JPH072877B2 - Colorant composition for thermoplastic resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a masterbatch colorant composition useful for coloring thermoplastic resins, particularly polyolefin resins such as polyethylene and polypropylene, ABS resins, polyvinyl chloride and the like. It is about things.

[Prior Art and Problems] In general, in order to mix a thermoplastic resin and a colorant, a colorant resin composition is manufactured by a Banbury mixer or an extruder, and various molded products are molded using the colorant resin composition. Has been done. This method has drawbacks such as high coloring processing cost and troublesome inventory management.

In addition, the maximum value of the total content of pigment and filler is approx.
It is known to prepare a masterbatch of colorant with an amount of 75% by weight mixed with a polyolefin resin such as polyethylene or polypropylene. This method
The produced masterbatch is kneaded with the same resin as the resin to be colored to give pellets, which are then molded into various molded products. Therefore, it has an advantage that the operation is simple, but when the content of the pigment is about 30% by weight or more, there is a problem that the kneading property and the moldability become difficult. Further, since the dispersibility of the pigment is deteriorated and color unevenness occurs, it is desired to disperse the pigment in a higher concentration in the masterbatch for the purpose of rationalizing the coloring processing cost.

As a method for improving the dispersibility of high-concentration pigments, a method by changing the design of the molding machine screw has been proposed, but it requires a large amount of capital investment and is expected to effectively disperse a large amount of high-concentration pigments. Not big enough.

On the other hand, a method of using atactic polypropylene as a carrier resin for a masterbatch has been proposed. In this case, since atactic polypropylene is a by-product during the production of polypropylene, it has the advantage of being inexpensive, but on the other hand, there are many catalyst and solvent residues, which makes color matching difficult when preparing a color masterbatch. Or
It was also a cause of odor. Also, because it is a by-product,
The physical properties, such as melt viscosity, fluctuate greatly and the fluidity becomes unstable during kneading, resulting in poor operability. Further, since it contains a solvent, there is a problem of environmental pollution due to generation of solvent vapor due to heating.

A method for producing an antistatic masterbatch using atactic polypropylene as a carrier (JP-A-62-62836),
A method for producing a masterbatch for coloring or modifying (JP-A-52-126449 and JP-A-53-67750) has been proposed. In all of these methods, since atactic polypropylene, which is a by-product of polypropylene production, is used as a raw material, the above-mentioned drawbacks are included.

[Means for Solving the Problem] Then, in order to solve the drawbacks of the conventionally known masterbatch, as a result of earnest research, as a result, pigments, lubricants and fillers have
By using a colorant composition characterized by containing 90% by weight and 65 to 10% by weight of amorphous polyolefin,
The present invention has been achieved by finding that the above-mentioned drawbacks are sufficiently solved.

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

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

As the lubricant of the present invention, metal stearates, waxes and higher alcohols, plasticizers such as esters thereof and the like are used. The amount used is 0 to 6% by weight. If it is more than 6% by weight, pelletization will be easy, but the amount of dyes and pigments used will be small, which is not preferable. If the amorphous polyolefin has a good melt fluidity, no lubricant may be used.

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

When the amorphous polyolefin has tackiness, the use of calcium carbonate has an anti-tacking effect and is preferably used. If there is almost no tackiness, the pelletizing operation will not be hindered even if no filler is used.
Calcium carbonate is also suitably used as an extender for amorphous polyolefin. When the amount of the filler used is 40% by weight or more, the amount of the dye / pigment used decreases, which is not preferable for rationalization of the coloring processing cost.

The amorphous polyolefin random copolymer in the present invention means a polymer which always maintains an amorphous state (a structural state lacking in crystallinity or bedding) without being crystallized [English-Plastic Industry Dictionary] (April 10, 1981, p. 36), also includes copolymers and terpolymers having block-like segments crystallized during manufacture. As one convenient measure, copolymers and terpolymers in which the polymer is extracted with boiling n-heptane and the residual amount of unextracted polymer is 40% by weight or less are included in the amorphous polyolefin random copolymer of the present invention. .

Amorphous polyolefin random copolymers include propylene and ethylene, propylene and butene-1, copolymers of propylene and α-olefin, terpolymers of propylene and ethylene and butene-1, propylene and ethylene and α-olefin. used.

In the copolymer of propylene and ethylene, propylene and butene-1, and propylene and α-olefin, the propylene content is 70 to 95% by weight, and the copolymer is a target product, not a by-product.

In the terpolymers of propylene, ethylene and butene-1, and propylene, ethylene and α-olefin, the propylene content is 40 to 55% by weight, the ethylene content is 30 to 40% by weight, and the target product is not a by-product. Is a terpolymer.

The amorphous polyolefin random copolymer is a copolymer or terpolymer having a number average molecular weight in the range of 4,000 to 30,000, and a mixture thereof is also preferably used.
Moreover, the ratio of the extraction residue due to boiling n-heptane is 40% by weight.
The following are copolymers and terpolymers.

Generally, the amorphous polyolefin is produced using a Ziegler-Natta catalyst. The ratio of the extraction residue by boiling n-heptane of the amorphous polyolefin produced by a supported catalyst-trialkylaluminum system in which titanium halide is supported on an inorganic carrier such as magnesium chloride is usually about 10% by weight or less. However, in the case of titanium trichloride-trialkylaluminum system, it may be 30% by weight or more.

To the produced amorphous polyolefin, if a usual phenolic antioxidant is added or if it has tackiness,
It is also possible to add an antiblocking agent. As the amorphous polyolefin, those modified with an acid can be used. The amount of the amorphous polyolefin used is preferably 10 to 65% by weight based on the total amount in the colorant composition.

In a conventional masterbatch, when a polyolefin resin such as polyethylene or polypropylene was used as a carrier resin as a resin to be colored, the pigment concentration limit was about 30% by weight. If the pigments are mixed more than this to try to rationalize the coloring processing cost, the kneading becomes difficult, and the dispersion of the pigments cannot be satisfactorily 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 very difficult to pelletize in terms of operation. became. Further, when atactic polypropylene produced as a by-product was used as the carrier resin, it was possible to sufficiently limit the pigment concentration to 30% by weight, but pelletization became difficult.

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

The colorant composition for thermoplastic resin of the present invention is produced by heating and melting according to a usual method. That is, the pigment, the lubricant, the filler, and the amorphous polyolefin random copolymer are simply mixed, and the mixture can be extruded by an ordinary extruder and pelletized. Of course, a Banbury mixer is used as a mixing method for imparting a very strong shearing force.

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

Analysis Method of Amorphous Polyolefin Random Copolymer The ratio of the boiling n-heptane insoluble matter of the amorphous polyolefin random copolymer in the present invention is the amount of insoluble polymer with respect to the charged amount when extracted with a Soxhlet extractor for 20 hours. Expressed as a weight percentage (%). The monomer composition in the amorphous polyolefin is H ¹ · NMR and C ¹³ · NMR.
Was quantified using. 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 described below with reference to examples, but the present invention is not limited to these examples.

[Example] Example 1 Production of amorphous polyolefin random copolymer Ti-supported catalyst supported on magnesium chloride (Ti content 2.
4% by weight) and tolyl aluminum catalyst system (Al / Ti
Molar ratio = 100), 80 in the presence of hydrogen as a molecular weight regulator
Ethylene was introduced into liquefied propylene at ℃ to produce an amorphous propylene-ethylene copolymer. To this copolymer, 0.1 phr of Irganox 1010 (trade name) as a phenolic antioxidant was added. The propylene content in the copolymer was 89.6% by weight and the ethylene content was 10.4% by weight. The number average molecular weight by GPC was 7,400. Boiling n
The proportion of insoluble copolymer to heptane is 9.1%
Met.

Manufacture of Colorant Composition 60 parts of titanium dioxide, 10 parts of calcium carbonate, 5 parts of calcium stearate and 25 parts of the copolymer prepared above were uniformly mixed in a high-speed mixer, and then extruded by an extruder and pelletized. In this operation, no problems occurred in melt kneading and pelletization by the extruder.

Blending with thermoplastic resin <Use in polyethylene> 98 parts of low-density polyethylene (UBE polyethylene J2522 manufactured by Ube Industries, Ltd.) and 2 parts of the above colorant composition are mixed, and the temperature is 190 to 200 ° C by an injection molding machine. Plates were prepared under a back pressure of 10 kg / cm ² . In this plate, the pigment and the filler were uniformly and finely dispersed, and neither aggregated particles nor color unevenness was observed.

(Use for polypropylene) Polypropylene (UBE polypropylene J manufactured by Ube Industries, Ltd.)
109G) 98 parts and 2 parts of the above colorant composition were mixed, and a plate was prepared by an injection molding machine under the conditions of a temperature of 210 to 230 ° C. and a back pressure of 10 Kg / cm ^2. The diffusivity was extremely good, and no color unevenness was observed.

<Use in ABS> 98 parts of uncolored ABS resin (Psycolac T made by Ube Saikon Co., Ltd.) and 2 parts of the above colorant composition are mixed, and the temperature is 220 to 240 ° C., the back pressure is 5 kg / cm by an injection molding machine. ^{When the} plate was prepared under the condition of ² , the pigment and the filler were uniformly and finely dispersed, and no color unevenness was observed.

Example 2 Production of amorphous polyolefin random copolymer Ti-supported catalyst supported on magnesium chloride (Ti content 2.
4% by weight) and triethylaluminum (Al / Ti molar ratio = 100), butene-1 and liquefied propylene were polymerized at 85 ° C. in the presence of hydrogen to produce a propylene-butene-1 copolymer. The antioxidant Irganox 1010 in the copolymer
(Trade name) was added at 0.1 phr. The propylene content of the copolymer was 65% by weight and the butene-1 content was 35% by weight. The number average molecular weight of this copolymer was 6700.
The proportion of insoluble matter in this copolymer due to boiling n-heptane was 9.5%.

Preparation of Colorant Composition Copper Phthalocyanine Bull-30 parts, Talc Part, 5 parts Calcium Stearate, Propylene-Butene-1 Copolymer
After mixing 55 parts by a Henschel mixer, it was extruded by an extruder and pelletized. In this operation, melt kneading and pelletization by an extruder did not cause any particular problem.

Blending with thermoplastic resin <Use in polypropylene> Polypropylene (UBE polypropylene J manufactured by Ube Industries, Ltd.)
309G) 98 parts and 2 parts of the colorant composition of Example 2 were mixed, and a plate was prepared by an injection molding machine at a temperature of 210 to 230 ° C. and a back pressure of 10 kg / cm ² . When the appearance of this plate was observed, it was found that the dispersion of the pigment and the filler and the diffusibility were very good, and no color unevenness was observed.

Example 3 Production of Amorphous Polyolefin Random Copolymer Using AA type titanium trichloride and triethylaluminum (Al / Ti molar ratio = 3) in the presence of hydrogen in a mineral spirit solvent, butene-1, liquefied propylene and Amorphous propylene-ethylene-butene
A terpolymer of 1 was produced. The antioxidant, Irganox 1010 (trade name), was added to the terpolymer in an amount of 0.1 phr. When the composition analysis of this terpolymer was conducted, the propylene content was 50.4% by weight, the ethylene content was 32.1% by weight, butene.
1 was 17.5% by weight. The proportion of insoluble matter in this terpolymer due to boiling n-heptane was 37.5%.

Manufacture of colorant composition 30 parts carbon black, 10 parts talc, 5 parts calcium stearate. Amorphous propylene-ethylene-butene-1
55 parts of the terpolymer of was mixed with a Henschel mixer, and then extruded with an extruder to form pellets. No problems occurred in the melt-kneading and pelletizing operations by the extruder.

Blending with thermoplastic resin <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 are mixed and a temperature of 190- Color plates were prepared under the conditions of 200 ° C and back pressure of 10 kg / cm ² . The dispersibility and diffusivity of the pigment and filler were very good.

Comparative Example 1 In the production of the colorant composition in Example 1, a commercial by-product atactic polypropylene (trade name Vistac L manufactured by Chiba Fine Chemical Co., Ltd.) was used in place of the amorphous polyolefin of the present application. Was similarly pelletized. When extruded by an extruder, a pulsating flow occasionally occurred and pelletizing was not easy. In addition, the pellets of the produced colorant composition were entirely colored in light gray.

2 parts of this colorant composition and 98 parts of polypropylene (UBE polypropylene J309G manufactured by Ube Industries, Ltd.) were mixed, and a plate was prepared by an injection molding machine under the conditions of a temperature of 210 to 230 ° C. and a back pressure of 10 kg / cm ² . However, a faint gray coloring was observed.

[Effects of the Invention] The colorant composition for a thermoplastic resin of the present invention retains excellent pigment dispersibility and moldability by using the objectively produced amorphous polyolefin random copolymer as a carrier resin. However, it is possible to add a high concentration of dyes and pigments.

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Claims (1)

[Claims] 1. 35-90% by weight of pigments, lubricants and fillers,
65 to 10% by weight of an amorphous polyolefin random copolymer represented by the following (a) or (b), which is not a by-product, but is produced by a purpose, and is a colorant composition for a thermoplastic resin. . When the amorphous polyolefin random copolymer (a) is a copolymer of propylene and ethylene, propylene and butene-1, and propylene and α-olefin, the propylene content is 70 to 95% by weight. (B) When the amorphous polyolefin random copolymer is a terpolymer of propylene, ethylene and butene-1, propylene, ethylene and α-olefin, the propylene content is 40 to 55% by weight and the ethylene content is 30 to 40. % By weight.