JPH0569865B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a compounding agent composition for resins, and more specifically, to a composition containing novel amorphous silica/alumina spherical particles and incorporating the particles and other compounding components into a resin. This invention relates to a resin compounding composition with improved dispersibility. (Prior art) Spherical amorphous silica and alumina-based spherical particles are used as fillers for various polymer films and other resins or rubbers, as fillers for cosmetics, as supports for fragrances and chemicals, and as chromatographs. Widely used as a filler for graphics. These silica-alumina spherical particles can be produced by spraying a silica-alumina sol or by colliding the spray with an air stream, by hydrolyzing an organometallic compound, or by producing a crystalline zeolite having a cubic or spherical particle morphology. A method for producing the zeolite is known in which the alkali metal content in the zeolite is removed by neutralization with an acid under conditions in which the zeolite is substantially destroyed but its particle morphology is not substantially impaired. JP-A-62-62842 describes a polyethylene resin composition in which the amorphous aluminosilicate treated with the acid described above is blended with polyethylene together with a fatty acid amide and an antistatic agent. (Problems to be Solved by the Invention) The present inventors have discovered that if P-type zeolite is first ion-exchanged with a specific divalent metal species such as a group element of the periodic table and then calcined, the ion-exchange Zeolite easily becomes amorphous; this ion exchange causes the particles to shift from strong alkali to weak alkali, and the hygroscopicity can be significantly reduced by amorphizing zeolite through calcination; and divalent metals. We proposed that by selecting the species, it would be possible to set and adjust the refractive index suitable for blending into resins, etc. (patent pending). The present inventor has discovered that when the amorphous silica-alumina-based spherical particles are spheroidized together with an organic compounding agent to form a compounding agent composition for resin, the dispersibility of the spherical particles in the resin is significantly improved. It has been found that the dispersibility of the organic compounding agent in the resin is improved, and problems such as plate-out during processing can be solved. That is, the object of the present invention is to provide amorphous silica/alumina based spherical particles with novel shapes and properties and an organic compounding agent, and to improve the dispersibility of the spherical particles in a resin and the dispersibility of the organic compounding agent in the resin. It is an object of the present invention to provide a compounding agent composition that also has improved dispersibility. (Means for Solving the Problems) According to the present invention, the following formula: mMO・nNa ₂ O・pSiO ₂・Al ₂ O ₃・qH ₂ O...(1) In the formula, M is 1 of a divalent metal. A metal consisting of a species or two or more species, where m+n is a number of 1.1±0.2,
The m:n ratio is in the range of 10:0 to 1:9,
p is a number of 4 ± 1.5, and q is a number of 0.5 or less. It has a chemical composition of and a jagged surface, and a moisture absorption of 13% or less at RH90%, room temperature, and 48 hours.
Contains as an inorganic component amorphous silica/alumina spherical particles having a refractive index of 1.61 or a combination of the amorphous silica/alumina spherical particles and at least one of other fillers and pigments, and has plasticity and lubricant properties. , contains at least one of an antistatic agent, an antifogging agent, an ultraviolet absorber, an antioxidant, and a low melting point resin as an organic component, and the inorganic component is bound via the organic component to form a powder. A compounding agent composition for a resin is provided. (Function) P-type zeolite is exceptional among various zeolites because it easily becomes amorphous when its sodium ions are ion-exchanged with divalent metal ions and then calcined. Accordingly, it has the characteristic of being able to suppress hygroscopicity to a low level. The raw material P-type zeolite contains sodium in its molecular structure, and its 5% aqueous dispersion is highly alkaline with a pH as high as 11. By ion exchange with ions, a similar aqueous dispersion exhibits a pH of only 7 to 9, indicating that it has been modified to be weakly alkaline. Therefore, when the amorphous silica/alumina particles used in the present invention are blended with various resins, etc., there is a significantly less tendency to deteriorate the resins, etc., and the stability of the blended resin compositions etc. is significantly improved. This tendency is particularly advantageous when used as a filler to be incorporated into resins having a tendency to hydrolyze, such as polyesters and polyamides. Secondly, the hygroscopicity of the amorphous silica/alumina spherical particles used in the present invention is suppressed to a smaller value than that of conventional zeolites and conventional amorphous silica/alumina fillers. It is a characteristic. The hygroscopicity of conventional amorphous silica-alumina is due to its high surface activity, and the hygroscopicity of conventional zeolite is due to the zeolite pores inherent in tectoaluminosilicate. The reason why the amorphous silica/alumina spherical particles used in the present invention exhibits only low hygroscopicity is that the crystal structure of the tectoaluminosilicate is destroyed by ion exchange and calcination without an increase in surface area. This is thought to be due to the fact that this occurs along with the occlusion of the foramen. The amorphous silica/alumina spherical particles used in the present invention have a concentration of 1.48 to 1.55, especially in relation to the fact that the sodium content is ion-exchanged with the divalent metal content.
The third characteristic is that the refractive index shifts to a high refractive index of 1.49 to 1.61. P-type zeolite used as a raw material generally only shows a refractive index of 1.48 or less, but by ion-exchanging it,
Although it is in an amorphous form, it is possible to increase the refractive index and make it compatible with the refractive index of the blended resin. Further, even within the above refractive index range, the refractive index can be easily adjusted to a predetermined value by selecting the type of divalent metal. The amorphous silica/alumina used in the present invention is also characterized in that each individual particle has a distinct spherical shape as a whole and a jagged surface. Figure 1 of the attached drawings is an electron micrograph (magnification) of amorphous silica/alumina spherical particles used in the present invention.
10,000 times), and Figure 2 is an electron micrograph (10,000 times) of P-type zeolite particles (used as a raw material) shown for comparison. These electron micrographs show that the amorphous silica-alumina-based spherical particles have a pear-shaped surface, although the overall shape is close to a true sphere, similar to P-type zeolite. Amazing features become clear. The fact that the amorphous silica/alumina spherical particles used have a spherical shape that is close to a true sphere means that they have properties such as good fluidity and large bulk density as a powder. Moreover, it shows the fact that it has excellent dispersibility in resins and the like. Furthermore, the fact that the particle surface is pear-like, that is, jagged, means that when this particle is combined with an organic compounding agent, the interfacial properties will be extremely unique. In fact, it has been found that when the compounding agent composition according to the present invention is blended into a resin, not only the dispersibility of spherical particles but also the dispersibility of organic compounding agents with strong bleeding properties into the resin is improved. This is because in the composition of the present invention, spherical particles are bound together with an organic compounding agent to form powder.
Since the jagged surface holds the organic compounding agent which also acts as a dispersion medium, the dispersibility of the spherical particles into the resin is improved, and the organic compounding agent is also well dispersed into the resin by being attracted to the spherical particles. It is. In addition, when the composition of the present invention is blended with a resin and molded, the resin and particles are interlocked with each other through the jagged surface, so even when this film is subjected to a stretching operation, voids etc. This effect is particularly noticeable when the particles are surface-treated. Furthermore, as will be described later, since the refractive index of the particles of the present invention approximates the refractive index of various resin films, a film with excellent transparency etc. can be obtained. Figure 3 shows the X-ray diffraction image (Cu-α) of the amorphous silica alumina spherical particles in Figure 1, and Figure 4 shows the
Figure 2 shows an X-ray diffraction image of P-type zeolite particles. From these X-ray diffraction images, it can be seen that the silica/alumina spherical particles used in the present invention have a particle shape similar to that of P-type zeolite particles. However, it is clear that they are completely different in that they are amorphous in terms of X-ray diffraction. (Preferred Embodiment of the Invention) Amorphous Silica/Alumina Spherical Particles When producing the amorphous silica/alumina spherical particles used in the present invention, first, they must have an X-ray diffraction pattern unique to P-type zeolite and The zeolite particles have a well-defined spherical shape and a pear-shaped surface as a whole. Such particle-shaped P-type zeolite can be obtained by mixing sodium silicate or activated silicate gel, silica sol, metakaolin, sodium aluminate, alumina sol, and sodium hydroxide to form an alkali aluminosilicate gel so as to satisfy the following conditions. , after homogenizing this gel, 80 to 200℃
It is produced by crystallization under normal pressure or hydrothermal conditions at a temperature of . Blend composition component ratio molar number Preferred molar ratio Na ₂ O/SiO ₂ 0.2-8 0.5-2.0 SiO ₂ /Al ₂ O ₃ 3-20 4-10 H ₂ O/Na ₂ O 20-200 30-100 Produced zeolite After washing with water and further classifying to a predetermined particle size, the next ion exchange treatment step is performed. An example of the chemical composition of the raw material P-type zeolite is as follows. _{KNa 2 O. _ _} It is a number. As divalent metals used for ion exchange, group metals of the periodic table, Ca, Mg, Zn, Ba, or Sr are advantageously used in terms of whiteness, but in addition,
Other metals such as Cu, Sn, Fe, Ni, Cr, etc. can be used. Ion exchange is carried out by using an aqueous solution of water-soluble salts of these metals, such as chlorides, nitrates, sulfates, etc., and bringing the metal salt solution into contact with the P-type zeolite. For ion exchange treatment, a method is adopted in which a metal salt aqueous solution and P-type zeolite are stirred in the state of an aqueous slurry, or a method in which P-type zeolite is brought into contact with a metal salt aqueous solution in a fixed bed or a fluidized bed. It can be carried out either in a formula or in a multi-stage manner, and in a continuous or batch manner. The ion exchange conditions are Na ₂ in P-type zeolite.
At least 10 mol% or more, particularly 30 mol% or more of the O content is substituted with MO (M is a divalent metal). For this reason, the metal salt aqueous solution in the treatment system should _be
The metal salt is used in an amount of 0.5 mol or more, especially 1.0 mol or more, and the initial concentration is generally 10 to 40% by weight, especially 20
It is preferable to contact with an aqueous salt solution of 50 to 50% by weight.
The temperature at the time of contact is suitably in the range of 20 to 100°C, particularly 30 to 70°C, and naturally the exchange process is shorter at higher temperatures. The contact time varies depending on the temperature and exchange rate, but is preferably in the range of 0.5 to 3 hours. After the treatment, the exchanged zeolite is separated into solid and liquid, washed with water, dried or crushed if necessary, and then subjected to the next firing step. The zeolite after ion exchange is calcined. The firing conditions are such that the ion-exchanged zeolite becomes substantially amorphous, and this temperature varies depending on the exchange rate and metal type, but is generally 200 to 700°C.
Especially in the range of 300 to 500°C. Generally, the heavier the metal species used, the more likely it will become amorphous even at relatively low temperatures. Calcination for amorphization can be carried out in a fixed bed, moving bed, or fluidized bed, and a treatment time of 0.5 to 5 hours is sufficient. The fired product is crushed or pulverized and, if necessary, classified to obtain the product of the present invention. The amorphous silica/alumina spherical particles used in the present invention each have a clear spherical shape close to a true sphere, and the particle surface is pear-shaped.
Preferably, the primary particle size (particle size as determined by electron micrograph) is in the range of 0.2 to 30 μm or less, particularly 0.3 to 10 μm. That is, each particle is generally expressed by the following formula: A=√r1・r2/r1...(3) where r1 represents the radius of the circumcircle of the electron micrograph outline of the particle, and r2 is its inscribed circle. The circularity A, which represents the radius, is in the range of 0.90 to 1.0, especially 0.95 to 1.0, and the following formula, B=△t/r1×100...(4) where △t is the particle size represents the depth between the peaks and valleys in the radial direction of the jagged irregularities in the outline of the electron micrograph of
It is within the range of 1.5 to 5%. That is, the roundness A is an index indicating the degree of sphericity of the particle, and the jaggedness B is an index indicating the degree of pear-like shape of the particle surface. Therefore, if the roundness A is within the above range,
This shows that each particle is extremely close to a true sphere, which results in good fluidity as a powder and granule.
It exhibits characteristics such as large bulk density, excellent fluidity for resins, etc., large bulk density, and excellent dispersibility for resins etc. In addition, by having a pear-like surface with a jaggedness degree B within the above range, when the particles are blended with a resin to form a stretched film, there are fewer fissure eyes, especially when surface treatment is applied. In this case, the formation of voids, etc. is reduced, and a film with excellent transparency can be obtained, and furthermore, the particles have excellent supporting ability as a carrier. If the degree of jaggedness B is smaller than the above range, the compatibility with the resin described above tends to decrease, while if the degree of jaggedness B is made larger than the above range, the strength of the particles themselves may decrease, or This is undesirable because it increases the tendency of equipment that comes into contact with it to wear out. Furthermore, if the primary particle size of the amorphous silica-alumina particles exceeds 30 μm, it becomes unsuitable for use as a resin filler, while if it is smaller than 0.2 μm, a tendency to secondary aggregation occurs, which is not so preferred. As mentioned above, in these silica-alumina particles, since there is no loss of alumina content during the manufacturing process, the molar ratio of SiO ₂ /Al ₂ O ₃ is in almost the same range as that of the P-type zeolite, which is the starting material. in general
It is in the range of 2.5 to 4.5, especially 3 to 4.5. Also,
In order to make the material amorphous and increase the refractive index, the divalent metal exchange rate (m/m+n) must be 20% or more, especially 40% or more. The refractive index of the amorphous silica/alumina particles used in the present invention is in the range of 1.48 to 1.61, and is listed in Table A as methacrylic, polyvinyl alcohol (PVA), nylon, linear low density polyethylene (LLDPE), It approximates the refractive index of various resin films such as density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), ethylene vinyl acetate (EVA), and vinyl chloride resin (PVC).

[Table] Furthermore, these amorphous silica/alumina spherical particles have a small BET specific surface area of 50 m ² /g or less, low surface activity, and little influence in the atmosphere. Moreover, among these spherical particles, those of divalent metal type have excellent whiteness, with a whiteness of 95% or more measured by the Hunter reflection method. The amorphous silica/alumina particles used in the present invention have a surface coated with an inorganic oxide, such as titanium oxide,
It can be coated or surface treated with a coupling agent such as silicon oxide, zirconium oxide, zinc oxide, barium oxide, magnesium oxide, calcium oxide, silane type, titanium type or zirconium type. Other Inorganic Compounds In the present invention, the aforementioned amorphous silica/alumina-based spherical particles can be used alone as an inorganic component, or in combination with other fillers or pigments. Inorganic ingredients used in combination include alumina, attapulgide, kaolin, carbon black, graphite, finely divided 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, waxite clay, gypsum, silicon carbide, zircon, glass beads, shirasu balloon,
Examples include asbestos, glass fiber, carbon fiber, rock wool, slag wool, boron watermelon, stainless steel fiber, titanium white, zinc white, red iron oxide, iron black, yellow iron oxide, titanium yellow, chromium oxide green, ultramarine, and navy blue. In the present invention, at least 60% of the total inorganic components
It is desirable that amorphous silica/alumina spherical particles account for 80% by weight or more by weight. Organic component The organic component used in the present invention includes a plasticizer, a lubricant, an antistatic agent, an antifogging agent, an ultraviolet inhibitor, an antioxidant, a low melting point resin, etc., and the organic component contains at least one of these as an organic component. In addition, the inorganic components are bound together via organic components to form powder and granules. When adding these useful components to a resin, it is important to take into account its use, type of resin,
They are used depending on the molding method, etc., and examples of each are given below. a Lubricant and antistatic agent, propylene homopolymer or copolymer film resin of propylene and at least one of ethylene, butylene-1, hexene-1, 4-methylpentene-1, and octene-1 In order to improve the transparency, slip properties, blocking resistance, and antistatic properties of the composition, the composition powder according to the present invention is used, which contains an organic component as a lubricant and an antistatic agent as described below. As the lubricant and antistatic agent used in the present invention, all those commonly used in polyolefin films can be used. That is, lubricants include (a) hydrocarbon-based lubricants such as liquid paraffin, natural or synthetic paraffin, micro wax, polyethylene wax, and chlorinated polyethylene wax, and (b) fatty acid-based lubricants such as stearic acid and lauric acid. , (c) fatty acid monoamide or bisamide such as stearamide, palmitic acid amide, oleic acid amide, erucic acid amide, methylene bis stearamide, ethylene bis stearamide, (di)butyl stearate, hardened Ester-based soaps such as castor oil and ethylene glycol monostearate; (e) alcohol-based soaps such as cetyl alcohol and stearyl alcohol; (f) metal soaps such as lead stearate and calcium stearate; Although mixed systems are generally used, fatty acid monoamide systems or bisamide systems are particularly preferred. On the other hand, antistatic agents include (a) primary amine salts, tertiary amines, quaternary ammonium compounds,
Cationic products such as pyridine derivatives, (b) sulfated oils, soaps, sulfated ester oils, sulfated amide oils, olefin sulfate ester salts, fatty alcohol sulfate ester salts, alkyl sulfate ester salts,
Fatty acid ethyl sulfonate, markylnaphthalene sulfonate, alkylbenzene sulfonate,
Anionic products such as succinic acid ester sulfonates and phosphoric acid ester salts, (c) partial fatty acid esters of polyhydric alcohols, ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of fatty acids, fatty aminos or fatty acid amides Ethylene oxide adducts of alkylphenols, ethylene oxide adducts of alkylnaphthols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols,
Non-ionic materials such as polyethylene glycol,
(d) Amphoteric compounds such as carboxylic acid derivatives and imidazoline derivatives can generally be used, but non-ionic compounds, especially polyoxyethylene alkylamines, polyoxyethylene alkylamides or their fatty acid esters, and fatty acid esters of glycerin are particularly useful. etc. are preferred. In the present invention, 0.06 to 100 parts by weight of resin
It is desirable that the blending agent composition powder is used in an amount of 10 parts by weight, preferably 0.14 to 5 parts by weight. b. Anti-fog agent Added to a linear low-density polyethylene film composition that has transparency, heat-sealing properties, and excellent mechanical properties, and improves its anti-fog properties especially for use in agricultural films without sacrificing transparency, anti-blocking properties, etc. For this purpose, the composition powder according to the present invention is used which also contains an antifogging agent as described below as an organic component or a fatty acid amide as a lubricant. Examples of the antifogging agent used in the present invention include stearic acid, monoglyceride, oleic acid monoglyceride, polyglycerol oleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan monooleate. In the present invention, 100 parts by weight of the resin contains a fatty acid amide such as oleic acid amide, stearic acid amide, behenic acid amide, etc. and an antifogging agent in a weight ratio of 1:1 to 1:3. It is desirable to use the powdered composition in an amount of 0.06 to 10 parts by weight, preferably 0.8 to 5 parts by weight. c. Thermal deterioration and antioxidant Furthermore, in order to prevent thermal deterioration particularly during high-temperature processing, the present invention contains an organic component consisting of a phosphorus compound and a phenolic antioxidant or a fatty acid amide as described below in linear low-density polyethylene. The powder and granular material of this composition is used. The phosphorus compound used in the present invention is at least one selected from phosphites, phosphonites, and phosphonic acid derivatives. Here, various phosphites are mentioned, such as triphenyl phosphite; diphenyl phosphite; didecyl phenyl phosphite; tridecyl phosphite; trioctyl phosphite; tridodecyl phosphite; triotadecyl phosphite; Nylphenyl phosphite; tridodecyl trithiophosphite;
Distearyl pentaerythritol diphosphite; 4,4'-butylidene bis(3-methyl-6-
t-Butylphenyl ditridecyl) phosphite; tris(2,4 di-t-butylphenyl) phosphite; bis(2,4 di-t-butylphenyl) pentaerythritol diphosphite, as well as alkyl having 12 to 15 carbon atoms. 4,4′-
Examples include isopropylidene diphenyl tetraalkyl diphosphite. Examples of the phosphonite include tetrakis(2,4-dialkyl phenyl)-4,4'-biphenylene diphosphonite. Note that the alkyl group here has 1 to 30 carbon atoms. Among these, especially tetrakis (2,4
-di-t-butylphenyl)-4,4'-biphenylene diphosphonite is preferred. Furthermore, as a phosphonic acid derivative, 4-hydroxy-3,5-di-t-butylbenzylphosphonic acid; 0-ethyl-(4-hydroxy-3,5-di-t-butylbenzyl)phosphonic acid; 0-(2 −
ethylhexyl)-(4-hydroxy-3,5-di-t-butylbenzyl)phosphonic acid; 0-ethyl-(4-hydroxy-3,5-di-t-butylbenzyl)phosphonic acid; 0-ethyl-( Examples include calcium salt of 4-hydroxy-3,5-t-butylbenzyl)phosphonic acid. The above-mentioned phosphorus compound is blended in a proportion of 0.01 to 1.0 parts by weight per 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 5,000. If a phenolic antioxidant with a molecular weight of less than 400 is blended here, the yellowness during high-temperature processing will increase, causing a decrease in quality, which is not preferable. There are various phenolic antioxidants with a molecular weight of 400 or more, such as octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; pentaerythryrutetrakis[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); Hexamethylene glycol-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 these can be used alone or in combination. The blending ratio of the phenolic antioxidant is
The amount is 0.01 to 1.0 parts by weight per 100 parts by weight. In the present invention, the composition powder containing a phosphorus compound and a phenolic antioxidant in a blending ratio of 0.5:1 to 1:1 to 100 parts by weight of the resin is mixed into 100 parts by weight of the resin.
It is desirable to use 10 parts by weight, preferably 0.05 to 5 parts by weight. d Organic peroxide and low melting point resin Furthermore, as an organic component used in the present invention, it is used for the purpose of improving the compatibility between the resin and the inorganic filler powder, such as dicumyl peroxide, lauroyl peroxide, benzoyl. By using the composition containing organic peroxides such as peroxide in combination with fatty acid amides such as oleic acid amide, lauric acid amide, and stearic acid amide, the organic peroxide can be This is added when heating and kneading the resin to cause crosslinking in the polymer, and therefore, the milder the reactivity, the more uniformly crosslinking will occur. Similarly, in order to improve the compatibility between resin and inorganic filler powder, terpene resin, a low melting point resin,
The powdered composition containing a petroleum resin and a rosin whose main components are abietic acid and dextropimaric acid is used. In the present invention, the former is a saturated polyester resin, and powders of the composition containing 0.1 to 30% by weight of organic peroxide per amorphous silica-alumina spherical particles can be used. In addition, the latter can be used in a stretched polypropylene film made of polypropylene resin, in which the granular composition containing 10 to 100% by weight of terpene resin per spherical particles is used in an amount of 0.3 to 8 parts by weight per 100 parts by weight of the resin. . e Plasticizer and UV absorber In the present invention, the following plasticizers and UV absorbers that are solid at room temperature are used as organic components. As a plasticizer, butyl stearate, P-toluenesulfamide, D-nitrobiphenyl, dicyclohexyl phthalate, diethylene glycol dizonbeate, triphenyl phosphate; As a UV absorber, 2-hydroxy-4-methoxy Benzophenone, 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 enyl acrylate, phenyl salicylate, 4-t-
Butylphenyl salicylate, p-octylphenyl salicylate, Ni-bisoctylphenyl sulfide, [2,2'-thiobis(4-t-octylphenolate)]-n-butylamine Ni, etc. can be mentioned. f.Other binding media Furthermore, as long as the organic component acts as a binding medium for the inorganic component, the following waxes and low melting point resins may be used. (1) Fatty acids and their metal saltsHigher fatty acids Fatty acids obtained from animal or vegetable oils and hydrogenated fatty acids having 8 to 22 carbon atomsHigher fatty acid metal saltsAlkali metal salts of the above fatty acids, alkali Earth metal salts, Zn salts, Al salts (2) Amides, amines Higher fatty acid amide Erucic acid amide Oleyl palmitamide Stearyl erucamide 2-Stearomide ethyl stearate Ethylene bis fatty acid amide N,N'-oleoyl stearyl ethylene diamine Diethyltoluamide N,N'-bis(2hydroxyethyl)alkyl( _C12 - _C18 )amide N,N'-bis(hydroxyethyl)lauroamide Reacted with N-alkyl( _C10 - _C18 ) trimethylenediamine Oleic acid Fatty acid diethanolamine Distearic acid ester of di-(hydroxyethyl)diethylenetriamine monoacetate (3) Fatty acid ester of monohydric and oligohydric alcohols n-butyl stearate Hydrogenated rosin methyl ester Dibutyl sebatate <n-butyl> Dioctyl sebatate < 2-ethylhexyl, n-octyl> 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 Ethanediolmontanic acid diester 1,3-butanediol montanic acid diester Diethylene glycol stearic acid diester Propylene glycol fatty acid diester Triglyceride wax Hydrogenated edible oils and fats Glycerin ester of 12-hydroxystearic acid Spam acetiwax 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-based wax Among these waxes, wax Class 1
Polar groups such as carboxylic acids, carboxylic anhydrides, carboxylates, carboxylic esters, carboxylic amides, ketones, ethers, and hydroxyl groups per gram.
Waxes containing in the molecule at a concentration of 0.1 to 20 mmol, particularly 0.5 to 10 mmol, and at least one long alkylene chain having 10 or more carbon atoms, particularly 12 or more carbon atoms, are preferred. Examples of the low melting point resin include various resins having a melting point or softening point of 40 to 200°C, particularly 70 to 160°C, such as epoxy resins, xylene-formaldehyde resins, styrene resins, chroman-indene resins, and other petroleum resins. Examples include alkyd resins, ethylene-vinyl acetate copolymers, ethylene-acrylic ester copolymers, low-melting acrylic resins, polyvinyl butyral, low-melting copolyamides, and low-melting copolyesters. These waxes and low melting point resins can be used alone or in combination of two or more. In the present invention, in addition to the organic components described above, insect repellents, insect repellents, odorants, antibacterial agents, fragrances, medicinal ingredients, etc. can also be used. Method for producing the composition powder To produce the formulation composition of the present invention, all inorganic components including the amorphous silica/alumina spherical particles according to the present invention or other inorganic fillers (hereinafter simply referred to as fillers) are prepared. 3 to 30% by weight, especially 5 to 15% by weight of organic components based on the total inorganic components, are mixed under grinding conditions as described in JP-A-64-36632 below. The mixing of the above-mentioned filler powder with the organic component under milling conditions can be carried out in various ways. For example, in wet milling mixing, a filler powder and an organic component are mixed while being milled in the presence of a solvent, and in soft milling mixing, a filler powder and an organic component powder are mixed in the presence of a solvent, etc. Mix under dry grinding. In any of these cases, it is important to grind the filler powder so that it is broken down into primary particles, and for this purpose grinders, sand grinders, mills, etc.
Atlighter. A high-speed shear stirrer, a Tokyo atomizer, a Nara type crusher, a disc vibrating mill, a vibrating ball mill, a rotary ball mill, a super mixer, etc., or a combination thereof are used. In these grinding mixers, the filler powder is broken down into primary particles and at the same time surface treatment with organic components is performed. In the former wet grinding mixing process, organic components are dissolved or dispersed in a solvent, filler powder is dispersed in this liquid to form a slurry, and this slurry is fed to the above-mentioned grinding mixer. The mixture is thoroughly ground and mixed, and then the solvent is distilled off under mixing or stirring conditions to obtain a surface-treated powder. As the solvent, it is preferable to use a non-polar solvent in order to prevent the agglomeration of the filler powder, and it is preferable to use a solvent that partially or completely dissolves the organic components.From this point of view, benzene, toluene, xylene, etc. Aromatic solvents, aliphatic solvents such as n-hexane, n-heptane, butane, alicyclic solvents such as cyclohexane, etc. are used, but solvents that can be used in the present invention include:
Of course, it is not limited to this. In this case, the amount of solvent used can range from 15 to 150 parts by weight per 100 parts by weight of filler powder. On the other hand, in the latter dry grinding and mixing process, the weighed powder filler and organic component powder are passed through the grinding mixer and mixed at a temperature lower than the melting point of the organic component. Remove from the mixer. The degree of grinding and mixing varies depending on the intensity of grinding, so it is difficult to define it unconditionally.
As already mentioned, the degree of surface treatment can be evaluated by testing its interfacial properties, dispersibility, fluidity, and particle size characteristics, so the treatment time can be determined depending on the type of mixer used. Bye. Generally, as grinding and mixing progresses, (1) the particle size distribution shifts toward the smaller diameter side, (2) the average particle size shifts toward the smaller diameter side, (3) water repellency increases, and (4) the angle of repose changes. (5) The dispersibility in the resin is significantly improved.
(6) The degree of grinding and mixing can be determined from the fact that almost no change is observed in the X-ray diffraction intensity. The above-mentioned wet grinding mixing has the advantage that it is easy to completely cover the primary particles with the binding medium, but on the other hand, there are problems such as increased cost due to the use of a solvent and the need to remove the solvent after mixing. There is also the problem that the primary particles tend to coagulate during heating to remove the solvent. Dry milling mixing is
Although the formation of the coating tends to be somewhat incomplete, there are many advantages in terms of ease of processing. The thus surface-treated powder is heated to a temperature above the melting point of the organic solid binding medium with an average particle size of 0.05 to 3.0 mm.
In particular, it is granulated to a size of 0.1 to 1.0 mm. The mixture can be used in powder form or can be granulated. For granulation, various granulation means known per se can be used, but since the surface-treated powder contains only a fairly small amount of organic components, rolling granulation is particularly advantageously used. For rolling granulation, ordinary rolling granulation 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 they are the same in that granulation is performed by relative movement between the powder and the machine wall. It may be advantageous to carry out this granulation at a temperature above the melting point of the organic component, which significantly increases the yield in granules. Since there is no compositional difference between the granules produced and the ungranulated powder, the granules of a predetermined particle size produced in the granulation process are collected by sieving, while the ungranulated powder is collected by sieving. It is also possible to circulate through the granulator and finally recover all the raw materials as granules. Furthermore, in order to obtain the formulation composition of the present invention, the total inorganic component containing the amorphous silica/alumina spherical particles and/or other inorganic filler, and 5% per total inorganic component.
90 to 90 times by weight, especially 10 to 80 times by weight of the organic component are mixed uniformly according to the method described in JP-A-64-36631 below. If the amount of organic components 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, and the mechanical strength of the resulting spherical particles also tends to be low. On the other hand, increasing the amount of the organic binding medium beyond the above range has adverse effects such as bleed-out and decreased transparency due to the blending of large amounts of unneeded components into the film-forming resin. Mixing of the two can be performed using a pulverizing mixer such as a Henschel mixer, super mixer, ball mill, or atomizer. This pulverized mixture is melt-kneaded in a melt-kneader such as a kneader,
It is granulated into spherical particles by extrusion from a nozzle and spray granulation, or by a disk granulation method in which it is dropped onto a rotating disk and granulated. The obtained spherical particles are sieved if necessary to obtain a formulation composition having an average particle size of 0.05 to 3 mm, particularly 0.1 to 1.5 mm. The composition powder obtained as above,
The organic component has the effect of increasing the adhesion between the filler particles and the molding resin at the interface and increasing the dispersibility of the filler particles in the resin. In addition, it can act as an antistatic agent, antifogging agent, etc., and if necessary, one or two other fillers such as charcoal, kaolin, talc, titanium, etc. It is also possible to combine more than one species and use it as a one-package formulation. Applications The formulation composition of the present invention can be applied to various resins, such as olefin resins such as polypropylene, polyethylene, crystalline propylene-ethylene copolymers, and ionically crosslinked olefin copolymers; polyethylene terephthalate, polybutylene terephthalate coatings, etc. Thermoplastic polyester such as 6-nylon, 6,6
- Polyamides such as nylon and 6,8-nylon:
Chlorine-containing resins such as vinyl chloride resin and vinylidene chloride resin; polycarbonate; polysulfones;
It can be used by blending with a thermoplastic resin such as polyacetal to give resin molded products such as films, slip properties or anti-blocking properties, and other desired properties. Of course, instead of being blended into the resin after polymerization, the compounding agent may be blended in advance into the monomer before polymerization so that the compounding agent is contained in the resin after polymerization. For such applications, the filler compositions of the invention are used in amounts of 0.001 to 50 parts by weight, especially 0.01 to 30 parts by weight per 100 parts by weight of resin. Effects of the Invention According to the present invention, the physical properties of the molded resin are significantly improved due to its ability to prevent abrasion during mixing or kneading with the resin, and to be uniformly and uniformly dispersed in the resin. In film forming, without creating voids in the final film,
A compounding agent composition for anti-blocking that can provide excellent transparency and a compounding agent composition that has excellent dispersibility of compounding agents even in fibrous molding can be obtained. (Examples) Example 1 Calcium-type amorphous silica/alumina particles according to the present invention were prepared below using a raw material P-type zeolite synthesized by the method described below. Synthesis of raw material P-type zeolite Commercially available reagent water glass (No. 3 sodium silicate SiO ₂
27wt%, Na ₂ O 9.0wt%), sodium aluminate (Al ₂ O ₃ 22.5wt%, Na ₂ O 15.5wt%), dilute sodium silicate using the following molar ratio using caustic soda so that the total amount is 16Kg. A diluted sodium aluminate solution was prepared. Na ₂ O / SiO ₂ = 0.8 SiO ₂ / Al ₂ O ₃ = 8.0 H ₂ O / Na ₂ O = 70 Next, 8.2 kg of dilute sodium silicate solution and dilute sodium aluminate were added in a stainless steel container with an internal volume of about 25 mm. 7.8
Kg was slowly mixed with stirring to obtain a homogeneous aluminosilicate alkali gel. Next, this aluminosilicate alkali gel was heated to 90°C with vigorous stirring.
The temperature was raised to 100, and treatment was carried out at that temperature for 48 hours to cause crystallization. Then, it was filtered and washed with water to obtain about 1.8 kg of P-type zeolite cake with a solid content concentration of 39%. Next, this cake was sufficiently dispersed by adding water to a concentration of 20%, and then classified several times using a small hydrocyclone to obtain a raw material slurry for use in the present invention. An electron micrograph of this raw material dried at 80 DEG C. (sample No. 1-0) is shown in FIG. 2, and an X-ray diffraction diagram is shown in FIG. Calcium-type amorphous silica/alumina particles Take 500g of the above raw material slurry into each beaker and place in a water bath at 40°C while stirring with a stirrer.
Warm to. Then contained in P-type zeolite
Calcium chloride (grade 1 reagent manufactured by Wako Pure Chemical Industries, Ltd.) is added in an amount of 1.0 times the mole of Na ₂ O, and the mixture is stirred for 1 hour. The mother liquor was separated by transition vacuum filtration, thoroughly washed with water, dried at 80℃ for 24 hours, ground in a small sample mill, and then calcined in a small electric furnace at a temperature of 300 to 400℃ for 2 hours, with an average particle size of 3.0μm. Sample No. 1-1 was prepared. The electron micrograph of this sample No. 1-1 is
The X-ray diffraction pattern is shown in FIG. 3. Example 2 The raw material composition of the P-type zeolite was as follows, except that fine particles of activated silicic acid gel obtained by acid-treating acid clay from Nakajo, Niigata Prefecture, which is a smectite group clay mineral, was used as the silicic acid content, and the raw material composition of the P-type zeolite was as follows. Calcium type amorphous silica alumina particles were prepared using the sample obtained in the same manner as in Example 1, and sample No. 2-1 with an average particle size of 1.8 μm was obtained. Raw material composition of P-type zeolite (molar ratio) Na ₂ O / SiO ₂ = 0.55 SiO ₂ /AI ₂ O ₃ = 6.0 H ₂ O / Na ₂ O = 65 Examples 3 to 10 Obtained in Examples 1 to 2 Sample No.1-1 and 2
-1 amorphous silica/alumina-based spherical particles and various organic binding media are mixed in a super mixer at the proportions (wt%) shown in Table 1, and then placed in a kneader heated to a predetermined melting temperature, weighing approximately 1 kg. /min, and the liquid material heated and melted by the kneader is
Rotating plate (disc) that rotates at 3000rpm with a length of 12cm
A spherical resin filler composition containing 90% or more in the range of 32 to 100 meshes was formed. The organic binding medium used was as follows. (1) Polyethylene wax Hiwax 110P
(Mitsui Petrochemical) (2) Polypropylene wax Viscole 550P
(Manufactured by Sanyo Chemical) (3) Erucic acid amide Alflo p-10
(Made by NOF) (4) Calcium stearate SC
(Made by NOF) (5) Polyglycerin monostearate
GS−106 (manufactured by NOF)

【table】

[Table] Examples 11 to 20 After mixing and melting the silica/alumina spherical particles used in Example 3, various organic binding media, and synthetic silica in the proportions (wt%) shown in Table 2 at the temperature, A spherical resin filler composition equivalent to that of Example 3 was obtained at a rotational speed of 3000 rpm. The organic medium used is as follows. (1) Calcium stearate SC
(Nippon Oil & Fats) (2) Erucic acid amide Areflo p-10
(Made by NOF) (3) Polyglycerin monostearate GS−
106 (NOF) (4) Solpitan fatty acid ester MP61℃ (5) Electrostripper TS
(Manufactured by Kao Atlas) (6) Terpene resin Kuroaron P-75
(manufactured by cheap crude oil) (7) BHT (8) Synthetic silica

[Table] Example 22 Melt flow rate is 1.5g/10min and density is
The samples shown in Table 3 were added to 0.920 g/cc low-density polyethylene, melt-kneaded using an extruder at a temperature of 150°C, and then pelletized. This pellet is fed to an extruder, and the melting part is 160℃,
A film with a thickness of 50 μm was formed by inflation at a die temperature of 170°C. The following physical properties of the obtained film were measured. The results are shown in Table 3. Haze level: Conforms to ASTM D1003 Blocking property: Overlapping two film surfaces,
After applying a load of 200g/ ^cm2 and leaving it at 40℃ for 24 hours,
Evaluation was made based on the ease with which the film peeled off. Items that peel off without resistance ◎ Items that do not peel off easily ○ Items that do not peel off △ Items that do not peel off very easily
The film was placed in a thermostatic chamber, covered with a film, and placed in a thermostatic chamber at 50° C. After the temperature was stabilized, it was transferred to a thermostatic chamber at 20° C. After 6 hours, the state of the film was observed and evaluated for antifogging properties. ◎ Transparent and not cloudy ○ Slight water droplets are present △ Large water droplets adhere and are opaque × Small water droplets adhere to the entire surface and are opaque Measuring surface resistance According to JIS K-6723, Resistance Meter manufactured by Heuretsu-Paccard Co., Ltd. using RH50
%, and the volume resistivity was measured after 3 days at a temperature of 25°C. In addition, the test piece is a T-die with a thickness of 0.7~
The one molded to 0.8m/m was used.

[Table] Example 22 The samples shown in Table 4 were added to polypropylene resin, and the resulting compounded composition was extruded into a T-die to obtain a raw film. Further, this original film was stretched 6 times vertically and 6 times horizontally to form a film with a thickness of 30 μm, and the film was evaluated in the same manner as in Example 19. The results are summarized in Table 4.

【table】 [Brief explanation of drawings]

Figures 1 and 2 are electron micrographs (10,000x magnification) of the particle structures of amorphous silica-alumina particles and P-type zeolite particles of the present invention, respectively, and Figures 3 and 4 are respectively 2 is an X-ray diffraction diagram of the amorphous silica-alumina particles shown in FIG. 1 and the P-type zeolite particles shown in FIG. 2. FIG.

Claims (1)

[Claims] 1 mMO・nNa ₂ O・pSiO ₂・Al ₂ O ₃・qH ₂ O In the formula, M is a metal consisting of one or more divalent metals, and m+n is 1.1±0.2 The number of
The m:n ratio is in the range of 10:0 to 1:9,
p is a number of 4±1.5 or more, and q is a number of 0.5 or less. It has a shape and a jagged surface, and a moisture absorption amount of 13% or less and 1.48 to 1.48% under the conditions of RH90%, room temperature and 48 hours.
Contains as an inorganic component amorphous silica/alumina spherical particles having a refractive index of 1.61 or a combination of the amorphous silica/alumina spherical particles and at least one other filler and pigment, and has plasticity and lubricant properties. ,
Contains at least one of an antistatic agent, an antifogging agent, an ultraviolet absorber, an antioxidant, and a low melting point resin as an organic component, and the inorganic component is bound via the organic component to form a powder. A resin compounding agent composition characterized by: