JPH06256532A - Coloring composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition free from color unevenness, excellent in pigment dispersibility, processability, coloring ability and uniformity, useful for textile products etc., comprising a specific silicone-modified resin and pigment at specified proportion. CONSTITUTION:This coloring composition comprising (A) 0.1-99wt.% of a silicone-modified resin produced by addition reaction between (1) a thermoplastic resin having at least one unsaturated double bond in the molecular chain such as an olefinic resin and (2) a compound having silyl group (e.g. methyldichlorosilane), (B) 1-90wt.% of a pigment such as of azo base and, pref. (C) another thermoplastic resin 0.1-400 in melt flow rate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin coloring composition (masterbatch).

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 their uses, but master batches are preferably used from the viewpoints of easy handling and preservation of working environment during use. However, due to the precision and speeding up of molding of polyolefin resins, the high masterbatch performance has a high pigment concentration, and the small effect on physical properties such as heat resistance and strength of the thermoplastic resin to be colored. At the same time, pigment dispersibility and distributability have become more demanding than ever 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 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-mentioned dispersant may not be satisfied. That is, yarn breakage during spinning due to poor pigment dispersion,
The filter of the melt spinning machine may be clogged and the film may be defectively formed. To solve these problems,
Efforts have been made to improve the pigment dispersibility by improving the processing method of the masterbatch or by using a powerful kneader, but the pigment does not exhibit sufficient pigment dispersibility.

Further, in the field of large-sized injection molding where colored pellets have been conventionally used, coloring with a masterbatch has increased, and color unevenness and flow marks have become a problem in coloring a molded product. In blow molding and film molding, which have been colored by a masterbatch, plasticization, mixing and kneading of resin and masterbatch are performed in the extruder part of the molding machine, but in the case of injection molding, plasticization and mixing are performed. And the kneading is carried out in the cylinder where the screw retracts. However, the kneading force is not sufficient as compared with the extruder, and the kneading force is becoming smaller as the molding cycle is shortened and the viscosity of the molding resin is lowered, and as a result, color unevenness easily occurs on the surface of the molded product. Came. in addition,
The increase in pigment content of master batches, which has been promoted for the purpose of cost reduction of coloring, has reduced the amount of master batch added to the resin to be colored due to the advent of so-called high-concentration master batches. Has become more likely to occur.

Although this problem is recognized in various thermoplastic resins, it is remarkable in polypropylene 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
Of the components (pigment, dispersant and base resin), increase the content of the dispersant, or use a base resin with a viscosity lower than that of the resin to be colored to lower the melt viscosity of the masterbatch Unevenness has been eliminated. However, for example, those filled with an inorganic filler with a polypropylene-based resin, or those whose melt flow rate exceeds 25 for the purpose of thin-wall molding,
Color unevenness and flow marks are likely to occur, and the solution of problems is awaited.

[0005]

DISCLOSURE OF THE INVENTION The present invention has improved the above-mentioned various drawbacks, and when coloring a polyolefin resin, it has a strength of 5 for each mechanical strength such as tensile strength, bending strength and impact strength. The present invention provides a composition for coloring a thermoplastic resin (masterbatch) which does not impair the physical properties of not less than 100% and is excellent in pigment dispersibility and capable of uniform coloring without color unevenness.

[0006]

The present invention is directed to a thermoplastic resin having at least one unsaturated double bond in the molecular chain.
0.1 to 99% by weight of a silicon-modified resin (A) obtained by an addition reaction of (a) with a compound (b) having a silyl group and a pigment (B) 1
Provided is a composition for coloring a thermoplastic resin, which comprises ˜90% by weight.

The thermoplastic resin (a) having at least one unsaturated double bond in the molecular chain is not particularly limited,
For example, in the polyolefin system, crystalline or amorphous polypropylene containing a small amount of diene, low density or high density polyethylene, random / block or graft copolymer of ethylene / propylene, copolymer of α-olefin and ethylene or propylene. , Ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer,
Examples thereof include ethylene / ethyl acrylate copolymers, ethylene / acrylic acid copolymers, and low polymers obtained by thermal decomposition thereof. Further, in the α-olefin, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-dococene, 1-having 10 or more carbon atoms
Tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetracontene, etc. and mixtures and polybutene- Polymers such as 1, polypentene-1, poly-4-methylpentene-1 and the like can be mentioned. As a commercially available product, Dialen 208 (C
20-28), Dialen 30 (C30 or above) (Mitsubishi Kasei Co., Ltd.), VYBAR # 260 (C30 or above), VYBAR # 604
1 (C30 and above) (Petrolite Co., Ltd.) and others.

In addition to polyolefin resins, polymethylpentene containing a small amount of double bonds, polystyrene, polyvinyl chloride, polyethylene terephthalate and polydiene polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-EPDM. -Styrene (AES) resins, other acrylic resins containing a small amount of double bonds, thermoplastic resins such as polyamide, polycarbonate, polyacetal, polyurethane, etc., and one or more of these may be used. Resins are preferred.

The compound (b) having a silyl group is not particularly limited, but an organic silicon compound is preferable. More specifically, for example, methyldichlorosilane, ethyldichlorosilane, dimethylchlorosilane, bis (2-chloroethoxy) methylsilane, tris (2-chloroethoxy) silane, n-hexyldichlorosilane, diisopropylchlorosilane, dichlorosilane, and dichlorosilane. -T-butylchlorosilane,
Trichlorosilane, methylsilane, ethylsilane, dimethylsilane, diethylsilane, methyldimethoxysilane, dimethoxymethylsilane, methyldiethoxysilane, dimethylethoxysilane, diethoxysilane, trimethoxysilane, triethoxysilane, diethylmethylsilane, butyldimethylsilane, Di-t-butylmethylsilane, triethylsilane, trihexylsilane, cyclohexyldimethylsilane, methylphenylchlorosilane, phenyldichlorosilane, diphenylchlorosilane, n-hexylsilane, n-octylsilane, tri-n-octylsilane, tripropylsilane , Triisobutylsilane, triisopropylsilane, tripentyloxysilane, trihexylsilane, n-octadecylsilane, phenylsilane, methylphenyl Silane, dimethylphenylsilane, methylphenylvinylsilane, dimethylbenzylsilane, diphenylsilane, triphenylsilane,
(Phenylethynyl) dimethylsilane, 1,1,2-trimethyldisilane, 1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylsilyl) benzene, methyltris (dimethylsiloxy) silane, tris (trimethyl Siloxy) silane, phenyltris (dimethylsiloxy) silane, tetrakis (dimethylsiloxy) silane, tetramethyldisilazane, dimethylsilyldimethylamine, bis (dimethylamino) methylsilane, tris (dimethylamino)
Silane, tris (dimethylsilyl) amine, N, N-dimethylaminomethylethoxysilane, diacetoxymethylsilane, N, O-bis (dimethylsilyl) acetamide, allyldimethylsilane, cyclopropanesilane, 1,1,4,4 -Tetramethyldisilylethylene, cyclohexanesilane,
Pentamethyldisiloxane, tetramethylcyclotetrasiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane , 1,1,3,3-tetrakis (trimethylsiloxy) disiloxane, 1,1,3,3-tetramethyldisilazane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1 , 3,3,5,5,7,7-octamethyltetrasiloxane,
1,1,3,3,5,5-hepta? Methyltrisiloxane, 1,1,1,3,
5,7,7,7-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,2,3,4 Examples include 5,5,6-hexamethylcyclotrisilazane, α, ω-bis (hydrogen) polydimethylsiloxane, long-chain dimethylsiloxane oligomer, and oily or waxy substances having a silyl group.

Thermoplastic resin (a) having at least one unsaturated double bond in the molecular chain and a compound having a silyl group
The addition reaction with (b) is an application of a hydrosilylation reaction to an unsaturated double bond, which can be produced by a solution reaction, a solventless reaction, etc., but is not particularly limited in these reaction methods and operations. Not something. As the reaction catalyst, a transition metal catalyst or a radical initiator used in a usual hydrosilylation reaction can be used. Transition metal catalysts include platinum, cobalt, rhodium, palladium,
A transition metal complex such as nickel or a halide is a radical initiator such as benzoyl peroxide, lauryl peroxide, cumene peroxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, t-butyl peroxybenzoate and the like. Oxides, azobisisobutyronitrile, azobis-2,
Examples include azo compounds such as 4-dimethylvaleronitrile, and chloroplatinic acid, which is widely used industrially, is preferable in consideration of safety, reaction efficiency, economic efficiency, reaction conditions and the like. The amount of catalyst can be set to an arbitrary amount, for example, when chloroplatinic acid is used, but it is better to reduce it as much as possible in view of both economic and hygiene. When 0.1 to 5 mmol% of chloroplatinic acid catalyst is used with respect to the silyl group-containing compound, hydrosilylation with a conversion of 98% or more can be performed by heating at 90 ° C. for 5 hours. Usually, these catalysts use a solution dissolved in a solvent or the like. Since this reaction proceeds quantitatively and the catalyst requires a very small amount, it is not necessary to purify it unless there is a problem such as residual hydrosilane or catalyst toxicity.

The pigment (B) includes organic pigments and inorganic pigments, and known pigments conventionally used for coloring thermoplastic resins can be used. As such a pigment,
Organic pigments such as azo, anthraquinone, phthalocyanine, quinacridone, isoindolinone, dioxane, berylene, quinophthalone, berinone, etc.,
There are inorganic pigments such as cadmium sulfide, cadmium selenide, ultramarine blue, titanium dioxide, iron oxide, chromate oxide, and carbon black.

The coloring composition of the present invention further comprises a thermoplastic resin (C) having a melt flow rate in the range of 0.1 to 400, preferably 10 to 250, and having compatibility with the resin to be colored.
It can be contained within the range of 90% by weight or less. The melt flow rate (hereinafter referred to as MFR) in the present invention is measured according to JIS K 7210. When the MFR of the thermoplastic resin (C) is less than 0.1, the compatibility with the resin to be colored becomes poor, causing color unevenness and the like, and adversely affecting the physical properties of the colored thermoplastic resin. If the MFR exceeds 400, the mechanical strength and heat resistance of the masterbatch itself will be low, making it difficult to manufacture the masterbatch and improving the heat resistance and physical properties such as strength of the colored thermoplastic resin. Have an adverse effect. The thermoplastic resin (C) may be functional group modified, crosslinked modified, grafted or blocked modified. Further, the thermoplastic resin (C) used for the compounding may be in the form of powder or pellets.

To the coloring composition of the present invention, various additives such as stabilizers such as antioxidants and ultraviolet absorbers and surfactants may be added within a range that does not impair the effects of the present invention. You can also The coloring composition of the present invention can be used for coloring almost all polyolefin resins,
It may contain a reinforcing material such as an inorganic filler or glass fiber or organic fiber for the purpose of improving the physical properties. For example, uniform coloring without unevenness in color without affecting mechanical properties such as strength and heat resistance, which could not be achieved by conventional masterbatch coloring, can be achieved with up to 50 inorganic fillers and fiber reinforcements.
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 comprises, in addition to the polyolefin resin, polymethylpentene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-EPDM-.
It can also be blended with thermoplastic resins such as styrene (AES) resin, acrylic resin, polyamide, polycarbonate, polyacetal, and polyurethane.

The coloring composition of the present invention is extremely effective for improving the dispersibility and coloring power of the pigment, but the improvement of the dispersibility and coloring power is based on the carboxyl group in the copolymer or the anhydride thereof. This is due to the affinity, and a polar bond is formed between the carboxyl group or its anhydride in the copolymer and the basic group in the pigment, and the surrounding structure is a protective colloidal structure surrounded by polyolefin. Is considered to be taking. Incidentally, the coloring composition of the present invention,
It can also be used for applications such as lubricants, hot melt resins, inks, paints and adhesives.

[0016]

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”. [Production Example 1] 450.0 g of α-olefin having 30 or more carbon atoms (“Dialene 30” manufactured by Mitsubishi Kasei), triethoxysilane 16
4.3 g and 0.1 mol of hexachloroplatinate (IV) acid hexahydrate
3.04 ml of / l isopropyl alcohol solution was charged into a flask, and after purging with nitrogen, the mixture was heated at 100 ° C. and reacted for 6 hours while stirring. After the reaction was completed, the contents were taken out while being hot, cooled and solidified. The progress of the reaction was confirmed by the disappearance of the infrared absorption spectrum 2190 cm ⁻¹ of the silyl group.

[Production Example 2] 500.0 g of heat-decomposable polyethylene wax (“Sun Wax 131P” manufactured by Sanyo Kasei Co., Ltd.), 23.5 g of tridimethylaminosilane, and 0.1 mol / l isopropyl hexachloroplatinate (IV) acid hexahydrate 0.43 ml of an alcohol solution was charged into a flask and, after purging with nitrogen, heated at 120 ° C. and reacted for 6 hours while stirring. After the reaction was completed, the contents were taken out while being hot, cooled and solidified. The progress of the reaction was confirmed by the disappearance of the infrared absorption spectrum 2190 cm ⁻¹ of the silyl group.

[Production Example 3] 350.0 g of α-olefin having 30 or more carbon atoms ("VYBER103" manufactured by Petrolite), 50.0 g of reactive silicone oil ("PS-537" manufactured by Chisso), and hexachloroplatinum (IV ) 0.92 ml of a 0.1 mol / l isopropyl alcohol solution of acid hexahydrate was charged into a flask and, after purging with nitrogen, heated at 120 ° C. and reacted for 6 hours while stirring. After the reaction was completed, the contents were taken out while being hot, cooled and solidified. The progress of the reaction depends on the infrared absorption spectrum of the silyl group.
It was confirmed by the disappearance of 2190 cm ^-1 .

[Production Example 4] 450.0 g of 1-butene copolymer (“APAORT2715” manufactured by Ube Lexen), 50.0 g of reactive silicone oil (“PS-537” manufactured by Chisso), and 3.6 g of di-t-butyl peroxide. Was charged into a flask and, after purging with nitrogen, heated at 150 ° C. and reacted for 6 hours while stirring.
After the reaction was completed, the contents were taken out while being hot, cooled and solidified. The reaction progressed according to the infrared absorption spectrum of the silyl group 2190
It was confirmed by the disappearance of cm ^-1 .

[Examples 1 and 3] Resins obtained in Production Examples 1 and 30 30% Phthalocyanine blue 50% ("Rio Noble-7110V" manufactured by Toyo Ink Mfg. Co., Ltd.) Polypropylene 20% (Mitsui Petrochemical Industry Co., Ltd. " Mitsui Noblen J4HG "MFR: 30) Kneading the above 3 components with a 3 roll mill, screw diameter
A masterbatch was obtained by pelletizing with a 65 mm extruder. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Mix 100 parts of polypropylene "Mitsui Noblen J4HG" with 3 parts of the obtained masterbatch, and use a vertical test spinning machine (Spinning tester manufactured by Fuji Filter Co.) 230 below the hopper.
C., kneading section, and die section at 230.degree. C., and spinning was carried out 3 times to obtain polypropylene fiber of 5 denier. Spinnability,
Good dispersibility was exhibited without any problems in clogging and stretchability.

Comparative Examples 1 and 3 Instead of the resin obtained in Production Example 1, a thermal decomposition type polyethylene wax (“Sun Wax 151P” manufactured by Sanyo Kasei Co., Ltd.) was used in Comparative Example 1 and Comparative Example 3 was used. A masterbatch was obtained in the same manner as in Example 1 except that the heat-decomposable polypropylene wax (“Viscor 660P” manufactured by Sanyo Kasei Co., Ltd.) was used. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Further, using the obtained masterbatch, spinning was performed in the same manner as in Example 1, but 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 3 and Comparative Examples 1 and 3 were mixed with 100 parts of polypropylene "Mitsui Noblen J4HG", respectively, and 500 at the tip. 3 kg of the mixture was extruded by a single-screw extruder with a screw diameter of 30 mm equipped with a mesh wire mesh, and the pressure rise value at the tip was measured. In addition, in order to compare the dispersive coloring properties of the pigments, 1 part of the master batches obtained in Examples 1 and 3 and Comparative Examples 1 and 3 was used as polypropylene "Mitsui Noblene J4".
A mixture of 100 parts of HG "and 5 parts of titanium oxide was kneaded with a two-roll mill, formed into a plate with 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). The results are shown in Table 1.

[0022]

[Table 1]

[Examples 2 and 4] Resins obtained in Production Examples 2 and 30 30% Titanium oxide ("Taipec CR-80" manufactured by Ishihara Sangyo Co., Ltd.) 50% Carbon black 5% (Mitsubishi Kasei Kogyo Co., Ltd. ) "Mitsubishi Carbon MA-100") Polyethylene (Sumitomo Chemical Co., Ltd. "Sumikasen G-808" MFR: 75) 15% The above 4 components were kneaded with a kneader and pelletized with an extruder with a screw diameter of 65 mm. A masterbatch was obtained. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. Polyethylene with MFR: 6.5 (“HIZEX 2100” manufactured by Mitsui Petrochemical Co., Ltd.)
J ") 3 parts of the obtained masterbatch were mixed with 100 parts and molded into a plate with a back pressure of 0 kg / cm ² using an injection molding machine.

Comparative Examples 2 and 4 In place of the resin obtained in Production Example 2, in Comparative Example 2, a heat-decomposable polyethylene wax (“Sun Wax 131P” manufactured by Sanyo Kasei Co., Ltd.) was used.
In Comparative Example 4, the polymerization type polyethylene wax (“High Wax 420P” manufactured by Mitsui Petrochemical Industry Co., Ltd.) was 10%.
1-butene copolymer ("APAORT271" manufactured by Ube Lexen Co., Ltd.
5 ") A masterbatch was obtained in the same manner as in Example 2 except that 20% was used. At this time, a masterbatch could be obtained smoothly without strand breakage or pulsating flow. 3 parts of the obtained masterbatch was mixed with 100 parts of the polyethylene composition used in Example 2 and molded into a plate with a back pressure of 0 kg / cm ² using an injection molding machine.

[0025]

[Table 2]

[0026]

The thermoplastic resin coloring composition of the present invention comprises
Despite its very high pigment content, it has excellent pigment dispersibility, and exerts a great effect on its coloring power and processability in the coloring of textile products that require a high degree of pigment dispersion. 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 enables coloring without color unevenness.

Claims (4)

[Claims] 1. A silicone-modified resin obtained by an addition reaction between a thermoplastic resin (a) having at least one unsaturated double bond in the molecular chain and a compound (b) having a silyl group.
A composition for coloring a thermoplastic resin, comprising 0.1 to 99% by weight of (A) and 1 to 90% by weight of a pigment (B). 2. The melt flow rate is 0.1 to 40.
The coloring composition according to claim 1, which contains a thermoplastic resin (C) in the range of 0. 3. The coloring composition according to claim 1, wherein the thermoplastic resin (a) having at least one unsaturated double bond in the molecular chain is an olefin resin. 4. The coloring composition according to claim 1, wherein the compound (b) having a silyl group is an organic silicon compound.