JPH0881592A - Colored polypropylene composition - Google Patents

Abstract

(57) [Summary] [Structure] Pigment (a), melt flow rate (MFR) is 1
Highly crystalline polypropylene (b) of 0 g / 10 min or more, embedded image A colored polypropylene composition obtained by adding and dispersing the colorant composition containing the organic phosphate-based nucleating agent (c) and calcium stearate (d) to the polypropylene (e) to be colored. . [Effect] It is possible to provide a colored molded product which is free from molding defects and has excellent physical properties such as bending strength and surface hardness. Further, even when the colored molded product is recycled and molded, the physical properties are hardly deteriorated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene composition which is excellent in dispersibility of a pigment and is colored with a colorant composition which does not impair the flowability and strength properties of polypropylene.

[0002]

When a colorant masterbatch for polypropylene is prepared, the base resin of the masterbatch is
It is necessary to disperse it uniformly in the polypropylene to be colored. Therefore, the base resin in the masterbatch is usually made of polyethylene or melt flow rate (hereinafter referred to as M
Polypropylene having a high FR) is used, or a method of adding a polyethylene wax to polypropylene to improve fluidity is used.

[0003]

However, in a colored polypropylene molding material obtained by adding and dispersing these colorant master batches having improved fluidity, the crystallization temperature of the molding material is also lowered, so that a sheet or the like is used. In extrusion molding and blow molding of bottles, the problem of drawdown was likely to occur. At the same time, the flexural modulus and the surface hardness were often lowered. Fillers such as talc and calcium carbonate must be filled in order to maintain the heat distortion temperature and rigidity, but at present, the aim is to reduce the weight of the material. Was not suitable because its use was limited. On the other hand, in order to prevent drawdown, polypropylene having a relatively low MFR must be used as the base resin of the masterbatch, but this will reduce the dispersibility of the masterbatch, and therefore, there will be problems with the uniformity of coloring. there were. For this reason, conventionally, there has not yet existed a colorant for polypropylene that simultaneously solves these problems.

[0004]

DISCLOSURE OF THE INVENTION As a result of earnest studies in view of such a situation, the present inventor has used a colorant composition comprising a pigment and polypropylene containing a specific nucleating agent and a specific dispersant. Then, it was found that a colored polypropylene composition free from the above-mentioned drawbacks was obtained, and the present invention was completed.

That is, according to the present invention, a pigment (a), a polypropylene (b) having a melt flow rate (MFR) of 10 g / 10 min or more, an organophosphate nucleating agent (c), and a calcium salt of a fatty acid (d). The present invention provides a colored polypropylene composition characterized by comprising adding and dispersing a colorant composition containing the above in polypropylene (e) to be colored.

The pigment (a) used in the colorant composition is not particularly limited, and generally, any of organic pigments and inorganic pigments which can be used for coloring polypropylene resin can be used.

The polypropylene (b) used as the base resin in the colorant composition has an MFR of 10 g / 10 because it is uniformly dispersed in the molding polypropylene to be colored.
It must be min or more. MF mentioned above
Any polypropylene having R can be used in any form such as a homopolymer, a block copolymer or a random copolymer with polyethylene, a copolymer with other olefinic elastomers, and a blend with these resins. Above all, it is preferable to use polypropylene having high crystallinity.
Here, the highly crystalline polypropylene is a polypropylene having an NMR method pentad value of 95% or more and a crystallinity of 65% or more, if it is defined by the stereoregularity (isotacticity) of polypropylene. .

As the organic phosphate-based nucleating agent (c), a substituted bisphenol phosphate ester salt is preferable,
The substituent is preferably a t-butyl group, and the cation is preferably sodium, lithium, potassium or magnesium. Among them, the following specific structure

[0009]

Embedded image

Preference is given to using compound 1 which exhibits Furthermore, the calcium salt (d) of a fatty acid is used as a dispersant for a pigment, and the fatty acid has a carbon number in the range of 8 to 20, preferably a straight chain having a carbon number in the range of 8 to 20. A carboxylic acid calcium salt having an alkyl group is preferred. A typical example of a suitable one is calcium stearate.

The polypropylene (e) to be colored by the colorant composition comprising (a), (b), (c) and (d) described above includes general-purpose polypropylene supplied for molding and polypropylene. Any of highly crystalline polypropylene and the like can be used. Highly crystalline polypropylene is preferably used.

The content ratio of each component in the colorant composition may be in an appropriate range, but in particular, the pigment (a) is 1 to 60% by weight, the polypropylene (b) is 15 to 97% by weight, and an organic phosphate type. It is preferable that the nucleating agent (c) is in the range of 1 to 15% by weight and the fatty acid calcium salt (d) is in the range of 1 to 10% by weight.

The colorant composition used in the present invention includes:
In addition to the above-mentioned essential components, if necessary, various additives such as antioxidants, inorganic fillers, ultraviolet absorbers,
An extender pigment or the like may be added.

The colorant composition of the present invention is supplied in the form of a masterbatch. The method for producing this masterbatch is, for example, after mixing a pigment, polypropylene, an organic phosphate-based nucleating agent and a calcium salt of a fatty acid,
Examples thereof include a method in which the mixture is melt-kneaded at the above temperature, and the pellet is shaped by a pelletizer or the like.

The masterbatch thus obtained is diluted (mixed) with polypropylene for coloring according to a conventional method, and extrusion molding, blow molding, vacuum molding,
It is used for molding such as compression molding and injection molding. The pigment concentration may be set according to the dilution ratio, but generally 20
It is preferable to use it at a dilution ratio of 2 to 40 times and to design it so that the pigment concentration in the final molded product is about 0.1% to 3%.

In various molding of polypropylene by coloring polypropylene by using the colorant composition of the present invention in which the above-mentioned essential components (a), (b), (c) and (d) are combined, It is the first time to obtain a colored molded product that is free from molding defects such as drawdown and is excellent in bending strength, surface hardness and luster.

In the production of colored polypropylene molded products, spool runners and defective molded products are actually generated, and inconveniences such as the edges of the sheet when the sheet is cut are actually generated. . There is a very strong demand for a molding material capable of performing a molding process involving so-called recycling, in which these non-consumables are crushed and supplied again to the molding machine. However, in the case of using an ordinary colorant for polypropylene, the physical properties were remarkably deteriorated when recycled and molded, and a molded product that could be used was not obtained. However, with the colored polypropylene composition of the present invention, it is possible to obtain a molded article with almost no deterioration in physical properties even by molding accompanied by such recycling, and the composition of the present invention is resistant to repeated heat history and is suitable for recycling molding. It is an excellent molding material.

Molded articles comprising the colored polypropylene composition of the present invention can be used in various fields using polypropylene molded articles. Household or commercial electrical products, logistics materials, packaging materials, etc., such as air conditioners, refrigerators, washing machines, telephones, tableware dryers, vacuum cleaners, containers,
Suitable for use in plastic products such as sheets and films.

[0019]

EXAMPLES Next, the present invention will be described in detail by way of examples, but this example is described only for the purpose of illustration.
The invention is not limited by these examples.

Examples 1 to 4 and Comparative Examples 1 to 4 Pigments (a), polypropylene (b), nucleating agents (c), and fatty acid metal salts (d) were used in the respective prescribed amounts shown in Table 1. , After mixing with a Henschel mixer,
After melt-kneading with an extruder at a temperature of 190 ° C., the mixture was shaped into pellets to obtain each colorant masterbatch.

[0021]

[Table 1]

The symbols in each component used in Table 1 are shown below. * Pigment A1: Cyanine blue GNPT (manufactured by Dainippon Ink and Chemicals, Inc.) A2: Titanium dioxide R-TC30 (manufactured by BTP TIOXIDE LIMITED) * Polypropylene D1: K5019 (high crystal polyphenylene homopolymer, MFR: 12g / 10min, Chisso stock) Company made) D2: K5330 (High crystal polypropene block copolymer), MFR: 30g / 10m
in, manufactured by Chisso Corporation) D3: K1008 (general polypropylene homopolymer, MFR: 11g / 10min, manufactured by Chisso Corporation) * Nucleating agent B1: Substituted bisphenol phosphate ester salt (Compound 1 having the above-mentioned molecular structural formula) B2: Para-tert-butyl human hydroxyaluminum benzoate B3: Benzidine sorbitol * Fatty acid metal salt C1: Calcium stearate C2: Aluminum stearate

(Test Example A for Evaluation) With respect to 3 parts of the above masterbatch, high crystalline polypropylene “K5016” (homopolymer, MF) was used as the polypropylene to be colored.
R: 6 g / 10 min, manufactured by Chisso Co., Ltd.) 97 parts were used to prepare test pieces for physical property measurement with an injection molding machine at 210 ° C.

As test items, initial physical properties were measured in terms of flexural modulus, heat distortion temperature and hardness. In addition, the drawdown property in the sheet processing, the dispersibility of the masterbatch, and the recyclability are also examined. The test results are shown in Table-2. The tested items are as follows.

<Test Items> (1) Flexural Modulus According to ASTM D790. (2) Heat distortion temperature According to ASTM D648.

(3) Hardness According to ASTM D785. (4) Drawdown property According to the sheet extrusion test method. (Evaluation criteria) ◎: excellent, ○: good, △: acceptable, ×: not acceptable

(5) Dispersibility of masterbatch: According to the disc hogle test method. (Evaluation criteria) ◎: excellent, ○: good, △: acceptable, ×: not acceptable

(6) Recycling suitability: Recycling molding was carried out three times, and the subsequent physical properties and processability were evaluated comprehensively. (Evaluation criteria) ◎: excellent, ○: good, △: acceptable, ×: not acceptable

[0029]

[Table 2]

Example 5 and Comparative Example 5 A pigment (a), a polypropylene (b), a nucleating agent (c), and a fatty acid metal salt (d) were used in a Henschel mixer by using predetermined amounts of the compounds shown in Table 3. After mixing
After melt-kneading with an extruder at a temperature of 190 ° C., the mixture was molded into pellets to obtain a colorant masterbatch.

[0031]

[Table 3]

The symbols in each component used in Table 3 are shown below. * Pigment A3: Benji 190 ED (manufactured by Toda Kogyo Co., Ltd.) * Polypropylene D3: K1008 (general polypropylene homopolymer, MFR: 11g / 10min, manufactured by Chisso Corporation) D4: K1011 (general polyphenylene homopolymer, MFR: 0.9g / 10 min, manufactured by Chisso Corporation) D5: K7030 (general polyproren block copolymer), MFR: 25g / 10mi
n, manufactured by Chisso Corporation) * Nucleating agent B1: Substituted bisphenol phosphate ester salt (Compound 1 having the above-mentioned molecular structural formula) B2: Para-tert-butyl human benzoyl aluminum benzoate * Fatty acid metal salt C1: Calcium stearate

(Test Example B for Evaluation) For each 3 parts of this masterbatch, high crystalline polypropylene "K5016" (homopolymer, MF) was used as the polypropylene to be colored.
R: 6 g / 10 min, manufactured by Chisso Co., Ltd.) 97 parts were used to prepare test pieces for physical property measurement with an injection molding machine at 210 ° C.

As test items, initial physical properties were measured in terms of flexural modulus, heat distortion temperature and hardness. In addition, the drawdown property in the sheet processing, the dispersibility of the masterbatch, and the recyclability are also examined. The test results are shown in Table 4.

[0035]

[Table 4]

Example 6 The pigment (a), the polypropylene (b), the nucleating agent (c), and the fatty acid metal salt (d) were each mixed with a Henschel mixer after mixing a predetermined amount of the compound shown in Table 5 with each other.
After melt-kneading with an extruder at a temperature of 190 ° C., the mixture was molded into pellets to obtain a colorant masterbatch.

[0037]

[Table 5]

The symbols in each component used in Table 5 are shown below. * Pigment A3: Benji 190ED (manufactured by Toda Kogyo Co., Ltd.) * Polypropylene D5: K7030 (general polypropylene block copolymer, MFR: 25g / 10mi)
n, manufactured by Chisso Corporation) * Nucleating agent B1: Substituted bisphenol phosphate ester salt (Compound 1 having the above-mentioned molecular structural formula) * Fatty acid metal salt C1: Calcium stearate

(Test Example C for Evaluation) 3 parts of this master batch was used as a polypropylene to be colored, a general-purpose polypropylene "K1011" (homopolymer, MFR:
Using 0.9 parts of 0.9 g / 10 min, manufactured by Chisso Co., Ltd., test pieces for measuring physical properties were prepared with an injection molding machine at 210 ° C.

As the test items, initial physical properties of flexural modulus, heat distortion temperature and hardness were measured. In addition, the drawdown property in the sheet processing, the dispersibility of the masterbatch, and the recyclability are also examined. The test results are shown in Table-6.

[0041]

[Table 6]

[0042]

The colored polypropylene composition of the present invention is
In various moldings of polypropylene, a colored molded product free from molding defects such as drawdown and excellent in bending strength, surface hardness and gloss is provided. Further, even if the colored molded product is recycled and molded, it is possible to provide a molded product with substantially no deterioration in physical properties.

Claims (8)

[Claims] 1. A pigment (a), a melt flow rate (MF
R) is 10 g / 10 min or more polypropylene (b), an organic phosphate-based nucleating agent (c), and a colorant composition comprising calcium salt of fatty acid (d), polypropylene (e) for coloring. A colored polypropylene composition characterized by being added to and dispersed in. 2. The composition according to claim 1, wherein the polypropylene (b) is a highly crystalline polypropylene. 3. The composition according to claim 1, wherein the organic phosphate-based nucleating agent (c) is a substituted bisphenol phosphate ester salt. 4. A substituted bisphenol phosphate ester salt having the following structural formula: The composition according to claim 3, which is represented by: 5. The composition according to claim 1, wherein the calcium salt (d) of the fatty acid is calcium stearate. 6. The colored polypropylene composition according to claim 1, wherein the polypropylene (e) to be colored is a highly crystalline polypropylene. 7. The use ratio of each component in the colorant composition is 1 to 60% by weight of the pigment (a), and MFR is 10 g / 1.
The range of 15 to 97% by weight of polypropylene (b) of 0 min or more, 1 to 15% by weight of organic phosphate-based nucleating agent (c), and 1 to 10% by weight of calcium salt of fatty acid (d). The composition as described. 8. The composition according to claim 1, which is a molding material which can be supplied for molding with recycling.