atom, an optionally substituted alkyl group or a phenyl group. ] Anthraquinone blue dye represented by the general formula (13)

[0029]

[Chemical 27]

[In the formula, the aromatic rings H, I, J and K may have a substituent. ] Anthraquinone green dye represented by the general formula (14)

[0031]

[Chemical 28]

[In the formula, R ₁₃ , R ₁₈ and R ₁₉ are the same or each independently a hydrogen atom, a linear or branched alkyl group, a cyclohexylalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an acyloxyalkyl group, an acylamino group. Alkyl group, halogenated alkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, alkenyl group,
Or an aralkyl group, R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are the same or each independently a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, a linear or branched alkoxy group, a cycloalkyloxy group, It represents an alkoxyalkyl group, an alkoxyalkoxy group, an aralkyl group or a halogen atom, and R ₁₄ and R ₁₅ or R ₁₆ and R ₁₇ may be linked to each other to form a ring, and X is a hydrogen atom, a halogen atom, Represents an alkoxy group or a hydroxyl group, a represents an integer of 1 to 4, b represents an integer of 0 to 5, and 2a + b + c represents 1
6 and M represents an integer of a metal atom or a metal oxide. ] It is a pigment | dye for optical cut filters which consists of at least 6 types of pigments selected from the phthalocyanine type pigments represented by these, and is a sheet | seat for optical cut filters which consists of this pigment and resin.

The present invention will be described in detail below. The present invention is a cut filter dye constituted by selecting six or more types of dyes from the above-mentioned dyes.
The cut filter dye of the present invention is 400 to 700 n.
In order to flatly cut the wavelength of m, that is, in order to keep the cut rate constant, it is preferable to divide 400 to 700 nm into 50 nm and select and configure a dye that cuts the wavelength of each range. In the present invention, 400-
The dyes of the general formulas (1) to (5) are used to cut the wavelength of 450 nm, and the general formula (5) is used to cut the wavelength of 450 to 500 nm.
Dyes of the general formulas (6) to (7) for wavelength cut of 500 to 550 nm, and dyes of the general formulas (8) to (10) of 600 to 650 for wavelength cut of 550 to 600 nm.
The dyes of the general formulas (11) to (12) are used to cut the wavelength of nm, and the general formula (1) is used to cut the wavelength of 650 to 700 nm.
The dyes 3) to (14) are preferable, and it is preferable to select one or more dyes applied to each range. Further, in the case of cutting at 400 nm or less, an ultraviolet absorber usually used for resins may be used together.

In the dye of the present invention, the aromatic rings A, B and C of the general formula (4), the aromatic ring D of the general formula (5), the alkoxy group or the phenoxy group of the general formula (6), and the general formula (7). Aromatic ring E, general formula (8) aromatic ring F, general formula (11) aromatic ring G, general formula (12) R ₁₂ alkyl group or phenyl group, general formula (13) aromatic ring H, I,
Specific examples of the J and K substituents include hydrogen atom, hydroxyl group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n.
-Pentyl group, 2-methylbutyl group, n-hexyl group,
Alkyl group such as 2-methylpentyl group, cycloalkyl group, methoxy group, ethoxy group, n-propoxy group, n-
Butoxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group and other alkoxy groups, trifluoromethyl group, fluorine atom, chlorine atom, bromine atom and other halogen atoms, cyano group, nitro group, methoxycarbonyl group , Ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group and other alkoxycarbonyl groups, methoxyethoxycarbonyl group , Ethoxyethoxycarbonyl group, alkoxyalkoxycarbonyl group such as (3-ethoxypropoxy) carbonyl group, methylaminocarbonyl group, ethylaminocarbonyl group, n-butylaminocarbonyl group, dimethylaminocarbyl group Alkylaminocarbonyl group such as a group, acetylamino group, ethylcarbonylamino group,
Examples thereof include alkylcarbonylamino groups such as n-propylcarbonylamino group, n-butylcarbonylamino group and i-butylcarbonylamino group, aralkyl groups such as benzyl group and phenethyl group, but are not limited thereto. .

In the present invention, as the resin for the cut filter, polystyrene, poly P-chlorostyrene,
Homopolymers of styrene such as polyvinyltoluene and its substitution products, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, styrene-ethyl acrylate copolymers, styrene-butyl acrylate copolymers,
Styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene- Acrylonitrile copolymer, styrene-
Vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isobrene copolymer, styrene-acrylonitrile-indene copolymer styrene-malein Acid copolymer, styrene-styrene copolymer such as styrene-maleic acid ester copolymer, polymethyl-methacrylate, polybutylmethacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, polyvinyl butyral, Examples thereof include polyacrylic acid resins, rosins, modified rosins, terpene resins, phenol resins, aliphatic or alicyclic hydrocarbon resins, aromatic stone resins, chlorinated paraffins and paraffin waxes alone or in a mixture. Add a dye to these resins,
By performing mixing, calendering and the like, a cut filter sheet applicable to various cut filters can be produced.

[0036]

EXAMPLES The present invention will be described in more detail below with reference to examples. The compound used was prepared by a conventional method. In addition, (the light resistance of the following examples and comparative examples is a fade meter carbon arc lamp), the judgment was performed after irradiation at 63 ° C. for 60 hours. Furthermore, the parts shown below represent parts by weight. Example 1

[0037]

[Chemical 29] 6.3 parts of a yellow dye,

[0038]

[Chemical 30] 14.7 parts of a perylene orange dye represented by

[0039]

[Chemical 31] 18.0 parts of a perylene red dye represented by

[0040]

[Chemical 32] 4.2 parts of a quinone red dye represented by

[0041]

[Chemical 33] 2.8 parts of quinone red dye represented by

[0042]

[Chemical 34] 14.0 parts of a quinone blue dye represented by

[0043]

[Chemical 35] 12.0 parts of quinone green dye represented by

[0044]

[Chemical 36]

27.8 quinone green dye represented by
Part is polyvinyl chloride resin powder [Vinicron 3000L (manufactured by Mitsui Toatsu Chemicals, Inc.)] (molecular weight: about 800) 19,90
After adding to 0 part and mixing with a mixer, calendering treatment (175 ° C./3 min) is performed to obtain a sheet having a thickness of 0.1 mm. The obtained cut filter sheet is 40
Uniform transmittance of all light with a wavelength of 0 to 700 nm 10%
Cut into Further, the light resistance of this sheet was grade 8, which was very excellent.

Example 2 A sheet was produced in exactly the same manner as in Example 1 except that the dye of Example 1 was changed as shown in Table 1 (Table 1 and Table 2) below. The obtained cut filter sheet is 400 to 70
All the light of 0nm wavelength is cut uniformly, and the light resistance is 8
It was a very good product.

[0047]

[Table 1]

[0048]

[Table 2]

Example 3 A sheet was prepared in exactly the same manner as in Example 1 except that the dyes used in Example 1 were changed as shown in Table 2 (Tables 3 and 4) below. The obtained cut filter sheet is 400 to 70
All the light of 0nm wavelength is cut uniformly, and the light resistance is 8
It was a very good product.

[0050]

[Table 3]

[0051]

[Table 4]

Example 4 A sheet was prepared in exactly the same manner as in Example 1 except that the dye of Example 1 was changed as shown in Table 3 (Table 5 and Table 6) below. The obtained cut filter sheet is 400 to 70
All the light of 0nm wavelength is cut uniformly, and the light resistance is 8
It was a very good product.

[0053]

[Table 5]

[0054]

[Table 6]

Example 5 A sheet was prepared in exactly the same manner as in Example 1 except that the dye of Example 1 was changed as shown in Table 4 (Table 7 and Table 8) below. The obtained cut filter sheet is 400 to 70
All the light of 0nm wavelength is cut uniformly, and the light resistance is 8
It was a very good product.

[0056]

[Table 7]

[0057]

[Table 8]

Example 6 A sheet was prepared in exactly the same manner as in Example 1 except that the dye of Example 1 was changed as shown in Table 5 (Table 9 and Table 10) below. The obtained cut filter sheet is 400 to 7
All of the light having a wavelength of 00 nm was uniformly cut, and the light resistance was grade 8, which was very excellent.

[0059]

[Table 9]

[0060]

[Table 10]

Example 7 A sheet was prepared in exactly the same manner as in Example 1 except that the dye of Example 1 was changed as shown in Table 6 (Table 11 and Table 12) below. The obtained cut filter sheet is 400-
All of the light having a wavelength of 700 nm was uniformly cut, and the light resistance was grade 8, which was very excellent.

[0062]

[Table 11]

[0063]

[Table 12]

Example 8 A sheet was produced in exactly the same manner as in Example 1 except that the dyes in Example 1 were changed as shown in Table 7 (Table 13 and Table 14) below. The obtained cut filter sheet is 400-
All of the light having a wavelength of 700 nm was uniformly cut, and the light resistance was grade 8, which was very excellent.

[0065]

[Table 13]

[0066]

[Table 14]

Comparative Example 1 A sheet was produced in exactly the same manner as in Example 1 except that the dye of Example 1 was changed as shown in Table 8 (Table 15) below.
400 to 700 n of the obtained cut filter sheet
The cut rate of m at each wavelength was non-uniform, and the light resistance was grade 3.

[0068]

[Table 15]

[0069]

Industrial Applicability According to the present invention, it is possible to provide a light-cutting filter that cuts the visible portion flat and is excellent in transparency, heat resistance, and light resistance, with easy processability and at low cost.

Claims (2)

[Claims] 1. General formula (1) (Chemical formula 1) [In the formula, X ₁ , X ₂ and X ₃ are each independently a hydrogen atom,
An alkyl group or a halogen atom is shown. ] A yellow dye represented by the general formula (2) (Chemical Formula 2) [In the formula, R ₁ represents a hydrogen atom or an alkyl group, and R ₂ represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, an allyl group or a phenyl which may have a substituent. Represents a group, and Ar represents a phenyl group which may have a substituent. ] The pyridoneazo yellow dye represented by the general formula (3) (Chemical Formula 3) [In the formula, R ₃ , R ₄ , R ₅ , R ₃ ′, R ₄ ′, and R ₅ ′ are the same or independently, a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an unsubstituted or A substituted aryl group, aralkyl group, alkoxy group, alkoxyalkoxy group, alkoxyalkyl group, alkoxycarbonyl group or acyloxy group is shown. ] Anthraquinone yellow dye represented by the general formula (4) (Chemical Formula 4) [In the formula, the aromatic rings A, B and C may have a substituent. A quinophthalone yellow dye represented by the following general formula (5) (Chemical Formula 5) [In the formula, the aromatic ring D may have a substituent. ] A perylene red dye represented by the general formula (6) (Chemical Formula 6) [In the formula, X ₄ represents a hydrogen atom, a halogen atom, an alkoxy group which may have a substituent or a phenoxy group. ]
Anthraquinone red dye represented by the general formula (7)
(Chemical formula 7) [Chemical formula 7] [In the formula, R ₆ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group, and Ring E represents an aromatic ring which may have a substituent or a cyclohexyl group. ] Anthraquinone red dye represented by the general formula (8) (Chemical Formula 8) [In the formula, the aromatic ring F may have a substituent. ] Anthraquinone-based blue dye represented by the general formula (9) (Chemical Formula 9) [In the formula, X represents a hydrogen atom or a halogen atom, and n represents an integer of 1 to 4. ] Anthraquinone red dye represented by the general formula (10) (Chemical Formula 10) [In the formula, R ₇ , R ₈ , R ₉ , R ₇ ′, R ₈ ′, and R ₉ ′ are the same or independently of each other, a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and an aralkyl. Group, alkoxy group, alkoxyalkoxy group, alkoxyalkyl group, alkoxycarbonyl group, and acyloxy group. ] Anthraquinone-based green dye represented by the general formula (11) (Chemical formula 11) [Wherein R ₁₀ and R ₁₁ are the same or independently of each other, a hydrogen atom,
A straight-chain or branched alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group is shown, and a ring G is an aromatic ring which may have a substituent or a cyclohexyl group. . ] Anthraquinone blue dye represented by the general formula (12)
2) [Chemical formula 12] [In the formula, X ₆ and X ₇ represent an oxygen atom or an NH group, and R ₁₂ represents a hydrogen atom, an alkyl group which may have a substituent or a phenyl group. ] Anthraquinone blue dye represented by the general formula (13) (Chemical Formula 13) [In the formula, the aromatic rings H, I, J, and K may have a substituent. ] Anthraquinone-based green dye represented by the general formula (14) [Wherein R ₁₃ , R ₁₈ and R ₁₉ are the same or each independently a hydrogen atom, a linear or branched alkyl group, a cyclohexylalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an acyloxyalkyl group, an acylaminoalkyl group, Represents a halogenated alkyl group, a cyanoalkyl group, an alkoxycarbonylalkyl group, an alkenyl group, or an aralkyl group, wherein R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are the same or each independently a hydrogen atom, a straight chain or branched alkyl group. , A cycloalkyl group, a linear or branched alkoxy group, a cycloalkyloxy group, an alkoxyalkyl group, an alkoxyalkoxy group, an aralkyl group or a halogen atom, and R
₁₄ and R ₁₅ or R ₁₆ and R ₁₇ may be linked to each other to form a ring, X represents a hydrogen atom, a halogen atom, an alkoxy group or a hydroxyl group, a represents an integer of 1 to 4, and b Represents an integer of 0 to 5, 2a + b + c is 16 and M
Represents an integer of a metal atom or a metal oxide. ] The dye for optical cut filters which consists of at least 6 or more types of dyes selected from the phthalocyanine type dyes represented by these. 2. A sheet for a light cut filter, which comprises the dye according to claim 1 and a resin.