JPH0753773A - Resin composition for coloring - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. which does not adversely affect mechanical strengths, such as tensile, bending, and impact strengths, of a polyolefin resin and is excellent in pigment dispersion, enabling uniform coloring. CONSTITUTION:This resin compsn. mainly comprises a thermoplastic resin, a pigment, and a dispersant comprising a primary long-chain alkyl alcohol represented by the chemical formula (wherein R is H or CH3; and (x) is, on average, 27-47).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for coloring a thermoplastic resin.

[0002]

2. Description of the Related Art Conventionally, a polyolefin resin coloring composition has a powdery dry color in which a pigment and a dispersant are mixed, a liquid color or a paste color in which a pigment is dispersed in a liquid dispersant at room temperature, There are pellet-like, flake-like, or bead-like master batches in which a pigment is dispersed in a resin that is solid at room temperature. These coloring compositions are properly used depending on the intended use, and among them, masterbatches are preferably used from the viewpoints of easy handling and preservation of working environment during use. And the performance required as a masterbatch,
The high pigment concentration and the small effect on various properties such as heat resistance and strength of the thermoplastic resin to be colored, as well as the precision and speed of molding of the polyolefin resin, make the pigment dispersibility better than before. And the need for distributability has come to be required.

As a dispersant for imparting pigment dispersibility to a masterbatch, stearic acid, zinc stearate, magnesium stearate, aluminum stearate, calcium stearate, ethylene bisamide, polyethylene wax, polypropylene wax, and derivatives thereof, One type or two or more types of acid-modified products and waxes composed of acid-modified products are generally used. However, for example, when a high degree of pigment dispersion is required, such as high-speed spinning of a thermoplastic resin with a diameter of a few tens of microns, or film formation, the above dispersant is insufficient. That is, yarn breakage at the time of spinning due to poor pigment dispersion, clogging of the filter of the melt spinning machine, and defective molding of the film occurred. In order to solve these problems, efforts have been made to improve the processing method of the masterbatch and to improve the pigment dispersibility by using a powerful kneader. However, it has not exhibited sufficient pigment dispersibility for solving the above problems.

Further, in the field of large-sized injection molding in which colored pellets have been conventionally used, color unevenness and flow marks have become a problem in the coloring of molded products as the coloring by the master batch increases. Conventionally, in blow molding and film molding in which coloring is performed by a masterbatch, plasticization, mixing and kneading of a resin and a masterbatch are performed in an extruder part of a molding machine. In the case of an injection molding machine, the plasticizing, mixing, and kneading steps are carried out in the cylinder in which the screw moves backward, but the kneading force is not sufficient compared to the extruder, and the molding cycle can be shortened and the viscosity of the molding resin can be reduced. Along with this, the kneading power has become smaller, and as a result, color unevenness has tended to occur on the surface of the molded product.

In addition, the pigment content of the masterbatch, which has been promoted for the purpose of reducing the cost of coloring, has been increased. With the advent of the high-concentration masterbatch, the addition amount of the masterbatch to the resin to be colored is reduced. Color unevenness and flow marks are becoming more likely to occur. These issues are
Although it is recognized in various thermoplastic resins, it is remarkable in polypropylene-based resins, which have been increasingly used in home appliances and automobile parts, and an urgent solution has been demanded. In order to solve this problem, increase the content of the dispersant among the three main components of the masterbatch (pigment, dispersant and base resin),
Alternatively, it has been attempted to eliminate the color unevenness by lowering the melt viscosity of the masterbatch such as using a base resin having a viscosity smaller than that of the resin to be colored. However, if the polypropylene resin is filled with an inorganic filler, or if the melt flow rate (hereinafter referred to as MFR) exceeds 25 for the purpose of thin-wall molding, color unevenness or flow marks are likely to occur, and this problem is solved. Was waiting.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventors to improve the above-mentioned various drawbacks, a coloring resin composition using a long-chain alkyl primary alcohol as a dispersant is a polyolefin. Tensile strength and bending strength of resin
The present invention has been completed by finding that 5% or more of physical strength values such as impact strength are not impaired with respect to each mechanical strength value, pigment dispersibility is excellent, and uniform coloring without color unevenness can be performed.

[0007]

The present invention provides a coloring resin composition containing a pigment, a dispersant, and a thermoplastic resin as main components, wherein the dispersant is a long-chain alkyl primary compound represented by the following chemical structural formula. Provided is a resin composition for coloring, which is a primary alcohol. R; H or CH ₃ x; 27 to 47 (average) As the commercially available dispersant,
Unilin Alcohol (manufactured by Petrolite) can be mentioned.

Examples of the pigment include organic pigments and inorganic pigments, and known pigments conventionally used for coloring thermoplastic resins can be used. Examples of such pigments include organic pigments such as azo, anthraquinone, phthalocyanine, quinacridone, isoindolinone, dioxane, berylene, quinophthalone, berinone, cadmium sulfide, cadmium selenide, ultramarine blue, There are inorganic pigments such as titanium dioxide, iron oxide, chromate oxide, and carbon black.

The thermoplastic resin is not particularly limited as long as it is a resin capable of producing a masterbatch, and polyolefin, polymethylpentene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-
Styrene (ABS) resin, acrylonitrile-EPDM
-Styrene (AES) resin, acrylic resin, polyamide, polycarbonate, polyacetal, polyurethane and the like.

Among them, a polyolefin resin having an MFR in the range of 0.1 to 400, preferably 10 to 100 has a good compatibility with the polyolefin resin and is therefore preferable when the polyolefin resin is colored. When the MFR of the polyolefin-based resin blended in the coloring resin composition is less than 0.1, the compatibility with the polyolefin-based resin to be colored becomes poor, and color unevenness occurs, and the various thermoplastic resins are colored. The physical properties are also adversely affected. MFR is 400
If it exceeds, the mechanical strength and heat resistance of the masterbatch itself becomes low, it becomes difficult to manufacture the masterbatch, and the heat resistance of the polyolefin resin to be colored,
It adversely affects physical properties such as strength. The polyolefin resin blended in the coloring resin composition may be functional group-modified, crosslinking-modified, grafted or blocked-modified, and may be in the form of powder or pellets.

To the coloring resin composition of the present invention, various additives such as stabilizers such as antioxidants and ultraviolet absorbers and surfactants are added within a range that does not impair the effects of the present invention. You can also The coloring resin composition of the present invention can be used for coloring almost all polyolefin-based resins, and may contain a reinforcing material such as an inorganic filler, glass fiber or organic fiber for the purpose of improving physical properties. .
For example, a uniform coloring that does not have an effect on mechanical properties such as strength and heat resistance, which could not be achieved by coloring using a conventional masterbatch, and has no color unevenness can be achieved with inorganic fillers and fiber reinforced materials up to 50%. It can be realized by adding a small amount of 4 parts by weight or less of the coloring resin composition of the present invention to 100 parts by weight of the polyolefin resin composition containing about 10% by weight.

The coloring resin composition of the present invention comprises polymethylpentene, polystyrene,
Polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-EPD
It can also be blended with thermoplastic resins such as M-styrene (AES) resin, acrylic resin, polyamide, polycarbonate, polyacetal, and polyurethane.

The improvement of the pigment dispersibility and the coloring power of the coloring resin composition of the present invention is due to the affinity of the hydroxyl group in the dispersant for the pigment, and there is a polar relationship between the hydroxyl group in the dispersant and the pigment. It is considered that various bonds are formed, and the surroundings are surrounded by long-chain alkyl groups to form a protective colloidal structure. The coloring resin composition of the present invention can also be used for applications such as lubricants, hot melt resins, inks, paints and adhesives.

[0014]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, “part” means “part by weight” and “%” means “% by weight”. The dispersants used are shown in Table 1.

[Table 1]

[Example 1] Dispersant A 10% Phthalocyanine blue "Riono Blue 7110V" 50% (Toyo Ink Mfg. Co., Ltd.) Polypropylene "Mitsui Noblen J4HG" 40% (Mitsui Petrochemical Mfg., MFR: 30) Kneading the above 3 components with a 3 roll mill, screw diameter
A 65 mm extruder was used to pelletize to obtain a masterbatch. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Mix 100 parts by weight of polypropylene "Mitsui Noblen J4HG" with 3 parts of the obtained masterbatch, and use a vertical test spinning machine (Fuji Filter Co., Ltd. spinning tester) to remove 230 parts below the hopper.
After spinning at ℃, kneading section, die section at 230 ℃, draw 3 times,
A polypropylene fiber of 5 denier was obtained. The spinnability, the clogging property, and the stretchability exhibited good dispersibility without problems.

Comparative Example 1 A masterbatch was obtained in the same manner as in Example 1 except that the polyethylene-based resin “APAO RT 2315” (manufactured by Ube Lexen) was used as the dispersant A. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Next, spinning was performed in the same manner as in Example 1, but yarn breakage due to clogging occurred.

[Example 2] A masterbatch was obtained in the same manner as in Example 1 except that the dispersant A was replaced with the dispersant B. Then, spinning was carried out in the same manner as in Example 1, and as a result, good dispersibility was exhibited without any problems regarding spinnability, clogging and stretchability. [Comparative Example 2] Example 1 except that the dispersant A was replaced with polypropylene wax "Viscor 660P" (manufactured by Sanyo Kasei Co., Ltd.).
A masterbatch was obtained in the same manner as. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Next, when spinning was performed in the same manner as in Example 1, yarn breakage due to clogging occurred.

In order to compare the clogging properties of undispersed pigments, 10 parts of the master batches obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were mixed with 100 parts of polypropylene "Mitsui Noblene J4HG", 5 each mixture at the tip
3 kg was extruded using a single screw extruder with a screw diameter of 30 mm equipped with a wire mesh of 00 mesh. Table 2 shows the pressure rise value at the tip
Shown in. Further, in order to compare the dispersive coloring properties of pigments, 1 part of the master batches obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were blended with 5 parts of titanium oxide and 100 parts of polypropylene "Mitsui Noblene J4HG", respectively. Then, the mixture was kneaded with a two-roll mill and formed into a plate having a thickness of 2 mm by a cooling press. Table 2 shows the results of measuring the reflection intensity at 600 nm using a color difference meter (manufactured by Hunter, USA).

[0019]

[Table 2]

[Example 3] Dispersant C 20% Titanium oxide "Taipec CR-80" (manufactured by Ishihara Sangyo Co., Ltd.) 50% Carbon black "Mitsubishi Carbon MA-100" (manufactured by Mitsubishi Kasei Co., Ltd.) 5% Polyethylene "Sumikasen" G-808 "(manufactured by Sumitomo Chemical Co., Ltd.) 25% The above four components were kneaded with a kneader and pelletized in the same manner as in Example 1 to obtain a masterbatch. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Next, MFR: 6.5 polyethylene "Hi-Zex 2100J" (Mitsui Petrochemical Co., Ltd.) 100
3 parts of the obtained masterbatch was mixed with parts by weight and molded into a plate with a back pressure of 0 kg / cm ² using an injection molding machine.

[Comparative Example 3] A masterbatch was obtained in the same manner as in Example 3 except that polyethylene wax "Sun Wax 131P" (manufactured by Sanyo Chemical Industry Co., Ltd.) was used in place of the dispersant C. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Then, a plate molded product was obtained in the same manner as in Example 3. [Example 4] A masterbatch was obtained in the same manner as in Example 3 except that the dispersant C was replaced with the dispersant D. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Then, a plate molded product was obtained in the same manner as in Example 3.

[Comparative Example 4] Dispersant C was 10% polyethylene wax "Sun Wax 131P" and styrene-butadiene-styrene copolymer "Califlex TRKX138S".
A masterbatch was obtained in the same manner as in Example 3 except that 10% (manufactured by Shell Chemical Co.) was used. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Then, a plate molded product was obtained in the same manner as in Example 3.

[Example 5] Dispersant E 20% Titanium oxide "Ty Pure R-101" (manufactured by EI DuPont) 20% Rouge "Toda Color 180ED" (manufactured by Toda Kogyo Co., Ltd.) 40% Polypropylene "Mitsui High Pole J740" ( Mitsui Petrochemical Co., Ltd.) 20% The above four components were kneaded with a three-roll mill, and a masterbatch was obtained in the same manner as in Example 1. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Then, 100 parts of a polyethylene composition "Sunlet TA-120" (manufactured by Mitsui Petrochemical Industry Co., Ltd.) containing 20% of talc was mixed with 3 parts of the obtained masterbatch, and plate molding was carried out in the same manner as in Example 3. I got the goods.

[Comparative Example 5] Polypropylene wax "Viscor 550P" 30% (manufactured by Sanyo Kasei Co., Ltd.) Titanium oxide "TIPURE R-101" (manufactured by EI DuPont) 20% Bengal "Toda Color 180ED" (manufactured by Toda Kogyo Co., Ltd.) ) 40% polypropylene "Mitsui Highpole J740" (manufactured by Mitsui Petrochemical Co., Ltd.) 10% The above four components were kneaded with a three-roll mill to obtain a masterbatch in the same manner as in Example 1. A pulsating flow was generated, and it was not possible to continuously and smoothly obtain a good masterbatch having a pellet shape. Then, a plate molded product was obtained in the same manner as in Example 5.

Table 3 shows the results of evaluations of the retention rate of mechanical properties, the color unevenness on the surface of the molded product, the degree of pigment dispersion, and the productivity of the masterbatch of the obtained plate molded product.
The evaluation method and evaluation criteria are shown below. Retention rate of mechanical properties: Retention rate of mechanical properties of resin colored with master batch (○: 96% or more, △: 90% to 96%, relative to mechanical properties of uncolored resin (100%). ×: 90% or less) Color unevenness of molded product: Visual judgment (○: No color unevenness, △: Some color unevenness, ×: Marked color unevenness) Masterbatch ： Productivity by extruder with screw diameter 65 mm Productivity ( ○: Good, ×: Bad)

Pigment dispersity: Polypropylene “Mitsui Noblene
J4HG ”100 parts by weight and 3 parts of masterbatch were kneaded, and the mixture was pressed under the condition of 170 ° C.
A film having a thickness of The number of particles of pigment of 1 μ or more and 50 μ or less in the film was measured with an image processor “Luzex 450” (manufactured by Toyo Ink Mfg. Co., Ltd.). (5: 1.0 × 10 ³ pieces / cm ² or less 4: 1.0 × 10 ³ to 7.0 × 10 ³ pieces / cm ² 3: 7.0 × 10 ³ to 2.7 × 10 ⁴ pieces / cm ² 2: 2.7 × 10 ⁴ to 7.0 X 10 ⁴ pieces / cm ² 1: 7.0 x 10 ⁴ pieces / cm ² or more)

[0027]

[Table 3]

[0028]

INDUSTRIAL APPLICABILITY The coloring resin composition of the present invention is excellent in pigment dispersibility even though it has a very high pigment content, and is suitable for coloring textile products requiring a high degree of pigment dispersion. It exerts a great effect on coloring power and workability. Further, conventionally, for the coloring of a polyolefin-based resin composition containing a high content of an inorganic filler or a fiber reinforcement in which physical properties such as mechanical properties and heat resistance, which were difficult to be uniformly colored by a masterbatch, are particularly important. However, it is extremely effective and can be colored without color unevenness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junichi Suzuki 2-13-3 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd.

Claims (2)

[Claims] 1. A coloring resin composition containing a pigment, a dispersant, and a thermoplastic resin as main components, wherein the dispersant is a long-chain alkyl primary alcohol represented by the following chemical structural formula: A coloring resin composition. R; H or CH ₃ x; 27 to 47 (average) 2. The thermoplastic resin has a melt flow rate of 0.1.
The coloring resin composition according to claim 1, wherein the coloring resin composition is a polyolefin resin in the range of 400 to 400.