JPH1046096A - Coloring agent composition and molded product using the coloring agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition high in the intrinsic viscosity- retentivity of a resin in the composition, excellent in dispersibility and free from the deterioration of physical properties on molding by mixing and thermally melt-kneading a polyester and titanium dioxide treated with a silane coupling agent. SOLUTION: Titanium dioxide treated with 0.05-3.0wt.% of a silane coupling agent and preferably 0.01-0.5wt.% (expressed in terms of calcium oxide and/or magnesium oxide) of calcium and/or magnesium salts, and a polyester resin (e.g. polyethylene terephthalate) are mixed each other, and subsequently thermally melted and kneaded with a melt-kneading machine to obtain the objective coloring composition. The coloring composition has the intrinsic viscosity- retentivity of the polyester resin in a value of >=80% in the coloring agent composition, contains the titanium dioxide in a high concentration, is excellent in dispersibility, and does not cause the deterioration of the physical properties of its molded product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorant composition used for coloring and molding a thermoplastic resin, and more particularly to a polyester molded article, and in particular, a thin film molded article such as a polyester film or a sheet or a fiber. The present invention relates to a colorant composition having excellent dispersibility suitable for a colorant. More specifically, the present invention relates to a colorant composition that does not cause deterioration in physical properties of a molded product, and a molded product using the colorant composition.

[0002]

2. Description of the Related Art A colorant composition used for coloring and molding a thermoplastic resin is prepared by mixing a pigment and a dispersant in a powdery dry color, and dispersing the pigment in a liquid dispersant at room temperature. Examples include a liquid color or paste color, and a masterbatch in the form of pellets or flakes obtained by dispersing a pigment at a high concentration in a solid resin at room temperature. In particular, a masterbatch excellent in ease of handling and preservation of the working environment during use is often used.

Hitherto, polyester resins have been used in many fields such as packaging and film applications by taking advantage of their excellent mechanical properties, dimensional stability and chemical resistance. In addition, titanium oxide is used in a large amount as a white pigment for resin coloring because of its excellent whiteness, high concealing property, and high coloring power. In recent years, a colorant composition containing a polyester resin having such excellent properties and a titanium oxide having an excellent concealing property has been used for a metal plate laminate film, a film for a credit card or a telephone card, or other various kinds of fibers and the like. Are widely used for moldings, and the range of use tends to be further expanded.

In particular, in recent years, in order to satisfy both the demand for thinner and thinner films and the required concealing properties of molded products such as films, the content of titanium oxide in the molded products has been increased (higher). Concentration), and it is necessary to improve the dispersibility of titanium oxide in a molded product. For fiber applications, there is a demand for prevention of yarn breakage during spinning and reduction of clogging frequency of a filter in a spinning machine, that is, high dispersibility of titanium oxide. In order to respond to this demand for molded articles, the colorant composition used when obtaining molded articles has the same requirements, that is, titanium oxide is contained in the colorant composition with good dispersibility and contains a high concentration. Is required.

[0005] On the other hand, titanium oxide used for coloring a polyester resin is generally subjected to various surface treatments in order to improve weather resistance, dispersibility and the like.
This surface treatment is roughly classified into an inorganic treatment (alumina, silica, titania, zirconia, etc.) and an organic treatment (polyol, silicon). By the treatment as described above, the dispersibility of titanium oxide in the polyester resin is improved, and the weather resistance of a molded article containing the titanium oxide is also improved.

However, even the titanium oxide treated as described above generally has moisture, and the moisture causes the polyester resin in the colorant composition to be hydrolyzed, resulting in a decrease in molecular weight. . And
The colorant composition containing such a polyester resin having a reduced molecular weight causes a decrease in the physical properties of a molded article using the colorant composition. In particular, when a high concentration of titanium oxide is contained in the colorant composition, the decrease in the molecular weight of the polyester resin becomes remarkable, and the use of the colorant composition containing a polyester resin having a remarkable decrease in the molecular weight also causes a remarkable decrease in the physical properties of the molded product. become.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a colorant composition containing titanium oxide at a high concentration, which is excellent in dispersibility and does not cause deterioration in the physical properties of a molded product. It is to be.

[0008]

That is, a first aspect of the present invention is a coloring method comprising heating and kneading a mixture containing 0.05 to 3.0% by weight of a titanium oxide treated with a silane coupling agent and a polyester resin. Agent composition, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80%
It is a colorant composition characterized by the above.

A second invention comprises a titanium resin treated with 0.01 to 0.5% by weight of calcium salt or magnesium oxide, calculated as calcium oxide or magnesium oxide, and a polyester resin, and is heated and kneaded. A colorant composition, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80% or more.

A third invention is a treatment with 0.01 to 0.5% by weight of calcium salt or magnesium salt in terms of calcium oxide or magnesium oxide and 0.05 to 3.0% by weight of a silane coupling agent. A colorant composition comprising a titanium oxide and a polyester resin, and heated and kneaded, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80% or more. Agent composition.

A fourth invention is directed to a titanium oxide treated with 0.01 to 0.3% by weight of an aluminate or silicate and 0.05 to 3.0% by weight of a silane coupling agent, and a polyester. A colorant composition containing a resin and heat-kneaded, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80% or more.

In a fifth aspect, a calcium salt or a magnesium salt in an amount of 0.01 to 0.5% by weight in terms of calcium oxide or magnesium oxide is mixed with an alumina in an amount of 0.01 to 0.3% by weight in terms of alumina or silica. A colorant composition comprising a titanium oxide treated with an acid salt or a silicate, and a polyester resin, which is heated and kneaded, wherein the polyester resin in the colorant composition has an intrinsic viscosity retention of 80%. It is a colorant composition characterized by the above.

[0013] A sixth aspect of the present invention is to provide a method for producing a composition, comprising 0.01 to 0.5% by weight of calcium salt or magnesium salt in terms of calcium oxide or magnesium oxide and 0.01 to 0.3% by weight of alumina in terms of alumina or silica. A colorant composition comprising a titanium oxide treated with an acid salt or a silicate and 0.05 to 3.0% by weight of a silane coupling agent, and a polyester resin, the mixture being heated and kneaded; The limiting viscosity retention of the polyester resin in the agent composition is 80
% Of the colorant composition.

A seventh aspect of the present invention is a colorant composition containing titanium oxide treated with 0.01 to 0.5% by weight of a calcium salt or a magnesium salt, and a polyester resin, and heated and kneaded, A colorant composition, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80% or more.

An eighth invention is a titanium oxide treated with 0.01 to 0.5% by weight of a calcium salt or a magnesium salt and 0.05 to 3.0% by weight of a silane coupling agent,
And a polyester resin, which is heated and kneaded, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80% or more. is there.

A ninth invention is a titanium oxide treated with 0.01 to 0.5% by weight of a calcium salt or a magnesium salt and 0.01 to 0.3% by weight of an aluminate or a silicate, and A colorant composition containing a polyester resin and heat-kneaded, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80% or more. .

A tenth aspect of the present invention is the method of the present invention, wherein 0.01 to 0.5% by weight
And calcium salt or magnesium salt with 0.01 to 0.3
Wt% aluminate or silicate and 0.05-3.0
A colorant composition containing titanium oxide treated with a silane coupling agent by weight and a polyester resin, and heated and kneaded, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80%. % Of the colorant composition.

The eleventh invention is characterized in that the calcium salt is selected from calcium chloride, calcium bromide, calcium iodide and calcium sulfate, or the fifth invention or the fifth invention or the third invention is characterized in that the calcium salt is selected from calcium chloride, calcium bromide, calcium iodide and calcium sulfate. A colorant composition according to any one of the tenth inventions.

A twelfth invention is characterized in that the magnesium salt is selected from magnesium chloride, magnesium bromide, magnesium iodide, and magnesium sulfate, or the fifth invention or the fifth invention is characterized in that: A colorant composition according to any one of the tenth inventions.

A thirteenth invention is the colorant composition according to any one of the first to twelfth inventions, wherein the titanium oxide is an anatase type.

A fourteenth invention is the colorant composition according to any one of the first to thirteenth inventions, which is a colorant composition for a polyester resin.

The fifteenth invention is directed to the first to fourteenth inventions.
A molded article comprising the colorant composition according to any one of the inventions.

A sixteenth invention is the molded article according to the fifteenth invention, which is a film or a fiber.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The silane coupling agent used in the present invention is used to fix the hydroxyl group by reacting with the hydroxyl group on the surface of titanium oxide and to make the titanium oxide hydrophobic, and to improve dispersibility. And those having a structure represented by the following general formulas (1) to (4), for example, methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacrylic acid. Roxypropyltrimethoxysilane, vinyltriethoxysilane, phenylalkoxysilane such as phenyltrialkoxysilane and diphenyldialkoxysilane, and dialkyldialkoxysilane such as dimethyldimethoxysilane and dimethyldiethoxysilane.

[0025]

Embedded image

Among the organic functional groups of the above general formula, a methyl group and an amino group are preferred, specifically, a dialkyldialkoxysilane is preferred, and dimethyldimethoxysilane is particularly preferred.

The titanium oxide contains the silane coupling agent in an amount of 0.05 to 3.0% by weight, preferably 0.05 to 1.0% by weight, and more preferably 0.1 to 1.0% by weight.
It is 0.5% by weight, most preferably 0.1-0.3% by weight. If the content exceeds 3.0% by weight, slip occurs during extrusion, and the ejection of the material becomes unstable, so that the colorant composition cannot be manufactured stably. In particular, when a film is produced using the colorant composition, the film thickness becomes non-uniform or the film breaks, making molding impossible. When the content is less than 0.1% by weight, the effect of hydrophobizing titanium oxide is small, and the amount of water absorbed over time after the production of the colorant composition is increased. Promotes hydrolysis of the polyester resin and causes a decrease in molecular weight.

The calcium salt or the magnesium salt used in the present invention is used for fixing the hydroxyl group by reacting with the hydroxyl group on the surface of the titanium oxide and hydrophobizing the titanium oxide similarly to the silane coupling agent. Things. Such calcium salts or magnesium salts include calcium chloride, calcium bromide, calcium iodide, calcium sulfate, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate and the like.

The content is 0.01 to 0.5% by weight in terms of calcium oxide or magnesium oxide. If the content is less than 0.01% by weight, the effect of hydrophobization is insufficient, and if the content is more than 0.5% by weight, the effect of hydrophobization hardly changes.

The content of the calcium salt or the magnesium salt as described above is 0.01 to 0.5% by weight. If the content is less than 0.01% by weight, the effect of hydrophobization is insufficient, and if the content is more than 0.5% by weight, the effect of hydrophobization hardly changes.

In the present invention, the treatment with the silane coupling agent and the treatment with a calcium salt, a magnesium salt or the like can be used in combination to fix the hydroxyl groups on the surface of the titanium oxide.

In the present invention, a treatment with a silane coupling agent, a treatment with a calcium salt or the like, or a combination of a treatment with a silane coupling agent and a treatment with a calcium salt or the like, further comprises an aluminate such as sodium aluminate or the like. Using a silicate, a treatment of alumina, silica or the like can be used in combination. That is, after treating titanium oxide with an aluminate or a silicate or the like, it may be treated with a silane coupling agent, or after treating the titanium oxide with a calcium salt or the like, and then with an aluminate or a silicate. The treatment may be performed, or the titanium oxide may be treated with a calcium salt or the like, then treated with an aluminate or a silicate, and further treated with a silane coupling agent.

Alumina, silica, and the like generally contain water of crystallization or are hydrated, and although it is preferable to reduce the water content as much as possible from the viewpoint of reducing the water content, strong concealing properties are required. In the field, it is preferable to contain as little alumina or silica as possible, preferably 0.3% by weight or less, more preferably 0.2% by weight or less based on titanium oxide.
If it exceeds 0.3% by weight, the water content increases, and the hydrolysis of the polyester resin is easily promoted. Alumina is more preferable in terms of excellent dispersibility.

The titanium oxide used in the present invention is:
The average particle size is preferably 0.01 to 1.0 μm,
More preferably, the thickness is 0.05 to 0.40 μm.
Most preferably, it is 15 to 0.20 μm. Any of rutile type and anatase type may be used, but anatase type is preferred from the viewpoint of whiteness.

When neither treatment with an organic treatment agent such as a silane coupling agent or treatment with an inorganic treatment agent such as alumina is performed, the dispersion of titanium oxide is extremely poor, and the dispersion of the colored resin molded product is extremely poor. Agglomerates are generated and clogging of the screen mesh of the molding machine is caused.

The polyester resin used in the present invention is a conventionally known resin. A polyester obtained by condensation polymerization of an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, and naphthalene-2,6-dicarboxylic acid, or an ester thereof and a glycol such as ethylene glycol, diethylene glycol or tetramethylene glycol. is there. Typical examples include polyethylene terephthalate and polybutylene terephthalate. These polyester resins may be a combination of plural kinds of carboxylic acid components and plural kinds of diol components.

In the colorant composition of the present invention, the above-mentioned titanium oxide and polyester resin may be blended in a ratio of 2/8 to 8/2, preferably 5/5 to 7/3, and The titanium oxide and the polyester resin may be heated and kneaded using a mixer, a disperser, or a kneader. Further, the colorant composition of the present invention is preferably a pellet-like or flake-like master batch.

The limiting viscosity of the polyester resin in the colorant composition of the present invention indicates the state of deterioration (hydrolysis) of the polyester resin. Containing titanium oxide and polyester resin, heat-kneading the colorant composition using a suitable solvent, dissolve the polyester resin in the colorant composition, separate the titanium oxide, different concentration Using a plurality of polyester resin solutions, the viscosity of each resin solution is determined, and the viscosity / concentration value is plotted against the concentration according to a standard method, and the value is extrapolated to a concentration of 0. The intrinsic viscosity retention rate is a ratio of the intrinsic viscosity of the polyester resin in the colorant composition to the intrinsic viscosity of the polyester resin (blank) used in the colorant composition. As the intrinsic viscosity of the polyester resin in the colorant composition approaches the intrinsic viscosity of the blank, the polyester resin in the colorant composition is not deteriorated.

[0039]

【Example】

Examples 1 to 11 and Comparative Examples 1 and 2 50% by weight of homopolyethylene terephthalate ((η) = 0.630) and 50% by weight of anatase type titanium oxide (each having been subjected to each treatment shown in Table 1) were added to a melt kneader. The mixture was melt-kneaded to obtain a pellet-shaped colorant composition (master batch), and the intrinsic viscosity retention of the polyester resin in the obtained master batch was determined according to the following method. Example 7 was 30% by weight of homopolyethylene terephthalate and 70% by weight of anatase type titanium oxide described in Table 1, and Example 8 was 70% by weight of homopolyethylene terephthalate and 30% by weight of anatase type titanium oxide described in Table 1. All operations were the same as in Example 6. In addition, while evaluating the dispersibility of the obtained master batch, using the obtained master batch,
Films and fibers were prepared and their physical properties were evaluated. Table 1 shows the results.

[Intrinsic Viscosity (η)] and [Intrinsic Viscosity (η) Retention] The intrinsic viscosity (η) of the polyester resin was 0.1%.
g, 0.3 g, 0.5 g of the masterbatch,
Using 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio), the polyester resin in the master batch was dissolved, and the titanium oxide was removed by centrifugation. It was measured and determined according to the usual method. In the case of a blank, the limiting viscosity was obtained in the same manner as described above, except that the polyester resin itself was used instead of the master batch and the titanium oxide was not removed by centrifugation. The intrinsic viscosity retention is the intrinsic viscosity of the polyester resin in the master batch / the intrinsic viscosity of the blank.

[Dispersibility evaluation method] A 40/80/120/500 outlet of a Labo Plastomill single screw extruder 20 mm (manufactured by Toyo Seiki Co., Ltd.) and a screen whose mesh became smaller in order were attached, and 50 rpm,
At an extrusion temperature of 300 ° C, low density polyethylene (specific gravity 0.916,
MFR 9.0 / 10min) and the masterbatch were passed through a pellet blended 1: 1 to determine the initial pressure (P1) at the start of passing, and the pellet blended 1: 1 was added in a predetermined amount (titanium oxide in the pellet). End pressure when passing through)
Find (P2). The smaller the pressure difference ΔP = P2-P1, the better the dispersibility of titanium oxide.

[Film forming method] 40 parts by weight of the obtained master batch, homopolyethylene terephthalate
((η) = 0.630), and melt-extruded at 270 to 300 ° C. to obtain a 200 μ sheet. 90 ° C the sheet
At the same time to produce a 20 μm film. The film formation state of the film and the smoothness of the obtained film were evaluated.

[Film Deposition State] A: A film could be formed smoothly without breaking. Δ: Occasional fracture. ×: Breaks frequently.

[Film smoothness]: Visual evaluation. ：: uniform and smooth. Δ: Slight bumps occur. ×: Markedly formed.

In Examples 10 and 11, the obtained films were measured using a colorimeter (manufactured by Kurabo Industries).
Table 2 shows the transmittance measured at each wavelength. The higher the transmittance, the poorer the concealment.

[Spinning Method] Master Batch 10 Obtained
Parts by weight, homopolyethylene terephthalate ((η = 0.633)
100 parts by weight were mixed and spun with a vertical type test spinning machine (Fuji Filter spinning tester), stretched four times, and then spun.
Heat treatment was performed at 0 ° C. to produce 3.00 denier fibers. The yarn breakage when preventing was evaluated.

[Yarn breakability] 紡: Smooth spinning was possible without yarn breakage. Δ: Occasionally thread breakage occurs. ×: The yarn breaks frequently.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

By using the colorant composition of the present invention, it is possible to obtain a polyester-colored molded article having high dispersion and little deterioration in physical properties. In particular, for a molded article such as a film or a sheet, extremely high dispersibility is required, and at the same time, physical properties are required to be maintained. Therefore, the colorant composition of the present invention is extremely useful.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C09C 1/36 PAW C09C 1/36 PAW

Claims (16)

[Claims] 1. A colorant composition comprising a titanium oxide treated with a silane coupling agent in an amount of 0.05 to 3.0% by weight, and a polyester resin, the composition being heated and kneaded,
A colorant composition, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80% or more. 2. A colorant composition comprising titanium oxide treated with 0.01 to 0.5% by weight of calcium oxide or magnesium oxide and calculated by heating and kneading, and a polyester resin. , Wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80% or more. 3. Titanium oxide treated with 0.01 to 0.5% by weight of calcium salt or magnesium salt in terms of calcium oxide or magnesium oxide and 0.05 to 3.0% by weight of a silane coupling agent, A colorant composition containing a polyester resin and heat-kneading, wherein the polyester resin in the colorant composition has an intrinsic viscosity retention of 80% or more. 4. A titanium oxide treated with 0.01 to 0.3% by weight of an aluminate or silicate and 0.05 to 3.0% by weight of a silane coupling agent, and a polyester resin. A colorant composition obtained by heating and kneading, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80% or more. 5. 0.01 to 0.5% by weight of calcium salt or magnesium salt in terms of calcium oxide or magnesium oxide and 0.00.0% in terms of alumina or silica.
A colorant composition comprising titanium oxide treated with 1 to 0.3% by weight of an aluminate or a silicate, and a polyester resin, and heated and kneaded, wherein the polyester in the colorant composition A colorant composition, wherein the resin has an intrinsic viscosity retention of 80% or more. 6. A calcium salt or magnesium salt of 0.01 to 0.5% by weight in terms of calcium oxide or magnesium oxide and 0.00.0% in terms of alumina or silica.
1 to 0.3% by weight of aluminate or silicate and 0.0
A colorant composition comprising titanium oxide treated with 5 to 3.0% by weight of a silane coupling agent and a polyester resin, and heated and kneaded, wherein the limit of the polyester resin in the colorant composition is A colorant composition having a viscosity retention of 80% or more. 7. A colorant composition comprising titanium oxide treated with 0.01 to 0.5% by weight of a calcium salt or a magnesium salt, and a polyester resin, and heated and kneaded, wherein the colorant composition is A colorant composition, wherein the intrinsic viscosity retention of the polyester resin in the product is 80% or more. 8. A heating method comprising: a titanium oxide treated with 0.01 to 0.5% by weight of a calcium salt or a magnesium salt and 0.05 to 3.0% by weight of a silane coupling agent; and a polyester resin. A colorant composition obtained by kneading, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80% or more. 9. Titanium oxide treated with 0.01 to 0.5% by weight of calcium or magnesium salt and 0.01 to 0.3% by weight of aluminate or silicate, and a polyester resin A colorant composition obtained by heating and kneading, wherein the intrinsic viscosity retention of the polyester resin in the colorant composition is 80% or more. 10. 0.01% to 0.5% by weight of calcium or magnesium salt, 0.01% to 0.3% by weight of aluminate or silicate and 0.05% to 3.0% by weight of silane. A colorant composition containing titanium oxide treated with a coupling agent and a polyester resin, and heated and kneaded, wherein the polyester resin in the colorant composition has an intrinsic viscosity retention of 80% or more. A colorant composition comprising: 11. The colorant according to claim 2, wherein the calcium salt is selected from calcium chloride, calcium bromide, calcium iodide, and calcium sulfate. Composition. 12. The coloring agent according to claim 2, wherein the magnesium salt is selected from magnesium chloride, magnesium bromide, magnesium iodide, and magnesium sulfate. Composition. 13. The colorant composition according to claim 1, wherein the titanium oxide is of an anatase type. 14. The colorant composition according to claim 1, which is a colorant composition for a polyester resin. 15. A molded article comprising the colorant composition according to claim 1. 16. The molded product according to claim 15, which is a film or a fiber.