JP3086483B2 - Colored resin and related technologies - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a colored resin colored with a red disazo dye having a triphenylmethane structure.
The present invention relates to a composition, a colored resin molded product, and a color filter.

[0002]

2. Description of the Related Art Various pigments and dyes are used for coloring a thermoplastic resin, a thermosetting resin, a color filter, and the like, depending on the use and purpose. For example, organic pigments
It has excellent light and heat resistance, is rich in colors, and is often used because of its vivid color.

[0003] Oil-soluble dyes and disperse dyes have excellent solubility in resins and are therefore used for obtaining transparent and glossy products. Colored resin compositions and colored resin molded products require light resistance, bleed resistance, heat resistance against heat during molding, and the like, and are often required to be transparent.

The optical color filters required for television cameras, liquid crystal televisions, flat panel displays mounted on computers, and the like must have good spectral characteristics and transparency.

As a red dye for an optical filter, for example, there is a dye disclosed in Japanese Patent Application Laid-Open No. 1-278569. It is also manufactured by dyeing a dyeable film based on a transparent resin or a glass substrate based on gelatin, casein, polyvinyl alcohol, or the like with a dye having predetermined spectral characteristics by printing, sublimation transfer, or the like. Although there are many color filters, it is of course desirable to color the resin itself from the viewpoint of durability.

[0006]

Of the above-mentioned conventional colorants, organic pigments are hardly soluble in resins, and thus cannot often satisfy the requirement for transparency. On the other hand, oil-soluble dyes and disperse dyes are prone to discoloration and bleed.

Accordingly, a colored resin set using a conventional colorant
With respect to a product, a colored resin molded product, or a color filter, it cannot be said that the above-mentioned necessary conditions are always sufficiently satisfied.

The present invention has been made in view of such problems in the prior art, and a first object of the present invention is to provide a colored resin having good light resistance, bleed resistance, heat resistance and transparency.
An object of the present invention is to provide a fat composition or a colored resin molded product. A second object is to provide a color filter having good transparency, spectral characteristics, bleed resistance and durability.

[0009]

Means for Solving the Problems In order to achieve the above object, the colored resin composition of the present invention contains at least one kind of disazo dye represented by the following general formula [I] in a dissolved state. Shall do.

[0010]

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In the formula [I], X represents a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, Y represents a hydrogen atom or a methyl group, and R ¹ and R ² are independent of each other. A hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and Q and Q ′ are represented by the following formulas

[0012]

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In the formula, R ³ independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a nitro group, and n represents 1, 2 or 3. Where R
⁴ independently represents a hydrogen atom, an alkyl group or a substituted alkyl group. However, at least one R ⁴ is not a hydrogen atom.カ プ ラ indicates a coupler residue selected from the group consisting of｝. ]

The dye represented by the general formula [I] used in the present invention can be synthesized as follows. That is, first, the anilines (A)

[0015]

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And benzaldehyde (B)

[0017]

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To condense the compound (C)

[0019]

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And then the compound (C) is tetrazotized and coupled with naphthol ASs,
The dye represented by the general formula [I] can be obtained.

X in the above formulas (A), (B) and (C)
Y, R ¹ and R ² have the same meanings as in general formula [I].

X represents a methyl group, an ethyl group or methoxy;
Y represents a hydrogen atom or a methyl group; R ¹ and R ² each independently represent a hydrogen atom; methyl, ethyl, propyl, ethoxy, propoxy, butoxy, etc. alkyl groups such as iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl, amyl and iso-amyl; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy or halogen atoms such as Cl, Br and I Show.

Q and Q ′ in the general formula [I] are, for example, residues of naphthol ASs represented by the following (a) to (k). Of course, Q and Q 'may be the same or different. All of these naphthol ASs are commercially available.

(A) Naphthol AS

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(B) Naphthol AS-D

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(C) Naphthol AS-RL

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(D) Naphthol AS-OL

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(E) Naphthol AS-PH

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(F) Naphthol AS-E

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(G) Naphthol AS-TR

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(H) Naphthol AS-BO

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(I) Naphthol AS-SW

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(J) Naphthol AS-BS

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(K) Naphthol BD-1

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Next, specific examples of the dye represented by the general formula [I] used in the present invention are shown in Table 1.

[0036]

[Table 1]

The column of λmax in Table 1 shows the maximum value of the absorption wavelength in the visible region of each dye example measured with an 8451A diode array spectrophotometer (trade name, manufactured by Hewlett-Packard Company) using chloroform as a solvent. . The near-ultraviolet-visible absorption spectra obtained by the same measurement for Dye Example 1, Dye Example 3, Dye Example 9 and Dye Example 10 are shown in FIGS. 1, 2, 3 and 4, respectively. 1 to 4, the horizontal axis represents wavelength and the vertical axis represents absorbance.

The resins constituting the colored resin composition of the present invention include thermoplastic resins such as styrene resin, acrylic resin, styrene-acryl copolymer, polycarbonate, polyamide, polybutylene terephthalate, polyethylene, polypropylene, polyacetal and polyester. And thermosetting resins such as polyurethane and phenolic resins. In particular, when the dye represented by the general formula [I] is applied to a styrene resin, an acrylic resin, a styrene-acryl copolymer or a polycarbonate, a colored resin composition having excellent transparency can be obtained.

The colored resin composition of the present invention can be produced, for example, by melt-mixing a disazo dye represented by the general formula [I] with a resin. When used for plastics molding, the disazo dye of the general formula [I] is usually added in an amount of 0.1 to 2% by weight based on the resin.

The colored resin molded product of the present invention is obtained by molding the above-described colored resin composition . For the molding, known means such as injection molding can be appropriately used.

The colored resin molded article of the present invention may be obtained by dyeing the resin molded article with at least one disazo dye represented by the above general formula [I]. The colored resin molded product is, for example, a disazo dye represented by the general formula [I] transferred to a molded product made of the same resin as that used in the above colored resin composition , for example, transfer, printing, sublimation deposition, or the like. Can be obtained by dyeing by the means described above.

[0042] Furthermore, the color filter of the present invention, wear
The colored resin composition is provided with the colored resin composition , or the resin molded article is provided with the colored resin molded article dyed with a disazo dye.

The color filter of the present invention can be produced, for example, by the method described in JP-A-1-278569 or a method analogous thereto. That is, a method in which a dye is mixed with a resin and a solvent, and the mixture is kneaded to form an ink, and the ink is used to dye a plastics substrate having dyeability such as polyester, polyamide, and acrylic resin.
A method of forming a colored resin coating film using such an ink on a resin or other transparent substrate, a method in which a dye is kneaded into a resin, and a method in which it is formed into a sheet, a synthetic resin film such as ethylene glycol is used. There are a method of dyeing in a solvent, a method of applying the ink composition to paper or the like, and transferring and dyeing the composition on a resin substrate.

In the colored resin composition , colored resin molded product and color filter of the present invention, other coloring agents can be used in combination as long as the objects and effects are not impaired.

[0045]

The colored resin compositions of claims 1 and 2 and the colored resin molded products of claims 3 and 4 have good light resistance, bleed resistance, heat resistance and transparency. The color filter according to claim 5 has good transparency, spectral characteristics, bleeding resistance and durability.

[0046]

Next, the present invention will be described in detail with reference to examples, but the present invention is of course not limited to these examples.

Synthesis Example of Disazo Dye Used in the Present Invention [ Synthesis of 4,4'-benzylidene-di-2,5-xylidine] 121 g (1 mol) of 2,5-xylidine, 53 g (0.5 mol) of benzaldehyde , 70 g of concentrated hydrochloric acid and 150 g of chlorobenzene were reacted under reflux for 7 hours.

After the reaction mixture was poured into an aqueous solution of caustic soda to make it alkaline, steam distillation was performed, the residue was filtered, and the residue was washed with water and dried to obtain 130 g of an unpurified base material. This was purified with about three times the amount of alcohol to obtain a white powder having a structure represented by the following formula. Its melting point is
203-205 ° C.

[0049]

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[Synthesis of Dye Example 1] 8.3 g of 4,4'-
Benzylidene-di-2,5-xylidine is added to concentrated hydrochloric acid 12
After dissolving and dispersing in 80 g of water containing g, cooled to 5 ° C. or lower, a solution obtained by dissolving 7 g of sodium nitrite in a small amount of water was dropped into the solution and tetrazotized.

In addition, 200 g of water containing 4.5 g of caustic soda
13.6 g of naphthol AS-D was dissolved in 1 g of the solution, 1 g of a nonionic dispersant was added thereto, and then ice was added to the solution.
C. or less to prepare a coupler solution. The tetrazonium salt solution was added dropwise to the coupler solution for coupling. The precipitate was separated by filtration, washed with water and dried to obtain 22.5 g of a dye as a red powder (Dye Example 1).

[Synthesis of Dye Example 11] 9.7 of 4,4 ′-(p-isobutylbenzylidene) di-2,5-xylidine
g was dissolved in 100 g of acetic acid, 10 g of concentrated hydrochloric acid was added thereto, and the mixture was cooled to 5 ° C. or lower. Then, a solution prepared by dissolving 3.5 g of sodium nitrite in a small amount of water was added dropwise to tetrazotize.

Further, 14.9 g of naphthol AS-E was dissolved in 100 g of DMF, and the nonionic activator 2 was added thereto.
g was added and the temperature was lowered to 10 ° C. or lower to prepare a coupler solution. Then, while keeping the coupler solution alkaline by the dropwise addition of a dilute aqueous sodium hydroxide solution, the above tetrazonium salt solution was dropped into the coupler solution to perform coupling. The precipitate was filtered off, washed with water and dried,
25 g of a red powdery dye (Dye Example 11) was obtained.

Example 1 500 g of a polystyrene resin [Dialex (trade name), manufactured by Mitsubishi Monsanto Co., Ltd.] and 0.25 as a colorant
g of Dye Example 1 was placed in a stainless steel tumbler and mixed well for 1 hour. This mixture was prepared by using a vented extruder (trade name: E30SV, manufactured by Enpla Sangyo Co., Ltd.) for 200 minutes.
The resulting mixture was melt-mixed at a temperature of ℃ and colored pellets were prepared by a conventional method.

Next, the pellets were dried at 80 ° C. for 3 hours, and then tested by an ordinary method (molding temperature: about 200 ° C.) using an injection molding machine (trade name: K-25C, manufactured by Kawaguchi Iron Works). When a plate was prepared, Dye Example 1 withstands heat during melt mixing and molding, and a molded plate having excellent red transparency was obtained. The light resistance of this molded plate was good, that is, class 6 and the bleed resistance was class 5.

The light fastness was determined by applying a fade meter (carbon arc type) for 40 hours, and comparing with a normal condition by a blue scale (JIS L0841). The same applies to the following examples and comparative examples. The bleeding resistance was measured by sandwiching the test plate with a load of 200 g / cm ² between two uncolored molded plates made of the same material as the test plate, and holding the test plate at 120 ° C. for 24 hours. Gray scale (JI
SL0805). The same applies to the following examples and comparative examples.

Example 2 500 g of methacrylic resin [Acrypet (trade name),
Manufactured by Mitsubishi Rayon Co., Ltd.] and 0.25 g of Dye Example 9 as a coloring agent were melt-mixed at 210 ° C. to prepare colored pellets by a conventional method. Next, the pellets were treated in the same manner as in Example 1 to obtain a red transparent molded plate. This molded plate had good light resistance of 6th grade and good bleeding resistance of 5th grade.

Comparative Example 1 In order to compare light resistance, bleed resistance and light transmittance,
Dye Example 1 used in Example 1 was replaced with C.I. I. A molded plate was prepared in the same manner as in Example 1, except that Pigment Red 61 was used. This molded plate had good light resistance and bleed resistance, but had poor compatibility with the resin and poor light transmittance.

Example 3 A dye for gravure printing was prepared by mixing Dye Example 1, acrylic resin and toluene, and kneading the mixture. This ink was printed on a polycarbonate substrate by a gravure printing method, and the ink coating film was dried to form a colored resin film to obtain a red optical filter. The light resistance of this filter is class 6,
The bleeding resistance was as good as Class 5 respectively. Further, its spectral characteristics were also good.

Example 4 A molded plate of a methacrylate resin [Acrypet (trade name), manufactured by Mitsubishi Rayon Co., Ltd.] was coated with 2 g of Dye Example 3, 10 g of Pylonal MD1200 (trade name, manufactured by Toyobo Co., Ltd.) and 1 g of silica gel. Place the transfer paper prepared from
After passing through a calendar, the molded plate was dyed to obtain a red filter. This filter has a lightfastness of 6
Grade and bleeding resistance were as good as Grade 5, respectively. Further, its spectral characteristics were also good as in Example 3.

Example 5 5 g of a polyester film and 2 g of Dye Example 10 were placed in 1000 g of ethylene glycol,
The polyester film was dyed for a minute to make a red filter. This filter had good light resistance of 6th grade and good bleeding resistance of 5th grade. Further, its spectral characteristics were also good as in Example 3.

Comparative Example 2 In order to compare light resistance and bleed resistance, Dye Example 1 used in Example 3 was replaced with C.I. I. A red filter was prepared in the same manner as in Example 3, except that the solvent was replaced with Solvent Red 54. This red filter had a light resistance of class 5 and a bleed resistance of class 4 to class 5.

[Brief description of the drawings]

FIG. 1 is a near ultraviolet-visible absorption spectrum of Dye Example 1.

FIG. 2 is a near ultraviolet-visible absorption spectrum of Dye Example 3.

FIG. 3 is a near ultraviolet-visible absorption spectrum of Dye Example 9.

FIG. 4 is a near ultraviolet-visible absorption spectrum of Dye Example 10.

──────────────────────────────────────────────────続 き Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08K 3/00-13/08 C08L 1/00-101/16 C09B 33/02-33/16

Claims (5)

(57) [Claims] 1. A wear with colored transparency by at least one disazo dye represented by the following general formula [I]
Color resin composition . Embedded image [In the formula [I], X represents a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, Y represents a hydrogen atom or a methyl group, and R ¹ and R ² independently of each other, Represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and Q and Q ′ are represented by the following formulas: In the formula, R ³ independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a nitro group, and n represents 1, 2 or 3. In the formula, R ⁴ independently represents a hydrogen atom, an alkyl group or a substituted alkyl group. However, at least one R ⁴ is not a hydrogen atom.カ プ ラ indicates a coupler residue selected from the group consisting of｝. ] 2. The resin according to claim 1, wherein the resin is a thermoplastic molding resin.
The colored resin composition according to the above . 3. A colored resin molded product obtained by molding the colored resin composition according to claim 1 or 2. 4. A colored resin molded article obtained by dyeing the resin molded article with at least one disazo dye represented by the following general formula [I]. Embedded image [In the formula [I], X represents a methyl group, an ethyl group or
Y represents a hydrogen atom or a methyl group, R ¹ and R ² independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and Q and Q ′ represent From the following formula: In the formula, R ³ independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a nitro group, and n represents 1, 2 or 3. In the formula, R ⁴ independently represents a hydrogen atom, an alkyl group or a substituted alkyl group. However, at least one R ⁴ is not a hydrogen atom.カ プ ラ indicates a coupler residue selected from the group consisting of｝. ] 5. A color filter comprising the colored resin molded product according to claim 3.