JP2920311B2 - Orange coloring composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a highly light-resistant orange-colored composition containing a novel methine compound and a hindered amine light stabilizer in a resin.

<Prior Art> Conventionally, perinone compounds are mainly known as orange colorants among resin colorants, and specifically, for example, perinone compounds represented by the following structural formulas are known.

Although this coloring agent has a feature of being excellent in heat resistance and light resistance, resin molded products colored with these coloring agents have insufficient performance such as elution resistance and bleeding resistance. Also, because it has sublimability, it contaminates the mold during molding,
Further, since the coloring power of the colorant is low, there is a problem that a large amount of the colorant is required to obtain a dark color.

In addition to the perinone compounds, methine compounds are used, and specifically, for example, methine compounds represented by the following structural formulas are known.

This coloring agent has a feature of being excellent in heat resistance and elution resistance. However, the resin molded product colored with this coloring agent had poor light resistance with polystyrene resin, and also had insufficient performance in elution resistance and bleed resistance.

<Problems to be Solved by Rain Invention> The present inventors have excellent heat resistance, bleed resistance, light resistance, elution resistance, sublimation resistance, and the like, and can provide a high-concentration colored molded article. A novel methine compound as a colorant having excellent performance in place of a conventional known compound;
No. proposed.

The novel methine compounds proposed in Japanese Patent Application No. 1-247413 exhibit extremely excellent performance in various resins, but in particular resins such as polystyrene-based polymers and polymethyl methacrylate exhibit particularly severe light resistance. It may be required, and in such a case, the methine compound may have other performances but only insufficient light fastness.

Therefore, the present inventors have further studied and found that by combining a novel methine compound and a hindered amine light stabilizer, a highly light-resistant orange-colored composition can be obtained even in the above specific resin. The present invention has been completed.

That is, an object of the present invention is to provide an orange color which has excellent performances of high concentration, high heat resistance, high bleeding resistance, high elution resistance, high sublimation resistance, and extremely excellent light resistance with a specific resin. It is to provide a composition.

<Means for Solving the Problems> The present invention relates to the following general formula [I] (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a lower carboxylic ester group, and R ² represents a lower alkyl group, a carboxylic amide group, or a lower carboxylic ester group. X is -SO
₂ NR ³ R ⁴ , -SO ₂ NCHNR ⁵ R ⁶ , or -SO ₂ R ⁷ , where
R ^3, R ⁴ each independently represents a hydrogen atom, a lower alkyl group or a phenyl group, R ^5, R ⁶ represents a lower alkyl group, R ⁷
Represents a lower alkyl group or a hydroxyethyl group. The gist of the present invention is an orange-colored composition comprising a methine compound represented by the formula (1) and a hindered amine light stabilizer in a resin.

The methine compound represented by the general formula [I] used in the present invention can be produced by the following method.

That is, the following structural formula [II] (Wherein, R ¹ has the same meaning as defined in the above general formula [I]) and a 2-methyleneindoline-ω-aldehyde represented by the following general formula [III] (Wherein X and R ² have the same meanings as defined in the above general formula [I].) Or a condensation reaction with a 5-pyrazolone represented by the following general formula [IV] (Wherein R ¹ has the same meaning as defined in the above general formula [I]) and a 1,3,3-trimethylindolenin compound represented by the following general formula [V] (Wherein X and R ² have the same meanings as defined in the above general formula [I].) The compound can be easily produced by a condensation reaction with a 4-formyl-5-pyrazolone compound represented by the following formula:

These condensation reactions are accomplished in an acidic solvent or in an inert solvent in the presence of an alkaline condensing agent, preferably at a temperature of 50 to 140 ° C.

In the condensation in an acidic solvent, a diluting solvent can be used.

Here, examples of the acidic solvent include glacial acetic acid, acetic anhydride, formic acid, propionic acid, sulfuric acid, polyphosphoric acid and the like, and these solvents can be used alone or in combination.

Examples of the inert solvent include alcohols such as methanol, ethanol, and isopropyl alcohol, halobenzenes such as monochlorobenzene and orthodichlorobenzene, and alkylbenzenes such as toluene and xylene.These solvents may be used alone or in combination. it can.

Examples of the alkali condensing agent used in the condensation reaction include pyridine, diethylamine, potassium hydroxide and the like, and preferably piperidine and the like.

The hindered amine light stabilizer used in the present invention has It is a light stabilizer generally referred to as HALS having a skeleton.

Specific product name is (Ciba-Geigy) Chimasorb94
4, Chimasorb119, Tinuvin744, Tinuvin765, Tinuvin622, Ti
nuvin144, (Sankyo) SanolLS-770, SanolLS-744, SanolLS
−765, SanolLS−2626, (Adeka Argus) MarkLA−57, M
arkLA-62, MarkLA-67, MarkLA-63, MarkLA-68 (BFGo
odrich) GoodriteUV-3034 (Sumitomo Chemical) SumisorbTM-06
1 (ACC) CyasorbUV-3346 and the like.

Examples of the resin used in the present invention include styrene homopolymer (GP-PS), impact-resistant polystyrene (HI-PS) obtained by blending or copolymerizing a synthetic rubber component with polystyrene, expandable polystyrene (EPS), and styrene-acrylonitrile. In addition to polystyrene copolymers such as copolymers (AS),
Polymethyl methacrylate (PMMA) can be mentioned.

The amount of the methine compound and the hindered amine light stabilizer used in the present invention is 5 parts by weight or more, preferably 10 to 500 parts by weight, based on 100 parts by weight of the methine compound.

The coloring composition of the present invention can be obtained by a known method. For example, a methine compound, a hindered amine light stabilizer, and a resin are mixed by an appropriate method, and heat, pressure, and the like are applied thereto to form a colored composition by a method such as injection molding, extrusion, or spinning.

Specifically, for example, a methine compound, a hindered amine light stabilizer and, if necessary, various additives are added to the resin, mixed, and then dissolved and dispersed in the resin using a kneader, a roll mill, a Banbury mixer extruder, or the like. Further, if necessary, molding such as pressure, injection, extrusion, blow, etc. is performed to obtain a target coloring composition.

It is also possible to add a methine compound, a hindered amine light stabilizer and, if necessary, various additives to a monomer containing a polymerization catalyst to obtain a desired colored composition by polymerization.

The amount of the methine compound to be added is not particularly limited, but it is used in the range of 0.01 to 5% by weight, preferably 0.01 to 1% by weight based on the resin in consideration of economy and the like.

Furthermore, dyes, contents, and various additives used in ordinary resins can be used in combination. For example, titanium dioxide
When used in an amount of 0.1 to 1.0% by weight, an opaque colored composition can be obtained. Polymer additives such as antioxidants, light stabilizers other than hindered amines, metal deactivators, ozone deterioration inhibitors, and heat stabilizers are also effective for improving the performance of the resin itself, and can be used in combination.

<Effects of the Invention> According to the present invention, by containing a methine compound and a hindered amine light stabilizer in a specific resin,
An orange colored composition having high coloring power, not only excellent heat resistance, sublimation resistance, bleeding resistance and elution resistance, but also extremely excellent light resistance can be obtained.

<Examples> Next, the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples. In the examples, parts represent parts by weight.

Example-1, Comparative Example-1 (1) Synthesis of methine compound The following structural formula 6.7 parts of the aldehyde compound represented by the following structural formula 5.3 parts of the indolenine compound represented by
The reaction is carried out for 5 hours under reflux in the presence of 2 parts of piperidine. After cooling, the resulting crystals are filtered off, washed with methanol,
After washing with water and drying, the following structural formula 5.9 parts cake of methine compound represented by (yield 56%)
I got This compound showed a single orange spot by thin-layer chromatography and FD-mass showed a peak at 525,
It was identical to the theoretical molecular weight. Also, this compound has λmax
(N, N-dimethylformamide) 479 nm, melting point 260-262
° C. This methine compound is referred to as a compound.

(2) Preparation and Evaluation of Colored Composition Using the compound obtained in (1) and the hindered amine-based light stabilizer, a colored composition was prepared under the following conditions, and the performance was evaluated.

(A) Resin used: S-bright 4-62 (GP made by Sumitomo Chemical)
-PS resin) (b) Light stabilizer: SanolLS-770 [HALS: Bis-
(2,2,6,6-tetramethyl-4-piperazinyl) sebacate] (c) Coloring method After mixing 500 parts of a resin, 0.1 part of a compound, 2.5 parts of titanium dioxide and 0.1 part of a light stabilizer, an extruder (200 ° C.) )
A colored pellet (composition) was obtained. The colored pellet was molded by an injection molding machine (220 ° C. × 1 minute cycle) to obtain a colored composition (molded product).

(D) Evaluation method An accelerating test (time: 320 hours) using a fade meter was performed according to JIS-L-0842. Judgment was made on the simultaneously irradiated blue scale. The above is Example 1 and the results are shown in Table 1.
It is shown in FIG.

Except not adding a light stabilizer, it carried out similarly to the actual example 1, and evaluated light resistance. This is referred to as Comparative Example 1 and the results are shown in Table 1.
Shown in In addition, in the light resistance effects of Tables 1 and 2, those having particularly excellent light resistance as compared with Comparative Example 1 were evaluated as ○, those with excellent light resistance as Δ, and those with less light resistance as x.

In the case where the light stabilizer was added, compared to the case where no light stabilizer was added, Table 1 was used.
As shown in the above, good light fastness was observed and no discoloration was observed.

Examples-2 to 6 The light stabilizers used in Example-1 were evaluated by changing the amount of addition as shown in Table-1. The results are shown in Table 1.

As shown in Table 1, the light stability is good when the light stabilizer is 5 parts by weight or more with respect to 100 parts by weight of the compound, and the effect becomes more remarkable when the light stabilizer is 10 parts by weight or more.

Examples -7 to 9 and Comparative Examples 2 to 4 Instead of the light stabilizer used in Example 1, another type of light stabilizer and an ultraviolet absorber shown in Table 2 were evaluated.
As shown in Table 2, the hindered amine light stabilizer shows good light fastness, but the UV absorber generally used for resins generally does not show so good light fastness.

Example-10 In the same manner as in Example-1, evaluation was made using the following compound instead of the compound. When used together with a hindered amine-based light stabilizer, good light resistance was exhibited.

Example-11 The following resin was evaluated in the same manner as in Example 1 except that the resin used was changed, and good light resistance was shown.

Styron 470 (HI-PS resin manufactured by Asahi Kasei) SUMIPEC B-LG (PMMA resin manufactured by Sumitomo Chemical) Reference Example-1 Colored composition obtained in the same manner as in Example-1 using known compounds A and B, and Example- For the colored composition of the present invention shown in No. 1, light resistance, sublimation resistance, bleed resistance and elution resistance were evaluated and compared. As shown in Table-3, the coloring composition of the present invention shows extremely excellent performance. In addition, the evaluation method of sublimation resistance, bleed resistance, and elution resistance in Table 3 is shown below.

(1) Sublimation resistance A high-concentration (10%) colorant is kneaded into a resin to form a colored pellet. Heat this colored pellet (220-240
° C), and the degree of sublimation contamination on the filter paper impregnated with dioctyl phthalate was visually determined.

(2) Bleed resistance A polystyrene-colored molded plate is superimposed on a soft vinyl chloride plate containing 1.0% of titanium dioxide (TiO ₂ ), and treated at 80 ° C. for 2 hours under a load of 100 g / cm ² to give a soft vinyl chloride plate. The degree of coloring was determined and evaluated using a gray scale for JIS-L-8085 contamination.

(3) Elution resistance In accordance with the testing method for color materials in food containers and packaging (PL list test method) specified by the Polyolefin Hygiene Council,
An elution test with n-heptane in a polystyrene resin was performed.

○ Can be used if dissolution is acceptable. Usage prohibited * Light stabilizer A 2-Methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4
-Piperidyl) propionamide Sumisorb300: a commercially available ultraviolet absorber manufactured by Sumitomo Chemical 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole Sumisorb400: a commercially available ultraviolet absorber manufactured by Sumitomo Chemical 2,4 -Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate Sumisorb 110: a commercially available ultraviolet absorber manufactured by Sumitomo Chemical 2-hydroxy-4-methoxybenzophenone

Continuation of the front page (56) References JP-A-3-109466 (JP, A) JP-A-58-120245 (JP, A) JP-A-55-161232 (JP, A) JP-A-5-27368 (JP, A) JP-A-5-45792 (JP, A) JP-A-58-152054 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 23/00, 67/02 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. An orange-colored composition comprising a methine compound represented by the general formula [I] and a hindered amine light stabilizer in a resin. (In the formula, R ¹ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a lower carboxylic ester group, and R ² represents a lower alkyl group, a carboxylic amide group, or a lower carboxylic ester group. X is -SO
₂ NR ³ R ⁴ , -SO ₂ NCHNR ⁵ R ⁶ , or -SO ₂ R ⁷ , where
R ^3, R ⁴ each independently represents a hydrogen atom, a lower alkyl group or a phenyl group, R ^5, R ⁶ represents a lower alkyl group, R ⁷
Represents a lower alkyl group or a hydroxyethyl group. ) 2. The orange-colored composition according to claim 1, wherein the resin is a polystyrene-based polymer or polymethyl methacrylate. 3. The orange colored composition according to claim 1, wherein the content of the hindered amine light stabilizer is at least 5 parts by weight based on 100 parts by weight of the methine compound represented by the general formula [I]. .