JP2540553B2 - Filler composition for resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a filler composition for a resin, and more specifically, a filler having a specific particle shape and particle size,
The present invention relates to a filler composition for a resin, which comprises an organic binding medium.

(Prior Art) Resin molded products such as films tend to block each other when they are stacked, and it has been a long time to mix various inorganic compounding agents into the resin in order to prevent this. Has been done.

It is already known that zeolite has such excellent characteristics. For example, in Japanese Patent Publication No. 52-16134, 0.01 to 5% by weight of zeolite powder having an average particle diameter of 20 microns or less is added to polypropylene. Show that the blocking resistance of the biaxially oriented polypropylene film is improved. Further, JP-A-54-34356 discloses that the thermal stability is improved by blending an aluminosilicate of a zeolite crystal having ion exchangeability with a chlorine-containing polymer in an amount of 0.01 to 10% by weight, It is disclosed that, as an additional advantage, external lubricity is significantly improved.

Further, JP-A-58-213031 discloses a cubic primary particle having a composition in which a molar ratio of Al ₂ O ₃ : SiO ₂ is in the range of 1: 1.8 to 1: 5 and having a side length of 5 μm or less. The particles are substantially amorphous by X-ray diffraction and have a BET of 100 m ² / g or less.
An alumina-silica resin compounding agent characterized by having a specific surface area is described.

Furthermore, when adding an inorganic filler to the resin, the filler is treated with an organic silane, a surfactant, a wax or the like in order to improve the affinity between the filler and the resin and impart desired properties to the resin molded product. However, measures have been taken to improve the compatibility between the inorganic filler and the resin.

(Problems to be Solved by the Invention) The above-mentioned zeolite and the amorphous silica-alumina-based filler have a uniform particle shape and particle diameter, and have good slip characteristics and anti-blocking properties in a blended film molded product. However, there are still problems to be solved regarding the transparency of the compounded film molded article and the compounding and dispersion of the filler in the resin in general resin molded articles including the film.

First, the above-mentioned cubic or spherical filler has a relatively good dispersibility in the resin matrix, but the adhesiveness between the filler particle surface and the resin matrix is relatively low. Voids are likely to be generated at the interface of, and this is considered to be the cause of impairing the transparency of the film. Further, the above-mentioned filler has properties as an abrasive and a lubricant, like many silicate compounds. Thus, when the compounding agent and the resins are dry-mixed with a Henschel mixer or the like, or melt-kneaded with a kneader, a roll, an extruder or the like, the mixing device or the wall of the kneading device, the stirring blade, the screw, etc. A tendency to wear the parts is observed.

The above-mentioned filler is completely different from the usual filler in which fine primary particles are aggregated to form secondary particles that are easily mechanically broken, and the primary particles themselves are the final particles (secondary particles). ), And since its shape is clear like a cube, it is considered that the abrasion tendency in the mixing or kneading device is remarkable.

Furthermore, generally, in the relationship between the dispersed state of the inorganic filler in the resin and the physical properties of the molded article, the more uniform and even the dispersed state of the filler, the better the mechanical properties such as elongation and impact resistance, It is also known that the properties such as slip property and anti-blocking property are improved, and from this viewpoint, the filler used is one that is uniformly and uniformly dispersed in the resin within a relatively short time. desirable.

Therefore, the object of the present invention is to eliminate the above-mentioned drawbacks in the conventional fillers made of silica, silica-alumina, or aluminosilicate, prevent the abrasion tendency at the time of mixing or kneading with a resin, and to obtain a resin molded article. A filler composition for a resin that has the property of being uniformly and uniformly dispersed in a resin in order to impart the above properties, and that can impart excellent transparency and good anti-blocking property to the final film in film molding. To provide things.

(Means for Solving the Problems) According to the present invention, amorphous silica, amorphous silica-alumina or a material having a clear cubic or spherical primary particle shape and an electron microscopy primary particle diameter of 5 microns or less is used. A homogeneous composition comprising a filler comprising an aluminosilicate and an amount of 0.1 to 10 times by weight per filler of an organic binding medium which is solid at room temperature and melts at a temperature lower than the molding temperature of the resin to be blended; A composition is provided for a resin filling, characterized in that the organic binding medium is in the continuous phase and the filler is present as spherical particles with a particle size of 0.05 to 3 mm in the dispersed phase.

(Working) In FIG. 1 showing an enlarged sectional structure of the filler composition for a resin of the present invention, the composition has a particle size of 0.05 to 3 mm.
Existing in the form of spherical particles 1 having a fine structure in the form of a continuous phase 2 of an organic binding medium which is solid at room temperature and melts at a temperature lower than the molding temperature of the resin to be blended, and primary particles in the continuous phase. It consists of a dispersed phase 3 of dispersed filler.

This filler 3 consists of amorphous silica, amorphous silica-alumina or aluminosilicate with a well-defined cubic or spherical primary particle shape and an electron microscopy primary particle diameter of 5 microns or less, The filler particles are present in the form of primary particles, and the remarkable characteristic is that the continuous phase of the organic binding medium is present around them.

Since the continuous phase of the organic binding medium has the property of melting at a temperature lower than the molding temperature of the resin to be blended, when kneaded with the molding resin, the filler is dispersed in the resin in the form of primary particles. Shows the action.

Moreover, since the periphery of the filler particles is covered with the continuous phase of the organic binding medium, the compatibility with the film-forming resin and the adhesiveness are good, for example, in film molding, and the cause of voids during film stretching Adhesion failure and the generation of minute voids are suppressed.

FIG. 2 is a conceptual cross-sectional view of a stretched film 4 containing the filler composition of the present invention, in which the filler particles 3 are dispersed in the resin 5 while being covered with the organic binding medium 2. The protrusions 6 formed by the distribution of the filler particles 3 in the vicinity of the film surface serve as a point of action for giving the film slipping property and anti-blocking property.

The filler composition of the present invention is a spherical particle having a relatively large particle size, and therefore has excellent fluidity and is easy to handle without dust scattering, and the particle size is also compounded in, for example, film molding. Since the particle diameters of the film-forming resin to be used can be almost equal to each other, there is an advantage that they can be easily mixed with each other and that they can be well incorporated into the resin during kneading.

(Preferable Embodiment of the Invention) Filler As the filler, all of amorphous silica, amorphous silica-alumina, and 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, and analcime.

These zeolites are sodium type, potassium type,
It may be of calcium type, magnesium type, zinc type or a combination thereof.

A-, X-, and Y-type zeolites are representative of cubic zeolites, P-type zeolites and sodalite are representative examples of spherical zeolites, and analcimes are examples of polyhedra (24-sided faces) located in the middle of them. .

The typical chemical composition of Na type among these zeolites is 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 15 to 30% SiO ₂ 50 to 75% Na ₂ O 5 to 20% H ₂ O 25% or less Na ₂ O in the above zeolite is 10 to 100 mol%, preferably 30 to 10% depending on the other metal components described above. 80 mol%
Can be exchanged in a range of.

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, and such an amorphous aluminosilicate Salts can also be used for the purposes of the present invention.

As the amorphous silica-alumina, those obtained by treating the zeolite or the like with an acid to remove the sodium content or a further alumina content sufficient to make the zeolite amorphous can be used. As the crystalline 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 amorphous silica-alumina or the acid used in the production of the amorphous silica may be an inorganic acid or an organic acid without particular limitation, but economically, acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid are used. Is 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 end of the addition, the pH of the liquid shifts to the alkaline side again and tends to be saturated to a certain pH value. . This saturated pH, that is, the stable pH is 7.
Amorphous silica-alumina is obtained by performing neutralization in the range of 0 to 3.0, particularly 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 is 50% of the alkali content in zeolite.
Above all, especially 70% or more must be removed.

Although the shrinkage of the particles naturally occurs with the removal of the sodium content and the alumina content, the particle size shrinkage is 10 to at most.
It is about 20%, the particle shape hardly changes, and the characteristic that the particle size distribution is relatively sharp is not lost.

When the zeolite is converted 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 crystal water generally called zeolitic water, and this crystal water separates under the processing or molding conditions of the resin to cause a so-called foaming problem, but amorphous silica-alumina, and Amorphous silica does not cause such a problem. In particular, the calcined amorphous silica-alumina has a remarkably small moisture absorption tendency.

In the filler used in the present invention, the cubic or spherical primary particles have a primary particle size of which the length of the diameter measured by an electron micrograph is 5 microns or less. From the standpoint of preventing agglomeration of the filler particles, this primary particle size is preferably greater than 0.1 micron.

Further, the filler particles used in the present invention have a BET specific surface area of 300 m ² / g or less, particularly 100 m ² / g or less, in relation to having the above-mentioned particle shape and particle size characteristics. That is, the alumina-silica cube or spherical particles of the present invention has a remarkably small specific surface area and is easy to knead with a resin.
It is excellent in molding workability since there is little tendency to increase the melt viscosity when molding films, sheets, etc., not to mention general resin molding.

Furthermore, the compounding agent particles used in the present invention have a bulk density in a relatively large range of 0.4 to 0.9 g / cc, which is related to the fact that they are cubic or spherical and have a relatively large primary particle size. The bulk density is not less than twice that of the inorganic particles generally used as a filler as well as the known silica-based antiblocking agent, and the incorporation into the resin is extremely easy.

Organic Coupling Medium As the organic coupling medium, waxes and low melting point resins that satisfy the above-mentioned restrictions 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 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,
Zn salt, Al salt (2) Amide, amine higher fatty acid amide oleyl palmitoamide stearyl erucamide 2 stearomidoethyl stearate ethylene bis fatty acid amide N, N 'oleoyl stearyl ethylenediamine N, N' bis (2 hydroxyethyl) Alkyl (C ₁₂ ~
C ₁₈ ) Amide N, N ′ bis (hydroxyethyl) lauroamide N alkyl (C ₁₀ -C ₁₈ ) oleic acid reacted with trimethylenediamine fatty acid diethanolamine di (hydroxyethyl) diethylenetriamine monoacetate cistearate (3) 1 And fatty acid esters of polyhydric alcohols n-butyl stearate hydrogenated 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 Wax Beeswax wax Wax monohydric fatty acid alcohol and fatty acid saturated acid ester <Example: Hardened whale oil Lauryl stearate, stearyl stearate> Lanolin Polyethylene wax Polypropylene wax Oxidized polyethylene wax Acid-modified polyolefin wax Epoxy-modified polyethylene wax Petroleum wax These waxes Among them, per gram of waxes, carboxylic acid, Carboxylic acid anhydrides, carboxylic acid salt,
0.1 to 20 millimoles of polar groups such as carboxylic acid ester, carboxylic acid amide, ketone, ether and hydroxyl group, especially 0.5
Waxes which are contained at a concentration of 10 to 10 mmol and contain at least one long-chain alkylene chain having 10 or more carbon atoms, particularly 12 or more carbon atoms in the molecule are preferable.

Low melting point resin has a melting point or softening point of 40 to 200
Various resins having a temperature of 70 ° C., particularly 70 to 160 ° C., for example, epoxy resin, xylene-formaldehyde resin, styrene resin, coumarone-indene resin, other petroleum resin, alkyd resin, ethylene-vinyl acetate copolymer, ethylene-acrylic Examples thereof include acid ester copolymers, low melting point acrylic resins, polyvinyl butyral, low melting point copolyamides, and low melting point copolyesters.

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

Composition and Granulation In order to prepare the filler composition of the present invention, the above-mentioned filler is uniformly mixed with 0.1 to 10 times by weight, particularly 0.2 to 3 times by weight, the organic binding medium per filler. When the amount of the organic binding medium is less than the above range, the organic binding medium becomes a continuous phase, and it is generally difficult to form a dispersed structure in which individual filler particles are dispersed in the form of primary particles, and a spherical shape is obtained. The mechanical strength of the particles also tends to be low.

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

The organic binding medium used in the present invention not only acts to enhance the adhesion between the filler particles and the molding resin at the interface and enhances the dispersibility of the filler particles in the resin, but some of them Some of them also function as stabilizers and lubricants for the molding resin. 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 compound known per se, such as an antioxidant, an ultraviolet absorber, other stabilizers, an antistatic agent, a colorant,
If necessary, charcoal, kaolin, talc, silica,
One kind or two or more kinds of magnesium oxide and other fillers may be blended and used as a one-package blending agent.

The both can be mixed with a crushing type mixer such as a Henschel mixer, a super mixer, a ball mill, or 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 obtain a compounding agent having an average particle size of 0.05 to 3 mm, particularly 0.1 to 1.5 mm.

Applications The filler composition of the present invention comprises various resins, for example, olefin resins such as polypropylene, polyethylene, crystalline propylene-ethylene copolymer, ion-crosslinked olefin copolymer; polyethylene terephthalate, polybutylene terephthalate, etc. Thermoplastic polyester; Polyamide such as 6-nylon, 6,6-nylon, 6,8-nylon: Chlorine-containing resin such as vinyl chloride resin and vinylidene chloride resin; Polycarbonate; Polysulfone; Blended with thermoplastic resin such as polyacetal Then, it can be used for imparting slip properties or anti-blocking properties and desired properties to a resin molded product such as a formed film. Of course,
Instead of blending with the resin after polymerization, it may be blended in advance with the monomer before polymerization so that the blending agent is contained in the resin after polymerization.

For such use, the filler composition of the present invention is
0.001 to 50 parts by weight per 100 parts by weight of resin, especially 0.01 to 30
Used in parts by weight.

(Effects of the Invention) According to the present invention, the tendency of abrasion during mixing or kneading with a resin is prevented, and the resin has the property of being uniformly and uniformly dispersed in the resin. Moreover, an anti-blocking filler composition capable of imparting excellent transparency can be obtained without generating voids in the final film in filter molding.

(Example) Example 1 2.5 kg of amorphous aluminum silicate particles (Silton AMT-25 manufactured by Mizusawa Chemical Co., Ltd .: average particle size 2.5 µ), which is an acid-treated zeolite, and polyethylene wax (Mitsui Petrochemical Industry) 2.5 kg of Hi Wax 110P manufactured by Co., Ltd. was mixed with a super mixer and then fed into a kneader heated to 150 to 160 ° C at a rate of about 1 kg / min. Dropped onto a rotating plate (disk) rotating at 2000 (Example 1-1) and 3000 (Example 1-2) [rpm], respectively, and the particle size was 85% in the range of 28 to 60 mesh and 60 to 120 mesh, respectively. The filler composition according to the present invention was collected as a clean spherical product (FIG. 3 attached).

Examples 2 to 7 The Shilton AMT-25 used in Example 1 and various organic binding media were mixed and melted in the formulations (% by weight) shown in Table 1 and then the disk rotation speed was 3000 (rpm). A spherical filler composition equivalent to that in Example 1 was recovered in the same manner as in 1-2. The organic coupling medium used is as follows.

(1) Polyethylene wax high wax 110P (Mitsui Petrochemical) (2) Polypropylene wax Biscol 550P (Sanyo Kasei) (3) Calcium stearate SC (NOF Corporation) (4) Ethylenebisstearic acid amide EB-F (KAO- W
AX) (5) Polyethylene glycol PEG ^# 4000 (NOF Corporation) Examples 8 to 14 Shilton AMT-25, fine powder silica (Mizukasil P-526 manufactured by Mizusawa Chemical Co., Ltd .: average particle size 1.5 μ), calcium carbonate (Escalon ^# 1500). ), Kaolin (NUCLAY), and various organic binding media are mixed and melted in the composition (% by weight) shown in Table 2, and then the disk is rotated at 3000 rpm in Example 1
A spherical filler composition equivalent to that in Example 1 was recovered in the same manner as in.

Examples 15 to 22 4A type zeolite powder (Milwasawa Chemical Co., Ltd. Shilton M: average particle size
2.5μ), 5A type zeolite powder (Silton EP manufactured by Mizusawa Chemical Co., Ltd .:
Table 3 shows the average particle size 3μ), X-type zeolite powder (Mizawa Chemical Shilton CP: average particle size 3μ) P-type zeolite powder (Mizawazawa Chemical Shilton PC: average particle size 3.5μ) and various organic binding media. The mixture (% by weight) shown below was mixed and melted, and a spherical filler composition equivalent to that of Example 1 was recovered at a disc rotation speed of 3000 [rpm] in the same manner as in Example 1-2. Shown in the table.

Examples 23 to 27 4A type zeolite calcined powder (Misawa Chemical Co., Ltd. Shilton PT: average particle size 2.3 μ, ignition loss (1000 ° C.) 2.8%), 5A type Zeolite calcined powder (Misawa Chemical Co., Ltd. Shilton EPT: average particle size 2.8)
μ, ignition loss (1000 ° C) 3.1%), X-type zeolite calcined powder (Mizawazawa Chemical Shilton CPT: average particle size 2.7μ, ignition loss 2.6%) and the organic binding medium shown in Table 5 4 Mix and melt with the formulation (% by weight) shown in Table 4, then rotate at 30
The same spherical filler composition as in Example 1 was recovered in the same manner as in Example 1-2 using a disk of 00 [rpm]. The results are shown in Table 4.

Examples 28-33 Cubic silica particles obtained by acid treatment of zeolite (AMT-Silica ^# 300A manufactured by Mizusawa Chemical Co., Ltd., average particle diameter 3.0 μ), spherical silica particles obtained by acid treatment (Mizawa Chemical Co., Ltd.) AM
T-silica ^# 300B average particle diameter 3.0 μ), and those obtained by firing them at 500 ° C. and the organic binding medium shown in Table 5 were mixed and melted in the composition (% by weight) shown in Table 5, and then mixed. Number of rotations
A spherical filler composition equivalent to that in Example 1 was recovered in the same manner as in Example 1-2 using a 3000 [rpm] disk, and the results are shown in Table 5.

Application Example 1 4 kg of low-density polyethylene having a melt flow rate of 1.5 g / 10 minutes and a density of 0.920 g / ml was used as shown in Table 7 in Example 1
-2, 6, 8, 16, 18 spherical filler composition prepared and diatomaceous earth (Dicalite: average particle size 3.
1μ), synthetic silica (Syloid ^# 244), Shilton AMT
-25 and Silton PC added with 0.3% in terms of solid matter were mixed by a super mixer for 1 minute, and then melt-kneaded at a temperature of 160 ° C. by an extruder to obtain chips.

These chips are then fed to the extruder and melted 160
The film was blown into a film having a thickness of 30 μm under the conditions of ℃ and die 170 ℃. The resulting film was examined for haze, blocking property, appearance (surface condition) and foaming property, and the results are shown in Table 7.

Here, the haze was measured by a digital haze meter TC-HDP manufactured by Tokyo Denshoku.

The blocking property is such that two films are stacked, a load of 20 kg is applied, and the film is left in an oven at 40 ° C for 24 hours and then two films are peeled off without resistance 1 Some resistance 2 Very resistance 3 Very peeling Difficult one 4 It was evaluated in 4 stages.

 The appearance was evaluated as follows.

Uniform and close to non-added product ○ Slightly roughened △ Fairly rough surface × Presence or absence of foamability was visually confirmed.

Application Example 2 Polypropylene resin 1 with melt flow rate 1.9g / 10min
2,6-di-t-butyl-p-cresol 0.10 in 00 parts by weight
Parts by weight, 0.05 parts by weight of calcium stearate and the spherical filler composition prepared in Examples 2, 6, 26 and 32, and as a comparative example, calcium carbonate (escaron ^# 1500), synthetic silica (average particle size 1.0 μ), sillton. After mixing AMT-25 and Shilton EP in the respective supermixers with the addition of the number shown in Table 8,
The mixture was melt-kneaded at 230 ° C. and made into chips.

These chips were formed into a film original plate by T-die extrusion and then stretched 5 times in the longitudinal direction and 9 times in the lateral direction to obtain a film of about 30 μm.

The haze, blocking property, appearance (surface condition) and foaming property of these films were examined, and the measuring method was the same as in Application Example 1.

Application Example 3 The filler composition according to the present invention (hereinafter referred to as composition A) obtained in Examples 16, 21, 22, and 23 was used as a stabilizing aid for vinyl chloride, and the vinyl chloride resin composition shown in Table 9 was used. The composition (hereinafter referred to as composition B) was combined into a vinyl chloride resin composition, and the effect of the composition A of the present invention on dispersibility in PVC, thermal stability, and Charby impact value was examined.

Preparation of Composition B Powder stabilizer 7- 9 pm powder stabilizer Stavinex Tc (manufactured by Mizusawa Chemical Industry Co., Ltd.) as an organic solid binding dispersion medium,
Low molecular weight polyethylene Lupax 2191 (Nippon Seiwa Co., Ltd. melting point 80 from among commercially available vinyl chloride resin lubricant powders)
℃), lymar S- which is a stearate of glycerin
200 (manufactured by Riken Vitamin Co., Ltd., melting point: 57-63 ° C.) and Stavinex NC ₁₈ (manufactured by Mizusawa Chemical Co., Ltd.) were mixed at the compounding ratio shown in Table 9, and this was rotated using a super mixer. Mix for 3 minutes under water cooling at several 500 rpm, and then mix by atomizing with an atomizer to prepare a surface-treated mixed powder of the dispersion medium into primary particles, and then use a super mixer at a temperature above the melting point of the dispersion medium. Granulation was carried out while rolling to obtain granular stabilizers each having a particle size of 1 to 2 m / m.

For 100 parts by weight of dispersible PVC (Smilit SX-11), 60 parts of DOP, 0.05 part of carbon, 5.0 parts of composition B, and 5 parts and 10 parts of composition A, 16 parts by 3.5 inch roll (rotation speed 28 rpm) respectively
Kneading at 0 ~ 165 ℃, 5.5 minutes, thickness 0.35 ~ 0.40 mm, width 12 cm,
It was formed into a sheet having a length of 45 to 50 cm.

Dispersion degree B is a macroscopic observation of 100 µm to 250 µm particles in the central 10 cm x 25 cm sheet section of the molded sheet prepared by the above method, and dispersity A is a microscopic observation of the central section of the molded sheet. The following method was followed.

That 10 during the molding seat surface 250 cm ² in dispersity B
White spots with a diameter of 0 to 250 μm were counted, and the number of white spots was displayed [ke / 250 cm ² ]. Moreover, in the dispersity A, 25 to 100
A microscope with a magnification of 60 μm for the white spot of μm diameter (Nippon Optical Industry Co., Ltd.)
EFM type) Counting in the lower sheet area of 30 cm ² , 25 to 50 each
The number of white spots of μm and 50 to 100 μm was divided by the counting area to obtain the value [ke / cm ² ].

The characteristic of the poor dispersion state on the molded sheet is the dispersity A >>
In the case of the same B, and the degree of dispersion A is roughly classified into the same B, A,
A poor dispersion state is expressed by both B values, and when both values are close to zero, the degree of dispersion is judged to be good.

Charpy impact test PVC (Zeon 103EP) 47.6g, composition B2.38g (5g), composition A2.38g (5 parts) and 4.76g (10 parts) 3.5 inch roll 1
Knead at 60 ℃ for 6 minutes to form a sheet with a thickness of 0.6-0.7 mm, and
Two pieces are kneaded and molded for each sample. One sheet of the above-mentioned formed sheet was divided into 3 equal parts, and 6 pieces per sample were press-formed with a press frame having a thickness of 0.3 cm.

A No. 1 test piece was prepared from the above-mentioned pressed sheet by the Charpy impact test method of JIS K7111 hard plastic, and an impact test was performed by a Charby impact tester.

100 parts by weight of heat-stable PVC (Zeon 103EP), 3 parts and 5 parts of composition B, and 5 parts and 10 parts of composition A were kneaded with a 3.5-inch kneading roll at 160 ° C for 5 minutes. Then, take out a 0.5 mm sheet, then cut this sheet into about 3 × 10 cm, and in the gear open kept at 180 ° C., crochet under that temperature condition, and heat deterioration of the sheet due to the baculo time. Observing the colored state due to, the colored state at this time was evaluated and expressed in 8 grades of 0, 1, 2, 3, 4, 5, 6, 7 and 0 at this time was made uncolored, and with the passage of the colored state The number was increased and the one that was completely blackened was set to 7, and the state of thermal deterioration was observed to make an evaluation test of thermal stability.

 The above results are shown in Table 9.

Application Example 4 [η] = 1.1 80 parts by weight of polytetramethylene terephthalate, the spherical filler composition prepared in Examples 2, 18, 23 and 30 (hereinafter referred to as Composition A) and talc as a comparative example,
5 each of carbon charcoal, Shilton AMT-25, Shilton CPT
30 parts by weight was melt-mixed with a 50 mmφ extruder at a cylinder temperature of 250 ° C. to form chips. Next, these chips were molded by an injection molding machine, and the Charpy impact value was measured as the impact strength and shown in Table 10.

[Brief description of drawings]

FIG. 1 shows the cross-sectional structure of the spherical filler composition of the present invention. FIG. 2 is a conceptual sectional view of a stretched film containing the spherical filler composition of the present invention. FIG. 3 is an electron micrograph showing the particle structure of the spherical filler composition of the present invention.

Continuation of the front page (56) References JP 62-20537 (JP, A) JP 61-258829 (JP, A) JP 61-43640 (JP, A)

Claims (1)

(57) [Claims] 1. A clear cubic or spherical primary particle shape,
Filler consisting of amorphous silica, amorphous silica-alumina or aluminosilicate having an electron microscopy primary particle diameter of 5 microns or less, and a solid at room temperature that melts below the molding temperature of the resin to be blended Consisting of a homogeneous composition with an amount of 0.1 to 10 times by weight per filler of organic binding medium of
A filler composition for a resin, wherein the composition is present as spherical particles having a particle size of 0.05 to 3 mm in which the organic binding medium is a continuous phase and the filler is a dispersed phase.