JPS6137292B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to colored polymeric resin materials. Conventionally, resins colored other than black, such as red, blue, green, and yellow, have been produced by simply mixing pigments and the like with the resin, and then molding the resin, forming a film, and the like. In this case, the pigment and resin molecules are in the form of a mixture in the resin. However, when such a mixture of pigments and resin components is exposed to external conditions, the pigments may flow out due to moisture, decompose due to direct sunlight etc., or the pigment itself may deteriorate due to the collapse of the resin molecules themselves. A leak occurred. Such pigment outflow means fading of the resin product. Therefore, in the past, even if colored resins other than black were used outdoors, they had to be replaced every few months, or they were left unused after being discolored. The present inventor added an electrophilic reagent to a polymer resin composition, a coloring agent selected from the group consisting of an organic pigment or dye having a group capable of forming a polar group at the end by the action of the electrophilic reagent, and an inorganic pigment, and When an oxide is added and heated, the pigment or dye chemically bonds with the molecules constituting the polymer resin due to the action of the electrophilic reagent, resulting in a colored polymer with excellent fading resistance. The inventors have discovered that a resin composition can be obtained, leading to the present invention. The present invention comprises one or more electrophilic reagents, a coloring agent selected from the group consisting of organic pigments or dyes and inorganic pigments having a group capable of forming a polar group at the end by the action of said electrophilic reagent, and a peroxide. When a polymer resin composition containing a substance is made, and the molecules constituting the polymer resin contain a polar group or a polar atom, the peroxide does not need to be included, and then the polymer resin composition During molding or film formation, or in a separate process, the composition is heated to convert the polar groups present at the ends of the organic pigment or dye or the metal atoms of the inorganic pigment into molecules constituting the polymeric resin material. The present invention relates to a method for producing a colored polymer composition, which comprises chemically bonding the main chain and/or side chain.
The bonding mechanism between the pigment or dye and the polymer substance is thought to be as follows. When the resin does not contain polar groups or atoms such as polyethylene or polypropylene, epoxy bonds or

[Formula] is formed. On the other hand, electrophilic reagents take electrons from terminal polar groups or atoms of organic pigments or dyes or metal atoms of inorganic pigments to charge them. Due to the action of polar groups or atoms existing in the resin molecule or peroxide, epoxy bonds or oxygen radicals and charged polar groups or atoms or metal atoms in the pigment or dye form ionic bonds, mixed bonds, Or by covalent bonding etc.

【formula】

and/or -C- C-A-C-C-, where -C-C- is a molecule in the resin and A is one or more molecules of pigment or dye. bring about a bond. Resins that can be colored by the method of the invention include polyethylene, polypropylene, polystyrene, polyacrylonitrile butadiene, polyamide, polyurethane, polyvinyl chloride, polyester, polyvinylidene chloride, polyvinyl alcohol, polycarbonate polyvinyl acetate, or polyacrylonitrile. Contains synthetic resins, semi-synthetic resins such as cellulose acetate or cellophane. The electrophilic reagent plays the role of taking electrons from the terminal polar groups of organic pigments or dyes or the metal atoms of inorganic pigments and charging them. It is a mixture of iodine quinones, trinitrobenzene, tin tetrachloride, aluminum chloride, and amphoteric metal oxides such as ZnO and PbO and weak acid salts of the metals. Especially tin tetrachloride, mixtures of ZnO and _ZnCO3 , quinones,
_AlCl3 is preferred. This electrophile is a resin composition
0.2-20 parts by weight per 100 parts, preferably 0.5-
5 parts by weight. Many of these electrophilic reagents can be used as long as they do not impair the properties of the resin composition or decompose during heating. As the organic pigment or dye, all known organic pigments or dyes having a group or atom which can lose an electron and become a polar group at the end can be used. Especially NH ₂ on the benzene nucleus,
Pigments or dyes in which NO ₂ , OCH ₃ , Cl, CF ₃ are present are preferred. Alternatively, almost all inorganic pigments have metal atoms and can therefore be used in the present invention. For example, zinc white, alumina white, titanium oxide, red iron oxide, litharge, red lead, yellow lead, lead white, zinc yellow, molybdenum red,
Cadmium yellow etc. The amount of pigment or dye used depends on the intended use of the resin composition. All pigments in amounts within the range commonly used are bound within the resin molecules. When the resin does not contain polar groups or atoms in the resin molecule, such as polyethylene, polypropylene and polystyrene, it is always preferable to use a peroxide. However, for resins containing polar groups or atoms, peroxides may or may not be used. Examples of peroxides are acetylcyclohexylsulfonyl peroxide, iso-butyl peroxide, di-isoproyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, Di(methoxyisopropyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, t-butylperoxyneodecanonate, 2,4-dichlorobenzoyl peroxide, t-butylperoxypivalate, 3, 5,5-trimethylhexanoyl peroxide, octanoyl peroxide, detanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propynyl peroxide,
succinic acid peroxide, acetyl peroxide,
t-Butylperoxy(2-ethylhexanoate), m-trioylperoxide, benzoylperoxide, t-butylperoxyisobutyrate, 1,1-bis(t-butylperoxy)
3,5,5-trimethylcyclohexane, 1,1
-bis(t-butylperoxy), cyclohexane, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy 3,5,5-trimethylhexanoate, cyclohexanonyperoxide, t -Butylperoxyisopropyl carbonate, 2,5-dimethyl-
2,5-di(benzoylperoxy)hexane,
t-Butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t
-butyl diperoxyisophthalate, methyl ethyl ketone peroxide, α,α′-bis(t-
butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-
Di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-isopropylbenzene hydroperoxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5
-dimethyl-2,5-di(t-butylperoxy)hexyne-3,1,1,3,3-tetramethylbutylhydroperoxide, 2,5-dimethylhexane-2,5-dihydro-oxide, cumene hydroperoxide and t-butyl hydroperoxide. The amount of such peroxide used is about 0.5 to 5 parts per 100 parts by weight of the resin. In the present invention, some or all of the pigment or dye molecules are crosslinked to the main chain or side chain of the resin component, so that fading or discoloration is less likely to occur than in the conventional method. Further, the strength of the resin is further increased by such crosslinking of the pigment. Examples of the present invention are shown below. Units are based on weight. Comparative Example 1-6 and Example 1-10

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Claims (1)

[Claims] 1. A polymeric composition containing one or more electrophiles, an organic pigment or dye, an inorganic pigment or a mixture thereof, and a peroxide is prepared, and the polymeric resin composition is molded or formed into a film or separately. In the process, the composition is heated, and the polar groups or atoms present at the ends of the organic pigment or dye or the metal atoms of the inorganic pigment are transferred to the main chain and/or side of the molecules constituting the polymeric resin material. A method for producing a colored polymeric composition comprising linking it to a chain.