JP3526364B2 - Resin antistatic method and permanent antistatic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for imparting a permanent antistatic ability to a resin composition. More specifically, the present invention shows a method of lowering the volume resistivity of a resin composition to semipermanently maintain an excellent antistatic ability even at low temperature and low humidity, and exhibits excellent permanent antistatic property even at low temperature and low humidity. It relates to a resin composition.

[0002]

2. Description of the Related Art Synthetic polymer materials are used in a wide range of fields because of their light weight and easy workability, but generally have a high volume resistivity of 10 ¹⁵ to 10 ¹⁷ Ω · cm or more. Since it has a high rate, it tends to be charged with static electricity, which causes various electrostatic troubles and adsorbs dust and dirt around the surface of the molded body, which seriously impairs the appearance. Therefore, various attempts have heretofore been made for the purpose of imparting antistatic properties to these synthetic polymer materials. The methods of imparting antistatic ability to resins are roughly classified into the following three methods. (1) A method in which a surfactant is applied to the surface and water in the atmosphere is adsorbed by the hydrophilic group to form a conductive layer having a low resistivity on the surface layer of the molded product. (2) A low molecular weight surfactant is kneaded into the resin and leached on the surface of the molded product during or after molding (bleeding
Out) and by adsorbing water in the atmosphere to the hydrophilic group, a conductive layer having a low resistivity is formed on the surface layer of the molded body. (3) Alloy the ionic conductive polymer into the target resin,
A conductive layer is formed by forming a thin layer of a conductive polymer phase near the surface layer during molding and adsorbing water in the atmosphere to this.

Of these, the method (2) is the most general and is widely spread. Unlike the method (1), this method does not require complicated coating work, and unlike the method (3), it is 0.05-
The greatest advantage is that it functions with the addition of a small amount of antistatic agent of 2 wt% and can be applied to molded articles of various shapes. On the other hand, it takes a long time to develop antistatic ability due to bleed-out delay, on the contrary, excessive bleed-out causes large volatilization loss during molding, deterioration of molding work environment, mold contamination, surface stickiness, There are various problems such as a decrease in printability, and it is troublesome that an appropriate antistatic agent type and its usage amount, molding conditions, aging conditions, and the like must be optimized according to the intended use. Also,
Basically, a low molecular weight compound that can migrate through the resin is used, so the active agent that bleeds out on the surface is easily removed by washing and wiping the surface of the molded body, and the antistatic property disappears and recovery occurs. do not do. In this sense, the antistatic agent of the present system is a “non-permanent antistatic agent” like the antistatic agent of (1) type. Further, for a molded product having a large specific surface area such as a sheet or a film, the required addition amount is significantly increased,
Moreover, the above-mentioned various problems become more remarkable. By the way, in principle, the method (2) is mainly applied to a resin having a glass transition point of about room temperature or lower so that a surfactant can migrate in the resin. That is, this method is mainly used for polypropylene, polyethylene, and partly for soft poly (vinyl chloride), but has a high glass transition temperature such as polystyrene, ABS resin, poly (methyl methacrylate), hard poly ( The effect is extremely low for vinyl chloride), polycarbonate, etc. The method (3) was developed as an antistatic method for these high glass transition point resins. This is ionic conduction containing polar groups such as polyether, polyamide, ammonium and sulfonate as represented by JP-A-60-23435, JP-A-2-255851 and JP-A-5-93118. Kneading a reactive polymer into the target resin /
Since it is alloyed, the conductive carrier is not removed even by surface cleaning, so the antistatic ability is not deactivated (“permanent antistatic”), but the conductive polymer phase develops inside the resin, so expensive ions There is a fatal drawback that a sufficient antistatic effect cannot be obtained unless the conductive polymer is blended in an amount of 20 to 30 vol% which is a threshold value based on the percolation theory. To reduce this, various compatibilizers are usually added to make the dispersed phase finer, and the melt viscosity characteristics of both phases are finely adjusted to form a thin polymer conductive polymer phase during injection molding. A method of preferentially condensing near the surface layer is adopted. However, the lower limit of the content of the conductive polymer phase that can surely exhibit the antistatic ability is about 15 vol%. Also, due to this, restrictions on molding become more strict, the function can be expressed only in an extremely narrow temperature range of a molding machine that can apply high share, addition of filler and third component, dilution use of high concentration masterbatch etc. However, this method has not yet been widely used because it cannot be used for a method that greatly changes the phase separation structure of an alloy. Further, the resin composition obtained by the present method (3) should originally have low volume resistance in the thickness direction of the molded body, but because of the layered conductive polymer phase structure arranged parallel to the surface, Actually, the volume resistivity in the thickness direction is 1 which is the value converted from the surface resistivity.
More than 00 times (SPE Tech. Paper (ANTEC), 1991,
49th, 551). Further, the polyolefin resin, which is a non-polar aliphatic polymer, is extremely difficult to mix with a different polymer (substance), so that this method using a polar group-containing polymer is practically not applicable. That is, at present, an effective antistatic method for polypropylene, polyethylene and the like has not been found yet. Further, until now, no effective antistatic method has been found for sheet- or film-like polyolefin resins. Furthermore, (1),
Both methods (2) and (3) are common in that the antistatic effect is significantly impaired under dry conditions, such as in winter, because ionic conduction due to adsorbed or stored water is the essence of the conduction mechanism. I had a problem.

In addition to this, a more positive static elimination effect is required for the periphery of high-voltage generating equipment and trays of IC chips which are extremely sensitive to static electricity, and metal powder, carbon black, etc. are used for such applications. There is. These are electronically conductive materials that do not require the participation of water, and are 10 ^-1 to 10 ⁵ Ω · c.
It imparts a volume resistivity of about m to the resin, but since it is basically insoluble in the resin, various particles can be formed in order to efficiently form a continuous or closest particle-particle distance close to about 100Å or less. In addition to various surface treatments, a large amount of 15-40 wt% must be used.
In addition, these conductive materials are expensive, and they are colored, and their major drawback is that they significantly deteriorate the physical properties of the resin.

By the way, the layered silicate is a typical layered inorganic compound which constitutes clay. For example, in a 2: 1 type layered silicate mineral, two silica tetrahedral silicate sheets contain magnesium or aluminum. By sandwiching the octahedral sheet in a sandwich type, one set of three inseparable silicate layers (thickness around 10Å) is formed, and these are laminated in parallel for several to several tens layers to form a primary aggregate. There is. Usually, this layered silicate primary aggregate further aggregates randomly and exists as a secondary aggregate having a particle size of several hundred nm to several μm. Smectite, vermiculite, talc, mica and the like are typical layered silicate compounds having such a structure. Among them, smectite and synthetic mica have a good interlayer charge density, so they are excellent in water swelling property, and are said to be capable of releasing secondary aggregation and uniformly dispersing in water, and even releasing strong primary aggregation and releasing it as a single-layer peeling dispersion depending on the variety. ("Clay Handbook 2nd Edition" edited by The Japan Clay Society). These have ion-exchange ability and can be brought into contact with various cationic compounds to form a complex in which they are introduced between the layers of smectite or synthetic mica instead of the original metal ions. At this time, if an organic ammonium salt that is an organic cation is used, a lipophilic (hydrophobic) organically modified layered silicate can be obtained (in this case, “organic modification” means the mere surface of the aggregate by the coupling agent or activator). Not a modification or surface treatment, but an altered state that involves exchange of interlayer ions). These organically modified layered silicates are produced in the form of secondary aggregates similar to the unmodified layered silicates described above. That is, although the interplanar spacing (including the thickness of one silicate layer) expands to about a dozen to 70 Å according to the structure of the organic ammonium taken in between the layers, it is based on a regular layered primary aggregation structure, This forms randomly aggregated secondary aggregates. Organic modified products of smectite clay minerals, especially modified products with dodecyl ammonium, octadecyl ammonium, trimethyl octadecyl ammonium, dimethyldioctadecyl ammonium, benzyl dimethyl octadecyl ammonium, etc. are commercialized under the name of organic bentonite, thickeners for paints, etc. Has been used since ancient times. These known organically modified layered silicates are, for the convenience of synthesizing an ammonium salt, a single long chain or two long chains having 18 or less carbon atoms (other substituents on the nitrogen atom are hydrogen, methyl group, or benzyl group). It is a modified product of alkylammonium, which is soluble in some aromatic solvents such as toluene and benzene, but has a low affinity for polar solvents such as alcohol and acetone, and aliphatic carbonization such as hexane and pentane. Does not dissolve in hydrogen solvent. In recent years, an organically modified layered silicate compound using a special organic ammonium has been developed for the purpose of improving the solubility in a polar solvent. JP-A-6-287014, JP-B-7-
The technology is disclosed in Japanese Patent No. 23210, Japanese Patent Publication No. 7-23212, etc., but these are also not uniformly dispersed in the aliphatic solvent. Incidentally, the organically modified layered silicate compound swells and uniformly disperses in a specific organic solvent (secondary cohesive dissociation), but it is generally accepted that even in these media, the primary agglomerated structure is firmly adhered and does not disperse. ing.

By the way, it is more difficult to disperse these existing organic modified clays in the resin because of the dependence of the solubility parameter on the molecular weight, and usually even secondary aggregation cannot be solved.

[0007] Single-chain organic modified clays such as dodecyltrimethylammonium modified clay and trimethyloctadecylammonium modified clay have low organic affinity, and in a resin such as polystyrene or polypropylene, they remain as secondary aggregates of almost several to several tens of μm. It exists unevenly. These huge layered silicate secondary aggregates in the resin can be easily recognized visually, and macroscopically the transparent resin also appears cloudy. Moreover, it can be confirmed by means of an electron microscope or the like that no diffusion of the silicate layer has occurred in the resin matrix portion (FIG. 1). The most widely spread 2 long-chain dimethyldioctadecyl ammonium modified clay improves the compatibility with the resin to some extent, but is still insufficient, for example, in a small kneader of the modified clay and polypropylene resin. A huge 2 with a thickness of 1 μm or more for a 10 min melt-kneaded product.
Secondary agglomerates remain ("Proceedings of the 4th Polymer Materials Forum", 1995, p.294), and even when mixed in a solvent with higher mixing efficiency, the transparency is greatly reduced [that is, the minor axis is visible light. It is known that only an organoclay-resin composition containing a large amount of aggregated particles having a wavelength longer than about 1 μm (= 1 μm or more) can be obtained (“38th Proceedings of the Clay Science Symposium” 1994, p.52). . For systems with poor dispersion, Japanese Patent Laid-Open No.
As clearly shown in Comparative Example 3 of 1-213231, the antistatic effect is not exhibited.

As a technique for providing a conductive inorganic powder for the purpose of imparting antistatic properties, there is a technique disclosed in JP-A-62-256724. This is an inorganic powder such as calcium carbonate or talc which is surface-treated with a quaternary ammonium salt.
Considering that the quaternary ammonium salt has a high resistivity, this method is considered to be ionic conduction due to incompletely dried and occluded water. In addition, the development of antistatic property when added to the resin is limited to only the poly (vinyl chloride) system containing a large amount of the low molecular weight plasticizer (DOP) and the stabilizer. The suspension system is a very peculiar system with rich polarity, extremely low glass transition point and high mobility of inclusions, which makes it an excellent ionic conduction medium. That is, the essence of the technology described in this publication is to provide a carrier that exhibits ionic conductivity without easily bleeding out / localizing in the field under consideration. Also, JP-A-64-6
Japanese Patent No. 5158 describes an antistatic poly (vinyl chloride) resin composition containing a clay mineral organically modified with dimethyldioctadecyl ammonium or the like, but also in this case, a plasticizer, a lubricant and a stabilizer coexist. The resistivity did not decrease in the non-treated system.

In the above-mentioned Japanese Patent Laid-Open No. 61-213231, an organically modified clay is added to a resin composition containing an organic antistatic agent to suppress bleeding of the organic antistatic agent to achieve long-term stability of antistatic ability. It describes the technology. Here, as a system in which the resistivity does not decrease, as a volume resistance value of a composition system composed of trimethyloctadecyl ammonium modified clay and poly (vinyl chloride) (containing a large amount of a plasticizer) exemplified in Comparative Example 8 of the publication, Although 7 × 10 ¹¹ Ω · cm is shown, 40 parts by weight of the organically modified clay is used for 100 parts by weight of the resin, and the resistivity of the system in which the usual percolation threshold is exceeded may be small. The decrease is self-evident, has no technical significance and industrial utility, and is essentially different from what the present inventors aim to achieve.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found a resin permanent antistatic method based on a completely new mechanism. That is, the moderately organically modified layered silicate compound has an extremely low electronic conductivity volume resistivity of 10 ⁸ to 10 ¹² Ω · cm, and these organically modified layered silicate compounds are uniformly dispersed in the resin. By doing so, it was found that the resin can be provided with a permanent antistatic property. Specifically, the volume resistivity is 10 ¹² Ω · c.
The organically modified layered silicate compound having a particle size of m or less is uniformly dispersed in the resin in the form of primary agglomerates and / or secondary agglomerates having a short diameter of 500 nm or less and an average closest particle distance of 500 n.
According to this method, a permanent antistatic property is imparted to various resin groups without impairing the performance of the resin composition molded body by wiping the surface thereof. it can. It is also applicable to non-polar polymers such as polyolefin resins. This antistatic ability is
It develops immediately after molding and does not require the intervention of adsorbed water, so it can function even under low humidity and low temperature. In addition, since it causes a uniform decrease in volume resistivity over the entire resin, it is also effective for thick products and film-shaped molded products with a large specific surface area.
There is no need for special molding conditions to realize the function, and there is basically no problem in using it in a filler or third component addition system, or diluting a high-concentration masterbatch. Moreover, at this time, the physical properties of the resin are not deteriorated, the color tone of the resin is not impaired at all, and the transparency of the transparent resin can be maintained. Further, it can be noted that the lower limit required addition amount of the organically modified layered silicate compound which becomes a conductive carrier in the permanent antistatic technique disclosed in the present invention is as small as 2-3 vol%.
Further, the permanent antistatic resin composition obtained by applying the method of the present invention has, as a secondary effect, weather resistance, heat resistance, dimensional stability, corrosion resistance, abrasion resistance, flame resistance, Excellent gas barrier property.

The technical point of the present invention is to finely disperse an organically modified layered silicate compound having a volume resistivity of about 10 ¹² Ω · cm or less at an average closest particle distance of 500 nm or less. As used herein, "particle" refers to the individual largest unit of a continuous organically modified clay phase that is independently present in the resin. In the phase forming the secondary aggregate, the secondary aggregate is to be referred to, not the primary aggregate unit. In addition, the “distance” between particles means not the distance L between the centers of gravity of the particles 1 in FIG. 2, but the distance L ₁ between the outer edges of the particles 1.

The unmodified layered silicate is usually an insulator having a resistance of 10 ¹³ Ω · cm or more in an absolutely dry state. However, the present inventors have found that an appropriately organically modified layered silicate compound is 10 ⁸
It has been found that it can have a very low electronically conductive volume resistivity of -10 ¹² Ω · cm. Furthermore, the present inventors have heretofore known that the distance between substances when a current substantially flows (charge transfer occurs) between two substances (particles / molecules / ions) isolated under an applied voltage of at most about 100V. Was less than 100 Å or less, while under the same applied voltage, 10
It has been found that in the world of antistatic properties of resin, where a very small current of about ^-9 to 10 ^-11 A can flow, a sufficient current can flow even between two bodies separated by a distance of 500 nm. . That is, if a substance having a volume resistivity of 10 ¹² Ω · cm or less fills the matrix while keeping the average closest particle distance of about 500 nm or less, the volume resistivity of the entire system can be effectively reduced with an extremely small amount. And need not be in contact with each other or in close proximity to a distance of 100Å or less. It is known that the minimum required volume fraction (percolation threshold value) of the low-resistivity substance required at this time may vary depending on various conditions such as the shape (anisotropic), size, and dispersity of the low-resistivity substance. However, the present inventors have found that fine particles such as an organically modified layered silicate compound that are extremely rich in shape anisotropy (in a primary aggregate, (several tens nm to several μm) × (several tens nm to several .mu.m) .times. (several to several tens of nm)], it has been found that it can be reduced to about 2-3 vol%. This is the lowest percolation threshold known so far.

However, a resin composition system which realizes the above concept has not been basically known so far. That is, there is no known inorganic compound that can be uniformly dispersed on a resin-suspended scale (glass fiber, carbon fiber,
Carbon black, mica, metal particles, etc. are themselves much larger than the above scale, while
Although the constitutional units of compounds such as calcium carbonate and aluminum oxide are fine, there is no example in which aggregates are disintegrated and dispersed on the above scale). A compound having a low compatibility is phase-separated as a huge particle and is not dispersed. Furthermore, high molecular weight compounds are generally difficult to be compatible with resins and have a huge phase separation structure of several μm or more.
Thus, the tendency that the additive is difficult to disperse is low-polarity polystyrene, hydrocarbon-based resin such as polyolefin-based resin,
Especially, it becomes remarkable in the case of an aliphatic hydrocarbon resin such as polypropylene or polyethylene. Of course, no matter how poor the dispersibility is, a large amount (about 40 to 70 vol% or more) of the low-resistivity dispersion (particles) can come into contact with each other.
It is obvious that the volume resistivity of the entire resin composition system is decreased by adding / using it in the above, but the system in question has no practical significance.

In the present invention, the volume resistivity is 10
^An organically modified layered silicate compound of ¹² Ω · cm or less
(1) The short diameter of the primary aggregate and / or the aggregate is 500 nm.
It is dispersed in the resin in the form of the following secondary agglomerates and (2) so that the average closest particle distance is 500 nm or less. The number of laminated primary aggregates is preferably several to ten and more on average. If the number of laminated primary aggregates is small, the volume resistivity increases. If it is too large (even with the same amount of use), the total number of particles will decrease, resulting in poor efficiency. The minor axis of the secondary aggregate is 500 nm or less, preferably 200 nm or less, more preferably 100 nm or less. By using a secondary aggregate having a minor axis of 500 nm or less, good transparency and impact strength can be obtained, and the number of particles can be increased, so that the probability of developing antistatic properties is improved even with the same addition amount.
Furthermore, the ratio of the primary agglomerates to the secondary agglomerates having a minor axis of 500 nm or less is preferably as high as the ratio of the primary agglomerates, and the more secondary agglomerates, the smaller the number of particles. The probability of developing sex decreases.

Regarding the quantification of the dispersibility of the organically modified layered silicate compound in the resin, it is generally extremely difficult to describe the dispersed state, and at present, a satisfactory notation has not been found. is there. Regarding the dispersion of spherical particles, the average number of particles contained in a unit volume is described together with the average particle size for convenience. However, the organic modification that brings about the antistatic property based on a new conductive mechanism, which is the object of the present invention, is described. It is not sufficient to describe the dispersion morphology of the layered silicate compound in the resin. Further, since the organically modified layered silicate compound used in the present invention is generally composed of extremely fine structural units of several hundred nm × several hundred nm × 1 nm, a high-resolution transmission electron microscope image can be used to determine its dispersion state. Is essential, making it difficult to solve the situation. However, as a result of detailed comparison of transmission electron microscope images of an extremely large number of organically modified layered silicate compound-resin composition having antistatic ability and organically modified layered silicate compound-resin composition not exhibiting antistatic property The present inventors have found that, except for special exceptional systems, the organically modified layered silicate compound having a volume resistivity of 10 ¹² Ω · cm or less releases its secondary agglomeration and primary agglomerates and / or
Alternatively, when the shortest diameter is dispersed in the form of a secondary aggregate having a maximum size of 500 nm or less and the matrix is filled while keeping the distance between adjacent particles to approximately 500 nm or less, the volume resistivity of the entire resin composition decreases. It was found that the antistatic property is exhibited. Even if a small amount of the organically modified layered silicate compound is added, if the distance between the closest particles is maintained at a distance of 500 nm or less and evenly dispersed, a conductive path is secured, and it is sufficient for the purpose of preventing resin charging. It seems that charge transfer occurs at various levels. At this time,
An organically modified layered silicate compound, which is a low-resistivity conductive carrier,
The volume fraction occupied in the resin composition is 70 to 80 vol% or more, no matter how poor the dispersibility is, and if it is a normal dispersity, it is 20 to 30 vol% (about 30 wt% to 40 w.
It is obvious that the volume resistivity of the resin composition as a whole can be lowered if it is at least (corresponding to t%), but in the present invention, the dispersibility of the above (1) and (2) can be realized. If 2 to 1
It is shown that the volume resistivity of the entire resin composition can be lowered even with an added amount of 5 vol% (corresponding to about 3.3 wt% to 23 wt%). In order to efficiently impart a permanent antistatic property to the resin, it is preferable that there are no huge secondary agglomerates having a short diameter of 500 nm or more, but 2 to 30 parts by weight of the organically modified layered silicate with respect to 100 parts by weight of the resin. In addition to the above, undissociated huge secondary aggregated particles and other fillers may be contained as long as the compound achieves the above dispersion state. In the case of a suspended system, it suffices if the volume fraction of the organically modified layered silicate substantially within the resin matrix is within the above range, and the lower limit of the amount of the organically modified layered silicate required for function expression is apparently smaller. Complete.

The volume resistivity of the organically modified layered silicate used in the present invention is 10 ¹² Ω · cm or less, preferably 1
It is 0 ¹⁰ Ω · cm or less, and more preferably 10 ⁹ Ω · cm or less. The lower the volume specific resistivity of the organically modified layered silicate, the lower the resistivity can be realized and the smaller the amount used. The volume resistivity of the organically modified layered silicate is 10 ¹² Ω · cm.
If it exceeds 30, even if 30 parts by weight is used, good antistatic property cannot be obtained.

Further, as the resin to which the present invention is applied,
Examples thereof include thermosetting resins, thermoplastic resins, and heat decomposable resins. The thermosetting resin is a resin that gives an infusible / insoluble resin after polymerization. Therefore, the organically modified layered silicate must be added to the prepolymer or monomer before the completion of polymerization.
Examples of the thermosetting resin include phenol resin, urea resin, melamine resin and epoxy resin. As the thermoplastic resin, polypropylene and polypropylene unit-containing resin, polyethylene and polyethylene unit-containing resin, thermoplastic polyolefin resin such as polybutadiene and polyisobutylene, polystyrene resin and styrene unit-containing thermoplastic resin such as styrene-butadiene copolymer resin. Resin, thermoplastic nitrile group-containing resin such as acrylonitrile-butadiene-styrene (ABS) resin, polyethylene terephthalate (PET), thermoplastic ester group-containing resin such as poly (meth) acrylic acid ester resin, poly (vinyl chloride), poly (Vinylidene chloride), fluororesin, silicone resin, polyamide resin such as nylon, polyurethane resin, polycarbonate resin, thermoplastic resin such as polyimide. Furthermore, examples of the thermoplastic resin include super engineering plastics such as polyphenylene sulfide (PPS) and polyether sulfone (PES). The thermoplastic polar group-containing resin is an ether bond.
(-O-), urethane bond (-NHCOO-), amide bond (-CONH
-), Imide bond, hydroxyl group (-OH), nitrile group (-
A resin having a polar bond or group such as (CN) in the molecule. Furthermore, the thermally decomposable resin is a resin that decomposes before being plasticized by heating, and examples thereof include polyvinyl alcohol and polyacrylonitrile. A thermoplastic resin is particularly preferable.

In the present invention, the compounding amount of the organically modified layered silicate is (1), based on 100 parts by weight of the resin.
The dispersed state of (2) is 2 to 30 parts by weight.
However, in the resin composition in the final use state, the amount is 2 to 20 parts by weight, preferably 3 to 15 parts by weight, and more preferably 5 to 10 parts by weight. In the range of this blending amount, good antistatic effect expression probability and resin physical properties can be obtained. In the master resin composition for diluted use, the amount is 5 to 30 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the resin. The organically modified layered silicate compound in a dispersed state other than the above (1) and (2) may or may not be contained in any proportion. Further, fillers such as calcium carbonate and clay, reinforcing agents such as glass fibers and carbon fibers, antioxidants, UV stabilizers, lubricants, weathering agents, nucleating agents, pigments, dyes, antifungal agents, and other resin additives, As long as the permanent antistatic property realized by the present invention is not impaired, it may be added and used at any ratio, or may not be used together.

The organically modified layered silicate compound-resin composition of the present invention exhibiting a permanent antistatic property is obtained by melt-kneading an organically modified layered silicate compound and a thermoplastic resin, or a monomer or an organically modified layered silicate uniformly dispersed. It can be obtained by any method of polymerization of prepolymer / resinification, mixing of organically modified layered silicate compound and resin in solvent / distillation of solvent, but is not limited to these methods. Not.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The organically modified layered silicate compound used in the present invention is a reaction between a layered silicate having a cation exchange capacity of 50 meq / 100 g or more and an organic ammonium salt having a total carbon number of 26 or more. Particularly preferred is the product. The amount of the organic ammonium salt used with respect to the layered silicate is the same as that of the organically modified layered silicate compound (1),
It is not particularly limited as long as it can be dispersed in the resin while maintaining the state of (2), but it is generally preferably 0.5 to 2.0 times equivalent to the cation exchange capacity of the layered silicate. Specific organic ammonium salts are shown below.

Organic ammonium salt represented by the following general formula (I)

[0022]

[Chemical 8] [In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 12 or more carbon atoms which may have a substituent. X represents a counter ion. ] An organic ammonium salt represented by the following general formula (II)

[0023]

[Chemical 9] [In the formula, R ³ and R ⁴ are the same or different and each independently represent an alkyl group having 12 or more carbon atoms which may have a substituent, and R ⁵ represents a hydrogen atom or a substituent. Is an alkyl group or aryl group having 2 to 7 carbon atoms, and R ⁶ is a hydrogen atom or an alkyl group or aryl group having 1 to 7 carbon atoms which may have a substituent. X represents a counter ion. ] An organic ammonium salt represented by the following general formula (III)

[0024]

[Chemical 10] [In the formula, R ⁷ , R ⁸ and R ⁹ are the same or different and each independently represent an alkyl group having 8 or more carbon atoms which may have a substituent, and R ¹⁰ represents a hydrogen atom or a substituent. It represents an alkyl group or an aryl group having 1 or more carbon atoms which may be added. X represents a counter ion. ] An organic ammonium salt represented by the following general formula (IV)

[0025]

[Chemical 11] [In the formula, R ¹¹ represents an alkyl group having 8 or more carbon atoms which may have a substituent, R ¹² represents an alkyl group having 1 to 11 carbon atoms which may have a substituent, and R ¹³ and R ¹⁴ are the same or different and each independently represent an alkyl group having 1 to 7 carbon atoms which may have a substituent. X represents a counter ion. ] An organic ammonium salt represented by the following general formula (V)

[0026]

[Chemical 12] [In the formula, R ¹⁵ represents a mono- or polyoxyalkylene group composed of an oxyalkylene unit having 2 to 4 carbon atoms, and R ¹⁶ and R ¹⁷ are the same or different and each may have a substituent. A substituent selected from the group of mono- or polyoxyalkylene groups consisting of an alkyl group having 1 to 30 carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms is shown. The number of added moles of the oxyalkylene unit is 1 to 50. R ¹⁸ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an aryl group. X represents a counter ion. ] An organic ammonium salt represented by the following general formula (VI)

[0027]

[Chemical 13] [In the formula, R ¹⁹ represents an alkyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms which may have a substituent and an oxyalkylene unit having 2 to 4 carbon atoms, a hydrogen atom or a substituent. An alkylphenyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms which may have, or having 2 or more carbon atoms which may have a substituent. Acyl unit (R
CO) and an acylmono- or polyoxyalkylene group consisting of an oxyalkylene unit having 2 to 4 carbon atoms, wherein R ²⁰ and R ²¹ are the same or different and each has 1 to 30 carbon atoms which may have a substituent. Alkyl group, a mono- or polyoxyalkylene group consisting of an oxyalkylene unit having 2 to 4 carbon atoms, an alkyl unit having 1 or more carbon atoms which may have a substituent, and 2 to 4 carbon atoms.
Alkylmono or polyoxyalkylene group consisting of oxyalkylene unit, alkylphenyl mono or poly consisting of an alkyl unit having 1 or more carbon atoms which may have a hydrogen atom or a substituent and an oxyalkylene unit having 2 to 4 carbon atoms An oxyalkylene group and a substituent selected from the group of an acyl mono- or polyoxyalkylene group consisting of an acyl unit having 2 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms which may have a substituent are shown. The number of added moles of the oxyalkylene unit is 1 to 50. R ²² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms or an aryl group. X represents a counter ion. ] An organic ammonium salt represented by the general formula (VII)

[0028]

[Chemical 14] [Wherein, R ²³ , R ²⁴ , and R ²⁵ are the same or different and each is a mono-alkyl group having 1 to 30 carbon atoms and optionally having a substituent, and an oxyalkylene unit having 2 to 4 carbon atoms. Or a polyoxyalkylene group, an alkyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms which may have a substituent and an oxyalkylene unit having 2 to 4 carbon atoms, a hydrogen atom or a substituent An alkylphenyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms,
And a substituent selected from the group consisting of an acyl mono- or polyoxyalkylene group consisting of an acyl unit having 2 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms which may have a substituent, and R ²⁶ is A hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent is shown. The number of added moles of the oxyalkylene unit is 1 to 50. Also, Y, Z, of the W, at least _{one, -CH 2 O -, - CH} 2 COO -, - CH 2 CH 2 COO -, - CH
₂ OCO-, -CH ₂ CH ₂ OCO-,-(CH ₂ ) _m NHCO-,-(CH ₂ ) _m NHCO-CH ₂ O
Represents a linking group selected from the group, and the rest represent a single bond directly bonded to the nitrogen atom of the ammonium group. m represents an integer of 1 to 4. ].

In addition, the organic ammonium salt is one of the above-mentioned organically modified layered silicate compounds (1),
Within the range in which the resin can be dispersed in the resin while maintaining the state of (2), they may be used alone or in combination of two or more.

The preferred interplanar spacing of the organically modified layered silicate compound modified with the organic ammonium salt is 23 to 50Å, more preferably 25 to 40Å, particularly preferably 25 to 35Å. Further, the organic modified layered silicate compound modified by the organic ammonium salt is preferably 23 to 70 Å, preferably 25 to 45 Å.
Is. Here, the "plane spacing" is crystallographically a layered repeating unit distance that gives reflection by X-ray diffraction, and in the case of a layered silicate having a substantial thickness, It also includes the thickness of one layer. That is, the surface spacing in the present invention is the distance L of the layered repeating unit 2 in FIG.
Say _two .

In order to disperse the organically modified layered silicate compound having a volume resistivity of 10 ¹² Ω · cm or less in the resin while maintaining the above-mentioned conditions (1) and (2), the organically modified layered silicate compound is used. It is necessary to consider the combination of and resin.
That is, in general, organic ammonium salt
It is possible to use an organically modified layered silicate compound modified by, but especially the resin is thermoplastic polyethylene or a polyethylene unit-containing resin, thermoplastic polypropylene or a polypropylene unit-containing resin, a thermoplastic polystyrene resin, a thermoplastic styrene unit. In the case of a low-polarity or non-polarity resin such as a contained resin, it is preferable to use an organically modified layered silicate compound modified with an organic ammonium salt. When the resin is relatively polar, it is preferable to use an organically modified layered silicate compound modified with an organic ammonium salt.

Further, for the purpose of improving the dispersibility of the organically modified layered silicate compound in the resin, a compatibilizer, an activator or a dispersion aid is used in combination, or the organically modified layered silicate compound itself is used as an activator or a cup. By treating with the ring agent, the range of combinations of the organically modified layered silicate compound and the resin capable of realizing the function is expanded, and the amount of the organically modified layered silicate compound used can be reduced.

The particle size of the organically modified layered silicate used in the present invention is 50 nm to 8 μm, preferably 100 nm to 5 nm.
μm, and more preferably 200 nm to 5 μm.
A particle size of 50 nm or more is preferred from the viewpoint of the advantage of shape anisotropy, and a particle size of 8 μm or less is preferred from the viewpoint of appearance such as transparency of resin and physical properties such as impact strength of resin.

The cation exchange capacity of the organically modified layered silicate used in the present invention is 50 meq / 100 g or more, preferably 70 to 120 meq / 100 g.
If the cation exchange capacity is too small, the substitution amount of the organic modifier will decrease, and the affinity for the resin will decrease (it can be covered to some extent by using an organic modifier having a large total number of carbon atoms). If it is too large, it cannot be replaced and residual metal ions are generated, which is not preferable.

[0035]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

<< Preparation Method of Organically Modified Layered Silicates (Compounds A to K and PX) >> Organic modified layered silicates (Compounds A to K are prepared by using the organic modifiers and layered silicates shown in Tables 1 to 3. And PX) were prepared. That is, 15 g of unmodified layered silicate is dissolved in 1 liter of ion-exchanged water at 70 ° C. With vigorous stirring, a solution prepared by dissolving 1.05 equivalent of the ion-exchange capacity of the layered silicate used in an organic modifier in 70 ° C. water, ethanol, or a water / ethanol mixture is added all at once. After stirring for 30 minutes, the mixture is left standing and the precipitated organically modified layered silicate compound is collected by filtration. After washing with warm water and then ethanol, it is dried at 0.5 mmHg / 80 ° C. for 72 hours. The unmodified layered silicates used in this example are the following four types.・ Kunipia F (made by Kunimine Industry Co., Ltd.)… Ion exchange capacity 119 meq / 100 g (Compound L) ・ Wenger 23 (made by Toyojun Yoko)… Ion exchange capacity 87 meq / 100 g ・ SWN (Corp Chemical stock) Company)… Ion exchange capacity 115 meq / 100 g ME-100 (made by Coop Chemical Co., Ltd.)… Ion exchange capacity 75 meq / 100 g In addition, the following three types of commercially available organically modified layered silicate compounds are available. They were used (the former two are modified with dimethyldioctadecyl ammonium, and the latter are modified with polyoxypropylene chain-containing ammonium).

SAN (manufactured by Co-op Chemical Co., Ltd.) ... Compound M-BENTONE 52 (manufactured by RHEOX, INC) ... Compound N-SPN (manufactured by Co-op Chemical Co., Ltd.) ... Compound Y Commercially available and synthesized organically modified layered silicic acid The interplanar spacing of the salt compound is determined by powder X-ray diffraction method (RU-20 manufactured by Rigaku Denki Co., Ltd.).
0, CuKα-40 kV), and the volume resistivity was determined by using an organically modified layered silicate compound sufficiently dried in a vacuum desiccator containing phosphorus pentoxide as a compressed pellet of φ = 20 mm and thickness of 1 mm. , Measured in a dry glove box. For the measurement, a digital ultra-high resistance / micro ammeter R8340A manufactured by Advantest and an HRS probe manufactured by DIA Instruments Co., Ltd. with a self-made shield jacket attached were used. The results are shown in Tables 1 to 3.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3] (Note) In compound X, EO is -CH ₂ CH ₂ O-, PO is -C
H ₂ CH (CH ₃ ) O −, and (1/2) means that the EO / PO molar ratio is 1: 2.

[Performance Evaluation] With respect to each organically modified layered silicate compound-resin composition shown in the following Examples and Comparative Examples,
The following evaluation was performed.

<< Evaluation of Dispersibility of Organically Modified Layered Silicate Compound in Resin >> An apparently homogeneous organically modified layered silicate compound-resin composition was obtained from three or more different parts of the resin composition. From a plurality of transmission electron microscope images (TEM photographs; images obtained from 100-nm-thick sections) with a magnification of 10,000 to 100,000 times, the primary aggregate or the shortest diameter was 500.
Only the secondary agglomerate particles of nm or less are picked up, and the total area occupied by the organically modified layered silicate particle phase on the TEM screen, the total area occupied by the resin matrix phase on the TEM screen, and both phases From the density (g / cm ³ ) of
It was determined whether or not the organically modified layered silicate particles satisfying the above-mentioned definition (1) of the dispersity were in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the resin [Evaluation (A)]. On the other hand, from multiple TEM photographs with the same magnification of 10,000 to 100,000 times, 50
Randomly extracted 200 sections of 0 nm square, and different particles of the organically modified layered silicate compound (in the case of independent primary agglomerates, refer to the primary agglomerated particles and form a continuous phase) In the case of a secondary agglomerate, the secondary agglomerate shall be regarded as one particle) and / or the probability that two or more fragments thereof are found is determined, and the system in which this probability is 50% or more is the above-mentioned dispersion. It was considered that the degree of regulation (2) was satisfied [Evaluation (B); in reality, this evaluation was based on the degree of dispersion (1).
It also contains information on the amount of the organically modified layered silicate compound and is often stricter than the dispersion degree regulation (2)]. With respect to a homogeneous organically modified layered silicate compound-resin composition system, if both of the evaluations (A) and (B) are satisfied, it is practically possible to obtain 2 to 3 of the organically modified layered silicate compound.
It can be said that 0 part by weight is dispersed in 100 parts by weight of the resin matrix, satisfying both the dispersion degree regulations (1) and (2). In any of the evaluations, the resin composition system containing the third component such as rubber-like particles incompatible with the organically modified layered silicate compound, the incompatible resin particle phase, the filler, etc. The above analysis was applied to the resin matrix site where the invaded area was eliminated. However, because the organically modified layered silicate compound has a special uneven distribution structure,
A system that shows an antistatic property although not microscopically uniform (for example, Example 4) was exceptionally excluded from the application of this analysis method, and was continuous over a sufficiently large TEM field of view. It was confirmed that an organically modified layered silicate phase was formed and that the dispersion states of (1) and (2) above were satisfied. The results are shown in Tables 4-7.

<< Evaluation of Antistatic Property of Organically Modified Layered Silicate Compound-Resin Composition >> As an evaluation of the antistatic property, the half-life of electrification voltage before and after washing and the specific volume resistivity were evaluated. Unless otherwise specified, measurement of the electrification voltage half-life and volume / surface resistivity of the organically modified layered silicate compound-resin composition was performed using a sample stored in a constant temperature and constant humidity chamber at 23 ° C. and a humidity of 60% for 24 hours. It was The antistatic property was confirmed by the fact that the electrification voltage half-life of the resin composition was 15 sec or less. The fact that the antistatic property is so-called "permanent antistatic property" means that the test piece is
It was confirmed by thoroughly washing with ethanol, then drying and re-measuring the voltage half-life, but the organically modified layered silicate particles are extremely huge from the molecular level and are virtually immobile in the resin, so The fact that the resistivity has dropped to 10 ¹³ Ω · cm or less can be replaced with the confirmation. Honest meter TYPE S-5109 for half-life measurement
(Manufactured by Shishido Electrostat., LTD.) Was used. The results are shown in Tables 4-7. Further, the surface resistivity and volume resistivity of the organically modified layered silicate compound-resin composition are measured using a digital ultra-high resistance / micro ammeter R8340A and a high resistance measurement chamber R12702A manufactured by Advantest.
It carried out based on K-6911.

Example 1 100 parts by weight of random polypropylene (PP) resin "F658H" manufactured by Grand Polymer Co., Ltd. was added with Compound A.
5 parts by weight of the twin-screw extruder “EC
M45-33.5 "was used for melt kneading (190 ° C,
100 rpm). From here by melt press 100 × 1
Ten test pieces of 00 × 1 mm were prepared and used for various measurements. The obtained compound A-polypropylene composition maintains transparency when the resin alone is used (haze value: 40),
The organically modified layered silicate particles were transparently and uniformly dispersed to the naked eye. The half-life of electrification voltage of each of the sample pieces was 0.2 sec or less, and it was confirmed that the present resin composition was in a category showing sufficient antistatic property. In addition, the half-life of the electrification voltage measured by washing the surface of the test piece with water / ethanol and then drying and re-measured was 0.2 sec or less, confirming that the resin composition has a permanent antistatic property.
Further, even when the resin composition was stored in a glove box at room temperature / humidity of 5% for 3 days, the half-life of electrification voltage did not change.

The volume resistivity of this compound A-polypropylene composition is 2.0 × 10 ¹¹ Ω · cm, which is much lower than that of the resin alone. On the other hand, the surface resistivity is 3.4 ×
Although exhibiting 10 ¹³ Ω / □, which is lower than when the resin alone was used, the conventional low molecular weight activator type antistatic agent-containing resin composition system and alloy type antistatic resin are considered because of the previous half-life of the electrification voltage. In the composition system, the "charge voltage half-life-surface resistivity" correlation greatly deviates from the value inferred in line with common sense, and is a large value of about two digits. However, when the counter electrode on the back surface of the sample at the time of measuring the surface resistivity was replaced with a Teflon plate, a surface resistance value of 2.1 × 10 ¹² Ω / □ was obtained. The fact that the surface resistivity of the sample piece having a thickness of 1 mm shows a hanging value indicates that the present resin composition has a completely uniform volume resistivity over the entire molded body.

A transmission electron microscope image of the compound A-polypropylene resin composition obtained in Example 1 is shown in FIG.
The organically modified layered silicate compound A is dispersed in a polypropylene resin in a unit of a primary aggregate having a thickness of several to several tens of nm, and a huge secondary aggregate having a minor axis of 500 nm or more has a screen of several tens of places. No change was found even if changed [Evaluation (A): ○;
The reason why there is no such huge secondary aggregate at all is that it looks transparent to the eye. Although the compounding amount of the compound A is as small as 5 parts by weight, the dissociated silicate primary aggregates are dispersed in close proximity to each other in the resin matrix, and no silicate particles are found in the 1 μm square compartment. No area was seen. In addition, 2 out of 200 sections of 500 nm square randomly extracted from multiple TEM photographs with the same magnification.
The probability of finding one or more organically modified layered silicate particles was 67% [Evaluation (B): ◯]. The ratio of the organically modified layered silicate compound A satisfying the dispersion degree regulations (1) and (2) to the total amount of the compound A was estimated to be about 96%.

In X-ray diffraction of the resin composition, the interplanar spacing was 28.3 Å, which was basically the same as when compound A was used alone, and sharp reflection was obtained. It is considered that the compound A hardly swelled in the polypropylene resin and was dispersed while maintaining its primary aggregation structure.

Example 2 100 parts by weight of polyethylene (PE) resin "Sumikasen F208-1" manufactured by Sumitomo Chemical Co., Ltd. was added with Compound A 3
0 parts by weight was added and melt kneading was carried out in the same manner as in Example 1 (190
C., 100 rpm). The compound A was virtually transparently dispersed in the polyethylene resin without leaving huge secondary aggregated particles having a short diameter of 500 nm or more. The voltage half-life of the resin composition is 0.2 seconds or less, and the volume resistivity is 7.6 × 10 ¹⁰ Ω · c.
It was m. The electrification voltage half-life after washing the surface of the sample piece with water / ethanol was also 0.2 sec or less. The compound A was slightly swollen in the resin composition (plane spacing: 31.5Å).

Example 3 100 parts by weight of the organically modified layered silicate compound-polyethylene resin composition obtained in Example 2 was melt-kneaded with 385 parts by weight of a polyethylene resin at 190 ° C. (100 rpm).
The obtained diluted resin composition has a charge voltage half-life of 0.7 se.
c, half-life of electrified voltage after washing with water / ethanol is 0.8 se
In c, good permanent antistatic property was exhibited. The volume resistivity is
It was 3.6 × 10 ¹¹ Ω · cm.

Example 4 High impact polystyrene (HIP) manufactured by Asahi Kasei Corporation
S) Compound B was added to 100 parts by weight of resin "H8652".
2 parts by weight were added, and the mixture was melt-kneaded in the same manner as in Example 1 (2
20 ° C., 100 rpm). The volume resistivity of this resin composition was 6.5 × 10 ¹¹ Ω · cm. The organically modified layered silicate compound in the present resin composition exhibits an exceptionally unique dispersion morphology. Compound B-HIPS obtained in Example 4
A transmission electron microscope image of the resin composition is shown in FIG. Figure 5
Among them, it is the polybutadiene phase blended with HIPS that is dyed with osmium oxide and forms multiple phases. In addition to this, it can be seen that the compound B is present in the polystyrene matrix portion in the form of a network composed of a band or a film-like structure having a short diameter (thickness) of 20 to 30 nm. This network itself is an extremely huge secondary agglomerate, and in fact, one side with a lower magnification is 50
From one end to the other end of the μm TEM screen, the continuous phase of Compound B or different aggregated particle phases separated by a distance of 500 nm or less can be traced and easily reached. That is,
It is considered that the compound B forms a highly efficient conductive path and imparts the permanent antistatic ability to the resin even with a small addition amount. In addition, the compound B in the present resin composition
The interplanar spacing was 29.9Å, which was slightly larger than that before compounding.

Example 5 Torayac 100, acrylonitrile-butadiene-styrene copolymer (ABS resin) manufactured by Toray Industries, Inc. 100
Compound C 3 parts by weight was added to parts by weight, and the mixture was melt-kneaded in the same manner as in Example 1 (220 ° C., 100 rpm) to give compound C-A.
A BS resin composition was obtained. In the resin composition, the interplanar spacing of compound C was increased to 34Å.

Example 6 100 parts by weight of a homopolypropylene resin "Mitsui Noblen JHH-G" manufactured by Mitsui Toatsu Chemicals, Inc. was added with Compound D 5.
Add parts by weight, melt-knead as in Example 1 (200 ° C.,
100 rpm) to obtain a transparent compound D-polypropylene resin composition. There was a 70% probability that two or more organically modified layered silicate particles were found in 200 sections of 500 nm square randomly extracted from a plurality of TEM photographs.

Example 7 To 100 parts by weight of filler-reinforced polypropylene resin "Sunlet TT7030" manufactured by Mitsui Petrochemical Co., Ltd., 5 parts by weight of Compound E was added and melt-kneaded in the same manner as in Example 1 (200 ° C., 100 rpm) to give a compound. An E- (filler-containing) polypropylene resin composition was obtained. Although there has been no effective antistatic method for the filler-containing polyolefin resin, the resin composition obtained here has a charge voltage half-life of 2.8 sec and a volume resistivity of 1.2 × 10 ¹² Ω · cm. And exhibited good permanent antistatic properties.

Example 8 A transparent compound F-polypropylene resin composition was obtained in exactly the same manner as in Example 1 except that the compound F was used as the organically modified layered silicate compound.

Example 9 10 parts by weight of compound G was added to 100 parts by weight of random polypropylene resin "F658H", and the mixture was kneaded using a baby inch roll manufactured by Nishimura Koki Co., Ltd. at 155 ° C. and 20 rpm for 15 minutes. The obtained compound G-polypropylene resin composition was transparent and had a volume resistivity of 6.4 × 10 ¹² Ω ·
cm.

Comparative Example 1 A compound G-polypropylene resin composition was obtained in the same manner as in Example 9 except that the kneading time was 5 min. Although the obtained resin composition is slightly clouded,
It was almost transparent. However, on the TEM photograph (Fig. 6), 1
There were many regions where the compound G dissociated into the secondary agglomerate units was not distributed, and most of them existed as secondary elongated agglomerates. Further, according to the image analysis, about 10% of the added compound G was present as secondary aggregated particles having a short diameter of 1 μm or more. Randomly extracted 500 nm square section 20
The probability of finding two or more organically modified layered silicate particles in 0 particles was 25%. The electrification voltage half-life of the resin composition is 30 sec or more, and the volume resistivity is 8.1 × 1.
It was 0 ¹³ Ω · cm.

Comparative Example 2 100 parts by weight of random polypropylene resin "F658H" and Compound G in an amount such that the inorganic content in the resin was 5.4 wt% were used in 29th of "Proceedings of 4th Polymer Material Forum".
Kneading was carried out by the method described on page 4. In the obtained resin composition, compound G particles were observable everywhere with the naked eye, and the haze value was increased to 55 as compared with 40 when the resin was alone. TEM
Above, the compound G was present as substantially band-shaped secondary aggregated particles (minor axis: 200 nm to 2 μm), and in addition to this, huge aggregated particles having a minor axis of 3 μm or more were also observed in various places. The dispersibility of the organically modified layered silicate compound is extremely poor, and the probability that two or more organically modified layered silicate particles are found in 200 randomly extracted sections of 500 nm square is 13%. It didn't pass. The volume resistivity of this resin composition is 1.2 × 10 ¹⁴ Ω.
It was cm.

Comparative Example 3 A compound H-polypropylene resin composition was obtained in the same manner as in Example 1 except that compound H was used instead of compound A. The resin composition appeared cloudy due to undissociated compound H particles. In the TEM observation, giant secondary particles of the compound H having a size of several to several hundred μm were found everywhere, and diffusion of the primary aggregate of the compound H was hardly seen in the resin matrix portion. The probability that two or more organically modified layered silicate particles are found in 200 randomly selected 500-nm square sections is 0.5%, and the volume resistivity is 5.2 × 1.
It was 0 ¹⁵ Ω · cm.

Comparative Example 4 A compound I-polypropylene resin composition was obtained in exactly the same manner as in Example 1 except that compound I was used instead of compound A. The resin composition appeared cloudy due to undissociated Compound I particles. In TEM observation, huge secondary aggregates of compound I having a size of several to several hundred μm were found everywhere, and diffusion of primary aggregates of compound I was hardly seen in the resin matrix part. The probability that two or more organically modified layered silicate particles are found in 200 randomly selected 500-nm square sections is 1%, and the volume resistivity is 7.7 × 10 ^15.
It was Ω · cm.

Comparative Example 5 A compound J-polypropylene resin composition was obtained in the same manner as in Example 1 except that the compound J was used in place of the compound A. The resin composition appeared cloudy due to undissociated Compound J particles. In the TEM observation, a large number of secondary agglomerates of the compound J having a size of several to several hundred μm are found everywhere, and the diffusion of the primary agglomerates of the compound J into the resin matrix portion is limited to the vicinity of the huge secondary agglomerates. It was being done. 500n randomly extracted
The probability that two or more organically modified layered silicate particles were found in 200 m square compartments was 11%, and the volume resistivity was 6.3 × 10 ¹³ Ω · cm.

Comparative Example 6 A compound K-polypropylene resin composition was obtained in the same manner as in Example 1 except that the compound K was used in place of the compound A. The resin composition appeared cloudy due to undissociated compound K particles. In the TEM observation, huge secondary aggregates of the compound K having a size of several to several hundred μm were found in various places, and diffusion of the primary aggregate of the compound K was hardly seen in the resin matrix portion. The probability that 2 or more organically modified layered silicate particles are found in 200 randomly selected 500 nm square sections is 3%, and the volume resistivity is 2.2 × 10 ^14.
It was Ω · cm.

Comparative Example 7 A compound L-polypropylene resin composition was obtained in the same manner as in Example 1 except that unmodified montmorillonite "Kunipia F" (compound L) was used in place of compound A.
The resin composition appeared cloudy due to undissociated compound L particles. In TEM observation, huge secondary aggregates of compound L having a size of several tens to several hundreds of μm were observed in various places, and no diffusion of primary aggregates of compound L was observed in the resin matrix portion. The probability of finding two or more layered silicate particles in 200 randomly selected 500 nm square sections is
The volume resistivity was 0% and the volume resistivity was 10 ¹⁶ Ω · cm or more.

Comparative Example 8 Organically modified layered silicate “SAN” (compound M) manufactured by Corp. Chemical Co., Ltd. was used as a polypropylene according to the method described in “The 38th Clay Science Symposium Proceedings”, page 52 (Otani et al.). A polypropylene resin composition containing 3 wt% of Compound M was added to the resin to obtain a polypropylene resin composition. The resin composition appeared cloudy due to undissociated Compound M particles. In TEM observation, huge secondary aggregates of compound M having a size of several to several hundred μm were found everywhere, and diffusion of primary aggregates of compound M was hardly seen in the resin matrix portion. The probability that two or more organically modified layered silicate particles are found in 200 randomly selected 500-nm square sections is 8%, and the volume resistivity is 2.8 × 10 ¹⁴ Ω · cm. there were.

Comparative Example 9 A polyethylene resin "Sumikasen F208-1" was used in place of the random polypropylene resin, and a compound A 5 was used.
"BENTON" made by RHEOX, INC instead of parts by weight
A compound N-polyethylene resin composition was obtained in exactly the same manner as in Example 1 except that 10 parts by weight of "E 52" (compound N) was used. The resin composition appeared cloudy due to undissociated compound N particles. In the TEM observation, huge secondary aggregates of the compound N having a size of several to several hundred μm were found in various places, and the diffusion of the primary aggregate of the compound N into the resin matrix portion was slight. Randomly extracted 500 nm square section 20
The probability that 2 or more organically modified layered silicate particles are found in 0 is 21%, and the volume resistivity is 5.6 × 10 ¹³ Ω.
・ It was cm.

Comparative Example 10 A compound O-polypropylene resin composition was prepared in exactly the same manner as in Example 1 except that 1.5 parts by weight of tetra-n-decyl ammonium bromide (Compound O) was used in place of 5 parts by weight of Compound A. I got a thing. The resin composition was transparent immediately after molding, but after 3 days, the surface was slightly clouded. The electrification voltage half-life of this resin composition was 30 sec or more, the surface resistivity was 10 ¹⁵ Ω / □ or more, and the volume resistivity was 10 ¹⁶ Ω · cm or more.

Example 10 5 parts by weight of compound P was added to 100 parts by weight of ABS resin "Toyolac 100", and the mixture was melt-kneaded at 220 ° C in the same manner as in Example 1. According to TEM analysis, the obtained compound P-
In the ABS resin composition, about 15% of the compound P was dissociated into primary aggregate units, and the rest was uniformly dispersed in the resin matrix as secondary aggregates having a minor axis of about 100 nm or less. The probability that two or more organically modified layered silicate particles were found in 200 randomly extracted 500 nm square sections was 90% (according to X-ray diffraction, the resin composition In the material, compound P swelled to a face spacing of 45.7Å). The resin composition had a charged voltage half-life of 0.6 sec, a charged voltage half-life of 4.2 sec after washing with water / ethanol, and a volume resistivity of 7.5 × 10 ¹¹ Ω · cm.
It was confirmed to have a permanent antistatic property. In addition, even though the compound P is uniformly dispersed in the resin, it is 1 mm.
The surface resistivity of this resin composition obtained by using a thick sample piece was 4.5 × 10 ¹¹ Ω / □, but the humidity was 5%.
This value increased to 3.8 × 10 ¹³ Ω / □ when stored for half a day in a glove box kept at. The half-life of the charged voltage is 7 seconds and the volume resistivity is 2.1 × 10 ¹² Ω.
・ Although it increased to cm, and the antistatic ability was slightly lower than that under the standard conditions, it was still in a good category.

Example 11 Polystyrene (PSt) resin "G" manufactured by Asahi Kasei Corporation
5 parts by weight of compound Q was added to 100 parts by weight of "P666" and kneaded at 200 ° C in the same manner as in Example 10 to give compound Q-
A polystyrene resin composition was obtained. According to TEM analysis,
In the obtained compound Q-polystyrene resin composition, about 30% of the compound Q was dissociated into primary aggregate units, and the rest was a minor axis 1
Secondary aggregates having a size of about 00 nm or less were uniformly dispersed in the resin matrix. 500n randomly extracted
The probability of finding two or more organically modified layered silicate particles in 200 m square compartments was 72%. The half-life of charged voltage of this resin composition was 4.2 sec, and the half-life of charged voltage after washing with water / ethanol was 7.3 sec.

Example 12 Compound RA was prepared in the same manner as in Example 10 except that 7 parts by weight of compound R was used instead of 5 parts by weight of compound P.
A BS resin composition was obtained. According to TEM analysis, in the obtained compound R-ABS resin composition, about 30% of the compound R is dissociated into primary aggregate units, and the rest is a secondary aggregate having a minor axis of about 100 nm or less. It was evenly dispersed in the matrix. Randomly extracted 500nm square section 2
The probability of finding two or more organically modified layered silicate particles in 00 was 90%. The electrification voltage half-life of this resin composition was 0.2 sec or less, and the electrification voltage half-life after washing with water / ethanol was also 0.2 sec or less.

Example 13 Polyethylene terephthalate (PE manufactured by Kuraray Co., Ltd.
T) To 100 parts by weight of the resin “Clapet 1030”, 10 parts by weight of the compound S was added, and in the same manner as in Example 10 at 270 ° C., a compound S-PET resin composition was obtained. According to TEM analysis, in the obtained compound S-PET resin composition,
80% or more of the compound S was uniformly dispersed in the resin matrix as a secondary aggregate having a short diameter of several tens to 200 nm.
2 out of 200 randomly selected 500 nm square sections
The probability of finding one or more organically modified layered silicate particles was 77%. The volume resistivity of this resin composition is 7.
It was 3 × 10 ¹¹ Ω · cm.

Example 14 Example 10 except that compound T was used in place of compound P
A compound T-ABS resin composition was obtained in exactly the same manner as. The volume resistivity of this resin composition is 5.0 × 10 ⁹ Ω · c
It was m.

Example 15 Polymethylmethacrylate (PM manufactured by Asahi Kasei Corporation)
MA) 7 parts by weight of compound U was added to 100 parts by weight of the resin "Delpet 560F", and kneading was carried out at 210 ° C in the same manner as in Example 10. -A PMMA resin composition was obtained. TEM
Randomly extracted 500-nm square section 200 on the photo
The probability of finding two or more organically modified layered silicate particles in the particles was 69%. The volume resistivity of this resin composition was 8.1 × 10 ¹² Ω · cm.

Example 16 Example 15 except that compound V was used in place of compound U.
A compound V-PMMA resin composition was obtained in exactly the same manner as. The volume resistivity of this resin composition is 3.6 × 10 ¹¹ Ω · c.
It was m.

Example 17 5 parts by weight of compound W, 100 parts by weight of a styrene monomer purified by distillation under reduced pressure after removal of an inhibitor, and 0.4 part by weight of a polymerization initiator "V-59" manufactured by Wako Pure Chemical Industries, Ltd. were dried and then put under argon. It was added to 200 parts by weight of distilled and purified toluene, and polymerization was carried out in an argon atmosphere at 75 ° C. for 12 hours while stirring. After cooling, the mixture was added to a large amount of hexane, and the resulting precipitate was reprecipitated with toluene / hexane. White compound W
-The polystyrene resin composition became almost transparent when melt-molded, although it was slightly cloudy. On the TEM photograph, most of the compound W exists as secondary agglomerate particles with a short diameter of 50 to 200 nm, and two or more organically modified layered silicates are included in 200 randomly extracted 500 nm square sections. The probability of finding particles was 64%. The volume resistivity of this resin composition was 4.1 × 10 ¹² Ω · cm.

Example 18 10 parts by weight of compound Q was mixed with 100 parts of a mixed solution of glycerin type polyether polyol (OHV = 235; manufactured by Mitsui Toatsu Chemicals, Inc.): ethylene glycol = 10: 1.
It was added to parts by weight and stirred at 60 ° C. for 1 hour to disperse. To this composition liquid, 97.2 parts by weight of a polyfunctional isocyanate monomer "TR-50" manufactured by Mitsui Toatsu Chemicals, Inc. and 1 part by weight of a polymerization catalyst "Kaorizer No. 1" manufactured by Kao Corporation are added, and the mixture is kept for 1 minute. After stirring, 100 mm x 100 mm
The compound Q-crosslinked polyurethane (PU) resin composition was obtained by developing in a mold of × 5 mm and reacting at 50 ° C. for 24 hours. According to TEM observation, in the resin composition, most of the compound Q was present as a secondary aggregate having a short diameter of several tens to 500 nm.

Example 19 Example 18 except that compound X was used in place of compound Q.
A compound X-crosslinked polyurethane resin composition was obtained in exactly the same manner as. According to TEM analysis, the obtained compound X-
In the crosslinked polyurethane resin composition, most of the compound X was present as a secondary aggregate having a short diameter of several tens to 500 nm.
2 out of 200 randomly selected 500 nm square sections
The probability of finding one or more organically modified layered silicate particles was 81%. The half-life of charged voltage of this resin composition was 0.8 sec, and the half-life of charged voltage after washing with water / ethanol was 3.4 sec.

Example 20 50 parts by weight of maleic anhydride and bisphenol A 128
After stirring 1 part by weight in an argon stream at 150 ° C. for 1 hour, the temperature was raised to 210 ° C. and the reaction was further continued for 2 hours while removing the produced water. After cooling, the obtained unsaturated polyester resin was pulverized, and 23 parts by weight of the compound X was added to 300 parts by weight of the styrene monomer and mixed for 30 minutes. After adding 10 parts by weight of benzoyl peroxide and 2.5 parts by weight of dimethylaniline to this mixed solution, 100 mm × 1
It was developed in a mold of 00 mm × 5 mm and left standing at 40 ° C. for 3 hours to polymerize. According to TEM analysis,
In the obtained compound X-unsaturated polyester resin composition,
Most of the compound X was dispersed as secondary aggregated particles having a short diameter of several tens to 500 nm. The volume resistivity of this resin composition was 5.4 × 10 ¹¹ Ω · cm.

Comparative Example 11 Homopolypropylene resin "Mitsui Noblen JHH-G"
To 100 parts by weight, 7 parts by weight of organic modified layered silicate “SPN (Compound Y)” manufactured by Cope Chemical Co., Ltd. was added, 2
Kneading was carried out in the same manner as in Example 10 at 00 ° C. to give compound Y-
A polypropylene resin composition was obtained. In this resin composition, compound Y particles can be found everywhere with the naked eye, but TEM
According to the analysis, 80% or more of the compound Y was unevenly distributed in the resin matrix as a secondary aggregate having a short diameter of 1 to several hundreds of μm. The probability of finding two or more organically modified layered silicate particles in 200 randomly extracted 500-square-square sections was 8%. The electrification voltage half-life of this resin composition was 30 sec or more, and the antistatic property was not shown.

Comparative Example 12 Compound V (7 parts by weight) was added to polystyrene resin "GP666" (100 parts by weight), and the mixture was kneaded at 200 ° C in the same manner as in Example 11 to obtain a compound V-polystyrene resin composition. T
According to EM analysis, 80% of compound V in the resin composition
The above was unevenly distributed in the resin matrix as a secondary aggregate having a minor axis of 1 to 100 to 10 μm. 500n randomly extracted
The probability of finding two or more organically modified layered silicate particles in 200 m-square sections was 10%. The electrification voltage half-life of this resin composition was 30 sec or more, and the antistatic property was not shown.

Comparative Example 13 A compound W-polypropylene resin composition was obtained in the same manner as in Comparative Example 11 except that 7 parts by weight of Compound W was used instead of Compound Y. The resin composition appeared cloudy due to undissociated compound W particles. In TEM observation, secondary aggregated particles of a huge compound W of several to several hundred μm are found everywhere,
Almost no diffusion of the primary aggregate of the compound W was observed in the resin matrix part. 500n randomly extracted
The probability that two or more organically modified layered silicate particles were found in 200 m square sections was 9%, and the volume resistivity was 7.9 × 10 ¹³ Ω · cm.

Comparative Example 14 To 100 parts by weight of ABS resin "Toyolac 100", 0.3 part by weight of dodecyldimethylpolyoxypropylene ammonium chloride (Compound Z) was added, and in the same manner as in Example 10, Compound Z-ABS resin A composition was obtained. The surface resistivity of this resin composition, which was 3.2 × 10 ¹⁵ Ω / □ immediately after molding, was 2.8 × 10 ¹² Ω / □ after storage at room temperature for 30 days.
It showed a low antistatic ability even though it was weak. However, if the surface of the sample piece is washed with water / ethanol and then dried,
The surface resistivity was 10 ¹⁶ Ω / □ or more.

Comparative Example 15 Only the random polypropylene resin "F658H" was used as 1
A polypropylene resin test piece was prepared by passing it through a twin-screw extruder at 90 ° C. (100 rpm) and performing the same treatment as in Example 1. The resin had a high half-life of electrification voltage of 30 sec or more and a volume resistivity of 10 ¹⁶ Ω · cm or more, and showed high insulation.

Comparative Example 16 Homopolypropylene resin "Mitsui Noblen JHH-G"
Only through a twin screw extruder at 200 ° C (100 rp
m), a polypropylene resin test piece was prepared in the same manner as in Example 1. The resin had a high half-life of electrification voltage of 30 sec or more and a volume resistivity of 10 ¹⁶ Ω · cm or more, and showed high insulation.

Comparative Example 17 Filler reinforced polypropylene resin "Sunlet TT70"
30 "through a twin screw extruder at 200 ° C (100
rpm), by the same treatment as in Example 1 (containing filler)
A polypropylene resin composition test piece was prepared. This resin composition has a charged voltage half-life of 30 sec or more and a volume resistivity of 10
High insulation was shown at ¹⁶ Ω · cm or more.

Comparative Example 18 Only the polyethylene resin "Sumikasen F208-1" was
A polyethylene resin test piece was prepared by passing it through a twin-screw extruder at 200 ° C. (85 rpm) and by the same treatment as in Example 1. The resin had a high half-life of electrification voltage of 30 sec or more and a volume resistivity of 10 ¹⁶ Ω · cm or more, and showed high insulation.

Comparative Example 19 A HIPS resin test piece was prepared in the same manner as in Example 1, except that only the HIPS resin "H8652" was passed through a twin-screw extruder at 220 ° C (100 rpm). The resin had a high half-life of electrification voltage of 30 sec or more and a volume resistivity of 10 ¹⁶ Ω · cm or more, and showed high insulation.

Comparative Example 20 Only ABS resin "Toyolac 100" was passed through a twin-screw extruder at 220 ° C. (85 rpm), and an ABS resin test piece was prepared in the same manner as in Example 1. The resin had a high half-life of electrification voltage of 30 sec or more and a volume resistivity of 10 ¹⁶ Ω · cm or more, and showed high insulation.

Comparative Example 21 A polystyrene resin test piece was prepared in the same manner as in Example 1, except that only the polystyrene resin “GP666” was passed through a 200 ° C. twin-screw extruder (100 rpm). This resin has a voltage half-life of 30 seconds or more and a volume resistivity of 10 ¹⁶ Ω.
・ Higher insulation was shown at cm or more.

Comparative Example 22 PMMA resin “Delpet 560F” alone was heated at 210 ° C.
After passing through the twin-screw extruder (100 rpm), a PMMA resin test piece was prepared in the same manner as in Example 1. This resin has a charged voltage half-life of 30 sec or more and a volume resistivity of 2 × 10.
^It showed high insulation at ¹⁵ Ω · cm.

Comparative Example 23 Only PET resin "Clapet 1030" was passed through a twin-screw extruder at 270 ° C (100 rpm), and a PET resin test piece was prepared in the same manner as in Example 1. This resin has a charged voltage half-life of 30 seconds or more and a volume resistivity of 7.8 × 10 ¹⁴
Ω · cm showed high insulation.

Comparative Example 24 A crosslinked polyurethane resin was obtained by the same procedure as in Example 18, except that the compound Q was not added.
This resin exhibited a high insulating property with a voltage half-life of 30 sec or more and a volume resistivity of 7.9 × 10 ¹² Ω · cm.

Comparative Example 25 An unsaturated polyester resin composition was obtained by the same procedure as in Example 20, except that the compound X was not added. The resin composition exhibited a high insulating property with a charged voltage half-life of 30 sec or more and a volume resistivity of 6.4 × 10 ¹³ Ω · cm.

[0092]

[Table 4]

[0093]

[Table 5]

[0094]

[Table 6]

[0095]

[Table 7] (Note) * 1 In the table, the compounding amounts are parts by weight based on 100 parts by weight of the resin. * 2 In the table, the symbols in the minor axis of the aggregate and the average closest particle distance are as follows. (A) Minor axis of agglomerate O: The proportion of primary agglomerates and secondary agglomerates having a minor axis of 500 nm or less is within the range of 2 to 30 parts by weight with respect to 100 parts by weight of the resin matrix. X: The fraction of the primary aggregate and the secondary aggregate having a minor axis of 500 nm or less is less than 2 parts by weight with respect to 100 parts by weight of the resin matrix. (B) Average closest particle distance ∘: The probability that two or more particles exist within a 500 nm square section is 50% or more. Poor: The probability that two or more particles are present within the 500 nm square section is less than 50%.

[Brief description of drawings]

FIG. 1 is an electron microscope image showing the particle structure of a commercially available trimethyloctadecyl ammonium modified clay-polypropylene resin composition.

FIG. 2 is a model diagram for explaining an average nearest neighbor particle in the present invention.

FIG. 3 is a model diagram for explaining the surface spacing in the present invention.

FIG. 4 is a transmission electron microscope image showing the particle structure of the compound A-polypropylene resin composition obtained in Example 1.

5 is a transmission electron microscope image showing the particle structure of the compound B-HIPS composition obtained in Example 4. FIG.

FIG. 6 is a transmission electron microscope image showing the particle structure of the compound G-polypropylene resin composition obtained in Comparative Example 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Isao Nishi Nishi 1334 Kao Co., Ltd., Wakayama City, Wakayama Prefecture Kao Co., Ltd. (72) Inventor Yuzo Tsunoda 1334 Minato Minato, Wakayama City, Wakayama Co., Ltd. (56) Ref. Flat 8-53572 (JP, A) JP 7-331092 (JP, A) JP 9-183910 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1 / 00-101/16 C08K 3/00-13/08 C08J 3/20

Claims (24)

(57) [Claims] 1. 1 to 30 parts by weight of an organically modified layered silicate compound having a volume resistivity of 10 ¹² Ω · cm or less based on 100 parts by weight of a resin, and (1) a primary aggregate and / or an aggregate. Has a minor axis of 500 nm
A method for antistatically dispersing a resin in the form of the following secondary agglomerates, and (2) so that the average closest particle distance is 500 nm or less, wherein the organically modified layered silicate compound is: A reaction product of a layered silicate having a cation exchange capacity of 50 meq / 100 g or more and an organic ammonium salt represented by the following general formula (I) having a total carbon number of 26 or more, the resin and the organically modified layered layer An antistatic method for a resin, which comprises kneading a silicate compound with a roll kneading method for 15 minutes or more. [Chemical 1] [In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 12 or more carbon atoms which may have a substituent. X represents a counter ion. ] 2. An organically modified layered silicate compound 2 having a volume resistivity of 10 ¹² Ω · cm or less in 100 parts by weight of a resin.
To 30 parts by weight, (1) the primary aggregate and / or the minor axis of the aggregate is 500 nm.
A permanent antistatic resin composition, which is dispersed in the form of the following secondary agglomerates, and (2) having an average closest particle distance of 500 nm or less, wherein the organically modified layered silicate compound is Is a reaction product of a layered silicate having a cation exchange capacity of 50 meq / 100 g or more and an organic ammonium salt represented by the following general formula (I) having a total carbon number of 26 or more. A permanent antistatic resin composition, which is obtained by kneading a modified layered silicate compound with a roll kneading method for 15 minutes or more. [Chemical 2] [In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 12 or more carbon atoms which may have a substituent. X represents a counter ion. ] 3. 1 to 3 parts by weight of an organically modified layered silicate compound having a volume specific resistance of 10 ¹² Ω · cm or less based on 100 parts by weight of a resin, (1) primary aggregate and / or aggregate Has a minor axis of 500 nm
A method for antistatically dispersing a resin in the form of the following secondary agglomerates, and (2) so that the average closest particle distance is 500 nm or less, wherein the organically modified layered silicate compound is: Layered silicate having a cation exchange capacity of 50 meq / 100 g or more and the following general formula (II), (III) or (IV) having a total carbon number of 26 or more
An antistatic method for a resin, which is a reaction product with an organic ammonium salt represented by: [Chemical 3] [In the formula, R ³ and R ⁴ are the same or different and each independently represent an alkyl group having 12 or more carbon atoms which may have a substituent, and R ⁵ represents a hydrogen atom or a substituent. Is an alkyl group or aryl group having 2 to 7 carbon atoms, and R ⁶ is a hydrogen atom or an alkyl group or aryl group having 1 to 7 carbon atoms which may have a substituent. X represents a counter ion. ] [Chemical 4] [In the formula, R ⁷ , R ⁸ and R ⁹ are the same or different and each independently represent an alkyl group having 8 or more carbon atoms which may have a substituent, and R ¹⁰ represents a hydrogen atom or a substituent. It represents an alkyl group or an aryl group having 1 or more carbon atoms which may be added. X represents a counter ion. ] [Chemical 5] [In the formula, R ¹¹ represents an alkyl group having 8 or more carbon atoms which may have a substituent, R ¹² represents an alkyl group having 1 to 11 carbon atoms which may have a substituent, and R ¹³ and R ¹⁴ are the same or different and each independently represent an alkyl group having 1 to 7 carbon atoms which may have a substituent. X represents a counter ion. ] 4. An organically modified layered silicate compound 2 having a volume resistivity of 10 ¹² Ω · cm or less in 100 parts by weight of a resin.
To 30 parts by weight, (1) the primary aggregate and / or the minor axis of the aggregate is 500 nm.
A permanent antistatic resin composition, which is dispersed in the form of the following secondary agglomerates, and (2) having an average closest particle distance of 500 nm or less, wherein the organically modified layered silicate compound is Is a layered silicate having a cation exchange capacity of 50 meq / 100 g or more and the following general formula (II), (III) or (IV) having a total carbon number of 26 or more.
A permanent antistatic resin composition, which is a reaction product with an organic ammonium salt represented by: [Chemical 6] [In the formula, R ³ and R ⁴ are the same or different and each independently represent an alkyl group having 12 or more carbon atoms which may have a substituent, and R ⁵ represents a hydrogen atom or a substituent. Is an alkyl group or aryl group having 2 to 7 carbon atoms, and R ⁶ is a hydrogen atom or an alkyl group or aryl group having 1 to 7 carbon atoms which may have a substituent. X represents a counter ion. ] [Chemical 7] [In the formula, R ⁷ , R ⁸ and R ⁹ are the same or different and each independently represent an alkyl group having 8 or more carbon atoms which may have a substituent, and R ¹⁰ represents a hydrogen atom or a substituent. It represents an alkyl group or an aryl group having 1 or more carbon atoms which may be added. X represents a counter ion. ] [Chemical 8] [In the formula, R ¹¹ represents an alkyl group having 8 or more carbon atoms which may have a substituent, R ¹² represents an alkyl group having 1 to 11 carbon atoms which may have a substituent, and R ¹³ and R ¹⁴ are the same or different and each independently represent an alkyl group having 1 to 7 carbon atoms which may have a substituent. X represents a counter ion. ] 5. An organically modified layered silicate compound having a volume resistivity of 10 ¹² Ω · cm or less based on 100 parts by weight of resin is added in an amount of 2 to 30 parts by weight, and (1) a primary aggregate and / or an aggregate. Has a minor axis of 500 nm
A method for antistatically dispersing a resin in the form of the following secondary agglomerates, and (2) so that the average closest particle distance is 500 nm or less, wherein the organically modified layered silicate compound is: An antistatic method for a resin, which is a reaction product of a layered silicate having a cation exchange capacity of 50 meq / 100 g or more and an organic ammonium salt represented by the following general formula (V) or (VII). [Chemical 9] [In the formula, R ¹⁵ represents a mono- or polyoxyalkylene group composed of an oxyalkylene unit having 2 to 4 carbon atoms, and R ¹⁶ and R ¹⁷ are the same or different and each may have a substituent. A substituent selected from the group of mono- or polyoxyalkylene groups consisting of an alkyl group having 1 to 30 carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms is shown. The number of added moles of the oxyalkylene unit is 1 to 50. R ¹⁸ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an aryl group. X represents a counter ion. ] [Chemical 10] [Wherein, R ²³ , R ²⁴ , and R ²⁵ are the same or different and each is a mono-alkyl group having 1 to 30 carbon atoms and optionally having a substituent, and an oxyalkylene unit having 2 to 4 carbon atoms. Or a polyoxyalkylene group, an alkyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms which may have a substituent and an oxyalkylene unit having 2 to 4 carbon atoms, a hydrogen atom or a substituent An alkylphenyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms,
And a substituent selected from the group consisting of an acyl mono- or polyoxyalkylene group consisting of an acyl unit having 2 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms which may have a substituent, and R ²⁶ is A hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent is shown. The number of added moles of the oxyalkylene unit is 1 to 50. Further, at least one of Y, Z and W is -CH ₂ O-, -CH.
₂ COO-, -CH ₂ CH ₂ COO-, -CH ₂ OCO-, -CH ₂ CH ₂ OCO-,-(CH ₂ ) _m
NHCO -, - (CH ₂₎ indicates a linking group selected from _m NHCO-CH ₂ O- groups and the remainder represents a single bond to bond directly to the nitrogen atom of the ammonium group. m represents an integer of 1 to 4. ] 6. An organically modified layered silicate compound 2 having a volume resistivity of 10 ¹² Ω · cm or less in 100 parts by weight of a resin.
To 30 parts by weight, (1) the primary aggregate and / or the minor axis of the aggregate is 500 nm.
A permanent antistatic resin composition, which is dispersed in the form of the following secondary agglomerates, and (2) having an average closest particle distance of 500 nm or less, wherein the organically modified layered silicate compound is Is a reaction product of a layered silicate having a cation exchange capacity of 50 meq / 100 g or more and an organic ammonium salt represented by the following general formula (V) or (VII), and is a permanent antistatic resin. Composition. [Chemical 11] [In the formula, R ¹⁵ represents a mono- or polyoxyalkylene group composed of an oxyalkylene unit having 2 to 4 carbon atoms, and R ¹⁶ and R ¹⁷ are the same or different and each may have a substituent. A substituent selected from the group of mono- or polyoxyalkylene groups consisting of an alkyl group having 1 to 30 carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms is shown. The number of added moles of the oxyalkylene unit is 1 to 50. R ¹⁸ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an aryl group. X represents a counter ion. ] [Chemical formula 12] [Wherein, R ²³ , R ²⁴ , and R ²⁵ are the same or different and each is a mono-alkyl group having 1 to 30 carbon atoms and optionally having a substituent, and an oxyalkylene unit having 2 to 4 carbon atoms. Or a polyoxyalkylene group, an alkyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms which may have a substituent and an oxyalkylene unit having 2 to 4 carbon atoms, a hydrogen atom or a substituent An alkylphenyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms,
And a substituent selected from the group consisting of an acyl mono- or polyoxyalkylene group consisting of an acyl unit having 2 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms which may have a substituent, and R ²⁶ is A hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent is shown. The number of added moles of the oxyalkylene unit is 1 to 50. Further, at least one of Y, Z and W is -CH ₂ O-, -CH.
₂ COO-, -CH ₂ CH ₂ COO-, -CH ₂ OCO-, -CH ₂ CH ₂ OCO-,-(CH ₂ ) _m
NHCO -, - (CH ₂₎ indicates a linking group selected from _m NHCO-CH ₂ O- groups and the remainder represents a single bond to bond directly to the nitrogen atom of the ammonium group. m represents an integer of 1 to 4. ] 7. An organically modified layered silicate compound having a volume resistivity of 10 ¹² Ω · cm or less based on 100 parts by weight of resin (excluding thermoplastic polyolefin resin and thermoplastic polystyrene resin) 2 to 30 parts by weight. (1) The primary aggregate and / or the minor axis of the aggregate has a diameter of 500 nm.
A method for antistatically dispersing a resin in the form of the following secondary agglomerates, and (2) so that the average closest particle distance is 500 nm or less, wherein the organically modified layered silicate compound is: An antistatic method for a resin, which is a reaction product of a layered silicate having a cation exchange capacity of 50 meq / 100 g or more and an organic ammonium salt represented by the following general formula (VI). [Chemical 13] [In the formula, R ¹⁹ represents an alkyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms which may have a substituent and an oxyalkylene unit having 2 to 4 carbon atoms, a hydrogen atom or a substituent. An alkylphenyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms which may have, or having 2 or more carbon atoms which may have a substituent. R represents an acyl mono- or polyoxyalkylene group consisting of an acyl unit and an oxyalkylene unit having 2 to 4 carbon atoms, R
²⁰ and R ²¹ are the same or different and each is an alkyl group having 1 to 30 carbon atoms, which may have a substituent, and 2 carbon atoms.
To mono- or polyoxyalkylene group consisting of oxyalkylene unit of 4 to 4, alkyl mono- or polyoxyalkylene group consisting of alkyl unit having 1 or more carbon atoms which may have a substituent and oxyalkylene unit having 2 to 4 carbon atoms An alkylphenyl mono- or polyoxyalkylene group comprising a hydrogen atom or an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms, which may have a substituent, and a substituent And a substituent selected from the group of acyl mono- or polyoxyalkylene groups consisting of an acyl unit having 2 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms. The number of added moles of the oxyalkylene unit is 1 to 50. R ²² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms or an aryl group. X represents a counter ion. ] 8. An organically modified layered silicate compound having a volume resistivity of 10 ¹² Ω · cm or less in 100 parts by weight of resin (excluding thermoplastic polyolefin resin and thermoplastic polystyrene resin) 2 to 30 parts by weight Part is (1) the primary aggregate and / or the minor axis of the aggregate is 500 nm
A permanent antistatic resin composition, which is dispersed in the form of the following secondary agglomerates, and (2) having an average closest particle distance of 500 nm or less, wherein the organically modified layered silicate compound is Is a reaction product of a layered silicate having a cation exchange capacity of 50 meq / 100 g or more and an organic ammonium salt represented by the following general formula (VI), and a permanent antistatic resin composition. [Chemical 14] [In the formula, R ¹⁹ represents an alkyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms which may have a substituent and an oxyalkylene unit having 2 to 4 carbon atoms, a hydrogen atom or a substituent. An alkylphenyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms which may have, or having 2 or more carbon atoms which may have a substituent. R represents an acyl mono- or polyoxyalkylene group consisting of an acyl unit and an oxyalkylene unit having 2 to 4 carbon atoms, R
²⁰ and R ²¹ are the same or different and each is an alkyl group having 1 to 30 carbon atoms, which may have a substituent, and 2 carbon atoms.
To mono- or polyoxyalkylene group consisting of oxyalkylene unit of 4 to 4, alkyl mono- or polyoxyalkylene group consisting of alkyl unit having 1 or more carbon atoms which may have a substituent and oxyalkylene unit having 2 to 4 carbon atoms An alkylphenyl mono- or polyoxyalkylene group comprising a hydrogen atom or an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms, which may have a substituent, and a substituent And a substituent selected from the group of acyl mono- or polyoxyalkylene groups consisting of an acyl unit having 2 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms. The number of added moles of the oxyalkylene unit is 1 to 50. R ²² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms or an aryl group. X represents a counter ion. ] 9. The permanent antistatic resin according to claim 2, which has a volume resistivity of 10 ¹³ Ω · cm or less after being stored for 24 hours in a thermo-hygrostat at 23 ° C. and a humidity of 60%. Composition. 10. A constant temperature and humidity room at 23 ° C. and a humidity of 60% for 24 hours.
The permanent antistatic resin composition according to claim 2, 4, 6, 8, or 9, which has a charged voltage half-life after storage for 15 seconds or less. 11. An organically modified layered silicate compound having a surface spacing of 2
It is 3 to 50Å, It is characterized by the above-mentioned.
The permanent antistatic resin composition described. 12. An organically modified layered silicate compound having a surface spacing of 2
The permanent antistatic resin composition according to claim 6 or 8, wherein the resin composition has a thickness of 3 to 70Å. 13. The permanent antistatic resin composition according to claim 2, 4 or 6, wherein the resin is a thermoplastic resin. 14. The permanent antistatic resin composition according to claim 2, 4 or 6, wherein the resin is a thermoplastic polyolefin resin. 15. The permanent antistatic resin composition according to claim 2, 4 or 6, wherein the resin is a thermoplastic polystyrene resin. 16. The permanent antistatic resin composition according to claim 2, wherein the resin is a thermoplastic polar group-containing resin. 17. The permanent antistatic resin composition according to claim 2, wherein the resin is thermoplastic polyethylene or a polyethylene unit-containing resin. 18. The permanent antistatic resin composition according to claim 2, wherein the resin is thermoplastic polypropylene or a resin containing a polypropylene unit. 19. The permanent antistatic resin composition according to claim 2, wherein the resin is a thermoplastic polystyrene resin. 20. The permanent antistatic resin composition according to claim 2, wherein the resin is a thermoplastic styrene unit-containing resin. 21. The permanent antistatic resin composition according to claim 2, wherein the resin is a thermoplastic nitrile group-containing resin. 22. The permanent antistatic resin composition according to claim 2, wherein the resin is a thermoplastic ester group-containing resin. 23. The permanent antistatic resin composition according to claim 6 or 8, wherein the resin is a thermoplastic polar group-containing resin. 24. The permanent antistatic resin composition according to claim 2, wherein the resin is a blend resin of a thermoplastic resin.