JP3131563B2 - Hydrophobic resin compounding agent and production method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophobic resin compounding agent and a method for producing the same, and more particularly, to a method in which a silicic or alumina resin compounding agent is used at 100.degree.
The present invention relates to a resin compounding agent obtained by substituting at least most of the bound water to be heated and dehydrated with a polar group-containing organic compound, and a method for producing the same.

[0002]

2. Description of the Related Art Silicic or alumina inorganic materials are widely used as resin compounding agents such as fillers, heat stabilizers, chlorine scavengers, infrared absorbers, and antiblocking agents.

[0003] Each of these silicic or alumina resin compounding agents has bound water, and when compounded into a resin and processed, there is a problem that the bound water is released to cause foaming of the resin composition. It has become.

It is also known that the adhesion of inorganic particles is significantly increased by water on the surface of the particles, and the above-mentioned siliceous or alumina resin compounding agent has a large tendency to agglomerate between the particles, and is likely to cause poor dispersion. Generating buttocks and fish eyes is also a problem.

There have been many proposals for making a silicic or alumina resin compound hydrophobic by coating.

JP-A-58-657 proposed by the applicant
No. 62, water-insoluble aluminosilicate particles having metal ion exchange properties and a higher fatty acid or a water-soluble salt thereof are mixed in the presence of water. It is described that a salt is added to form a metal soap coating layer on the surface of aluminosilicate particles.

[0007] JP-A-60-245654 discloses that the surface of an inorganic filler is treated with 1- (trimethoxysilyl) -3-.
A surface-treated filler for a polyolefin resin obtained by treating with a silane compound such as (4'-hydroxy-3 ', 5'-di-t-butyl) phenylpropane is described.

Japanese Unexamined Patent Publication (Kokai) No. 62-7747 describes an antibacterial zeolite composition having a hydrophobic property which comprises a natural or synthetic zeolite having an antibacterial metal and a silicone coating agent coated on the surface thereof. I have.

[0009]

However, simply providing a metallic soap or silicone coating layer on the surface of a silicic or alumina resin compounding agent causes active sites to adsorb water molecules inside the particles. However, the resin still has a large tendency to absorb moisture and is not sufficient to prevent the tendency to foam during processing of the resin.

[0010] Accordingly, an object of the present invention is to provide a hydrophobic resin in which the silicic or alumina resin compounding agent is kept substantially free of moisture and the tendency to absorb moisture is suppressed for a long time. An object of the present invention is to provide a compounding agent and a method for producing the same.

It is another object of the present invention to provide a resin compounding agent which suppresses hygroscopicity and imparts hydrophobicity with a very small amount of an organic compound used, and a method for producing the same.

[0012]

According to the present invention, 100
At least a part of the bound water of the silicic or alumina resin compounding agent which is heated and dehydrated at 300 to 300 ° C. is replaced with a polar group-containing organic compound having a molecular weight of 30 or more, and the polar-containing organic compound is adsorbed on the surface. A hydrophobic resin compounding agent having the following formula (1): R = (A / A ₀ ) × 100 (1) where A ₀ is the wave number of the silicic or alumina resin compound before the substitution treatment. Absorbance of infrared absorption peak at 1643 ± 21 Kaiser, or relative absorbance between the absorbance of the standard in the sample and the peak absorbance of 1643 ± 21 Kaiser; A is the wave number 16 of the siliceous or alumina resin compound after the substitution treatment
Absorbance of infrared absorption peak in 43 ± 21 Kaiser, or absorbance of standard in sample and wave number 1643 ± 21
Absorbance ratio (R) defined by the relative absorbance with respect to the Kaiser's peak absorbance is 95% or less, and / or the following formula (2): R ′ = (B / B ₀ ) × 100 (2) B ₀ is the absorbance of the infrared absorption peak at the wave number of 3435 ± 17 Kaiser of the silicic or alumina resin compound before the substitution treatment, or the relative absorbance of the absorbance of the internal standard and the peak absorbance of the wave number of 3435 ± 17 Kaiser; Is defined as the absorbance of the infrared absorption peak at the wave number of 3435 ± 17 Kaiser of the silicic or alumina resin compound after the substitution treatment, or the relative absorbance of the absorbance of the standard in the sample and the peak absorbance of the wave number of 3435 ± 17 Kaiser. A hydrophobic resin compounding agent characterized by having an absorbance ratio (R ') of 95% or less.

According to the present invention, the combined water of the silicic or alumina resin compound is heated and dehydrated at 100 to 300 ° C.
By lowering the temperature to room temperature in an atmosphere in a dry state replaced with a gas containing the vapor of the polar group-containing organic compound, the absorbance ratio (R) defined by the formula (1) becomes 95%.
The binding water is replaced with the polar group-containing organic compound such that the absorbance ratio (R ′) defined below and / or the formula (2) is 95% or less, and the polar group-containing organic compound is formed on the surface. And a method for producing a hydrophobic resin compounding agent, characterized by adsorbing a compound.

In the present invention: Silicate resin compounding agent is amorphous silica, amorphous aluminosilicate, calcium silicate, magnesium silicate,
1. It is a phylloaluminosilicate, formite-based clay mineral or tectoaluminosilicate; Alumina resin compounding agent is alumina, hydrated alumina,
2. It is magnesium aluminum carbonate hydroxide, lithium aluminum carbonate hydroxide or sodium aluminum carbonate hydroxide; 3. The polar group-containing organic compound is at least one selected from an organic compound having a hydroxy group, an ether group, a carbonyl group, a carboxyl group, and a siloxane group, or an organic silane compound. The polar group-containing organic compound is at least one selected from organic silanes to polyorganosiloxanes, monohydric alcohols having 1 or more carbon atoms, polyhydric alcohols having 3 or more carbon atoms, and polyalkylene polyols having 3 or more carbon atoms. , 5. Formula (1) R = (A / A ₀ ) × 100 (1) In the formula, A ₀ is the absorbance of an infrared absorption peak at a wave number of 1643 ± 21 Kaiser of a silicic or alumina resin compounding agent before the substitution treatment. Or the relative absorbance between the absorbance of the internal standard and the peak absorbance of the wave number 1643 ± 21 Kaiser; A is the absorbance of the infrared absorption peak at the wave number of 1643 ± 21 Kaiser of the silicic or alumina resin compound after the substitution treatment, or The absorbance ratio (R) defined by the relative absorbance between the absorbance of the in-sample standard and the peak absorbance of the wave number 1643 ± 21 Kaiser is 95% or less, particularly 50% or less, and / or the following formula (2) R ′ = ( _{B / B 0) × 100 ..} (2) formula, B ₀ is the infrared absorption peak at a wave number 3435 ± 17 Kaiser siliceous or alumina resin formulation pretreatment process Or the relative absorbance of the absorbance of the standard in the sample and the peak absorbance of the wave number 3435 ± 17 Kaiser; B is the absorbance of the infrared absorption peak at the wave number 3435 ± 17 Kaiser of the silicic or alumina resin compounding agent after the substitution treatment Alternatively, the absorbance ratio (R ′) defined by the relative absorbance between the absorbance of the standard in the sample and the peak absorbance of the wavenumber of 3435 ± 17 Kaiser is 95% or less, particularly 50% or less; It is preferable that the polar group-containing organic compound is contained in an amount of 0.01 to 30 parts by weight, particularly 0.5 to 2 parts by weight, per 100 parts by weight of the silicic or alumina resin compounding agent.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, bound water is
It is defined as water bound by physical and / or chemical adsorption within the inorganic surface and / or structure. The bound water in the siliceous or aluminous filler has a wave number of 16
Since the peaks appear as infrared absorption peaks at 43 ± 21 cm ⁻¹ and 3435 ± 17 cm ⁻¹ , the presence of bound water can be confirmed from this absorption.

The inventors of the present invention heat-dehydrate the silicic or alumina resin compounding agent at 100 to 300 ° C. and convert the heat-dehydrated resin compounding compound to a vapor of a polar group-containing organic compound having a molecular weight of 30 or more. When the temperature is lowered to room temperature in a dry atmosphere replaced with the containing gas, the bound water of the silicic or alumina resin compounding agent is effectively replaced by the polar group-containing organic compound. In the siliceous or alumina resin compounding agent, the moisture content is maintained substantially free, the tendency to absorb moisture is suppressed for a long time, and the amount of the organic compound used is extremely small. Thus, it was found that suppression of hygroscopicity and provision of hydrophobicity were performed.

Please refer to FIG. 1 of the accompanying drawings. FIG.
Amorphous calcium silicate untreated (A), amorphous calcium silicate substituted with polyorganosiloxane (B), and the substituted product were treated at 25 ° C and RH8.
The infrared absorption spectrum of the sample (C) left for 800 hours in an atmosphere of 5% was measured (for details, see examples described later). Calcium silicate has a wave number of 960 to 980 cm ^-1 , and polyorganosiloxane has a wave number of 1
The sample (B) shows characteristic absorption at 259 cm ^-1.
In (C) and (C), the presence of the polyorganosiloxane was confirmed, but the wave number 163 of the bound water observed in the sample (A) was confirmed.
The surprising fact that the characteristic absorption of 7 cm ^-1 disappeared in the sample (B) and the absorption was not restored even in the sample (C) left under high humidity conditions becomes apparent.

The fact that the bound water in the siliceous or aluminous particles is replaced by a polar group-containing organic compound is clear from the measurement results of the infrared absorption spectrum, but can also be confirmed from the following phenomenon. When the dehydrated siliceous or alumina particles are heated under reduced pressure and brought into contact with the vapor of the organic compound containing a polar group, the temperature rise due to heat generation is observed when the amount of the sample is considerably small. In general, the heat of adsorption due to physical adsorption is quite small, and the heat of adsorption due to chemical adsorption is much larger than this.In the treatment of the present invention, the polar group-containing organic compound is chemically adsorbed instead of the bound water. Is confirmed.

The adhesive force of the powder is complex and not necessarily simple. However, three types of force, namely, intermolecular force (van der Waals force), capillary force due to moisture, and electrostatic force are used. Large contribution. Among these, the intermolecular force can be said to be a proximity force that is inversely proportional to the distance between particles from the second power to the third power, but the trouble is the capillary force due to moisture. That is, the capillary force is not related to the distance as long as there is a crosslinked water film between the particles, but there is a characteristic that the adhesive force acts more as the water content is smaller. In the hydrophobic resin compounding agent of the present invention, since the formation of the above-mentioned crosslinked water film and the increase in the adhesive force due thereto are prevented, there is little tendency to agglomerate, the fluidity as a powder is excellent, and the resin It has the advantage of being excellent in dispersibility in.

Furthermore, since this resin compounding agent has substantially no water content and has a low tendency to absorb moisture, it has the advantage of being less likely to foam when blended with a resin and subjected to processing such as melt kneading, extrusion and injection. give. Thus, when the resin compounding agent of the present invention is used, the above-mentioned advantages can be achieved and the original effect of the resin compounding agent can be obtained.

The resin compounding agent of the present invention also has the advantage that moisture absorption can be suppressed and hydrophobicity can be imparted by using a very small amount of an organic compound.

[Silica or alumina resin compounding agent]
In the present invention, as the silicic or alumina resin compounding agents, all those used as resin compounding agents such as fillers, reinforcing agents, heat stabilizers, chlorine scavengers, infrared absorbers, antiblocking agents, etc. Can be used.

Such a silicic or alumina resin compounding agent includes wave numbers of 1643 ± 21 cm ⁻¹ and 34
Any material having an infrared absorption peak at 35 ± 17 cm ⁻¹ can be used.

Examples of the siliceous resin compounding agent include, but are not limited to, amorphous silica, amorphous to low crystalline silicate, amorphous aluminosilicate, calcium silicate, magnesium silicate, Examples include phylloaluminosilicates, formite-based clay minerals, and tectoaluminosilicates.

The alumina-based resin compounding agent is not limited to these, but may be alumina, hydrated alumina,
Examples thereof include aluminum magnesium carbonate hydroxide, lithium aluminum carbonate hydroxide, and sodium aluminum carbonate hydroxide.

The inorganic resin compounding agent is used in the form of powder having a particle size of 0.1 to 100 μm in terms of compoundability with the thermoplastic polymer.
In general, from the viewpoint of handleability and prevention of dusting, it is preferably a granular material, and generally has a particle size of 1 to 10 mm, particularly preferably 2 to 5 mm. The particle shape may be any shape such as a sphere, a cube, a column, a prism, a granule, a tablet, an irregular shape, a flake, and a fiber.

Preferred inorganic resin compounding agents suitable for the treatment of the present invention will be further described.

A) Amorphous silica: The amorphous silica may be either a gel type or a precipitation type amorphous silica. These amorphous silicas are useful as anti-blocking agents and the like. (I) As an example of the former type, porous spherical silica obtained by an instant granulation method can be cited, which is prepared by using a two-fluid nozzle under the condition that the pH at the time of mixing becomes 8 to 9; -Instantaneously mix the sodium silicate solution or the sodium silicate solution containing the silica hydrogel with the sulfuric acid and spray the mixture into the air to instantaneously gel into silica spherical particles, and form the resulting gel in the lower acidic solution. Drop in, then wash with water,
Obtained by drying. This type of inorganic porous powder has a particle size of 0.1 to 4 mm, a BET specific surface area of 300 to 800 m ² / g, and a pore volume of 0.6 to 2 ml / g by a nitrogen adsorption method. . This type of carrier has a spherical shape, a smooth surface, excellent fluidity, no dusting, and easy handling. (Ii) Another gel-type amorphous spherical silica includes hydrogel spray granulation silica, which is prepared by mixing an aqueous solution of an alkali silicate and an aqueous solution of an acid such as sulfuric acid so that the pH of the sol is 2 to 10. 6, the reaction mixture is gelled, the resulting gel is crushed, washed with water,
If necessary, hydrothermal treatment is performed at a temperature in the range of 100 to 150 ° C., and the obtained silica hydrogel is wet-pulverized, and the aqueous slurry of the silica hydrogel is spray-dried and granulated. This type of amorphous silica has a particle size of 10 to 100 μm, especially 25 μm, as measured by the Coulter Counter method.
Spherical particles having a volume-based median diameter of from 0.1 to 80 μm, an apparent density (JIS K-6220 method) in the range of 0.2 to 0.5 ml / g, and a pore volume of 18 based on the mercury intrusion method. 0.5-3.5 ml / g in the range of ~ 43500 Angstroms. Further, the spherical amorphous silica particles have a mesopore having a pore radius of 75 to 1000 Å as measured by a mercury intrusion method,
The pore volume is 0.2 ml / g or more. (Iii) Examples of the precipitated spherical amorphous silica include porous spherical silica and silicate particles according to the method described in Japanese Patent Application Laid-Open No. 5-193927 by the present applicant. These are water-soluble silica such as carboxymethylcellulose. Using a polymer as a coagulant, a partially neutralized product of an aqueous solution of alkali silicate is grown spherically and neutralized, or the granular material is further mixed with a hydroxide or salt of a Group II metal of the periodic table. In an aqueous solvent. The spherical particles of silica or silicate are porous because they are aggregates of silica primary particles. This amorphous silica is a clear spherical particle having a primary particle size of 0.2 to 20 μm by scanning electron microscopy and a sphericity of each particle of 0.9 or more, and an apparent density (JISK). -6220 method) is 0.1 to 0.5 ml / g, the pore volume measured by the nitrogen adsorption method is in the range of 0.5 to 2 ml / g, and the oil absorption is 100.
From 400 ml / 100 g.

B) Amorphous to low crystalline silicate: The amorphous to low crystalline silicate comprises an anti-blocking agent,
It is useful as a stabilizer, a deodorant and the like. (I) Amorphous or layered microcrystalline silicate derived from the amorphous silica of A) (iii) can also be used.
Examples of the metal component of the silicate include zinc, magnesium, and calcium. That is, spherical particles composed of partially or completely neutralized alkali silicate obtained by the above method, and hydroxides or salts of inorganic salts such as magnesium, calcium, and zinc hydroxides or nitrates, chlorides, and sulfates. Is reacted in the presence of an aqueous medium, whereby magnesium phyllosilicate, calcium phyllosilicate or zinc phyllosilicate can be formed on at least the surface of the spherical particles. (Ii) Particularly preferred phyllosilicates are (1) Zinc phyllosilicate having an X-ray diffraction image of a flypontite type described in JP-A-61-10021 and a BET specific surface area of 100 m ² / g. Or aluminum-containing zinc phyllosilicate or (2) a composite phyllosilicate described in Japanese Patent Publication No. 5-79602, ie, amorphous porous silica or silica-alumina, and formed on the surface of the primary particles thereof. Zinc and magnesium phyllosilicates and zinc and magnesium phyllosilicates containing aluminum are exemplified.

C) Amorphous aluminosilicate: As the amorphous aluminosilicate, various zeolites, for example, A
Type, X type, Y type, Pc type, T type zeolite and the like, analcyme, chabazite, mordenite, erionite,
Amorphous shaped particles obtained by applying at least one means such as an acid treatment, an ion exchange treatment, and a calcination treatment to various crystalline structures such as clinopatilolite are used. The individual particles are independent and have a well-defined cubic or spherical particle shape as a whole. Generally, 50 m ² / g
Those having the following BET specific surface area and having a primary particle diameter in the range of 0.2 to 30 μm by electron microscopy are suitable. In order to make the zeolite amorphous, the zeolite is acid-treated with a mineral acid such as sulfuric acid, hydrochloric acid, nitric acid and the like, and then calcined if necessary. Alternatively, zeolite is subjected to an ion exchange treatment with divalent metal ions, and then becomes amorphous by firing.
As the divalent metal used for ion exchange, a metal belonging to Group II of the periodic table, Ca, Mg, Zn, Ba or Sr is advantageously used in terms of whiteness. The calcination conditions are such that the acid-treated or ion-exchanged zeolite becomes substantially amorphous,
This temperature varies depending on the conditions of the acid treatment, the ion exchange rate and the metal species, but is generally 200 to 700 ° C., particularly
It is in the range of 00 to 500 ° C.

D) Calcium Silicate: (i) As crystalline calcium silicate, Nekoite, Okenite, Zonotolite (Xonite)
otlite), Foshagite, Gen Knight
Wollastonite groups such as (Jennite) and Metajennite; Tobermorite groups such as 14 Tobermorite, 11 tobermorite, 9.3 tobermorite; Gyrolite, Truscotite (Tru)
Gyrolite groups such as scottite, Z-Phase, etc .; Calcio-chondrodit
e), γ-C2S group such as Afwillite and the like can be used. (Ii) A preferred calcium silicate is microcrystalline calcium silicate hydrate, ie, the formula CaO.xSiO ₂ .nH ₂ O, where x is a number from 1.0 to 2.0, and n is 0. It has a chemical composition represented by the following formula: 3 to 1.0, and has X-ray diffraction peaks at spacings of 3.04 to 3.08, 2.78 to 2.82, and 1.81 to 1.84. And microcrystalline calcium silicate hydrate having a refractive index of 1.49 to 1.57. The microcrystalline calcium silicate hydrate has a number average particle diameter of 0.1 to 10 μm, an oil absorption of 50 to 250 mL / 100 g, and an oil absorption of 60 to 200 m ² under an electron microscope.
/ G specific surface area. This synthetic calcium silicate can be produced by reacting activated silica obtained by acid treatment of a clay mineral with calcium hydroxide.

E) Magnesium silicate: As the magnesium silicate, a synthetic layered magnesium phyllosilicate, especially one having a chemical composition of the formula Mg ₃ SiO ₁₀ (OH) ₂ .nH ₂ O is used. N for water of hydration
Is usually 5 or less, preferably n is in the range of 0.5 to 3, and the synthetic layered magnesium phyllosilicate is
It mainly has a three-layer structure in which two tetrahedral layers of SiO ₄ are sandwiched with an octahedral layer of MgO ₆ interposed therebetween. This synthetic layered magnesium phyllosilicate has an X-ray diffraction image peculiar to the above-mentioned layered structure, and has an interplanar spacing of 4.
5 to 4.6 angstroms ([020] plane, [11
0] plane, 2.5 to 2.6 (corresponding to the [200] plane), and 1.5 to 1.6 (corresponding to the [060] plane). This synthetic layered magnesium phyllosilicate has a particle size of 300 m ² / g or more, particularly 500 m ² / g.
While having a large BET specific surface area that reaches
Methylene blue decolorizing power measured by JIS K-1470 shows a large value reaching 100 mL / g or more, especially reaching 250 mL / g or more. For example, acid clay, bentonite, sub-bentonite, montmorillonite group clay minerals such as flourse earth and beidellite, saponite and other clay minerals, sulfuric acid, hydrochloric acid, until the X-ray diffraction peak of plane index [001] substantially disappears. It is treated with a mineral acid such as nitric acid or an organic acid such as benzenesulfonic acid at a temperature of 60 to 300 ° C. to form active silicic acid or active aluminosilicic acid.
The synthetic layered magnesium phyllosilicate can be produced by preparing an aqueous slurry and performing a hydrothermal treatment under pressure at a temperature of 110 to 200 ° C.

F) Philoaluminosilicate: Various natural or synthetic clay minerals or chemically modified products thereof are used as the above-mentioned phylloaluminosilicates. For example, montmorillonite, bentonite, beidellite, nontronite, saponite, hectorite, sauconite,
Examples include smectite-group clay minerals such as stevensite, metakaolin, halloysite, metahalloysite, kaolin-group clay minerals such as antigolite, vermiculite, and the like. Examples of the chemically modified product include activated clay obtained by activating montmorillonite such as acid clay and the like by acid treatment, activated bentonite obtained by activating montmorillonite such as acid clay and the like by alkali treatment, and the like. Further, activated bentonite and activated clay containing aluminum sulfate are also preferably used.

G) Chain Clay Minerals The formite sepiolite and palygorskite belonging to the chain clay minerals have a fibrous appearance or a condensate, and their basic structure is a main component forming the skeleton of an octahedral layer. Is a 3-octahedral magnesium silicate clay mineral composed of magnesium. This magnesium silicate clay mineral has a three-dimensional chain-like crystal structure, and has a fiber having an external appearance and voids formed in gaps between the converging bodies. Since the pores have a BET specific surface area of 100 to 600 m ² / g and a convergent structure, they are porous chain-like clay minerals having an adsorption action. Before using these clay minerals for the purpose of the present invention, they are crushed with a ball mill, a hammer mixer, kneaded and crushed with a super mixer, a mortar, etc., an atomizer, a jet or the like. After performing primary pulverization such as impact pulverization with a mill, etc., and partially defibrating or loosening the chain structure as a converging body and the lamination structure as a scale,
It is more preferable to use.

H) Tectoaluminosilicate: Tectoaluminosilicate is generally known as zeolite, has a regular particle shape that can be easily dispersed in a resin, and is useful as a heat stabilizer and as a filler. . A type, X type, Y
Zeolite such as type, Pc type, T type, and various crystal structures such as analcyme, chabazite, mordenite, erionite, and clinoptilolite are used. The individual particles are independent, have a well-defined cubic to spherical particle shape as a whole, have a refractive index of 1.48 to 1.61, and have a primary particle size of 0.2 to 30 by electron microscopy.
Those in the range of μm are suitable.

I) Alumina and alumina hydrate: Aluminum hydroxide or hydrated alumina is used as a resin compounding agent having excellent flame retardancy, and has excellent texture, heat resistance and abrasion resistance. And the like. In addition to gibbsite, vialite, boehmide and diaspore, boehmite gel (pseudo boehmite) is applicable. The hydrated alumina used in the present invention is generally 5 μm
In particular, a particle size of 3 μm or less and 200 to 400 m ² /
Those having a BET specific surface area of 0.2 g and a pore volume of 0.2 to 0.6 ml / g are preferred. Activated alumina obtained by firing pseudo-boehmite is also used.

J) Aluminum magnesium carbonate hydroxide: Examples of aluminum magnesium carbonate hydroxide include:
Known are hydrotalcites, which are resin compounding agents having excellent hydrogen chloride trapping ability, flame retardancy, etc., and are represented by the general formula: M2 _x M3 _y (OH) _{2x + 3y-2z} (A ⁺⁺ ) _z · aH ₂ O In the formula, M2 is a divalent metal ion such as Mg, and M3 is A
a trivalent metal ion of l such, A ⁺⁺ is a divalent anion such as CO _3, x, y and z is 8 ≧ x / y ≧ 1/ 4 and z /
x + y is a positive number satisfying 1/20, and a is 0.25 ≦ a / x + y ≦
It is a number that satisfies 1.0. Is used. Among these composite metal hydroxides, the compound represented by the formula Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) .4H ₂ O is a natural mineral known as hydrotalcite, and this mineral and its homologues No. 47-32198 filed by Kyowa Chemical Industry Co., Ltd.
JP-B-48-29777 and JP-B-48-29478
It is synthesized by the method described in Japanese Patent Publication No. It has been already known that these hydrotalcites, particularly compounds represented by the formula Mg _4.5 Al ₂ (OH) ₁₃ (CO ₃ ) .3H ₂ O, have excellent chlorine ion trapping performance. It can also be used as a raw material. By taking advantage of the property that these hydrotalcites are easily ion-exchanged in a state where they are sufficiently dispersed in water, that is, the property that carbonate ions are ion-exchanged with other anions, the perhalogen oxygenate ion is removed. The introduced one can also be used.

K) Lithium aluminum carbonate hydroxide:
Lithium aluminum carbonate hydroxide is a resin compounding agent excellent in infrared absorption performance, hydrogen chloride scavenging property, etc., and generally, X in the following formula [Al ₂ Li (OH) ₆ ] n X · mH ₂ O Or, it is an organic anion, n is a valence of anion X, and m is a number of 3 or less. The lithium aluminum composite hydroxide salt represented by the following formula is used.
X is preferably an anion selected from the group consisting of carbonic acid, sulfuric acid, oxyacid of chlorine or oxyacid of phosphorus,
Carbonate anions are preferred. This lithium aluminum carbonate hydroxide is preferably composed of hexagonal plate-like crystal particles having a primary particle size of 0.05 to 1 μm from the viewpoint of compoundability with a resin, and 0.1 to 0.25 g / cm ³ . It should have a bulk density and a BET specific surface area of 20 to 40 m ² / g.

Sodium aluminum carbonate hydroxide: Sodium aluminum carbonate hydroxide is a resin compounding agent having excellent infrared absorption performance and flame retardancy, and is generally a basic aluminum carbonate double salt having a d-sonite type crystal structure. In particular, the following formula: mAl ₂ O ₃ · (n / p) M _{2 / p} O · X · kH ₂ O In the formula, X is an inorganic or organic anion mainly composed of a carbonate group, and M is an alkali metal or An alkaline earth metal, m is a number from 0.3 to 1, and n is from 0.3 to 2
K is a number from 0.5 to 4, and p is a metal M
The one having a composition represented by the following valence is used. In the above formula, it is preferable that M is sodium and X is a carbonate group. The basic aluminum carbonate double salt desirably has substantially no weight loss at a temperature of 300 ° C. or less in thermogravimetric analysis. Further, the basic aluminum carbonate double salt generally has a fiber shape, and a fiber diameter of 0.01 to 1 is used.
The range of μm and the aspect ratio in the range of 2 to 100 are suitable as a resin compounding agent.

[Polar Group-Containing Organic Compound] In the present invention, the organic compound used in the treatment of the resin compounding agent has at least one group such as a polar group, a hydroxy group, an ether group, a carbonyl group, a carboxyl group, and a siloxane group. And the molecular weight is 3
Zero or more organic compounds and / or organic silane compounds. This organic compound is used in a vapor phase to allow contact with the siliceous or alumina resin compounding agent particles,
It preferably has a vapor pressure of at least 20 mmHg or more, preferably 150 to 760 mmHg, at a temperature of from 0 to 300 ° C.

The polar group-containing organic compound is preferably a polyorganosiloxane or a silane, a monohydric alcohol having 1 or more carbon atoms, a polyhydric alcohol having 3 or more carbon atoms, or a Ethers or polyethers, ketones or keto esters having 3 or more carbon atoms,
An epoxy compound or a carboxylic acid having 3 or more carbon atoms is preferable. Suitable examples of the compound are as follows.

A) Polyorganosiloxane: The polyorganosiloxane used in the present invention includes polydimethylorganosiloxane, polydiphenylorganosiloxane, polymethylphenylorganosiloxane, polymethylhydrogenorganosiloxane, polyphenylhydrogenorganosiloxane, The polyorganosiloxane may be a polyether-modified polyorganosiloxane, an epoxy-modified polyorganosiloxane, or a urethane-modified polyorganosiloxane. The polyorganosiloxane may be cyclic, linear or branched. In general,
Preferably, the molecular weight is in the range of 100 to 10,000. By using these polyorganosiloxanes in the treatment of the present invention, remarkable hydrophobicity can be imparted.

B) Organosilanes: As such organosilanes, in the general formula, R _n Si (OR ₁ ) _4-n , 0 ≦ n ≦ 3, and R is a hydrocarbon group such as an alkyl group. , A cycloalkyl group, an aryl group, an alkenyl group, a haloalkyl group, an aminoalkyl group and the like, or a halogen atom, and R ₁ is a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group and an alkoxyalkyl group. And an organosilicon compound represented by the following formula: More specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,
Diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane , Ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethyl silicate, Butyl silicate, trimethylphenoxysilane, methyltriaryloxy silane, vinyl tris (β-methoxyethoxy) silane, vinyl triacetoxy silane, diethyl tetraethoxy Xydisiloxane, phenyldiethoxydiethylaminosilane and the like can be exemplified.

C) Polyhydric alcohols: polyols having 3 or more carbon atoms include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentane glycol, glycerin, and pentaerythritol , Dipentaerythritol and the like are used.

D) Monohydric alcohol: Monohydric alcohols having one or more carbon atoms include isopropanol, butanol, amyl alcohol, octanol, palmityl alcohol, stearyl alcohol, tert-butyl alcohol, allyl alcohol, cyclohexanol, benzyl alcohol, and ethylene. Chlorohydrin, ethyl alcohol, isopropyl alcohol, isobutyl alcohol,
tert-pentyl alcohol, p-nitrobenzyl alcohol, α-phenylethyl alcohol, triphenylcarbinol, triethylcarbinol, sec-butylcarbinol, methanol, 2-methylbutanol, 2-phenylethanol, 2-methyl-2- Butanol, 3-methyl-2-butanol, 2-chloroethanol, 3-butanol-2-ol, n-propyl alcohol, n-hexyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-heptyl alcohol, n-dodecyl Alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, crotyl alcohol, β-phenylethyl alcohol, dibenzyl carb Knol, cinnamyl alcohol, n-decyl alcohol, methyl vinyl carbinol, n-octyl alcohol. E) Ethers or polyethers. As ethers or polyethers, polyethylene oxide, polypropylene oxide, polyethylene oxide / propylene oxide copolymer, cellosolve, butyl cellosolve, carbitol, butyl carbitol and the like are used.

F) Ketones and keto esters: β-
Diketones or β-keto acid esters are preferably used,
For example, 1,3-cyclohexadione, methylenebis-
1,3-cyclohexadione, 2-benzyl-1,3-
Cyclohexadione, acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetyl-1,3-cyclohexanedione, benzoyl-p-chlorobenzoylmethane, bis (4-methylbenzoyl) methane, bis (2
-Hydroxybenzoyl) methane, benzoylacetone, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoylmethane, bis (4-chlorobenzoyl) methane, bis (methylene-3,4- Dioxybenzoyl) methane,
Benzoylacetylphenylmethane, stearoyl (4
-Methoxybenzoyl) methane, butanoylacetone,
Distearoylmethane, acetylacetone, stearoylacetone, bis (cyclohexanoyl) -methane, dipivaloylmethane, and the like can be used.

G) Epoxy compounds: Epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized tallow oil, epoxidized castor oil, epoxidized safflower oil, Epoxidized linseed oil fatty acid butyl, tris-8 epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,2-epoxypropane, bisphenol-A
Diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4
-Epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate, glycidyl methacrylate, glycidyl acrylate and the like.

H) Carboxylic acid: As carboxylic acid, higher fatty acids and unsaturated carboxylic acids are used. As the higher fatty acid, a saturated or unsaturated fatty acid having 10 to 22 carbon atoms, particularly 14 to 18 carbon atoms, for example, a saturated fatty acid such as capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachiic acid, etc. And unsaturated fatty acids such as lindelic acid, tuzunic acid, petroselinic acid, oleic acid, linoleic acid, linolenic acid and arachidonic acid. Stearic acid is the preferred one. The fatty acids may of course be mixed fatty acids such as tallow fatty acids, coconut oil fatty acids and palm oil fatty acids. Further, succinic anhydride, adipic acid, sebacic acid, pyromellitic acid and the like can be used as the polycarboxylic acid. Specific examples of unsaturated carboxylic acids or derivatives thereof include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and bicyclo [ 2,2,1] Hept-2-ene-
Unsaturated carboxylic acids such as 5,6-dicarboxylic acid, α, β unsaturated carboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride;
An anhydride of an unsaturated carboxylic acid such as bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride is used. I) Polyalkylene polyol As the polyalkylene polyol, polyethylene oxide (degree of polymerization: 200, 300, 400, 600, 1
000, 2000, 4000, 6000, 2000
0), polypropylene oxide (degree of polymerization: 400, 6)
00, 900, 1100, 3000, 4000, 110
00), polybutylene oxide and the like.

[Production Method] According to the present invention, the combined water of the silicic or alumina resin compound is dehydrated by heating at 100 ° C. to 300 ° C. A hydrophobic resin compounding agent is manufactured by lowering the temperature in a dry atmosphere replaced with a gas containing a vapor of a polar group-containing organic compound having a molecular weight of 30 or more.

The dehydration of the silicic or alumina resin compounding agent is carried out by removing the silicic or alumina resin compounding agent by 100%.
The heating is performed by heating to a temperature of from 300 to 300 ° C, preferably from 150 to 250 ° C. At the time of this heating, it is effective to maintain the inside of the system at reduced pressure, and it is effective to depressurize the system at a negative pressure of 20 mmHg or more, particularly 150 mmHg or more.

Next, in order to bring the dehydrated silicic or alumina resin compounding agent into contact with a polar group-containing organic compound having a molecular weight of 30 or more in a dry state, the atmosphere of the treatment system is changed to the polar group-containing organic compound. With a gas containing steam. That is, since the dehydration process is performed in the above-described step, dehydrated water exists in the atmosphere. Therefore, in order to contact the polar-containing organic compound in a dry state, it is necessary to replace the atmosphere with a gas containing the vapor of the polar-group-containing organic compound.

Replacing the atmosphere of the treatment system with a gas containing a vapor of a polar group-containing organic compound involves heating the polar group-containing organic compound to a temperature lower than its decomposition temperature, generally 100 ° C. or higher, to obtain a polar group. This is performed by generating a vapor of the group-containing organic compound and introducing the vapor into the treatment system.For example, a silicic or alumina resin compounding agent is filled in the column, and exhaust is performed from one end of the column. The vapor of the polar group-containing organic compound can be introduced from the other end of the column. In order to efficiently introduce the vapor of the polar group-containing organic compound, an inert gas such as nitrogen can be used as a carrier gas.

When the polar group-containing organic compound is introduced into the treatment system in the form of a liquid or an organic solvent solution, the temperature in the treatment system is, of course, within the above-mentioned temperature range in which the vapor of the polar group-containing organic compound is generated. Must be maintained. The use of the organic solvent solution of the polar group-containing organic compound is advantageous because the polar group-containing organic compound is efficiently evaporated with the evaporation of the organic solvent.

In the present invention, the dehydrated silicic or alumina resin compounding agent is cooled to room temperature in an atmosphere containing the vapor of the polar group-containing organic compound as described above, so that the surface of the polar compound has the polar compound. A hydrophobic resin compounding agent in which the group-containing organic compound is adsorbed and at least a part of the bound water is replaced by the polar group-containing organic compound is obtained.

It is desirable to carry out the treatment so that the polar group-containing organic compound is contained in an amount of 0.01 to 30% by weight, particularly 0.5 to 2 parts by weight, based on the silicic or alumina resin compounding agent.

According to the present invention, by the above-described processing,
The following formula (1): R = (A / A ₀ ) × 100 (1) In the formula, A ₀ is the infrared absorption peak at a wave number of 1643 ± 21 Kaiser of the silicic or alumina resin compound before the substitution treatment. Absorbance, or relative absorbance of the absorbance of the standard in the sample and the peak absorbance of the wave number 1643 ± 21 Kaiser; A is the absorbance of the infrared absorption peak at the wave number of 1643 ± 21 Kaiser of the silicic or alumina resin compound after the substitution treatment; Alternatively, the absorbance ratio (R) defined by the relative absorbance between the absorbance of the standard in the sample and the peak absorbance of the wave number of 1643 ± 21 Kaiser is 95% or less, particularly 50% or less, and / or the following formula (2): R ′ = _(B / B ₀₎ × in 100 ‥ (2) formula, _{B 0} is the infrared at a wave number 3435 ± 17 Kaiser siliceous or alumina resin formulation before substitution treatment Absorbance of the absorption peak or relative absorbance between the absorbance of the standard in the sample and the peak absorbance of the wave number 3435 ± 17 Kaiser; B is the infrared absorption peak at the wave number 3435 ± 17 Kaiser of the silicic or alumina resin compounding agent after the substitution treatment Or the relative absorbance between the absorbance of the standard in the sample and the peak absorbance of the wave number of 3435 ± 17 Kaiser is 95% or less, particularly 50% or less.

That is, as shown in the examples described below, in a dry state substantially free of moisture, a vapor of a polar group-containing organic compound is brought into contact with a dehydrated siliceous or alumina resin compounding agent. Then, by lowering the temperature, at least a part of the bound water is replaced with the polar group-containing organic compound, and the absorbance ratios (R) and (R ′) become 95% or less, particularly 50% or less.

[Thermoplastic Polymer Composition] According to the present invention, there is provided a thermoplastic polymer composition obtained by blending the above-mentioned hydrophobic resin compounding agent with a thermoplastic polymer or elastomer. The compounding agent can be uniformly and finely dispersed in the coalesced, and the original performance of the compounding agent can be exhibited while solving problems such as foaming during processing.

Examples of the thermoplastic polymer include resins synthesized using a metallocene catalyst, as well as low-density polyethylene, high-density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene and ethylene. Polyolefins such as random or block copolymers of α-olefins such as propylene, 1-butene and 4-methyl-1-pentene;
Ethylene-vinyl compound copolymer such as vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS, α-methylstyrene-styrene copolymer Styrene resin such as coalescence, polyvinyl chloride,
Polyvinylidene chloride, polyvinyl chloride / vinylidene chloride copolymer, polyvinyl compounds such as polymethyl acrylate and polymethyl methacrylate, nylon 6, nylon 6-6,
The resin may be any of polyamide such as nylon 6-10, nylon 11 and nylon 12, thermoplastic polyester such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyphenylene oxide and the like, or a mixture thereof. Of course, by using a biodegradable resin, an environmentally friendly resin molded product can be provided.

As the elastomer polymer, for example, nitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), polybutadiene (BR), polyisoprene (IIB), butyl rubber, natural rubber, ethylene rubber Propylene rubber (EP
R), ethylene-propylene-diene rubber (EPD)
M), polyurethane, silicone rubber, acrylic rubber, etc .; thermoplastic elastomers such as styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, hydrogen Styrene-isoprene-styrene block copolymer.
Among them, hydrocarbon elastomers, especially EPR
And EPDM are preferred. Of course, they can also be used in the form of a blend of two or more.

The hydrophobic resin compounding agent is added in an amount of 0.01 to 200 parts by weight, particularly 0.1 to 10 parts by weight, per 100 parts by weight of the thermoplastic resin or the elastomer, depending on the kind of the compounding agent. Is preferably blended.

For compounding the compounding agent into the polymer, a so-called dry blending or melt blending method can be adopted. Further, a master batch containing a resin compounding agent at a relatively high concentration can be used.
A method of blending with an unblended polymer can also be adopted.

The resin compounding agent of the present invention can be mixed into a coating material known per se to form a coating composition. As the paint, nitrocellulose paint, alkyd resin paint, amino alkyd paint, vinyl resin paint, acrylic resin paint, epoxy resin paint, polyester resin paint, chlorinated rubber paint, phenolic resin, modified resin Phenolic resin, alkyd resin, vinyl resin, petroleum resin, epoxy resin, polyester resin, styrene resin, silicone resin, chlorinated resin, urethane resin, polyamide resin, polyimide resin, fluorine resin 1 such as resin
Paints containing one or more species. Also,
The paint to be used may be an arbitrary one such as a solvent-based paint, a water-based paint, an ultraviolet-curable paint, a powder paint, or the like, depending on how the paint is used. Examples of the organic solvent for the solvent type paint include toluene, xylene n-heptane, n-hexane, cyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone ethanol, propanol, butanol, diacetone alcohol tetrahydrofuran, dioxane ethyl cellosolve, and butyl cellosolve acetate. , Dimethyl sulfoxide solvent or the like. As the water-based paint, a self-emulsifying paint or a surfactant-emulsifying paint is used in addition to an aqueous paint. As the resin of the water-based paint, an alkyd resin, a polyester resin, an acrylic resin, an epoxy resin, or a combination of two or more of these, which are water-soluble or self-emulsified in an aqueous medium, can be used. The resin concentration is generally in the range from 10 to 70% by weight, in particular from 20 to 60% by weight.

[0064]

EXAMPLES In the following examples, measurement of raw materials and products was carried out by the following methods.

(1) Infrared absorption spectrum The absorption of transmitted light was measured using a TGS sensor of FTIR8000 manufactured by JASCO Corporation. The sample was formed into a wafer with KBr powder, and the measurement was performed in an air atmosphere at a relative humidity of 45% using a KBr wafer containing no sample as a reference.

(2) Differential thermal analysis and measurement of condensate rate Seiko Denshi Kogyo SSC-5200TG-DTA system
M Standard substance α-Al _TwoO_ThreeAt 200 ° C using
The heat loss (% by weight) of each sample was measured.

(3) Water Absorption The heat-dried sample was allowed to cool in a silica gel desiccator, then placed in a desiccator of a saturated aqueous potassium chloride solution at 25 ° C., kept at a relative humidity of 85% for 24 hours, and the water absorption of the sample (% by weight) Was measured.

(4) Amount of Adsorption The absorbance ratio between the characteristic peak of the adsorbed substance and the standard peak in the sample was measured by the infrared absorption spectrum of the sample of each example, and the amount of adsorbed substance was determined by the calibration curve method. Is quantified.

(5) Hydrophobicity ratio 1 The hydrophobicity of each sample is evaluated by the following equation (1): R = (A / A ₀ ) × 100 (1)

(6) Hydrophobicity ratio 2 The hydrophobicity of each sample is evaluated by the following equation (2): R ′ = (B / B ₀ ) × 100 (2)

(7) Foaming test The PVC admixture of Formulation 1 was formed into a sheet having a thickness of 1.0 mm, and the sheet was sandwiched between smooth stainless steel plates and sealed under sealed conditions.
The sheet is heated and pressed at 150 ° C./cm ² for 15 minutes at 00 ° C., and the foaming state of the generated sheet is visually evaluated. ×: Intense foaming △: Little foaming ○: No foaming

(8) Dispersion test The PVC admixture of Formulation 1 was formed into a sheet having a thickness of 0.5 mm, and this was viewed under transmitted light under a microscope with a magnification of 60 times and a visual field of 0.5 cm.
Particles of 25 μm or more in × 8.0 cm are counted, and the dispersibility of each sample in the resin is evaluated. ×: 25 μm or more, 10 or more particles Δ: 1 to 9 particles ○: None

(9) Haze The polyethylene film produced in Application Example 1 was subjected to JIS
It was measured by an automatic digital haze meter NDH-20D manufactured by Nippon Denshoku Co., Ltd. based on K-6714. The value of the blank sheet to which no sample is added is 1.8%.

(10) Transparency The PVC mixture of Formulation 1 was molded into a sheet having a thickness of 1.0 mm, and the white light transmittance was measured using a 1001DP colorimeter manufactured by Nippon Denshoku Industries. The value of the blank sheet without addition of the sample is 90%.

(Example 1) CSH-1 type calcium silicate
(Indicative formula: 0.8CaO.SiO_Two・ 0.84H _TwoO)
1.0 g of the powder is placed in a 200 ml three-necked pear-shaped flask,
After dehydration by heating at 230 ° C for 30 minutes, dimethylpolysiloxane
(Shin-Etsu Chemical's KF96L-2CS) Steam into the flask
After replacing with air and steam in the flask, dry
It cooled to room temperature in the state. The sample (Sample 1-1)
Tables 1, 2 and 3 show the properties and FIG. 1 shows the infrared absorption spectrum.
(B).

Comparative Example 1 The procedure of Example 1 was repeated, except that dimethylpolysiloxane was not introduced.
Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 2-1).

(Example 2) CSH-1 type calcium silicate of Example 1 was added to 4A type zeolite (Mizucalizer DS manufactured by Mizusawa Chemical Co., Ltd.), dehydration temperature at 200 ° C, and dimethylpolysiloxane to propylene glycol (Wako Pure Chemical Industries, Ltd.). ) Was carried out in the same manner as in Example 1. The sample (Sample 1-
The physical properties of 2) are shown in Tables 1, 2 and 3.

(Comparative Example 2) The procedure of Example 2 was repeated, except that propylene glycol was not introduced. Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 2-2).

(Example 3) The CSH-1 type calcium silicate of Example 1 was replaced with amorphous silica (Silbead M manufactured by Mizusawa Chemical).
Example 1 was changed to S) by changing the heating dehydration temperature to 200 ° C. and changing dimethylpolysiloxane to octanol (manufactured by Wako Pure Chemical Industries, Ltd.).
The same was done. Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 1-3).

(Comparative Example 3) The procedure of Example 3 was repeated, except that octanol was not introduced. Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 2-3).

Example 4 The CSH-1 type calcium silicate of Example 1 was replaced with amorphous alumina (Neobead manufactured by Mizusawa Chemical).
In the same manner as in Example 1, the heating and dehydrating temperature was changed to 200 ° C., and dimethylpolysiloxane was changed to butanol. Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 1-4).

(Comparative Example 4) The procedure of Example 4 was repeated, except that butanol was not introduced. Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 2-4).

Example 5 The CSH-1 type calcium silicate of Example 1 was replaced with sepiolite (Aid Plus, manufactured by Mizusawa Chemical).
In the same manner as in Example 1, the heating and dehydrating temperature was changed to 200 ° C., and the dimethylpolysiloxane was changed to polyethylene oxide (degree of polymerization: 200). Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 1-5).

(Comparative Example 5) The procedure of Example 5 was repeated, except that polyethylene oxide (polymerization degree: 200) was not introduced. Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 2-5).

Example 6 CSH-1 type calcium silicate of Example 1 was converted to activated clay (Galeon Earth manufactured by Mizusawa Chemical).
In the same manner as in Example 1, the heating and dehydrating temperature was changed to 180 ° C., and the dimethylpolysiloxane was changed to a [propylene glycol: methanol = 1: 3 mixed solution (Vol / Vol)]. Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 1-6).
It was shown to.

(Comparative Example 6) The procedure of Example 6 was repeated, except that the mixture of propylene glycol: methanol = 1: 3 (Vol / Vol) was not used. Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 2-6).

(Example 7) The CSH-1 type calcium silicate of Example 1 was replaced with acid clay (Galeon Earth manufactured by Mizusawa Chemical).
In the same manner as in Example 1 except that the heat dehydration temperature was changed to 220 ° C. and dimethylpolysiloxane was changed to oleic acid. Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 1-7).

Comparative Example 7 The procedure of Example 7 was repeated, except that oleic acid was not introduced. Table 1, Table 2, and Table 3 show the physical properties of the sample (Sample 2-7).

Example 8 The CSH-1 type calcium silicate of Example 1 was changed to zinc phyllosilicate (Mizukanite PH, manufactured by Mizusawa Chemical), the dehydration temperature was changed to 200 ° C., and the dimethylpolysiloxane was changed to acetylacetone. The same was done. Tables 1 and 2 show the physical properties of the sample (Sample 1-8).
The results are shown in Table 3.

Comparative Example 8 The procedure of Example 8 was repeated except that acetylacetone was not introduced. Tables 1, 2, and 3 show the physical properties of the sample (Sample 2-8).

(Example 9) The CSH-1 type calcium silicate of Example 1 was changed to an amorphous aluminosilicate, the heat dehydration temperature was set to 200 ° C, and the dimethylpolysiloxane was changed to γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.). KBE903) and carried out in the same manner as in Example 1. The sample (Sample 1-
Table 1, Table 2, and Table 3 show the physical properties of 9).

Comparative Example 9 The procedure of Example 9 was repeated, except that γ-aminopropyltriethoxysilane was not used. Table 1 shows various physical properties of the sample (Sample 2-9).
The results are shown in Tables 2 and 3.

Comparative Example 10 Calcium Silicate CSH-1
(Rational _{formula: 0.8CaO · SiO 2 · 0.84H 2} O)
50 g was dispersed in 950 g of distilled water to prepare a slurry having a pH of 10.5 and a concentration of 5%. Separately, 100 parts of distilled water
1 ml of 5N ammonia water and 0.5 ml of stearic acid
g of ammonium stearate suspension prepared in g was added, and the mixture was heated and stirred at 90 ° C. for 1 hour, washed with filtered water, and dried at 110 ° C. for 10 hours and pulverized. As a result of IR spectrum analysis, CSH-1 (sample 2-10) containing 2% by weight of calcium stearate was obtained. The physical properties and performance are shown in Tables 1, 2 and 3.

Comparative Example 11 Calcium Silicate CSH-1
(Rational _{formula: 0.8CaO · SiO 2 · 0.84H 2} O)
50 g was dispersed in 950 g of distilled water to prepare a slurry having a pH of 10.5 and a concentration of 5%. Separately, 100 parts of distilled water
1.5 ml of 5N ammonia water and 0.1 ml of lauric acid.
An ammonium laurate suspension adjusted to 5 g was added, and the mixture was heated and stirred at 90 ° C. for 1 hour, washed with filtered water, dried at 110 ° C. for 10 hours, and pulverized. As a result of IR spectrum analysis, C containing 2% by weight of calcium laurate was obtained.
SH-1 (sample 2-11) was obtained. The physical properties and performance are shown in Tables 1, 2 and 3.

Comparative Example 12 Calcium Silicate CSH-1
(Rational _{formula: 0.8CaO · SiO 2 · 0.84H 2} O)
20 g of dimethylpolysiloxane (KF96L-2CS manufactured by Shin-Etsu Chemical) and 100 ml of benzene separately adjusted to 1 kg
Was mixed into a 10 L super mixer manufactured by Kawada Seisakusho at 800 rpm for 3 minutes, then the temperature of the mixed system was increased to 90 ° C., and the mixture was rotated at 100 rpm for 30 minutes to volatilize and remove benzene. As a result of IR spectrum analysis, CSH-1 (sample 2-12) containing 2% by weight of dimethylpolysiloxane KF96L-2CS was obtained. Table 1, Table 2,
The results are shown in Table 3.

(Application Example 1) Melt flow rate is 1.5
0.5 part by weight of a sample was added to 100 parts by weight of low-density polyethylene having a density of 0.920 g / cc for / 10 min, and the mixture was melt-kneaded at 150 ° C. by an extruder and pelletized. The pellets are supplied to an extruder, and the extruder 160
The film was blown into a film having a thickness of 50 µm under the conditions of a temperature of 170 ° C and a die of 170 ° C. The haze of the obtained film was measured. The results are shown in Table 2.

(Application Example 2) A composition having the following composition was subjected to roll mill kneading at a temperature of 170 ° C. for 6 minutes, and a thickness of 0.5
mm of uniform blend. The foamability, dispersibility, and transparency of the obtained sheet were measured, and the results were shown in Table 3.
It was shown to. (Blending) Vinyl chloride resin (degree of polymerization 1050) 100 parts by weight Dioctyl phthalate 30 parts by weight Calcium stearate 1.0 part by weight Zinc stearate 0.5 part by weight Dipentaerthritol 1.0 part by weight Dibenzoylmethane 0.3 Parts by weight sample 1.0 parts by weight

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

According to the present invention, the silicic or aluminous resin compounding agent replaces at least most of the dehydration-bound water heated at 100 ° C. to 300 ° C. with a polar group-containing organic compound having a molecular weight of 30 or more. In addition, the water content of the silicic or alumina resin compounding agent is maintained substantially free of moisture, and the tendency to absorb moisture is suppressed for a long period of time. This hydrophobic resin compounding agent has excellent dispersibility. ,
There is also an advantage that foaming during processing is prevented.
In addition, there is also an advantage that the use of a very small amount of the organic compound can suppress the hygroscopicity and impart hydrophobicity.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an amorphous calcium silicate untreated (A), an amorphous calcium silicate substituted with a polyorganosiloxane (B), and the above substituted substance at 25 ° C. The sample (C) left for 800 hours in an atmosphere of RH 85% was measured (for details, see the example described later).
3 shows an infrared absorption spectrum.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C09C 3/08 C09C 3/08 (56) References JP-A-48-72097 (JP, A) JP-A-59-74165 (JP) , A) JP-A-61-73774 (JP, A) JP-A-8-48910 (JP, A) JP-B-46-39681 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C09C 1/28 C09C 1/40 C09C 3/08 C08K 3/22 C08K 3/34-3/36 C08K 9/04

Claims (7)

(57) [Claims] 1. A method according to claim 1, wherein at least a part of bound water of a siliceous or alumina resin compound which is heated and dehydrated at 100 to 300 ° C. is replaced with a polar group-containing organic compound having a molecular weight of 30 or more. A hydrophobic resin compounding agent adsorbed on the surface, wherein the following formula (1): R = (A / A ₀ ) × 100 (1) wherein A ₀ is silicic acid or alumina before the substitution treatment Absorbance of infrared absorption peak at wave number 1643 ± 21 Kaiser of porous resin compounding agent, or relative absorbance of standard sample absorbance and wave number 1643 ± 21 Kaiser peak absorbance; A is siliceous or alumina resin after substitution treatment Wave number of compounding agent 16
Absorbance of infrared absorption peak in 43 ± 21 Kaiser, or absorbance of standard in sample and wave number 1643 ± 21
Absorbance ratio (R) defined by the relative absorbance with respect to the Kaiser peak absorbance of 95% or less, and / or the following formula (2): R ′ = (B / B ₀ ) × 100 (2) B ₀ is the absorbance of the infrared absorption peak at a wave number of 3435 ± 17 Kaiser of the silicic or alumina resin compound before the substitution treatment, or the relative absorbance of the absorbance of the in-sample standard and the peak absorbance of the wave number of 3435 ± 17 Kaiser; Is the wave number of the silicic or alumina resin compounding agent after the substitution treatment.
Absorbance of infrared absorption peak at 35 ± 17 Kaiser, or absorbance of internal standard and wave number 3435 ± 17
A hydrophobic resin compounding agent characterized by having an absorbance ratio (R ′) defined by a relative absorbance with respect to the Kaiser peak absorbance of 95% or less. 2. The silicic resin compounding agent is amorphous silica, amorphous aluminosilicate, calcium silicate, magnesium silicate, phylloaluminosilicate, formite clay mineral or tectoaluminosilicate. 2. The resin compounding agent according to 1. 3. The resin composition according to claim 1, wherein the alumina resin composition is alumina, hydrated alumina, magnesium aluminum carbonate hydroxide, lithium aluminum carbonate hydroxide or sodium aluminum carbonate hydroxide. 4. The polar group-containing organic compound is a hydroxy group,
The resin compounding agent according to claim 1, which is at least one selected from an organic compound having an ether group, a carbonyl group, a carboxyl group, and a siloxane group, or an organic silane compound. 5. The polar group-containing organic compound is at least one selected from a polyorganosiloxane, a monohydric alcohol having 1 or more carbon atoms, a polyhydric alcohol having 3 or more carbon atoms, a carboxylic acid having 3 or more carbon atoms, and a polyalkylene polyol. The resin compounding agent according to claim 4, which is 6. The method according to claim 1, wherein the polar group-containing organic compound is contained in an amount of 0.01 to 30 parts by weight per 100 parts by weight of the silicic or alumina resin compounding agent. Resin compounding agent. 7. The combined water of a siliceous or alumina resin compound is heated and dehydrated at 100 to 300 ° C., and the heat-dehydrated resin compound contains vapor of a polar group-containing organic compound having a molecular weight of 30 or more. by cooling to room temperature in an atmosphere of dry substituted with gas, the following formula (1): R = (a / a 0) × in 100 ‥ (1) formula, _{a 0} is the pre-replacement process silicic acid Absorbance of infrared absorption peak at wave number 1643 ± 21 Kaiser of natural or alumina resin compounding agent, or relative absorbance of standard sample absorbance and wave number 1643 ± 21 Kaiser peak absorbance; Wave number 16 of alumina resin compounding agent
Absorbance of infrared absorption peak in 43 ± 21 Kaiser, or absorbance of standard in sample and wave number 1643 ± 21
Absorbance ratio (R) defined by the relative absorbance with respect to the Kaiser's peak absorbance is 95% or less, and / or the following formula (2): R ′ = (B / B ₀ ) × 100 (2) B ₀ is the absorbance of the infrared absorption peak at the wave number of 3435 ± 17 Kaiser of the silicic or alumina resin compound before the substitution treatment, or the relative absorbance of the absorbance of the internal standard and the peak absorbance of the wave number of 3435 ± 17 Kaiser; Is defined as the absorbance of the infrared absorption peak at the wave number of 3435 ± 17 Kaiser of the silicic or alumina resin compound after the substitution treatment, or the relative absorbance of the absorbance of the standard in the sample and the peak absorbance of the wave number of 3435 ± 17 Kaiser. The bound water by the polar group-containing organic compound so that the absorbance ratio (R ′) becomes 95% or less;
A method for producing a hydrophobic resin compounding agent, wherein the polar group-containing organic compound is adsorbed on the surface.