WO1997024392A1

WO1997024392A1 - Masterbatch containing titanium oxide

Info

Publication number: WO1997024392A1
Application number: PCT/JP1996/003845
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: AU1209397A; JP3215979B2

Abstract

A masterbatch which comprises a thermoplastic resin containing titanium dioxide. The titanium dioxide contains 0.02 to 1.0 wt.% aluminum and 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

Membrane damage Masterbatch containing titanium oxide Technology

The present invention relates to a masterbatch used for coloring and processing a thermoplastic resin, and more particularly, to a masterpatch which is excellent in whiteness, heat-resistant, light-resistant, and weather-resistant. The present invention relates to a resin molded product which is excellent in high-speed high-temperature workability, is uniform and has excellent concealing properties, and particularly relates to a master batch suitably used for a contact extrusion lamination film. Background technology

The coloring composition used for coloring and molding thermoplastic resin includes a powdery dry color in which a pigment and a dispersant are mixed, and a liquid in which the pigment is dispersed in a liquid at room temperature. Masterbatch in the form of pellets, flakes, or pellets by dispersing a pigment in a high concentration in a solid resin at room temperature, such as dyed color or pasted color. Above all, master batches are often used because they are easy to handle and preserve the working environment during use. As a master batch for white color, a thermoplastic resin containing titanium dioxide has been used. This 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 terms of whiteness, the anatase type is excellent, and the rutile type has a yellow tint. Therefore, the anatase type is generally suitably used for applications requiring whiteness.

In recent years, there has been an increasing demand for more invasive whiteness in terms of product quality, design and differentiation, and methods of increasing whiteness include adding fluorescent whitening agents and blue. It is generally known to add taste pigments or other white pigments, but they have not been sufficiently satisfactory.

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, and dispersibility.

For example, there is titanium oxide treated with a polyol-based or polysiloxane-based surface treatment agent, but 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 the master batch using the surface-treated titanium oxide and the thermoplastic resin also has a small hydrophobicity, and thus contains a large amount of water.

Titanium oxide that has been surface-treated with a polysiloxane-based treating agent has a favorable effect of beading, but because of the weak chemical bonding force between the titanium oxide surface and the treating agent, such surface treatment oxidation When a master batch is manufactured using titanium and thermoplastic resin, the surface treatment agent is peeled off due to kneading conditions and extrusion conditions during manufacturing, resulting in uneven dispersion of titanium oxide in the master batch. Problems such as an increase in water content due to a decrease in hydrophobicity have occurred.

If an attempt is made to produce a colored resin molded product using a masterbatch with a high water content and a thermoplastic resin, the water generated from the masterbatch in the extruder will cause the masterbatch and the thermoplastic resin to be formed. 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 extrusion extrusion laminating, which requires high-temperature processing of 280 to 350 ^, where desorption of water of crystallization occurs, the water content is extremely important. At the time of extrusion, 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 was not practically used.

The present invention has solved the above-mentioned problems in the conventional masterbatch, and has higher whiteness than the conventional one, and is used for heat discoloration resistance, weather discoloration resistance, and light discoloration resistance, and is rich in dispersibility and hydrophobicity. It is intended to provide a titanium oxide-containing masterbatch containing less moisture generated during high-temperature processing. Disclosure of the invention

The present invention enhances high whiteness and color stability by containing 0.02 to 1.0% by weight of aluminum-aluminum (A1), and is excellent in heat discoloration resistance, weather discoloration resistance, and light discoloration resistance. The present invention also relates to a masterbatch containing titanium dioxide and a thermoplastic resin, which have been improved in dispersibility and hydrophobicity by performing a surface treatment. Specifically, titanium dioxide treated by the following method is used.

(1) Titanium oxide treated with a calcium salt of 0.01 to 0.5: 1 in terms of calcium oxide, (2) 0.01 to 0.5% by weight of calcium salt in terms of calcium oxide and 0.05 to 3.0 (3) 0.01 to 0.5% by weight of calcium salt in terms of calcium oxide and 0.01 to 0.3% by weight of aluminate in terms of alumina (4) 0.01 to 0.5% by weight of calcium salt in terms of calcium oxide and 0.05 to 3.0% by weight of silane coupling agent and 0.1% in terms of alumina. Titanium oxide treated with 0.1 to 0.3% by weight of aluminate, (5) Calcium oxide 0.01 to 0.5% by weight of calcium salt and silica equivalent of 0.01 to 0.3% by weight of calcium (6) 0.01 to 0.5% by weight of calcium salt in terms of calcium oxide and 0.05 to 3.0 weight Of the silane coupling agent and in terms of silica 0.0 1 to 0.3 wt% of the treated titanium oxide and Kei salt.

In the processing method of the above (1) to (6), instead of the calcium salt, oxide mug Neshiumu terms 0.0 1 to 0.5 wt ^0/6 magnesium salts may be used titanium oxide treated.

Also, titanium oxide treated with 0.05 to 3.0% by weight of a silane coupling agent without using a calcium salt and magnesium, or 0.05 to 3.0% by weight of a silane coupling agent and 0 in terms of alumina. Titanium oxide treated with 0.1 to 0.3% by weight of aluminate clay, or 0.05 to 3.0% by weight of silane coupling agent and 0.01 to 0.3% by weight of silicic acid in terms of silicic acid Titanium oxide treated with a salt may be used.

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 clay. When these calcium salts or magnesium salts, silane coupling agents, aluminate lumps or citric acid are used in combination, the treatment is performed by adding a calcium salt / magnesium salt and then adding an aluminate or silicate. After that, it is preferable that the material is treated by adding a silane coupling agent. As the calcium salt, calcium chloride, calcium bromide, calcium iodide or calcium nitrate can be used.

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

As the silane coupling agent, methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, phenyltrialkoxysilane, or dialkyldialkoxysilane can be used.

The above-mentioned 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-mentioned titanium dioxide has a water content of 1200 ppm or less which can be volatilized in 280 to 35, and is suitable as a masterbatch for an extruded laminate film. It is. BEST MODE FOR CARRYING OUT THE INVENTION

(1) A1 containing titanium oxide

The masterbatch of the present invention suppresses and prevents discoloration due to heat by using titanium oxide containing A1, increases whiteness, and specifies the titanium oxide containing A1! : Surface treatment using a silane rubbing agent or a specific amount of calcium salt to reduce the amount of volatile water and improve dispersibility, hydrophobicity, concealment, light discoloration resistance, weather discoloration resistance, etc. Things.

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 master batch containing titanium oxide containing Nb, Ta, and W in the crystal is used in fields requiring high-temperature processing of 280 to 350 ^, for example, in the field of melt extrusion lamination. At low temperature The blue and black of the colored molded product becomes remarkable as compared with the case where it is used.

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 350, and is therefore melt-extruded. When manufacturing a molded article such as a film, 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, W present as an impurity taken into the titanium dioxide crystal as an ion. Specifically, the content is 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 fast discoloration resistance, light discoloration resistance, and weather discoloration resistance. On the other hand, if the content exceeds 1.0% by weight, free A1 which does not enter the crystal is mixed in an oxide state, which is not preferable.

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 hydrated titanium dioxide obtained by the sulfuric acid method, drying the mixed slurry, and drying the mixed slurry at 850 to 110. Obtained by a wet process of firing at 0. Alternatively, it can also be manufactured by a dry manufacturing 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

The masterbatch of the present invention contains the above-mentioned A1-containing titanium dioxide which has been subjected to a surface treatment using a calcium clay or magnesium salt, a silane coupling agent, an aluminate clay or a silicate.

The silane coupling agent used in the present invention is used for hydrophobizing the A1-containing titanium oxide and improving dispersibility, and has a structure represented by the following general formulas (1) to (4). Are suitable, and specifically, for example, methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminobuguchi piltriethoxysilane, V—methacryloxypropyltrimethoxysilane, biertriethoxysilane, phenyltrisilane Phenyl alcohols such as alkoxysilanes and diphenyldialkoxysilanes Xylane, and dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethylethoxysilane.

(1) (2)

X X

I

X— S-R-Y X-S ― Υ X X

(3) (4)

Y Y

I

X-S i-R-Y X-S i Υ

I I

X x

X: hydrolyzable group

CH ₃ 0—, C ₂ H ₅ 0—, CH ₃ OC ₂ H, Ο-, C 1—, etc.

R: divalent aliphatic chain, divalent aromatic spear

Y: Organic functional group

Methyl group, ethyl group, vinyl group, epoxy group, amino group, mercapto group, acryl group, methacryl group, etc. Among the organic functional groups of the above general formula, those having a methyl group or an amino group are preferable, and in particular, dialkyl Dialkoxysilane is preferred, and dimethyldimethoxysilane is particularly preferred.

The use amount of the silane coupling agent is suitably 0.05 to 3.0% by weight, preferably 0.05 to: 1.0% by weight, more preferably 0.1 to 0.5% by weight, and most preferably 0.1. ~ 0.3% by weight.

If the amount of the silane coupling agent exceeds 3.0% by weight, a slip occurs when the master batch is extruded, 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. If the amount used is less than 0.05% by weight, the effect of water-hydrophobicity on the A1-containing titanium oxide is small, and water adsorption over time after the production of the master batch increases. Therefore, the same problem as the conventional one occurs.

The calcium salt or the magnesium salt used in the present invention reacts with the hydroxyl group on the surface of the A1-containing titanium oxide to fix the hydroxyl group and hydrophobize the A1-containing titanium oxide in the same manner as the silane coupling agent. It is used for

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. These are used in an amount of 0.01 to 0.5% by weight in terms of calcium oxide or magnesium oxide. If the amount used is less than 0.01% by weight, the effect of sessification is insufficient, and if it is used in excess of 0.5% by weight, the effect of hydrophobization hardly changes.

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, and further, an aluminate such as sodium aluminate or a silicate are used. Using a salt, treatments such as alumina and sily can be applied together. That is, after treating the A1-containing titanium oxide with an aluminate, a silicate, or the like, it may be treated with a silane coupling agent, or after treating the A1-containing titanium oxide with a calcium salt or the like, and then treating the aluminum oxide with an aluminum salt. A1 containing titanium oxide may be treated with a calcium salt, etc., then treated with an aluminate, a silicate, etc., and further treated with a silane coupling agent. May be.

Alumina, silica, and the like generally contain water of crystallization or are hydrated, and although it is preferable to reduce it as much as possible from the viewpoint of reducing water content, it has the effect of increasing the shielding power. Yes, in areas where concealment is strongly required. However, the amount used is preferably as small as possible, and is suitably 0.3 wt.% Or less, and preferably 0.2 wt.% 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 over silica in that it is easy to separate. The AI-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, but anatase type is particularly preferable from the viewpoint of whiteness.

If the titanium oxide has not been treated with an organic treating agent such as a silane coupling agent, or with an inorganic treating agent such as alumina, the dispersion of the titanium oxide is extremely poor, and the coloring resin molded product has Agglomerates are generated and clogging of the screen mesh of the molding machine is caused.

(3) Titanium dioxide containing masterbatch

Examples of the thermoplastic resin used in the present invention include polyolefin resins, polyester resins, polystyrene resins, and nylon resins, which are common thermoplastic resins. In the field of (1), polyolefin resin and polyester resin are listed. Polyolefin resin is particularly preferable for the melt extrusion lamination to the paper base, and polyethylene resin is particularly preferable. Further, for melt extrusion lamination on a metal substrate, a polyester resin is particularly preferable, and among them, polyethylene terephthalate is preferable.

The masterbatch of the present invention may contain the surface-treated titanium oxide and the thermoplastic resin in a ratio of 2-8 to 8-2, preferably 5Z5-7-7, more preferably 6-4. ~ 7 Z3.

The masterbatch of the present invention composed of the above components has a volatile water content of less than 120 O ppB at 280 to 350, preferably less than 80 O ppai, more preferably less than 300 O ppai. With a volatile water content of less than 60 O ppm. The above-described various problems occur when an attempt is made to obtain a colored resin molded product using a master batch and a thermoplastic resin having a volatile water content of more than 1200 ρριι within the above temperature range. The moisture is the amount of moisture generated at a predetermined temperature under a nitrogen atmosphere using a Karl Fischer 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. The configuration examples of the masterbatch of the present invention described above are shown in the following table.

table 1

(4) Example

Example 16 and Comparative Example 15

40% by weight of low-density polyethylene (specific gravity: 0.917, MFR 7. Og / lOnin.) Was mixed with 60% by weight of titanium oxide shown in Table 2, and heated and mixed in a kneader, followed by cooling and pulverization. Then, it is extruded with an extruder to obtain a pellet-shaped master batch. Was. Various evaluations were performed using the obtained master batch. The evaluation method is shown below, and the results are shown in Table 2.

(1) Moisture measurement method:

1 g of the above master batch was used to measure the amount of water generated at each temperature using a Karl Fischer moisture meter (manufactured by Hiranuma Sangyo Co., Ltd.). The values in the table are shown in ppii units.

(2) Dispersibility evaluation method:

At the outlet of the Labo Plastomill single-screw extruder 20 mm (manufactured by Toyo Seiki Co., Ltd.), a screen with a finer mesh of 40/80/120/500 was attached in order, at 50 rpm, at an extrusion temperature of 300. Then, a low-density polyethylene (specific gravity: 0.916, MFR 9.0 g / 10min.) And a master batch were passed through a 1: 1 blended pellet, and the initial pressure P1 at the start of passing was determined. : Determine the end pressure P2 when the pellets blended in 1 pass a predetermined amount (ft containing 360 g of titanium oxide in the pellets). It can be said that the smaller the pressure difference ΔP = P2-P1, the better the dispersibility of titanium oxide.

(3) T-die film deposition method:

The above master batch 67 weight <½, low density polyethylene (specific gravity 0.918, MFR 4. Og / lOain.) 33 3% by weight is blended and molded using a T-die film molding machine (Toyo Seiki Co., Ltd.) At a temperature of 200 ° C, 280 °, 300 °, and 350 °, T-die films having a film thickness of 30 / iB were prepared, and the film forming properties (appearance), hue, etc. were evaluated. .

(4) Growth evaluation:

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

◎: No racing or foaming.

〇: There are racing and some foaming.

Δ: Racing, foaming.

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

(5) Color measurement method:

The whiteness and hue of a 30-a-thick T-die film extruded and prepared at each temperature by the above method were measured with a colorimeter (manufactured by Kurabo Industries, Ltd.). Hue and whiteness are Industry standard (JIS Z-8715). The larger the whiteness W is, the whiter the color is, and the smaller the hue b is, the more bluish it is. Are thermally stable. Specifically, 0.10 or less is appropriate, and 0.05 or less is preferable. As shown in Table 2, the masterbatch of the present invention using titanium dioxide containing A1 in the crystal has a hue difference Δb of 0.05 or less in all cases, and the mature stability is extremely convenient. Have been. On the other hand, in each of the comparative examples (No. 4) having no A 1 in the crystal 內, the hue difference Δb was at least significantly larger than 0.1 and the thermal stability was significantly low.

In addition, the masterbatch of the present invention using surface-treated titanium dioxide has good dispersibility and has a significantly small amount of volatile water. On the other hand, the masterbatch of Comparative Example (No. 5) using titanium dioxide without surface treatment is inferior in dispersibility, has a remarkably large amount of volatile water, and is inferior in film formability.

Table 2

Industrial applicability

According to the present invention, a titanium oxide-containing masterbatch having a higher degree of whiteness, excellent heat discoloration resistance, light discoloration resistance, and weather discoloration resistance, rich in dispersibility and hydrophobicity, and low in moisture generated during high-temperature processing. Is provided. This masterbatch has a small amount of volatile moisture under high-temperature treatment, and does not cause inconveniences such as poor dispersion in an extruder and lacing, so that a high-quality colored resin product can be produced.

Claims

The scope of the claims

(1) 0.0 2 1 include A 1 0 weight ^_0/0, containing 0.0 1 to 0.5 wt% titanium oxide treated with calcium salts, and Jukuka plastic榭脂oxide Karushiumu terms A master batch characterized by:

(2) 0. comprise from 0 2 to 1. eight 1 0 wt%, 0.1 0 1 0.5 5 wt% of the calcium salt 0.5 with calcium oxide in terms 05 to 3.0 wt ^_0/0 of silane Master patch characterized by containing titanium oxide treated with a coupling agent and thermoplastic resin.

(3) 0.02 ~: Contains 1.0% by weight of A1, 0.01 to 0.5% by weight of calcium salt in terms of calcium oxide, and 0.01 to 0.3% in weight of alumina in terms of alumina A master batch comprising titanium oxide treated with an acid salt and a thermoplastic resin.

(4) 0.0 2 to 1.0 include A 1 weight ⁰ 6, 0.0 1 to 0.5 wt <½ calcium salt of from 0.05 to 3.0 wt% of Shiranka coupling agent with calcium oxide in terms A master notch characterized in that it contains titanium oxide treated with 0.1 to 0.3% by weight of alumina acid in terms of alumina and thermoplastic resin.

(5) 0.0 2 to 1.0 comprises by weight percent A 1, 0. 0 1~ 0. 3 in 0.0 1 to 0.5 wt ^_0/0 calcium salt and silica terms calcium oxide in terms A masterbatch containing titanium oxide treated with a weight percent of a silicate and a thermoplastic resin.

(6) 0.0 2 1 include A 1 0 wt%, and the calcium salt of 0.0 1 to 0.5 wt ⁰ 6 calcium oxide conversion and 0.0 5 to 3.0 wt% silane force coupling agent A masterbatch comprising: titanium oxide treated with 0.01 to 0.3% by weight of silica clay in terms of silica; and a thermoplastic resin.

(7) It contains 0.02 to 1.0% by weight of A 1, contains titanium oxide treated with 0.01 to 0.5% by weight of magnesium salt in terms of magnesium oxide, and a thermoplastic resin. A master patch characterized by the following:

(8) 0.01 to 1.0% by weight of A1 and 0.01 to 0.5% by weight of magnesium salt in terms of magnesium oxide and 0.05 to 3.0% by weight of ⁰ / o silane coupling agent A masterbatch comprising titanium oxide treated with, and a thermoplastic resin.

(9) 0.02 to: Contains 1.0% by weight of A1, 0.01 to 0.5% by weight of magnesium salt in terms of magnesium oxide and 0.01 to 0.3% by weight of aluminate in terms of alumina A masterbatch comprising: titanium oxide treated with a salt; and a thermoplastic resin.

(1 0) 0.0 2 1 includes eight 1 0 wt%, Maguneshiumu salt 0.0 1 to 0.5 wt% magnesium oxide in terms and 0.05 to 3.0 wt ^_0/0 of silane Katsupuri ring agent A master / knob characterized by containing titanium oxide treated with 0.1% to 0.3% by weight of aluminate in terms of alumina, and a thermoplastic resin.

(1 1) Contains 0.02 to 1.0% by weight of 1, containing 0.01 to 0.5% by weight of magnesium salt in terms of magnesium oxide and 0.01 to 0.3% in weight of silicate in terms of silicic acid. A masterbatch comprising titanium oxide treated with a thermoplastic resin and a thermoplastic resin.

(1 2) Contains 0.02 to 1.0% by weight of 8 1, calculated as magnesium oxide 0.0:! To 0.5% by weight of magnesium salt and 0.05 to 3.0% by weight of silane coupling agent and silicic acid A master batch characterized in that it contains titanium oxide treated with 0.01 to 0.3% by weight (½) of a silicate and a thermoplastic resin.

(1 3) 0.02 ~ 1.0 weight! : A masterbatch containing% A1 and characterized by containing 0.05 to 3.0% by weight of a titanium oxide treated with a silane coupling agent, and a thermoplastic resin.

(14) 0.02 or more: titanium oxide containing 1.0% by weight of A1, treated with 0.05 to 3.0% by weight of a silane coupling agent and 0.01 to 0.3% by weight of aluminate in terms of alumina, and A masterbatch characterized by containing a thermoplastic resin.

(15) 0.02 to: I containing 0.0% by weight of A 1 and 0.05 to 3.0% by weight A master's stick characterized by containing titanium oxide treated with a silane coupling agent and 0.01 to 0.3% by weight of a silicate in terms of silicic acid, and a thermoplastic resin.

(16) After the calcium salt or magnesium salt is added and treated, the one treated with the aluminate is treated with the addition of the calcium salt or the magnesium salt, and the one treated with the silane coupling agent is treated with the titanium oxide. A master batch described in claims 2, 3, 4, 8, 9 or 10 containing.

(17) After adding and treating calcium salt or magnesium salt, those treated with silicate are added and treated, and those treated with silane force agent are added and treated. A master batch according to claim 5, 6, 11 or 12 containing titanium.

(18) The masterbatch according to the above (14) or (15), comprising a titanium oxide treated with an aluminate or a silicate and then treated with a silane bonding agent.

(19) The masterbatch according to any one of claims 1 to 6, wherein calcium chloride, calcium bromide, calcium iodide or calcium nitrate is used as the calcium salt.

(20) The masterbatch according to any one of claims 7 to 12, wherein agglomerated magnesium, magnesium bromide, magnesium iodide or magnesium sulfate is used as the magnesium salt.

(21) It is characterized in that methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, biertriethoxysilane, phenyltrialkoxysilane or dialkyldialkoxysilane is used as the silane coupling agent. Claims 2, 4, 6, 8,

Master batch described in any one of 10 and 13 to 15.

(22) The masterbatch according to any one of claims 1 to 15, wherein A1 is contained in the crystal.

(23) The masterbatch according to any one of claims 1 to 15, wherein the titanium oxide is an anatase type titanium oxide.

(24) The water that can be volatilized in 280-350 is less than 1200 ppm. The master batch according to any one of claims 1 to 15, wherein the master batch is a master batch for an extruded laminated film. Master badge described in Crab