JP3434598B2 - Resin compound composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compounding agent composition for a resin, and more particularly, to a resin containing specific porous spherical silica or silicate particles and containing the particles or other compounding ingredients. It relates to a resin compounding agent composition having improved dispersibility and improved functionality.

[0002]

BACKGROUND OF THE INVENTION Spherical particles of amorphous silica or silicate are fillers for various polymer films and other resins or rubbers, fillers for cosmetics, support carriers for perfumes and chemicals, Widely used in applications such as packing materials for chromatography.

The spherical particles of amorphous silica or silicate substantially destroy the crystal structure of crystalline zeolite having a method of hydrolyzing an organosilicon compound or having a cubic or spherical particle morphology. There is known a method of producing by neutralizing with an acid under conditions where the particle morphology is not substantially impaired to remove the alkali metal component in the zeolite.

Japanese Unexamined Patent Publication (Kokai) No. 62-62842 describes a polyethylene resin composition in which an amorphous aluminosilicate obtained by the above acid treatment is mixed with polyethylene together with a fatty acid amide and an antistatic agent.

Japanese Patent Publication No. 5-69865 discloses the following formula: m MO.n Na ₂ O.Al ₂ O ₃ .q H ₂ O (1) In the formula, M is one of divalent metals or 2 A metal of at least one species, m + n is a number of 1.1 ± 0.2, the ratio of m: n is in the range of 10: 0 to 1: 9, and p is 4 ± 1.
5 and q is a number of 0.5 or less, X-ray diffractiologically substantially amorphous, and the individual particles as a whole have a well-defined spherical shape and jaggedness. Amorphous silica-alumina-based spherical particles having a moisture absorption amount of 13% or less and a refractive index of 1.48 to 1.61 under the conditions of RH 90%, room temperature and 48 hours, or the amorphous thereof. Containing a combination of high-quality silica / alumina spherical particles with at least one of other fillers and pigments as an inorganic component, and having plasticity, lubricant, antistatic agent, antifogging agent, ultraviolet absorber, antioxidant and low melting point. A compounding agent composition for resin is described, which contains at least one kind of resin as an organic component, and the inorganic component is bound through the organic component to form a granular material. .

[0006]

Problems to be Solved by the Invention Amorphous silica
Alumina-based spherical particles have the advantage that even an organic compound having a strong bleeding property can be well dispersed in a resin, but these amorphous silica-alumina-based spherical particles are blended in a resin film. When the rubbed film is rubbed, it tends to damage the film, and there is a demand for a compounding agent for a resin, which is an alternative to the amorphous silica / alumina spherical particles and other inorganic spherical particles and an organic compounding agent.

The present inventors previously found that when partially neutralizing an alkali silicate with an acid, a water-soluble organic polymer or a combination of a water-soluble organic polymer and an amorphous silica nucleating agent coexists. It was found that the partially neutralized product of (1) grew to a porous porous granular material having a regular shape with good yield. Further, it was found that the porous silica spherical particles easily react with a Group II metal of the periodic table to be silicate particles having the above particle structure.

The present inventors have added a resin compounding organic component to the above-mentioned specific porous spherical silica or silicate particles and made it into a powder or granule, which has good dispersibility in the resin. ,
It has been found that not only is the combination of rapid and long-lasting compounding effects excellent, but also the scratch resistance and scratch resistance that the surface of a molded article such as a film is not damaged.

That is, the object of the present invention is not only excellent in the dispersibility in the resin and the combination of the rapid effect and the sustainability of the compounding effect, but also not damaging the surface of the molded product such as the compounded resin film. Another object of the present invention is to provide a compounding agent composition for resins which is also excellent in scratch resistance and scratch resistance.

[0010]

The inorganic substrate particles used in the present invention are represented by a weight ratio based on oxides of SiO ₂ : MO.
= 100: 0 to 50:50 (wherein M represents a Group II metal of the Periodic Table) of silica or silicate,
An X-ray diffraction studies to amorphous or fine layered crystal, the ratio of the clear spherical particles of diameter of the individual particles are independently (D _L) and the minor axis _{(D S) (D S /} D L ), The sphericity is 0.8 to 1.0, and in the formula D ₂₅ / D ₇₅ , D ₂₅ represents the particle size of 25% of the volume-based cumulative particle size distribution curve by the Coulter counter method. , D ₇₅ represents the particle size of the 75% value. The sharpness of the particle size distribution defined by is 1.2 to 2.0
Has a BET specific surface area of 50 to 800 m ² / g, a refractive index of 1.40 to 1.55, and a fine pore radius of 10 to 100 Å (angstrom) as measured by a nitrogen adsorption method. It has a peak of pore volume distribution and is 0.
2 to 2.0 cc / g, especially 0.3 to 1.0 cc / g
Porous spherical silica or silicate particles having a pore volume of. Alternatively, it contains a combination of the porous spherical silica or silicate particles and at least one of other fillers and pigments as an inorganic component, and has plasticity, lubricant, antistatic agent, antifogging agent, ultraviolet absorber, infrared absorption. Characterized in that it contains at least one of an agent, an antioxidant, an antibacterial agent and a low melting point resin as an organic component, and the inorganic component is bound through the organic component to form a granular material. Provided is a compounding agent composition for resins.

The porous spherical silica or silicate particles to be used in the present invention are particles comprising partially or completely neutralized products of alkali silicate produced by using a water-soluble polymer as an aggregative growth agent, or the particles and the periodic rule. It is preferably obtained by reacting a Group II metal hydroxide or salt in an aqueous solvent.

[0012]

The inorganic particles used in the composition of the present invention are represented by the weight ratio of oxides, SiO ₂ : MO = 100: 0 to 5.
Composition of 0:50 (wherein M represents a Group II metal of the periodic table)
X-ray diffraction amorphous or fine layered crystalline particles composed of silica or silicate of the above composition and having a different base composition from the above-mentioned conventional amorphous silica / alumina particles. Is provided. That is, although inorganic particles containing alumina generally have strong solid acid properties, the present invention provides resin compounding agents of different categories which can be used in compounding applications in which solid acidic properties are not desirable.

The inorganic particles used in the present invention are defined as individual, independent spherical particles and are represented by the ratio (D _S / D _L ) of the major axis (D _L ) and the minor axis (D _S ) of the particles. Sphericity is 0.8
The first characteristic is that the sharpness of the particle size distribution defined by Formula 1 (D ₂₅ / D ₇₅ ) is 1.2 to 2.0. That is, since the inorganic particles are spherical and have excellent particle size sharpness, they are excellent in fluidity themselves, and are also excellent in blendability with a resin and dispersibility in a resin. Further, when compounded in a resin, there is little tendency to damage the film surface even if it is exposed to the film surface or rubbed.

Please refer to FIG. 1 and 2 are scanning electron micrographs (magnification: 10000) showing the particle structures of the porous spherical amorphous silica and silicate used in the present invention, and these particles have a substantially spherical shape. It is understood that they have a uniform particle shape.

FIG. 3 is a volume-based particle size distribution curve of the porous spherical silica used in the present invention. From this graph, it can be seen that the particles used in the present invention have a uniform particle size distribution close to monodispersion.

Generally, the degree of uniformity of particle size (particle size) is
It can be evaluated by the ratio (D ₂₅ / D ₇₅ ) of the particle size corresponding to the integrated value 25% in the integrated particle size distribution curve (D ₂₅ ) and the particle size corresponding to the integrated value 75% in the same curve (D ₇₅ ). That is, the smaller this value, the narrower the particle size distribution, and the larger this value, the wider the particle size distribution.
Porous spherical silica or silicate particles used in the present invention,
In the volume standard distribution, the ratio of D ₂₅ / D ₇₅ is 2.0 or less,
In particular, the particle size is 1.6 or less, the particle size is uniform, the fluidity is good, the fine powder does not stand up, and the mixing and dispersion are good.

Further, sphericity in spherical particles, the major axis of the particle cross section (Torukagemen) (D _L) and minor axis (D _S)
The ratio (D _S / D _L ) can be evaluated. The porous spherical silica or silicate particles used in the present invention have the sphericity (D _S
/ D _L) is in the range of 0.80 to 1.00, is easy to handle, are remarkably excellent in terms of dispersibility.

The inorganic particles used in the present invention are silica or silicate particles which are spherical and have a uniform particle size, but have a pore radius of 10 to 100 as measured by a nitrogen adsorption method.
Å has a peak of pore volume distribution and is 0.2 to 2.0
A second and salient feature is the porous particles having a pore volume of cc / g.

When the above inorganic particles are combined with an organic compounding agent, when the compounding agent composition is compounded in a resin, not only the dispersibility of spherical particles but also an organic compounding agent having a strong bleeding property is dispersed in the resin. It was found that the property improves. This is because in the composition of the present invention, spherical particles are bound with an organic compounding agent to form a granular material, but the porous structure of the inorganic particles retains the organic compounding agent that also acts as a dispersion medium. Therefore, the dispersibility of the spherical particles in the resin is improved, and the organic compounding agent is also well dispersed in the resin along with the spherical particles.

Moreover, it has been found that, in the composition of the present invention, when the porous spherical particles are combined with an organic compounding agent, the action of the organic compounding agent also has an optimum combination of fast-acting and long-acting. This is because the inorganic spherical particles serving as a carrier are porous and have a soft porous structure on the surface, and when they are blended in a resin and molded, a part of the surface of the spherical particles of amorphous silica or silicic acid is used. The primary particles of the salt are dispersed in the resin matrix, and in the resin matrix, the organic compound carried by the relatively large spherical inorganic particles and the organic compound carried by the relatively small primary inorganic particles are There will be two species. By such a double dispersion structure, the bleeding tendency of the organic compound is suppressed, and the lasting effect is sustained, while the rapid effect of the organic compound supported on the fine primary particles. Is obtained.

In addition, the compounding agent composition for resins of the present invention comprises
Due to the surface structure of porous spherical silica or silicate particles that easily disintegrates, there is little tendency to damage the resin surface even when the resin films are rubbed together, and the advantage that the appearance characteristics of the compounded resin can be maintained well Is to give.

Further, when the composition of the present invention is blended with a resin and molded, since an organic compounding agent is present between the inorganic particles and the resin, even when this film is subjected to a stretching operation or the like, The formation of voids and the like is reduced, which gives the advantage of excellent appearance characteristics such as transparency. Moreover, as described above, since the refractive index of the base particles of the composition of the present invention is close to the refractive index of various resin films, a film having excellent transparency and the like can be provided.

[0023]

Preferred Embodiment of the Invention

[Inorganic Substrate Particles] The inorganic substrate particles used in the present invention are represented by a weight ratio based on oxides, and SiO ₂ : MO = 100: 0.
To 50:50, preferably 99: 1 to 50:50 (wherein M represents a Group II metal of the Periodic Table) of silica or silicate, and X-ray diffraction amorphous To fine layered crystallinity, each particle is an independent and distinct spherical shape, and the ratio of the major axis (D _L ) and the minor axis (D _S ) of the particles (D _S /
D _L ) has a sphericity of 0.8 to 1.0, and in the formula D ₂₅ / D ₇₅ , D ₂₅ is a particle size of 25% of the volume-based cumulative particle size distribution curve by the Coulter counter method. And D ₇₅ represents the particle size of the 75% value. The sharpness of the particle size distribution defined by 1.
0, particularly 1.2 to 1.6, and a BET specific surface area of 3
0 to 800 m ² / g, especially 100 to 500 m ² / g
And the refractive index is in the range of 1.40 to 1.55, especially 1.48 to 1.53, and measured by the nitrogen adsorption method,
Porous spherical silica or silicate particles having a pore volume distribution peak at a pore radius of 10 to 100Å and having a pore volume of 0.2 to 2.0 cc / g.

Since the porous spheres used in the present invention are aggregates of silica primary particles as described later, they have a relatively large BET specific surface area, generally 30 to 800 m ² / g, particularly 100 to 500 m ² / g. Since it is in the range and the degree of aggregation is higher than that of silica gel, the refractive index (2
5 ° C.) is as large as 1.46 to 1.50.

The porous spherical silica or silicate particles to be used in the present invention is a granular material composed of a partially or completely neutralized product of an alkali silicate produced by using a water-soluble polymer as an aggregating growth agent, or this granular material and a periodical method. It is obtained by reacting a hydroxide or salt of a Group II metal in the table in an aqueous solvent.

As the alkali silicate, m is a number of 1 to 4, particularly 2.5 to 3.5 in the formula Na ₂ O · mSiO ₂ . An aqueous solution of an alkali silicate having the composition of, especially sodium silicate, is used.

The composition of the alkali silicate is related to the stability of the mixed solution and the yield and particle size of the formed granules. When the molar ratio (m) of SiO ₂ is smaller than the above range, precipitation of partially neutralized particles becomes difficult to occur, yield tends to decrease, particle shape and particle morphology are likely to be uneven, and a large amount is required for partial neutralization. This is not preferable because it requires the above acid. On the other hand, S
If the molar ratio of iO ₂ is larger than the above range, the stability of the mixed solution is lowered and the particle morphology deviates from the true spherical shape, and the particle size distribution is not sharp. The concentration of alkali silicate is SiO ₂ in the mixed solution.
It is preferable to set the concentration as 3 to 9% by weight, particularly 5 to 8% by weight.

As the water-soluble organic polymer, anionic or nonionic water-soluble organic polymer is used. Examples of the anionic polymer include sodium polyacrylate or a copolymer of sodium polyacrylate and polyacrylamide, sodium polymethacrylate, sodium alginate, ammonium alginate, carboxymethyl starch, carboxymethyl cellulose, acrylamide-acrylic acid. Copolymers, maleic anhydride-vinyl ether copolymers, chitosan, sodium styrenesulfonate copolymers and the like are used. Examples of nonionic polymers include polyacrylamide and polyvinyl alcohol (P
VA), starch, cyanated starch, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, bee gum, gelatin, polyethylene glycol and the like.

These water-soluble polymers can be used alone or in combination of two or more.

It has been found that there is a close relationship between the anionic character of the water-soluble organic polymer used to produce the porous spherical silica or silicate particles and the particle size of the final granules. In general, the larger the anionic property, the smaller the particle size of the final granules, and the one having a small anionic property or the nonionic product produces a large particle size. The anionic property of the water-soluble organic polymer is such that the concentration (mmole number) of the acid group (carboxyl group) per 100 g of the water-soluble polymer is 0 to 1070 m.
It is an advantage of this synthetic method that granules of any particle size can be obtained by varying in the range of eg / 100g.

The acrylamide polymer preferably used as a coagulation growth agent for silica particles in the present invention contains an acrylamide repeating unit. This acrylamide polymer is preferably a homopolymer of acrylamide, but can be copolymerized with acrylamide repeating units within the range of 70 mol% or more, particularly 90 mol% or more of the total acrylamide repeating units. Repeating units of various monomers such as ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, vinyl ethers, (meth)
It may contain acrylic acid esters and the like.
Further, the acrylamide polymer may contain an anionic unit modified to a carboxyl group by hydrolysis or a cationic unit esterified with an aminoalkyl group or a quaternary ammonium alkyl group.

It is preferable that the acrylamide polymer is not so high in molecular weight, and its weight average molecular weight (M _W ).
Is generally in the range of 10,000 to 3,000,000, particularly 100,000 to 2,000,000. If the molecular weight of the acrylamide polymer is too high, it tends to be difficult to form and precipitate the particulate matter. This is considered to be because when the molecular weight becomes too high, the entanglement of the molecular chains increases, and it becomes difficult to form the tufted aggregate structure described above.

In the acrylamide polymer, the relationship between the weight average molecular weight (M _W ) and the intrinsic viscosity (η) is expressed by the following equation η = 3.73 × 10 ⁻⁴ × (M _W ) 0.66 where the intrinsic viscosity η Is represented by measurement at 30 ° C. in 1N-sodium nitrate solution.

The acrylamide polymer preferably used has a carboxyl group in the form of a free or a salt in the polymer 10.
0.2 to 50 mmol, especially 0.5 to 2 per 0 g
It is contained at a concentration of 0 mmol. The anionic groups in the polymer chains seem to act to stretch the molecular chains in water by the electrostatic repulsion of their homopolar groups, facilitating the formation of tufted aggregate structure of primary silica particles. .

As the amorphous silica nucleating agent optionally used in combination with the water-soluble polymer, any silica sol, silica gel or anhydrous silica powder is used as long as the particle size is fine. Submicron particles with a particle size of 1 μm or less, 1 on the basis of SiO _{2 based on the} total weight of silica.
It is preferable to add 20 to 20%.

Furthermore, if necessary, sol and slurry, which are submicron particles of hydroxides and oxides of titanium, zirconium, tin, etc. other than silica, may be added to the mixed solution. The spherical silica particles used in the present invention in which the particles are uniformly dispersed and included can be obtained.

As a suitable example of silica sol, Snowtex (manufactured by Nissan Kagaku Co., Ltd.) Ryudox or the like is preferably used, but acidic silica sol obtained by treating alkali silicate with mineral acid can also be used. .

Aerosil (manufactured by Nippon Aerosil Co., Ltd.), fumed silica (manufactured by WR Grace), etc. are preferably used as the silica sol or anhydrous silica powder having a fine particle size. These dry process silicas have a fine primary particle size, but they are aggregated into fairly large secondary particles, so it is important to use wet pulverization and use as a slurry having a dispersed particle size of 1 μm or less. is there. Silica obtained by hydrolyzing an organic silane is suitable for the purpose of the present invention because it has a fine primary particle size and few agglomerated particles.

As the acid, various inorganic acids and organic acids are used. From the economical point of view, it is preferable to use mineral acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid. Sulfuric acid is the best in terms of product yield and uniformity of particle size and morphology.

In order to carry out a homogeneous reaction, it is preferable to use it in the form of a dilute aqueous solution, and it is generally preferable to use it at a concentration of 1 to 15% by weight. Further, a neutral salt may be added to these acids. The amount of acid used during mixing is such that a homogenous mixed solution (clear) is produced by partial neutralization, and the pH of the mixed solution is 10.2 to 11.2, particularly 10.5 to 11 It is preferable to use it in such an amount that it becomes 0.0.

In the synthesis of porous spherical silica or silicate particles, the order of addition of the above respective components is not limited, and for example, an acid is added to an alkali silicate aqueous solution, and then a water-soluble polymer or a nucleating agent is added. Alternatively, conversely, the acid may be added after adding the water-soluble polymer or the nucleating agent to the aqueous solution of alkali silicate. Of course, these may be added at the same time.

This water-soluble polymer is preferably added in an amount of 5 to 100% by weight, particularly 10 to 50% by weight, based on SiO ₂ , and when the amount is less than the above range, the precipitation yield of the particulate matter becomes small. However, there is no particular merit even if it is used in a larger amount than the above amount, and it is rather disadvantageous economically.

After thoroughly mixing the components and homogenizing,
The mixture is left to stand to precipitate the partially neutralized granular material.

The precipitation conditions are generally 1 to 10
It is suitable to leave it at a temperature of 0 ° C. for about 1 to 50 hours.
Generally, the lower the temperature, the larger the particle size of the deposited particles, and the higher the temperature, the smaller the particle size of the deposited particles. Thus, by controlling the temperature, the particles can be controlled.

The precipitated particles and the mother liquor are separated, and the dispersed particles are neutralized with an acid, and then washed with water, dried, classified and the like to obtain a product. Since the separated mother liquor and the separated liquid after neutralization contain unprecipitated silica content and water-soluble polymer, these can be effectively used for the next mixed precipitation.

According to another embodiment of the synthetic method, spherical particles comprising a partially or completely neutralized product of alkali silicate obtained by the above method and one or two of hydroxides or salts of Group II metal of the periodic table. The seed or species are reacted in the presence of an aqueous medium.

I. Hydroxide or salt: Examples of the Group II metal of the periodic table include magnesium, calcium, barium, strontium and zinc. These are hydroxides or inorganic acid salts such as nitrates, chlorides and sulfates. Or
It can be used as an organic acid salt such as acetate or sulfonate. When the spherical particles used as the precursor are completely neutralized products of alkali silicate, that is, amorphous silica, it is preferable to use hydroxide. This combination does not contain other contaminants, etc., and is excellent in terms of the purity of the silicate and the convenience of the manufacturing operation.

On the other hand, when the spherical particles used as the precursor are partially neutralized products of alkali silicate, it is preferable to use a metal salt or a combination of a metal salt and a metal hydroxide as a raw material. This is because the metathesis reaction occurs between the alkali silicate content remaining in the spherical particles and the metal salt, and the production of the metal silicate proceeds smoothly and efficiently.
Of course, it is desirable that the alkali content in the spherical particles and the acid radical of the metal salt have an equivalent relationship.

Ii. Reaction conditions: The reaction between the granular material composed of a partially or completely neutralized product of alkali silicate and the metal hydroxide is
It should be carried out in the above-mentioned quantitative ratio. This reaction is preferably carried out in an aqueous medium, and when an excess amount of alkali or acid radicals is present in the reactant, an acid or alkali corresponding to this can be added to the aqueous medium.

The reaction conditions are not particularly limited as long as the granular structure of the precursor is maintained and the silicate is formed, and the reaction temperature is generally 50 to 300 ° C., particularly 90 to 200 ° C. The reaction time is preferably 0.5 to 100 hours, particularly 2 to 8 hours. During the reaction, the concentration of SiO ₂ in the aqueous medium is preferably in the range of 2 to 30% by weight, particularly 5 to 25% by weight, and the order of the reaction is such that the metal hydroxide is added to the aqueous dispersion of the silica precursor. Alternatively, a one-sided pouring method in which salt is poured, a simultaneous pouring method in which both raw materials are poured into an aqueous medium, or a simultaneous charging method in which an aqueous medium in which both raw materials are dispersed is heated to a predetermined concentration can be adopted.

The spherical silicate particles thus obtained are separated from the reaction mother liquor by a solid-liquid separation method such as filtration, washed with water if necessary, and dried at a temperature of up to 150 ° C., or at a temperature of 150 to 1000 ° C. It is calcined and manufactured. In the case of calcination, the specific surface area, the pore volume, the amount of moisture absorption, etc. can be reduced as the temperature rises.

Amorphous silica-alumina particles used in the present invention have an inorganic oxide surface such as titanium oxide, silicon oxide, zirconium oxide, zinc oxide, barium oxide, magnesium oxide, calcium oxide; silane-based and titanium-based. Alternatively, it may be coated with a zirconium-based coupling agent or surface-treated. The granular amorphous silica may be coated with metal soap, resin acid soap, various resins or waxes, silane-based or titanium-based coupling agents, oxides or hydroxides of various metals, silica coating, etc., if desired. You can

[Other Inorganic Blending Agent] In the present invention, the above-mentioned porous silica or silicate spherical particles can be used alone as an inorganic component, or can be used as an inorganic component in combination with other fillers or pigments. It can also be used. As the inorganic components used in combination, alumina, attapal guide, kaolin, carbon black, graphite, finely powdered silicic acid, calcium silicate, diatomaceous earth, magnesium oxide, magnesium hydroxide, aluminum hydroxide, slate powder, sericite, flint, Calcium carbonate, talc, feldspar powder, molybdenum disulfide, barite, vermiculite, whiting, mica, wax stone clay, gypsum, silicon carbide, zircon, glass beads, silas balloon, asbestos, glass fiber, carbon fiber, rock wool, Slag wool, Boron squid, stainless steel fiber, titanium white, zinc white, red iron oxide, iron black, yellow iron oxide,
Zeolite, hydrotalcite, lithium, aluminum, carbonate, titanium yellow, chromium oxide green, ultramarine blue, dark blue and the like can be mentioned.

In the present invention, it is desirable that the porous spherical silica or silicate particles occupy at least 30% by weight, especially 40% by weight or more of the total inorganic components.

[Organic component] The organic component used in the present invention includes a plasticizer, a lubricant, an antistatic agent, an antifogging agent, an ultraviolet absorber, an infrared absorber, an antioxidant, an antibacterial agent and a low melting point resin. , Containing at least one of these as an organic component, and the inorganic component is bound through the organic component to form a granular material, and when adding these useful components to the resin, Its application, type of resin,
It is properly used depending on the molding method and the like, and each is exemplified below.

A) Lubricants and antistatic agents Homopolymers of propylene or copolymerization of propylene with at least one of ethylene, butyne-1, hexene-1, 4-methylpentene-1 and octene-1. In order to improve the transparency, slip property, blocking resistance, and antistatic property of the united film resin composition, the composition powder and granules according to the present invention containing an organic component which is a lubricant and an antistatic agent described below are Used.

As the lubricant and antistatic agent used in the present invention, all those generally used for polyolefin films can be applied. That is, the lubricants are (a) hydrocarbon-based ones such as fluid, natural or synthetic paraffin, microwax, polyethylene wax and chlorinated polyethylene wax, (b) fatty acid-based ones such as stearic acid and lauric acid, (c) Stearic acid amide, palmitic acid amide,
Fatty acid monoamides or bisamides such as oleic acid amide, esyl acid amide, methylene bis stearamide, ethylene bis stearamide, etc., (di) butyl stearate, hydrogenated castor oil, ester type ethylene glycol monostearate, etc. Those of alcohol type such as (e) cetyl alcohol, stearyl alcohol,
(F) Metal soaps such as lead stearate and calcium stearate and (g) mixed systems thereof are generally used, and fatty acid monoamide type or bisamide type is particularly preferable.

On the other hand, as the antistatic agent, (a) primary amine salt, tertiary amine, quaternary ammonium compound,
Cationic compounds such as pyridine derivatives, (b) sulfated oils, soaps, sulfated ester oils, sulfated amide oils, sulfated ester salts of olefins, sulfated ester salts of fatty alcohols, ester salts of alkylsulfates, and fatty acid ethylsulfonic acid Anions such as salts, alkylnaphthalene sulfonates, alkylbenzene sulfonates, succinic acid ester sulfonates, and phosphoric acid ester salts, (c) Partial fatty acid esters of polyhydric alcohols, ethylene oxide addition of aliphatic alcohols Products, ethylene oxide addition products of fatty acids, ethylene oxide addition products of aliphatic amines or fatty acid amides, ethylene oxide addition products of alkylphenols, ethylene oxide addition products of alkylnaphthols, ethylene oxide addition products of partial fatty acid esters of polyhydric alcohols. Those nonionic such as polyethylene glycol, (d) carboxylic acid derivatives, those of amphoteric system such as imidazoline derivatives are generally available,
Particularly, nonionic compounds, particularly polyoxyethylene alkylamine, polyoxyethylene alkylamide or fatty acid ester thereof, fatty acid ester of glycerin, and the like are preferable.

In the present invention, it is desirable that the compounding agent composition powder is used in an amount of 0.06 to 10 parts by weight, preferably 0.14 to 5 parts by weight, per 100 parts by weight of the resin.

B) Anti-fogging agent A linear low-density polyethylene or other ethylene-based polymer film composition having transparency, heat sealability, and excellent mechanical properties can be used without impairing transparency, blocking resistance and the like. In particular, for the purpose of improving the antifogging property as an agricultural film, the powder composition of the present invention containing an antifogging agent described below as an organic component or a fatty acid amide as a lubricant is used.

Examples of the antifogging agent used in the present invention include stearic acid monoglyceride, oleic acid monoglyceride, polyglycerin oleic acid ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate and sorbitan monooleate. .

In the present invention, 100 parts by weight of resin,
0.06 to 0.06 of the composition powder containing the fatty acid amide typified by oleic acid amide, stearic acid amide, behenic acid amide and the like and the antifogging agent in a weight ratio of 1: 1 to 1: 3 It is desirable to use 10 parts by weight, preferably 0.8 to 5 parts by weight.

C) Heat deterioration and antioxidant Furthermore, in order to prevent heat deterioration especially during high temperature processing, linear low density polyethylene is added with an organic component consisting of the following phosphorus compound and phenolic antioxidant or fatty acid amide. The composition powder according to the present invention containing is used.

The phosphorus compound used in the present invention is at least one selected from phosphite, phosphonite and phosphonic acid derivatives. Examples of the phosphite include various compounds such as triphenyl phosphite; diphenyl phosphite; didecyl phenyl phosphite; tridecyl phosphite; trioctyl phosphite; tridodecyl phosphite; trioctadecyl phosphite; Nylphenylphosphite; Tridodecyltrithiophosphite; Distearyl pentaerythritol diphosphite; 4,4'-butylidene bis (3-methyl-6-t-butylphenylditridecyl) phosphite; Tris (2,4di-t -Butylphenyl) phosphite; bis (2,4di-t-butylphenyl) pentaerythritol diphosphite, and 4,4 'having an alkyl group having 12 to 15 carbon atoms
-Isopropylidene diphenyl tetraalkyl diphosphite etc. can be mentioned.

Examples of the phosphonite include tetrakis (2,4-dialkylphenyl) -4,4'-biphenylene diphosphonite. The alkyl group has 1 to 30 carbon atoms. Among these, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonite is particularly preferable.

Further, 4-hydroxy-3,5-di-t-butylbenzylphosphonic acid as a phosphonic acid derivative;
O-ethyl- (4-hydroxy-3,5-di-t-butylbenzyl) phosphonic acid; O- (2-ethylhexyl)
-(4-hydroxy-3,5-di-t-butylbenzyl) phosphonic acid; O-ethyl- (4-hydroxy-3,
5-di-t-butylbenzyl) phosphonic acid; calcium salt of O-ethyl- (4-hydroxy-3,5-t-butylbenzyl) phosphonic acid and the like.

The phosphorus compound as the above component is blended in an amount of 0.01 to 1.0 part by weight based on 100 parts by weight of the resin.

The phenolic antioxidant in the present invention has a molecular weight of 400 or more, preferably 400 to 5000.
belongs to. When a phenolic antioxidant having a molecular weight of less than 400 is blended here, the yellowness at the time of high temperature processing increases, which causes deterioration of quality, which is not preferable.

As the phenolic antioxidant having a molecular weight of 400 or more, various compounds can be mentioned, for example, octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; pentaerystyryl-tetrakis [ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]; 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene; 1,3,5-tris-
[Ethylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] -s-triazine-
2,4,6- (1H, 3H, 5H) trione; 1,1,
3-tris (2-methyl-4-hydroxy-5-t-butylphenolbutane; 4,4'-methylene-bis (2,6-di-t-butylphenol); hexamethyleneglycol-bis [β- (3 , 5-di-t-butyl-
4-hydroxyphenol) propionate] 6- (4
-Hydroxy-3,5-di-t-butylanilino)-
2,4-bis-octyl-thio-1,3,5-triazole; 2,2'-thio [diethyl-bis-3 (3,5-
Di-t-butyl-4-hydroxyphenol) propionate]; 2,2'-methylene-bis (4-methyl-6)
-T-nonylphenol) and the like, and these can be used alone or in combination.

The mixing ratio of the phenolic antioxidant is 0.01 to 1.0 part by weight based on 100 parts by weight of the resin.

In the present invention, 100 parts by weight of resin,
0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, of the composition powder containing the phosphorus compound and the phenolic antioxidant in a mixing ratio of 0.5: 1 to 1: 1. It is desirable to be able to.

D) Antibacterial Agent Examples of the antibacterial organic compound include bactericides and preservatives generally used in the art. Examples thereof include tropolones such as hinokitiol; chitosans; paraoxybenzoic acid esters; organic acids such as benzoic acid and dehydroacetic acid; salts of these organic acids; quaternary ammonium salts such as benzalkonium chloride; be able to. More specifically, hinokitiol, chitosan, benzoic acid, benzoates, isopropylmethylphenol, undecylenic acid monoethanolamide, benzalkonium chloride, alkyltrimethylammonium chloride, cetylpyridinium chloride, benzenetonium chloride,
Alkylaminoethylglycine chloride, chlorhexidine chloride, cresol, chloramine, chloroxylenol,
Chlorocresol, chlorobutanol, salicylic acid, salicylates, alkylisoquinolinium bromide, domiphen bromide, sorbic acid and salts, thymol, tiram,
Dehydroacetic acid and salts, trichlorocarbanilide, p-
Examples thereof include oxybenzoic acid ester, p-chlorophenol, halocarban, phenol, hexachlorophen, sodium lauroylsarcosine, and resorcin.

These antibacterial organic compounds can be supported on the porous spherical particles used in the present invention by a conventional method. As an example thereof, an organic compound is dissolved in a solvent such as water or alcohol and brought into contact with the base particles to be adsorbed and supported,
This is achieved by removing the solvent under reduced pressure and drying. The amount to be carried at this time is 0.1 to 20 of the base weight.
Suitably, it is in the range of 0.5% by weight, preferably 0.5 to 15% by weight.

As the antibacterial metal ions, silver, copper, zinc,
One or more selected from tin, mercury, lead, bismuth and thallium metal elements can be used. These metal elements are preferably selected from water-soluble salts, and can be selected from general industrial chemicals and complex compounds. Examples thereof include silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, ammine silver sulfate, etc. in the case of silver ion; copper (II) nitrate, copper perchlorate (II) in the case of copper ion. ), Copper acetate (II), copper sulfate (II) and the like; in the case of zinc ion, zinc nitrate, zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate and the like can be mentioned.

Among the antibacterial metal ions, silver is preferably used because it is nontoxic to humans and has a bactericidal effect on fungi. The amount of silver supported on the porous spherical particles of the base is 0.01 to 20% based on the oxide. Preferably 0.05 to 1
It is effective to set it to 0%. Furthermore, in combination with silver, copper,
In order to improve the antibacterial action, it is preferable to support one or more metal elements of zinc, tin, mercury, bismuth, and thallium in the range of 0.01 to 20% based on the oxide.

E) Organic peroxide and low melting point resin Furthermore, the organic peroxide and low melting point resin are used as an organic component used in the present invention for the purpose of improving the compatibility between the resin and the inorganic filler powder. To be For example, the composition powder containing the organic peroxide represented by dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, etc. in combination with fatty acid amides such as oleic acid amide, lauric acid amide and stearic acid amide. Used. The organic peroxide is added to the resin when the resin is heated and kneaded to cause crosslinking in the polymer. Therefore, the milder the reactivity, the more uniform the crosslinking occurs.

Similarly, for the purpose of improving the compatibility between the resin and the inorganic filler powder, a terpene resin having a low melting point, a petroleum resin, and a rosin whose main components are abietic acid and dextropimaric acid are contained. A composition powder is used.

In the present invention, the former is a saturated linear polyester resin, and the composition powder containing 0.1 to 30% by weight of organic peroxide per amorphous silica-alumina spherical particles is used. I can.

The latter is a stretched polypropylene film of polypropylene resin, wherein the composition powder containing 10 to 100% by weight of the spherical particles of the terpene resin or the like is added to 100 parts by weight of the resin, 0.3 to 8 parts by weight. Can be used in.

F) Plasticizer and UV Absorber In the present invention, the following plasticizers and UV absorbers which are solid at room temperature are used as organic components.

As a plasticizer, butyl stearate, P-
Toluene sulphamide, D-nitrobiphenyl,
Dicyclohexyl phthalate, diethylene glycol dizonbeate, triphenyl phosphate,

As a UV absorber, 2-hydroxy-4
-Methoxybenzophenone, 2,2'-dihydroxy-
4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, resorcinol monobenzoate, 2 (2 '
-Hydroxy-5-methylphenyl) benzotriazole, substituted benzotriazole, ethyl-2-cyano-
3,3-diphenyl acrylate, phenyl salicylate, 4-t-butylphenyl salicylate, p-octylphenyl salicylate, Ni-bisoctylphenyl sulfide, [2,2′-thiobis (4-t-octyl) Phenolato)]-n-butylamine Hi and the like.

G) Other binding medium Furthermore, the following waxes and low melting point resins are used as long as the organic component acts as a binding medium for the inorganic component. (1) Fatty acids and their metal salts Higher fatty acids Fatty acids obtained from animals or vegetable oils and fats and hydrogenated fatty acids thereof, having 8 to 22 carbon atoms Higher fatty acid metal salts Alkali metal salts of the above fatty acids, alkalis Earth metal salt, Z
n salt, Al salt (2) Amide, amine higher fatty acid amide, erucic acid amide, oleyl palmitoamide, stearyl erucamide, 2-stearomidoethyl stearate, ethylenebis fatty acid amide,
N, N′-oleoylstearylethylenediamine, diethyltoluamide, N, N′-bis (2hydroxyethyl) alkyl (C ₁₂ -C ₁₈ ) amide, N, N′-bis (hydroxyethyl) lauroamide, N-alkyl (C ₁₀ -C ₁₈₎ oleic acid reacted with trimethylene diamine, fatty diethanolamine, di - (hydroxyethyl) distearate (3) monovalent amount alcohol fatty acid ester stearic acid n- butyl diethylenetriamine monoacetate, water Added rosin methyl ester,
Dibutyl sebacate <n-butyl>, dioctyl sebacate <2-ethylhexyl, 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, propylene glycol fatty acid diester, triglyceride wax, hydrogenated edible oil and fat, 1
Glycerin ester of 2-hydroxystearic acid,
Spam acetyl wax, montan wax, carnauba wax, beeswax, wood wax, monohydric fatty acid alcohol and fatty acid saturated acid ester, <Example: hydrogenated whale oil lauryl stearate, stearyl stearate>, lanolin, polyethylene wax, polypropylene wax, oxidized polyethylene wax, Acid-modified polyolefin wax, epoxy-modified polyethylene wax, petroleum wax

Among these waxes, 0.1 gram of polar group such as carboxylic acid, carboxylic acid anhydride, carboxylic acid salt, carboxylic acid ester, carboxylic acid amide, ketone, ether and hydroxyl group is added to 1 gram of wax. To 20 millimoles, especially 0.5 to 10 millimoles, and at least 1 having 10 or more carbon atoms, particularly 12 or more carbon atoms.
Waxes containing one long alkylene chain in the molecule are preferred.

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, chroman-indene resin, and others. Petroleum resin, alkyd resin, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer,
Examples thereof include low melting point acrylic resin, polyvinyl butyral, low melting point copolyamide, low melting point copolyester and the like.

These waxes and low melting point resins can be used alone or in combination of two or more.

In addition to the above-mentioned organic components, insect repellents, insect repellents, deodorants, fragrances, medicinal components and the like can also be used in the present invention.

[Manufacturing Method of Powder of Composition] In order to manufacture the compounding agent composition of the present invention, all the inorganic components including the porous spherical particles of the present invention or further other inorganic fillers (hereinafter referred to simply as a filler) And 3 to 30% by weight, especially 5 to 15% by weight of organic components based on the total inorganic components.
The method of mixing under the milling conditions described in JP-A No. 2-9 is carried out.

The mixing of the above-mentioned filler powder and organic component under milling conditions can be carried out by various methods. For example, in the wet milling mixing, the filler powder and the organic component are mixed in the presence of a solvent while milling, and in the soft milling mixing, the filler powder and the organic component powder are mixed in the solvent and the like. Mix under milling dry in the presence.

In all of these cases, it is important to grind the filler powder so that it is broken down into primary particles. For this purpose, a plaster, sand grinder mill, attritor, high-speed shearing machine are used. Stirrer, atomizer, Nara crusher,
A disk vibrating mill, a vibrating ball mill, a rotary ball mill, a super mixer or the like or a combination thereof is used. In these grinding mixers, the filler powder is disintegrated into primary particles, and at the same time, the surface treatment with organic components is performed.

In the former wet milling and mixing treatment, an organic component is dissolved or dispersed in a solvent, a filler powder is dispersed in this liquid to form a slurry, and the slurry is fed to the above-described milling and mixing machine. After being supplied, the mixture is thoroughly ground and mixed, and then the solvent is distilled off under the conditions of mixing and stirring to obtain a surface-treated powder.

As the solvent, it is preferable to use a nonpolar solvent from the viewpoint of preventing the agglomeration of the filler particles, and it is preferable to use a solvent that partially or completely dissolves the organic component. From this viewpoint, benzene, toluene, Aromatic solvent such as xylene, n
Aliphatic solvents such as -hexane, n-heptane, butane, alicyclic solvents such as cyclohexane, etc. are used, but the solvent usable in the present invention is not limited to these. In this case, the amount of the solvent used is 15 per 100 parts by weight of the filler powder.
It may be in the range of 150 to 150 parts by weight.

On the other hand, in the latter dry milling and mixing treatment, the weighed powder filler and the powder of the organic component are passed through the above-mentioned milling mixer and milled and mixed at a temperature lower than the melting point of the organic component. Then, it is taken out from the mixer.

The degree of milling and mixing differs depending on the strength of milling, so it is difficult to specify in a general way, but as already mentioned, its interfacial properties, dispersibility, fluidity, or particle size are Since the degree of the surface treatment can be evaluated by testing the characteristics, the treatment time may be determined according to the type of mixer used.

Generally, as the grinding and mixing progresses, (1) the particle size distribution is biased toward the small diameter direction, (2) the average particle size shifts to the small diameter side, (3) the water repellency increases, (4) ) It is possible to know the degree of milling and mixing from the fact that the angle of repose becomes small, (5) the dispersibility in resin is remarkably improved, and (6) there is almost no change in the X-ray diffraction intensity. it can.

The above-described wet milling mixing has the advantage that the coating of the binding medium on the primary particles tends to be perfect, but on the other hand, the cost is increased by the use of the solvent and the removal of the solvent is required after the mixing. There is also a problem that the primary particles tend to condense when the solvent is removed and heated. Dry milling tends to result in slightly incomplete coating formation, but has many advantages in terms of ease of processing.

The powder thus surface-treated has an average particle size of 0.05 to 3 at a temperature above the melting point of the organic solid binding medium.
Granulate to 0 mm, especially 0.1 to 1.0 mm.

The mixture can also be used in powder form,
It can also be granulated. Although various granulation means known per se can be used for granulation, the tumbling granulation method is particularly advantageously used because the surface-treated powder contains a considerably small amount of organic components. For the rolling granulation, a usual rolling granulator is used, and in addition, a mixer type granulator such as a Henschel mixer or a super mixer is used. In the former device, the machine wall moves, and in the latter device, the powder moves, but it is consistent in that granulation is performed by the relative movement of the powder and the machine wall.

In some cases, it may be advantageous to carry out the granulation at a temperature equal to or higher than the melting point of the organic component, which significantly improves the yield of the granules.

Since there is no difference in composition between the formed granules and the ungranulated powder, the granules of a predetermined particle size formed in the granulation step are recovered by sieving, while the ungranulated powder is collected. This can be circulated in the granulator and finally all the raw materials can be recovered as granules.

Further, to prepare the compounding agent composition of the present invention,
Total inorganic components, including porous spherical silica or silicate particles and / or other inorganic fillers, and 5 to 90 per total inorganic components
A weight ratio, particularly 10 to 80 times the weight of the organic component is uniformly mixed according to the method described in JP-A-64-36631.

When the amount of the organic component is less than the above range, it is generally difficult to form a dispersed structure in which the organic binding medium becomes a continuous phase and individual filler particles are dispersed in the form of primary particles. The mechanical strength of the spherical particles formed also tends to be low.

On the other hand, if the amount of the organic coupling medium is larger than the above range, there is an adverse effect such as bleed-out and deterioration of transparency due to the addition of a large amount of an unnecessary component in the film-forming resin.

The both can be mixed by a crushing type mixer such as a Henschel mixer, a super mixer, a ball mill and an atomizer. This pulverized mixture is melt-kneaded in a melt-kneading machine such as a kneader and extruded from a nozzle for spray granulation, or it is granulated into spherical particles by a disk granulation method in which the granules are dripped onto a rotating disk for granulation.

The obtained spherical particles are sieved if necessary to have an average particle size of 0.05 to 3 mm, particularly 0.1 to 1.
The compounding agent composition has a size of 5 mm.

The organic component of the powder composition of the composition obtained as described above enhances the adhesion between the filler particles and the molding resin at the interface and disperses the filler particles in the resin. In addition to acting as a stabilizer, a lubricant, etc. to the molding resin, it can impart functions such as an antistatic agent and an antifogging agent to the molding resin, and if necessary, carbon It is possible to mix one or more kinds such as cal, kaolin, talc, titanium and other fillers and use them as a one-package compounding agent.

[Use] The compounding agent composition of the present invention contains various thermoplastic resins, for example, a homopolymer of propylene as a crystalline propylene copolymer, or an ethylene-propylene copolymer, low-, medium-, high-polymer. -Density or linear low density polyethylene, one or more copolymers of ethylene and α-olefin having 4 to 10 carbon atoms, ion-crosslinked olefin copolymer, ethylene-vinyl acetate copolymer, ethylene- Olefinic resins such as acrylic acid ester copolymers, polyethylene terephthalate (for example, it can be added at the time of polymerization in addition to the resin alone), thermoplastic polyesters such as polybutylene terephthalate, 6-nylon,
Polyamide resin such as 6,6-nylon or 6,8-nylon (for example, it can be added at the time of polymerization in addition to the resin alone), chlorine-containing resin such as vinyl chloride and vinylidene chloride,
It is formed by blending with polycarbonate, polysulfone and the like. For example, it can be used for imparting slip properties, anti-blocking properties, deodorizing / deodorizing functions, and desired properties to resin molded products such as various stretched, non-stretched and blown films. Of course, instead of blending with the resin after polymerization, it may be blended in advance with the monomer before polymerization so that the compounding agent is contained in the resin after polymerization.

For such use, the filler composition of the present invention is used in an amount of 0.001 to 50 parts by weight, particularly 0.01 to 30 parts by weight, based on 100 parts by weight of the resin.

[0109]

The present invention will be described in detail by the following examples. The measurement of the powder physical properties of the porous silicate particles and the evaluation test were carried out by the following methods. (1) Chemical composition It was measured according to JIS M-8852 silica stone analysis method. (2) Apparent specific gravity It was measured according to JIS K-6220.6. (3) Oil absorption amount Measured in accordance with JIS K-5101.19. (4) Specific surface area and pore volume Sorptomatic Seri manufactured by Carlo Erba Co.
It was measured by BET method using es 1800. (5) Aperture tube 50μ by a particle size Coulter counter (TA-II type manufactured by Coulter Electronics Co.)
It was measured using m. (6) Particle size by SEM Particle size scanning electron microscope (Hitachi S-570) Obtained from the photographic image, representative particles are selected, the major axis and minor axis of the particle image are measured using a scale, It is shown as the particle size. (7) Representative particles are selected from photographic images obtained with a sphericity scanning electron microscope (S-570 manufactured by Hitachi), and the major axis and minor axis of the particle image are measured using a scale, and the following formula is used. I asked from. Sphericity = with minor (D _S) / long diameter (D _L) (8) refractive index previously Abbe refractometer, the refractive index known solvent (alpha-bromonaphthalene, kerosene) to adjust. Then Lar
According to Sen's oil immersion method, a few mg of the sample powder was taken on a slide glass, 1 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 Becke line was moved with an optical microscope. Observe and ask. (9) Abrasion amount A wear tester (manufactured by Nippon Filcon Co., Ltd.) was used to measure wear under the following conditions. Rolls used Ceramics roll speed 1500 rpm Contact angle 111 ° Test piece size 40 × 140 mm Test piece weight approx. 2 g Test piece material Plastic wire weight 850 g Solid content concentration 2% Measurement time 180 minutes Result expression value Weight loss Porous spherical silica and porous spherical silicate (hereinafter referred to as regular particles) used in the present invention were prepared in the following reference examples.

Reference Example-1 Commercially available No. 3 sodium silicate (SiO ₂ 21.9%, Na ₂ O) was placed in a stainless steel reaction tank having an internal volume of 0.75 m ^{3 with} a stirrer.
7.1%, SiO ₂ / Na ₂ O = 3.19) 160k
g (7% as SiO ₂ concentration in the total liquid volume) was weighed and water 1
After adding 10 L, adjust the temperature to 20 ° C., and add 105 kg of an acrylamide polymer aqueous solution (10% aqueous solution, average molecular weight 500,000) while slowly stirring (30% as polyacrylamide anhydride with respect to SiO ₂ content) to sufficiently disperse. Let Next, 125% 5% sulfuric acid adjusted to 20 ° C in advance.
kg was added in about 3 minutes (the pH after the addition was 10.8), the stirring was stopped after the addition, and the mixture was allowed to stand for 12 hours. After standing for 12 hours, the mixture was stirred and dispersed to separate the precipitate and mother liquor by filtration, and the obtained cake was redispersed in water and sufficiently dispersed.
5% sulfuric acid (about 100 kg) was added until the pH reached 2.0, and when the pH was almost stable at 2.0, the mixture was stirred for 2 hours as it was, filtered and washed with water, and the cake was repulped to obtain a 15% concentration. Spherical silica particle slurry (Sample No1-
1). Then, this cake was dried overnight in a constant temperature dryer at 110 ° C. and then pulverized with a sample mill to have a particle diameter of 2 to 3 μm.
No. 1-2 of porous spherical silica powder was obtained. Table 1 shows electron micrographs (SEM) of the properties of this powder.
Is shown in FIG. 1, and the particle size distribution chart by the Coulter Counter method is shown in FIG. 2 (volume basis) and FIG. 3 (number basis).

Reference Example-2 160 kg of No. 3 sodium silicate used in Reference Example 1 was weighed in a stainless steel reactor having an internal volume of 0.75 m ³ equipped with a stirrer, 110 kg of water was added, and the temperature was adjusted to 28 ° C. An aqueous solution of acrylamide polymer (about 10
% Aqueous solution, average molecular weight 1,000,000, ionization degree 10%) was added thereto and sufficiently dispersed (30% as polyacrylamide anhydride relative to SiO ₂ content). After that, 2 in advance
Sample No. 1-3 of porous spherical silica particle powder having a particle diameter of about 1 to 1.5 μm was prepared in the same manner as in Reference Example 1 except that 5% sulfuric acid adjusted to 8 ° C. was used. The properties of this powder are shown in Table 1.

Reference Example-3 112 kg of sodium silicate No. 3 used in Reference Example 1 was placed in a stainless steel reaction tank with an internal volume of 0.75 m ³ equipped with a stirrer.
Weigh out, add 116 kg of water, then 5 wt with stirring
% 100% sulfuric acid was added (H ₂ SO ₄ / Na ₂ O = 0.
41), pH was adjusted to 10.5 and kept at 20 ° C.
While further stirring, 52.5 kg of silica sol (Snowtex C manufactured by Nissan Chemical Co., Ltd.) was slowly added so as not to cause cloudiness, and 112.5 kg of a 4 wt% solution of sodium alginate, which is a weak anionic polymer, was added to sufficiently disperse. After that, the stirring was stopped and the mixture was allowed to stand at that temperature for 12 hours. The pH at the start of standing was 10.4. Thereafter, the sample was prepared in the same manner as in Reference Example 1 to obtain a porous spherical silica powder sample No. 1-4 having a particle size of about 2 to 3 μm, and the properties of this powder are shown in Table 1.

Reference Example-4 183 kg of sodium silicate No. 3 used in Reference Example 1 was placed in a stainless steel reaction tank with an agitator having an internal volume of 0.75 m ^3.
After weighing and adding 60 kg of water, while stirring, carboxymethyl cellulose (hereinafter referred to as CMC, degree of etherification 1.25, degree of polymerization about 550, viscosity of 1% aqueous solution 75 cp /
80 kg of 3% aqueous solution (25 ° C.) (CMC / SiO ₂ =
0.15) was added, and after sufficiently dispersing, the temperature was adjusted to 20 ° C. Then, 177 kg of 5% sulfuric acid adjusted to 20 ° C. under stirring.
(H ₂ SO ₄ / Na ₂ O = 0.43) was slowly added (pH after pouring sulfuric acid was 10.8), stirring was stopped after pouring, and the mixture was allowed to stand at that temperature for 12 hours. Thereafter, the sample was prepared in the same manner as in Reference Example 1 to obtain a porous spherical silica powder sample No. 1-5 having a particle size of about 3 to 4 μm, and the powder was characterized by the first
Shown in the table.

Reference Example-5 Sample 1-1 slurry was placed in a 20 L stainless steel container.
Weigh 5 kg, 20% of the solid content in terms of MgO
Hydroxide powder equivalent to (Kamijima Chemical # 20
0) was added and sufficiently dispersed, then heated to 98 ° C. in a warm bath, treated at that temperature for 8 hours, filtered, washed with water, further dried at 110 ° C., pulverized with a sample mill, then 40
Sintered at 0 ° C. for 1 hour to obtain spherical porous magnesium silicate powder sample No. 2-1.
Shown in the table.

Reference Examples 6 to 8 Samples 1-3 and 1-in a 20 L stainless steel container.
2.25 kg of each of Sample 4 and Sample 1-5 was weighed, water was added so as to form a 15% slurry, and the solid content of Mg was mixed with stirring under stirring.
Magnesium hydroxide powder (# 200 manufactured by Kamishima Chemical Co., Ltd.) corresponding to 20% in terms of O was added, and thereafter, the preparation was performed in the same manner as in Reference Example 5 to obtain spherical porous magnesium silicate powders as sample Nos. 2-2 to 2-4. The properties of the powder are shown in Table 2.

Reference Examples 9 and 10 Prepared in the same manner as in Reference Example 5 except that barium hydroxide and calcium hydroxide were used in place of magnesium hydroxide in Example 5 and BaO and CaO were added so as to be 15% each. Then, sample Nos. 4-1 and 4-2 were obtained, and the properties of the powders are shown in Table 1.

Reference Example 11 Sample 1-1 was placed in a beaker made of stainless steel having an internal volume of 1 L in an amount of 80.
After weighing 0 g and adding zinc hydroxide in place of magnesium hydroxide in Reference Example 5 so as to be 20% as ZnO, the mixture was placed in an autoclave having an internal volume of 1 L and stirred for 180
The temperature was raised to ° C (pressure 9 kg / cm ² ) and treatment was carried out for 5 hours. After that, filtration, washing with water, drying, crushing and firing were performed to obtain a spherical zinc silicate powder sample No. 4-1. The properties of this powder are shown in Table 1.

Reference Example 12 To 50 g of the powder obtained in Reference Example 11, pure water was added to prepare a slurry of spherical zinc silicate particles having a solid content concentration of 10%. Next, the slurry was heated under stirring at 50 ° C. to
l ₂ O ₃ concentration of 5% aluminum chloride solution and 4% sodium hydroxide solution were used, and the mixture was simultaneously added over 1 hour within a pH range of 7 to 9 to reach 8% in terms of Al ₂ O _3. The coating reaction was carried out as described above. After completion of the reaction, the mixture was aged with stirring for 1 hour, filtered, washed with water, dried, and pulverized to obtain an aluminum compound-coated spherical zinc silicate powder sample No. 5-1. The powder properties are shown in Table 1.

[0119]

[Table 1]

Examples 1 to 18 The porous spherical silica-based particles of Samples 1-2 to 5-1 obtained in Reference Examples 1 to 12 and various organic binding catalysts are shown in Tables 2 and 3.
After mixing with a supermixer at the blending ratio (wt%) shown in Tables and Tables 4, the liquid was heated and melted in the kneader by supplying at a rate of about 1 kg / min into the kneader heated to a predetermined melting temperature. Was dripped onto a rotating plate (disk) having a diameter of 12 cm and rotating at 3000 rpm, and molded into a clean spherical resin filler composition containing 90% or more in the range of 32 to 100 mesh. The organic coupling medium used is as follows. (1) Polyethylene wax High wax 110P (manufactured by Mitsui Petrochemical) (2) Polypropylene wax Biscol 550P (manufactured by Sanyo Kasei) (3) Erucamide amide Alflo P-10 (manufactured by NOF Corporation) (4) Calcium stearate SC (NOF CORPORATION) (5) Polyglycerin monostearate GS-106 (manufactured by NOF CORPORATION) (6) Sorbitan fatty acid ester MP61 ° C (7) Electrostripper TS (manufactured by Kao Atlas) (8) Terpene resin chloralon P-75 (manufactured by Yasuhara Resin) ) (9) BHT (10) Synthetic silica

[0121]

[Table 2]

[0122]

[Table 3]

[0123]

[Table 4]

Application Example 1 Samples shown in Table 5 were added to 100 parts by weight of low-density polyethylene having a melt flow rate of 1.5 g / 10 min and a density of 0.920 g / cc, and the temperature of the extruder was 150 ° C. After melt-kneading, pelletized. The pellets were supplied to an extruder and inflation-formed into a film having a thickness of 50 μm under the conditions of a melting section of 160 ° C. and a die of 170 ° C.
The following physical properties of the obtained film were measured. The results are shown in Table 5. Haze: Compliant with ASTM D1003 Blocking property: Two films are stacked, 200 g / c
After a load of m ² was applied and the mixture was left at 40 ° C. for 24 hours, the peeling of the film was evaluated. ◎ Peeling without resistance ○ Slightly difficult to peel △ Hard to peel × Very difficult to peel Anti-fog resistance: Put 300 ml of 50 ° C warm water in a 500 ml beaker and cover with a film, put in a constant temperature layer of 50 ° C to stabilize the temperature After that, the film was transferred to a constant temperature layer at 20 ° C. and the state of the film after 6 hours was observed, and evaluated as antifogging property. ◎ It is transparent and has no cloudiness. ○ Slight water droplets △ Large water droplets are opaque × Fine water droplets are opaque on the entire surface Scratchability; 10 on film with 10 × 10 cm cross section
The haze after applying a load of kg and rubbing three times was measured, and the haze was determined from the difference between the haze before and after the rubbing. Measurement of surface resistance; according to JISK-6723, Hured Packard's Resistance Mete
r, RH 50%, temperature 25 ° C
After 3 days, the volume resistivity was measured. The test piece used was a T-die molded to a thickness of 0.7 to 0.8 mm.

[0125]

[Table 5]

Application Example 2 Samples shown in Table 6 were added to polypropylene resin, and the resulting blended composition was subjected to T-die extrusion molding to obtain a raw film. Further, this raw film was stretched 6 times in the longitudinal direction and 6 times in the lateral direction to form a film having a thickness of 30 μm, and then the film was evaluated in the same manner as in Application Example 1. The results are summarized in Table 6.

[0127]

[Table 6]

Application Example 3 The samples shown in Table 7 were added to 100 parts by weight of polypropylene resin powder, and the kneading temperature was adjusted to 2 by using a uniaxial extruder.
The mixture was melt mixed at 30 ° C. and pelletized. Using this pellet, an unstretched film having a thickness of 30 μm was obtained by T-die molding at the same temperature. The obtained film was evaluated for the film in the same manner as in Application Example 1, and the results are shown in Table 7.

[0129]

[Table 7]

[0130]

According to the present invention, an organic component for compounding a resin is added to a specific porous spherical silica or silicate particle, and this is made into a granule, whereby the dispersibility in the resin and the compounding ratio are improved. It is excellent in a combination of rapid effect and long-lasting effect, and is also excellent in scratch resistance and scratch resistance so as not to damage the surface of a molded product such as a compounded film.

That is, when the compounding agent composition for a resin of the present invention is used, the tendency of the molding resin to wear is prevented and the resin is evenly distributed.
In addition, since it has a property of being uniformly dispersed, it is a compounding composition for anti-blocking that can remarkably improve the physical properties of the molding resin and can impart excellent transparency without forming voids in the final film in film molding. A resin composition having excellent dispersibility of the compounding agent can be obtained even in the case of molding products and fibrous materials.

[Brief description of drawings]

FIG. 1 is a scanning electron microscope photograph at 10000 times showing the particle structure of porous spherical amorphous silica obtained in Reference Example 1 of the present invention.

FIG. 2 is a scanning electron microscope photograph at 10000 times showing the particle structure of the porous spherical silicate obtained in Reference Example 5 of the present invention.

FIG. 3 is a volume-based particle size distribution curve of the porous spherical amorphous silica obtained in Reference Example 1 of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-171925 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (4)

(57) [Claims] 1. SiO ₂ expressed as a weight ratio based on oxides:
MO = 100: 0 to 50:50 (wherein M represents a Group II metal of the periodic table) of silica or silicate, and is X-ray diffraction amorphous or fine layered crystalline. Yes,
In sphericity 0.8 to 1.0 represented by clear spherical particles of diameter of the individual particles are independently (D _L) and the minor axis (D _S) ratio (D _S / D _L) In the formula D ₂₅ / D ₇₅ , D ₂₅ represents the particle size of 25% value of the volume-based cumulative particle size distribution curve by the Coulter Counter method, and D ₇₅ represents the particle size of the 75% value. The sharpness of the particle size distribution defined by is 1.2 to 2.0
The BET specific surface area is 30 to 800 m ² / g, the refractive index measured by the liquid immersion method is in the range of 1.40 to 1.55, and the pore radius is 10 to 10 measured by the nitrogen adsorption method. Porous spherical silica or silicate particles having a peak of pore volume distribution at 100Å and having a pore volume of 0.2 to 2.0 cc / g or the porous spherical silica or silicate particles and other It contains a combination with at least one of a filler and a pigment as an inorganic component, and contains a plasticizer, a lubricant, an antistatic agent, an antifogging agent, an ultraviolet absorber, an infrared absorber, an antioxidant, an antibacterial agent and a low melting point resin. A compounding agent composition for a resin, comprising at least one kind as an organic component, and the inorganic component being bound via an organic component to form a granular material. 2. The porous spherical silica or silicate particles are particles formed of partially or completely neutralized alkali silicate produced by using a water-soluble polymer as a coagulation growth agent, or the particles and the periodic table. The compounding agent composition for resins according to claim 1, which is obtained by reacting a hydroxide or salt of a Group II metal in an aqueous solvent. 3. The compounding agent composition for resins according to claim 1, wherein the silicate comprises magnesium phyllosilicate. 4. The compounding agent composition for resins according to claim 1, wherein the silicate is zinc phyllosilicate or aluminum-containing zinc phyllosilicate.