JPH05125223A - Hydrotalcite-coated particle, its preparation and resin additive - Google Patents

Abstract

PURPOSE:To provide a resin additive comprising hydrotalcite-coated particles having the merits of the constituents by coating well-dispersible irregular-shape particles with fine hydrotalcite particles. CONSTITUTION:The title particles is prepared by coating irregular-shape particles of amorphous silica, amorphous silica-alumina or an amorphous or crystalline aluminosilicate having a primary particle diameter of 0.3-20mum with 0.5-30wt.% fine hydrotalcite particles through 0.01-5 wt. % organic binder. When compared with uncoated irregular-shape particles, the coated particles can give improved flow, markedly improved abrasive resistance and scratch resistance and improved antiblocking properties. Further, the title particles do not suffer drawbacks such as poor dispersion and fish eye formation encountered when hydrotalcite is used alone.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to hydrotalcite-coated particles, a method for producing the same, and a compounding agent for a resin. More specifically, the compound has excellent compoundability and dispersibility in a resin, The present invention relates to a hydrotalcite-coated particle used for imparting various properties to a particle and a method for producing the particle.

[0002]

2. Description of the Related Art It has long been known to use hydrotalcites as a chemical modifying compounding agent or a physical property modifying compounding agent for resins, for example, JP-A-53-9285.
JP-A-58-46 describes that hydrotalcites are blended in a thermoplastic resin as a flame retardant.
No. 146 discloses that a halogen-containing thermoplastic resin derived from a catalyst or a monomer has a BET specific surface area of 30 m ² / g.
It is described that the following hydrotalcites are compounded as a stabilizer. On the other hand, resin molded products such as films and sheets tend to block each other when they are stacked, and various inorganic compounding agents are added to the resin in order to prevent this and further impart slip properties. Blending has been done for a long time.

It is already known that zeolite is excellent in such characteristics, for example, Japanese Examined Patent Publication No. 52-1613.
Japanese Unexamined Patent Publication (Kokai) No. 4 discloses that by adding 0.01 to 5% by weight of zeolite powder having an average particle size of 20 microns or less to polypropylene, the biaxially stretched polypropylene film is improved in blocking resistance. .. Further, in JP-A-54-34356, thermal stability is improved by compounding a chlorine-containing polymer with an aluminosilicate of a zeolite crystal having ion exchangeability in an amount of 0.01 to 10% by weight. And, as an additional advantage, the external lubricity is significantly improved.

Further, in JP-A-58-213031, the molar ratio of Al ₂ O ₃ : SiO ₂ is 1: 1.8 to 1 :.
Consisting of cubic primary particles with a side length of less than 5 microns having a composition in the range of 5, said particles being substantially amorphous by X-ray diffraction and having a BET specific surface area of less than 100 m ² / g. An alumina-silica resin compounding agent characterized by the above is described.

It is already known to combine a plurality of kinds of the above-mentioned compounding agents into a resin, for example, Japanese Patent Laid-Open No. 2-1.
In JP 63143, 0.01 to 2.0 parts by weight of an anti-blocking agent, 0.01 to 0.2 parts by weight of a hydrotalcite compound, and 0.01 of a higher fatty acid metal salt are used with respect to 100 parts by weight of a polyolefin resin. A polyolefin-based resin composition is described which is characterized by containing 0.2 to 0.2 parts by weight.

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The above-mentioned hydrotalcites capture hydrogen chloride generated by thermal decomposition from a chlorine-containing polymer, or a polymerization catalyst residue (halide) remaining in an olefin polymer or the like. It is excellent in the effect of blocking the resin and stabilizing the resins, but the dispersibility in the resin is poor, and many fish eyes are generated during film molding, and dispersibility such as foaming when added in a large amount. However, there is a problem in moldability, and further there is a problem in composition that dust is likely to be generated during compounding.

Cubic or spherical zeolite, amorphous silica, or alumina-silica or the like shaped particles are
It has excellent dispersibility in resin, good transparency of the compounded molded product, and has the advantage that there is no powdering during compounding, while it has poor fluidity when handled as powder, and also has a wall surface. There is a problem in handling that it is liable to adhere to the surface to cause bridges and the like, and the resin composition containing the regular particles tends to have great abrasion or polishing properties and damage die slips, etc. There is a drawback that scratches are likely to occur if the two are rubbed together.

[0008] When these compounding agents are combined in the resin, the thermal stability and anti-blocking property of the molded product can be improved. However, the above-mentioned dispersibility and moldability peculiar to hydrotalcites can be improved. Difficulties, compounding difficulties, and handling problems peculiar to the regular particles and defects such as abrasion and scratches have not yet been solved, and will remain as problems. Therefore, the object of the present invention is to eliminate the fixed particles of zeolite and its amorphized product, and various drawbacks that occur when using hydrotalcite, and to have excellent handleability as a powder and The present invention provides a fixed particle-hydrotalcite-coated particle which is excellent in dispersibility in water and has significantly improved abrasion resistance and scratch resistance, and a method for producing the same.

[0009]

According to the present invention,
(A) Amorphous silica, amorphous silica in which each particle independently has a well-defined cubic or spherical primary particle shape and has a primary particle diameter of 0.3 to 20 μm as measured by electron microscopy. Formed core particles made of alumina or amorphous or crystalline aluminosilicate, (B) hydrotalcite particles and (C) organic binder, and most of the core hydrotalcite particles are Provided are coated particles which are characterized in that they coat the surface. According to the present invention, there is provided a resin compounding agent comprising the above coated particles.

Further in accordance with the present invention, the individual particles are amorphous having an independently defined cubic or spherical primary particle shape and having a primary particle diameter of 0.3 to 20 μm as measured by electron microscopy. Core particles of silica, amorphous silica-alumina or amorphous or crystalline aluminosilicate, 0.01 to 5% by weight of organic binder per core particle and 0.5 to 30% by weight of hydrotal per core particle. There is provided a method for producing hydrotalcite-coated particles, which comprises mixing the site particles in a wet or dry manner under the condition that the organic binder is softened or melted.

[0011]

In FIG. 15, which schematically shows the cross-sectional structure of the coated particles of the present invention, the coated particles are the cores of the regular particles.
A and a fine particle coating (shell) B that covers the surface of the core, and an organic binder C is interposed therebetween.
In the present invention, as the core particles A, an amorphous material in which each particle independently has a clear cubic or spherical primary particle shape and has a primary particle diameter of 0.3 to 20 μm measured by an electron microscope method. A fixed particle of silica, amorphous silica-alumina or amorphous or crystalline aluminosilicate is selected, and hydrotalcite fine particles are selected as the fine particle coating (shell) B to have the above-mentioned coated particle structure.

In the regular core particles, each individual particle independently has a well-defined cubic or spherical primary particle shape, which means that the mutual aggregation of the regular core particles does not occur even at the primary particle size, and therefore the individual regular core particles are not formed. This enables the uniform coating of the particles of hydrotalcite on the surface of the particles, and has the advantage that the coated particles are also held in distinct, well-defined cubic or spherical shapes.

[0013] The chemical composition of the regular core particles is
Amorphous silica-alumina or amorphous or crystalline aluminosilicate is defined as the above-mentioned particle shape is originally derived from the crystalline shape of crystalline aluminosilicate such as zeolite. When the crystalline aluminosilicate is converted to amorphous silica and amorphous silica-alumina by acid treatment of the crystalline aluminosilicate, and the crystalline aluminosilicate is ion-exchanged and then calcined, the crystalline skeleton still remains. By being converted into an amorphous aluminosilicate while retaining the above. Of course, the regular particles having the above-mentioned shape and the above-mentioned chemical structure have an excellent feature of imparting antiblocking property, transparency, or thermal stability to the compounded resin.

It is also important that the regular core particles have a primary particle diameter of 0.3 to 20 μm, especially 1 to 5 μm, measured by electron microscopy. When the particle shape is smaller than the above range, the primary particles have a strong tendency to aggregate with each other, and the independence of the primary particles tends to be lost. When the particle size is larger than the above range, the film-forming property of the resin composition is lowered,
The physical properties of the film will deteriorate. By coating the surface of the regular core particles with hydrotalcite fine particles, an unexpected advantage is achieved as compared with the case where both are simply used in a mixture. First, the poor fluidity and the tendency to adhere to the vessel wall, which are observed when the regular core particles are used alone, are eliminated, and the fluidity and the smoothness are remarkably improved. It is considered that this is because the hydrotalcite fine particles attached to the surface of the regular core particles show a kind of roller slipping property.

Next, the abrasion resistance and the scratch resistance when the regular core particles alone are blended in the film are remarkably improved. The abradability observed when using the regular core particles alone is due to the fact that this particle is a very hard primary particle, but by providing a soft coating of hydrotalcite on its surface,
This is considered to be the cause of the above improvement. Furthermore, the above-mentioned coating structure increases the bulk as a whole, and therefore the anti-blocking performance is also improved as compared with uncoated particles.
Further, since the hydrotalcite is in a state of being retained on the surface of the regular core particles, the problem of poor dispersion in the resin, which is a drawback of hydrotalcite, is solved, and excellent resin dispersibility is obtained, and the fish Trouble such as eye generation is also eliminated. Naturally, the problem of dusting when handling hydrotalcite powder is also eliminated.

By the way, when it is attempted to coat the regular core particles and the hydrotalcite fine particles simply by mixing,
A part of the hydrotalcite fine particles will be attached to the surface of the fixed core particle, while the remaining part will coexist in the form of powder independent of the fixed core particle. The free form of hydrotalcite fine particles causes poor dispersion and further causes powdering when compounded in a resin, but in the present invention, the fixed core particles and hydrotalcite fine particles are intercalated through an organic binder. Since they are bonded, it is possible to effectively prevent the hydrotalcite fine particles from becoming free.

FIG. 3 is a particle structure of an amorphous aluminosilicate (fixed core particle) alone, FIG. 7 is a particle structure of a mixture of amorphous aluminosilicate and hydrotalcite fine particles, and FIG. It is an electron micrograph showing the particle structure of the coated particles of the present invention comprising a porous aluminosilicate, hydrotalcite fine particles and an organic binder, respectively, but in the coated particles of the present invention, the hydrotalcite fine particles are not released, and the fixed core particles are formed. The fact of being retained as a coating on the surface becomes clear. For details of these, refer to Examples described later.

[0018]

Preferred Embodiment of the Invention

(Fixed Core Particles) As the fixed core particles, all of amorphous silica, amorphous silica-alumina, and amorphous aluminosilicate that satisfy the above-mentioned restrictions can be used.
Examples of the aluminosilicate include various zeolites having a clear cubic or spherical primary particle shape, for example, A-type zeolite, X-type zeolite, Y-type zeolite, P-type zeolite, sodalite, analcime and the like. These zeolites may be of the sodium type, potassium type, magnesium type, zinc type or combinations thereof. A-, X-, and Y-type zeolites are typical examples of cubic zeolites, P-type zeolites and sodalites are typical examples of spherical zeolites, and analcime is an example of polyhedra (24-hedra) located in the middle of them. Is.

Typical chemical compositions of these Na-type zeolaoites are shown below. A type Al ₂ O ₃ 25 to 45% SiO ₂ 30 to 55% Na ₂ O 15 to 25% H ₂ O 25% or less X type Al ₂ O ₃ 20 to 40% SiO ₂ 35 to 60% Na ₂ O 10 to 25% H ₂ O 25% or less Y type Al ₂ O ₃ 15 to 30% SiO ₂ 40 to 65% Na ₂ O 8 to 20% H ₂ O 25% or less P type Al ₂ O ₃ 15 to 35% SiO ₂ 35 to 70% Na ₂ O 8 to 20% H ₂ O 25% less sodalite Al ₂ O ₃ 25 to 50% SiO ₂ 30 to 55% Na ₂ O 15 to 25% H ₂ O 25% less analcime Al ₂ O ₃ 25 to 50% SiO ₂ 50 to 75% Na ₂ O 5 to 20% H ₂ O 25% or less

Na ₂ O in the zeolite can be exchanged with the above-mentioned other metal components in the range of 10 to 100 mol%, preferably 30 to 80 mol%. The zeolite to be used shows a characteristic X-ray diffraction image depending on its type, but it is known that the X-type, Y-type and P-type zeolite are amorphized by firing. Acid salts may also be used for the purposes of the present invention.

As the amorphous silica-alumina, the above-mentioned zeolite or the like is treated with an acid to remove the sodium content or the alumina content sufficient to make the zeolite amorphous. As the amorphous silica, one obtained by thoroughly treating the zeolite with an acid to remove the sodium content and the alumina content in the zeolite is used. Of course, the amorphous silica-alumina and the amorphous silica should have the particle shape and particle size characteristics peculiar to zeolite substantially as they are.

The acid used in the production of amorphous silica-alumina and amorphous silica may be an inorganic acid or an organic acid without particular limitation, but economically, hydrochloric acid, sulfuric acid,
Acids such as nitric acid and phosphoric acid are used. These acids are used in the form of dilute aqueous solution for the neutralization reaction with the crystalline zeolite.

When an acid is added to an aqueous slurry of crystalline zeolite, the pH naturally shifts to the acidic side as the acid is added, but after the addition is completed, the pH of the liquid shifts to the alkaline side again.
It tends to saturate to a certain pH value. This saturated p
Amorphous silica-alumina is obtained by performing neutralization so that H, that is, the pH at the time of stability is in the range of 7.0 to 3.0, especially 6.5 to 4.0. After the obtained amorphous silica-alumina is dried or calcined, the acid treatment is further continued to obtain amorphous silica. The amount of acid used must be sufficient to remove 50% or more, especially 70% or more, of the alkali content in the zeolite. Although the shrinkage of the particles naturally occurs with the removal of the sodium content and the alumina content, the shrinkage of the particle size is at most about 10 to 20%, the particle shape hardly changes, and the particle size distributions are comparable. The characteristic of sharpness is not lost. When converting zeolite to amorphous silica-alumina or amorphous silica, the basic component in the zeolite is removed, so that the coloration of the resin molded product due to the presence of the basic component is prevented over time. There is. Zeolite contains water of crystallization which is generally called zeolitic water, and the water of crystallization is desorbed under the processing or molding conditions of the resin to cause a so-called foaming problem. Also, such problems do not occur with amorphous silica. In particular, the calcined amorphous silica-alumina has a remarkably small hygroscopic tendency.

As the amorphous aluminosilicate, it is possible to use an amorphous aluminosilicate which is obtained by calcining zeolite, and as a particularly preferable one, it has an X-ray diffraction image peculiar to P-type zeolite and The steps of synthesizing zeolite particles in which the particles as a whole have clear spherical particles and a jagged surface,
And the zeolite particles are ion-exchanged with divalent metal ions, and then the ion-exchange particles are heated to 200 ° C to 700 ° C.
An amorphous aluminosilicate obtained by firing at.

This is the following formula

[Chemical formula 1] mMO / nNa ₂ O / pSiO ₂ / Al ₂ O ₃
QH ₂ O In the formula, M is a metal of one or more divalent metals, m + n is a number of 1.1 ± 0.2, and the ratio of m: n is from 10: 0 to 1 : 9 and p is 4 ± 1.
Is a number of 5 and q is a number of 0.5 or less. X-ray diffractiometrically amorphous, individual particles having a well-defined spherical shape and a jagged surface as a whole, and RH 90%, room temperature and 48 hours condition At 13
% And a refractive index of 1.48 to 1.61.

In the regular core particles used in the present invention, the cubic or spherical primary particles have a primary particle size of 0.3 to 20 μm in diameter, particularly 1 to 5 μm in diameter measured by an electron micrograph. Furthermore, shaped nucleus particles used in the present invention, with respect to that having the particle shape and particle size characteristics described above, 300 meters ² / g or less, particularly 100 m ² /
It has a BET specific surface area of g or less.

(Hydrotalcite fine particles) Hydrotalcite originally has the formula

Embedded image A mineral represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, but as the divalent metal cation (M ²⁺ ), various cations other than magnesium, such as zinc ion, As the trivalent metal cation (M ³⁺ ), various cations other than aluminum, and as the anion, various anions other than carbonate, such as borate ion and sulfate ion,
Is already known, and a wide range of molar ratios of divalent metal and trivalent metal are known. ． In the present invention, any hydrotalcites can be used as long as they satisfy the condition of being fine particles.

Suitable hydrotalcites have the formula:

Embedded image In the formula, Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O, where x is 0 <x ≦ 0.5, particularly 0.2 <x ≦ 0.4 Yes, m is 2 or less, particularly 0 to 1. The magnesium, aluminum, carbonate and hydroxide represented by

The X-ray diffraction peaks of hydrotalcites are shown in the table below.

[Table 1] The particle size of hydrotalcite is preferably 0.01 to 1 μm, particularly 0.1 to 0.5 μm, as measured by an electron microscope, and is particularly one fifth or less of the primary particle diameter of core particles. Especially, those having a particle size of 1/10 or less are preferable.

Hydrotalcite which is particularly preferably used for the purpose of the present invention has the following formula:

## EQU1 ## Is = tan θ ₂ / tan θ ₁ where θ ₁ is the angle between the peak perpendicular and the tangent line on the included angle side in the X-ray diffraction peak with the interplanar spacing of 2.49Å to 2.05Å, and θ ₂ is It is the angle formed by the peak perpendicular to the peak and the wide-angle peak tangent. The stacking irregularity index (Is) defined by the above is 1.2 or more, particularly 1.2 to 4.0,
The most suitable are hydrotalcites having a content of 1.5 to 3.5.

The stacking irregularity index (Is) represents the irregularity of stacking of layers, and has the following meaning in the hylotalcite class. That is, the hydrotalcites have a basic layer in which Mg ²⁺ of the Mg (OH) ₆ octahedral layer is replaced with Al ³⁺ , and the basic layer is formed. It is said that such anions are incorporated, and a large number of these basic layers are stacked to form a layered crystal structure. The diffraction peak of the above-mentioned plane spacing corresponds to the plane index (015), and the similar stacking irregularity also appears in the plane index (018). Therefore, in this stacking irregular hydrotalsat, the dimensions of each basic layer ( It is recognized that the length and area are not uniform, the distribution is wide, and the basic layers are twisted, curved, etc. to form a non-planar structure.

This laminated asymmetric hydrotalcite has a very excellent trapping property for chlorine or hydrogen chloride, and has a fine particle size, which is particularly preferable for the purpose of the present invention. This laminated asymmetric hydrotalcite is obtained by adding a water-soluble magnesium salt, a water-soluble aminium salt and a water-soluble ammonium salt to an aqueous medium containing sodium carbonate and caustic soda, but not limited thereto, and reacting them. .. In this case, it is important to add the water-soluble ammonium salt at the same time as the magnesium salt and the aluminum salt in order to produce hydrotalcite having a stacking disorder index (Is) within the above range.

(Organic Binder) As the organic binder, waxes, various coupling agents or resins, especially those having a low melting point are used. The following waxes can be used. (1) Fatty acids and metal salts thereof Higher fatty acids Fatty acids obtained from animal or vegetable oils and fats and those fatty acids obtained by hydrogenation, and those having 8 to 22 carbon atoms Higher fatty acid metal salts Alkali metal salts of the above fatty acids, Alkaline earth metal salt, Z
n salt, Al salt

[0034] (2) amide, amine higher fatty acid amide oleyl palmityl amide thread allyl erucamide 2 stearothermophilus bromide ethyl stearate ethylenebis fatty acid amide N · N ^'oleoyl stearyl ethylenediamine N · ^N' bis (2-hydroxyethyl) alkyl (C ₁₂ ~
C ₁₈ ) Amide N · N ^′ Bis (hydroxyethyl) laurylamide N alkyl (C ₁₀ -C ₁₈ ) trimethylenediamine reacted oleic acid Fatty acid diethanolamine Di (hydroxyethyl) diethylenetriamine monoacetate distearate ester

(3) Fatty Acid Ester of Monohydric or Polyhydric Alcohol n-Butyl Stearate Hydrogenated Rosin Methyl Ester Dibutyl Sebacate <n-Butyl> Dioctyl Sebacate <2-Ethylhexyl and n-octyl Co> Glycerin Fatty Acid Ester Pentaerythritol Tetrastearate Polyethylene glycol fatty acid ester Polyethylene glycol distearate Polyethylene glycol dilaurate Polyethylene glycol dioleate Polyethylene glycol coconut fatty acid diester Polyethylene glycol tall oil Fatty acid diester Ethanediol montanic acid diester 1,3 butanediol montanic acid diester Diethylene glycol stearic acid diester

(4) Triglyceride, wax Hydrogenated edible oil and fat 12-Hydroxystearic acid glycerin ester Sperm aceti wax Montan wax Carnauba wax Beeswax Beeswax Monohydric fatty acid alcohol and fatty acid saturated ester <Example: Hardened whale oil Lauryl stearate, stearyl steaer Rayto> Lanolin Polyethylene wax Polypropylene wax Oxidized polyethylene wax Acid-modified polyethylene wax Epoxy-modified polyethylene wax Petroleum wax

Among these waxes, carboxylic acid, carboxylic acid anhydride, carboxylic acid salt, carboxylic acid ester, carboxylic acid amide, per gram of waxes,
0.1 to 20 polar groups such as ketones, ethers and hydroxyl groups
Waxes containing at least one long-chain alkylene chain having a carbon number of 10 or more, especially 12 or more, which is contained in a concentration of millimole, particularly 0.5 to 10 millimole, is preferable.

As the low melting point resin, various resins having a melting point or a softening point of 40 to 200 ° C., particularly 70 to 160 ° C., for example, epoxy resin, xylene-formaldehyde resin, styrene resin, coumarone-indene resin, and others. Examples thereof include petroleum resin, alkyd resin, ethylene-vinyl acetate copolymer, low melting point acrylic resin, polyvinyl butyral, low melting point copolyamide, low melting point copolyester and the like.

As the coupling agent, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, β- (3,4epoxycyclohexyl). ) Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopripyryltrimethoxysilane, N-β (aminoethyl) γ-aminoprepylmethyldimethoxysilane, γ- Aminopripyrtriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, tris- (2-methoxyethoxy) vinylsilane, γ (2-amino Ethyl) Silane coupling agents such as Roh trimethoxysilane,

Isopropyltriisostearoyl titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) ethylene titanate, bis (dioctylpyrophosphate) oxyacetate titanate, isopropyl trioctanoyl titanate, isopropylate Lydimethacrylisostearoyl titanate, isopropyl isostearoyl diacrylic titanate, isopropylate (Dioctyl phosphate) titanate, Issy propyltrimethoxysilane (N- aminoethyl - aminoethyl) titanium-based coupling agents such as titanates,

Aluminum isopropylate, mono se
Aluminum-based coupling agents such as c-butoxyaluminum diisopropylate, aluminum ethylate, aluminum ethylacetoacetate diisopropylate, aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), and acetoalkoxyaluminum diisopropylate, Is used. These organic coupling media may be used alone or in combination of two or more.

(Coated Particles and Manufacturing Method Thereof) In the production of the coated particles of the present invention, the fine particles of hydrotalcite are 0.5 to 30% by weight, preferably 5 to 20, based on the regular core particles.
It is preferred to use 0.5% to 30% by weight of organic binders, especially 0.1 to 1% by weight. That is, when the amount of hydrotalcite fine particles is less than the above range,
The improvement in abrasion resistance and scratch resistance is smaller than that in the above range, and the improvement in fluidity is also small. On the other hand, if it exceeds the above range,
Poor dispersion and easy occurrence of fisheye. Further, when the amount of the organic binder is less than the above range, the hydrotalcite fine particles tend to be released without being coated, and when the amount exceeds the above range, the organic binder causes the coated particles to coalesce with each other, or the resin. When blended in, it tends to plate out.

The coated particles are produced by mixing the above three components in a wet or dry manner under the condition that the organic binder is softened or melted. The mixing order may be such that the three components are mixed at the same time, or two of the three components may be mixed first, and then the remaining one component may be mixed. Preferably, an aqueous slurry of regular core particles is prepared, and an aqueous slurry in which hydrotalcite is finely dispersed is separately prepared,
An aqueous slurry of hydrotalcite and an organic binder are added to the regular core particle slurry, and the whole is sufficiently stirred and mixed at a temperature equal to or higher than the softening point of the organic binder, then filtered, dried, and pulverized if necessary to obtain a product.

It is also possible to coat the surface of the regular core particles with an organic binder in advance and mix the regular core particles with hydrotalcite fine particles to prepare coated particles. The organic binder used in the present invention acts to increase the adhesiveness between the regular core particles and the hydrotalcite fine particles at the interface and enhance the dispersibility of the coated particles in the resin, and some of them are used. Is a stabilizer for molding resin,
There are some that also function as lubricants and the like. For example, many waxes have a function as a lubricant, and fatty acid salts have a function as a stabilizer. Of course,
The composition of the present invention includes a resin compounding agent known per se, for example, an antioxidant, an ultraviolet absorber, another stabilizer, an antistatic agent,
Mixing one or more kinds of colorants, other fillers, etc.,
It can also be used as a one-package compounding agent.

(Use) The hydrotalcite-coated particles (compounding agent for resin) of the present invention are various resins, for example, olefins such as polypropylene, polyethylene, crystalline propylene-ethylene copolymer, ion-crosslinked olefin copolymer and the like. Resins; thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as 6-nylon, 6,6-nylon, 6,8-nylon; chlorine-containing resins such as vinyl chloride resin and vinylidene chloride resin, polycarbonate A polysulfone; a polyacetal, or the like, which can be blended with a thermoplastic resin such as polyacetal to be used for imparting slipping property or anti-blocking property to a resin molded product such as a film formed. Of course, the compounding agent may be contained in the resin after polymerization. It can also be used as a heat stabilizer and filler for chlorine-containing polymers. For such applications, the coated particles of the present invention are used in an amount of 0.001 to 10 parts by weight, particularly 0.01 to 3 parts by weight, per 100 parts by weight of the resin.

[0046]

The present invention will be described in more detail by the following examples. Example 1 Reagent sodium hydroxide (NaOH content 96%) 39.2
g, reagent sodium carbonate (Na ₂ CO ₃ content 99.7%) 1
Add 1.2 g to 1 L of ion-exchanged water under stirring, and add about 40
Warm up to ℃, then add the reagent magnesium chloride (Mg
O content 19.7%) 61.3 g, reagent aluminum chloride (Al ₂ O ₃ content 20.5%) 33.1 g, reagent ammonium chloride (NH ₃ content 31.5%) 1.0 g, and ion-exchanged water 500 ml. Mg / Al molar ratio additionally prepared = 2.
0, an aqueous solution of NH ₃ / Al molar ratio = 0.35 was gradually added. The pH after the addition was 10.4.

After aging for 1 hour at the same temperature with stirring, 90
The temperature was raised to 0 ° C., and the reaction was carried out at the same temperature for 18 hours. After completion of the reaction, filtration and washing with water gave a cake of hydrotalcite. Next, ion-exchanged water was added to this cake to adjust it to 5% based on the dry matter, and then the mixture was crushed with a ball mill for 2 hours to prepare a coating slurry. (Hereinafter, this slurry is referred to as HTS-1. The chemical composition of HTS-1 is MgO / Al ₂ O ₃ =
3.88, Al ₂ O ₃ / CO ₃ = 1.05. The properties of powder obtained by drying this slurry are shown in Table 2, an electron micrograph (SEM photograph) image is shown in FIG. 1, and an X-ray diffraction pattern is shown in FIG.

Next, in a 1 L beaker, 400 m of ion-exchanged water
1. While stirring with a magnetic stirrer, Silton JC-30 which is amorphous aluminosilicate spherical particles
(Mizawazawa Chemical Co., Ltd. average particle size 3.1 μm, SEM
100 g of the photograph image shown in FIG. 3) was added and sufficiently dispersed, and then 200 g of HTS-1 was added (10 parts on a dry matter basis relative to spherical particles), and 0.5 g of a reagent stearic acid was further added.
In addition, the temperature was gradually raised, and when it reached 90 ° C., the hydrotalcite coating reaction was carried out at that temperature for 2 hours. After completion of the reaction, the beaker was put in an oven at 80 ° C., dried for 24 hours, and then pulverized with a sample mill to obtain hydrotalcite-coated particles. The powder properties of this product are shown in Table 2, the SEM photograph image is shown in FIG. 4, and the X-ray diffraction pattern is shown in FIG.

The test was conducted by the following method. (1) Specific surface area Automatic BET specific surface area measuring device (CAROL-ERBA, Sorpto
Nitric gas adsorption amount Vm (cc / g) adsorbed by the monolayer on the sample surface using the matic Serise 1800) and calculated from the specific surface area (SA) = 4.35 × Vm (m ² / g) To determine the BET specific surface area.

(2) Oil absorption amount The oil absorption amount was determined based on the JIS K 5101-19 method of the pigment test method. (3) Primary particle diameter Scanning electron microscope WET-S manufactured by Akashi Beam Technology
Using EM (WS-250), each particle diameter (μm) in the selected area image was arithmetically averaged to obtain the primary particle diameter. (4) Dispersibility According to the fisheye measurement method of Example 12.

(5) Refractive index Using an Appe refractometer, a solvent (α-
Bromnaphthalene, kerosene). Then La
According to rsen's permeation method, a few mg of sample powder was placed on a slide glass, a drop of a solvent with a known refractive index was added, a cover glass was placed, and the solvent was sufficiently immersed, and then the movement of the Becke line was observed with a polarizing microscope. And ask. (Larsen's Immersion Method) When the powder is dipped in a liquid and the transmitted light is observed with a polarization microscope, the boundary line between the powder and the liquid appears bright. This is called a Becke line (Backe). At this time, if the tube of the microscope is moved up and down, this Becke line moves. When the tube is lowered, the bright line moves to the inside of the particle and the particle looks bright.When the tube is raised, the bright line moves to the outside and the particle looks dark.If the liquid has a higher refractive index than the powder. is there. The opposite phenomenon is seen when the refractive index of the powder is higher. By measuring with a suitable liquid and selecting one having a refractive index larger than that of the powder and one having a smaller refractive index than the powder, the refractive index of the powder can be obtained as an intermediate value between the refractive indexes of these two types of liquids.

(6) pH value The pH value was determined according to the JIS K 5101-24A method of the pigment test method. (7) Abrasivity Abrasivity was measured by making a round blade made of iron (Mohs hardness 4.5) having a thickness of 1 m / m and a diameter of about 40 m / m, and using a special machine T.K. K. It was attached to a Homo Mixer, and the measured powder was submerged in a 50 ml ointment bottle filled with 70 Vol% of the total volume, and the weight reduction rate when rotated at 5,000 rpm for 2 hours was expressed. (8) Adhesion 20 g of a sample in a plastic bag with a chuck of 170 × 120 × 0.04 m / m (Unipack F-4 manufactured by Japan Manufacturing Co.).
The state of adhesion when placed in an appropriate bulge and shaken sufficiently to stand still was visually determined by the following. ○ Almost no adhesion △ Adhesive to the extent that it can be seen through × Not adhering to see through (9) Apparent specific gravity and angle of repose Measured with the Hosokawa Powder Tester PT-D type.

Example 2 Example 2 is a coated particle prepared in the same manner as in Example 1 except that HTS-1 was changed to 400 g (20 parts on a dry matter basis relative to spherical particles). Table 2 shows the powder properties of this product.
The SEM photograph image is shown in FIG.

Example 3 In Example 1, HTS-1 was 100 g (5 parts on a dry matter basis with respect to spherical particles), and the amorphous aluminosilicate spherical particles of the regular core particles had an average particle diameter of 2.0 μm. The coated particles were prepared in the same manner as in Example 1 except that Shilton JC-20 (manufactured by Mizusawa Chemical Industry Co., Ltd.) was used.
The powder properties of this product are shown in Table 3.

Example 4 Silane JC particles obtained in Example 3 which were previously surface-treated (2%) with stearic acid amide as the regular core particles.
The coated particles were prepared in the same manner as in Example 3 except that -20 was used and stearic acid was not added. The powder properties of this product are shown in Table 3.

Example 5 Shilton JC-20 coated with 2% of stearic acid amide used as the standard core particles in Example 4 and 10 parts by dry weight of HTS-1 of the core particles were dried.
% In a super mixer and coated with the super mixer at 80 ° C. for 2 hours. The powder properties of this product are shown in Table 3.

Comparative Example 1 A powder prepared in the same manner as in Example 1 except that stearic acid was not added in Example 1. SEM of this powder product
The photographic image is shown in FIG.

Comparative Example 2 The same preparation as in Example 1 was carried out except that 700 g of HTS-1 (35 parts by weight of dry particles based on spherical particles) was added. The SEM photograph image of this powder product is shown in FIG.

Example 6 400 ml of ion-exchanged water was weighed in a 1 L beaker and stirred with a magnetic stirrer to obtain spherical silica particles AMT silica # 300B (manufactured by Mizusawa Chemical Industry Co., Ltd., average particle size 3.1 μm). After 100 g was added and sufficiently dispersed, 200 g of HTS-1 was added (10 parts on a dry matter basis with respect to spherical particles), and 0.5 g of a reagent stearic acid.
In addition, the temperature was gradually raised, and when it reached 90 ° C., the hydrotalcite coating reaction was carried out at that temperature for 2 hours. Then, the same preparation as in Example 1 was carried out to obtain hydrotalcite-coated silica spherical particles. The powder properties of this product are shown in Table 3, and the SEM photograph image is shown in FIG.

Example 7 400 ml of ion-exchanged water was weighed in a 1 L beaker and stirred with a magnetic stirrer, and surface-treated (2%) with a silane coupling agent (A1100 manufactured by Nippon Unicar) in advance to give a slightly rounded cubic shape. After adding 100 g of Silton AMT-25 (manufactured by Mizusawa Chemical Industry Co., Ltd., average particle diameter 2.6 μm), which are amorphous aluminosilicate particles, and sufficiently dispersing, 200 g of HTS-1 was added (dry to spherical particles. (10 parts based on material), gradually heating up to 90 ° C
When the temperature reached, the hydrotalcite coating reaction was carried out at that temperature for 2 hours. Then, the same preparation as in Example 1 was carried out to obtain hydrotalcite-coated aluminosilicate particles.

Example 8 400 ml of ion-exchanged water was weighed in a 1 L beaker and stirred with a magnetic stirrer while being Ca-A type zeolite Shilton EP (manufactured by Mizusawa Chemical Industry Co., Ltd.,
After adding 100 g of (average particle size 3.4 μm) and sufficiently dispersing, 200 g of HTS-1 was added (10 parts on a dry matter basis to spherical particles), 0.5 g of reagent stearic acid was further added, and the temperature was gradually raised. When the temperature reached 90 ° C., the hydrotalcite coating reaction was carried out at that temperature for 2 hours. Thereafter, the same preparation as in Example 1 was carried out to obtain hydrotalcite-coated Ca-A type zeolite particles. The powder properties of this product are shown in Table 4.

Example 9 400 ml of ion-exchanged water was weighed in a 1 L beaker and stirred with a magnetic stirrer while Ca-Pc type zeolite (manufactured by Mizusawa Chemical Co., Ltd., average particle size 3.5 μm).
m), 100 g, and sufficiently dispersed, HTS-1 was added to 2
00 g was added (10 parts by dry matter based on Ca-Pc zeolite), 0.5 g of reagent stearic acid was further added, and when the temperature was gradually raised to 90 ° C, the hydrotalcite coating reaction was carried out at that temperature for 2 hours. It was After completion of the reaction, the beaker was placed in an oven at 80 ° C., dried for 24 hours, and then pulverized with a sample mill to obtain hydrotalcite-coated Ca-Pc type zeolite particles. The powder properties of this product are shown in Table 4, SEM
The photographic image is shown in FIG.

Example 10 Reagent Sodium hydroxide (NaOH content 96%) 39.2
g, reagent sodium carbonate (Na ₂ CO ₃ content 99.7
%) 11.2 g was added to 1 L of ion-exchanged water under stirring,
While keeping it warm at 40 ° C., 61.3 g of reagent magnesium chloride (MgO content 19.7%), reagent salt aluminum (Al ₂ O ₃ content 20.5%) 33.1 g, reagent ammonium chloride (NH ₃ (31.5% min.) 1.0 g of ion-exchanged water was added to 1.0 g of Mg / Al molar ratio =
An aqueous solution of 2.0 and NH ₃ / Al molar ratio = 0.35 was gradually added. The pH after the addition was 10.4. After aging for 1 hour at the same temperature with stirring, the temperature was raised to 90 ° C. and the reaction was carried out at the same temperature for 18 hours. After the reaction was completed, it was filtered, washed thoroughly with water, dispersed in ion-exchanged water and treated in an autoclave. A hydrotalcite slurry was obtained. Next, ion-exchanged water was added to this slurry to adjust it to 5% based on the dry matter, and the mixture was crushed for 2 hours with a ball mill to prepare a coating slurry. (Hereinafter, this slurry is referred to as HTS-2. H
The chemical composition of TS-2 is MgO / Al ₂ O ₃ = 4.0.
2, Al ₂ O ₃ / CO ₃ = 1.01. The properties of the dry powder product of this slurry are shown in Table 2, an SEM photographic image in FIG. 11 and an X-ray diffraction pattern in FIG. Next, in the same manner as in Example 1, 10 parts by weight of HTS-2 on a dry matter basis was added to Shilton JC-30 (manufactured by Mizusawa Chemical Co., Ltd., average particle size 3.1 μm), which is amorphous aluminosilicate-based spherical particles. The powder properties of this product are shown in Table 4, and the SEM photograph image is shown in Table 13.
As shown in the figure.

Comparative Example 3 Example 1 except that stearic acid was not added in Example 10.
Prepared as for 0. The SEM photograph image of this powder product is shown in FIG.
Shown in FIG.

Example 11 Example 1 was repeated except that Silton JC-30 was replaced with Silton AMT-Silica # 200B (manufactured by Mizusawa Chemical Industry Co., Ltd., average particle size 2.2 μm) which is spherical silica particles.
Hydrotalcite-coated spherical silica particles were obtained in the same manner as in 0. The powder properties of this product are shown in Table 4.

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4]

Example 12 Samples shown in Table 5 were added to linear low-density polyethylene having a melt index (MI) of 1.2 g / 10 minutes and a density of 0.92 g / ml, and the temperature was 180 ° C. in an extruder. After melt mixing, pelletizing was performed. Next, the pellets were supplied to an extruder and inflation-formed into a film having a thickness of 30 μm, and the obtained film was measured for the following physical properties. The results are shown in Table 5.

[0070]

[Table 5]

Haze: JIS K-671
4 was measured by an automatic digital haze meter NDH-20D manufactured by Nippon Denshoku Co., Ltd. Blocking property: Two films are stacked, and 200
After a load of g / cm ² was applied and the mixture was allowed to stand at 40 ° C. for 24 hours, the peelability of the film was evaluated as follows. ◎ Peeling without resistance ○ Slightly difficult to peel △ Hard to peel × Extremely hard to peel Fisheye: Film 5 under an optical microscope
It is shown by the number of 0.1 m / m or more in 00 cm ² . Scratchability: It was shown as follows depending on the degree of scratching when two films were stacked and rubbed with fingers after 5 hours from film formation. ◎ Almost no scratches ○ Slight scratches △ Slight scratches × Scratches gross: By gloss meter

Example 13 The additives shown in Table 6 were added to 100 parts by weight of polypropylene resin powder (HIPOL F657P manufactured by Mitsui Petrochemical Industry Co., Ltd.), and the mixture was thoroughly mixed with a supermixer, and the kneading temperature was 200.
The raw film obtained by T-die extrusion molding at 220 ° C and a die temperature of 210 ° C was stretched 5 times in the longitudinal direction and 9 times in the transverse direction to obtain a film having a thickness of 30 µm. The physical properties of the obtained film were measured by the same methods as in Example 12, and the results are shown in Table 6.

Example 14 Polyvinyl chloride resin (Nippon Vinyl 4000M; degree of polymerization 1)
050) Add the additives shown below to 100 parts by weight, thoroughly mix with a super mixer, and then knead with a 3.5-inch differential roll mill at 160 ° C. for 5 minutes, and
Press molding was performed at 85 ° C. to a thickness of 1 m / m. With respect to the obtained sheet, the transparency, the presence / absence of poor dispersion, and the heat resistance (heat coloring property) were visually determined. When the hydrotalcite-coated particles of Example 1 were used for molding, only the regular core particles were used. It was possible to obtain a more excellent molded sheet as compared with the case where the regular core particles and the commercial hydrotalcite were used at a weight ratio of 10/1.

* Polyvinyl chloride resin blend Polyvinyl chloride resin 100 (parts by weight) Dioctyl phthalate (manufactured by Kyowa Hakko Kogyo Co., Ltd.) 50 Ba-Zn stabilizer (manufactured by Mizusawa Chemical Co., Ltd.) 3.0 Agent 1.0 * Thermal stability Cut the above sample sheet into approximately 3 cm x 10 cm and cut it into 185
In a gear oven kept at 0 ° C, the sheet was kept under that temperature condition, and the thermal stability was evaluated by the degree to which the sheet was colored due to thermal deterioration.

[0075]

[Table 6]

[0076]

[Effects of the Invention] 0.5 to 30% by weight of fixed core particles composed of amorphous silica, amorphous silica-alumina or amorphous or crystalline aluminosilicate having a primary particle size of 0.3 to 20 µm. By coating the above hydrotalcite fine particles with 0.01 to 5% by weight of an organic binder, improvement in fluidity, abrasion and scratch resistance are observed as compared with the case of using the fixed core particles alone. Blocking performance was also improved, and it also contributed to the thermal stabilization of PVC, which generates hydrogen chloride and thermally decomposes it. This also makes it possible to make the polyolefin resin-based catalyst residue absorbed and harmless. Further, the drawbacks such as poor dispersion and generation of fish eyes, which are the drawbacks when using hydrotalcite alone, have been solved, and it has been possible to provide a resin compounding agent having the advantages of each of hydrotalcite and regular core particles.

[Brief description of drawings]

FIG. 1 is an electron micrograph showing the particle structure of hydrotalcite (dried product of HTS-1).

FIG. 2 is an X-ray diffraction diagram of hydrotalcite (dried product of HTS-1).

FIG. 3 is an electron micrograph showing the particle structure of the regular core particles used in the present invention.

4 is an electron micrograph showing the particle structure of the coated particles of the present invention obtained in Example 1. FIG.

5 is an X-ray diffraction diagram of the coated particles of the present invention obtained in Example 1. FIG.

FIG. 6 is an electron micrograph showing the particle structure of the coated particles of the present invention obtained in Example 2.

7 is an electron micrograph showing the particle structure of the powder obtained in Comparative Example 1. FIG.

8 is an electron micrograph showing the particle structure of the powder obtained in Comparative Example 2. FIG.

9 is an electron micrograph showing the particle structure of the coated particles of the present invention obtained in Example 6. FIG.

FIG. 10 is an electron micrograph showing the particle structure of the coated particles of the present invention obtained in Example 9.

FIG. 11: Hydrotalcite (dried product of HTS-2)
3 is an electron micrograph showing the particle structure of

FIG. 12: Hydrotalcite (dried product of HTS-2)
2 is an X-ray diffraction diagram of FIG.

13 is an electron micrograph showing the particle structure of the coated particles of the present invention obtained in Example 10. FIG.

FIG. 14 is an electron micrograph showing the particle structure of the powder obtained in Comparative Example 3.

FIG. 15 is a schematic diagram showing a cross-sectional structure of the coated particles of the present invention.

[Explanation of symbols]

A, B, and C respectively represent a fixed core particle, hydrotalcite, and an organic binder.

[Procedure amendment]

[Submission date] July 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction content]

Comparative Example 2 The same procedure as in Example 1 was carried out except that 940 g of HTS-1 was added ( 47 parts on a dry matter basis relative to spherical particles). The SEM photograph image of this powder product is shown in FIG. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 25, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

(Use) The hydrotalcite-coated particles (compounding agent for resin) of the present invention include various resins such as polypropylene, polyethylene, crystalline propylene-ethylene copolymer, low-, medium- and high-density. Or linear low density
Polyethylene, where linear low density polyethylene (LLDP
E) is ethylene and an α-olefin having 4 to 18 carbon atoms (p
Ropylene, butene-1, pentene-1, hexene-1,
4-methylpentene-1, octene-1, decene-1
Etc.) one or more copolymers; olefinic resins such as ion-crosslinked olefin copolymers; thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate; 6-nylon, 6,6-nylon, 6,
Polyamides such as 8-nylon; chlorine-containing resins such as vinyl chloride resin and vinylidene chloride resin; polycarbonates; polysulfones; slips onto resin molded products such as films formed by blending with thermoplastic resins such as polyacetal It can be used to impart anti-blocking property or anti-blocking property. Of course, the compounding agent may be contained in the resin after polymerization. It can also be used as a heat stabilizer and filler for chlorine-containing polymers. For such applications, the coated particles of the present invention are used in an amount of 0.001 to 10 parts by weight, particularly 0.01 to 3 parts by weight, per 100 parts by weight of the resin.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09C 1/40 PAP 6904-4J PBC 6904-4J

Claims (6)

[Claims] 1. (A) Amorphous silica in which each particle independently has a well-defined cubic or spherical primary particle shape and has a primary particle diameter of 0.3 to 20 μm as measured by electron microscopy. , Amorphous silica-alumina or regular core particles composed of amorphous or crystalline aluminosilicate, (B) hydrotalcite fine particles and (C) organic binder, and most of the hydrotalcite fine particles are organic binders. The coated particles are characterized in that the surfaces of the core particles are coated with the particles. 2. The hydrotalcite fine particles are 0.5 to 30% by weight based on the fixed core particles, and the organic binder is 0.01 to 5% by weight based on the fixed core particles. Coated particles. 3. The coated particles according to claim 1, wherein the hydrotalcite fine particles have a particle size in the range of 0.01 to 1.0 μm and not more than about 1/5 of the primary particle diameter of the core particles. 4. The coated particle according to claim 1, wherein the organic binder comprises a wax, a resin or a coupling agent. 5. Amorphous silica, in which the individual particles independently have a well-defined cubic or spherical primary particle shape and have a primary particle diameter of 0.3 to 20 μm as measured by electron microscopy, amorphous. Particles of crystalline silica-alumina or amorphous or crystalline aluminosilicate, 0.01 per core particle
To 5% by weight of organic binder and 0.5 per core particle
To 30% by weight of hydrotalcite fine particles are mixed by a wet or dry method under the condition that the organic binder is softened or melted. 6. (A) Amorphous silica in which each particle independently has a well-defined cubic or spherical primary particle shape and has a primary particle diameter of 0.3 to 20 μm as measured by electron microscopy. , Amorphous silica-alumina or regular core particles composed of amorphous or crystalline aluminosilicate, (B) hydrotalcite fine particles and (C) organic binder, and most of the hydrotalcite fine particles are organic binders. A compounding agent for resin, which comprises coated particles in which the surface of the core particles is coated via