JP2844698B2 - Composition for coloring - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a novel coloring composition that provides stable extrudability.

(Prior art) Conventional polyolefins such as T-die extrusion and wire coating extrusion processing have a thin colored polyolefin film with a thickness of 30 to 100 μm and are required to have weather resistance and heat resistance. Coloring compositions have been used in which excellent pigments are further compounded with UV stabilizers.

(Problems to be Solved by the Invention) However, when such a coloring composition is used, it is easy to slip in the cylinder of the extruder due to the addition of an ultraviolet stabilizer in continuous extrusion at a high temperature for a long time. For this reason, the residence time of the colored polyolefin composition in the cylinder becomes longer, and the adhesion of carbides such as pigments, which are not captured by the screen, inside the cylinder of the extruder, especially on the inner wall of the extruder die tip, gradually progresses. However, this has the disadvantage that streaks and rough skin occur on the surface of the colored extruded product.

(Means for Solving the Problems) The present inventors have used an extruder for extruding a colored thermoplastic resin by adding a coloring composition containing a pigment and an ultraviolet stabilizer as described above to the thermoplastic resin. As a result of intensive research to prevent thermal decomposition due to stagnation of the melt inside the cylinder, etc., silicon oxide, magnesium oxide, calcium oxide, aluminum oxide and magnesium hydroxide were added to 100 parts by weight of pigment and ultraviolet stabilizer in total. When using a coloring composition obtained by adding 2 parts by weight or more of an inorganic substance containing at least one selected from the group consisting of, the adhesion of carbide to the inside of the cylinder of the extruder or the inner wall of the die tip is not recognized for a long time, The present inventors have found that a smooth colored extruded product can be obtained, and have completed the present invention.

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

The pigment (A) used in the present invention is not particularly limited. For example, titanium oxide, red iron oxide, ultramarine, cobalt blue,
Inorganic pigments such as titanium yellow, calcined pigments, graphite pigments, and carbon black; organics such as quinacridone, polyazo, isoindolinone, copper phthalocyanine, perylene, perinone, dioxazine, disazo, and monoazo series And one or more pigments selected from the above. The amount of the pigment (A) varies depending on the type of the pigment, the dilution ratio of the coloring composition at the time of coloring, and the like, but is usually in the range of 5 to 70% by weight in the coloring composition.

Examples of the ultraviolet stabilizer (B) used in the present invention include so-called ultraviolet absorbers (radical generation inhibitors) and HALS (radical chain inhibitors). As the former, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Octoxybenzophenone, 2,2'-dihydroxy-4,
Benzophenone compounds such as 4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone; 2 (2'-hydroxy-5'-methylphenyl) Benzotriazole, 2 (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy-3,5'-di-tert-butylphenyl)- 5-chlorobenzotriazole, 2
There are benzotriazole compounds such as (2'-hydroxy-4'-octoxyphenyl) benzotriazole and the like.
Hindered amine compounds such as 2,6,6-tetramethylpiperidine and bis (2,2,6,6-tetramethyl-4-piperidine) sebacate.

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

The inorganic substance (C) used in the present invention includes silicon oxide,
Any material containing at least one selected from the group consisting of magnesium oxide, calcium oxide, aluminum oxide and magnesium hydroxide, such as diatomaceous earth, asbestos, activated clay, clay oxide, dolomite, aluminum hydroxide, magnesium hydroxide , Calcium oxide, aluminum oxide, wollastonite, zeolite,
Sericite, kaolin clay, calcined clay, talc, dolomite, etc., are preferred, and those containing at least 50% by weight of silicon oxide are preferred, and diatomaceous earth is particularly preferred.

The amount of the inorganic substance (C) varies depending on the type of the pigment, the dilution ratio of the coloring composition at the time of coloring, the extrusion conditions, etc., but the total amount of the pigment (A) and the ultraviolet stabilizer (B) is 100 parts by weight. On the other hand, it is usually at least 2 parts by weight, preferably 5 to 20 parts by weight.

The coloring composition of the present invention includes the above (A) to (C)
It is preferable to further add a resinous dispersing agent (D) and / or a carrier resin (E) to the above three components in terms of excellent handling workability, pigment dispersibility, and the like. Master batches obtained by melting, kneading, adding (D) and the carrier resin (E) are particularly preferred.

Examples of the resinous dispersing agent (D) used here include low-molecular-weight polyethylene, polypropylene, polybutene-1, and ethylene-vinyl acetate copolymer, alone or in combination.
0,000 polyethylene and polypropylene are preferred. The amount of the resinous dispersing aid (D) used varies depending on the type and amount of the pigment in the coloring composition, the presence or absence of the use of the carrier resin (E), and the like. It is in the range of ~ 40% by weight.

As the carrier resin (E), a thermoplastic resin which is the same as or similar to the thermoplastic resin to be colored is preferable, but may be any one having excellent compatibility, and is not necessarily limited to this. Specifically, polyolefin-based resins are preferable, and among them, low-density, medium-density, high-density or linear low-density polyethylene alone or a mixture, or polyethylene and other polymers, for example, ethylene-vinyl acetate copolymer And the like.

The amount of the carrier resin (E) varies greatly depending on the type of the pigment, the dilution ratio of the coloring composition at the time of coloring, and the like, but generally, the content in the coloring composition is in the range of 10 to 90% by weight. It is.

Various additives, for example, antioxidants and the like can be added to the coloring composition of the present invention as necessary.

The coloring object of the coloring composition of the present invention may be a thermoplastic resin, and among them, a polyolefin resin is preferable. As the polyolefin resin, low density, medium density, high density or linear low density polyethylene is particularly preferable. However, as a coloring object 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 be in any form, but the most preferred is a masterbatch. As a typical example of the masterbatch coloring composition, a specific amount of a pigment (A) may be used.
The resinous dispersing aid (D) and the carrier resin (E) are sufficiently kneaded with a mixing roll or the like, and the kneaded material is pulverized. Then, a predetermined amount of an ultraviolet stabilizer (B), an inorganic substance such as diatomaceous earth is added to the pulverized material. (C) If necessary, an additional carrier resin (D), other additives and the like are added and mixed, and then kneaded and extruded with an extruder or the like, and pelletized to obtain a master batch-shaped coloring composition. is there.

The coloring composition of the present invention obtained as described above, for example, when manufacturing an electric wire by an electric wire coating extruder according to a conventionally known method, unlike when using a conventional coloring composition, a long time Even when continuous work is performed, no carbide is observed on the inner wall of the extruder cylinder or die tip, and a smooth electric wire can be obtained. At the same time, when a colored extruded sheet formed by T-die extrusion by a conventionally known method is subjected to lamination processing on a steel sheet, a colored laminated steel sheet having a smooth surface can be obtained even after a long continuous operation.

(Examples) Hereinafter, the present invention will be described by way of examples, but all parts are by weight unless otherwise specified.

Example 1 11.2 parts of condensed azo yellow, copper phthalocyanine green
5.7 parts, rutile type titanium oxide 34 parts, low molecular weight polyethylene 30 parts, low density polyethylene (melt index 1.2 g
1/10 parts) was kneaded with a heated three-roll mill to obtain a pigment composition (I). The pigment composition (I) and 2 (2'-hydroxy-3'-t-butyl-5 'as an ultraviolet stabilizer
-Methylphenyl) -5-chlorobenzotriazole (Titabin 326, manufactured by Ciba Geigy) and bis (2,2,6,6-
Tetramethyl-4-piperidine) sebacate [Sanol
LS770, manufactured by Sankyo Co., Ltd.), tetrakis (2,4-di-t-butylphenyl) 4,4′-bisphenylenediphosphonite (PEPQ manufactured by Side Co.) as an antioxidant, and [tetraximethylene- 3 (3 ', 5'-di-t-butyl-4'-
Hydroxyphenyl) propionate] methane (Irganox 1010, manufactured by Ciba Geigy), diatomaceous earth (Radiolite-F, manufactured by Showa Chemical Co., Ltd.) and high-density polyethylene (melt index: 0.8 g / 10 min) Pigment composition (I) 70 parts High density polyethylene 21.5 parts Yoshinox SR 0.3 parts Irganox 1010 0.2 parts Sanol LS770 2.0 parts Tinuvin # 326 2.0 parts Radiolight F 4 parts 100.0 parts The mixture is 65 m / m extruder To obtain a master batch-shaped 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. Thus, a master batch-shaped coloring composition having the composition shown in Table 1 was obtained.

Test Example 1 100 parts of each of the masterbatch coloring compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were mixed with 1400 parts of high-density polyethylene (melt index 0.8 g / 10 min), and then coated with an electric wire. 65m / m, L / D = 24 extruder, high density polyethylene foaming compound containing azodicarbonamide 1% on the conductor in advance, thickness 40 ~ 50μm, foaming degree 40 ~ 45
% And a resin temperature of 210-230 ° C and a thickness of 40μm
And the state of the coated surface was observed, and the time required to maintain a smooth surface without generation of streaks or the like was determined. Table-Results
It is shown in FIG.

Test Example 2 After mixing 100 parts of each of the masterbatch coloring compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3 with 2000 parts of low-density polyethylene (melt index 3 g / 10 min), T-die extrusion was performed. Extrusion lamination was performed at a temperature of 310 ° C. on a steel sheet to which an adhesive was previously applied by a machine, and a time required to maintain a smooth surface was determined. The results are shown in Table 1.

(Effect 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 a high temperature, and a colored extruded product excellent in weather resistance can be obtained.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08J 3/22, 3/20 C09C 3/06 C08L 23/00

Claims (5)

(57) [Claims] 1. A pigment (A), an ultraviolet stabilizer (B), and an inorganic substance (C) containing at least one selected from the group consisting of silicon oxide, magnesium oxide, calcium oxide, aluminum oxide and magnesium hydroxide. A coloring composition comprising: an inorganic substance (C) in an amount of 2 parts by weight or more based on 100 parts by weight of the total 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 at least 50% by weight of silicon oxide. 3. The coloring composition according to claim 1, wherein the inorganic substance (C) is diatomaceous earth. 4. The coloring composition according to claim 1, further comprising a resinous dispersing aid (D) and / or a carrier resin (E). 5. A total of 10 of pigment (A) and ultraviolet stabilizer (B).
The coloring composition according to claim 1, wherein the composition contains 5 to 20 parts by weight of the inorganic substance (C) based on 0 parts by weight.