JPS6236446A - Method for stabilizing halogen-containing resin composition containing rhodamine dye - Google Patents

Abstract

PURPOSE:To obtain the titled compsn. which has improved thermal stability and gives fluorescent pigmented moldings which have marketability and economical advantages, by adding a specified metal salt to a halogen-contg. resin compsn. contg. a Rhodamine dye. CONSTITUTION:0.01-10pts.wt. Rhodamine dye (e.g. Rhodamine B of the formula) is incorporated in a halogen-contg. resin (e.g. polyvinyl chloride). 0.01-2.0pts.wt. alkaline earth metal perchlorate [e.g. anhydrous or hydrous Ba(ClO4)2] is added thereto. Optionally, a polymer contg. a Na or K compd. as thermal stabilizer, butylated p-cresol as antioxidant, natural wax as lubricant and butyl acrylate as processing aid is added thereto. The mixture is kneaded to obtain a halogen- contg. resin compsn. contg. Rhodamine dye.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention improves processability and reduces commercial value by significantly reducing thermal stability by incorporating a rhodamine colorant into a halogen-containing resin. The present invention relates to a method for stabilizing a halogen-containing resin composition containing a rhodamine-based colorant to prevent this.

(Prior Art) What is the method of molding a halogen-containing resin composition containing a rhodamine colorant prior to the present invention?

Adding a large amount of the most efficient and expensive tin-based heat stabilizer known to date.

Alternatively, we have been content to add highly toxic lead-based stabilizers and cadmium-based stabilizers, shorten processing time, sacrifice production, and obtain molded products with slightly impaired surface properties.

Furthermore, since it was not possible to sufficiently increase the amount of the rhodamine colorant added, it was not possible to develop the desired color.

The rhodamine colorant referred to in the present invention is represented by the structural formula 1 shown below. At least one compound having II and ■ (
or multiple types).

The low thermal stability of rhodamine colorants and their tendency to react with halogen compounds is thought to be due to the quaternary imide ions commonly present in their structural formulas.

Formula 1 Formula ■ Formula ■ (Objective) The present invention improves the thermal stability of a halogen-containing resin composition containing such an unstable rhodamine colorant, makes it suitable for heat processing, and is economical and marketable. An object of the present invention is to provide a halogen-containing resin composition that gives a fluorescently colored molded article.

(Summary) In order to achieve [Objective 1] of Section 111j, the present inventors have made extensive studies and found that by adding an alkaline earth metal salt of perchlorate to a halogen-containing resin composition containing a rhodamine colorant. , has the same processability as a normal halogen-containing resin composition that does not contain a rhodamine colorant, and by molding the composition, it has fluorescence containing a rhodamine colorant with excellent coloring properties and surface properties. It is now possible to obtain halogen-containing resin molded products.

(Range) The rhodamine colorant as used in the present invention refers to a pigment that contains a compound represented by Structural Formulas 1, [, and II and can be used to color a so-called resin composition.

Among the compounds having these three structures, the pigment added to the resin composition is Rhodamine B (color index Pigment No., Vio-1e
t, 1), and the other two compounds are hardly commercially available. Therefore, the coloring agent used in the examples of the present invention was Scarlet I-VC Knee 1000 manufactured by Sumika Color Co., Ltd.

The halogen-containing resin composition referred to in the present invention includes, for example, polyvinyl chloride, vinyl chloride-α-olefin copolymer, vinyl chloride-vinyl acetate copolymer, vinylidene chloride, chlorinated polyolefin, chlorinated polyvinyl chloride, and hydrochloric acid rubber. , chloroprene, ethylene-vinyl acetate-vinyl chloride graftomer, chlorinated polyethylene-acrylonitrile-styrene graftomer and other resins with halogen bonded to the main chain, and halogen-free resins such as ethylene-vinyl acetate copolymers, Ethylene-acetic acid-carbonic acid copolymer, acrylonitrile-butadiene-styrene terpolymer,
Examples include polymer blends of acrylonitrile-acrylic ester-styrene terpolymers, methacrylic ester-butadiene-styrene terpolymers and halogen-containing resins, or polymer blends of halogen-containing resins. There is also a halogen-containing resin composition obtained by adding a halogen-containing low molecular weight flame retardant to the above-mentioned halogen-containing resin, halogen-free resin, and their mutual polymer blends. Examples of halogen-containing low molecular weight flame retardants are hexabromobenzene, tetrabromobisphenol A.

These include decabromo biphenyl ether, octabromocyclododecane, tris(2,3 dibromopropyl) phosphate, and chlorinated paraffin.

In addition to the above-mentioned resins, the resin composition also contains plasticizers, reinforcing agents, fillers, other colorants, heat stabilizers, light stabilizers, antioxidants, lubricants, processing aids, dustproofing agents, and moldproofing agents. , an antistatic agent, etc. may be contained.

Since it is heated and molded, at least a heat stabilizer, an antioxidant, a lubricant, and a processing aid are added.

Others have some influence on the molding itself, but rather are added after processing to impart properties to the molded product.

As heat-resistant stabilizers, Na, Lit Mg+Ca,
Ba, Zn, Cd, Al, Sn (In the case of Sn, dialkyltin and monoalkyltin are included).

PB metals and various carboxylic acids and mercaptans.

A combination of one or more compounds selected from salts with phenol.

Also included are inorganic compounds of the above metals, tri-, di-, and mono-esters or thioesters of phosphorus and boron. Hydrazide compounds, β
-Diketone compounds, etc.

Butylated P-cresol is used as an antioxidant.

2.2'-methylenebis(4-methyl-6-tert-butyl-phenol), tetrakis[methylene-3(3,5
- Contains alkylphenol compounds such as di-tert-butyl-4-hydroxy-phenyl) propionate comethane, distearylthiodipropionate, 4,4'-thiobis(2-methyl-6-t-butylphenol), etc. These include sulfur compounds.

Examples of lubricants include low-molecular polyolefins and their oxides, natural waxes such as rice bran wax and processed products thereof, and fatty acid derivatives such as stearic acid and its esters and amides.

Processing aids include polymers and copolymers containing 1-butyl acrylate.

In the present invention, general commercially available additives can be used without being limited to the compounds exemplified above.

(Example) The advantages of the present invention will be explained with examples.

Example 1 A composition consisting of the formulation shown in Table 1 was mixed in advance, and wired for 4 minutes with a 6-inch test roll heated to 180"C to form a sheet. After cooling, the composition was heated to 185°C. Kneading was continued using an 8-inch test roll heated to C, samples were taken out every 3 minutes, and the color tone, surface properties (gloss), and releasability from the roll were observed.

Below is the blank space in Table 1 1) Polyvinyl chloride manufactured by Sumitomo Chemical Co., Ltd. 2) Rhodamine pigment manufactured by Sumika Color Co., Ltd. 3) Dibutyltin mercapto type heat stabilizer manufactured by Kyodo Yakuhin Co., Ltd. 4) Same as above B a -Z n type Heat-resistant stabilizer 5) Made by Nippon Carlit Co., Ltd. Used after pulverization.
The units of numbers for compounding agents in the table are parts by weight.

Example 2 Compositions consisting of the ingredients shown in Table 2 were compared in roll kneading properties in the same manner as in Example 1.

Table 2 1) Same as footnote 1) in Table 1 2) Propylene-vinyl chloride copolymer resin manufactured by Sunarrow Co., Ltd. 3) MBS-based reinforcing agent manufactured by Kanebuchi Chemical Industry Co., Ltd. 4) Same as footnote 2) in Table 1 5) Same as footnote 4) in Table 1 6) Composite lubricant manufactured by Kyodo Yakuhin Co., Ltd. 7) Same as footnote 5) in Table 1 The units of numbers for compounding agents in Table 1 are parts by weight.

Example 3: Third test on soft polyvinyl chloride with flame retardant formulation
The formulation was as shown in the table. Each mixed composition was rolled using a 6-inch die roll heated to 170°C to prepare a 0.1 mm thick film, which was then placed in a gear oven at 180°C to compare thermal stability.

Table 3 with blank space below 1) Polyvinyl chloride manufactured by Nippon Zeon Co., Ltd. 2) Phosphate ester flame retardant manufactured by Ajinomoto Co., Ltd. 3) -Ba-Zn composite stabilizer manufactured by Kyodo Yakuhin Co., Ltd. 4) Same as above
Ba-Zn Composite Stabilizer 5) Same as footnote 2) in Table 1 Note that the units of numbers for compounding agents in the table are parts by weight.

Claims (1)

[Claims] 1. Adding 0.01 to 2.0 parts by weight of an alkaline earth metal perchlorate to a halogen-containing resin composition containing 0.01 to 10 parts by weight of a rhodamine colorant. A method for stabilizing a halogen-containing resin composition containing a rhodamine colorant. 2. Stabilization of the halogen-containing resin composition according to claim 1, wherein the alkaline earth metal perchlorate salt according to claim 1 is an anhydride or a hydrate of barium perchlorate. Law.