JPH01261440A - Colorant composition for thermoplastic resin - Google Patents

Abstract

PURPOSE:To obtain the title composition which has excellent pigment dispersibility and formability and to which a dye or a pigment can be added in a high concentration, by mixing an amorphous polyolefin with a pigment, a lubricant and a filler. CONSTITUTION:65-10wt.% amorphous polyolefin of a numberaverage MW of 4000-30000, selected from among an ethylene/propylene copolymer, a propylene/butene-1 copolymer and a propylene/alpha-olefin copolymer all of which have a propylene content of 70-95wt.%, is melt-kneaded with 35-90wt.% total of 5-90wt.% pigment (e.g., TiO2), 0-6wt.% lubricant (e.g., metal stearate) and 0-40wt.% filler (e.g., CaCO3) of a particle diameter of 0.5-15mum and, optionally, a flame retardant (e.g., Sb2O3).

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to thermoplastic resins, particularly polyethylene.

Polyolefin resins such as polypropylene.

The present invention relates to a masterbatch colorant composition useful for coloring ABS resin, polyvinyl chloride, etc.

[Prior Art and Problems] Generally, in order to mix a thermoplastic resin and a colorant, a colorant resin composition is manufactured using a pan remixer or an extruder, and this is then used to make various molded products. Molded. This method has drawbacks such as high coloring processing costs and troublesome inventory management.

In addition, a colorant masterbatch with a maximum total content of about 75% by weight of pigments and fillers,
It is known that it can be produced by mixing it with polyolefin resins such as polyethylene and polypropylene. In this method, the produced masterbatch is kneaded with the same resin as the resin to be colored, and then formed into pellets, which are then molded into various molded products. Therefore, although it has the advantage of being easy to operate, when the pigment content is increased to about 30% by weight or more, the problem arises that kneading and shaping properties become difficult. In addition, the dispersibility of the pigment deteriorates, causing color unevenness, and therefore, for the purpose of rationalizing the cost of coloring processing, it is desired to disperse a higher concentration of pigment in the masterbatch.

A method to improve the dispersibility of highly concentrated pigments has been proposed by changing the design of the molding machine screw, but this requires a large amount of capital investment.''-1 It is also expected to be effective in efficiently dispersing highly concentrated pigments. It's not as big as it seems.

On the other hand, a method has been proposed in which atactic polypropylene is used as a carrier resin for a masterbatch. In this case, atactic polypropylene is a by-product when manufacturing polypropylene, so it has the advantage of being inexpensive, but because there is a lot of catalyst and solvent residue, it is difficult to match colors when preparing a color masterbatch. or
It also caused odor. Also, since it is a by-product,
Physical properties, such as melt viscosity, vary greatly, resulting in unstable fluidity during kneading and poor operability. Furthermore, since it contains a solvent, there is a problem of environmental pollution due to the generation of solvent vapor by heating.

Method for producing an antistatic masterbatch using atactic polypropylene as a carrier (Japanese Patent Laid-Open No. 62-6283
No. 6), a method for producing a masterbatch for coloring or modification (JP-A-52-126449, JP-A-53-677)
No. 50) have been proposed. These methods all use atactic polypropylene, which is a by-product during the production of polypropylene, as a raw material, and therefore have the above-mentioned drawbacks.

[Means for solving the problem] Therefore, in order to solve the drawbacks of the conventionally known master patch, as a result of intensive research, pigments, lubricants, and fillers were
It has been found that the above-mentioned drawbacks can be satisfactorily solved by using a colorant composition characterized in that the content of the amorphous polyolefin is ~90% by weight and the amorphous polyolefin is 65-10% by weight. Reached.

Examples of thermoplastic resins include polyolefin resins such as polyethylene and polypropylene, ABS resins, polyvinyl chloride, and polystyrene.

Pigments of the present invention include all known dyes and pigments used for coloring thermoplastic resins, such as titanium dioxide, carbon black, organic dyes, organic pigments, and inorganic pigments. The amount of these dyes and pigments to be used is preferably 5 to 90% by weight, particularly 10 to 45% by weight of the colorant composition. If it is less than 5%, the effect of streamlining the coloring processing cost as a masterbatch will be reduced, and 90% by weight. If it exceeds 100%, it becomes difficult to manufacture the colorant composition, especially to pelletize it.

The lubricant of the present invention is a stearic acid metal salt.

Plasticizers such as waxes, higher alcohols, and esters thereof are used. O~6 for use! I! Pickled%
It is. If the amount exceeds 6% by weight, pelletization becomes easier, but the amount of dye and pigment used is less, which is undesirable.If the amorphous polyolefin has good melt flowability, no lubricant may be used at all. good.

Fillers include carbonaceous calcium, clay, silica, or talc. The amount used is 0 to 1 colorant composition.
~40% by weight. In particular calcium carbonate having a particle size in the range from 0.5 to 15 microns is advantageously used as filler according to the invention.

When the amorphous polyolefin has adhesive properties, calcium carbonate is preferably used since it has an anti-adhesive effect. If there is almost no tackiness, there is no problem in pelletizing operations even if no filler is used.
Calcium carbonate is also suitably used as an extender for amorphous polyolefins. When the amount of filler used exceeds 40% by weight, the amount of dye and pigment used decreases, which is not beneficial for rationalizing coloring processing costs.

In the present invention, the amorphous polymer refers to a polymer that always maintains an amorphous state (a structural state lacking crystallinity or bedding) without crystallizing [English-Japanese Plastic Industry Dictionary (Industrial Research issue 19814F April IO date, 3
(page 6)] also includes copolymers and terpolymers having blocky segments that are crystallized during manufacture. As a convenient measure, copolymers and terpolymers in which the polymer is extracted with boiling 11n-heptane and the residual amount of unextracted polymer is 40% by weight or less are included in the virgin UJ1 amorphous polymer.

As the amorphous polyolefin, there are used copolymers of propylene and ethylene, propylene and butene-1, propylene and α-olefin, terpolymers of propylene, ethylene and butene-1, propylene, ethylene and α-olefin.

Copolymers of propylene and ethylene, propylene and butene-1, and propylene and α-olefin have a propylene content of 70 to 95% by weight, and are copolymers that are not by-products but intended products.

In terpolymers of propylene, ethylene and butene-1, propylene, ethylene and α-olefin, the propylene content is 40-55% by weight.

The terpolymer has an ethylene content of 30 to 40% by weight and is a desired product rather than a by-product.

The number average molecular weight of amorphous polyolefin is 4,000 to 3
Copolymers and terpolymers in the range 0.000 and mixtures thereof are also preferably used. Also, copolymers and terpolymers in which the proportion of extraction residue with boiling n-hebutane is 401i% or less.

Generally, amorphous polyolefins are produced using Ziegler-Natsuta catalysts. The proportion of the residue extracted with boiling n-hebutane from amorphous polyolefin produced using a supported catalyst-trialkylaluminum system in which titanium halide is supported on an inorganic carrier such as magnesium 11-muide is usually about 10% by weight. However, in the case of a titanium trichloride-trialkylaluminum system, it may be 30% by weight or more.

The produced amorphous polyolefin may be added with ordinary phenolic antioxidants, or if it is sticky,
It is also possible to add antiblocking agents. Furthermore, amorphous polyolefins modified with acids or the like can also be used. The amount of amorphous polyolefin used is preferably 10 to 65% by weight based on the total amount in one colorant composition.

In conventional masterbatches, when a polyolefin resin such as polyethylene or polypropylene is used as a carrier resin, the limit of pigment concentration is about 30% by weight. If an attempt was made to rationalize the cost of coloring by mixing in more pigments, kneading etc. would become difficult and satisfactory dispersion of the pigments could not be achieved.

If low-molecular-weight polyethylene or polypropylene is used as the carrier resin, it is possible to increase the pigment concentration limit to 30% by weight or more, but in the end, it is extremely difficult to pelletize it due to operational reasons. became. Furthermore, when atactic polypropylene produced as a by-product was used as a carrier resin, it was possible to limit the pigment concentration to 30% by weight, but it became difficult to pelletize.

In order to impart flame retardancy in the present invention, antimony trioxide, chlorinated paraffin, magnesium hydroxide, aluminum hydroxide, or the like may be kneaded and added during production of the colorant composition.

The colorant composition for thermoplastic resins of the present invention is produced by heating and melting according to a conventional method. That is, it is produced by simply mixing pigments, lubricants, fillers, and amorphous polyolefins, extruding them with a conventional extruder, and pelletizing them II).
It is Noh. Of course, a /hen/helimixer is used as a mixing method that provides very strong shearing force.

The colorant composition of the present invention is preferably applied to similar unpigmented thermoplastic resins, but can also be applied to dissimilar unpigmented thermoplastic resins.

V-polyolefin) The proportion of $IIAn-hebutane insolubles in the amorphous polyolefin in the present invention is 1 percentage (%) of the amount of insoluble polymer relative to the charged amount when extracted with a Soxhlet extractor for 20 hours. It is expressed as

The seven-mer composition in the amorphous polyolefin is Hl/NM
It was quantified using R and C10 NMR.

The number average molecular weight of the amorphous polyolefin was calculated by the GPC method using polystyrene as a standard substance.

The present invention will be explained below with reference to examples, but the present invention is not limited in any way by these examples.

[Example] Example 1 River 1 ・Polyolefin ゛11' 11! Ti supported catalyst (T
Ethylene was introduced into liquefied propylene at 80 °C in the presence of hydrogen as a molecular weight regulator using a triethylaluminum catalyst system (AM/Ti molar ratio = 100) and a triethylaluminum catalyst system (AM/Ti molar ratio = 100). A crystalline propylene-ethylene copolymer was produced. To this copolymer, 0.1 phr of Irganoxl 010 (trade name) was added as a phenolic antioxidant. The propylene content in the copolymer was 89.6% by weight and the ethylene content was 10.4% by weight. Number average molecule (i) by GPC.

It was 7400. The ratio of insoluble copolymer to n-hebutane was 9.1%.

L color plate ■Imaginary 1m 60 parts of titanium dioxide, 99,610 parts of cal carbonate.

5 parts of calcium stearate and 25 parts of the above-produced copolymer were uniformly warmed in a high-speed mixer and then extruded in an extruder to form pellets. In this operation, no problems occurred with regard to melt kneading and pelletization using the extruder.

■-゛ (Use for polyethylene) Mix 98 parts of low density polyethylene (UBE polyethylene J2522 manufactured by Ube Industries, Ltd.) and 2 parts of the above colorant composition,
Temperature 190-200℃, back pressure 10Kg by injection molding machine
A plate was prepared under conditions of /cm'. In this plate, the face 11 and the filler were uniformly and finely dispersed, and no agglomerated particles or uneven color were observed.

(Use for polypropylene) Polypropylene (UBE Polypropylene J manufactured by Ube Industries)
109G) and 2 parts of the above colorant composition were mixed and molded using an injection molding machine at a temperature of 210 to 230°C and a back pressure of 10 kg.
When a plate was prepared under the condition of /cm', the dispersibility and diffusibility of the pigment and filler were extremely good, and no color unevenness was observed.

(Use for ABS) Uncolored ABS resin (Cycolac T manufactured by Ube Cycon Co., Ltd.)
98 parts of the colorant MIJ and 2 parts of the above colorant were mixed and molded using an injection molding machine at a temperature of 220 to 240°C and a back pressure of 5 Kg/
When a plate was prepared under the conditions of cm', the face
The filler was uniformly and finely dispersed, and no color unevenness was observed.

Example 2 J゛■ Polyolefin 1゛'1 Using a Ti-supported catalyst (Ti content 2.4% by weight) supported on magnesium chloride and triethylaluminum (
A/Ti molar ratio = 100).

In the presence of hydrogen, butene-1 and liquefied propylene were polymerized at 85°C to produce a propylene-butene-i copolymer. The copolymer contains the antioxidant Irganox l 01
0.0 (trade name) was added at 0.1 phr. The propylene content in the copolymer was 65% by weight, and the butene content was 35% by weight. The number average molecular weight of this copolymer was 6,700.

The proportion of insoluble matter in this copolymer with Nll-n-hebutane was 9.5%.

L Animals M Hunting Bureau” L Light 30 parts of copper phthalocyanine blue, 30 parts of talc.

Calcium stearate 5 parts, propylene-butene-1
After mixing 55 parts of the copolymer with a Henschel mixer, the mixture was extruded using an extruder and pelletized.

In this operation, no particular problem occurred during melt kneading and pelletization using an extruder.

-1 <Use for polypropylene> 98 parts of polypropylene (UBE polypropylene J309G manufactured by Ube Ko + IU) and 2 parts of the colorant composition of Example 2 were mixed, and the mixture was molded using an injection molding machine at a temperature of 210~ A plate was prepared under conditions of 230° C., back pressure of 10 Kg/am'. When the appearance of this plate was observed, the dispersibility and diffusibility of the pigment and filler were extremely good, and no single color unevenness was observed.

Example 3, 2 days Polyolefin 1''1 AA type Using titanium trichloride and triethylaluminum (AM/Ti molar ratio = 3), in the presence of hydrogen in a mineral spirit solvent, butene 1. Introducing liquefied propylene and ethylene, amorphous propylene-ethylene-
A terpolymer of butene.l was prepared. The terpolymer contains the anti-disfiguring agent Irganox l 010 (trade name)
0.1 phr was added. A compositional analysis of this terpolymer revealed that the propylene content was 50.4% by weight.
, ethylene content is 32.1% by weight, butene 1 is 17
．． The ball amount was 5%. The proportion of insoluble matter in this terpolymer with Mtn-hebutane was 37.5%.

After mixing 30 parts of cocarpon black made by Gomu Mouseai Kyomonogo, 10 parts of talc, 5 parts of calcium stearate, and 55 parts of an amorphous propylene-ethylene-butene terpolymer in a Henschel mixer, extrusion was performed using an extruder. Pelleted. No problems occurred during the melt-kneading and pelletizing operations using an extruder.

Upward 1 <Use in polyethylene> 98 parts of low-density polyethylene (UBE polyethylene J1019 manufactured by Ube Industries, Ltd.) and 2 parts of the colorant composition of Example 3 were mixed, and heated at a temperature of 190 to 200'O by an injection molding machine. A color plate was prepared under a back pressure of 10 K g/am' (7). The dispersibility and diffusibility of pigments and fillers were very good.

Comparative Example 1 Same as in Example 1 except that by-product Shuppan Atactic Polypropylene (manufactured by Chiba Fine Chemicals, trade name: Vistak L) was used instead of the amorphous polyolefin of the present application. pelletized.

When extruding with an extruder.

Pulsating flow sometimes occurred and pelletization was not easy.

Moreover, the pellet of the produced colorant composition was colored pale gray as a whole.

2 parts of this colorant composition and 98 parts of polypropylene (UBE Polypropylene J309G manufactured by Ube Industries, Ltd.) were mixed and heated in an injection molding machine at a temperature of 210 to 230'0 and a back pressure of 10
When a plate was prepared under the condition of Kg/cm', slight gray coloration was observed.

[Effects of the Invention] The colorant composition for thermoplastic resins of the present invention maintains excellent pigment dispersibility and moldability when used as a carrier resin of a purpose-produced amorphous polyolefin, and can be used at high concentrations. It has the advantage of being able to add dyes and pigments.

Patent applicant: Ube Industries Co., Ltd.

Claims (4)

[Claims] (1) A colorant composition for a thermoplastic resin, characterized in that it contains 35 to 90% by weight of a pigment, a lubricant, and a filler, and 65 to 10% by weight of an amorphous polyolefin. (2) The amorphous polyolefin is propylene and ethylene,
Copolymer consisting of propylene and butene-1, propylene and α-olefin, propylene, ethylene and butene-1
1. The colorant composition for thermoplastic resins according to claim 1, which is a terpolymer consisting of propylene, ethylene, and α-olefin. (3) Propylene and ethylene, propylene and butene-1
The coloring for thermoplastic resins according to claim 2, wherein the copolymer of propylene and α-olefin has a propylene content of 70 to 95% by weight and is a copolymer consisting of a target product rather than a by-product. agent composition. (4) A terpolymer of propylene, ethylene and butene-1, propylene, ethylene and α-olefin has a propylene content of 40 to 55% by weight and an ethylene content of 30 to 50% by weight.
The colorant composition for thermoplastic resins according to claim 2, which is a terpolymer comprising 40% by weight of the desired product.