WO1997024393A1

WO1997024393A1 - Masterbatch containing titanium oxide

Info

Publication number: WO1997024393A1
Application number: PCT/JP1996/003846
Authority: WO
Inventors: Susumu Miyasita; Noburu Sakuma; Masaru Hosokawa
Original assignee: Toyo Ink Manufacturing Co., Ltd.
Priority date: 1995-12-27
Filing date: 1996-12-27
Publication date: 1997-07-10
Also published as: AU1174397A

Abstract

A masterbatch which comprises a thermoplastic resin containing titanium dioxide. The titanium dioxide contains 0.02 to 1.0 wt.% aluminum and preferably has been undergone a surface treatment with a specific agent. The masterbatch hence has a high whiteness and an excellent thermal stability, and is greatly reduced in the content of water evaporating in a high-temperature treatment.

Description

Description Masterbatch containing titanium oxide Technology

TECHNICAL FIELD The present invention relates to a master batch used for coloring and molding a thermoplastic resin. More specifically, the master batch has excellent whiteness, and in a preferable embodiment thereof, has excellent heat discoloration resistance, light discoloration resistance, and weather discoloration resistance. More particularly, the present invention relates to a resin molded product which is excellent in high-speed high-temperature processability and uniform and excellent in concealing property, and particularly to a masterbatch suitably used for a melt-extruded laminating film. Background technology

Coloring compositions used for coloring and processing thermoplastic resins include powdery dry color in which a pigment and a dispersant are mixed, and liquid color in which the pigment is dispersed in a liquid dispersant at room temperature. Alternatively, there is a paste color, a masterbatch prepared by dispersing a pigment in a room temperature solid resin at a low temperature to form a pellet, a flake, or a pellet. Above all, a masterbatch is often used because it is easy to handle and convenient for the working environment during use. As a masterbatch for white, a thermoplastic resin containing titanium dioxide has been used. This titanium oxide is used in a large amount as a white pigment for fat coloring because of its excellent whiteness, high concealing property, and high coloring power. In terms of whiteness, the anatase type is convenient, and the rutile type has a yellowish tint. Therefore, the anatase type is generally suitably used for applications requiring whiteness.

In recent years, there has been a growing demand for more convenient whiteness in terms of product quality, design, and differentiation, and as a method for achieving whiteness, adding a fluorescent brightener,方法 A method of adding a taste pigment or other white pigments is generally known, but has not been at a satisfactory level yet.

Furthermore, in the case of a colored resin molded product that conventionally requires high-temperature processing, the whiteness of the molded product is impaired by heat during manufacturing, or the whiteness of the molded product is reduced by light after molding. There were problems such as deterioration over time.

In addition, titanium oxide is inherently hydrophilic, and is subjected to a surface treatment with an inorganic or organic substance to improve weather resistance, hydrophobicity, dispersibility, and the like. For example, there are titanium oxides treated with a polyol-based or polysiloxane-based surface treatment agent.Titanium oxide surface-treated with a polyol-based surface treatment agent has good dispersibility but a small effect of hydrophobization. Therefore, a large amount of water is adsorbed, and a master batch using the surface-treated titanium oxide and the thermoplastic resin also has a low hydrophobicity, and thus easily contains a large amount of water.

Titanium oxide that has been surface-treated with a polysiloxane-based treatment agent has a good hydrophobic effect, but the titanium oxide surface and the treatment agent have a weak chemical bonding force. When a master batch is manufactured using a thermoplastic resin and a thermoplastic resin, the surface treatment agent is peeled off due to kneading conditions and extrusion conditions during manufacturing, causing variations in the distribution of titanium oxide in the master batch, As a result, problems such as an increase in water content have arisen.

Wet! : A masterbatch with a high content and a thermoplastic resin are used to produce a colored resin molded product. There were problems such as slippage, poor dispersion, and the return of water to the raw material supply port side of the processing machine, making it impossible to supply raw materials smoothly.

In particular, in the field of melt extrusion lamination, which requires high-temperature processing of 280 to 350 at which desorption of crystallization water and the like occurs, the water content is extremely important, and when the water content increases, the film is extruded. At that time, there was a problem that water was volatilized and a net-like hole was formed in the film, so-called racing occurred, and the film became unusable.

The present invention has solved the above-mentioned problems in the conventional masterbatch, and has higher whiteness than the conventional masterbatch, and has excellent heat discoloration resistance, weather discoloration resistance, and light discoloration resistance. It is intended to provide a titanium oxide-containing master patch that is rich in water resistance and hydrophobicity and generates less moisture during high-temperature processing. Disclosure of the invention

TECHNICAL FIELD The present invention relates to a masterbatch containing titanium dioxide and thermoplastic resin, which have high whiteness and color stability by containing 0.02 to 1.0% by weight of aluminum (A1).

Further, the present invention relates to a masterbatch using titanium dioxide containing A1 of the above-mentioned content S, which is further subjected to a surface treatment with triethanolamine to improve dispersibility and hydrophobicity.

Specifically, titanium dioxide treated by the following method is used. (A) Titanium oxide treated with 0.01 to 0.5% by weight of calcium salt and 0.05 to 3.0% by weight of triethanolamine in terms of calcium oxide, (mouth) oxidizing power 0.0 1 to 0.5% by weight of calcium salt of the 0.05-3. 0.0 0 by weight ^_0/0 triethanolamine and alumina conversion from 1 to 0.3 weight ⁰ /. Titanium oxide treated with the following aluminate, (c) 0.01 to 0.5% by weight of calcium salt in terms of calcium oxide and 0.05 to 3.0% by weight of triethanolamine in terms of silica 0.0 1 to 0.3% by weight of a titanium oxide treated with a potassium salt, (di) 0.01 to 0.5% by weight of magnesium salt in terms of magnesium oxide and 0.05 to 3.0% by weight of triethanola Min and treated with titanium oxide emissions, and 0.0 1 to 0.5 wt ^_0/0 magnesium salts with 0.0 5 to 3.0 weight ^0/6 preparative triethanolamine in (e) oxidizing Maguneshiumu terms comprises titanium oxide treated with a 0. 0 1 to 0.3 wt ^_0/0 aluminate in terms of alumina, (viii) 1 0. 0 2 to 1.0 wt% (to), 0. magnesium oxide in terms 0 1 to 0.5% by weight of magnesium salt and 0.05 to 3.0% by weight of triethanolamine and 0.01 to 0.3% by weight of silicic acid (G) Titanium oxide treated with 0.05 to 3.0% by weight of triethanolamine, (h) 0.05 to 3.0% by weight of triethanolamine and 0,0 in terms of alumina. 0 Titanium oxide treated with 1 to 0.3% by weight of aluminate, (b) 0.05 to 3.0% <1% of triethanolamine and 0.01 to 0.3% by weight in terms of silica Titanium oxide treated with silicate of the formula.

In the above treatment method, the magnesium salt is used in place of the calcium salt, and the silicate is used in place of the aluminate. When a calcium salt, a magnesium salt, an aluminate or a gay acid is used together with triethanolamine, the treatment is performed by adding a calcium salt and a magnesium salt and then adding an aluminate or a silicate. Then, those treated with triethanolamine are preferred.

As the calcium, calcium chloride, calcium bromide, calcium iodide or calcium sulfate can be used.

As the magnesium salt, magnesium chloride, magnesium bromide, magnesium iodide or magnesium sulfate can be used.

A1 contained in the titanium dioxide is contained in the crystal, and is preferably an anatase-type titanium oxide.

The masterbatch of the present invention containing the above titanium dioxide preferably has a water content that can be volatilized at 280 to 350 ^ is 1200 ppm or less, and is used as a masterbatch for an extruded laminated film. It is suitable. BEST MODE FOR CARRYING OUT THE INVENTION

(1) A1 containing titanium oxide

The masterbatch of the present invention suppresses / prevents discoloration due to heat by using titanium oxide containing A1, enhances whiteness, and further converts the titanium oxide containing A1 into a specific amount of triethanolamine. The surface treatment using a specific amount of calcium salt or the like suppresses the amount of volatile water and improves the dispersibility, beading properties, hiding properties, light discoloration resistance, weather discoloration resistance, and the like.

Metals Nb, Ta, and W remaining as impurities in titanium oxide obtained by the sulfuric acid method enter into crystal defects of titanium oxide during firing, and become titanium oxide containing Nb, Ta, and W in the crystal. . A masterbatch containing titanium oxide containing Nb, Ta, and W in the crystal can be used in fields requiring high-temperature processing at 280 to 350, for example, in the field of contact extrusion lamination. The blackening of the colored molding becomes remarkable as compared with the case of using at a low temperature.

However, the masterbatch containing titanium dioxide in which Nb, Ta, and W in this crystal were replaced with A1 prevents discoloration during high-temperature processing of 280 to 35, so that the melt-extrusion was performed. When manufacturing molded products such as films In addition, it is possible to obtain a molded article whose whiteness is not impaired.

The amount of A 1 contained in the titanium dioxide crystal may be an amount capable of replacing the amount of the metal Nb, Ta, or W existing as an impurity that is taken into the titanium dioxide crystal as an ion. Specifically, the content is from 0.02 to 1.0% by weight, and preferably 0.3% by weight or less. If the content is less than 0.02% by weight, no effect can be obtained in heat discoloration resistance, light discoloration resistance and weather discoloration resistance. Also, 1.0 weight. If it exceeds / o, it is not preferable because free A1 which does not enter the crystal is mixed in an oxide state.

The titanium dioxide containing A 1 in the crystal is obtained by adding a water-soluble aluminum compound such as aluminum sulfate to a slurry of hydrous titanium dioxide obtained by the sulfuric acid method, and drying the mixed slurry. It is obtained by a wet production method in which firing is performed at about 110 ° C. Alternatively, it can also be produced by a dry production method in which alumina powder is added to titanium dioxide powder, and the mixed powder is fired at the above temperature.

(2) Surface treated titanium oxide

As the masterbatch of the present invention, a masterbatch obtained by surface-treating the above-mentioned A1-containing titanium dioxide with triethanolamine is preferably used. Surface treatment may be carried out using a calcium salt or a magnesium salt, an aluminate or a silicate together with triethanolamine.

It is not clear yet what mechanism the triethanolamine used in the present invention acts on common polyols such as trimethylolpropane and trimethylroleethane, but it is not clear yet. A master batch containing the treated titanium oxide is richer in hydrophobicity than ordinary polyols, has a lower water content, and has better dispersibility and high-temperature processability.

The amount of triethanolamine to be used is suitably 0.05 to 3.0% by weight, preferably 0.05 to: 1.0% by weight, and more preferably 0.05 to 0.5% by weight. Most preferably, it is 0.1 to 0.3% by weight. If the amount is less than 0.05% by weight, the effect of hydrophobizing the titanium oxide containing A1 is small, and Moisture adsorption over time after production increases, causing the same problem as in the past. Further, even when the amount is more than 3.0% by weight, the effect is hardly changed as compared with the case where the amount is within the above range.

The calcium salt or magnesium salt used in the present invention is used to fix the hydroxyl group by reacting with the hydroxyl group on the surface of the A 1 -containing titanium oxide and to make the A 1 -containing titanium oxide hydrophobic.

Examples of the calcium salt or magnesium salt include calcium chloride, calcium bromide, calcium iodide, calcium sulfate, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate and the like. The amount of these used is 0.01-0.5 wt% in terms of calcium oxide or magnesium oxide. If the amount used is less than 0.01% by weight, the effect of hydrophobization is insufficient, and if it is used in excess of 0.5% by weight, the effect of hydrophobization hardly changes as compared with the case where the amount is within the above range.

In the present invention, the above treatment with triethanolamine and the treatment with calcium salt and magnesium salt for fixing hydroxyl groups on the surface of titanium oxide can be used in combination. That is, after treating A1-containing titanium oxide with aluminate, silicate, etc., it may be treated with triethanolamine, or after treating A1-containing titanium oxide with calcium salt, etc., aluminum Alternatively, the treatment may be carried out with a phosphate, caustic acid, etc., and further with triethanolamine.

Alumina, silica, etc. generally contain water of crystallization or are hydrated, and although it is preferable that they are reduced as much as possible from the viewpoint of low water content, they have the effect of increasing concealment power. However, it is necessary in fields where strong continuity is required. However, the amount used is preferably as small as possible, and is suitably 0.3% by weight or less, preferably 0.2% by weight or less based on titanium oxide. If the amount used exceeds 0.3% by weight, the water content is low and troubles during processing are likely to occur. Alumina is preferred to silica in terms of excellent dispersibility.

The A1-containing surface-treated titanium dioxide preferably has an average particle size of 0.01 to 1.0 μm. The crystal type may be either rutile type or anatase type. The anatase type is preferred from the viewpoint of whiteness.

If the titanium oxide has not been treated with an organic treating agent such as triethanolamine, or with an inorganic treating agent such as alumina, the dispersion of the titanium oxide is poor and the colored resin molded product Agglomerates are generated and the screen mesh of the molding machine is clogged.

(3) The above titanium dioxide-containing masterbatch

Examples of the thermoplastic resin used in the present invention include common thermoplastic resins such as polyolefin resin, polyester resin, polystyrene resin, and nylon resin. In the field of (1), polyolefin resins and polyester resins are available. Polyolefin resins are particularly preferable for extrusion ftt lamination of a paper base, and polyethylene resins are particularly preferable. In addition, a polyester resin is particularly preferred for the melt extrusion lamination on a metal substrate, and polyethylene terephthalate is particularly preferred.

In the masterbatch of the present invention, the surface-treated titanium oxide and the thermoplastic resin may be blended in a ratio of 2Z8 to 8Z2, preferably 55 to 73, more preferably 6Z4 to 7/3.

The masterbatch of the present invention containing the titanium dioxide subjected to the above-mentioned surface treatment has a volatile water content of not more than 120 ρρηι at 280 to 350 °, preferably not more than 80 Oppm, more preferably not more than 300 ppm. "The volatile moisture content in C is 600 ppm or less. The volatile moisture content in the above temperature range is more than 120 Oppm. Attempt to obtain a colored resin molding using a masterbatch and a thermoplastic resin. In this case, the above-mentioned various problems occur: The moisture is an amount of moisture generated at a predetermined temperature under a nitrogen atmosphere using a Karl-Fischer complete moisture system.

The masterbatch of the present invention may contain, if necessary, other known additives such as other pigments and ultraviolet absorbers, as long as the effect is not impaired, other than the above components. (4) Example

Examples 1 and 2, Comparative Examples 1 and 2

40% by weight of titanium oxide shown in Table 1 was mixed with 40% by weight of low-density polyethylene (specific gravity: 0.917, MFR 7.0g / 10min.), Mixed by heating with a kneader, and cooled and pulverized. Thereafter, the mixture was extruded by an extruder to obtain a pellet-shaped master batch. Various evaluations were performed using the obtained master batch. The evaluation method and the like are shown below, and the results are shown in Table 1.

(1) Moisture measurement method:

1 g of the above master batch was measured for the amount of water generated at each temperature using a Karl-Busher complete moisture meter (manufactured by Hiranuma Sangyo Co., Ltd.). The values in the table are shown in ppiD units.

(2) Dispersibility evaluation method:

At Rabopurasu Tomiru exit the finer screen sequentially mesh with 40/80/120/500 is attached to a single-screw extruder 2 O mn (manufactured by Toyo Seiki Co.), 5 0 r _P n, extrusion temperature 3 0, A low-density polyethylene (specific gravity: 0.916, MFR 9.0g / 10min.) And a master batch are passed through a 1: 1 blended pellet, and the initial pressure P1 at the start of passing is determined. The end pressure P 2 when the blended pellet is passed through a predetermined amount (an amount containing 360 g of titanium oxide in the pellet) is determined. It can be said that the smaller the pressure difference P = P2-P1, the better the dispersibility of titanium oxide.

(3) T-die film deposition method:

The above master batch 67 weight ⁰ , low density polyethylene (specific gravity 0.918, MFR 4.0g / 10min.) 33 3% by weight is blended, and the molding temperature is adjusted using a T-die film molding machine (manufactured by Toyo Seiki Co., Ltd.). T-die films of 200, 280 ^, 300 ^, and 350, each having a thickness of 30 / im, were prepared, and the film forming properties (appearance), hue, and the like were evaluated.

(4) Evaluation of film formability:

The presence or absence of racing was visually evaluated. The symbols in the table are as follows.

◎: No racing or foaming.

〇: Lace, foaming slightly. Δ: Racing, foaming.

X: Racing and foaming are remarkable and film formation is impossible.

(5) Color measurement method:

The whiteness and hue of a Τ die film having a thickness of 30 μιη extruded at each temperature by the above method were measured with a colorimeter (manufactured by Kurabo Industries, Ltd.). Hue and whiteness were determined based on Japanese Industrial Standards (JIS II-8715). The larger the whiteness W is, the whiter the color is, and the smaller the hue b is, the more bluish. The temperature change of this hue b (hue difference A b = bm—bn, bm, bn is the hue of mt :,) is small. Thermally stable. Specifically, 0.10 or less is appropriate, and 0.05 or less is preferable. As shown in Table 1, all masterbatches of the present invention using titanium dioxide containing A1 in the crystal have a hue difference Δb force of 0.05 or less, and are extremely excellent in thermal stability. . In addition, the masterbatch using the surface-treated titanium dioxide of the present invention has a good dispersibility and a significantly small amount of volatile water. On the other hand, the master batch of the comparative example (No. 2) using titanium dioxide treated with a general polyol has a remarkably large amount of volatile moisture, and cannot form a film at a high temperature of 280 ^ or more.

table

Comparative example

Master /, Moisture in petit T-type film film formability & hue In-crystal “Etal Inorganic Dispersibility 200 280 300 350¾

A 1 Amin Other surface treatment agent ΔΡ Film forming property Film forming property

At 280 at 300

The content processing volume throughput Kg / cm ² Whiteness Whiteness

b b

◎ © © ©

% H-Ethano-lamine calcium chloride

9 465 533 591 87 87 87 87 0.2 0.3% 0.3%

1.21 1.20 1.20 1.21 mm △ X

%

o 2 47 1210 1465 2160 86 86 86 86

0.2

1.42 1.41 1. 0 1.40 Tyroleethane 〇 X X X

Alumina

0 1460 1850 2430 87

0.5% 0.6%

1.33

M Met P-Luetane 〇 X X X

Alumina

2 21 4 1250 1452 2100 87

0.3% 0.3%

1.85

In Comparative Examples 1 and 2, film formation was impossible at 280 ^, 300 ^, 350

Hue (whiteness, b) could not be measured.

Whitening

Replacement color b

Sex ¾

Whitening film color b Industrial applicability

According to the present invention, it is possible to obtain a masterbatch having a higher degree of whiteness than before and having excellent heat discoloration resistance, light discoloration resistance, and weather discoloration resistance. More preferably, there is provided a titanium oxide-containing masterbatch that is rich in dispersibility and hydrophobicity and generates little water during high-temperature processing. This masterbatch can produce high-quality colored resin products because the amount of volatile water under high temperature processing is significantly low, and there is no risk of causing problems such as poor dispersion or lacing in the extruder. .

Claims

The scope of the claims

(1) A masterbatch containing 0.02 to 1.0% by weight of titanium oxide containing A1 and a thermoplastic resin.

(2) 0.02 to: containing 1.0% by weight of A 1, containing 0.1 to 0.5% by weight of calcium salt and 0.05 to 3.0% by weight of triethanolamine in terms of calcium oxide A masterbatch containing treated titanium oxide and thermoplastic resin.

(3) 0.02 to 1.0 weight: Contains 0.1%, 0.01 to 0.5% by weight of calcium salt and 0.05 to 3.0% by weight of triethanolanolamine and alumina in terms of calcium oxide. Ma Sutano Tutsi characterized in that it contains terms with 0.0 1 to 0.3 wt ⁰ 6 titanium oxide treated with an aluminate salt, and a thermoplastic榭脂.

(4) 0.02 to 1.0% by weight of 81, containing 0.1 to 0.5% by weight of calcium salt and 0.05 to 3.0% by weight of triethanolanolamine in terms of calcium oxide. A masterbatch comprising titanium oxide treated with 0.01 to 0.3% by weight of a silicate and a thermoplastic resin.

(5) titanium oxide containing 0.02 to 1.0% by weight of 81, and treated with 0.01 to 0.5% by weight of a magnesium salt and 0.05 to 3.0% by weight of triethanolamine in terms of magnesium oxide; And a masterbatch containing a thermoplastic resin.

(6) 0.0 2 1 include A 1 0 wt%, 0.0 1 to 0.5 wt ^0/6 Maguneshiumu salt and 0.05 to 3.0 fold ¾% of triethyl Tanoruamin alumina Conversion oxide Maguneshiumu terms 0.0 1 to 0.3 titanium oxide treated with an aluminate weight ^0, and thermoplastic榭脂master / Ku Tutsi, characterized in that it contains a.

(7) 0.02 to 1.0% by weight of 81, containing 0.01 to 0.5% by weight of magnesium salt in terms of magnesium oxide and 0.05 to 3.0% by weight of triethanolamine in terms of siliric force. A master characterized by containing titanium oxide treated with 0.01 to 0.3% by weight of a silicate and a mature plastic resin. ~ Batchi.

(8) 0.02 ~: It contains A1 of 0 weight ⁰ / ί>, contains 0.05 to 3.0 weight ⁰ of titanium oxide treated with trietanolamine, and contains thermoplastic resin. Masterbatch to feature.

(9) 0.0 2:. 1.0 includes a weight percent of A 1, 0.0 5 to 3 0% by weight of tri Etano one Ruamin and terms of alumina in 0.0 1 to 0.3 wt ^_0/0 aluminate A master batch characterized by containing a titanium oxide treated with a salt and a thermoplastic resin.

(10) Oxidation containing 0.02 to 1.0 weight <A1 and treated with 0.05 to 3.0% by weight of triethanolamine and 0.01 to 0.3% by weight of silicate in terms of sily power A master patch comprising titanium and a thermoplastic resin.

(11) Claims containing a titanium oxide which is treated by adding a calcium salt or a magnesium salt, followed by an aluminate treatment, and then treated by adding a triethanolamine treatment. Masterbatch described in any of 2, 3, 5 or 6.

(12) Claims containing calcium oxide or magnesium salt, followed by treatment with silicate, after addition of calcium salt or magnesium salt, containing titanium oxide treated with triethanolamine. Or the masterbatch described in 7.

(13) The masterbatch according to claim 9 or 10, comprising a titanium oxide treated by adding an aluminate or a silicate and then treated by adding triethanolamine.

(14) Claims 1 to 4, wherein calcium chloride, calcium bromide, calcium iodide or calcium nitrate is used as the calcium salt.

Master batch described in any of 4 above.

(15) The masterbatch according to any one of claims 5 to 7, wherein magnesium chloride, magnesium bromide, magnesium iodide or magnesium sulfate is used as the magnesium salt.

(16) The method according to any one of claims 1 to 10, wherein A1 is contained in the crystal. Master batch described in any of them.

(17) The master batch according to any one of claims 1 to 10, wherein the titanium oxide is an anatase type titanium oxide.

(18) The masterbatch according to any one of claims 2 to 10, wherein the water that can be volatilized in 280 to 350 ^ is 1,200 ppm or less.

(19) The master batch according to any one of claims 2 to 10, which is a master batch for a melt-extruded laminate film.