JPH09301713A - New modified clay composite material, its production, resin composition consisting of modified clay composite material and resin, and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modified clay composite material which gives desired rheological characteristics to various kinds of matrix by addition of a small amt. of the composite material by introducing specified groups into the surface of silicate in a unit layer state under specified conditions. SOLUTION: This composite material is prepared by introducing one or more kinds of functional groups by covalent bonds into the surface of silicate which is in a unit layer state and is preferably a kaolin-based clay mineral, talc-based clay mineral or mica-based clay mineral. It is preferable that the distance between bottom planes of the unit layer state silicate is increased by the presence of the functional groups and/or the average layer thickness of the silicate in the c-axis direction is controlled to <=200Å. This clay composite material is prepared by adding physical external force on the silicate to cause cleavage to divide the silicate into a unit layer state and then adding a surface treating agent having one or more functional groups (e.g. silane coupling treating agent) to introduce one or more functional groups (e.g. amino groups and ethylene groups) into the surface of the silicate by covalent bonds.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel modified clay composite, a method for producing the same, a resin composition containing the modified clay complex, and a method for producing the same.

[0002]

2. Description of the Related Art Layered silicates in which a large number of unit layers are laminated have the property of being dispersed in various compounds serving as a matrix to adjust or improve rheological properties. Therefore, the layered silicate is used as a viscosity modifier for fluid fine chemical products such as paints, printing inks and cosmetics. Alternatively, the layered silicate is used as a filler or a reinforcing agent for the purpose of improving rigidity, mechanical properties, and physical properties such as heat distortion resistance of polymer materials such as rubber and plastic. Examples of the layered silicate used in this way include kaolin group clay minerals, talc, and mica group clay minerals.

However, there are various problems when the above-mentioned layered silicate is used as a viscosity modifier in various fluid chemical products. For example, when kaolin clay minerals, talc, mica clay minerals, etc. are mixed in various solvents, these layered silicates are hardly swollen, and many unit layers remain laminated. Exists. As described above, layered silicates such as kaolin group clay minerals, talc, and mica group clay minerals, which have poor swelling properties, have poor dispersibility in various solvents. When adjusting the rheological properties, it is necessary to increase the concentration. The presence of a large amount of layered silicate causes high cost and also causes problems such as impairing the color tone of the product. Furthermore, problems such as filter clogging and film breakage occur in the process of forming a film or the like.

There are also various problems when the layered silicate is used as a filler or a reinforcing agent. In many cases, these layered silicates have a low affinity for the macromolecular compound forming the matrix and no bond or very weak bond with the macromolecular compound. Therefore, various problems such as deterioration of impact properties of the obtained product and poor appearance of the molded product occur. Since the dispersibility in the matrix is insufficient when a large number of layered silicate unit layers are laminated, the rheology-modifying effect is hardly obtained even with a small amount of the compounded compound even when compounded with the polymer compound. Therefore, it is necessary to increase the mixing ratio. In addition, as a matter of course, if a large amount is blended, the cost becomes high.

In order to solve such a problem, the layered silicate is treated with a surface treatment agent such as a silane coupling agent to improve the adhesiveness at the interface between the layered silicate and the polymer. It is generally practiced to improve the impact characteristics. As such an example, for example, a composite system of a surface-treated filler obtained by treating a layered silicate with a silane coupling agent and a polyester resin is disclosed (JP-A-51-24653 and JP-A-51-24653). 51-24654
No.).

Further, in order to improve the dispersibility of the layered silicate, for example, in kaolinite belonging to the kaolin group clay mineral, the number of laminated layers is reduced by treatment with physical external force, etc., and the state is as close as possible to a unit layer. Non-laminated (delamination) grade cleaved up to 1 or fine grain size kaolinite with an average grain size of 0.3 μm is produced,
And is being used. Regarding the use of the delamination grade, for example, a composition in which delamination grade kaolinite is compounded in PET to improve the surface smoothness of a molded article, particularly a composition for a lamp reflector after metal plating is known. (JP-A-58-122789
Issue). Delamination grade Kaolinite is
U.S. Pat. Nos. 2,904,267 and 3,798,044,
It is manufactured by the method described in Japanese Patent No. 4125411.

For the purpose of improving the slipperiness or abrasion resistance while maintaining the transparency of polyester films and fibers, calcined kaolinite (JP-A-54-57).
No. 562) or synthetic spherical kaolinite (Japanese Patent Laid-Open No. Hei 2 (1999) -211).
-80455) is disclosed.

However, although the impact properties of the silicate-containing resin composition are improved to some extent by the treatment with the surface-treating agent such as the silane coupling agent as described above, they are never satisfied. In the conventional method as described above, since the surface-treated layered silicate is also an agglomerate of the μm order size in which the unit layers are laminated in multiple layers, clogging of the filter in the molding step of the film, breakage of the film, etc. Problem still occurs. As a product appearance problem, there is a fish eye, and in addition, there is a dropout in a magnetic tape.

In the case of the delamination grade kaolinite as described above, even if it is cleaved by a physical external force, when it is compounded in the resin, due to the characteristics of the crystal structure of kaolinite, the hydroxyl groups and oxygen atoms on the crystal surface There is a problem that the desired properties cannot be obtained because the unit layers are laminated again to return to the secondary agglomerates through hydrogen bonds between them. In order to prevent secondary agglomeration due to hydrogen bonds, there is also a technique of cleaving kaolinite and then performing a firing treatment to release structured water of kaolinite. However, in that case, there is a problem that the surface treatment of kaolinite becomes difficult because the hydroxyl group, which is a reaction point of kaolinite, disappears.

The fine particle size kaolin having an average particle size of 0.3 μm also has a large number of unit layers laminated even if the average particle size is 0.3 μm. Furthermore, this fine particle size kaolin also contains coarse particles of 3 to 4 μm.

The incorporation of calcined kaolinite or synthetic spherical kaolinite provides some improvement in the slipperiness of the film or fiber. However, the average particle size of these is 0.01 to 5.0 μm for synthetic spherical kaolinite and 0.7 to 5.0 μm for calcined kaolinite, and these are also formed by laminating a large number of unit layers. And contains coarse particles of μm size.

As described above, when the layered silicate unit layers are used while being laminated in multiple layers, a large number of parts should be added in order to improve mechanical properties such as elastic modulus and heat distortion resistance. I need. As a result, the cost is increased and the impact characteristics are also deteriorated.

Therefore, the present situation is that there has not yet been provided a modified silicate that can be well uniformly dispersed in various matrices and can give desired properties to the matrix even when added in a small amount.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems, and a desired rheology for a matrix such as various low molecular weight compounds, oligomers and high molecular weight compounds can be obtained by adding a small amount thereof. (EN) Provided are a modified clay composite capable of imparting properties, and a method for producing the same. A further object of the present invention is to provide a resin composition excellent in various properties such as mechanical properties and heat distortion resistance by forming a composite of this modified clay composite and a resin, and a method for producing the same. . Still another object of the present invention is to provide a method for economically and efficiently producing a thermoplastic resin composition using the modified clay composite.

[0015]

According to the present invention, there is provided a modified clay composite in which at least one functional group is covalently introduced on the surface of a silicate in a unit layer state.

In a preferred embodiment, the basal plane spacing of the silicate in the unit layer state is expanded by the presence of the functional group.

In a preferred embodiment, the silicate in the unit layer state has an average layer thickness in the c-axis direction of 200 Å or less.

In a preferred embodiment, the silicate is a kaolin group clay mineral, a talc group clay mineral, or a mica group clay mineral.

According to the present invention, there is provided a method of making a modified clay composite. This method comprises the steps of cleaving a silicate by applying a physical external force to separate the silicate into a unit layer state, and adding a surface treatment agent having at least one functional group, A step of covalently introducing a group having at least one functional group into the silicate separated into a unit layer state is included.

In a preferred embodiment, the surface treatment agent is a silane coupling treatment agent represented by the general formula (I) Y _n SiX _4-n (I), where n is 0 to 3 And Y is independently a hydrocarbon group having 1 to 25 carbon atoms, a vinyl group, an ester group, an ether group, an epoxy group, an amino group, a carbonyl group, a mercapto group, a halogen, and a hydroxyl group. Is a group having at least one functional group selected from the group, and X is independently a hydrolyzable group selected from the group consisting of an alkoxy group, an acyl group, and a halogen.

In still another embodiment, the surface treatment agent is represented by the following general formula (II), (III), or (IV)

[0022]

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A titanate-based coupling treatment agent represented by the formula: wherein R ¹ , R ² , R ³ , R ⁴ , and R are
⁵ are each independently a hydrocarbon group having 1 to 25 carbon atoms, a vinyl group, an ester group, an ether group, an epoxy group,
A functional group having at least one group selected from the group consisting of an amino group, a carbonyl group, a mercapto group, a halogen, a hydroxyl group, a phosphoric acid ester group, and a polyphosphoric acid ester group, and Z is a methylene group or a carbonyl group. .

Further, according to the present invention, there is also provided a resin composition containing the above modified clay composite and a resin.

In a preferred embodiment, the interlayer distance of the modified clay composite in the resin composition is 2 on average.
0 ° or more.

In another preferred embodiment, the above resin 1
The amount of the modified clay complex is 0.01 to 100 parts by weight.
400 parts by weight are included.

The method for producing the resin composition of the present invention is a method including a step of preparing a mixture of the modified clay complex and a polymerizable monomer, and a step of polymerizing the monomer in the mixture.

Another method for producing the resin composition of the present invention is a method in which the modified clay composite and the resin are melt mixed.

Another method for producing the resin composition of the present invention is a step of preparing a composition master product containing a thermoplastic resin and the modified clay composite, and the composition master product and the thermoplastic resin. And a step of melt-kneading.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The layered silicate used as a raw material for the modified clay composite of the present invention comprises a tetrahedral sheet mainly composed of tetrahedrons in which Si ⁴⁺ is surrounded by four O ^{2 −} , It is formed from an octahedron sheet consisting of octahedrons surrounded by six (OH) ⁻ or O ^{2 −} cations of Al ³⁺ , Mg ²⁺ and Fe ²⁺ . As this layered silicate, a 2: 1 layered layered silicate in which two octahedral sheets sandwich one tetrahedral sheet in a sandwich form to form a unit layer with one set of three sheets, Alternatively, there is a 1: 1 layer type layered silicate in which one octahedral sheet and one tetrahedral sheet form a set of two unit layers.

Examples of the 2: 1 layer type layered silicate include mica group clay minerals, talc, pyroferrite and chlorite.

Mica group clay minerals include muscovite, sericite, illite, fengite, glauconite, celadonite, paragonite, brammalite, etc. as the dioctahedral type, or biotite as the trioctahedral type. There are three octahedral illites. These may be used alone or in combination of two or more. Among the mica group or mica / smectite mixed layer minerals, those having a large amount of mica layer are also included in the mica group clay mineral. The mica that can be used in the present invention is a natural mica as described above, or a mica synthesized by a hydrothermal synthesis method (for example, B. Velde, Am. Miner., 50, 436 (196
5)) can also be preferably used.

Talc can be represented by the following chemical formula Mg ₃ Si ₄ O ₁₀ (OH) ₂ , but may contain a small amount of Fe ²⁺ , Ni, Al and the like. Willemsite substituted with Ni for talc Mg or Fe ²⁺ rich Minnesotaite may also be used. As the talc used in the present invention, in addition to the natural ones as described above, synthetic ones can be used. Synthetic talc is, for example, MgO / S
Starting with a composition ratio of iO ₂ of 0.75 or less, 2
It can be stably synthesized under the conditions of 00 to 300 ° C. and 1.5 kbar (JC Yang, J. Am. Ceram. Soc., 43, 542 (1
960)). Pyroferrite having a composition similar to talc uses a gel mixture of SiO ₂ : Al ₂ O ₃ = 2 to 4: 1 as a starting material, and is 400 to 500 ° C. and 225 to 225.
Synthesized by hydrothermal treatment at 1700 atm (W. Noll, Neues Jahrb. Miner. Geol. Beil. Bd., 7
0, 65 (1935)).

Chlorite is classified into a trioctahedral type and a dioctahedral type. The trioctahedral type has the following general formula (R _6-x ²⁺ R _x ³⁺ ) (Si _4-x Al _x ) O ₁₀ (OH) ₈ (wherein R ²⁺ is Mg, Fe, Represents at least one metal selected from the group consisting of Mn and Ni, R
³⁺ represents at least one metal selected from the group consisting of Al, Fe, and Cr, and X is 0.8 to
There is an ortho chlorite or a lept chlorite having a chemical composition represented by 1.6). Examples of these include clinochlore, chamosite, nimite, pennantite. Examples of the dioctahedral type include sudoite, kukkeite, and donbasite. The chlorite used in the present invention may be synthetic as well as natural ones as described above. Synthetic chlorite is, for example, 1.52 at 520 to 680 ° C. at a temperature of 520 to 680 ° C. using a Clinochlore composition 5MgO.Al ₂ O ₃ .3SiO ₂ .nH ₂ O as a starting material as shown in the following formula.
Method for synthesizing clinochlore by hydrothermal synthesis under the condition of ~ 2.03 kbar (HS Yoder, Am. J. Sci., Bow
en Vol., 569 (1952)) or using the following composition (Si _4-x Al _x ) (Mg _6-x Al _x ) O ₁₀ (OH) ₈ as a starting material, 0.25 <x ≦ 2 .0, a method of synthesizing chlorite at 450 to 620 ° C. (FHG
illery, Am, Miner., 44, 143 (1959)) and the like.

Examples of the 1: 1 layer type layered silicate include kaolin group clay minerals and serpentine.

Examples of kaolin group clay minerals include naturally or chemically synthesized kaolinite, dicalite, and halloysite, or their substitution products or derivatives, and these may be used alone or in combination of two or more. Synthetic kaolin clay minerals, for example,
It can be produced by the following method. For example, synthetic kaolinite is precipitated by mixing colloidal silica and alumina sol at a kaolinite composition ratio as a starting raw material, and setting the raw material concentration to a high value in a hydrothermal treatment method and treating at 150 to 300 ° C. (S . Tomura et al., Clays Clay
Miner., 33, 200 (1985)). Synthetic halloysite is obtained by leaching feldspar with a Soxhlet extractor (WE Parham, Clays Clay Miner., 17, 13 (196
9)).

As the serpentine, for example, chrysotile,
Examples include lizardite and amesite, and their substitution products, derivatives, or mixtures thereof can also be used.

These 2: 1 layer type and 1: 1 layer type layered silicates may be used alone or in combination of two or more kinds. It is desirable that the crystal structure of the silicate has a high degree of purity in which it is regularly stacked in the c-axis direction, but a so-called mixed layer mineral in which the crystal cycle is disturbed and a plurality of kinds of crystal structures are mixed can also be used.

In the modified clay composite of the present invention, at least one functional group is covalently bonded to the surface of the silicate in the unit layer state. In the present specification, “unit layer state” means that 50% or more of the modified clay composite is
This means that the average layer thickness is 100 Å or less, or that the average layer thickness of all the modified clay composites is 200 Å or less. Here, the average layer thickness can be obtained, for example, by measuring a plurality of layer thicknesses of the individual modified clay composites using an electron microscope or the like and determining an average value thereof.

The functional group introduced into the surface of the silicate in the unit layer state by a covalent bond is an arbitrary functional group depending on the type of matrix in which the modified clay composite of the present invention is dispersed, the purpose of use, and the like. possible. Preferably, this functional group is a hydrocarbon group having 1 to 25 carbon atoms, a vinyl group, an ester group, an ether group, an epoxy group, an amino group, a carbonyl group, a mercapto group, a halogen (preferably chlorine), and a hydroxyl group. It may be at least one functional group selected from the group consisting of: In the present specification, the hydrocarbon group is
It means a linear or branched (that is, having a side chain) saturated or unsaturated monovalent or polyvalent hydrocarbon group, and examples thereof include an alkyl group, an alkenyl group and an alkynyl group. In the present specification, for example, the term “alkyl group” is intended to include a polyvalent hydrocarbon group such as “alkylene group” unless otherwise specified. Similarly, alkenyl and alkynyl include alkenylene and alkynylene, respectively. Examples of the alkyl group include a lower alkyl group such as a methyl group and an ethyl group, or a higher alkyl group having a polymethylene chain structure such as a decyl group. It is also effective to combine two or more functional groups in order to adjust the polarity and the like in consideration of the affinity with the matrix.

The modified clay composite of the present invention comprises a step of separating the silicate into a unit layer state by cleaving the silicate by applying a physical external force (first step), and at least one functional group. By adding a surface treatment agent having a group,
It can be produced by a method including a step (second step) of introducing at least one functional group to the surface of the silicate in the unit layer state by covalent bond.

In the first step, when the silicate is cleaved by applying a physical external force to separate it into a unit layer state, the physical external force can be obtained by using a generally-used pulverizing method of filler. Can be added. As a general method of finely pulverizing a filler, for example, a method of utilizing hard particles can be mentioned. In this method, the hard particles, the silicate, and the solvent are mixed and stirred at high speed, and the silicate is separated into a unit layer state by physical collision between the hard particles and the silicate. The hard particles that are usually used are filler crushing beads, and examples thereof include glass beads and steel beads. These grinding beads are selected in consideration of the hardness of the silicate or the material of the stirrer, and are not limited to the above-mentioned glass or steel.
Since its particle size is also determined in consideration of silicate,
Although not limited by a numerical value, the diameter is 0.1 to 6.0.
Those in the range of mm are preferable. The solid dispersion concentration of the silicate separated into the unit layer state in the solvent can be freely set as long as it is within the concentration range in which the silicate can be sufficiently dispersed, and 1 to 15 wt% is preferable. The solvent used here is not particularly limited, but a solvent preferable for the surface treatment of the silicate in the second step, for example, an aqueous solvent is preferable. The aqueous solvent is an organic solvent compatible with water or a mixed solvent of such an organic solvent and water. As such a water-soluble organic solvent, alcohols such as methanol and ethanol, glycols such as ethylene glycol and propylene glycol, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether and tetrahydrofuran, etc. are used. Can be done. In the present specification, when simply referring to “aqueous solvent”, it is intended to include water itself in addition to the organic solvent or the mixed solvent of water and the organic solvent.

In the second step, the surface treatment agent having at least one functional group is added to the system composed of the silicate and the dispersion medium separated into the unit layer state in the first step to obtain the unit layer state. At least one functional group is covalently introduced onto the surface of the silicate. This functional group can be introduced by the reaction between the hydroxyl group existing on the surface of the silicate and the surface treatment agent.

The surface treatment agent used in the second step is various commonly used surface treatment agents, for example, a silane coupling treatment agent, a titanate coupling treatment agent, or an alumina coupling treatment agent. is there.

[0045] The silane-based coupling treatment agent is preferably a silane coupling treatment agent represented by the general formula _{(I) Y n SiX 4-} n (I). Here, n is an integer of 0-3. Preferably, Y is each independently a hydrocarbon group having 1 to 25 carbon atoms, a vinyl group, an ester group, an ether group, an epoxy group, an amino group,
It is a group having at least one functional group selected from the group consisting of a carbonyl group, a mercapto group, a halogen, and a hydroxyl group. X is a hydrolyzable group, preferably each independently selected from the group consisting of alkoxy groups, acyl groups, and halogens.

In the above formula (I), Y has 1 to 25 carbon atoms.
Examples of the hydrocarbon group are those having a polymethylene chain such as decyltrimethoxysilane, those having a lower alkyl group such as methyltrimethoxysilane, and unsaturated such as 2-hexenyltrimethoxysilane. Examples thereof include those having a hydrocarbon group and those having a side chain such as 2-ethylhexyltrimethoxysilane. Examples of the case where Y is a group having a vinyl group include vinyltrimethoxysilane, vinyltrichlorosilane, and vinyltriacetoxysilane.
Examples of the case where Y is a group having an ester group include γ
-Methacryloxypropyltrimethoxysilane. Examples of the case where Y is a group having an ether group include 2-ethoxyethyltrimethoxysilane. Examples of the case where Y is a group having an epoxy group include γ-glycidoxypropyltrimethoxysilane. When Y is a group having an amino group, examples thereof include γ-aminopropyltriethoxysilane and γ-aminopropyltriethoxysilane.
(2-aminoethyl) aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane. Examples of a case where Y is a group having a carbonyl group include γ-ureidopropyltriethoxysilane. An example of the case where Y is a group having a mercapto group is γ-mercaptotrimethoxysilane. Examples of the case where Y is a group having halogen include γ-chlorotriethoxysilane.

In addition to the above, a silane coupling agent in which Y in the formula (I) is a group having a hydroxyl group can also be used. Examples of such coupling treatment agents include:
N, N-di (2-hydroxyethyl) amino-3-propyltriethoxysilane may be mentioned. The hydroxyl groups can be in the form of silanol groups (Si-OH). Examples of those having a silanol group include oligomers of dimethyldihydroxysilane represented by the following formula.

[0048]

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Substitutes or derivatives of the above silane coupling agents can also be used. These silane coupling agents can be used alone or in combination of two or more.

The titanate type coupling treatment agent is
Preferably, the following general formula (II), (III), or (IV)

[0051]

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A titanate-based coupling agent represented by the following formula, wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ is preferably, independently of each other, 1 to 25 carbon atoms.
At least a group selected from the group consisting of a hydrocarbon group, a vinyl group, an ester group, an ether group, an epoxy group, an amino group, a carbonyl group, a mercapto group, a halogen, a hydroxyl group, a phosphoric acid ester group, and a polyphosphoric acid ester group. 1
Z may be a methylene group or a carbonyl group.

Examples of the monoalkoxy type titanate type treating agent represented by the general formula (II) include isopropyl tris isostearoyl titanate and isopropyl tris-
Examples thereof include n-dodecylbenzenesulfonyl titanate and isopropyldimethacryloyl isostearoyl titanate. Examples of the chelate-type titanate treatment agent represented by the general formula (III) include, for example, bis (dioctylpyrophosphate) -oxyacetate titanate, bis (dioctylpyrophosphate) -ethylene titanate, and dicumylphenyloxyacetate titanate. Is mentioned. Examples of the coordination type titanate treating agent represented by the general formula (IV) include, for example, tetraisopropyl-bis (ditridecylphosphite).
Examples include titanate, tetraoctyl-bis (ditridecyl phosphite) titanate, and the like. Substitutes or derivatives of the titanate-based treating agents as described above may also be used. These titanate coupling agents may be used alone or in combination of two or more.

Examples of the alumina-based coupling treatment agent used in the present invention include those represented by the following general formula:

[0055]

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(In the formula, R is a hydrocarbon group having 1 to 25 carbon atoms.) And the like, acetoalkoxyaluminum diisopropylate and the like. Substitutes or derivatives of these alumina-based coupling agents may also be used. These alumina-based coupling treatment agents may be used alone or in combination of two or more.

The above silane coupling treatment agent, titanate coupling treatment agent, and alumina coupling treatment agent may be used alone or in combination of two or more.

The step of covalently introducing a group having at least one functional group to the surface of the silicate in the unit layer state using the above-mentioned surface treatment agent is performed in a single step or multistep. obtain. In the case of a single step, the surface treatment agent as described above forms a covalent bond by the reaction of the silicate with the hydroxyl group present on the surface of the unit layer. In the case of multi-step, for example, in the first step, a reactive functional group such as a hydroxyl group or an epoxy group is introduced into the surface of the silicate by a surface treatment agent through a covalent bond. Then, as a second step, a compound having a functional group that reacts with the reactive functional group introduced in the first step is newly added and reacted. By this second step, it is possible to increase the chain length of the covalently bonded group or change the polarity. As the compound added in the second step, any compound may be used depending on the purpose, and examples thereof include an epoxy group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, and a hydroxyl group-containing compound.

The reaction between the silicate separated into unit layers and the surface treating agent in the second step is carried out by adding an appropriate amount of the surface treating agent to the dispersion liquid containing the separated silicate. . The dispersion liquid in which the separated silicate is present is usually a dispersion liquid dispersed in an aqueous solvent. Therefore, when the silicate is separated into the unit layer state by using the aqueous solvent together with the physical external force in the first step, the dispersion liquid obtained in the first step can be used as it is.
Alternatively, the silicate in the unit layer state obtained in the first step may be dispersed in an aqueous solvent to prepare a dispersion liquid in advance. The amount of the surface treatment agent added to the dispersion liquid can be adjusted so as to be as close as possible to the polarity value in consideration of the polarity of the compound used as the matrix in which the finally obtained modified clay complex is dispersed. If necessary, a plurality of surface treatment agents having different functional groups can be used in combination. Therefore,
The amount of the surface treatment agent added is not limited by the numerical value. The reaction proceeds sufficiently at room temperature, but may be heated if necessary. The maximum temperature during heating is governed by the heat resistance of the functional group of the surface treatment agent used, and can be arbitrarily set as long as it is below its decomposition temperature.

Furthermore, after the second step, an isolation step can be performed as a third step. When the functional group introduced in the second step is non-polar, the modified clay complexes are secondarily aggregated and precipitated in the aqueous solvent. The precipitated modified clay complex can be easily isolated by ordinary filtration or centrifugation. On the contrary, when the introduced functional group is polar and has a sufficient affinity for the aqueous solvent, the modified clay complex is so finely dispersed that it cannot be isolated by a usual filtration or centrifugation method. In this case, an aqueous dispersion containing the modified clay complex is put into a non-polar solvent such as hexane to make the modified clay complex into agglomerates of micron order size and isolated by filtration or centrifugation. The isolated modified clay complex is dried by a usual method, and after drying, it is ground if necessary to obtain a final product.

The modified clay composite of the present invention obtained as described above is separated into unit layers as described above. The average layer thickness of the silicate in the unit layer state in the c-axis direction is preferably 200 Å or less, more preferably 150 Å or less, and further preferably 100 Å or less.

In the modified clay composite of the present invention, by introducing a functional group on the surface of the silicate, the interlayer distance of the silicate in the unit layer state can be expanded. this is,
It is considered that this is due to the interaction between the introduced functional groups.

The modified clay composite of the present invention obtained as described above has an affinity for various matrices and therefore can be well dispersed in various matrices. The modified clay composite of the present invention is uniformly dispersed in the unit layer state without agglomeration even in the matrix. By “uniformly dispersed” is meant that the modified clay complex is present in a matrix of various low molecular weight compounds, oligomers, polymeric compounds, etc., evenly dispersed. As described above, the modified clay composite of the present invention uniformly dispersed in the matrix in a unit layer state has an excellent thickening effect on the matrix and a modifying / modifying effect such as rheological properties even in a small amount. This is because the compatibility between the functional group introduced on the surface of the silicate by a covalent bond and the matrix is good, or the physical interaction such as a hydrogen bond between the functional group and the matrix or the functional group. It is considered that the solvent or the polymer compound which is the matrix penetrates between the layers of the silicate and widens the layer interval due to a chemical reaction with the matrix.

The characteristics of the modified clay composite of the present invention, and the characteristics such as the dispersion state when they are dispersed in a matrix are selected from the following analytical items, depending on the need and purpose, and may be one or more. Can be selected and evaluated. The measurement can be done by conventional methods: (1) infrared spectroscopy (I
R), (2) X-ray diffraction method, (3) Nuclear magnetic resonance method (NM
R), (4) chemical analysis method, (5) rheological properties in various polar solvents, (6) swelling power in various polar solvents,
(7) Thermal analysis (DSC), (8) Transmission electron microscope (T
EM), (9) dynamic viscoelastic spectrum, etc.

When the functional group species introduced into the surface of the modified clay composite of the present invention by a covalent bond, and a plurality of types of functional groups are introduced by a covalent bond, the ratio is the Fourier transform (FT). -May be measured using IR. When the modified clay complex is a powder, a sufficiently dried modified clay complex and a window material such as powdered potassium bromide (KBr) etc. are sufficiently mixed in a mortar or the like at a predetermined ratio, It can be measured by the permeation method by tableting under pressure. When more accurate measurement is desired, or when the amount of functional groups introduced by covalent bonding is small, a sufficiently dried powdered modified clay complex is directly subjected to the diffuse reflection method (DRIFT). It is preferable to measure.

The formation of the modified clay complex can be easily confirmed by measuring the diffraction peak of the (001) plane by the small angle X-ray diffraction method (SAXS). For example, a unit layer of halloysite that is preferably used as a kaolin group clay mineral has a bottom spacing of 7Å in a dehydrated state and 10Å at normal temperature and humidity. On the other hand, the bottom spacing of the dispersion layer in the unit layer state of the modified clay composite of the present invention depends on the type of the surface treatment agent introduced, but in any case, it is larger than 10Å. in this way,
It is confirmed that the modified clay complex is generated because the bottom surface interval of the unit layer is expanded.

The inter-layer distance between the dispersed layers of the modified clay complex in various matrices can be measured by the above SAXS, or can also be measured by using a transmission electron microscope (TEM). For example, when the dispersion state of the solvent in which the modified clay complex of the present invention is dispersed or the resin composition containing the modified clay complex of the present invention is observed by TEM, the layers of the dispersion layer of the modified clay complex in the unit layer state It was confirmed that the distance was larger than 20Å.

The rheological properties of the dispersion system in which the modified clay composite of the present invention is dispersed can be easily grasped by visually observing its viscous behavior, but it is desirable to measure it more quantitatively. In this case, for example, it can be easily measured by a B-type viscometer.

Since the modified clay composite of the present invention has good dispersibility in various matrices as described above, it can be used in various fields.

The resin composition of the present invention contains the modified clay composite of the present invention obtained as described above and a resin. The resin used in the resin composition of the present invention may be any thermoplastic resin or thermosetting resin. As the thermoplastic resin, polyester resin, polyamide resin, vinyl-based polymer compound, polyimide resin, polycarbonate resin, polyphenylene sulfide, polyphenylene oxide, polyacetal, polysulfone, polyether sulfone, fluororesin, polyolefin, polyolefin-based copolymer, elastomer , Rubber, and any other thermoplastic resin. One or more of these thermoplastic resins may be used.

Examples of the thermosetting resin include epoxy resin, phenol resin, melamine resin, unsaturated polyester resin, alkyd resin, furan resin, urea resin, polyurethane, aniline resin, and thermosetting polyimide resin. Can be mentioned. One or more of these thermosetting resins may be used.

The molecular weight of the resin used in the present invention is selected in consideration of the molding fluidity in the molding step and the physical properties of the final product, and it is not preferable if it is too low or too high. Since the optimum molecular weight is mainly determined by the primary structure of each resin, it is necessary to set an appropriate molecular weight for each resin.

For example, as for the molecular weight of the thermoplastic polyester resin, the intrinsic viscosity measured at 25 ° C. using a phenol / tetrachloroethane (5/5 weight ratio) mixed solvent is 0.3 to 2.0 (dl · g ⁻ Those which are ¹ ) are preferred.
When the intrinsic viscosity is less than 0.3 (dl · g ⁻¹ ), the molded product of the obtained polyester resin composition has low mechanical properties and impact resistance, while the intrinsic viscosity is 2.0 (dl · g ⁻¹ ). ^-1 )
If it is larger than the above range, there is a problem in processability such as fluidity during molding, which is not preferable.

In the resin composition of the present invention, the resin 100
The modified clay complex is preferably 0.01% by weight.
To 400 parts by weight, more preferably 0.1 to 150 parts by weight, still more preferably 0.5 to 50 parts by weight.
If it is less than 0.01 part by weight, the reinforcing effect due to the addition of the modified clay complex cannot be sufficiently obtained, which is not preferable. If it exceeds 400 parts by weight, the amount of the resin is reduced, and the excellent mechanical properties, electrical properties, chemical resistance, processability, and appearance of the molded product, which are peculiar to the resin, are impaired, which is not preferable.

In the resin composition of the present invention, the interlayer distance of the modified clay composite may be preferably 20 Å or more, more preferably 30 Å or more, still more preferably 40 Å or more on average.

The resin composition of the present invention can be prepared by combining the modified clay composite and the resin by various conventional methods. When manufacturing the resin composition,
The dispersion medium (solvent) used in the production of the modified clay complex is usually
Removed in advance. However, when the solvent does not adversely affect the deterioration of the resin and the like, the drying step of removing the solvent from the modified clay complex and the crushing step are omitted, and the modified clay complex containing the solvent is used to prepare the resin composition. Manufacture of goods can be performed. As described above, the modified clay complex containing the solvent is preferable because it has good uniformity with respect to the resin.

The resin composition of the present invention comprises, for example, a mixing step of mixing the modified clay composite of the present invention previously produced and isolated with a polymerizable monomer, and a polymerization step of polymerizing the polymerizable monomer in the mixture. Can be manufactured by a manufacturing method including.

The resin composition of the present invention is preferably produced by the following method. That is, by reacting a silicate separated into a unit layer state and a surface treatment agent in a dispersion medium, and introducing a group having at least one functional group to the surface of the silicate by a covalent bond, Production including a surface treatment step for forming a modified clay composite, a mixing step for mixing the modified clay composite containing a dispersion medium and a polymerizable monomer, and a polymerization step for polymerizing the polymerizable monomer in the mixture Is the way. Here, the dispersion medium and the polymerizable monomer may be the same or different.

The polymerizable monomers used to obtain the above resin are exemplified below. The monomer for obtaining the polyester resin may be an acid component containing an aromatic dicarboxylic acid or its ester derivative as a main component, and a diol component. As the aromatic dicarboxylic acid, for example,
Terephthalic acid, isophthalic acid, orthophthalic acid, 2,5
-Naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,
4'-diphenylsulfone dicarboxylic acid, 4,4'-
Examples thereof include diphenyl isopropylidene dicarboxylic acid and the like, and their substitution products or derivatives can also be used. Two or more of these monomers may be mixed and used.
If the amount is a small amount that does not impair the properties of the obtained polyester resin, one or more kinds of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, sebacic acid, etc. are mixed with these aromatic dicarboxylic acids. Can be used. As the diol component, ethylene glycol,
Aliphatic diols such as propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, etc., alicyclic diols such as 1,4-cyclohexanedimethanol, bis (4,4'-dihydroxidiphenyl) ethane, etc. Aromatic diols such as, and their substitution products or derivatives may also be used. Two or more of these may be mixed and used. Furthermore, if the amount is such that the elastic modulus of the polyester resin is not significantly reduced, long-chain diols (eg, polyethylene glycol, polytetramethylene glycol, etc.), and alkylene oxide addition polymers of bisphenols (eg, bisphenol A). Ethylene oxide addition polymer, etc.) can be mixed.

As the monomer for obtaining the polyamide resin, amino acids such as 6-amino-n-caproic acid and 12-aminododecanoic acid, adipic acid salt (nylon salt) of hexamethylenediamine, and caprolactam, butyrolactam, And lactams such as capryl lactam and dodecanolactam.

As the monomer for obtaining the vinyl polymer compound, ethylene, propylene, butadiene, vinyl chloride, vinylidene chloride, styrene, acrylic acid, methacrylic acid, t-butylacrylamide, acrylonitrile, norbornadiene, N-vinylcarbazole, Examples thereof include vinyl pyridine, vinyl pyrrolidone, 1-butene, isobutene, vinylidene cyanide, 4-methylpentene, vinyl acetate, vinyl isobutyl ether, methyl vinyl ketone, phenyl vinyl ketone, phenyl vinyl sulfide and acrolein.

Examples of the monomer for obtaining the fluororesin include tetrafluoroethylene and chlorotrifluoroethylene.

Other resins can also be obtained from any of the commonly used monomers.

The resin composition of the present invention can also be produced by directly melt mixing the modified clay composite of the present invention with a resin. This melt mixing is carried out by sufficiently mixing the modified clay composite of the present invention and the resin with a powerful stirrer, and then kneading a known kneader (for example, an extruder and a Banbury mixer).
Can be carried out by a process of melt kneading.

When a thermoplastic resin is used as the resin, the resin composition of the present invention can be produced economically and efficiently, particularly by using the method described below. That is, first, a composition master product containing a thermoplastic resin and the modified clay composite of the present invention is prepared, and then the composition master product and the thermoplastic resin are melt-kneaded to obtain the resin composition of the present invention. Get things. Preferably, the composition master product contains 10 to 40 parts of the modified clay complex based on 100 parts by weight of the thermoplastic resin.
0 parts by weight, more preferably 15 to 300 parts by weight, still more preferably 20 to 200 parts by weight. The composition master product can be prepared by any method described above as a method for producing the resin composition of the present invention, but preferably, the modified clay complex containing a dispersion medium and a polymerizable monomer are mixed. It is prepared by a method including a mixing step and a polymerization step of polymerizing the polymerizable monomer in the obtained mixture.

The thermoplastic resin melt-kneaded with the composition master product is usually the same resin as the composition master product, but other thermoplastic resins may be used if necessary. The thermoplastic resin to be melt-kneaded with the composition master product is used in any amount, but preferably the composition master product 10
The thermoplastic resin is kneaded in an amount of 1 to 10000 parts by weight, more preferably 10 to 1000 parts by weight, relative to 0 parts by weight.
The melt-kneading of the composition master product and the thermoplastic resin can be carried out by a commonly used melt-kneading method, for example, a process of melt-kneading with a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll or the like. Particularly, it is efficient to use a meshing twin-screw extruder having a kneading disk portion and a Banbury mixer.

By using the method of preparing the composition master product in advance as described above, it becomes possible to easily produce resin compositions of various compositions from one type of composition master product. The melt-kneading method is simpler than the method for producing a resin composition comprising three steps of surface treatment, mixing and polymerization. Therefore, by preparing the composition master products collectively in advance and performing the melt-kneading step as needed, it is possible to significantly save the manufacturing equipment, energy, time, etc., and it is easy to switch the manufacturing type. become.

The resin composition of the present invention may be used depending on the purpose.
Additives such as pigments or dyes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, flame retardants, and antistatic agents, or glass fibers, inorganic fillers, inorganic fibers, metal fibers. , Metal flakes, and reinforcing agents such as carbon fibers may be added. The resin composition of the present invention can be molded by injection molding or hot press molding, and can also be used for blow molding. Alternatively, the resin composition of the present invention can be subjected to reaction molding in a mold to obtain a molded body.

The resin composition of the present invention has an excellent appearance and further excellent mechanical properties or heat distortion resistance, and therefore, for example, automobile parts, household electric appliance parts, household products, packaging materials, and other general industrial materials. Can be suitably used.

The modified clay composite of the present invention can be used in various applications as a thickening agent or gelling agent for various solvents having various polarities. This object can be easily achieved by adding the modified clay complex to a solvent and dispersing it by an operation such as ordinary stirring. The more the amount of the modified clay complex added is such that it can be dispersed, the higher the thickening effect is. Since the specific amount of addition may vary depending on the solvent, it cannot be determined unconditionally, but generally 0.01 to 5
It is added in an amount of 0% by weight, preferably 0.05 to 30% by weight.

It is also possible to disperse the modified clay composite of the present invention in various solvents having various polarities to obtain a modified clay composite dispersion. Examples of the solvent in which the modified clay complex of the present invention can be dispersed include benzene, toluene, aromatic hydrocarbons such as xylene, ethers such as tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, methanol, ethanol. , Lower alcohols such as propanol and isopropanol, higher alcohols such as decanol and hexanol, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, halogenated hydrocarbons such as perchloroethylene and chlorobenzene, amides such as dimethylformamide, Esters such as ethyl acetate, and solvents such as dioctyl phthalate, dimethyl sulfoxide, methyl cellosolve, N-methyl-2-pyrrolidone and the like. In addition, polysiloxanes and silicone oils can also be dispersed. These solvents may be used alone or in combination of two or more.

The above modified clay composite dispersion can be obtained by adding the modified clay composite of the present invention to an arbitrary solvent and stirring. Alternatively, such a modified clay composite dispersion is directly produced without isolating the modified clay composite obtained after the surface treatment in the second step of the method for producing a modified clay composite of the present invention. You can also do it. That is, after the desired medium is added after the surface treatment, the solvent used in the surface treatment of the second step is removed by an ordinary fractional distillation operation using an apparatus equipped with a rectification column to obtain the modified clay of the present invention. A modified clay composite dispersion comprising the composite and a new medium can be obtained.

According to the method of the present invention, a functional group can be introduced by covalent bonding between the layers of the modified clay composite. It is considered that the functional group introduced by this covalent bond creates a layer space. By utilizing this layer space, it is also possible to utilize the modified clay composite of the present invention as an organic substance storage agent, sustained release agent, catalyst, adsorbent, carrier, filler, etc.

[0094]

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.

Example 1 (Kaolin Group Clay Mineral) Kaolinite from Georgia, USA and halloysite from New Zealand were used.

(Production of modified clay complex by silane coupling treatment) In a container having a volume of 250 ml, 50 m of pure water was added.
l, 150 g of spherical glass beads having an average particle diameter of 0.8 mm,
10 g of kaolinite was added and stirred at 5000 rpm for 10 minutes. Then, while stirring at 300 rpm, 600 ml of pure water was added to remove the glass beads. Thereafter, 2.5 g of a silane treatment agent NH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ represented by the following formula was gradually added dropwise using a simple pipette. About 30 minutes after the addition of the silane treating agent, it became cloudy. After continuing stirring for about 3 hours, methyl ethyl ketone was added until the silanized clay aggregated and the system became cloudy, filtered and dried to obtain the modified clay complex (a) of the present invention.

(Identification of Covalently Bonded Functional Group by FT-IR) The modified clay complex (a) of the present invention was added to tetrahydrofuran (THF) and stirred for 15 minutes to physically adsorb the surface treatment agent. Was washed. The supernatant was separated by centrifugation. This washing was repeated three times. Approximately 1 mg of fully modified modified clay complex of the present invention and approximately 200 KBr powder.
After thoroughly mixing mg with mg in a mortar, a KBr disk for measurement was prepared using a tabletop press. Then, it measured by the transmission method using an infrared spectroscope. An MCT detector was used as a detector, and the resolution was 4 cm ⁻¹ and the number of scans was 100 times. In the modified clay complex (a), absorption bands derived from amino groups and ethylene groups were observed by the above method.

(Measurement of Bottom Spacing of Modified Clay Complex by Small Angle X-ray Diffraction Method) X-ray generator (RU-2 manufactured by Rigaku Denki Co., Ltd.)
00B), target CuKα ray, Ni filter, voltage 40 kV, current 200 mA, scan angle 2θ = 0.
The modified clay complex (a) of the present invention and the modified clay complex (a) are dispersed in ethylene glycol at a concentration of 5 wt% under the measurement conditions of 2-16.0 ° and step angle = 0.02 °. The (001) basal plane spacing in the dispersion thus obtained was measured. The results are shown in Table 1.

(Thickening effect) Modified clay composite (a) of the present invention
The presence or absence of the thickening effect in the dispersion obtained by dispersing the above in ethylene glycol at a concentration of 5 wt% was visually observed. The results are shown in Table 1.

Comparative Example 1 The (001) basal plane spacing was measured in the same kaolinite as in Example 1 and in a dispersion obtained by dispersing this kaolinite in ethylene glycol at a concentration of 5 wt%. In addition, the thickening effect of this dispersion was visually observed. The results are shown in Table 1.

Example 2 (Production of Modified Clay Complex by Titanate Coupling Treatment) A container having a capacity of 250 ml was charged with 50 ml of pure water, 150 g of spherical glass beads having an average particle diameter of 0.8 mm and 10 g of halloysite, and 5000 rpm, 10 rpm. Stir for minutes. Then 600 ml of pure water while stirring at 300 rpm
Was added and the glass beads were removed. Was then slowly added dropwise using a simple pipette titanate treating agents i-PrO-Ti- (OC ( O) C 17 H 35) 3 2.5g of the following formula. About 3
After continuing stirring for a period of time, n-hexane was added to the extent that the titanate-treated clay aggregated and the system became cloudy, filtered and dried to obtain the modified clay complex (b) of the present invention.

(Identification of Covalently Bonded Functional Group by FT-IR) As a result of measurement in the same manner as in Example 1, in the modified clay composite (b) of the present invention, carbonyl group, ester group, and ethylene group The derived absorption band was obtained.

(Measurement of Bottom Spacing of Modified Clay Complex by Small Angle X-ray Diffraction Method) In the same manner as in Example 1, the modified clay complex (b) of the present invention and 2-pentanone were modified with the modified clay complex. The (001) basal plane spacing in the dispersion obtained by dispersing (b) at a concentration of 5 wt% was measured. The results are shown in Table 1.

(Thickening Effect) Modified Clay Composite (b) of the Present Invention
Was dispersed in 2-pentanone at a concentration of 5 wt%, and the presence or absence of a thickening effect in the dispersion obtained was visually observed. The results are shown in Table 1.

Comparative Example 2 The (001) basal plane spacing in the same halloysite as in Example 2 and a dispersion obtained by dispersing this halloysite in 2-pentanone at a concentration of 5 wt% was measured. Further, the presence or absence of a thickening effect in this dispersion was visually observed. The results are shown in Table 1.

[0106]

[Table 1]

Example 3 (Mica group clay mineral) As the mica, a natural mica produced in India was used.

(Production of Modified Clay Complex by Silane Coupling) A modified clay complex (c) was obtained in the same manner as in Example 1 except that the above-mentioned natural mica was used as the layered silicate.

(Production of Resin (Thermoplastic Polyester) Composition) Modified clay composite containing water as a dispersion medium
(a) (65 g) and 2020 g of ethylene glycol (hereinafter abbreviated as EG), which is a monomer and serves as a dispersion medium, are mixed, and then water is completely fractionated under reduced pressure at 100 ° C. to obtain the modified clay complex (a). ) / EG dispersion was obtained. In a 7-liter scale autoclave equipped with a rectification column and a distillation tube,
This dispersion, dimethyl terephthalate (hereinafter abbreviated as DMT) 2020 g, hindered phenolic stabilizer (AO60, manufactured by Asahi Denka Co., Ltd.) 6.0 g, titanium tetrabutoxide (Ti (OBu) ₄ ) 0.4 as an ester exchange catalyst.
9 g were added. The mixture was stirred at a reaction temperature of about 190 ° C. for about 4 hours to transesterify DMT and EG to generate bishydroxyethyl terephthalate (hereinafter abbreviated as BHET). Then, the rectification column is removed, 0.20 of a polymerization catalyst, antimony trioxide (Sb ₂ O ₃ ) is added, and the reaction temperature is about 280 ° C. under reduced pressure in the presence of the modified clay complex B.
A thermoplastic polyester resin composition (A) was obtained by polymerizing HET to form polyethylene terephthalate (hereinafter abbreviated as PET).

(Measurement of Intrinsic Viscosity) Pelletized thermoplastic polyester resin composition (A) was dried at 140 ° C. for 4 hours or more, and about 100 mg was precisely weighed to obtain phenol / 1,
20 ml of 1,2,2-tetrachloroethane = 5/5 (weight ratio) mixed solution was added and dissolved at 120 ° C. Using an Ubbelohde viscometer, the solution viscosity was measured at a measurement temperature of 25 ° C. using an automatic viscosity measuring device (Viscotimer manufactured by Lauda), and the intrinsic viscosity (IV) was measured from the following formula.

IV = {ln (t / t ₀ )} / C (where, t: solution viscosity, t ₀ : solvent viscosity, C: concentration (g / dl)) (preparation of injection-molded test piece) pellet form After drying the thermoplastic polyester resin composition (A) of 4 at 140 ° C. for 4 hours,
Using an injection molding machine with a mold clamping pressure of 75t, set temperature 270 ° C,
ASTM dumbbell molded product (A) under the condition that the mold temperature is 120 ° C
Was produced.

(Measurement of Bottom Spacing by Small Angle X-ray Diffraction (SAXS)) A dumbbell molded article was prepared in the same manner as in Example 1.
The X-ray diffraction measurement of (A) was performed. The results are shown in Table 2.

(Appearance of injection-molded product) The glossiness and color tone were visually observed. The surface of the molded product (A) was glossy, the color tone was uniform, and a molded product having a beautiful appearance was obtained.

Comparative Example 3 (Production of Composition Containing Natural Mica and PET) Mica and PET were prepared in the same manner as in Example 3 except that the same Indian natural mica as in Example 3 was used. A composition (B) was obtained.

(Intrinsic viscosity) A composition was prepared in the same manner as in Example 3.
As a result of measuring the intrinsic viscosity of (B), it was IV = 0.62.

(Interval between Bottom Surfaces of Mica) An ASTM dumbbell molded article B obtained by injection molding the resin composition (B) in the same manner as in Example 3 was subjected to SAXS measurement in the same manner as in Example 3. . Table 2 shows the results.

(Appearance of Molded Product) The surface of the molded product (B) was rough and lacked in glossiness, which was not preferable in appearance.

[0118]

[Table 2]

Example 4 (Production of Composition Master Product) Modified clay complex (a) (dry weight 1000 g) containing water as a dispersion medium, and ethylene glycol (hereinafter referred to as a dispersion medium) serving as a monomer. After mixing 5000 g (abbreviated as EG), water was completely fractionated under reduced pressure at 100 ° C. to obtain a modified clay complex (a) / EG dispersion. This dispersion, dimethyl terephthalate (hereinafter abbreviated as DMT) 2020 g, hindered phenol stabilizer (AO60, manufactured by Asahi Denka Co., Ltd.) was placed in a 7-liter scale autoclave equipped with a rectification column and a distillation tube.
6.0 g and 0.49 g of titanium tetrabutoxide (Ti (OBu) ₄ ) as a transesterification catalyst were added. The mixture was stirred at a reaction temperature of about 190 ° C. for about 4 hours to transesterify DMT with EG to generate bishydroxyethyl terephthalate (hereinafter abbreviated as BHET). Then, the rectification column was removed, and the polymerization catalyst antimony trioxide (S
b ₂ O ₃ ) 0.20 g was added and the reaction temperature was about 280 ° C.
Polyethylene terephthalate (hereinafter abbreviated as PET) is obtained by polymerizing BHET in the presence of a modified clay complex under reduced pressure.
To form a composition master product having a weight ratio of PET / modified clay composite = 100/50 (parts by weight).

(Production of PET) In a 25 liter scale autoclave equipped with a rectification column and a distillation column,
EG 10000 g, DMT 9700 g, hindered phenolic stabilizer (AO60 manufactured by Asahi Denka Co., Ltd.) 28.8 g,
2.35 g of Ti (OBu) ₄ was added to the reaction temperature of about 1
Transesterify DMT and EG at 90 ° C, then use BHET
Was generated. Then, the rectification column was removed, 0.96 g of Sb ₂ O ₃ was added, and the reaction system was depressurized at a reaction temperature of about 280 ° C. to polymerize PET. The obtained PET had an intrinsic viscosity of 0.64 (dl · g ⁻¹ ). The above polymerization was carried out twice to obtain a total of 18800 g of PET.

(Production of Resin Composition by Melt Kneading Composition Master Product and PET) 3000 g of the composition master product obtained above, 18000 g of PET, and 54 g of hindered phenol-based stabilizer (AO60 manufactured by Asahi Denka Co., Ltd.) Add and use the same direction twin-screw extruder to set temperature 280
By melt-kneading at ℃, 100 rpm,
Weight ratio PET / modified clay composite = 100/5 (parts by weight)
21000 g of the resin composition (C) was prepared.

(Production of injection-molded test piece) The obtained resin composition (C) was pelletized, and AST was prepared in the same manner as in Example 3.
An M dumbbell molded product (C) was produced.

(Measurement of Intrinsic Viscosity) Intrinsic viscosity of the composition (C) was measured by the same method as in Example 3 and found to be IV = 0.63.
Met.

(Measurement of Bottom Surface Interval) The dumbbell molded article (C) was subjected to X-ray diffraction measurement in the same manner as in Example 1. Table 3 shows the results.

(Appearance of Injection Molded Article) The gloss and color tone were visually observed. The surface of the molded product (C) was glossy, the color tone was uniform, and a molded product having a beautiful appearance was obtained.

(Manufacturing Time) The time from when the raw materials were charged until the resin composition was obtained was measured. However, the time required for assembling and preparing the experimental equipment and manufacturing the modified clay composite is not included. The results are shown in Table 3.

Example 5 A resin composition (D) was obtained in the same manner as in Example 4 except that 100 g of the modified clay composite was used. The weight ratio is PET / modified clay composite = 100/5 (parts by weight). To obtain 21000 g of the composition in the same weight ratio, the same method was used.
I went over and over again.

(Measurement of Intrinsic Viscosity) As a result of measuring the intrinsic viscosity of the composition (D) by the same method as in Example 3, IV = 0.6.
It was 2.

(Measurement of Bottom Distance) Dumbbell molded article (D) was subjected to X-ray diffraction measurement in the same manner as in Example 1. Table 3 shows the results.

(Appearance of Injection Molded Product) The glossiness and color tone were visually observed. The surface of the molded product (D) was glossy, the color tone was uniform, and a molded product having a beautiful appearance was obtained.

(Manufacturing time) Measurement was carried out in the same manner as in Example 4.
The results are shown in Table 3.

[0132]

[Table 3]

As is clear from a comparison of Examples 4 and 5, the method of preparing the composition master product
The time required to obtain the same amount of the resin composition can be significantly shortened, and the resin composition can be manufactured extremely efficiently and economically. Even when this method is used, the modified clay complex in the resin composition is uniformly dispersed in the resin matrix, and it is clear that the dispersibility is maintained.

[0134]

As described above, according to the present invention, a modified clay composite capable of imparting desired rheological properties to a matrix such as various low molecular weight compounds, oligomers, and high molecular weight compounds even when added in a small amount, and A manufacturing method is provided.

According to the present invention, the affinity between various matrices and the modified clay complex can be enhanced by selecting the type and combination of the functional groups to be introduced on the surface of the silicate in the unit layer state. Therefore, for example, the modified clay composite of the present invention makes it possible to adjust the rheological properties such as viscosity of solvents having various polarities. The modified clay complex of the present invention has an affinity with various solvents or polymer compounds, is easily finely dispersed, and has an excellent rheology modifying effect even when added in a small amount. , Sanitizers, adhesives, paints, coating materials, various plastic products, various products such as the textile industry or industrial processes, can be used as compositions such as viscosity modifiers, dispersants, emulsifiers, binders, etc. It is useful. The modified clay composite of the present invention can be easily obtained with a commonly used surface treating agent such as a silane type treating agent.

According to the present invention, a resin composition excellent in various properties such as mechanical properties and heat distortion resistance and a method for producing the same are provided by forming a composite of the modified clay composite and a resin. . In the resin composition of the present invention, the modified clay composite of the present invention is uniformly and finely dispersed in the resin matrix at the nanometer level.
Provided is a resin composition having excellent mechanical properties and heat distortion resistance.

The present invention further provides a method for economically and efficiently producing a thermoplastic resin composition using the modified clay composite of the present invention. According to this method, the time required to obtain the same amount of the resin composition can be greatly shortened by preparing the composition master product in advance.

Claims (15)

[Claims] 1. At least one functional group is covalently introduced onto the surface of a silicate in a unit layer state,
Modified clay complex. 2. The modified clay composite according to claim 1, wherein the bottom spacing of the silicate in the unit layer state is expanded by the presence of the functional group. 3. The modified clay composite according to claim 1, wherein the silicate in the unit layer state has an average layer thickness in the c-axis direction of 200 Å or less. 4. The modified clay composite according to claim 1, wherein the silicate is a kaolin group clay mineral. 5. The modified clay composite according to claim 1, wherein the silicate is a talc group clay mineral. 6. The silicate is a mica group clay mineral,
The modified clay composite according to claim 1. 7. A method for producing the modified clay composite according to claim 1, wherein the silicate is cleaved by applying a physical external force to the silicate to form a unit layer. And a step of adding a surface treatment agent having at least one functional group to introduce a group having at least one functional group onto the surface of the silicate in the unit layer state by covalent bond. Including the method. 8. The surface treatment agent is a silane coupling treatment agent represented by the general formula (I) Y _n SiX _4-n (I), wherein n is an integer of 0 to 3. , Y are each independently selected from the group consisting of hydrocarbon groups having 1 to 25 carbon atoms, vinyl groups, ester groups, ether groups, epoxy groups, amino groups, carbonyl groups, mercapto groups, halogens, and hydroxyl groups. The method according to claim 7, wherein X is a hydrolyzable group selected from the group consisting of an alkoxy group, an acyl group, and a halogen, each group having at least one functional group. 9. The surface treatment agent is represented by the following general formula (II):
(III), or (IV) Is a titanate-based coupling treatment agent, wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently a hydrocarbon group having 1 to 25 carbon atoms or a vinyl group. A functional group having at least one group selected from the group consisting of an ester group, an ether group, an epoxy group, an amino group, a carbonyl group, a mercapto group, a halogen, a hydroxyl group, a phosphoric acid ester group, and a polyphosphoric acid ester group. , Z is a methylene group or a carbonyl group. 10. A resin composition comprising the modified clay composite according to claim 1 and a resin. 11. The resin composition according to claim 10, wherein the modified clay composite has an interlayer distance of 20 Å or more on average. 12. The resin composition according to claim 10, wherein the modified clay complex is contained in an amount of 0.01 to 400 parts by weight based on 100 parts by weight of the resin. 13. A method for producing the resin composition according to any one of claims 10 to 12, wherein the mixture of the modified clay composite according to any one of claims 1 to 6 and a polymerizable monomer is used. A method comprising preparing and polymerizing the monomer in the mixture. 14. A method for producing the resin composition according to any one of claims 10 to 12, wherein the modified clay composite according to any one of claims 1 to 6 is melt-mixed with a resin. . 15. A method for producing the resin composition according to any one of claims 10 to 12, which comprises a thermoplastic resin and the modified clay composite according to any one of claims 1 to 6. A method comprising a step of preparing a composition master product and a step of melt-kneading the composition master product and a thermoplastic resin.