KR20030068491A - A layered organic clay, a process of preparing for the clay and a composites comprising the clay - Google Patents

Abstract

PURPOSE: Layered organic clay is provided to prevent the color changing of the clay at a high temperature. A polymer resin-layered organic clay complex having improved mechanical properties, heat resistance and gas permeability is also provided. CONSTITUTION: The organic clay has a layered structure by demineralizing with onium ions. The layered organic clay is characterized by comprising (a) hydrocarbon oil or modified oil represented by the formula I and/or (b) silicone oil or modified oil represented by formula II. The polymer resin-layered organic clay complex is obtained by dispersing the layered organic clay into a polymer resin.

Description

A layered organic clay, a process of preparing for the clay and a composites comprising the clay}

The present invention relates to a layered organic clay, a manufacturing method thereof and a polymer resin-organic clay composite (hereinafter referred to as "composite") including the same.

More specifically, the present invention relates to a layered organic clay, in which inorganic ions existing between clay layers are organicized with onium ions and treated with oil or modified oil to reduce particle size of organic clay, and having excellent dispersibility and discoloration resistance. It relates to a manufacturing method and a composite comprising the same.

Recently, many attempts have been made to add nano-particles as a method for improving the physical properties of polymer resins, and a lot of layered clays have been applied as additives.

However, in the case of clay is hydrophilic, it is well dispersed in water, but there is a disadvantage that it is not dispersed in the lipophilic solvent or in the molten resin. As a result, polymer resin and layered clay are incompatible, and clay is not well dispersed in the polymer resin during composite production, so improvement of the physical properties of the composite cannot be expected, and polymer resin penetrates well between layers of clay due to the narrow space between layers of clay. There were problems that were not.

In order to facilitate uniform dispersion of the layered inorganic material to the polymer resin, U.S. Patent No. 4,889,885 et al. Provides sodium or calcium ions which exist in a natural state between the unit layers of the multilayered particulate material such as inorganic silicates. Techniques for mixing such layered materials with monomers or oligomers of the polymer after replacement with Um (eg alkylammonium ions) are shown. This cation exchange can render the existing hydrophilic silicates lipophilic and extend the interlayer distance of the layered material, thereby improving dispersibility to the resin.

Specifically, US Pat. No. 6,203,901 discloses a method for preparing fibers by dispersing a layered organic clay organicized with organic onium in a polyurethane urea resin. In the patent, examples of the organotium ions include 1-4 ammonium ions, pyridinium ions, imidazolinium ions, phosphonium ions, and sulfonium ions.

In addition, U.S. Pat. In order to provide a layered organic clay applicable to an ink, a paint, and the like.

However, the layered organic clays using such organic organizing agents have low thermal stability at 100-110 ° C., so that the organic clays are thermally decomposed when preparing the polymer resin-organic clay composite, so that the color of the resin is oxidized or decomposed to black or dark brown, or the composite There was a problem that the physical properties of the.

In addition, US Pat. No. 6,057,035 discloses a method of using an organic agent in which clay is organicized with a phosphonium compound and an alkyl group of an emulsifier is reacted with an alkoxysilane compound in order to improve the thermal stability of the organic clay. However, the above method can improve the thermal stability of the organic clay to 250 ° C. level, but the manufacturing cost is high, which makes it difficult to apply to the commercialized composites.

In addition, in Journal of Appl.Polym.Scien., Vol.55, pp. 119-123 (1995), a polyamide peelable composite was produced using inorganic silicate treated with 12-aminolauric acid. The technique is reported.

On the other hand, Japanese Patent Application Laid-Open No. Hei 10-182892 intercalates a polyolefin oligomer containing a functional group in an organic layered clay mineral to extend the interlaminar distance of the clay mineral to some extent, and then mix this composite material with an olefin resin. A method is described in which a layered clay mineral is dispersed in a matrix of an olefinic resin.

In addition, Korean Patent Laid-Open Publication No. 2002-7588 discloses a layered organic clay organicized with an organizing agent in which the functional group of the modified polypropylene and the amine-based non-halogen flame retardant are chemically bonded, (ii) the modified polypropylene and (iii) poly A polypropylene-organic clay composite consisting of propylene resin (metrics) is disclosed. However, the layered organic clay used in the patent has a problem that only compatibility with polypropylene is improved and compatibility with other polymer resins is not improved.

The purpose of the present invention is to solve the problems of the conventional organic clay, excellent dispersibility with various polymer resins in the production of polymer resin-organic clay composite, and to produce a composite for increasing physical properties (including discoloration) The purpose of the present invention is to provide an organic clay containing oil (including modified oil) that can reduce the particle size of the organic clay while preventing the organic clay from being oxidized or decomposed to discolor the composite.

Another object of the present invention is to provide a process for producing an organoclay containing said oil (including modified oil), ie treated with oil or modified oil.

It is another object of the present invention to provide a polymer resin-organic clay composite having improved physical properties and colors by containing the organic clay.

In the present invention, sodium or calcium ions, which are present in a natural state between each layer of layered clay, are organicized with conventionally known onium ions and have a layered structure, and include silicone-based oils or modified oils (hereinafter referred to as "silicone oils"). And / or hydrocarbon-based or modified oils (hereinafter referred to as "hydrocarbon-based oils") to contain these oils or modified oils (hereinafter referred to as "oils") to reduce particle size. It is intended to provide a layered organic clay that is low in color and excellent in discoloration prevention and dispersion with various resins.

The layered organic clay of the present invention for achieving these problems, (a) a hydrocarbon-based oil or modified oil of the general formula (I), (b) a silicone oil or modified oil of the general formula (II) or ( c) a hydrocarbon oil or a modified oil of the following general formula (I) and a silicone oil or a modified oil of the following general formula (II).

In formula (I), R ₅ is an aliphatic compound having ₅ to 40 carbon atoms, an aromatic compound or a mixture thereof, and each of B ₁ and B ₂ is an ester group (-COO-), an ether group (-O-), an amide A group (-CONH-) or a methylene group (-CH _2- ), each of T ₁ and T ₂ is hydrogen, polyethylene oxide or polypropylene oxide or polybutylene oxide having 0 to 20 repeating units, or 1 carbon atom. -30 aliphatic or aromatic compounds or mixtures thereof.

In the formula (II), n and m are each an integer of 1 to 30, Y is a methyl group (-CH ₃ ), polyethylene oxide, polypropylene oxide or polybutylene oxide, respectively, and each of B ₃ and B ₄ is carbon number An aliphatic compound, an aromatic compound, or a mixture thereof, wherein each of T ₃ and T ₄ is a hydrogen group (-H), a hydroxyl group (-OH), an acid group (-COOH), or an alkyl group having 1 to 20 carbon atoms. And a polyethylene oxide having 0 to 20 repeating units, a polypropylene oxide having 0 to 20 repeating units, or a polybutylene oxide having 0 to 20 repeating units.

In addition, the method for preparing a layered organic clay of the present invention is to prepare an organic clay having a layered structure by reacting clay with an organic agent capable of forming Onium ions, and before reacting the clay with the organic agent, (A) a hydrocarbon-based oil or modified oil of the following general formula (I), or (b) a silicone oil or a modified oil of the following general formula (II) to a solution or to a slurry solution of organic clay after reacting the clay with the organic agent. Or (c) adding a hydrocarbon oil or modified oil of the following general formula (I) and a silicone oil or a modified oil of the following general formula (II).

In addition, the high molecular weight resin-organic clay composite of the present invention is characterized in that it comprises the layered organic clay of the present invention described above.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, the layered organic clay of the present invention is organicized with Onium ions as in the conventional layered organic clay, and (a) a hydrocarbon-based oil (including modified oil) of the following general formula (I), (b) Silicone oil of general formula (II) (including modified oil) or (c) Hydrocarbon oil of general formula (I) (including modified oil) and silicone oil of general formula (II) (including modified oil) It is characterized by containing.

In formula (I), R ₅ is an aliphatic compound having ₅ to 40 carbon atoms, an aromatic compound or a mixture thereof, and each of B ₁ and B ₂ is an ester group (-COO-), an ether group (-O-), an amide A group (-CONH-) or a methylene group (-CH _2- ), each of T ₁ and T ₂ is hydrogen, polyethylene oxide or polypropylene oxide or polybutylene oxide having 0 to 20 repeating units, or 1 carbon atom. -30 aliphatic or aromatic compounds or mixtures thereof.

In the formula (II), n and m are each an integer of 1 to 30, Y is a methyl group (-CH ₃ ), polyethylene oxide, polypropylene oxide or polybutylene oxide, respectively, and each of B ₃ and B ₄ is carbon number An aliphatic compound, an aromatic compound, or a mixture thereof, wherein each of T ₃ and T ₄ is a hydrogen group (-H), a hydroxyl group (-OH), an acid group (-COOH), or an alkyl group having 1 to 20 carbon atoms. And a polyethylene oxide having 0 to 20 repeating units, a polypropylene oxide having 0 to 20 repeating units, or a polybutylene oxide having 0 to 20 repeating units.

In other words, the layered organic clay of the present invention is organicized with an organic agent and at the same time treated with a hydrocarbon oil of general formula (I) and / or a silicone oil of general formula (II) to contain these oil (s). have.

Conventional organic agents capable of forming Onium ions have the structure of general formula (III).

In formula (III), R _1, R _2, R ₃ and R ₄ are each hydrogen, an alkyl group having 1-30 carbon atoms or hydroxyalkyl, polyethylene oxide, polypropylene oxide, aliphatic compound having 1-20 carbon atoms, aromatic compound Or mixtures thereof, and M ⁺ represents ammonium ions, sulfonium ions, imidazolium ions, pyridinium ions, phosphonium ions, imidazolinium ions, triazinium ions or amines oxide ion or the like, X is F ^- is a halogen-atom, an acetate, hydroxide, nitrate (nitrate) or sulfate, etc. ^{-, Cl -, Br -,} I. In addition, each of R _1, R _2, R ₃ and R ₄ may have a hydroxyl group on the side or may include a bonding group such as an ester group, an amide group, an ether group, a ketone group or a sulfoxide group in the molecular chain.

The organoclay of the present invention comprises a hydrocarbon oil of formula (I) (including modified oil) and / or a silicone oil of formula (II) (including modified oil) before or after the clay and the organic agent are reacted. ) Can be added.

Specifically, when the oil or modified oil is added before reacting the clay and the organic agent, the oil or modified oil is added to the organic agent solution before the reaction with the clay, and the oil or the modified oil is reacted after the clay and the organic agent are reacted. When oil is added, the oil or modified oil is added to a slurry solution of organic clay formed by reacting clay with an organic agent.

More specifically, the hydrocarbon-based oil of formula (I) (including modified oil) or the silicone-based oil of formula (II) (including modified oil) in an organic agent solution capable of forming Onium ions. Or a mixture thereof is added to disperse and dissolve evenly, and then react with an aqueous solution, an organic solvent or a mixture thereof in which clay is dispersed at room temperature or by heating, and then, filtered and washed with sodium chloride as a reaction by-product. The remaining amount of unreacted organic agent is removed, and then dried and powdered in a spray dryer or a freeze dryer to prepare the organic clay of the present invention.

In this case, as an organic agent capable of forming onium ions, imino melamine formaldehyde resin (imino melamine-formaldehyde resin, manufactured by CYTEC Co., Ltd.) having a polymerization degree of 2 to 3 is used, and as an oil (including modified oil) component KONION NP-3, 5, 10, 20 from Korea Polyol, BY16-201, Q4-3669 from Dow Corning, Tegomer H-Si 2111 from Gold Schmidt, etc. are used.

In the above process, oil (including modified oil) may be added to the slurry of organic clay after the reaction between the organic agent and the clay is completed, but it may be added to the molecular chain such as KONION NP-3 or H-Si 2111. In the case of compounds with few hydrophilic groups, mixing with an organizing agent prior to reaction is advantageous for even dispersion. It can further reduce the particle size of the organic clay because the organic agent acts as a dispersing agent of lipophilic oil components, and the compound of the modified oil component having many hydrophilic groups may be added to the organic clay slurry after the reaction.

Particle size reduction effect by adding oil (including modified oil) component was evaluated primarily by how much it is filtered in filter paper having a certain size, and color change and dispersibility improvement were evaluated secondarily by color change and physical properties during composite manufacturing. . In addition, the interlayer distance of organic clay was measured by X-ray diffraction.

The clay used in the above may be montmorillonite, saponite, hectorite, batellite, bentonite, nontronite, laponite, vermiculite, illite, muscobite, pyrophyllite or mica. ) Etc.

The polymer component-organic clay composite of the present invention may be prepared by mixing and polymerizing the oil component-containing layered organic clay of the present invention described above with a monomer from the initial polymerization of the polymer resin.

In addition, the polymer resin may be melt compounded with organic clay, or the polymer resin and the organic clay may be prepared by dispersing, coating and drying the polymer resin and the organic clay in a solvent.

In the present invention, it does not specifically limit the manufacturing method of the polymer resin-organic clay composite.

The polymer resin-organic clay composite of the present invention prepared as described above is dispersed in the polymer resin and (ii) the polymer resin, and is treated with an oil (including modified oil) component to contain the layered organic clay of the present invention. It is made of.

The content of the layered organic clay in the polymer resin is preferably 0.1 to 15% by weight. If it is less than 0.1% by weight, the effect of improving the physical properties of the composite is insufficient, and if it exceeds 15% by weight, the dispersibility is lowered and the manufacturing cost is increased.

The amount of the oil (including modified oil) component is appropriately in the range of 0.05 to 10 times the total weight of the organic agent. Too small an effect of improving the fineness or dispersibility of the size of the organic clay is too small, and too many additional effects are not economical.

The effect of reducing the particle size of organic clay and improving dispersibility by adding oil (including modified oil) component is increased by increasing the interlayer spacing and increasing lipophilicity by oil (including modified oil) component. It is understood that the action is increased due to the delamination phenomenon in which the layered organic clay is more peeled into the unit layer, and the degradation of discoloration is reduced to oil (including modified oil) before oxidation or carbonization of the organic agent by heat at high temperature. ), It absorbs and blocks the heat, so it can be used without discoloration at a higher temperature than before.

As the polymer resin, polyester resin, polyamide resin, epoxy resin, polyurethane resin, polyurethane urea resin, polyimide resin, polysiloxane resin, ABS resin or polyolefin resin can be used.

The layered organic clay of the present invention described above is excellent in compatibility and dispersibility with various resins, and has excellent heat resistance with no discoloration even at a polyester processing temperature. As a result, the composite containing the layered organic clay of the present invention greatly improves physical properties such as strength and is not discolored so much that the color is excellent.

In the present invention, the physical properties of each of the layered organic clay and the composite were evaluated as follows.

Interlayer distance of layered organic clay

It is measured by X-ray diffraction. Specifically, RIG-2000 Co., Ltd., Japan, was used, and coca (CoKa, α = 0.15 nanometer) light was used for observation.

Dispersibility of layered organic clay

It measures by the said X-ray diffraction method. Here, the observation And evaluated by dividing by △ and ×, The good dispersibility means that there is no specific peak of organic clay at 2θ = 10 ° or less as the result of X-ray diffraction of the organic clay mineral and the polymer resin composite. do. In addition, Δ is a dispersibility, which means that a specific peak of the organic clay appears at 2θ = 10 ° or less as a result of X-ray diffraction, and that dispersibility is normal when the interlayer distance of the organic clay is extended to 50 Å or more. In addition, X is a poor dispersibility, a specific peak of organic clay appears at 2θ = 10 ° or less as a result of X-ray diffraction.

Tensile strength / elongation / tensile modulus of composite (plastic specimen)

It was measured by ASTM D-638 method.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited only to the following examples.

Example 1

96.4 g of imino melamine formaldehyde resin (manufactured by CYTEC Co., Ltd.-organizer) having a degree of polymerization of 3 was added to 500 g of deionized water such as 44 g of 10% hydrochloric acid solution, and stirred at 80 ° C. for 1 hour to completely dissolve it. After preparing the imino melamine formaldehyde resin, 48.2 g (0.5 times the weight of the organic agent) of Tegomer H-Si 2111 (manufactured by Goldschmidt), a silicone-based oil, was added, stirred, dispersed, and dissolved. On the other hand, the clay is dispersed for 1 hour while maintaining the temperature of 70 ℃ in 100g of Na-montmorillonite (clay) (cationic exchange capacity: 119 meq / 100g) in 5L of deionized water. Into this, an imino melamine formaldehyde resin in the form of onium ions added with the oil component prepared above was subjected to an ion exchange reaction with stirring at 80 ° C. for 1 hour, filtered and washed with NaCl and unreacted organic reaction product. The agent is removed, dried and powdered to form a layered organic clay. In the initial filtration, as a result of filtration with filter paper having a pore size of 3㎛, the amount of filtered organic clay was 14% of the total amount, and the passed organic clay was filtered through a 0.5㎛ size filter paper and dried and powdered in a lyophilizer. 3% by weight of the layered organic clay is mixed and polymerized together with the monomers (dimethyl terephthalate and 1,4-butanediol) from the initial stage of the polyester polymerization to prepare a polyester-layered organic clay composite. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Example 2

96.4 g of imino melamine formaldehyde resin (manufactured by CYTEC Co., Ltd.-organizer) having a degree of polymerization of 3 was added to 500 g of deionized water such as 44 g of 10% hydrochloric acid solution, and stirred at 80 ° C. for 1 hour to completely dissolve it. After preparing the imino melamine formaldehyde resin, 289.2 g of the Tegomer H-Si 2111 (manufactured by Goldschmidts), a silicone oil, which is three times the weight of the organic agent, was added, stirred, and dissolved. On the other hand, the clay is dispersed for 1 hour while maintaining the temperature of 70 ℃ in 100g of Na-montmorillonite (clay) (cationic exchange capacity: 119 meq / 100g) in 5L of deionized water. Into this, an imino melamine formaldehyde resin in the form of onium ions added with the oil component prepared above was subjected to an ion exchange reaction with stirring at 80 ° C. for 1 hour, filtered and washed with NaCl and unreacted organic reaction product. The agent is removed, dried and powdered to form a layered organic clay. After the initial filtration, the filter paper was filtered with a pore size of 3㎛, and the amount of filtered organic clay was 2.8% based on the total amount of the injected material.The organic clay passed through was filtered with a filter size of 0.5㎛ and dried and powdered in a freeze dryer. It was. 3% by weight of the layered organic clay is mixed and polymerized together with the monomers (dimethyl terephthalate and 1,4-butanediol) from the initial stage of the polyester polymerization to prepare a polyester-layered organic clay composite. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Example 3

96.4 g of imino melamine formaldehyde resin (manufactured by CYTEC Co., Ltd.-organizer) having a degree of polymerization of 3 was added to 500 g of deionized water such as 44 g of 10% hydrochloric acid solution, and stirred at 80 ° C. for 1 hour to completely dissolve it. After preparing the imino melamine formaldehyde resin, 96.4 g of 1.0 times the weight of the organic agent is added, stirred, and dissolved by dissolving Tegomer H-Si 2111 (manufactured by Goldschmidt), a silicone oil. On the other hand, the clay is dispersed for 1 hour while maintaining the temperature of 70 ℃ in 100g of Na-montmorillonite (clay) (cationic exchange capacity: 119 meq / 100g) in 5L of deionized water. Into this, an imino melamine formaldehyde resin in the form of onium ions added with the oil component prepared above was subjected to an ion exchange reaction with stirring at 80 ° C. for 1 hour, filtered and washed with NaCl and unreacted organic reaction product. The agent is removed, dried and powdered to form a layered organic clay. 3% by weight of the layered organic clay is mixed and polymerized together with the monomers (dimethyl terephthalate and 1,4-butanediol) from the initial stage of the polyester polymerization to prepare a polyester-layered organic clay composite. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Example 4

96.4 g of imino melamine formaldehyde resin (manufactured by CYTEC Co., Ltd.-organizer) having a degree of polymerization of 3 was added to 500 g of deionized water such as 44 g of 10% hydrochloric acid solution, and stirred at 80 ° C. for 1 hour to completely dissolve it. After preparing the imino melamine formaldehyde resin, 96.4 g of 1.0 times the weight of the organic agent is added, stirred, and dissolved by dissolving Tegomer H-Si 2111 (manufactured by Goldschmidt), a silicone oil. On the other hand, the clay is dispersed for 1 hour while maintaining the temperature of 70 ℃ in 100g of Na-montmorillonite (clay) (cationic exchange capacity: 119 meq / 100g) in 5L of deionized water. Into this, an imino melamine formaldehyde resin in the form of Onium ions added with the oil component prepared above was subjected to an ion exchange reaction with stirring at 80 ° C. for 1 hour, filtered and washed with NaCl and unreacted organic reaction product. The agent is removed, dried and powdered to form a layered organic clay. 3 wt% of the layered organic clay is melt compounded with 97 wt% of polyester (PBT) resin to prepare a polyester-layered organic clay composite. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Example 5

52.5 g of dihydroxyethylmethylhydrogenated tallowalkylammonium chloride (organizing agent) was added to 500 g of deionized water, stirred at 80 ° C. for 1 hour to completely dissolve, and then 52.5 g of Do16 Corning oil compound BY16-201 was dissolved in an aqueous solution. It is thrown in, stirred, dispersed and dissolved. On the other hand, the clay is dispersed for 1 hour while maintaining the temperature of 70 ℃ in 100g of Na-montmorillonite (clay) (cationic exchange capacity: 119 meq / 100g) in 5L of deionized water. Into this, an imino melamine formaldehyde resin in the form of onium ions added with the oil component prepared above was subjected to an ion exchange reaction with stirring at 80 ° C. for 1 hour, filtered and washed with NaCl and unreacted organic reaction product. The agent is removed, dried and powdered to form a layered organic clay. 3 wt% of the layered organic clay is melt compounded with 97 wt% of polyester (PBT) resin to prepare a polyester-layered organic clay composite. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Example 6

52.5 g of dihydroxyethyl methyl hydride tallow alkylammonium chloride (organizing agent) was added to 500 g of deionized water, stirred at 80 ° C. for 1 hour to completely dissolve, and then KONION NP-3 (Korea Polyol) 52.5g) is added to an aqueous solution, stirred, dispersed, and dissolved. On the other hand, the clay is dispersed for 1 hour while maintaining the temperature of 70 ℃ in 100g of Na-montmorillonite (clay) (cationic exchange capacity: 119 meq / 100g) in 5L of deionized water. Into this, an imino melamine formaldehyde resin in the form of onium ions added with the oil component prepared above was subjected to an ion exchange reaction with stirring at 80 ° C. for 1 hour, filtered and washed with NaCl and unreacted organic reaction product. The agent is removed, dried and powdered to form a layered organic clay. After the initial filtration, the filter paper was filtered with a pore size of 3㎛, and the amount of filtered organic clay was 0.4% of the total amount of the injected material.The organic clay passed through was filtered with a filter of 0.5㎛ size and dried and powdered in a freeze dryer. It was. 3 wt% of the layered organic clay is melt compounded with 97 wt% of polyester (PBT) resin to prepare a polyester-layered organic clay composite. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Comparative Example 1

96.4 g of imino melamine formaldehyde resin (manufactured by CYTEC Co., Ltd.-organizer) having a degree of polymerization of 3 was added to 500 g of deionized water such as 44 g of 10% hydrochloric acid solution, and stirred at 80 ° C. for 1 hour to completely dissolve it. Prepares imino melamine formaldehyde resin in form. On the other hand, the clay is dispersed for 1 hour while maintaining the temperature of 70 ℃ 100g Na-montmorillonite (clay) (cation exchange capacity: 119 meq / 100g) in 5L of deionized water. Into this, an imino melamine formaldehyde resin in the form of onium ions added with the oil component prepared above was subjected to an ion exchange reaction with stirring at 80 ° C. for 1 hour, filtered and washed with NaCl and unreacted organic reaction product. The agent is removed, dried and powdered to form a layered organic clay. In the initial filtration, the filter paper was filtered with a pore size of 3 μm, and the amount of the filtered organic clay was 100% based on the total amount of added clay and organic agent. 3 wt% of the layered organic clay is melt compounded with 97 wt% of polyester (PBT) resin to prepare a polyester-layered organic clay composite. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Comparative Example 2

52.5 g of dihydroxyethylmethylhydrogenated tallowalkylammonium chloride (organizing agent) is added to 500 g of deionized water and stirred at 80 ° C. for 1 hour to completely dissolve. On the other hand, the clay is dispersed for 1 hour while maintaining the temperature of 70 ℃ in 100g of Na-montmorillonite (clay) (cationic exchange capacity: 119 meq / 100g) in 5L of deionized water. Into this, an imino melamine formaldehyde resin in the form of onium ions added with the oil component prepared above was subjected to an ion exchange reaction with stirring at 80 ° C. for 1 hour, filtered and washed with NaCl and unreacted organic reaction product. The agent is removed, dried and powdered to form a layered organic clay. In the initial filtration, the filter paper was filtered with a pore size of 3 μm, and the amount of the filtered organic clay was 100% based on the total amount of added clay and organic agent. 3 wt% of the layered organic clay is melt compounded with 97 wt% of polyester (PBT) resin to prepare a polyester-layered organic clay composite. The results of evaluating the physical properties of the prepared layered organic clay and the composite are shown in Table 1.

Physical property measurement result division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Layered organic clay Interlayer Distance (℃) 26.2 or more 31.4 or more 27.8 and above 27.8 and above 23.9 or more 21.5 or more 24.0 18.5 Dispersibility △ △ Complex Flexural modulus (kg / ㎠) 26,900 31,600 32,100 31,700 27,500 27,200 24,800 26,300 Flexural Strength (kg / ㎠) 879 873 899 862 864 859 847 856 Tensile Strength (kg / ㎠) 527 561 584 563 531 529 552 518 color Colorless Colorless Colorless Colorless Light yellow yellow yellow Dark brown

The layered organic clay of the present invention has excellent compatibility and dispersibility with various polymer resins, and has excellent heat resistance, so that the discoloration prevention (color improvement) effect is remarkable even when the conventional ammonium salt is used at the processing temperature of the polyester. In addition, since the particle size of the organic clay is small, the physical properties such as strength, elasticity, and heat resistance of the composite are excellent when the composite is prepared with the polymer resin. Therefore, even if the amount of organic clay is reduced, there is an economic advantage that can obtain properties similar to those of conventional composites.

Claims (7)

In organic clay organicized with Onium ions and having a layered structure, (a) a hydrocarbon oil or modified oil of the following general formula (I), and (b) a silicone oil or a modified oil of the following general formula (II) An oil or (c) a layered organic clay comprising a hydrocarbon-based oil or modified oil of the following general formula (I) and a silicone oil or a modified oil of the following general formula (II). In formula (I), R ₅ is an aliphatic compound having ₅ to 40 carbon atoms, an aromatic compound or a mixture thereof, and each of B ₁ and B ₂ is an ester group (-COO-), an ether group (-O-), an amide A group (-CONH-) or a methylene group (-CH _2- ), each of T ₁ and T ₂ is hydrogen, polyethylene oxide or polypropylene oxide or polybutylene oxide having 0 to 20 repeating units, or 1 carbon atom. -30 aliphatic or aromatic compounds or mixtures thereof. In the formula (II), n and m are each an integer of 1 to 30, Y is a methyl group (-CH ₃ ), polyethylene oxide, polypropylene oxide or polybutylene oxide, respectively, B ₃ and B ₄ each have carbon number An aliphatic compound, an aromatic compound, or a mixture thereof, wherein each of T ₃ and T ₄ is a hydrogen group (-H), a hydroxyl group (-OH), an acid group (-COOH), or an alkyl group having 1 to 20 carbon atoms. And a polyethylene oxide having 0 to 20 repeating units, a polypropylene oxide having 0 to 20 repeating units, or a polybutylene oxide having 0 to 20 repeating units. The inorganic component of the layered organic clay is montmorillonite, saponite, hectorite, batellite, bentonite, nontronite, laponite, vermiculite, illite, muscobite, pyrophyllite or the like. Layered organic clay, characterized in that the mica (Mica). The layered organic clay according to claim 1, wherein the total amount of oil or modified oil is 0.05 to 10 times the weight of the organic agent. In preparing organic clay having a layered structure by reacting clay with an organizing agent capable of forming Onium ions, after reacting the clay with the organizing agent or after reacting the clay with the organizing agent before reacting the clay with the organizing agent (A) a hydrocarbon oil or modified oil of the following general formula (I), (b) a silicone oil or a modified oil of the following general formula (II), or (c) a general formula (I) A process for producing a layered organic clay comprising adding a hydrocarbon-based oil or modified oil and a silicone oil or modified oil of the following general formula (II). In formula (I), R ₅ is an aliphatic compound having ₅ to 40 carbon atoms, an aromatic compound or a mixture thereof, and each of B ₁ and B ₂ is an ester group (-COO-), an ether group (-O-), an amide A group (-CONH-) or a methylene group (-CH _2- ), each of T ₁ and T ₂ is hydrogen, polyethylene oxide or polypropylene oxide or polybutylene oxide having 0 to 20 repeating units, or 1 carbon atom. -30 aliphatic or aromatic compounds or mixtures thereof. In the formula (II), n and m are each an integer of 1 to 30, Y is a methyl group (-CH ₃ ), polyethylene oxide, polypropylene oxide or polybutylene oxide, respectively, and each of B ₃ and B ₄ is carbon number An aliphatic compound, an aromatic compound, or a mixture thereof, wherein each of T ₃ and T ₄ is a hydrogen group (-H), a hydroxyl group (-OH), an acid group (-COOH), or an alkyl group having 1 to 20 carbon atoms. And a polyethylene oxide having 0 to 20 repeating units, a polypropylene oxide having 0 to 20 repeating units, or a polybutylene oxide having 0 to 20 repeating units. A polymer resin-organic clay composite comprising a polymer resin and a layered organic clay dispersed in the polymer resin, the polymer resin-organic clay composite comprising the layered organic clay of claim 1. The polymer resin-organic clay composite according to claim 5, wherein the layered organic clay content in the polymer resin-organic clay composite is 0.1-15% by weight. The polymer resin-organic clay according to claim 5, wherein the polymer resin is a polyester resin, a polyamide resin, an epoxy resin, a polyurethane resin, a polyurethane urea resin, a polyimide resin, a polysiloxane resin, an ABS resin or a polyolefin resin. Complex.