Disclosed is an alumina-silica resin additive consisting of amorphous alumina-silica particles in which a definite cubic or spherical shape is retained in primary particles and the particle sizes of both the primary particles and the secondary particles are controlled to very small values. This additive is excellent in dispersibility in a resin, non-blowing property, slip characteristic and anti-blocking property. A product obtained by surface-treating the amorphous alumina-silica particles with a certain amount of an organic lubricant is very valuable as a filler.

BACKGROUND OF THE INVENTION 
(1) Field of the Invention 
The present invention relates to an alumina-silica resin additive. More 
particularly, the present invention relates to an additive which has a 
fine particle size and a definite particle shape and which gives good slip 
characteristic and anti-blocking property to a resin when it is 
incorporated in the resin, and process for the preparation of this resin 
additive. 
(2) Description of the Prior Art 
When shaped resin articles such as films and sheets are kept piled to one 
another, blocking is readily caused, and from oil, various inorganic 
additives have been incorporated into resins for imparting a slip 
characteristic to the resins. 
It is known that zeolites are excellent in this property. For example, 
Japanese Patent Publication No. 16134/77 teaches that if a zeolite powder 
having an average particle size smaller than 20 microns is added in an 
amount of 0.01 to 5% by weight to polypropylene, the blocking resistance 
of a biaxially drawn polypropylene film can be improved. Furthermore, 
Japanese Patent Application Laid-Open Specification No. 34356/79 teaches 
that if an aluminosilicate of the zeolite crystal having an ion exchange 
capacity is incorporated in an amount of 0.01 to 10% by weight into a 
chlorine-containing polymer, the thermal stability is improved and 
improvement of the exterior lubricating property is attained as an 
additional advantage. 
As described above, zeolite particles are excellent in a slip 
characteristic (external lubricating property) and an anti-blocking 
property to a shaped resin article. However, a zeolite contains 
considerable amounts of basic components such as sodium, potassium, 
calcium and magnesium components in the form of an aluminosilicate, and 
therefore, because of the presence of these basic components, the shaped 
resin article is colored with the lapse of time. Moreover, since a zeolite 
has an adsorbing property, especially a water-adsorbing property, blowing 
is caused when the zeolite is incorporated into a resin. 
Japanese Patent Application Laid-Open Specification No. 213031/83 discloses 
an alumina-silica additive comprising cubic primary particles having an 
Al.sub.2 O.sub.3 SiO.sub.2 molar ratio of from 1/1.8 to 1/5 and having one 
side smaller than 5 microns, wherein said particles are X-ray 
diffractometrically substantially amorphous and a BET specific surface 
area smaller than 100 m.sup.2 /g. It also is taught that the 
alumina-silica cubic particles can be prepared by acid-treating a 
crystalline zeolite having a cubic particle shape under such conditions 
that the crystallinity is substantially lost but the particle shape is not 
marred, and that cubic particles having such a particle size distribution 
that the content of particles having a size smaller than 10 .mu. is at 
least 98% by weight and particles having a size of 1 to 5 .mu. occupy at 
least 70% by weight of the total particles are preferred. 
Various problems which arise when zeolite particles are incorporated into 
resins are solved by amorphous alumina-silica particles formed by the acid 
treatment of a zeolite. However, in the use where a thin thickness is 
required, for example, when this additive is used for a household wrapping 
material or a base film of a magnetic tape, the particles are too coarse. 
Accordingly, development of an additive for imparting an excellent slip 
characteristic and an excellent blocking resistance, which has a fine 
particle size and an excellent dispersibility in a resin, is desired. 
However, if the zeolite to be subjected to the acid treatment is finely 
divided, the regular cubic shape of primary particles of the zeolite is 
destroyed during the acid treatment and the primary particles come to have 
an indeterminate shape. Furthermore, these indeterminate primary particles 
are agglomerated to form coarse particles. 
SUMMARY OF THE INVENTION 
It is therefore a primary object or the present invention to provide an 
amorphous silica-alumina additive in which the above-mentioned defects of 
the conventional amorphous silica-alumina additive are effectively 
eliminated, and a process for the preparation of this amorphous 
silica-alumina additive. 
Another object of the present invention is to provide an amorphous 
silica-alumina resin additive in which a definite shape of primary 
particles is retained and the sizes of both the primary particles and 
secondary particles are controlled to small values, and which has an 
excellent combination of dispersibility in a resin, non-blowing property, 
slip characteristic and blocking resistance. 
Still another object of the present invention is to provide a process in 
which an amorphous silica-alumina having the above-mentioned 
characteristics assuredly and easily can be prepared. 
A further object of the present invention is to provide an amorphous 
alumina-silica resin additive suitable for incorporation into a thin film 
substrate of a household wrapping material or a magnetic tape. 
We found that if a synthetic zeolite having a primary particle size smaller 
than 0.6 .mu.m is selected and this synthetic zeolite is acid-treated 
under such a buffer condition that local reduction of the pH value is 
controlled and under such a condition that the final pH value is not lower 
than 5 and the acid-treated zeolite is then heat-treated, an amorphous 
alumina-silica resin additive having novel particle size characteristics 
and adsorption characteristics described below can be obtained and the 
foregoing objects can be attained by this resin additive. We have now 
completed the present invention based on this finding. 
More specifically, in accordance with one aspect of the present invention, 
there is provided an alumina-silica resin additive consisting of amorphous 
particles having an Al.sub.2 O.sub.3 /SiO.sub.2 molar ratio of from 1/1.8 
to 1/5.0, wherein the alumina-silica particles have a definite cubic or 
spherical primary particle shape and an average primary particle size 
smaller than 0.6 .mu.m as determined by the electron microscope method, 
the alumina-silica particles have such a secondary particle size 
distribution that the content of particles having a particle size smaller 
than 1 .mu.m as determined by the weight precipitation method is at least 
50% by weight, said alumina-silica particles have a BET specific surface 
area smaller than 80 m.sup.2 /g, and when the alumina-silica particles are 
heated at 550.degree. C. for 3 hours and then allowed to stand still in an 
atmosphere maintained at a relative humidity of 75% and a temperature of 
25.degree. C. for 24 hours, the water absorption is smaller than 10% by 
weight. 
In accordance with another aspect of the present invention, there is 
provided a process for the preparation of an alumina-silica resin 
additive, which comprises preparing an aqueous slurry of a synthetic 
zeolite consisting of fine cubic particles having an Al.sub.2 O.sub.3 
/SiO.sub.2 molar ratio of from 1/1.8 to 1/5.0 and an average primary 
particle size smaller than 0.6 .mu.m, contacting the aqueous slurry with 
an acid under such a buffer condition that local reduction of the pH value 
is avoided and under such a condition that the final pH value is not lower 
than 5, thereby to effect an acid treatment of the synthetic zeolite, and 
calcining the acid-treated zeolite at a temperature higher than 
300.degree. C. 
In the process of the present invention, it is preferred that the acid 
treatment be carried out in an aqueous medium containing an acid and an 
alkali metal salt in an amount of at least 1.0 mole% based on the acid.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The present invention will now be described in detail. 
The present invention is characterized in that a synthetic zeolite having a 
primary particle size smaller than 0.6 .mu.m is selected and this 
synthetic zeolite is acid-treated under such a buffer condition that local 
reduction of the pH value is controlled and under such a condition that 
the final pH value is not lower than 5. 
As the result of our research, it was found that in the acid treatment of a 
synthetic zeolite, the particle shape or secondary particle size of the 
obtained amorphous particles is greatly influenced by the particles of the 
starting zeolite particles. For example, in the case where zeolite 
particles having a primary particle size larger than 0.8 .mu.m are 
acid-treated, amorphous alumina-silica particles substantially retaining 
the cubic shape of the starting zeolite particles are formed 
irrespectively of the acid treatment conditions. However, if a zeolite 
having a primary particle size smaller than 0.6 .mu.m is acid-treated, the 
cubic shape of the zeolite particles is frequently lost and indeterminate 
amorphous alumina-silica particles are produced. 
Generally, in case of a powder of an inorganic compound, especially a 
powder of an amorphous substance, the finer is the primary particle size, 
the more conspicuous is the tendency of secondary agglomeration and the 
larger becomes the secondary particle size. 
The present invention is based on the novel finding that even in case of 
fine synthetic zeolite particles having an average primary particle size 
smaller than 0.6 .mu.m, if the acid treatment is carried out under the 
above-mentioned conditions, the inherent primary particle shape of the 
zeolite particles is completely retained in the formed amorphous particles 
and a fine primary particle size and a fine secondary particle size 
distribution can be obtained. The buffer condition referred to in the 
present invention means a condition controlling reduction of the pH value 
in the acid treatment system, and for example, this condition can be 
attained by making a buffering agent present in the acid treatment system. 
Another prominent characteristic feature of the present invention is that 
it is possible to render a zeolite amorphous by the acid treatment at a 
final pH value of at least 5. It is believed that one reason why the 
zeolite can be rendered amorphous under such mild acid treatment 
conditions is that the primary particle size of the starting zeolite is 
fine. Under ordinary acid treatment conditions, that is, under such 
conditions that local reduction of the pH value is caused or the final pH 
value is lower than 5, the definite primary particle shape is lost and the 
particles are made indeterminate, and secondary agglomeration becomes 
conspicuous and the dispersed particle size is increased. 
FIG. 1 of the accompanying drawings is an electron microscope photograph 
showing the particulate structure of the alumina-silica additive of the 
present invention, and FIG. 2 is an electron microscope photograph showing 
the particulate structure of alumina-silica particles outside the scope of 
the present invention (prepared according to the process shown in 
Comparative Example 1-(2) given hereinafter). From these photographs, it 
is understood that the alumina-silica particles of the present invention 
are surprisingly characterized in that even though the average primary 
particle size is smaller than 0.6 .mu.m, especially 0.2 to 0.5 .mu.m, the 
cubic or spherical shape of the primary particles is definitely retained 
and the degree of secondary agglomeration is conspicuously low. 
FIG. 3 is an X-ray diffraction diagram or the alumina-silica particles 
shown in FIG. 1, and FIG. 4 is an X-ray diffraction diagram of the 
synthetic zeolite used as the starting material. From these FIGS. 3 and 4, 
it is understood that the alumina-silica particles of the present 
invention are completely amorphous and they have the above-mentioned 
particulate structure and particle size characteristics even though they 
are amorphous. 
FIG. 5 is a particle size distribution curve of the silica-alumina particle 
of the present invention, and FIG. 6 is a particle size distribution curve 
of the silica-alumina particles outside the scope of the present 
invention, shown in FIG. 6. From these FIGS. 5 and 6, it is understood 
that the additive of the present invention is characterized in that the 
secondary particle size is controlled to a very fine level such that the 
content of particles having a particle size smaller than 1 .mu.m is at 
least 50% by weight, especially at least 70% by weight. 
Since the alumina-silica particles of the present invention have the 
above-mentioned particulate structure and particle size characteristics, 
if the alumina-silica particles of the present invention are incorporated 
into a resin for the production of a thin film, the particles are finely 
dispersed in the resin very easily and the blocking resistance and slip 
property can be prominently improved without degradation of the 
transparency and continuity of the film. 
Since the alumina-silica additive of the present invention is stabilized in 
the amorphous state though it has the above-mentioned fine particle size, 
the water absorption of the additive is controlled to a level much lower 
than that of the zeolite. Furthermore, the additive of the present 
invention has an exceptionally small BET specific surface area as the 
amorphous alumina-silica. Accordingly, when the additive of the present 
invention is incorporated, blowing by adsorbed water or adsorbed gas is 
completely prevented. 
Chemical Composition and Other Characteristics of Additive 
The alumina-silica resin additive of the present invention has a 
composition in which the Al.sub.2 O.sub.3 /SiO.sub.2 molar ratio is from 
1/1.8 to 1/5, especially from 1/2 to 1/4. If the Al.sub.2 O.sub.3 
/SiO.sub.2 molar ratio is outside the above-mentioned range, it is 
difficult to form alumina-silica into cubic or spherical particles having 
a certain particle size and the characteristics such as the slip property 
are inferior to those of the additive of the present invention. 
In the alumina-silica additive of the present invention, the presence of a 
small amount of a basic component, especially an alkali metal component, 
in addition to the essential alumina and silica component is allowed. 
Incidentally, the content of the alkali metal component is lower than 50%, 
especially lower than 30%, of the alkali metal content in the zeolite in 
which the Al.sub.2 O.sub.3 /SiO.sub.2 molar ratio is within the same 
range. Namely, it must be noted that the content of the basic component is 
extremely low in the additive of the present invention. 
When this alumina-silica additive is heated at 550.degree. C. for 3 hours 
and then allowed to stand still in an atmosphere maintained at a relative 
humidity of 75% and a temperature or 25.degree. C. for 24 hours, the water 
absorption (moisture regain) is smaller than 10% by weight, especially 
smaller than 6% by weight. The additive may contain water in an amount 
exceeding this moisture regain, but it is generally preferred that the 
water content in the additive be lower than the water regain. 
Several examples of the composition of the alumina-silica additive of the 
present invention suitable for attaining the objects of the present 
invention are as follows. 
Type I 
Al.sub.2 O.sub.3 : 27 to 45% by weight 
SiO.sub.2 : 32 to 55% by weight 
Na.sub.2 O: 0.1 to 20% by weight 
H.sub.2 O: 0 to 25% by weight 
Type II 
Al.sub.2 O.sub.3 : 38 to 54% by weight 
SiO.sub.2 : 32 to 64% by weight 
Na.sub.2 O: 0.1 to 20% by weight 
H.sub.2 O: 0 to 30% by weight 
Type III 
Al.sub.2 O.sub.3 : 47 to 64% by weight 
SiO.sub.2 : 38 to 78% by weight 
Na.sub.2 O: 0.1 to 20% by weight 
H.sub.2 O: 0 to 30% by weight 
The additive of the present invention has the above-mentioned composition 
and is amorphous, and furthermore, it has chemical properties not 
possessed by zeolites. For example, an aqueous suspension of a zeolite 
having a solid content of 1% has generally a pH value higher than 10.5, 
while an aqueous suspension of the amorphous alumina-silica particles of 
the present inventin have a pH value lower than 10. 
A zeolite, for example, zeolite A, has an endothermic peak at a temperature 
of 780.degree. to 920.degree. C. in the differential thermal analysis and 
is converted to carnegieite at this peak temperature. On the other hand, 
the amorphous alumina-silica cubic particles of the present invention have 
an endothermic peak at a higher temperature, that is, 900.degree. to 
1000.degree. C., and is converted to Al.sub.2 SiO.sub.5 at this peak 
temperature. 
Known amorphous alumina-silica has a specific surface area much larger than 
100 m.sup.2 /g. On the other hand, the alumina-silica cubic particles of 
the present invention have an extremely small specific surface area and 
the BET specific surface area is smaller than 80 m.sup.2 /g, preferably 
smaller than 50 m.sup.2 /g, especially preferably smaller than 30 m.sup.2 
/g. 
Furthermore, the oil absorption of the amorphous alumina-silica particles 
of the present invention is generally 120 to 20 ml/100 g, especially 60 to 
30 ml/100 g, as determined according to the method of JIS K-5101. 
Preparation Process 
In view of the easiness of synthesis, the easy availability and the 
treatment easiness, zeolite A, zeolite X and zeolite Y, recited in the 
order of importance, are used as the starting crystalline zeolite. It is 
important that the primary particle size of the starting zeolite should be 
smaller than 0.6 .mu.m, especially 0.2 to 0.5 .mu.m. The starting zeolite 
having such a fine primary particle size and being uniform in the particle 
size is a synthetic zeolite prepared from lamellar active silicic acid or 
lamellar active aluminosilicic acid obtained by acid-treating solid 
silicic acid, especially a smectite clay mineral such as acid clay, as 
disclosed in Japanese Patent Publication No. 51992/83 proposed by us. The 
synthetic zeolite of this type is characterized in that the zeolite can be 
rendered amorphous by the acid treatment even under mild conditions, for 
example, a higher pH value or a shorter reaction time. 
The zeolite is formed into an aqueous slurry, and the slurry is subjected 
to the acid treatment. Either an inorganic acid or an organic acid can be 
used without any particular limitation. From the economical viewpoint, use 
of hydrochloric acid sulfuric acid, nitric acid, phosphoric acid and 
carbonic acid is preferred. The acid in the form of a dilute aqueous 
solution is used for the neutralization reaction of the crystalline 
zeolite. 
When the acid is added to the aqueous slurry of the crystalline zeolite, 
the pH value is naturally shifted to the acidic side with addition of the 
acid. In the present invention, the acid treatment is carried out in such 
a manner that the above-mentioned two conditions are satisfied. In order 
to control abrupt and local reduction or the pH value, a medium having a 
ph-buffering property is used as the acid treatment medium. Namely, it is 
preferred that the acid treatment be carried out in the presence of an 
alkali metal salt in an amount of at least 1.0 mole %, especially at least 
3.0 mole %, based on the acid in the medium. When sulfuric acid is used as 
the acid, sodium sulfate is preferred as the alkali metal salt, and when 
hydrochloric acid is used as the acid, it is preferred that sodium 
chloride be used as the alkali metal salt. Accordingly, a method in which 
an additional amount of the acid is supplied to the alkali metal 
salt-containing mother liquor prepared as the by-product in the acid 
treatment of the zeolite and the resulting acid-alkali metal salt solution 
is used for the subsequent treatment of the zeolite is advantageously 
adopted for the acid treatment of the zeolite. 
It is important that the pH value of the medium at the acid treatment 
should not be lower than 5 even at the final stage. 
The obtained amorphous alumina-silica is washed with water and is dried or 
calcined at a temperature higher than 300.degree. C. according to need, 
whereby the intended product is obtained. 
Of course, the surfaces of the particles are covered in advance with a 
metal soap, a resin acid metal soap or other dispersant according to known 
means. 
Use 
The alumina-silica resin additive is incorporated into various resins, for 
example, olefin resins such as polypropylene, polyethylene, a crystalline 
propylene/ethylene copolymer and an ion-crosslinked olefin copolymer, 
thermoplastic polyesters such as polyethylene terephthalate and 
polybutylene terephthalate, polyamides such as 6-nylon, 6,6-nylon and 
6,8-nylon, chlorine-containing resins such as a vinyl chloride resin and a 
vinylidene chloride resin, polycarbonates, polysulfones, polyacetal resins 
and other thermoplastic resins and is effective for imparting a good slip 
property and a good blocking resistance to shaped articles of these 
resins. Furthermore, the resin additive of the present invention may be 
incorporated in a kneaded composition or liquid composition for forming a 
coating to impart a blocking resistance to the coating. 
In this application, the amorphous alumina-silica cubic particles of the 
present invention are incorporated in an amount of 0.001 to 10 parts by 
weight, especially 0.01 to 3 parts by weight, per 100 parts by weight of 
the resin. 
Filler 
In the amorphous alumina-silica cubic particles of the present invention, 
the alkali component content is low, coloration or deterioration of the 
resin is not caused and the kneading property with the resin is good. 
Accordingly, the product of the present invention can be used as a filler 
for a resin. 
When the amorphous alumina-silica cubic particles of the present invention 
are used as the filler, the surfaces of the particles are covered with an 
organic lubricant in an amount of 0.01 to 30% by weight, especially 1 to 
10% by weight, based on the particles. 
In this embodiment, a certain amount or the organic lubricant applied to 
the surfaces of the amorphous silica-alumina cubic particles maintains 
good bite of the particles into the resin at the kneading step and 
prominently reduces the abrasion at the step of mixing or kneading with 
the resin. 
Generally, the lubricant is defined as an agent for improving the 
flowability of a thermoplastic resin at the heat-molding operation and 
facilitating the processing or the parting of a molded article from the 
mold. However, according to the present invention, the lubricant applied 
to the surfaces of the amorphous silica-alumina particles exerts the 
function of prominently reducing the abrasion of a mixing or kneading 
apparatus by the particles. This will become apparent from the examples 
given hereinafter. 
In the case where the surfaces of filler particles are treated with a 
lubricant, when the filler is mixed with a resin, bite of the filler with 
the resin is generally degraded. The degree of bite is evaluated by 
supplying a composition comprising, for example, a vinyl chloride resin 
and the filler to a plastograph tester and measuring the time of 
initiation of rise of the torque from the point of initiation of kneading. 
In case of a filler having a good bite, this rising time is shorter and in 
case of a filler having an insufficient bite, the rising time is long. It 
is presumed that the lubricant on the surfaces of particles effectively 
acts for preventing the abrasion of a mixer or kneader but kneading with 
the resin is more greatly influenced by the shape of the particles. 
In the present embodiment where the amorphous silica-alumina cubic 
particles are used as the filler, the organic lubricant present on the 
surfaces of the particles promotes uniform dispersion of the particles 
into the resin. The fact that dispersion of the additive is uniformly 
effected in respective individual particles can be confirmed by observing 
the obtained resin film by an electron microscope. 
It is critical that the organic lubricant should be applied to the particle 
surfaces in an amount of 0.01 to 30% by weight, especially 1.0 to 10% by 
weight. If the amount of the organic lubricant is too small and below the 
above-mentioned range, no effect of preventing the abrasion is attained 
and if the amount of the lubricant is too large and exceeds the 
above-mentioned range, bite of the filler into the resin is degraded. 
All of known organic lubricants can be used in the present invention. 
Preferred examples are aliphatic hydrocarbons such as liquid paraffin, 
industrial white mineral oil, synthetic paraffin, petroleum wax and 
odorless light hydrocarbon, silicones such as organopolysiloxane, fatty 
acids and metal salts thereof such as higher fatty acids having 8 to 22 
carbon atoms, obtained from animal or vegetable oils and by hydrogenating 
these fatty acids, and alkali metal, alkaline earth metal, Zn and Al salts 
of these higher fatty acids, amides and amines such as higher fatty acid 
amides, e.g., oleyl palmitoamide, stearyl erucamide and 2-stearomidoethyl 
stearate, ethylene-bis-fatty acid amides, e.g., N,N'-oleyulstearyl 
ethylemediamine, N,N'-bis(2-hydroxyethyl)alkyl (C.sub.12 -C.sub.18) amide, 
N,N'-bis(hydroxyethyl) lauroamide and oleic acid reacted with N-alkyl 
(C.sub.10 -C.sub.18) trimethylenediamine and fatty acid diethanolamines, 
e.g., a distearic acid ester of di(hydroxyethyl)diethylenetriamine 
monoacetate, fatty acid esters of monohydric and polyhdyric alcohols such 
as n-butyl stearate, dibutyl (n-butyl) debacate, dioctyl (2-ethylhexyl and 
n-octyl) sebacate, glycerol fatty acid esters, pentaerythritol 
tetrastearate, polyethylene glycol fatty acid esters, polyethylene glycol 
distearate, polyethylene glycol dilaurate, polyethylene glycol dioleate, 
polyethylene glycol coconut oil fatty acid diester, polyethylene glycol 
tall oil fatty acid diester, ethanol-diol montanic acid ester, 
1,3-butane-diol montanic acid diesters, diethylene glycol stearic acid 
diester and propylene glycol fatty acid diesters, triglycerides and waxes 
such as hydrogenated edible oil and fat, cotton seed oil, other edible 
oils, linseed oil, palm oil, a glycerol ester of 12-hydroxystearic acid, 
hydrogenated fish oil, beef tallow, spermaceti wax, montan wax, carnauba 
wax, bees wax, wood wax, monohydric fatty alcohol-aliphatic saturated acid 
esters, e.g., hardened whale oil lauryl stearate and stearyl stearate, and 
other lubricants such as propylene glycol alginate and dialkylketones. 
In the present invention, a lubricant containing a polar group such as a 
carboxylic acid, a carboxylic anhydride, a carboxylic acid salt, a 
carboxylic acid ester, a carboxylic acid amide, a ketone, an ether or a 
hydroxyl group at a concentration of 0.5 to 20 millimoles, especially 1 to 
10 millimoles, per gram of the lubricant and having at least one 
long-chain alkyl group having at least 10 carbon atoms, esepcially 12 to 
18 carbon atoms, is preferably used among the foregoing lubricants. Such 
preferred lubricants are easily available as fatty acid, fatty acid 
derivatives, alipahtic alcohols and aliphatic alcohol derivatives. In view 
of the above-mentioned function, a fatty acid amide type lubricant is 
preferred. 
In view of the easiness of handling at the surface treatment, that is, the 
flowability or caking resistance as the powder, it is preferred that the 
melting point of the lubricant be higher than 30.degree. C., especially 
50.degree. to 150.degree. C. The lubricant satisfying this requirement is 
an ethylene-bis-fatty acid amide such as ethylene-bis-stearic acid amide. 
The surface treatment of the amorphous silica-alumina cubic particles with 
the organic lubricant is accomplished by mixing the cubic particles with 
0.01 to 30% by weight, especially 1 to 10% by weight, of the organic 
lubricant. 
The organic lubricant may be applied to the surfaces of the cubic particles 
directly or in the form of a solution or dispersion. 
It is preferred that mixing be carried out by using an attrition type mixer 
such as a Henschel mixer or a super mixer. By using such a mixer, the 
respective particles are uniformly surface-treated with the lubricant. 
The alumina-silica resin additive of the present invention is excellent in 
the dispersibility in a resin, the non-blowing property, the slip 
characteristic arid the anti-blocking property. 
The present invention will now be described in detail with reference to the 
following examples that by no means limit the scope of the present 
invention. 
EXAMPLE 1 
The zeolite used in this example was zeolite 4A synthesized according to 
the following method. 
A finely divided silicic acid gel obtained by acid-treating an acid clay 
produced at Nakajo, Niigata, Japan, which is a smectite clay mineral, was 
selected and used as the silicic acid component. 
This acid clay contained 45% by weight of water in the as-obtained state, 
and the contents of the main components based on the dry product (dried at 
110.degree. C.) were 72.1% by weight of SiO.sub.2, 14.2% by weight of 
Al.sub.2 O.sub.3, 3.87% by weight of Fe.sub.2 O.sub.3, 3.25% by weight of 
MgO and 1.06% by weight of CaO. The ignition loss was 3.15% by weight. The 
starting acid clay was molded into columns having a diameter of 5 mm and a 
length of 5 to 20 mm. The columns in an amount corresponding to 765 g as 
the dry product were charged in a conical beaker having a capacity of 5 
liters, and 2 l of an aqueous solution or sulfuric acid having a 
concentration of 50% by weight was added. The mixture was acid-treated in 
the granular state at 90.degree. C. for 7 hours. The sulfates of the basic 
components, formed by reaction with sulfuric acid, were washed away and 
removed by decantation using a dilute solution of sulfuric acid and water. 
The residue was washed with water until the sulfate radical was not 
detected, whereby a granular acid-treated product of the acid clay was 
obtained. 
In order to attain a particle size distribution suitable for the synthesis 
of the zeolite in the acid-treated granular product, a household mixer 
(Hitachi Mixer Model VA-853 supplied by Hitachi Seisakusho) was charged 
with the acid-treated granular product and water was added so that the 
solid content was 20% by weight. The mixture was stirred for 20 minutes to 
effect pulverization, and the mixture was classified by a 200-mesh net and 
pulverized by a ball mill having a capacity of 7 liters for 3 hours to 
obtain a slurry or a particle size-adjusted acid-treated clay. 
The particle size distribution (%) was determined. The obtained results are 
shown in Table 1. 
TABLE 1 
______________________________________ 
Particle Size (.mu.m) 
Content (% by weight) 
______________________________________ 
0 to 1 49.3 
1 to 2 37.3 
2 to 3 13.0 
above 3 0.4 
______________________________________ 
The results of the chemical analysis (% by weight based on the product 
dried at 110.degree. C.) of the obtained acid-treated clay were as 
follows. 
Ignition loss: 3.93 
SiO.sub.2 : 94.19 
Al.sub.2 O.sub.3 : 1.05 
Fe.sub.2 O.sub.3 : 0.15 
CaO: 0.49 
MgO: 0.10 
The following oxide molar ratios were chosen for the production of the 
zeolite. 
Na.sub.2 O/SiO=1.2 
SiO /Al.sub.2 O.sub.3 =2.0 
H.sub.2 O/Na.sub.2 O=35 
For attaining the above-mentioned molar ratios, the alumina component in an 
amount to be additionally added, the alkali component to be reacted with 
the alumina component and water necessary for the reaction were added to 
the acid-treated clay mineral by using a commercially available solution 
of an alkali metal aluminate (Na.sub.2 O=21.0%, Al.sub.2 O.sub.3 =18.8%), 
commercially available caustic soda (NAOH) and water, mixing them, 
purifying the liquid mixture and supplying the refined liquid mixture to 
the slurry of the acid-treated clay in a stainless steel vessel having a 
capacity of 10 liters. Namely, the refined liquid mixture was mixed with 
the slurry under stirring at 70.degree. C. so that the total amount of the 
reaction liquid was about 7 l. The mixture temporarily passed through a 
gel state and was formed into a homogeneous slurry. Then, the slurry was 
heated at 95.degree. C. and stirred for 3 hours, whereby crystal particles 
of an alkali metal silicate (zeolite) were obtained. After formation of 
the crystals, aging was conducted at the same temperature for 2 hours. The 
reaction mixture was separated into a crystal-containing reaction product 
and a mother liquor by filtration. The filter cake was recovered and one 
part by weight as the dry product of the filter cake of the reaction 
product was mixed with 4 parts by weight of deionized water, and the 
mixture was stirred to obtain a homogeneous slurry. The mother liquor was 
separated by conducting filtration again. The pH value of the filtrate was 
12.5. The primary particle size determined by a scanning type electron 
microscope was about 0.5 .mu.m. 
Then, 1000 g (515 g as the anhydrous product) or the filter cake of Zeolite 
4A was dispersed in 5 l or dilute sulfuric ac the pH value adjusted to 2, 
and the dispersion and the above-mentioned dilute sulfuric acid were 
simultaneously poured into a 200-liter vessel equipped with a high-speed 
stirrer. The amount used of the dilute sulfuric acid was 172 l and the pH 
value at the time of completion of pouring was 5.8. Then, the mixture was 
heated at 50.degree. C. and maintained at this temperature for 1 hour, and 
the mixture was filtered, washed with water, dried, calcined at 
350.degree. C. for 2 hours and pulverized by an atomizer to obtain an 
amorphous aluminosilicate. The physical properties of the obtained 
aluminosilicate are shown in Table 2. 
Incidentally, the physical properties were determined according to the 
following methods. 
(1) Pack Density 
The peak density was determined according to the method of JIS K-6220. 
(2) Specific Surface Area 
The sample was dried at 150.degree. C. until the weight was not changed any 
more, and 0.5 to 0.6 g of the dried sample was charged in a weighing 
bottle, dried in a thermostat drier maintained at 150.degree. C. for 1 
hour and immediately weighed precisely. The sample was charged in an 
absorption test tube (2 to 5 ml) and was heated at 200.degree. C., and 
evacuation was effected so that the vacuum degree in the adsorption test 
tube became 10.sup.-4 mmhg. The test tube was naturally cooled and placed 
in liquid nitrogen at about -196.degree. C. and the amount adsorbed of 
N.sub.2 gas was measured at 4 to 5 points in the range where the PN.sub.2 
/Po ratio (PN.sub.2 stands for the nitrogen gas pressure and Po stands for 
the atmospheric pressure at the measurement) was from 0.05 to 0.30. The 
amount adsorbed of nitrogen gas, from which the dead volume was 
subtracted, was covnerted to the amount adsorbed at 0.degree. C. under 1 
atmosphere. The obtained value was substituted in the equation of BET to 
obtain Vm (ml/g) (the amount of adsorbed nitrogen gas necessary for 
formation of a monomolecular layer on the surface of the sample). 
The specific surface area S was calculated according to the following 
formula: 
EQU S=4.35.times.Vm (m.sup.2 /g) 
(3) Oil Absorption 
The oil absorption was determined according to the method of JIS K-5101. 
(4) Whiteness 
The whiteness was determined according to the method of JIS P-8101. 
(5) Particle Size by Electron Microscope 
An appropriate amount of a fine powder sample was placed on a metal sample 
plate and was sufficiently dispersed thereon, and a metal was coated by 
using a metal coating device (ion sputtering apparatus Model E-101 
supplied by Hitachi Seisakusho) to obtain a sample to be photographed. 
According to the customary procedures, four electron microscope images of 
10,000 magnifications were obtained while changing the visual field by 
using a scanning electron microscope (Model S-570 supplied by Hitachi 
Seisakusho). Typical 6 particles were selected from cubic particle images 
in the visual field and the length of one side of each cubic particle 
image was measured by using a scale and this length was designated as the 
primary particle size in the instant specification. 
(6) Crystallinity by X-Ray Diffractometry 
The sample was passed through a 200-mesh standard sieve and dried in an 
electric thermostat drier at 105.degree. C. for 3 hours together with a 
standard sample (standard sample of zeolite Na-A supplied by UCC). Then, 
the sample was naturally cooled in a dessicator, and the X-ray diffraction 
was measured and the crystallinity was calculated according to the 
following equation: 
Crystallinity of Zeolite Na-A 
##EQU1## 
Apparatus 
X-ray diffraction apparatus including goniometer PCG-S2 and rate meter 
ECP-D2 (supplied by Rigaku Denki), 
Measurement Conditions: 
Target: Cu 
Filter: Ni 
Voltage: 35 KV 
Ampere: 20 mA 
Count full scale: 4.times.10.sup.3 C/S 
Time constant: 1 sec 
Chart speed: 1 cm/min 
Scanning speed: 1.degree./min 
Diffraction angle: 1.degree. 
Slit width: 0.15 mm 
Measurement range: 2.theta.=20.degree. to 32 
(7) Particle Size Distribution 
The measurement was carried out by using Micron Photosizer Model SKN-1000 
supplied by Seishin Kogyo. An aqueous solution of sodium pyrophosphate 
having a concentration of 0.2% was used as the dispersion medium. Before 
the measurement, the adjustment of the zero point of a recorder and the 
adjustment of the shaking width were carried out. The light transmission 
of the blank was set at Log 1.95. 
The sample dispersion was carried out in the following manner. Namely, 100 
ml of the dispersion medium was charged in a 200-ml beaker and about 15 mg 
of the sample was added to the dispersion medium. The mixture was 
dispersed for about 2 minutes by an ultrasonic disperser (SK Disperser). 
The mixture was sometimes stirred by a stirrer during the dispersing 
operation. Then, the dispersion was heated or cooled to a predetermined 
liquid temperature. The dispersion was charged in a glass cell to a marked 
line. The cell was set at a cell holder and a light source lamp was 
lighted. When a pen of the recorder was located between Log 1.3 and Log 
1.4, it was judged that the concentration of the dispersion was 
appropriate. If the position of the pen was smaller than Log 1.3, the 
concentration was too high, and if the position of the pen was larger than 
Log 1.4, the concentration was too low. Accordingly, the dispersion was 
prepared again in such cases. The measurement was conducted under such 
conditions that the maximum particle size was 30 .mu.m. 
EXAMPLE 2 
In 2 l of dilute sulfuric acid having the pH value adjusted to 2 was 
dispersed 200 g (103 g in the anhydrous state) of the same filter cake of 
zeolite 4A as prepared in Example 1, and the dispersion was 
vacuum-filtered by a Buchner funnel. 2 l of dilute sulfuric acid having a 
pH value of 3 was added during the filtration before the exposure of the 
filter cake, and then, 5 l or industrial water (pH=5.8) was added to 
complete the filtration. The post treatment was carried out in the same 
manner as described in Example 1. The physical properties of the obtained 
product are shown in Table 2. 
EXAMPLE 3 
In a buffer solution (comprising 250 ml of 1M sodium acetate, 75 ml of 1N 
hydrochloric acid and 1000 ml of water and having a pH value of 4.9) was 
poured 100 g (51.5 g in the anhydrous state) of the same filter cake of 
zeolite 4A as prepared in Example 1 with stirring, and the temperature was 
elevated to 50.degree. C. and the mixture was maintained at this 
temperature for 3 hours. At this point, the pH value was 5.6. The post 
treatment was carried out in the same manner as described in Example 1 
except that the calcination temperature was changed to 500.degree. C. The 
physical properties of the obtained product are shown in Table 2. 
TABLE 2 
__________________________________________________________________________ 
Base Zeolite 
Example 1 
Example 2 
Example 3 
__________________________________________________________________________ 
Specific Surface Area (m.sup.2 /g) 
-- 29 30 21 
pH (1% suspension) 
12.0 7.9 8.9 8.5 
Primary Particle Size (.mu.m) by 
about 0.5 
about 0.5 
about 0.5 
about 0.5 
Electron Microscope 
Appearance by Electron 
beautiful cubic 
beautiful cubic 
beautiful cubic 
beautiful cubic 
Microscope or spherical 
or spherical 
or spherical 
or spherical 
shape shape shape shape 
Crystallinity by X-Ray 
98 amorphous 
amorphous 
amorphous 
Diffractometry (slight peaks) 
Partical Size Distribution (%) 
0-0.5 .mu.m 52.0 40.6 41.3 52.9 
0.5-1.0 .mu.m 35.1 34.5 35.1 27.5 
1.0-2.0 .mu.m 11.7 16.1 17.3 17.9 
2.0-3.0 .mu.m 1.1 7.3 6.1 1.6 
3.0-5.0 .mu.m 0.1 1.5 0.2 0.1 
Moisture Absorption (% by weight) 
22.8 4.7 3.4 3.1 
at Relative Humidity of 75% 
Chemical Composition (%) 
Ignition loss 13.13 4.70 5.14 2.45 
SiO.sub.2 37.59 50.08 48.33 51.13 
Al.sub.2 O.sub.3 31.51 41.51 40.46 42.49 
Na.sub.2 O 17.31 3.40 5.37 3.71 
Total 99.54 99.69 99.30 99.78 
SiO.sub.2 /Al.sub.2 O.sub.3 
2.03 2.05 2.03 2.05 
__________________________________________________________________________ 
COMATIVE EXAMPLE 1 
Three zeolites differing in the primary particle size were acid-treated. 
Namely, (1) the same zeolite as used in Example 1 (the primary particle 
size was about 0.5 .mu.m), (2) a zeolite for a detergent (Silton B 
supplied by Mizusawa Kagaku Kogyo; the primary particle size was about 0.8 
.mu.m) and (3) a commercially available zeolite for a detergent (the 
primary particle size was about 0.2 .mu.m) were used as the zeolite. To 
500 ml of a 3% zeolite slurry was dropped 0.5N hydrochloric acid at room 
temperature with stirring by means of a buret so that the pH value was 
adjusted to 4 over a period of about 30 minutes. Then, at an interval of 1 
hour, the pH adjustment was carried out by 0.5N hydrochloric acid so that 
the pH value in the stable state was about 4. The reaction was conducted 
in this state for 10 hours as a whole. The slurry was filtered, washed 
with water and dried to obtain an amorphous aluminosilicate. The physical 
properties of the obtained products are shown in Table 3. 
From the results shown in Table 3, it is seen that each product could not 
be used for attaining the objects of the present invention because the 
content or particles having a particle size smaller than 1 .mu.m was much 
lower than in the products obtained in Examples 1 through 3. 
TABLE 3 
__________________________________________________________________________ 
Comparative 
Comparative 
Comparative 
Comparative 
Example 1-(1)-1 
Example 1-(1)-2 
Example 1-(2) 
Example 1-(3) 
__________________________________________________________________________ 
Primary Particle Size (.mu.m) 
about 0.5 
about 0.5 
about 0.8 
about 2.0 
of Starting Zeolite 
pH Value of Slurry in 
5.11 4.03 4.51 4.02 
Stable State 
Crystallinity by X-Ray 
amorphous 
amorphous 
amorphous 
amorphous 
Diffractometry (slight peaks) 
Appearance by Electron 
agglomeration 
cubic shape con- 
agglomeration 
slight agglome- 
Microscope of cubes 
siderably marred, 
of cubes 
ration of cubes 
and gelatinous 
substance formed 
with violent 
agglomeration 
Particle Size Distribution (%) 
0-1 .mu.m 12.9 4.1 5.2 0.2 
1-2 .mu.m 29.7 8.8 7.9 3.5 
2-4 .mu.m 19.7 33.8 28.8 36.4 
4-6 .mu.m 30.3 30.0 26.5 29.5 
6-10 .mu.m 3.5 19.1 20.3 16.9 
10-15 .mu.m 3.7 3.2 7.6 9.3 
15-20 .mu.m 0.2 1.0 3.3 3.2 
20-30 .mu.m -- -- 0.4 0.8 
30-40 .mu. m -- -- -- 0.2 
__________________________________________________________________________ 
EXAMPLE 4 
A predetermined amount, shown in Table 4, of calcium stearate (SC supplied 
by Nippon Yushi), ethylene-bis-stearic acid amide (KAO-WAX EB-F supplied 
by Kao Soap) or polyethylene glycol (PEG 4,000 supplied by Nippon Yushi) 
was added to 2 kg of the amorphous aluminosilicate obtained in Example 1, 
and the mixture was stirred by a super mixer (Type VNM 5AL supplied by 
Nippon Spindle) for 30 to 40 minutes to effect the surface treatment. The 
abrasive property of the surface-treated aluminosilicate was tested in the 
following manner. 
Circular vanes (having the same configuration) having a thickness of 1 to 
1.5 mm and a diameter of 5 to 6 cm (the weight was 20 to 35 g) were 
prepared from a lead plate, a copper plate, an iron plate and a stainless 
steel plate, which differed in the Mohs hardness and they were attached to 
a homogenizing mixer (Homo Mixer supplied by Tokushu Kika Kogyo) and the 
mixer was immersed in a fixed ointment bottle having a capacity of 1 l, 
70% of which was filled with the sample powder. Each vane was rotated at 
4000 rpm for 2 hours, and the abrasive property was evaluated based on the 
weight decrease ratio. The obtained results are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
Example 1 
Example 4-1 
Example 4-2 
Example 4-3 
Example 4-4 
__________________________________________________________________________ 
Treatment Conditions 
lubricant not added 
calcium 
calcium 
calcium 
calcium 
stearate 
stearate 
stearate 
stearate 
amount (% by weight) 
-- 0.2 2.0 10.0 20.0 
rotation number (rpm) 
-- 0.2 2.0 10.0 20.0 
treatment temperature (.degree.C.) 
-- 150 2.0 10.0 20.0 
Abrasion Ratio (%) 
lead plate (1.5) 
0.081 0.042 0.041 0.007 0.003 
copper plate (3.0) 
0.052 0.018 0.000 0.001 0.001 
iron plate (4.5) 
0.028 0.006 0.002 0.000 0.001 
stainless steel plate (6.5) 
0.019 0.008 0.000 0.000 0.000 
__________________________________________________________________________ 
Example 
Example 
Example 
Example 
Example 
Example 
4-5 4-6 4-7 4-8 4-9 4-10 
__________________________________________________________________________ 
Treatment Conditions 
lubricant polyethylene glycol 
ethylene-bis-stearic acid amdie 
amount (% by weight) 
0.2 2.0 10.0 0.2 2.0 10.0 
rotation number (rpm) 
0.2 2.0 10.0 0.2 2.0 10.0 
treatment temperature (.degree.C.) 
80 2.0 10.0 150 2.0 10.0 
Abrasion Ratio (%) 
lead plate (1.5) 
0.051 
0.043 0.010 
0.031 0.030 
0.002 
copper plate (3.0) 
0.023 
0.020 0.003 
0.016 0.002 
0.000 
iron plate (4.5) 
0.010 
0.006 0.000 
0.005 0.000 
0.001 
stainless steel plate (6.5) 
0.008 
0.002 0.000 
0.006 0.000 
0.000 
__________________________________________________________________________ 
Note 
Each parenthesis value indicates the Mohs hardness. 
EXAMPLE 5 
The sample surface-untreated in Example 1 or the sample surface-treated in 
Example 4 was incorporated in a vinyl chloride resin and the lubrication 
test was carried out by using a plastograph. The sample test was carried 
out without adding any inorganic additive (Comparative Example 2). 
Resin Composition 
Vinyl chloride resin (Geon EP-103): 100 parts by weight 
Dibasic lead sulfate: 0.5 part by weight 
Lead stearate: 1.0 part by weight 
Sample: 1.0 part by weight 
Plastograph Conditions 
Oil trap: 200.degree. C. 
Rotation number of rotor: 40 rpm 
Amount of resin composition: 61 g 
The obtained results are shown in Table 5. 
TABLE 5 
______________________________________ 
Sample No. 
Amount Added (PHR) 
G.T. (min) 
M.T. (kg-m) 
______________________________________ 
Comparative 
0 3.8 2.80 
Example 2 
Example 1 
1 2.8 2.70 
(untreated) 
Example 4-2 
1 2.6 2.65 
Example 4-3 
1 2.5 2.60 
Example 4-4 
1 2.3 2.60 
______________________________________ 
Note 
G.T.: time (minutes) required for attaining maximum torque 
M.T.: maximum torque (kgm) 
EXAMPLE 6 
The surface-treated sample obtained in Example 4 was melt-kneaded in an 
amount shown in Table 6 at 190.degree. C. into low density polyethylene 
having a melt flow index of 2.0 g/10 min and a density of 0.925 g/ml by an 
extruder and the kneaded mixture was pelletized. 
Pellets were similarly prepared by using synthetic silica (Comparative 
Example 4) or calcium carbonate (Comparative Example 5) as the inorganic 
additive or without adding any inorganic additive (Comparative Example 3). 
Each pellet was supplied to an extruder and was extruded in the tubular 
form at 180.degree. C. from a die, and the extrudate was formed into a 
film having a thickness of 30 .mu.m. With respect to each film, the haze, 
the blocking property, the slip characteristic and the scratching property 
were determined according to the methods described below. 
The obtained results are shown in Table 6. 
(1) Haze 
The haze was determined according to the method of ASTM D-1003. 
(2) Blocking Property 
Two films were piled and allowed to stand still under a load of 20 kg in an 
oven maintained at 40.degree. C. for 24 hours. The force necessary for 
pealing the films were measured and this force was designated as the 
blocking property. 
(3) Slip Characteristic 
The slip characteritic was determined according to the method of ASTM 
D-1894. 
(4) Scratching Property 
Two films were piled, and they were rubbed by the finger and the scratching 
property was evaluated according to the following scale. 
.circleincircle.: not scratched 
.largecircle.: slightly scratched 
.DELTA.: somewhat scratched 
X: considerably scratched 
TABLE 6 
______________________________________ 
Amount Slip 
Added Blocking Char- Scratch- 
(part by Haze Property acter- 
ing 
Sample No 
weight) (%) (Kg/10 cm.sup.2) 
istic Property 
______________________________________ 
Example 1 
0.15 3.9 0.37 0.16 .DELTA. 
Example 4-2 
0.05 3.2 0.38 0.08 .largecircle. 
Example 4-2 
0.15 3.6 0.37 0.15 .circleincircle. 
Example 4-2 
0.25 3.7 0.36 0.13 .circleincircle. 
Example 4-3 
0.15 3.5 0.37 0.15 .circleincircle. 
Example 4-6 
0.15 3.5 0.37 0.15 .circleincircle. 
Example 4-9 
0.15 3.7 0.36 0.15 .circleincircle. 
Comparative 
0 2.3 3.90 -- .DELTA. 
Example 3 
Comparative 
0.15 4.6 0.41 0.28 .DELTA. 
Example 4 
Comparative 
0.15 5.2 0.46 0.35 X 
Example 5 
______________________________________