JPH0362859A - Coloring composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of continuous extrusion molding for a long time even at high temperature and giving colored extruded article having excellent weather resistance containing a specific amount of specific inorganic substance such as pigment, ultraviolet stabilizer and silicon oxide. CONSTITUTION:(A) Preferably 5-70wt.% pigment (e.g. titanium oxide or red oxide) is mixed with (B) preferably 2-6wt.% ultraviolet stabilizer (e.g. 2,4- dihydroxybenzophenone) and (C) inorganic substance containing at least one species selected from the group of silicon oxide, magnesium oxide, calcium oxide, aluminum oxide and magnesium hydroxide to afford the objective composition. At least 2 pts.wt., preferably 5-20 pts.wt. the component C is contained in 100 pts.wt. total of the components A+B in the said composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel coloring composition that provides stable extrudability.

(Prior art) Conventionally, the thickness of the colored polyolefin coating is 30 to 100 μm, such as in T-die extrusion or wire coating extrusion processing of polyolefin.
For coloring polyolefins that are thin and require good weather resistance, coloring compositions containing pigments with excellent weather resistance and heat resistance and an ultraviolet stabilizer have been used.

(Problem to be Solved by the Invention) However, when using such a coloring composition, during continuous extrusion molding at high temperatures for a long time, the addition of an ultraviolet stabilizer causes slippage within the cylinder of the extruder. For these reasons, the residence time of the colored polyolefin composition in the cylinder becomes longer, and carbides such as pigments that are not captured by the screen gradually adhere to the inside of the cylinder of the extruder, especially the inner wall of the tip of the extruder goo. This has the disadvantage that streaks and rough skin appear on the surface of the colored extruded product.

(Means for Solving the Problems) The present inventors added a coloring composition containing a pigment and an ultraviolet stabilizer as described above to a thermoplastic resin, and used an extruder for extrusion molding the colored thermoplastic resin. As a result of intensive research to prevent thermal decomposition due to stagnation of molten material inside the cylinder,
2 or more parts by weight of an inorganic substance containing at least one member selected from the group consisting of silicon oxide, magnesium oxide, calcium oxide, aluminum oxide, and magnesium hydroxide are added to 100 parts by weight of the pigment and ultraviolet stabilizer in total. We have discovered that when a coloring agent is used, carbide does not adhere to the inside of the cylinder of the extruder or the inner wall of the die tip for a long time, and a smooth colored extruded product can be obtained, and the present invention has been developed. .

That is, the present invention provides pigment (A) and ultraviolet stabilizer (B).
and an inorganic substance (C) containing at least one member selected from the group consisting of silicon oxide, magnesium oxide, calcium oxide, aluminum oxide, and magnesium hydroxide, and a pigment (A) and an ultraviolet stabilizer (B). ), the coloring composition is characterized in that it contains 2 parts by weight or more of an inorganic substance (C) based on a total of 100 parts by weight.

The pigment (A) used in the present invention is not particularly limited, and includes, for example, inorganic pigments such as titanium oxide, Bengara, ultramarine, cobalt blue, titanium yellow, fired pigments, yellow lead pigments, and carbon black; quinacridone pigments; Examples include organic pigments such as polyazo type, isoindolinone type, copper phthalocyanine type, perylene type, perinone type, dioxazine type, disazo type, and monoazo type, and one or more pigments selected from these are used as appropriate. The amount of this pigment (A) used varies depending on the type of pigment and the dilution ratio of the coloring Mi precept during coloring, but it is usually within a range where the content in the coloring composition is 5 to 70% by weight. .

Examples of the ultraviolet stabilizer (B) used in the present invention include so-called ultraviolet absorbers (radical generation inhibitors) and HALS (radical chain inhibitors).

Examples of the former include 2,4-dihydroxyhensiphenone, 2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-octoxybenzophenone, 2.
2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxyhensiphenone, 2.2', 4.4'tetrahydroxybenzophenone and other hensifhenone compounds; 2(2)
'-hydroxy-5'methylphenyl)benzotriazole, 2(2'hydroxy-3'-1-butyl-5'-
methylphenyl)-5-chlorohencitriazole, 2
Henzotriazole compounds such as (2'-hydroxy-3,5'-disavetylphenyl)-5-chlorohenzotriazole, 2(2'-hydroxy-4'-octoxyphenyl)henzotriazole, etc. Examples of the latter include 4-hendiyloxy-2,2,6,
6-titramethylpiperidine, bis(2,2,6,6-
Examples include hindered amine compounds such as tetramethyl-4-piperidine) sepacate.

The amount of the ultraviolet stabilizer (B) used varies depending on the dilution ratio of the coloring composition during coloring, but the content in the coloring composition is usually 1 to 10% by weight, preferably 2 to 6% by weight. This is the range.

The inorganic substance (C) used in the present invention may contain at least one selected from the group consisting of silicon oxide, magnesium oxide, calcium oxide, aluminum oxide, and magnesium hydroxide, such as diatomaceous earth,
Asbestos, activated clay, oxidized clay, dolomite, aluminum hydroxide, magnesium hydroxide, calcium oxide,
Examples include aluminum oxide, wollastonite, zeolite, sericite, kaolin clay, calcined clay, talc, and dolomite, among which those containing 50% by weight or more of silicon oxide are preferred, and diatomaceous earth is particularly preferred.

The amount of this inorganic substance (C) used varies depending on the type of pigment, the dilution ratio of the coloring composition during coloring, extrusion conditions, etc.
The amount is usually 2 parts by weight or more, preferably 5 to 20 M parts, based on a total of 100 parts by weight of the pigment (A) and the ultraviolet stabilizer (B).

The coloring composition of the present invention includes the above three components (A) to (C) plus 1. Further, those to which a resinous dispersion aid (D) and/or a carrier resin (E) are added are preferable from the viewpoint of excellent handling workability, pigment dispersibility, etc., and in particular, those to which a resinous dispersion aid (D) and/or a carrier resin (E) are added are preferred.
Particularly preferred is a master hatch-shaped product obtained by adding D) and carrier resin (E), melting and kneading.

Examples of the resinous dispersion aid (D) used here include low molecular weight polyethylene, polypropylene, polybutene-1, ethylene-vinyl acetate copolymer, etc. alone or in mixtures, with molecular weights of 1,000 to 1,000 to 1,000.
io, ooo polyethylene and polypropylene are preferred. The amount of this resinous dispersion aid (D) to be used varies depending on the type and amount of pigment in the coloring composition, whether or not a carrier resin (E) is used in combination, etc., but usually the content in the coloring composition is 1
The content is in the range of 40% by weight.

The carrier resin (E) is preferably the same or similar thermoplastic resin to the thermoplastic resin to be colored, but is not necessarily limited thereto as long as it has excellent compatibility. Specifically, polyolefin resins are preferred, and among them,
Low-density, medium-density, high-density or vertical low-density polyethylene may be used alone or in mixtures, or mixtures of polyethylene with other polymers, such as ethylene-vinyl acetate copolymers.

The amount of carrier resin (E) used varies greatly depending on the type of pigment and the dilution ratio of the m-acid for coloring, but generally the content in the coloring composition is 10 to 90% by weight. range.

Various additives such as antioxidants may be added as other components to the coloring composition of the present invention, if necessary.

The material to be colored in the coloring composition of the present invention may be any thermoplastic resin, and polyolefin resins are particularly preferred. As the polyolefin resin, low density, medium density, high density or linear low density polyethylene is particularly preferred. However, as a coloring target of the coloring composition containing the carrier resin (D), a thermoplastic resin having compatibility with the carrier resin (D) is preferable.

The coloring composition of the present invention may have any form, but the most preferred form is a master hatch.

To cite an example of the manufacturing method as a representative example of this masterbatch-like coloring composition, a predetermined amount of pigment (A), resinous dispersion aid (D), and carrier resin (E) can be easily mixed using a kissing roll or the like. After kneading and pulverizing the kneaded material, a predetermined amount of ultraviolet stabilizer (B) and inorganic substances such as diatomaceous earth (
C), if necessary, add and mix additional carrier resin [D), other additives, etc., and then knead and extrude this using an extruder etc., and pelletize it to obtain a master bunch-shaped coloring composition. .

For example, when the coloring composition of the present invention obtained as described above is used to manufacture electric wires using a wire coating extruder according to a conventionally known method, unlike when using conventional coloring compositions, it takes a long time to manufacture electric wires. Even during continuous operation, no carbide is observed on the inner wall of the extruder cylinder or the tip of the gou, making it possible to obtain wires with a smooth appearance. At the same time, if a colored extruded sheet produced by T-die extrusion is laminated onto a steel plate by a conventionally known method, a colored laminated steel plate with a smooth surface can be obtained even after continuous operation for a long time.

(Example) The present invention will be described below with reference to examples, and unless otherwise specified, all parts represent parts by weight.

Example 1 11.2 parts of condensed azo yellow, 5.7 parts of copper phthalocyanine green, 34 parts of rutile titanium oxide, 30 parts of low molecular weight polyethylene, and 19.1 parts of low density polyethylene (melt index 1.2 g/10 m1n). heating 3
The pigment composition (I) was obtained by kneading with this roll. This pigment composition (I) and 2(2'-hydroxy-3'-L-butyl-5'-methylphenyl)-5 as an ultraviolet stabilizer
-Chlorobenzotriazole (Titabin 32G, manufactured by Ciba Geigy) and bis(2,2,6,6-tetramethyl-4-piperidine) sebacate [Sanol LS770, manufactured by Sankyo ■], tetrakis (2 , 4-dibutylphenyl) 4.4'-bisphenylene diphosphonite (PEPQ manufactured by Side Co., Ltd.) and [tetraxymethylene
3(3',5'-di-t-butyl-4'hydroxyphenyl)propionate comethane (Irganox 10
10. A pigment composition (manufactured by Ciba Geigy), diatomaceous earth (Radiolyl---F, manufactured by Showa Kagaku ■), and high-density polyethylene (melt index 0-8 g/10 m1n) were mixed in the following proportions. I) 70 parts High density polyethylene 21.5 parts Yoshinox S R'0.3 part Irganox 1010 0.2 parts Sunol LS770 2.0 parts Tinuvin #326
2.0 parts 1 The mixture was kneaded using a trowel of a 65 m/m extruder to obtain a masterbatch-like coloring composition.

Examples 2 to 8 and Comparative Examples 1 to 3 Same as Example 1 except that the proportions of pigment, ultraviolet stabilizer, diatomaceous earth, low molecular weight polyethylene, carrier resin, and antioxidant were changed as shown in Table 1. A masterbatch-like coloring composition having the composition shown in Table 1 was obtained.

Test Example 1 100 parts each of the masterbatch coloring compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3 and high density polyethylene (melt index 0.8 g/l 0 m1n)
65 m/m for wire coating after mixing with 1400 parts
, Using an extruder with L/D = 24, the conductor was coated with a high-density polyethylene foaming compound containing 1% azodicarbonamide to a thickness of 40 to 50 μm and a foaming degree of 40 to 45%, and the resin temperature was 210. Thickness 40 at ~230°C
A coating of .mu.m was applied, the condition of the coated surface was observed, and the time required to maintain a smooth surface without streaks was determined. The results are shown in Table 2.

Test Example 2 100 parts each of the masterbatch coloring compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3 and 200 parts of low density polyethylene (melt index 3 g/10 m1n)
After mixing with 0 parts, extrusion lamination was performed at a temperature of 310'C on a steel plate coated with adhesive in advance using a T-die extruder, and the time required to maintain a smooth surface was determined. The results are shown in Table-1.

/ / / (Effects of the Invention) When the coloring composition of the present invention is used, continuous extrusion molding can be performed for a long time even at high temperatures, and colored extruded products with excellent weather resistance can be obtained.

Claims (1)

[Claims] 1. A pigment (A), an ultraviolet stabilizer (B), and an inorganic substance (C ) and 2 or more parts by weight of an inorganic substance (C) based on a total of 100 parts by weight of the pigment (A) and the ultraviolet stabilizer (B). 2. The coloring composition according to claim 1, wherein the inorganic substance (C) is an inorganic substance containing 50% by weight or more of silicon oxide. 3. The coloring composition according to claim 1, wherein the inorganic substance (C) is diatomaceous earth. 4. Furthermore, a resinous dispersion aid (D) and/or a carrier resin (
The coloring composition according to claim 1, which also contains E). 5. The coloring composition according to claim 1, which contains 5 to 20 parts by weight of the inorganic substance (C) based on a total of 100 parts by weight of the pigment (A) and the ultraviolet stabilizer (B).