JP2003034759A - Method for producing surface-treated inorganic particle and surface-treated inorganic particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for treating the surface of inorganic particles having high productivity in which much amount of solvent is not required without concern about loss of the quality of the surface treatment. SOLUTION: A system including the inorganic particles and treating agents is kneaded with a kneader, thereby treating the surface of inorganic substances.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing surface-treated inorganic particles, which comprises surface-treating an inorganic substance by kneading a system containing inorganic particles and a treating agent with a kneader, and the resulting surface-treated inorganic particles. Regarding particles.

[0002]

2. Description of the Related Art Conventionally, surface treatment of inorganic particles has been
Water, or a solvent method in which a treating agent is dissolved in an organic solvent containing water and a catalyst for hydrolysis if necessary, and inorganic particles and a treating agent are stirred and mixed in the solvent using a stirrer or the like,
A spray method has been adopted in which the treatment agent or a treatment agent diluted with a solvent is directly sprayed while vigorously stirring the inorganic particles.

According to the method of (3), it takes time and cost to treat a large amount of solvent, and especially when the inorganic particles are swellable layered compounds, the system thickens and stirring / mixing becomes difficult. , To stir, the concentration of inorganic particles must be low. Therefore, productivity is low. According to the method of
The method is superior to the method in terms of solvent treatment and productivity, but the resulting surface treatment may be non-uniform, which is problematic in terms of quality.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art. It does not require a large amount of solvent, does not impair the quality of surface treatment, and has high productivity. It is an object of the present invention to provide a method for producing high surface-treated inorganic particles.

[0005]

The present inventors have completed the present invention as a result of intensive studies to achieve the above object. That is, the present invention provides a method for producing surface-treated inorganic particles, which comprises surface-treating the inorganic particles by kneading a system containing the inorganic particles and a treating agent, preferably by a kneader. . In one preferred embodiment, the system comprises a solvent, more preferably the solvent comprises water. In another preferred embodiment, the inorganic particles are layered compounds, more preferably swellable layered compounds. Furthermore, the present invention provides surface-treated inorganic particles obtained by any one of the above-described production method of the present invention or a preferred embodiment thereof.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a system containing inorganic particles and a treating agent is preferably kneaded by a kneader. As the kneader in the present invention, a conventionally known kneader can be used, and there are a batch type and a continuous type kneader. Examples of the batch-type kneader include an open roll, a closed Banbury type kneader and a kneader type kneader. Although any batch-type kneader can be used, rolls are preferable in that heat generation can be suppressed and switching can be easily performed in multi-product production, and Banbury-type kneaders are preferable in terms of mixing and productivity, or equipment cost can be increased. However, a kneader type kneader is preferable because it is inexpensive. Among these batch type kneaders, the Banbury type kneader is particularly preferable. In the Banbury type, the rotor shape is appropriately exchanged depending on the purpose, but in terms of efficient mixing, the 2-blade standard type rotor and the 4-blade swirl flow type rotor are preferable. If the filling rate of the system containing the inorganic particles to be kneaded and the treating agent is too small, pressure is less likely to be applied, and the kneading speed becomes slower. On the contrary, if the filling rate is too high, some parts cannot be kneaded. Therefore, the filling rate depends on the viscosity of the material to be filled, but it is approximately 70-8.
0% is preferable.

Examples of the continuous kneader include a single-shaft rotor kneader, a twin-shaft rotor kneader, a single-screw kneader, a twin-screw kneader, and a multi-screw kneader. In the rotor-type kneader, a 2-blade rotor is preferable when heat generation is desired to be suppressed, and a 3-blade rotor is preferable when high pressure is required for efficient treatment of inorganic particles. The mesh type is preferable when there are many types of product switching. Further, the screw kneader means a so-called kneading extruder. The kneading extruder is operated by changing conditions such as screw configuration, barrel configuration, and screw rotation speed. It is preferable to use a kneading disk from the viewpoint of applying high pressure to the material and improving the processing efficiency. The rotor segment is preferable in terms of applying pressure while suppressing heat generation.

The processing time depends on the pitch of the screw segments, the number of revolutions of the screw, and the L / D of the screw and barrel.
Depends on. Generally, when it takes time to process, it is necessary to knead for a long time while applying high pressure, but in that case,
For example, the pitch of the segments is made as short as possible, and a 3-thread screw is preferable. The screw rotation speed is preferably 100 rpm or more, more preferably 150 rpm or more, and 200
Especially rpm or more is preferable. L / D is preferably 5 or more, more preferably 7 or more, and particularly preferably 10 or more.

The order and position of adding the inorganic particles, the treating agent and the solvent vary depending on the purpose. In addition to the method of collectively adding the inorganic particles, the treating agent, and the solvent used as needed, the following method may be mentioned. If you want to treat the inorganic particles after loosening the aggregates of the inorganic particles to form primary particles, first use a method in which the inorganic particles are thoroughly kneaded and dispersed with a solvent, and then a treatment agent is added in the middle and further kneaded. You can When there is a possibility that the treating agent may self-react, a method of adding the treating agent from several places can be adopted. When the treating agent has a hydrolyzable group involved in the treating reaction such as a silane compound, or when the treating agent requires a reaction initiator, the reaction initiator is added from the middle after kneading and dispersing the inorganic particles and the treating agent. A method of adding may be adopted.

As the inorganic particles used in the present invention, conventionally known inorganic particles, for example, layered compounds such as montmorillonite, metal hydroxides such as magnesium hydroxide, metal oxides such as silica and alumina, calcium carbonate and barium carbonate. Other examples include carbonate compounds such as, and sulfate compounds such as calcium sulfate and barium sulfate, as well as carbon black and wood flour, but are not limited thereto. Among the above inorganic particles, a layered compound is preferable.

The above-mentioned layered compounds include silicates, phosphates such as zirconium phosphate, titanates such as potassium titanate, tungstates such as sodium tungstate, uranates such as sodium uranate, Vanadate such as potassium vanadate, molybdate such as magnesium molybdate, niobate such as potassium niobate,
It is at least one inorganic compound selected from the group consisting of graphite. A layered silicate is preferably used from the viewpoints of easy availability and handleability.

Examples of the above-mentioned layered silicate include silicates formed mainly from a tetrahedral sheet of silicon oxide and an octahedral sheet of metal hydroxide, such as smectite group clay and swelling mica. To be

The above smectite group clay is represented by the following general formula (1):

[Chemical 1] X¹ _{0.2 ~ 0.6}Y¹ _2-3Z¹ _FourO_Ten(OH)₂・ NH₂O (1) (In the formula, X¹Is K, Na, 1 / 2Ca, and 1 / 2Mg
At least one metal atom selected from the group consisting of
R, Y¹Is Mg, Fe, Mn, Ni, Zn, Li, A
l, and at least one selected from the group consisting of Cr
A metal atom, Z ¹Is from the group consisting of Si and Al
It is at least one atom selected. Incidentally, H_TwoO is a layer
Represents a water molecule that is bound to an interstitial ion, where n is an interlayer ion.
It is a number that varies depending on the temperature and relative humidity. )
Natural, or synthetic.

Specific examples of such a smectite group clay include, for example, montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, sauconite, stevensite, bentonite, etc., or their substitution products, derivatives, or these. A mixture of In the initial aggregation state of the smectite group clay, the bottom spacing is about 10 to 17Å, and the average particle size of the smectite group clay in the aggregation state is about 1
It is 000Å to 1,000,000Å.

The swellable mica is represented by the following general formula (2):

_{Embedded image} X ² _{0.5 to 1.0} Y ^{2 2 to} ₃ (Z ² ₄ O ₁₀ ) (F, OH) ₂ (2) (In the formula, X ² is Li, Na, K, Rb, Ca, Ba, and It is at least one metal atom selected from the group consisting of Sr, Y ² is at least one metal atom selected from the group consisting of Mg, Fe, Ni, Mn, Al and Li, and Z ² is Si , Ge, Al, Fe, and B, which is at least one atom selected from the group consisting of Ge, Al, Fe, and B).

These swellable mica are substances having a property of swelling in water, a polar solvent which is compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. For example, lithium-type teniolite, Sodium-type teniolite, lithium-type tetra-silicon mica, and sodium-type tetra-silicon mica, etc.,
Alternatively, a substitution product or derivative thereof, or a mixture thereof may be used. The basal plane spacing of the swelling mica in the initial aggregation state is about 10 to 17Å, and the average particle diameter of the swelling mica in the aggregation state is about 1,000 to 1,000.
It is 10,000Å.

Some of the above swelling mica has a structure similar to that of vermiculites, and such vermiculites or equivalents can be used. The vermiculite-equivalent products include a trioctahedral type and a dioctahedral type, and the following general formula (3):

Embedded image (Mg, Fe, Al) _{2 to 3} (Si _4-X Al _X ) O ₁₀ (OH) ₂ · (M ⁺ , M ²⁺ _1/2 ) _X · nH ₂ O (3) (formula Where M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x is a number from 0.6 to 0.9,
n is a number of 3.5 to 5). The vermiculite-equivalent product has an initial bottom surface interval of about 10 to 17Å in the agglomerated state, and an average particle size in the agglomerated state of about 1,000 to 5,000,000Å.

It is desirable that the crystal structure of the layered silicate has a high degree of purity with regular stacking in the c-axis direction.
A so-called mixed layer mineral in which the crystal period is disordered and a plurality of types of crystal structures are mixed can also be used. The layered silicate may be used alone or in combination of two or more kinds. Among these, montmorillonite, bentonite, hectorite, and swellable mica having sodium ions between layers are preferable from the viewpoint of dispersibility in the obtained resin molded product, heat resistance, and surface gloss.

The treating agent used in the present invention is not particularly limited, and known treating agents can be used, and examples thereof include a silane compound containing silicon, a polyether compound having a polyether chain, and titanium. Titanate compounds,
Examples thereof include organic onium salt compounds having ammonium ions and phosphonium ions, water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone.

As the above-mentioned silane compound, any generally used compound is used, and the following general formula (4): Y _n SiX _4-n (4) (wherein, n is an integer of 0 to 3) And Y is a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, and X is a hydrolyzable group and / or a hydroxyl group.).

When the hydrocarbon group having 1 to 25 carbon atoms in the general formula (4) has a substituent, examples of the substituent include a group bonded by an ester bond and a group bonded by an ether bond. , Epoxy group, amino group, carboxyl group, terminal carbonyl group, amide group, mercapto group, group bound by sulfonyl bond, group bound by sulfinyl bond, nitro group, nitroso group, nitrile group , Halogen atoms, hydroxyl groups and the like. The hydrocarbon group is
One of these may be substituted, or two or more may be substituted.

X is a hydrolyzable group and / or a hydroxyl group, and examples of the hydrolyzable group include an alkoxy group,
It is one or more selected from the group consisting of an alkenyloxy group, a ketoxime group, an acyloxy group, an amino group, an aminoxy group, an amide group, and a halogen atom. In the general formula (4), when n or 4-n is 2 or more, n Y's or 4-n X's may be the same or different.

In the above general formula (4), Y has 1 carbon atom.
Examples of the hydrocarbon group of ~ 25 are those having a linear long-chain alkyl group such as decyltrimethoxysilane, those having a lower alkyl group such as methyltrimethoxysilane, and 2-hexenyltrimethoxy. Those having an unsaturated hydrocarbon group such as silane, those having an alkyl group having a side chain such as 2-ethylhexyltrimethoxysilane, those having a phenyl group such as phenyltriethoxysilane, and 3-β-naphthyl. Examples thereof include those having a naphthyl group such as propyltrimethoxysilane, and those having an aralkyl group such as p-vinylbenzyltrimethoxysilane.

Examples of the case where Y is a group having a vinyl group among the hydrocarbon groups having 1 to 25 carbon atoms include vinyltrimethoxysilane, vinyltrichlorosilane, and vinyltriacetoxysilane. An example of the case where Y is a group having a group substituted with a group bonded with an ester group is γ-methacryloxypropyltrimethoxysilane. Examples of the case where Y is a group having a group substituted with a group bonded with an ether group include γ-polyoxyethylenepropyltrimethoxysilane and 2-ethoxyethyltrimethoxysilane. Examples of the case where Y is a group substituted with an epoxy group include γ-glycidoxypropyltrimethoxysilane.

When Y is a group substituted with an amino group, examples thereof include γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane. Methoxysilane may be mentioned. An example of the case where Y is a group substituted with a group having a carbonyl group at the terminal is γ-ureidopropyltriethoxysilane. Examples of the case where Y is a group substituted with a mercapto group include γ-mercaptopropyltrimethoxysilane. Examples of the case where Y is a group substituted with a halogen atom include γ-chloropropyltriethoxysilane. Examples of the case where Y is a group having a group substituted with a group bonded with a sulfonyl group include:
gamma-phenyl sulfonyl propyl trimethoxysilane is mentioned. Examples of the case where Y is a group having a group substituted with a group bonded with a sulfinyl group include γ
-Phenylsulfinylpropyltrimethoxysilane.

An example of the case where Y is a group substituted with a nitro group is γ-nitropropyltriethoxysilane. Examples of the case where Y is a group substituted with a nitroso group include γ-nitrosopropyltriethoxysilane. Examples of the case where Y is a group substituted with a nitrile group include γ-cyanoethyltriethoxysilane and γ-cyanopropyltriethoxysilane. Examples of the case where Y is a group substituted with a carboxyl group include γ- (4-carboxyphenyl) propyltrimethoxysilane.

Besides the above, a silane compound in which Y is a group having a hydroxyl group can also be used. One such example is
N, N-di (2-hydroxyethyl) amino-3-propyltriethoxysilane may be mentioned. The hydroxyl groups can also be in the form of silanol groups (SiOH). Substitutes or derivatives of the above silane compounds can also be used. These silane compounds may be used alone or in combination of two or more.

The above-mentioned polyether compound used as a treating agent means a compound whose main chain is polyoxyalkylene such as polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer, and the repeating unit. It is intended that the number is about 2 to 100. The above-mentioned polyether compound may have an arbitrary substituent in the side chain and / or the main chain as long as it does not adversely affect the thermoplastic resin or the layered compound. Examples of the substituent include a hydrocarbon group, a group bonded by an ester bond, an epoxy group, an amino group, a carboxyl group, a group having a carbonyl group at the terminal, an amide group, a mercapto group, and a sulfonyl bond. Group, a group bound by a sulfinyl bond,
Examples thereof include a nitro group, a nitroso group, a nitrile group, an alkoxysilyl group and a silanol group, and a Si-containing atomic functional group capable of forming a Si—O— bond, a halogen atom and a hydroxyl group. It may be substituted with one of these 2
It may be substituted with one or more species.

The above-mentioned hydrocarbon group used as a treating agent is a linear or branched (that is, having a side chain) saturated or unsaturated monovalent or polyvalent aliphatic hydrocarbon group,
It means an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a phenyl group and a naphthyl group. In the present specification, the term “alkyl group” means
Unless otherwise specified, it is intended to include polyvalent hydrocarbon groups such as "alkylene groups". Similarly an alkenyl group,
The alkynyl group, cycloalkyl group, phenyl group, and naphthyl group include an alkenylene group, an alkynylene group, a cycloalkylene group, a phenylene group, a naphthylene group, and the like, respectively.

The composition ratio of the substituents in the polyether compound is not particularly limited, but it is desirable that the composition is selected so that the polyether compound is soluble in water or a polar solvent containing water. Specifically, for example, room temperature water 1
Solubility in 00g is 1g or more, preferably 2
g or more, more preferably 5 g or more, further preferably 10 g or more, particularly preferably 20 g or more. The polar solvent is, for example, methanol,
Ethanol, alcohols such as isopropanol, ethylene glycol, propylene glycol, glycols such as 1,4-butanediol, ketones such as acetone and methyl ethyl ketone, diethyl ether, ethers such as tetrahydrofuran, N, N-dimethylformamide, N An amide compound such as N-dimethylacetamide,
Other solvents include pyridine, dimethyl sulfoxide, N-methylpyrrolidone and the like. Also, carbonic acid diesters such as dimethyl carbonate and diethyl carbonate can be used. These polar solvents may be used alone or in combination of two or more.

Specific examples of the polyether compound used in the present invention include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol, polyethylene glycol-polytetramethylene glycol,
Polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol diethyl ether, polyethylene glycol monoallyl ether, polyethylene glycol diallyl ether, polyethylene glycol monophenyl ether, polyethylene glycol diphenyl ether, polyethylene glycol octyl phenyl ether, polyethylene glycol methyl Ethyl ether, polyethylene glycol methyl allyl ether, polyethylene glycol glyceryl ether, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate Relate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monoacrylate, polyethylene glycol-polytetramethylene glycol monomethacrylate, polyethylene glycol-polytetramethylene glycol monoacrylate, methoxy polyethylene glycol monomethacrylate, methoxy polyethylene glycol monoacrylate, Octoxy polyethylene glycol-polypropylene glycol monomethacrylate, octoxy polyethylene glycol-polypropylene glycol monoacrylate, lauroxy polyethylene glycol monomethacrylate, lauroxy polyethylene glycol monoacrylate, stearoxy polyethylene Recall monomethacrylate, stearoxy polyethylene glycol monoacrylate, allyloxy polyethylene glycol monomethacrylate, allyloxy polyethylene glycol monoacrylate, nonylphenoxy polyethylene glycol monomethacrylate, nonylphenoxy polyethylene glycol monoacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene Glycol-polytetramethylene glycol dimethacrylate, polyethylene glycol-polytetramethylene glycol diacrylate, bis (polyethylene glycol) butylamine, bis (polyethylene glycol) octylamine, polyethylene glycol bisphenol A ether, polyethylene glycol Cole-polypropylene glycol bisphenol A
Ether, ethylene oxide modified bisphenol A dimethacrylate, ethylene oxide modified bisphenol A diacrylate, ethylene oxide-propylene oxide modified bisphenol A dimethacrylate, polyethylene glycol diglycidyl ether, polyethylene glycol ureidopropyl ether, polyethylene glycol mercaptopropyl ether, polyethylene glycol Examples thereof include phenylsulfonyl propyl ether, polyethylene glycol phenylsulfinyl propyl ether, polyethylene glycol nitropropyl ether, polyethylene glycol nitrosopropyl ether, polyethylene glycol cyanoethyl ether and polyethylene glycol cyanoethyl ether. These polyether compounds may be used alone or
Combinations of two or more species can be used.

Among the polyether compounds used in the present invention, those having a cyclic hydrocarbon group such as an aromatic hydrocarbon group or an alicyclic hydrocarbon group are preferable, and among them, the following general formula (5):

[Chemical 4] (In formula, -A- is -O-, -S-, -SO-, -SO.
_2- , -CO-, an alkylene group having 1 to 20 carbon atoms, or an alkylidene group having 6 to 20 carbon atoms, R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each is a hydrogen atom, a halogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ⁹ , R
¹⁰ are the same or different and is a divalent hydrocarbon group of 1 to 5 carbon ^{atoms, R} 1 ^{1, R 12} are the same or different, a hydrogen atom, a monovalent hydrocarbon having 1 to 20 carbon atoms It is a base. m and n represent the number of repeating units of the oxyalkylene unit, and 2 ≦ m + n ≦ 50. What is represented by these is preferable from the viewpoint of dispersibility of the layered compound.

Further, the titanate compound is represented by the general formula (I)
Examples of the monoalkoxy titanate-based treating agent represented by the formula include isopropyl tris-isostearoyl titanate, isopropyl tris-n-dodecylbenzene sulfonyl titanate, and isopropyl dimethacryl isostearoyl titanate represented by the general formula (II). As a chelate-type titanate treatment agent such as
For example, bis (dioctylpyrophosphate) -oxyacetate titanate, bis (dioctylpyrophosphate) -ethylene titanate, dicumylphenyloxyacetate titanate and the like are represented by the general formula (III)
As the coordination type titanate treating agent as represented by, for example, tetraisopropyl-bis- (dioctylphosphite) titanate, tetraoctyl-bis (ditridecylphosphite) titanate and the like, and further, these It may be a substitution product or a derivative. These are used alone or in combination of two or more.

[0034]

[Chemical 5]

The above-mentioned organic onium salt compound used as a treating agent is a conventionally known onium salt containing anion such as onium ion and halogen ion. The onium ion has a structure represented by an ammonium ion, a phosphonium ion, a sulfonium ion, a heteroaromatic ring-derived onium ion, or the like.
Among these, ammonium ions, phosphonium ions, and onium ions derived from a heteroaromatic ring can be preferably used from the viewpoints of easy availability and stability.

Examples of the ammonium ions include dodecyl ammonium, hexadecyl ammonium, octadecyl ammonium, methyl dodecyl ammonium, butyl dodecyl ammonium, methyl octadecyl ammonium, dimethyloctyl ammonium, dimethyl dodecyl ammonium, dimethyl hexadecyl ammonium,
Dimethyl octadecyl ammonium, trimethyl dodecyl ammonium, triethyl tetradecyl ammonium, tributyl hexadecyl ammonium, dimethyl didodecyl ammonium, diethyl ditetradecyl ammonium, dibutyl dihexadecyl ammonium, tridecyl methyl ammonium and other alkyl ammonium, dimethyl phenyl ammonium, diphenyl dodecyl Ammonium having a phenyl group such as ammonium, diphenyloctadecyl ammonium, methylbenzyl didodecyl ammonium, dibenzyl dihexadecyl ammonium, [PEG] ammonium (hereinafter [PEG] represents a polyethylene glycol chain), methyl [PEG] ammonium, Dodecyl [PEG] ammonium, hexadecyl [PEG] Moniumu, dimethyl [PEG] ammonium, methyl dodecyl [PEG] ammonium,
Ammonium having hydrophilic groups such as methyl octadecyl [PEG] ammonium, methyl bis [PEG] ammonium, dodecyl bis [PEG] ammonium, and hexadecyl bis [PEG] ammonium, glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, threonine , Serine, bronine, tryptophan, methionine, cystine, cysteine, asparagine, aspartic acid, glutamine, glutamic acid,
Examples include ammonium of α-amino acids such as lysine, arginine, and histidine, ammonium of ω-amino acids such as 6-aminocaproic acid, 8-aminooctanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. .

Examples of the phosphonium ion include tetrabutylphosphonium, tetraoctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributyldodecylphosphonium, tributylhexadecylphosphonium, and tributyloctadecylphosphonium. [PEG] phosphonium, methyl [PEG] phosphonium, dodecyl [PEG] phosphonium, hexadecyl [PEG] phosphonium, dimethyl [PEG] phosphonium, methyl dodecyl [PEG] phosphonium, methyl octadecyl [PEG] phosphonium, methyl bis [PEG] phosphonium, dodecyl bis [PEG] phosphonium, hexa Shirubisu [PEG] phosphonium, and the like.

Examples of the sulfonium ion include tridodecylsulfonium and didodecyltetradecylsulfonium. Examples of the onium ion derived from the heteroaromatic ring include pyridinium, methylpyridinium, dimethylpyridinium, 2-phenylpyridinium, 2-aminopyridinium, nicotinium, nicotinamide onium, quinolinium, and isoquinolinium. Substitutes or derivatives of the above onium salts may also be used. These onium salts may be used alone or in combination of two or more.

Specific examples of the water-soluble polymer include polyvinyl alcohol, sodium polyacrylate, polyvinylpyrrolidone, polyacrylic acid ester, oligosaccharides such as polyacrylamide, disaccharide and trisaccharide, cellulose-based processed natural polymer and starch. Examples include, but are not limited to, system-processed natural polymers. These may have a substituent as long as the water solubility is not impaired.
In addition to the above compounds, starch, mannan, seaweed, plant mucilage, microbial mucilage, natural polymeric compounds such as proteins, and polymeric substances such as polyvinylimine and ethylene-vinyl alcohol copolymer are also used. it can.

The solvent used in the present invention is not particularly limited, but means, for example, water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. Examples of the polar solvent include alcohols such as methanol, ethanol and isopropanol, ethylene glycol,
Glycols such as propylene glycol and 1,4-butanediol, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether and tetrahydrofuran, amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide, and others Examples of the solvent include pyridine, dimethyl sulfoxide, N-methylpyrrolidone, and the like. Further, carbonic acid diesters such as dimethyl carbonate and diethyl carbonate can also be used. These polar solvents may be used alone or in combination of two or more.

The amount of the above-mentioned polyether compound or silane compound used can be adjusted so that the dispersibility of the layered compound in the resin molding is sufficiently enhanced. If necessary, a plurality of types having different functional groups can be used in combination. Therefore, the addition amount is not limited numerically, but the lower limit of the amount of the polyether compound or the silane-based compound compounded with respect to 100 parts by mass of the layered compound is 0.1 part by mass, and preferably 0.1.
2 parts by mass, more preferably 0.3 parts by mass,
It is more preferably 0.4 parts by mass, and particularly preferably 0.5 parts by mass. The upper limit of the compounding amount of the layered compound with respect to 100 parts by mass of the layered compound is 200 parts by mass,
It is preferably 180 parts by mass, more preferably 160 parts by mass.
It is preferably 100 parts by mass, more preferably 140 parts by mass, and particularly preferably 120 parts by mass. If the lower limit is less than 0.1 part by mass, the effect of finely dispersing the layered compound tends to be insufficient. Further, since the effect does not change at 200 parts by mass or more, it is not necessary to use more than 200 parts by mass.

The surface treatment of the inorganic particles by the treatment method of the present invention can be confirmed by a conventionally known analysis method. For example, when the silane compound represented by the general formula (4) is introduced on the surface of the inorganic particles, the following method can be adopted. That is, first, the surface-treated inorganic particles are washed with an organic solvent such as tetrahydrofuran or chloroform to simply wash and remove the adsorbed silane compound. The washed inorganic particles are pulverized in a mortar or the like and then thoroughly dried. Then, the inorganic particles are sufficiently mixed with a window material such as powdered potassium bromide (KBr) at a predetermined ratio to form tablets under pressure, and Fourier transform (F
The absorption band derived from the silane-based compound is measured by a transmission method or the like using T) -IR. When more accurate measurement is desired or when the amount of introduced silane compound is small, the sufficiently dried powdery surface-treated inorganic particles should be directly measured by the diffuse reflection method (DRIFT method). Is desirable.

When the inorganic particles are a swellable layered compound and are surface-treated with a silane compound, an organic onium salt compound, a polyether compound, a water-soluble polymer, etc., the bottom spacing of the swellable layered compound before and after the surface treatment Examples include measurements. That is, after thoroughly drying the surface-treated inorganic particles of the present invention, the bottom surface spacing can be confirmed by a small angle X-ray diffraction method (SAXS) or the like. In this method, the X-ray diffraction peak angle value derived from the (001) plane of the surface-treated swellable layered inorganic compound is measured by SAXS, and the value is applied to the Bragg equation to calculate the bottom spacing. . Similarly, the bottom surface interval of the swellable layered compound before the treatment is measured, and the expansion of the bottom surface interval can be confirmed by comparing the two.

Since the surface-treated inorganic particles obtained in the present invention are extremely efficiently and uniformly surface-treated, they can be used as a strengthening agent for various injection molding resins, a dimensional stability imparting agent, a heat resistance imparting agent and the like. In addition to being used as a strengthening agent for film products and bottle products, a gas barrier imparting agent, etc., it can be used in various fields such as a viscosity modifier for organic solvents and paints.

[0045]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The main raw materials used in Examples and Comparative Examples are summarized below. Unless otherwise specified, the raw materials were not purified.

(Raw Material) Inorganic particles A-1: Montmorillonite (Kunipia F manufactured by Kunimine Industries Co., Ltd., bottom spacing = 13Å) Inorganic particles A-2: Swelling mica (Corp Chemical Co., Ltd.)
Somasif ME100 manufactured, bottom spacing = 12Å) -Treatment agent B-1: Polyether compound (Toho Chemical Co., Ltd.)
Bis-all 18EN manufactured) -Treatment agent B-2: Silane compound (Nippon Unicar Co., Ltd.
A1120) -Treatment agent B-3: Organic onium salt compound (Esocard C25 manufactured by Lion Corporation) -Treatment agent B-4: Polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.)

(Bottom Distance) An X-ray generator (RU-200B manufactured by Rigaku Denki Co., Ltd.) was used to measure the bottom distance under the following measurement conditions: target CuKα ray, Ni filter, voltage: 40 kV, current: 200 mA. , Scan angle 2θ
= 0.2 to 16.0 °, step angle = 0.02 °.

The bottom spacing was calculated by substituting the small angle X-ray diffraction peak angle value into the Bragg equation. However, if it is difficult to confirm the small angle X-ray peak angle value, confirm that the layer has been sufficiently cleaved and the crystallinity has substantially disappeared, or the peak angle value is approximately 0.8 ° or less. However, the evaluation result of the bottom surface spacing was set to> 100 Å.

(FT-IR) About 1 mg of surface-treated inorganic particles and about 200 mg of KBr powder were thoroughly mixed in a mortar, and then a KBr disk for measurement was prepared using a tabletop press. Then, it was measured by a transmission method using an infrared spectrometer (8100M, manufactured by Shimadzu Corporation). The detector used was an MCT detector cooled with liquid nitrogen, and the resolution was 4 cm-
1, the number of scans was 100 times.

(Ash content) Measured according to JIS K 7052.

Example 1 A KRC kneader manufactured by Kurimoto Iron Works Co., Ltd. was used as a kneading machine. 100 parts by mass (hereinafter referred to as "part") of inorganic particles A
-2 and 100 parts of ion-exchanged water were simultaneously added to the KRC kneader and kneaded at a rotation speed of 200 rpm. Then, 30 parts of the treating agent B-1 was added from the midway addition port, and kneading was continued. The time during which the inorganic particles stayed in the KRC kneader, that is, the kneading time was about 40 seconds.
Then, it was dried in an oven and pulverized by a hammer mill to obtain powdered treated inorganic particles. The surface state and bottom surface spacing of the obtained inorganic particles were measured. The results are shown in Table 1.

Comparative Example 1 Using a method other than the kneader, it was evaluated whether the inorganic particles A-2 could be treated with the same composition ratio as in Example 1. That is, a wet stirrer was used. An attempt was made to mix ion-exchanged water and inorganic particles A-2 with the same composition as in Example 1, but the stirring was impossible and the treatment could not be performed.

Comparative Example 2 The same wet stirrer as in Comparative Example 1 was used. Using 1000 parts of ion-exchanged water for 100 parts of the inorganic particles A-2,
The mixture was diluted more than in Comparative Example 1 and stirred. Then treatment agent B-1
Was added and stirring was continued for another 15 minutes. Drying, crushing and evaluation were carried out in the same manner as in Example 1. Inorganic particles A-2 according to the above method
Had the same functional groups as in Example 1, and the bottom spacing was also widened. In other words, although a surface treatment was applied, a large amount of water was used during stirring, so 4
It takes 0 hours, which proves to be unsuitable in terms of productivity.

Comparative Example 3 A ribbon blender was used as a device capable of stirring even if the composition ratio of water was small. First, ion-exchanged water and inorganic particles A-1 were mixed with the same composition as in Example 1. After mixing for 30 minutes, the treating agent B-1 was added and kneading was continued for 30 minutes. The processing time was 60 minutes in total. Then, it was dried and pulverized into a powder. The drying time was as short as that of Example 1, but when no functional group was observed, the bottom spacing did not change at all, or even if it changed, the bottom spacing of the inorganic particles obtained in Example 1 It was smaller and smaller. That is, it is understood that an apparatus having no kneading action, such as a ribbon blender, is unsuitable because the processing is insufficient and non-uniform even if the processing takes a long time.

[0055]

[Table 1]

Examples 2 to 4 Inorganic particles and treating agents of the types and mass ratios shown in Table 2 were used, and the inorganic particles were treated in the same manner as in Example 1 using a kneader. The results are shown in Table 2.

[0057]

[Table 2]

Example 5 Thermoplastic polyester resin (EFG70 manufactured by Kanebo Co., Ltd.) 1
00 parts by mass and 13 parts by mass of the inorganic particles obtained in Example 1 were melt-kneaded and pelletized by a twin-screw extruder (TEX44 manufactured by Japan Steel Manufacturing Co., Ltd.). After drying the obtained pellets at 130 ° C. for 4 hours, using an injection molding machine with a mold clamping pressure of 75 t (IS-75E manufactured by Toshiba Machine Co., Ltd.), a size of about 10 × 100 ×
A 6 mm test piece was injection molded and the deflection temperature under load (AST
MD-648), flexural strength and flexural modulus (AST
MD-790) was measured. Separately, the size is about 12
A 0x120x2mm flat plate test piece is injection-molded to obtain molding shrinkage and a surface roughness meter Surfcom1 manufactured by Tokyo Seimitsu Co., Ltd.
Centerline roughness was measured using 500A. The results are shown in Table 3.

Comparative Example 4 Evaluation was made in the same manner as in Example 5 except that the inorganic particles obtained in Comparative Example 3 were used instead of the inorganic particles obtained in Example 1. The results are shown in Table 3. From Table 3, it can be seen that the inorganic particles obtained in the present invention were kneaded with a thermoplastic resin to obtain a resin composition, which was excellent in mechanical properties, heat resistance and molding shrinkage without impairing surface properties.

[0060]

[Table 3]

[0061]

As described in detail above, by treating a system containing inorganic particles and a treating agent with a kneader, it is possible to produce inorganic particles having high efficiency and uniform treated surface in a short time. . The inorganic particles obtained by the surface treatment method are a reinforcing agent for various resins for injection molding, a dimensional stability imparting agent, a heat resistance imparting agent, a reinforcing agent for a film product or a bottle product, and a gas barrier imparting agent without impairing the surface properties of the resin composition. It can be used in various fields such as agents, organic solvents and viscosity modifiers such as paints.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 101/00 C08L 101/00 (72) Inventor Kimihiko Nakano 6-27- Honda, Tarumi-ku, Kobe-shi, Hyogo 4F term (reference) 4J002 AA011 AA021 DE186 DH036 DJ006 FB086 FD016 4J037 AA02 AA08 AA10 AA17 AA18 AA21 AA25 AA27 AA30 CB15 CB19 CB22 CB23 CB26 CC10 CC02 CC11 CC12 CC15 CC03 CC25 DD25

Claims (6)

[Claims] 1. A method for producing surface-treated inorganic particles, which comprises surface-treating the inorganic particles by kneading a system containing the inorganic particles and a treating agent. 2. The method for producing inorganic particles according to claim 1, wherein the system contains a solvent. 3. The method for producing inorganic particles according to claim 2, wherein the solvent contains water. 4. The inorganic particle is a layered compound.
4. The method for producing inorganic particles according to any one of 3 to 3. 5. The layered compound is a swellable layered compound,
The method for producing the inorganic particles according to claim 4. 6. Surface-treated inorganic particles obtained by the method for producing inorganic particles according to claim 1.