JP2861589B2 - Composition for coloring - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition for coloring a thermoplastic resin (masterbatch).

2. Description of the Related Art Conventionally, polyolefin resin coloring compositions include a powdery dry color obtained by mixing a pigment and a dispersant, a liquid color or paste color obtained by dispersing a pigment in a liquid dispersant at ordinary temperature, Pellet, flake, or bead-shaped master batches in which a pigment is dispersed in a resin that is solid at room temperature are available. These coloring compositions and their uses are properly used depending on their characteristics, but masterbatches are preferably used from the viewpoint of easy handling and preservation of the working environment during use. However, with the precision and speeding up of molding of polyolefin resin, the performance of the masterbatch is such that the pigment concentration is high and the influence on various physical properties such as heat resistance and strength of the thermoplastic resin to be colored is small. At the same time, pigment dispersibility and dispersibility have been required more than before.

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, For example, one kind or two or more kinds of an acid-modified product and a wax made of the acid-modified product are generally used.
However, when a high degree of pigment dispersion is required, for example, when a thermoplastic resin is spun at a high speed of several tens of microns or formed into a film, the above dispersant may not be satisfied. That is, yarn breakage during spinning due to poor pigment dispersion, clogging of a filter of a melt spinning machine, molding failure in a film, and the like occur. 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 high-power kneader, but they have not exhibited sufficient pigment dispersing ability.

[0003] Further, in the field of large-sized injection molding in which colored pellets have been conventionally used, coloring with a master batch has increased, and color unevenness and flow marks have become a problem in coloring of molded products. In blow molding and film molding, which have been conventionally colored with a masterbatch, plasticization, mixing and kneading of the resin and the masterbatch are performed in the extruder portion of the molding machine.In the case of injection molding, plasticization and mixing are performed. And the kneading is performed in the retreating cylinder of the screw. However, the kneading force is not sufficient compared to the extruder, and the kneading force has become smaller with the shortening of the molding cycle and the lower viscosity of the molding resin, and as a result, color unevenness tends to occur on the surface of the molded product. Have been. in addition,
This reduction in the amount of masterbatch added to the resin to be colored due to the emergence of the so-called high-concentration masterbatch, which has increased the pigment content of the masterbatch, which has been promoted for the purpose of reducing the cost of coloring, has resulted in color unevenness and flow marks. Is becoming more likely to occur.

[0004] This problem is observed in various thermoplastic resins, but is remarkable in polypropylene-based resins which have been increasingly used in home electric appliances and automobile parts, and an urgent solution has been demanded. To solve this problem, master batch 3
By increasing the content of the dispersant among the components (pigment, dispersant and base resin), or by lowering the melt viscosity of the masterbatch by using a base resin that is smaller than the viscosity of the resin to be colored, Elimination of unevenness has been performed. However, for example, those filled with an inorganic filler with a polypropylene-based resin or those having a melt flow rate of more than 25 for the purpose of thin-wall molding are likely to cause color unevenness and flow marks, and the solution of the problem is awaited. I have.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned various disadvantages and improves the strength of mechanical properties such as tensile strength, bending strength and impact strength even when coloring a polyolefin resin. An object of the present invention is to provide a thermoplastic resin coloring composition (master batch) which is excellent in pigment dispersibility and does not cause color unevenness, and does not impair physical properties of at least%.

[0006]

That is, the present invention provides a pigment (a) having 1 to 90% by weight, 1-decene, 1-dodecene,
1-tetradecene, 1-hexadecene, 1-octadece
, 1-eicosene, 1-docosene, 1-tetracosene
, 1-hexacocene, 1-octacocene, 1-tria
Content, 1-Dotria content, 1-tetratoacon
Ten, 1-hexatriaconten, 1-octatriako
Content, selected from among 1-tetraconten
And one or more monomers (1) and maleic anhydride
A polymer resin or derivative thereof with a molecular weight of 5000
(B) 5 to 50 weight in the range of up to 500,000
%, Melt flow rate (hereinafter, referred to as MFR) is 0.
A composition for coloring a thermoplastic resin, comprising a polyolefin or its derivative (c) in the range of 1 to 300 by 0 to 50% by weight.

In the present invention, pigments (a) 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-based, anthraquinone-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, dioxane-based, berylen-based, quinophthalone-based, and verinone-based pigments, cadmium sulfide, cadmium selenide, ultramarine, Titanium dioxide, iron oxide, chromate oxide,
There are inorganic pigments such as carbon black.

In the present invention, the monomer (1) and the anhydrous monomer
The copolymer resin (b) with oleic acid has a molecular weight of 5000
~ 500,000, preferably 10
It is a copolymer in the range of 000 to 200,000. If the molecular weight exceeds 500,000 , the workability of the master batch becomes a problem, and color unevenness tends to occur in the molding resin. On the other hand, if the molecular weight is less than 5000, a problem arises in the suitability of the masterbatch for granulation, and the pigment dispersibility is not so good.

The monomer used in the present invention (1)
Commercially available products include Dialen 208 (C20-28) and Dialen 30 (C30 or more) (Mitsubishi Chemical Corporation).

Copolymer of monomer (1) and maleic anhydride
The union (b) can be produced by solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or the like, but is not particularly limited in these polymerization methods and reaction operations. Examples of the polymerization initiator include peroxides such as benzoyl peroxide, lauryl peroxide, cumene oxide, diisopropyl peroxycarbonate, di-tert-butyl peroxide, t-butyl peroxybenzoate, and azobis. Isobutyronitrile, azobis-
An azo compound such as 2,4-dimethylvaleronitrile is exemplified.

Copolymer of monomer (1) and maleic anhydride
The compound (b) is obtained by esterifying a carboxyl group based on a carboxylic anhydride in the copolymer with a compound having at least one or more hydroxyl group in the molecule and amidating with a compound having at least one or more amino group in the molecule. Alternatively, modification such as imidation may be performed. By the modification, various physical properties such as acid value, molecular weight, viscosity, softening point, strength, various resistances, flexibility, compatibility and pigment dispersibility can be freely controlled.

The hydroxide used for the esterification is not particularly limited as long as it has one or more hydroxyl groups in the molecule, and examples thereof include methanol and ethanol.
, Propanol, isopropanol, butanol, se
c-butanol, tert-butanol, pentanol, amyl alcohol, hexanole, heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol −
And cetyl alcohol, stearyl alcohol, oleyl alcohol, α-oxybutyric acid, 12-hydroxystearic acid and the like, and mixtures thereof.

The amino compound used for amidation and imidation is not particularly limited as long as it has one or more amino groups in the molecule. Examples thereof include methylamine, ethylamine and propylamine. Isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, aniline, o-toluidine, 2-ethylaniline,
2-fluoroaniline, o-anisidine, m-toluidine, m-anisidine, m-phenetidine, p-toluidine, 2,3-dimethylaniline, 5-aminoindane,
Aspartic acid, glutamic acid, γ-aminobutyric acid, and the like, and mixtures thereof.

These reactions may be carried out in an aqueous system, without a solvent, or in combination with a solvent, but the acid value of the reaction product is preferably in the range of 5 to 500, preferably 20 to 100. If the acid value is less than 5, good pigment dispersibility and coloring property are hardly obtained, and color unevenness and flow mark are liable to occur in the colored molded article. On the other hand, if the acid value exceeds 500 , it easily absorbs moisture and causes not only silver stroke and foaming on the surface of the molded product, but also adversely affects the weather resistance and heat resistance of the resin to be colored.

Polyolefin or its derivative (c)
Has an MFR of 0.1 to 300, preferably 10 to 10
It is not particularly limited as long as it is in the range of 0 and is compatible with the resin to be colored. The MFR is an MFR measured according to JIS K7210. MFR of polyolefin or its derivative used for compounding
When is less than 0.1, the compatibility with the resin to be colored becomes poor,
In addition to causing color unevenness, various physical properties of the colored thermoplastic resin are adversely affected. When the MFR exceeds 300, the mechanical strength and heat resistance of the masterbatch itself become low, making the production of the masterbatch difficult.
It adversely affects various physical properties such as heat resistance and strength of the colored thermoplastic resin. The polyolefin or derivative derived from functional group modification, crosslinking modification, grafting and blocking modification used in the compounding may be in the form of powder or pellet. To the coloring composition of the present invention, a small amount of various additives such as a stabilizer such as an antioxidant and an ultraviolet absorber and a surfactant can be added as long as the effects of the present invention are not impaired.

The coloring composition of the present invention can be used for coloring almost all polyolefin resins, and contains a reinforcing material such as an inorganic filler, glass fiber or organic fiber for the purpose of improving physical properties. May be. For example, uniform coloring without color unevenness without affecting mechanical properties such as strength or heat resistance, which was not possible with coloring using a conventional masterbatch, can be achieved with inorganic fillers and fiber reinforcing materials up to 50%.
It can be realized by adding a small amount of 4 parts by weight or less of the coloring composition of the present invention to 100 parts by weight of the polyolefin resin composition containing about 10% by weight. The coloring composition of the present invention may be, in addition to polyolefin resin, polymethylpentene, polybutene-1, polystyrene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) resin And acrylonitrile-EPDM-styrene (AES) resin, acrylic resin, polyamide, polycarbonate, polyacetal, and thermoplastic resin such as polyurethane. The coloring composition of the present invention is extremely effective in improving the dispersibility and coloring power of the pigment, but the improvement in dispersibility and coloring power depends on the affinity for the pigment due to the carboxyl group or its anhydride in the copolymer. A polar bond is formed between the carboxyl group or its anhydride in the copolymer and the basic group in the pigment, and the surroundings take on a protective colloidal structure surrounded by polyolefin. It is thought that there is. The monomer (1) of the present invention
The copolymer (b) of and maleic anhydride can also be used for applications such as lubricants, hot melt resins, inks, paints, and adhesives.

[0017]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples. In the examples, “parts” means “parts by weight” and “%” means “% by weight”. [Production Example 1] 757.4 g of 1-octadecene, 2.7 g of di-t-butyl peroxide, and 10 g of toluene were charged into a flask and purged with nitrogen. Then, while heating and stirring at 150 ° C., 294.2 g of maleic anhydride was added every 2 minutes. 9.8 g and 2.1 g of di-t-butyl peroxide were added every 20 minutes, 0.7 g each.
After the addition was completed, the temperature of the system was maintained at 160 ° C., and the reaction was further performed for 6 hours. After the completion of the reaction, the content was taken out with heating, cooled and solidified to obtain a resin having an acid value of 320.

[Production Example 2] 1276 g of Dialen 208 (manufactured by Mitsubishi Chemical Corporation), 3.6 g of di-t-butyl peroxide,
After charging 14 g of toluene into a flask and purging with nitrogen, 150 g
While heating and stirring at ℃, 13.7 g of maleic anhydride and 11.8 g of di-t-butyl peroxide were added every 2 minutes.
0.9 g was added every 0 minutes. After the addition is complete,
1 g of butyl peroxide was added, the temperature of the system was maintained at 160 ° C., and the reaction was further performed for 6 hours. After the completion of the reaction, the content was taken out with heating, cooled and solidified to obtain a resin having an acid value of 234. [Production Example 3] 200 g of the resin obtained in Production Example 1 and 34.0 g of cyclohexylamine were charged into a flask, melted in a nitrogen stream with stirring, and reacted at a reaction temperature of 180 ° C for 5 hours.
After the completion of the reaction, the content was taken out with heating, cooled and solidified to obtain a resin having an acid value of 108.

Production Example 4 200 g of the resin obtained in Production Example 2
74.7 g of stearylamine was charged into a flask, melted in a nitrogen stream while stirring, and reacted at a reaction temperature of 180 ° C. for 5 hours. After the completion of the reaction, the contents were taken out while heating, cooled and solidified to obtain a resin having an acid value of 71.9. [Production Example 5] 200 g of the resin obtained in Production Example 1 and 64.0 g of benzyl alcohol were charged into a flask, melted in a nitrogen stream with stirring, and reacted at a reaction temperature of 180 ° C for 5 hours.
After the completion of the reaction, the content was taken out with heating, cooled and solidified to obtain a resin having an acid value of 91. [Production Example 6] 100 g of the resin obtained in Production Example 3 and 1.5 g of stearylpropylenediamine were charged into a flask, melted in a nitrogen stream while stirring, and reacted at a reaction temperature of 180 ° C for 3 hours. After the completion of the reaction, the content was taken out with heating, cooled and solidified to obtain a resin having an acid value of 50.

[Production Example 7] 100 g of the resin obtained in Production Example 5 and 3.
7 g was charged into a flask, melted in a nitrogen stream while stirring, and reacted at a reaction temperature of 180 ° C. for 3 hours. After the reaction is completed, the contents are taken out when heated, cooled, solidified, and acid value
42 resins were obtained.

[0021]

[0022]

Example 1 Resin obtained in Production Example 1 30% Phthalocyanine Blue "Lionoble-7110V" 50% (manufactured by Toyo Ink Mfg. Co., Ltd.) Polypropylene "Mitsui Noblen J4HG" 20% (Mitsui Petrochemical Industries, Ltd.) (MFR: 30 manufactured by K.K.) The above three components were kneaded with a three-roll mill, and the screw diameter was adjusted.
A master batch was obtained by pelletizing with a 65 mm extruder. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of polypropylene “Mitsui Noblen J4HG” was mixed with 3 parts of the obtained masterbatch, and the mixture was placed under a hopper with a vertical test spinning machine (Fuji Filter Co., Ltd. spinning tester).
After spinning at 30 ° C., a kneading section and a die section at 230 ° C., drawing was performed three times to obtain a 5-denier polypropylene fiber. Spinnability,
Good dispersibility was exhibited without any problem in both clogging and stretching properties.

Comparative Example 1 A masterbatch was obtained in the same manner as in Example 1 except that polypropylene wax “VISCOL 550” (manufactured by Sanyo Chemical Industries, Ltd.) was used instead of the resin obtained in Production Example 1. Was. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Further, spinning was performed in the same manner as in Example 1 using the obtained master batch, but yarn breakage due to clogging occurred. In order to compare the clogging property of the undispersed pigment, the masterbatch obtained in Example 1 and Comparative Example 1 was used.
10 parts of polypropylene “Mitsui Noblen J4
HG ”100 parts, 3 kg of the mixture with a single screw extruder with a screw diameter of 30 mm equipped with a wire mesh of 500 mesh at the tip
It extruded and the pressure rise value in the front-end | tip part was measured. In order to compare the dispersive color development of the pigment, 1 part of the master batch obtained in Example 1 and Comparative Example 1 was mixed with 100 parts of polypropylene “Mitsui Noblen J4HG” and 5 parts of titanium oxide, respectively. The mixture was kneaded with this roll mill, formed into a plate having a thickness of 2 mm by a cooling press, and the reflection intensity at 600 nm was measured with a color difference meter (manufactured by Hunter, USA). Table 1 shows the results.

[0025]

[Table 1]

Example 2 Resin obtained in Production Example 2 30% Titanium oxide "Taipek CR-80" (manufactured by Ishihara Sangyo Co., Ltd.) 50% Carbon black "Mitsubishi Carbon MA-100" 5% (Mitsubishi Kasei Polyethylene “Sumikasen G-808” (manufactured by Sumitomo Chemical Co., Ltd.) 15% The above four components were kneaded with a kneader, and pelletized with an extruder having a screw diameter of 65 mm to obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Three parts of the obtained master batch was mixed with 100 parts of polyethylene "HIZEX 2110J" (manufactured by Mitsui Petrochemical Co., Ltd.) having an MFR of 6.5, and formed into a plate with an injection molding machine at a back pressure of 0 kg / cm ² . .

Comparative Example 2 Instead of the resin obtained in Production Example 2, polyethylene wax "Sunwax 165P" was used.
A master batch was obtained in the same manner as in Example 2 except that (manufactured by Sanyo Chemical Industries, Ltd.) was used. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of the polyethylene composition used in Example 2 was mixed with 3 parts of the obtained master batch and molded into a plate with an injection molding machine at a back pressure of 0 kg / cm ² .

Examples 3 to 5 Resins obtained in Production Examples 3 to 5 40% Titanium oxide "Typure R-101" (manufactured by EI Dupont) 20% Red handle "Todacolor 180ED" (Toda Kogyo Co., Ltd.) Co., Ltd.) 40% The above three components are kneaded with a three-roll mill, and the screw diameter is adjusted.
Pelletization was performed using a 65 mm extruder to obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of a polyethylene composition containing 20% of talc was mixed with 3 parts of the obtained master batch, and the back pressure was 0 kg / cm by an injection molding machine.
Formed into plates at ² .

[Comparative Example 3] Polypropylene "Mitsui Hypol J740" (manufactured by Mitsui Petrochemical Co., Ltd.) 10% Polypropylene wax "Viscol 550P" (manufactured by Sanyo Chemical Industries, Ltd.) 30% Titanium oxide "Typure R-101" (Manufactured by EI Dupont Co., Ltd.) 20% Red handle "Todacolor 180ED" (manufactured by Toda Kogyo Co., Ltd.) 40%
An attempt was made to obtain a master batch by pelletizing with a 65 mm extrusion molding machine, but at this time strand breaks and pulsation occurred, and it was not possible to obtain a master batch having a good pellet shape continuously and smoothly. As in Examples 3-5, talc
To 100 parts of a polyethylene composition containing 20%, 3 parts of the obtained master batch was mixed, and a back pressure of 0 part was injected using an injection molding machine.
It was molded into a plate at kg / cm ² .

[ Examples 6 to 7] Resin obtained in Production Examples 6 to 7 40% Titanium "Typure R-101" (manufactured by EI Dupont) 20% Petal "Todakara-180ED" (Toda 40% The above three components are kneaded with a three-roll mill, and the screw diameter is adjusted.
The mixture was pelletized by a 65 mm extruder to obtain a master batch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. 100 parts of a polyester composition containing 20% of talc was mixed with 3 parts of the obtained master batch, and the back pressure was 0 kg / cm by an injection molding machine.
^The plate was molded in ² .

[0031]

[0032]

[0033]

Table 2 summarizes the results of evaluating the mechanical properties, surface color unevenness and pigment dispersity of the molded articles obtained in Examples 2 to 7 and Comparative Examples 2 and 3, and the productivity of the master batch.

[0035]

[Table 2]

* 1 Mechanical properties of uncolored resin (100
%), The retention of the mechanical properties of the resin colored with the masterbatch. : 96% or more Δ: 90 to 96% ×: 90% or less * 2 Color unevenness on the surface of the molded product was visually evaluated. ○: no color unevenness △: slight color unevenness ×: remarkable color unevenness * 3 A kneaded mixture of 100 parts of the resin to be colored and 3 parts of the master batch was pressed at a press temperature of 170 ° C.
A film having a thickness of 0.1 mm was obtained. In the obtained film,
The size and number of the coarse particles of the pigment were measured with a Luzex450 image processor (manufactured by Toyo Ink Co., Ltd.). 5: Number of particles of 50 μ or less 1.0 * 10 ³ particles / cm ² or less 4: Number of particles of 50 μ or less 1.0 * 10 ^{3 to} 7.0 * 10 ³ particles / cm ²
cm ² 3: 50μ or less of the number of particles 7.0 * 10 ³ to 2.7 * 10 ⁴ cells /
cm ² 2: Number of particles of 50 μ or less 2.7 * 10 ^{4 to} 7.0 * 10 ⁴ particles /
cm ² 1: Number of particles of 50 μ or less 7.0 * 10 ⁴ particles / cm ² or more * 4 Productivity of master batch by an extruder having a screw diameter of 65 mm. : Good ×: bad

[0037]

The composition for coloring a thermoplastic resin of the present invention comprises:
Despite having a very high pigment content, it has excellent pigment dispersibility, and exerts a great effect on the coloring power and processability in coloring textiles that require a high degree of pigment dispersion. Also, conventionally, it was difficult to uniformly color the master batch, physical properties such as mechanical properties and heat resistance, which is particularly important for the coloring of polyolefin-based resin compositions containing a high content of inorganic fillers and fiber reinforcements. This is extremely effective, and coloring without unevenness in color can be achieved.

Continuation of the front page (56) References JP-A-6-500143 (JP, A) JP-A-2-91160 (JP, A) JP-A-58-108240 (JP, A) JP-B-50-5018 (JP, A) , B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 23/00-23/36, 35/00

Claims (1)

(57) [Claims] 1 to 90% by weight of a pigment (a), 1-decene, 1-dodecene, 1-tetradecene, 1-f
Xadecene, 1-octadecene, 1-eicosene, 1-
Dococene, 1-tetracocene, 1-hexacocene, 1-
Octacocene, 1-triaconten, 1-dotriacon
Ten, 1-tetratoaconten, 1-hexatriacon
Ten, 1-octatriconten, 1-tetraconten
At least one or more monomers selected from
(1) Copolymer resin of maleic anhydride or its derivative
Conductor whose molecular weight is in the range of 5,000 to 500,000
(B) 5 to 50% by weight of a polyolefin or a derivative thereof having a melt flow rate in the range of 0.1 to 300 (c) 0 to 50% by weight for coloring a thermoplastic resin. Composition.