JPH02281046A - Colorant composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition for finely powdery thermoplastic synthetic resin having excellent adhesion to pellet resin, dispersibility, etc., free from scattering even in the case of possession of a large amount of dye or pigment by blending a specific high-density polyethylene wax with pigment or oil-soluble dye. CONSTITUTION:10 to 90 pts.wt. high-density polyethylene wax having 2,000 to 8,000 number-average molecular weight, 100 to 130 deg.C melting point and 0.93 to 0.97g/cm<2> density prepared by high-pressure radical polymerization method is blended with 90 to 10 pts.wt. high-density pigment or oil-soluble dye (preferably 30 to 85 pts.wt.:70 to 15 pts.wt.) and optionally a filler, an antioxidant, etc., kneaded by a blender under heating, cooled to normal temperature and ground to give the objective composition. Polyamide resin, polyethylene terephthalate resin, etc., may be cited as the thermoplastic synthetic resin to be colored by the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a colorant composition for thermoplastic synthetic resins. More specifically, the present invention provides a thermoplastic synthetic resin in the form of a fine powder that is non-scattering even with a high dye and pigment content and has good adhesion to pellet resin, dispersibility, color development stability, and color mixing properties. The present invention relates to a colorant composition.

<Prior art> There are various types of colorants used for coloring thermoplastic synthetic resins. For example, various colorants such as raw pigment type, dry color type, masterbatch type, and master powder type are in practical use. It is provided.

<Problems to be Solved by the Invention> Raw pigment type colorants are highly scattering and contaminate equipment, and lack uniformity in dispersion, causing poor appearance and poor physical properties.

Dry color type colorants are simply a mixture of dyes and pigments with metal soaps, waxes, inorganic powders, etc., and are difficult to use in applications that require a high degree of dispersion. It also has the disadvantage of contaminating the Masterbatch type colorants are made by kneading dyes and pigments into thermoplastic synthetic resins, and have the disadvantage that the thermoplastic synthetic resins that can be colored are limited and the properties of the thermoplastic synthetic resins that are colored are reduced. There is.

Conventional master powder type colorants are produced by, for example, kneading and dispersing dyes and pigments in low-density polyethylene wax, and then crushing this. J is left behind. However, in this case, if a known pulverizer such as an atomizer is used for pulverization, gelation occurs inside the pulverizer and it is difficult to form a fine powder, so a special pulverizer such as a frozen pulverizer must be used. . Furthermore, when the dye and pigment content is extremely high in order to improve the crushability, there is a problem with the dispersibility during molding.

As mentioned above, currently known colorants cannot be used in a wide range of applications due to their respective drawbacks.

<Means for Solving the Problems> In view of the above-mentioned drawbacks, the present inventors have developed a method for coloring thermoplastic synthetic resins that can be easily pulverized and has no scattering property even if the dye and pigment content is high. No adhesion to pellet resin,
Dispersibility 1: Good color development stability and color mixing properties, does not deteriorate processability during molding, does not deteriorate the physical properties of molded products,
As a result of intensive research to obtain a coloring agent that is convenient to handle and versatile, we obtained a coloring agent with a number average molecular weight of 2000 to 5000, a melting point of 100 to 130°C, and a density of 0.93 to 0.97 g/am, which was obtained by high-pressure radical polymerization. A composition comprising 90 to 10 parts by weight of a pigment or oil-soluble dye to 10 to 90 parts by weight of high-density polyethylene wax can be uniformly mixed and dispersed under heating and pulverized at room temperature, and The present inventors have discovered that a fine powder coloring agent that does not have the above-mentioned drawbacks can be obtained, and have completed the present invention.

Any pigment or oil-soluble dye used in the present invention can be used satisfactorily as long as it is suitable for coloring thermoplastic synthetic resins. For example, organic pigments include monoazo, polyazo, phthalocyanine, quinacridone, and other heterocyclic pigments, and inorganic pigments include carbon black, titanium oxide, Bengara, ultramarine,
Examples include yellow lead, barium sulfate, and fired pigments. Examples of oil-soluble dyes include monoazo dyes, disazo dyes, anthraquinone dyes, perinone dyes, and other heterocyclic dyes. The above-mentioned pigments or oil-soluble dyes are used after selecting suitability according to the purpose of use, such as light resistance, weather resistance, heat resistance, chemical resistance, and migration resistance.

The polyethylene wax used in the present invention is obtained by high-pressure radical polymerization and has a number average molecular weight of 2000 to 5.
ooo, melting point 100-130°C, density 0.93-0.9
7g/cm2, preferably number average molecular ff13000~
6000, melting point 105-125°C, density 0.94-0.
': J6g/cm2 high density polyethylene wax.

It is particularly important that the polyethylene wax used in the present invention be produced by a high-pressure radical polymerization method. The purpose of the invention cannot be achieved.

In this polyethylene wax, the number average molecular weight is 2
If the density is less than 0.000, the density is less than 0, 93 g/am2, or the melting point is less than 105°C, it is difficult to pulverize it at room temperature using an atomizer or the like. In addition, the number average molecular weight is 8000
If the melting point is higher than 130°C, the performance as a polyethylene wax may be impaired and the properties of the thermoplastic synthetic resin to be colored may be reduced. Dispersion of pigments or oil-soluble dyes becomes difficult.

The weight ratio of the pigment or oil-soluble dye to the high-density polyethylene wax obtained by high-pressure radical polymerization in the colorant composition of the present invention is 10 to 90 parts by weight: 90 to 1
It is 0 parts by weight. If the weight ratio of the pigment or oil-soluble dye is less than the above lower limit, it will be difficult to pulverize it at room temperature with an atomizer, etc. If it is more than the above upper limit, the fluidity will decrease during heating and kneading, and the pigment or oil will be mixed. Since it may cause poor dispersion of the soluble dye, the amount is preferably 30 to 85 parts by weight or 0 to 15 parts by weight.

Although the colorant composition of the present invention has the above two components as essential components, fillers such as calcium carbonate, clay, and talc, antioxidants, ultraviolet absorbers, etc. may be added as necessary. I can bring it.

The colorant composition of the present invention can be prepared by, for example, heating and kneading all the components in a kneading machine such as a three-roll mill, kneader, or Banbury mixer, cooling to room temperature, and using a known pulverizer, for example, using a screen with a diameter of 1 rm. It can be easily produced by pulverizing it with an atomizer equipped with.

Thermoplastic synthetic resins colored by the colorant composition of the present invention are mainly engineering plastics, such as polyamide resins (for example, nylon 6.66.610.11.12.46), polybutylene, etc. Terephthalate resins, polyethylene terephthalate resins, polyoxymethylene resins, polyphenylene ether resins, etc., and their mutual blends are preferred <Effects of the Invention> The above engineering plastics have mechanical properties,
Due to its excellent heat resistance, its uses have expanded in recent years, and the need for coloring has increased accordingly. In addition, the masterbatch type had a lack of versatility because the coloring agent had to be made separately for each resin.

The colorant composition of the present invention solves the various problems mentioned above, has no scattering property even at high dye and pigment contents, and has good adhesion to pellet resin, dispersibility, color stability, and color mixing properties. It shows excellent effects and can be widely used in a wide range of resins.

<Examples> The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, parts in Examples and Comparative Examples represent parts by weight.

Example 1 50 parts of copper phthalocyanine blue, polyethylene wax (AH-6 wax BASF, molecular weight 6000, melting point 1)
15-122℃, density 0.94-0, 96g/cm"
, high-density type) and 0.1 part of an antioxidant (Sumilizer BPIOI) were mixed, heated and kneaded in a three-roll mill, cooled, and then milled in a pulverizer (atomizer) equipped with a screen of diameter Im. Grind at room temperature using
A finely powdered non-colorant composition that passed through 32 meshes was obtained. When 10 parts of the obtained composition and 500 parts of polybutylene terephthalate resin pellets (Toshi PBT1400L) were mixed in a small blender, the adhesion to the resin was good, and when molded into a plate with a direct injection molding machine, 1 dispersion was achieved. A molded product with good properties and uniform coloring was obtained.

Example 2 In Example 1, AH-3 wax BASF (molecular weight 3000, melting point 1
05-112℃, density 0.94-0, 95g/cm"
A finely powdered non-colorant composition was obtained in the same manner as in Example 1, except for using a high-density type polyethylene wax. When 10 parts of the obtained composition and 500 parts of nylon resin pellets (Unitika Nylon A1030BRL) were mixed in a small blender, the adhesion to the resin was good, and when molded into a plate with a direct injection molding machine, the dispersibility was good. A good and uniformly colored molding was obtained.

Comparative Example 1 In Example 1, A I-I-6 wax 15ASF
Instead, use Mitsui Petrochemical High Wax 600P (polyethylene wax produced by medium/low pressure anionic polymerization, molecular weight 5700, melting point 139°C, density 0°97g/cm)
A finely powdered non-colorant composition was obtained in the same manner as in Example 1 except that the composition was changed to a high-density type. When the obtained composition was molded into a plate in the same manner as in Example 1, the dispersibility was poor (compared to the plate obtained in Example 1, only 70% of the coloring strength was obtained).

Example 3 40 parts of carbon black, AH-6 wax BASF3
0 parts of AH-3 wax BASF, and 001 parts of Sumilizer BPIOI were mixed, heated and kneaded in a Banbury mixer, and then cooled to obtain a finely powdered non-colorant composition in the same manner as in Example 1. The obtained composition was prepared in Example 1.
When molded into a plate in the same manner as above, a molded product with good dispersibility and uniform coloring was obtained.

Example 4 80 parts of titanium oxide, 20 parts of AH-6 wax BAS F, and 1 part of Sumilizer BPIOI O were mixed,
After heating and kneading with a kneader, the mixture was cooled, and the same procedure as in Example 1 was carried out to obtain a finely powdered non-colorant composition. When the obtained composition was molded into a plate in the same manner as in Example 1, a uniformly colored molded product with good dispersibility was obtained.

Example 5 85 parts of titanium yellow, 15 parts of AH-6 wax BASF, and 0.1 part of Sumilizer BPIOI were mixed,
A finely powdered non-colorant composition was obtained in the same manner as in Example 1. When the obtained composition was molded into a plate in the same manner as in Example 1, a uniformly colored molded product with good dispersibility was obtained.

Comparative Example 2 In Example 5, A wax BASF (polyethylene wax produced by high-pressure radical polymerization method, molecular weight 5000, melting point 97-10) was used instead of AH-6 wax BASF.
When the same operation as in Example 1 was performed except that the temperature was changed to 3℃, density 0.91 to 0.93 g/cm2, low density type), the composition gelled inside the pulverizer, resulting in a finely powdered non-colorant composition. Comparative Example 3 In Example 5, instead of AH-6 wax BASF, Sanyo Chemical's Sunwax 165P (polyethylene wax produced by polyethylene decomposition method, molecular ff 15000,
Melting point: 107°C, density: 0.91g/cm2. When the same operation as in Example 1 was performed except that the powder was changed to a low-density type (low-density type), the composition gelled inside the pulverizer and a finely powdered non-colorant composition could not be obtained.

Example 6 Nylon resin pellets (Unitika Nylon A1030B
RL) 5000 parts, 10 parts of the colorant composition obtained in Example 1 (blue composition), 5 parts of the colorant composition obtained in Example 3 (black composition), the coloring obtained in Example 4 75 parts of the colorant composition (white acid compound) and 10 parts of the colorant composition (yellow composition) obtained in Example 5 were mixed in a super mixer, and the mixture was directly molded into a plate with an injection molding machine. , ■ The mixture is made into a color compound using a single-screw extruder, and then a plate is formed using an injection molding machine. ■ The mixture is made into a color compound using a twin-screw extruder, and then a plate is formed using an injection molding machine.
When comparing the three colored plates from ■ to ■ above,
A uniform gray plate with good color mixing properties and color development stability was obtained, with no hue difference observed.

Comparative Example 4 Nylon resin pellets (Unitika Nylon A1030B
RL) 5,000 copies of dry color with the composition shown in Table 1 (pigment and metal soap processed with an atomizer), blue 10
After mixing 5 parts of black, 75 parts of white, and 10 parts of yellow in a super mixer, three colored plates (■ to ■) were formed in the same manner as in Example 6, and when the colored plates were compared, it was found that the dispersibility was Unfortunately, there was a big difference in hue.

Table-1

Claims (2)

[Claims] (1) Number average molecular weight 2000 to 8000, melting point 100 to 130°C, density 0.
A finely powdered coloring agent composition for thermoplastic synthetic resins, comprising 90 to 10 parts by weight of a pigment or oil-soluble dye to 10 to 90 parts by weight of high-density polyethylene wax of 93 to 0.97 g/cm^2. thing. (2) The composition according to claim 1, wherein the thermoplastic synthetic resin is a polyamide resin, a polybutylene terephthalate resin, a polyethylene terephthalate resin, a polyoxymethylene resin, a polyphenylene ether resin, or the like.