JP2016121041A - Powdery substance, resin composition, and gas barrier material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier material which enhances affinity between a filler and a resin and improves insufficient dispersibility of the filler and thereby improves gas barrier properties, and has excellent gas barrier performance.SOLUTION: In a powdery substance in which a crystal end face of a silicate compound is treated with a silane coupling agent, the silicate compound is a non-swelling laminar silicate compound having interlayer ions. A resin composition contains the same.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a powdery substance, a resin composition containing the powdery substance, and a gas barrier material obtained using the resin composition.

Food packaging materials need to protect their contents from various distribution, storage such as refrigeration, freezing, heating, heat sterilization, etc., and therefore durability such as strength, resistance to cracking, cold resistance, heat resistance, and retort resistance. Desired. In addition, transparency that allows the contents to be visually recognized and barrier properties against oxygen and water vapor for maintaining quality are required.
As a material having a barrier property, an Al vapor-deposited film obtained by vapor-depositing Al (aluminum) on a base film such as nylon, PET, PP, or a transparent vapor-deposited film obtained by vapor-depositing silica or alumina is known. However, since the Al vapor-deposited film is opaque, the contents cannot be visually recognized, microwave heating cannot be performed, and the transparent vapor-deposited film has problems that the barrier property is deteriorated due to cracks or pinholes in the vapor-deposited layer.

  On the other hand, an attempt has been made to improve the barrier property by adding an inorganic filler such as clay to the resin to obtain a composite material and imparting the barrier property of the filler to the resin. However, clay has a high hygroscopic property and is therefore effective for oxygen barriers, but is less effective for water vapor.

  In Patent Document 1, as an improvement, water resistance is improved by substituting Li in the clay layer by replacing Na in the clay layer with Li and further heat-treating it. However, the heat treatment temperature needs to be at least 150 ° C., and it is difficult to heat treat the resin used for the food packaging material at such a temperature.

  Moreover, although it is specialized for an oxygen barrier, Patent Document 2 describes a composite material of a layered compound and polyamide. This is because a smooth film is obtained by classifying a layered compound and using a specific diameter, and the barrier property is improved. However, since the filler itself is conventionally known, it is difficult to disperse it in the matrix resin at a high concentration, and therefore, it is difficult to significantly improve the barrier property.

  Further, Patent Document 3 proposes an intercalation technique for a mica-based mineral having a large crystal diameter. However, a mica-based mineral having a large crystal diameter and aspect ratio is considered to be effective in developing gas barrier properties. There is no specific description regarding the gas barrier material.

JP 2008-247719 A JP-A-10-1608 Japanese Patent No. 5024783

To date, there are many composites of layered minerals and polyamides, but most of them intercalate organic agents between layers. In addition, some of the crystal end faces are subjected to hydrophilic silylation treatment for the purpose of increasing viscosity and thixotropy. Interlayer organic treatment and crystal end face treatment are used to improve gas barrier properties by improving filler dispersibility. There is no combination.
Therefore, the present invention aims to provide a gas barrier material having an excellent gas barrier performance by improving the gas barrier property by further increasing the affinity between the filler and the resin and improving the dispersibility of the filler, which is insufficient. Is. Here, the significance of the excellent gas barrier performance aimed at by the present invention is that both the oxygen barrier performance and the water vapor barrier performance have excellent performance.

  The present invention is a powdery substance in which the crystal end face of a silicate compound is treated with a silane coupling agent, and the silicate compound is a non-swellable layered silicate compound having an interlayer ion The above-mentioned problems are solved by a powdery substance, a resin composition containing the powdery substance, and a gas barrier material obtained using the resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, gas barrier property can be improved by raising the affinity of a filler and resin more, and improving the dispersibility of the filler which is inadequate, and can provide the gas barrier material which has the outstanding gas barrier performance.

4 is a drawing showing the results of TEM observation of the film obtained in Example 2. FIG. 4 is a drawing showing a result of TEM observation of a film obtained in Comparative Example 1. FIG.

The present invention includes the following items.
1. The crystalline end face of the silicate compound is a powdery substance treated with a silane coupling agent,
A powdery substance, wherein the silicate compound is a non-swellable layered silicate compound having intercalation ions,
2. 1. A silicate compound is a non-swellable organic-inorganic composite in which an organic onium compound is intercalated in a non-swellable layered silicate compound having interlayer ions. A powdery substance, as described in
3. 1. The silane coupling agent is a (meth) acrylic silane coupling agent. Or 2. A powdery substance, as described in
4). 1. Interlayer ions are potassium ions ~ 3. A powdery substance according to any one of
5. 1. The organic onium compound is a primary to tertiary amine salt having 8 or more carbon atoms, a quaternary ammonium salt, or an amino acid salt. ~ 4. A powdery substance according to any one of
6.1. ~ 5. A resin composition comprising a thermoplastic resin containing the powdery substance according to any one of
7). 5. The thermoplastic resin is a polyamide resin. The resin composition according to
8.6. Or 7. A gas barrier material obtained using the resin composition described in 1.
9. 7. The gas barrier material is a gas barrier film. Gas barrier material according to
10. 7. The gas barrier material is a gas barrier molded article. The gas barrier material described in 1.

  In this invention, a well-known and usual silicate compound can be used. By using the silicate compound, the barrier performance of the gas barrier material obtained using the resin composition of the present invention can be improved.

  The silicate compound used in the present invention is characterized by being non-swelling having interlayer ions. If there is no intercalation ion, the ion exchange reaction cannot be performed. Therefore, the organic treatment for improving the dispersibility in the resin composition is not sufficient, which is not preferable. Is significantly inferior and is not preferred.

  On the other hand, in the case of non-swelling property, even if the addition amount is increased, it is difficult to become thickened or thixotropic, so that the coating suitability can be secured. Examples of the silicate compound used in the present invention include hydrous silicates (phyllosilicate minerals, etc.), kaolinite-serpentine clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.) Light, chrysotile, etc.), pyrophyllite-talc group (pyrophyllite, talc, kerolai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc.), vermiculite clay Minerals (vermiculite, etc.), mica or mica group clay minerals (mica, such as muscovite, phlogopite, margarite, tetrasilic mica, teniolite, etc.), chlorite group (cukeite, sudite, clinochlore, chamosite, nimite, etc.) Hydro Lucite, tabular barium sulfate, boehmite, and aluminum polyphosphate and the like. These minerals may be natural clay minerals or synthetic clay minerals. An inorganic layered compound can be used individually or in combination of 2 or more types.

  The shape of the silicate compound of the present invention is not particularly limited, but a plate shape is more preferable because the barrier property is improved. The average particle diameter in the case of a plate shape is not particularly limited, but is preferably 0.1 μm or more, more preferably 1 μm or more. If the average particle size is 0.1 μm or less, the length of the long side is short, which causes a problem that it is difficult to improve the gas barrier ability without lengthening the detour path of gas molecules. The side with a large average particle diameter is not particularly limited. When a large silicate compound is contained by the coating method, when defects such as streaks occur on the coated surface, a material having an average particle diameter of 100 μm or less, more preferably 20 μm or less is preferably used.

  In the case of a plate shape, the aspect ratio is preferably high in order to improve the barrier ability due to the gas maze effect. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.

Furthermore, the silicate compound of the present invention may be a non-swellable organic-inorganic composite in which an organic onium compound is intercalated in a non-swellable layered silicate compound having interlayer ions.
Examples of preferable organic-inorganic composites include those described in Japanese Patent No. 5024783.

That is, in the present invention, a layered silicate having a mica composition in which the general formula is preferably represented by the following formula, the average particle diameter of primary particles is 2 μm to 500 μm, and the interlayer ions are K (potassium) ions, is positively charged. In the organic-inorganic composite obtained by intercalating an organic compound, a layered silicate satisfying the following formula is used.
_{[(K a M 0.1-b} ) (X c Y d) (Si 4-e Al e) O 10 (OH f F 2-f)]
However, 0.6 ≦ a ≦ 1.0, 0 ≦ b ≦ 0.1, 0 ≦ c ≦ 3, 0 ≦ d ≦ 2, 2 ≦ c + d ≦ 3, 0 ≦ e <4, 0 ≦ f ≦ 2. Yes, M is a cation other than K between the layers, Li, Na, Rb, Cs, NH ₄ , Be, Mg, Ca, Sr, Ba, Mn, Fe, Ni, Cu, Zn, Al At least one, X and Y are metals that enter the octahedron formed in the 2: 1 type sheet, wherein X is at least one of Mg, Fe, Mn, Ni, Zn, Li, Y is at least one of Al, Fe, Mn, and Cr.

Further, a mica clay mineral of 0.6 ≦ a ≦ 0.9 represented by the following formula is preferably used.
_{[(K a M 0.1-b} ) (X c Y d) (Si 4-e Al e) O 10 (OH f F 2-f)]
However, 0.6 ≦ a ≦ 0.9, 0 ≦ b ≦ 0.1, 0 ≦ c ≦ 3, 0 ≦ d ≦ 2, 2 ≦ c + d ≦ 3, 0 ≦ e <4, and 0 ≦ f ≦ 2. Yes, M is a cation other than K between the layers, Li, Na, Rb, Cs, NH ₄ , Be, Mg, Ca, Sr, Ba, Mn, Fe, Ni, Cu, Zn, Al At least one, X and Y are metals that enter the octahedron formed in the 2: 1 type sheet, wherein X is at least one of Mg, Fe, Mn, Ni, Zn, Li, Y is at least one of Al, Fe, Mn, and Cr.
Specifically, the layered silicate defined by the above composition formula in the range of 0.6 ≦ a ≦ 1.0 specifically includes mica such as muscovite, phlogopite, biotite, brittle mica, and the like. Examples thereof include vermiculites such as 2-octahedral vermiculite and 3-octahedral vermiculite, which are altered minerals.
Further, specific examples of the mica clay mineral defined in the above composition formula in the range of 0.6 ≦ a ≦ 0.9 include illite, sericite, sea green stone (Groconite), and ceradonite.

  Furthermore, as the non-swellable layered silicate used in the present invention, those having an average particle diameter of 2 μm to 500 μm are applied, and the range of 2 μm to 200 μm is more preferable. Since the particle size is large, the aspect ratio becomes extremely large by swelling and reducing the number of layers in the polymer matrix, and the heat resistance, rigidity, In addition, it has the effect of dramatically improving the barrier properties. When the average particle diameter exceeds 500 μm, it becomes difficult to intercalate the positively charged organic compound between the layers.

  As a method for measuring the particle size, a method of measuring the particle size by directly observing the particles with a sedimentation type particle size measurement method in a solvent such as water, a light scattering method, or a microscope can be applied. Since the layered silicate is a plate-like crystal, the a- and b-axis directions of the crystal are directly observed with a transmission electron microscope and a scanning electron microscope rather than the sedimentation-type particle size measurement method or light scattering method obtained by spherical conversion, A method for obtaining the ratio of the major axis to the minor axis from the projected two-dimensional image is suitable, and this method is also used in the present invention.

  Furthermore, the amount of ions in the interlayer is substituted between the layers so as to balance the negative charge of the silicate sheet, and is expressed by the coefficient a in the chemical formula, that is, the number of charges per half unit lattice (charge density). it can. In the present invention, the one in the range of 0.6 ≦ a ≦ 1.0 is applied, and the higher the charge density, the stronger the attractive force between the laminated sheets. Therefore, 0.6 ≦ a ≦ 0.9 is more preferable. . If the charge density is less than 0.6, the particle size tends to be small because it becomes a smectite region, and if it is larger than 1.0, the attractive force between the laminated sheets becomes too strong, and the interlayer is replaced with an organic substance. Becomes difficult.

  The method for measuring the amount of interlayer ions in non-swellable layered silicates is the cation exchange capacity (CEC) measurement method applied to swellable clay minerals: column permeation method (see: "Clay Handbook" 2nd edition Japan Clay Society, pp. 576-577, Gihodo Publishing) and methylene blue adsorption method (Japan Bentonite Industry Association Standard Test Method, JBAS-107-91) are not applicable. Therefore, a method of estimating by chemical composition analysis is applied. Specifically, plasma spectroscopy (ICP) analysis, fluorescent X-ray analysis (XRF), X-ray microanalyzer (EPMA), or the like is used.

  The organic-inorganic composite of the present invention can be obtained by intercalating an organic cation with such a unique non-swellable silicate. The positively charged organic compound used in the present invention is not particularly limited to its kind, but preferred examples include primary amines, secondary amines, tertiary amines and their chlorides and quaternary ammonium salts having 8 or more carbon atoms. , Amine compounds, amino acid derivatives, nitrogen-containing heterocyclic compounds or phosphonium salts.

  Specifically, primary amines represented by octylamine, laurylamine, tetradecylamine, hexadecylamine, stearylamine, oleylamine, acrylamine, benzylamine, aniline, etc .; dilaurylamine, ditetradecylamine, diamine Secondary amines typified by hexadecylamine, distearylamine, N-methylaniline, etc .: dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dilaurylmonomethylamine , Tertiary amines represented by tributylamine, trioctylamine, N, N-dimethylaniline, etc .; tetrabutylammonium ion, tetrahexylammonium ion, dihexyldimethylammoni Ion, dioctyldimethylammonium ion, hexatrimethylammonium ion, octatrimethylammonium ion, dodecyltrimethylammonium ion, hexadecyltrimethylammonium ion, stearyltrimethylammonium ion, dococenyltrimethylammonium ion, cetyltrimethylammonium ion, cetyltriethylammonium ion, Hexadecyl ammonium ion, tetradecyl dimethyl benzyl ammonium ion, stearyl dimethyl benzyl ammonium ion, dioleyl dimethyl ammonium ion, N-methyldiethanol lauryl ammonium ion, dipropanol monomethyl lauryl ammonium ion, dimethyl monoethanol lauryl ammonium ion , Polyoxyethylene dodecyl monomethyl ammonium ions, quaternary ammonium and alkyl aminopropyl amine quaternized like. Further, leucine, cysteine, phenylalanine, tyrosine, aspartic acid, glutamic acid, lysine, 6-aminohexylcarboxylic acid, 12-aminolaurylcarboxylic acid, N, N-dimethyl-6-aminohexylcarboxylic acid, Nn-dodecyl- Amino acid derivatives such as N, N-dimethyl 10-aminodecylcarboxylic acid and dimethyl-N-12 aminolaurylcarboxylic acid; nitrogen-containing complexes such as pyridine, pyrimidine, pyrrole, imidazole, proline, γ-lactam, histidine, tryptophan, and melamine A ring compound etc. are mentioned.

  The amount of the positively charged organic compound in the organic-inorganic composite of the present invention preferably contains 0.6 to 5 equivalents relative to the amount of interlayer cations of the layered silicate, particularly 0.8 to 2.0. Equivalents are most preferred. The positively charged organic compound content mentioned here is not only intended for positively charged organic compounds that are ion-exchanged with K ions between layers, but is positively physically adsorbed on the surface of the organic-inorganic composite. Charged organic compounds are also included, and are the total amount of organic substances estimated from thermogravimetry. If the amount of the positively charged organic compound in the organic-inorganic composite is less than 0.6 equivalents relative to the amount of interlayer cations, the dispersibility of the organic-inorganic composite in the polymer material may be impaired. When it exceeds, there exists a possibility that the heat resistance of a polymer composite material may be reduced with an excess positively charged organic compound.

  In the method for producing an organic-inorganic composite of the present invention, the concentration of the positively charged organic compound solution is 0.01 N or more, and the solid-liquid ratio of the non-swellable layered silicate / positively charged organic compound solution is 0.1 ( (Mass ratio) or less. When the concentration is less than 0.01 N, a sufficient ion exchange reaction cannot be induced, and even if a long-time treatment is performed, only replacement with potassium ions between some layers can be performed. It cannot be used as a preparation. The concentration of the positively charged organic compound solution can be up to the limit concentration obtained as a solution. If the solid-liquid ratio of the non-swellable layered silicate / positively charged organic compound solution is lower than 0.001, it is not desirable in terms of cost.

  The ion exchange reaction for intercalating the positively charged organic compound between the layers of the non-swellable layered silicate is carried out by adding the layered silicate powder to a concentrated solution of the positively charged organic compound and heat-treating it. This is done by replacing the K ion between the layers of the layered silicate crystal with a positively charged organic compound and organically modifying it. The treatment temperature at this time is preferably in the range of 40 to 200 ° C. When the temperature is lower than 40 ° C., the positively charged organic compound cannot be uniformly intercalated between the layers, and when the temperature is higher than 200 ° C., decomposition of organic substances and polymerization may occur.

  Thereafter, washing and filtration are repeated, and the unsubstituted organic cation is sufficiently removed and dried. In this treatment step, the positively charged organic compounds that can be substituted with K ions are limited, so that the two steps of first forming an organic-inorganic complex with the specific positively charged organic compound and then resubstituting with a different positively charged organic compound. Any organic-inorganic composite can be produced by this ion exchange method.

  As a treatment method for obtaining an arbitrary organic-inorganic complex by a two-stage ion exchange reaction, the positively charged organic compound used in the first treatment step is a primary to tertiary amine salt having 8 to 18 carbon atoms, A quaternary ammonium salt is preferred. More preferably, the carbon number is in the range of 10-14. If the number of carbon atoms is less than 8, it cannot be inserted between the layers of the layered silicate. If the number of carbon atoms exceeds 18, the positively charged organic compound is firmly fixed between the layers to facilitate the second-stage ion exchange reaction. Can't progress.

  The positively charged organic compound used in the second step, which is different from the positively charged organic compound used in the first treatment step, is not particularly limited, but has a molecular weight higher than that of the positively charged organic compound used in the first treatment step. Larger and more polar ones allow easier ion exchange. Further, even if the molecular weight is smaller than that of the positively charged organic compound used in the first treatment step and the polarity is low, ion exchange is possible by treating a high concentration solution under high temperature conditions.

  The organic-inorganic composite of the present invention is used as a filler for a polymer composite material dispersed in the polymer material. The content of the organic-inorganic composite in the polymer material is 0.1 to 40% by mass, preferably 1.0 to 10% by mass. If it is less than 0.1% by mass, a sufficient reinforcing effect on the polymer material cannot be obtained, and if it exceeds 40% by mass, the dispersibility of the organic-inorganic composite may be impaired.

  More specific examples of the non-swellable layered silicate compound used in the present invention include phlogopite, sericite, vermiculite and the like.

Examples of the silane coupling agent used in the present invention include known and commonly used silane coupling agents.
More specifically, such silane coupling agents include methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, acryloxypropylmethyldimethoxysilane, methacryloxypropyltriethoxysilane. And (meth) acrylic silanes such as acryloxypropyltriethoxysilane, methacryloxypropylmethyldiethoxysilane, and acryloxypropylmethyldiethoxysilane.

The surface treatment can be performed as follows, for example.
A non-swellable layered silicate that has been organicized with a positively charged organic compound is added to an organic solvent such as alcohol or glycol ether. Add about 5%. Next, a silane coupling agent is added in an amount of about 0.5 to 100% of the weight of the non-swellable layered silicate, and the mixture is stirred at a liquid temperature of 80 to 130 ° C. for about 2 to 6 hours. Thereafter, the target filler is obtained by filtration and washing. Although there is no restriction | limiting in particular in the solvent to be used, Since water produces | generates by condensation, an amphiphilic solvent can be used preferably. Although there is no restriction | limiting in particular in the acid to be used, What is melt | dissolved in an organic solvent is preferable.

The resin is not particularly limited as long as it is a thermoplastic resin, but in view of the dispersibility of the powdery substance, a medium to high polarity resin is preferably used. Of these, polyamide resin is preferable.
The resin composition is obtained by melt-kneading the powdery substance, a thermoplastic resin, and, if necessary, an additive. For kneading, it is preferable to use a kneading extruder. The kneading extruder may be a continuous kneader or a biaxial kneader.

(Gas barrier material)
The gas barrier material of the present invention is characterized in that it is obtained using the resin composition containing the powdery substance.
Examples of the gas barrier material obtained using the resin composition include a gas barrier film and a gas barrier molded article.
About a gas barrier film, it can produce by performing a well-known and usual film process to the said resin composition using a well-known and usual method.
For example, extrusion molding using an extruder such as a twin-screw extruder or single-screw extruder, or press molding using a press molding machine can be used.
Moreover, about a gas-barrier molded object, it can produce by performing a well-known and usual molded object process to the said resin composition using a well-known and usual method.
For example, methods such as injection molding, blow molding, and vacuum molding can be used depending on the required shape.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

(Production Example 1)
A 2 L 4-necked flask was charged with 53.3 g of octadecylamine hydrochloride and 1500 g of distilled water, and stirred while heating in an oil bath to prepare an aqueous solution. While stirring, 75.0 g of non-swelling phlogopite (S-XF manufactured by Repco Co., Ltd .: average particle size 3 μm) was added thereto, and the liquid temperature was raised to 95 ° C. and held for 24 hours. Thereafter, pressure filtration, washing (mixed solution of distilled water / IPA = 1/1) and drying were performed to obtain 96.0 g of modified filler A. The octadecylamine hydrochloride used was 1 eq. Of the theoretical cation exchange capacity of phlogopite. It was.

Example 1
The organic modification to the crystal end face portion of the modified filler A obtained in Production Example 1 was performed as follows. 5.0 g of modified filler A, 250 g of 1-butanol, and 12.5 g of acetic acid were added to a 500 mL flask, and heating was started in an oil bath. While stirring, 1.0 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise. The solution was heated as it was to the boiling point of the liquid and refluxed for 3 hours. Thereafter, filtration, washing, and drying were performed to obtain a modified filler B in which the crystal end face was organically modified.

(Example 2) Non-swelling layered silicate compound-organic onium compound insertion-coupling agent treated polyamide 6 (UBE Nylon 1022B manufactured by Ube Industries, Ltd.) 8.48 g and modified filler B 1 prepared in Example 1 .52 g was charged into a lab plast mill (Toyo Seiki Co., Ltd. 4C150) and melt-kneaded. The obtained product was press-molded to produce a film. Measurement of oxygen transmission rate and water vapor transmission rate and TEM observation were performed. The results are shown in Table 1.

Example 3
To a 500 mL flask, 5.0 g of phlogopite S-XF, 250 g of 1-butanol and 12.5 g of acetic acid were added, and heating was started in an oil bath. While stirring, 0.25 g of 3-methacryloxypropyltrimethoxysilane was added dropwise. The solution was heated as it was to the boiling point of the liquid and refluxed for 3 hours. Thereafter, filtration, washing and drying were performed to obtain a modified filler C.

(Example 4) Non-swelling layered silicate compound-no organic onium compound inserted-Coupling agent treated 9.0 g of polyamide 6 and 1.0 g of modified filler C prepared in Example 3 were charged into a lab plast mill. Was melt kneaded. The obtained product was press-molded to produce a film. The oxygen transmission rate and water vapor transmission rate were measured.

(Comparative Example 1) Non-swellable layered silicate compound-organic onium compound inserted-no coupling agent treatment used in the same manner as in Example 2 except that the modified filler A produced in Production Example 1 was used. Films were prepared by melt kneading and press molding, and oxygen permeability and water vapor permeability were measured and TEM observation was performed. The results are shown in Table 1.

(Comparative Example 2) Non-swelling layered silicate compound-no organic onium compound inserted-no coupling agent treatment The same as in Example 4 except that the used filler was S-XF without any modification. A film was prepared by melt kneading and press molding, and the oxygen transmission rate and the water vapor transmission rate were measured.

(Comparative Example 3) Swellable layered silicate compound-no organic onium compound inserted-Coupling agent treated Yes Modified by the same method as in Example 3 using swellable bentonite (Bengel manufactured by Hojun Co., Ltd.) Filler D was prepared, and in the same manner as in Example 4, 1.0 g of modified filler D and 9.0 g of polyamide 6 were melt-kneaded in a lab plast mill. Films were produced by press molding, and oxygen permeability and water vapor permeability were measured.

When Example 2 and Comparative Example 1 are compared, it can be seen that the permeability of both oxygen and water vapor is low in Example 2 and the gas barrier property is high. When Example 4 and Comparative Example 2 are compared, it can be seen that the gas barrier property of the example is high at a high humidity oxygen permeability.
In general, it is known that the performance of the gas barrier property at high humidity is lower than that at low humidity. However, in Example 4, the degree of decrease is smaller than that of the comparative example, and the gas barrier property can be used as a barrier material. The results show that
Since Comparative Example 3 uses a swellable layered silicate, it can be seen that the oxygen permeability at high humidity is very high, and the water vapor permeability is worse than that of polyamide 6 alone.
Furthermore, from the comparison of FIGS. 1 and 2, the gas barrier material obtained by the present invention showed a good dispersion of the filler.

<Conditions>
Mixer unit KF15V
Kneading temperature 240 ° C
Shaft speed 210rpm
Kneading time 5 minutes The kneaded product was press-molded to produce a film having a film thickness of about 40 μm, and the oxygen permeability and water vapor permeability were measured and TEM observation was performed.

(Measurement of oxygen permeability)
The measurement was performed under the conditions of 23 ° C. 0% RH (relative humidity) and 90% RH using MOCON model 1/20. The film thickness was calculated in terms of 30 μm.
The results are shown in Table 1. In addition, as a reference example, the case where nylon that does not contain a powdery substance was used as a reference example (measurement of water vapor permeability)
The measurement was carried out under the conditions of 40 ° C. and 90% RH using a model 7011 manufactured by Illonois. Table 1 shows the results calculated in terms of a film thickness of 30 μm.
(TEM observation)
After embedding the sample with an epoxy resin, a thin sample was prepared with a cryomicrotome (set temperature: −140 ° C.) and subjected to TEM observation (JEM-2200FS acceleration voltage 200 kV, manufactured by JEOL).
The results of Example 1 are shown in FIG. 1, and the results of Comparative Example 2 are shown in FIG.

  Since the film and molded product obtained from the resin composition containing the powdery substance of the present invention have excellent gas barrier properties, they can be widely used as various packaging materials that require gas barrier properties.

Claims (10)

The crystalline end face of the silicate compound is a powdery substance treated with a silane coupling agent,
A powdery substance, wherein the silicate compound is a non-swellable layered silicate compound having interlayer ions. The powdery substance according to claim 1, wherein the silicate compound is a non-swellable organic-inorganic composite in which an organic onium compound is intercalated in a non-swellable layered silicate compound having interlayer ions. The powdery substance according to claim 1 or 2, wherein the silane coupling agent is a (meth) acrylic silane coupling agent. The powdery substance according to any one of claims 1 to 3, wherein the interlayer ions are potassium ions. The powdery substance according to any one of claims 2 to 4, wherein the organic onium compound is a primary to tertiary amine salt having 8 or more carbon atoms, a quaternary ammonium salt, or an amino acid salt. The resin composition which consists of a thermoplastic resin containing the powdery substance in any one of Claims 1-5. The resin composition according to claim 6, wherein the thermoplastic resin is a polyamide resin. A gas barrier material obtained using the resin composition according to claim 6. The gas barrier material according to claim 8, wherein the gas barrier material is a gas barrier film. The gas barrier material according to claim 8, wherein the gas barrier material is a gas barrier molded article.

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