JP2001254021A - Polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer composition which contains an intermediately polar polymer having a solubility parameter of 9-14 (cal/cm3)1/2 and a layered clay mineral finely dispersed therein. SOLUTION: This composition contains a polymer having a solubility parameter of 9-14 (cal/cm3)1/2 and a layered clay mineral provided the mineral has been organized with an organizing agent having at least one functional group selected from among hydroxyl, mercapto, amido, and ester groups and having a number average mol.wt. of 800 or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer composition containing an organized layered clay mineral.

[0002]

2. Description of the Related Art In order to improve physical properties such as rigidity of a polymer, it has been conventionally used to add a layered clay mineral such as kaolinite or montmorillonite. Although various chemical species are used as the polymer to which the layered clay mineral is added, most of the highly polar polymers are expected to have excellent gas barrier properties. Researches are being made to add a layered clay mineral to a polymer to improve physical properties such as rigidity and also improve gas barrier properties.

As a polymer used in such a research field, a commercially available vinyl alcohol copolymer can be mentioned. Vinyl alcohol copolymers have high polarity, and polyethylene vinyl alcohol, which is a type of vinyl alcohol copolymer, is known as a polymer having particularly excellent gas barrier properties.

When a layered clay mineral is added to a highly polar polymer such as a vinyl alcohol copolymer,
It is very difficult to improve the dispersibility of the layered clay mineral. It is thought that this is because only a limited amount of high-polarity polymer penetrates (intercalates) between layers of the layered clay mineral.

It is known that such dispersion difficulty can be solved by the method disclosed in, for example, JP-A-10-158449. That is, when the layered clay mineral is mixed with the vinyl alcohol copolymer, the layered clay mineral is treated with an organic agent having a specific mole% of hydroxyl groups and a number average molecular weight of 1,000 or more. Can be finely dispersed in the vinyl alcohol copolymer.

[0006]

However, since the components contained in the composition obtained by the method disclosed in Japanese Patent Application Laid-Open No. 10-158449 have high polarities, other components whose polarity is not so high are all included. Is considered to be insufficient even if it is further added, and there is a limit in the diversity of the resulting composition. Therefore, as a moderately polar polymer that can be mixed in various ways, the solubility parameter is 9
There is a demand for a method of obtaining a polymer composition having excellent dispersibility of a layered clay mineral by using one having a thickness of 〜14 (cal / cm ³ ) ^1/2 .

The present invention has been made in view of such problems of the prior art, and has a solubility parameter of 9-1.
Provided is a polymer composition comprising a polymer having a medium polarity of 4 (cal / cm ³ ) ^1/2 and a layered clay mineral, wherein the layered clay mineral is finely dispersed. The purpose is to do.

The solubility parameter (SP value) is a value defined as the square root of the evaporation energy per unit volume of a molecule. Since polymers generally do not vaporize, it is impossible to determine the SP value from the evaporation energy,
The SP value can be calculated based on the solubility in a solvent having a known SP value or the chemical structure of the polymer. The SP value of the polymer obtained in this way serves as an index for judging whether or not the mixing property between the polymers or between the polymer and another substance is good, and also serves as an index for the polarity of the polymer. That is,
In general, it is known that a substance having a higher SP value mixes better, and a substance having a higher SP value has higher polarity.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have at least one functional group selected from the group consisting of a hydroxyl group, a mercapto group, an amide group and an ester group. By using a layered clay mineral having a group and having a number average molecular weight of 800 or less, which is organized by an organic agent, the solubility parameter is 9 to
14 (cal / cm ³⁾ found that the layered clay compound it is possible to finely dispersed in ^1/2 in the polymer, thereby completing the present invention.

[0010] That is, the polymeric compositions of the present invention, the solubility parameter includes a ^{9~14 (cal / cm 3) 1} /2 of a polymer, and a layered clay mineral dispersed in the polymer, wherein The layered clay mineral has at least one functional group selected from the group consisting of a hydroxyl group, a mercapto group, an amide group, and an ester group, and has a number average molecular weight of 800 or less. It is a mineral.

In the present invention, the number average molecular weight is 800
Since the layered clay mineral is organized with the following organic agent, the organic agent easily penetrates between the layers of the layered clay mineral, and the interlayer distance of the layered clay mineral increases. In addition, the polarity of the layered clay mineral whose interlayer distance has been increased in this way, the organic
Because it has at least one functional group selected from the group consisting of a mercapto group, an amide group, and an ester group, the solubility parameter is close to the polarity of a polymer of 9 to 14 (cal / cm ³ ) ^1/2 It will be. Therefore, the layered clay mineral is very finely dispersed in the polymer.

In the present invention, the polymer is preferably a polymer containing a nitrile group. A polymer having a solubility parameter of 9 to 14 (cal / cm ³ ) ^1/2 and having a nitrile group is particularly excellent in compatibility with the layered clay mineral that has been organically treated by the above-mentioned organic agent used in the present invention. Therefore, the dispersibility of the layered clay mineral tends to be further improved.

In the present invention, it is preferable that the organic agent is an organic onium compound. Organic onium compounds having a functional group and a molecular weight as described above have excellent reactivity with the layered clay mineral, so that the layered clay mineral can be easily organized and the stability of the organic layered clay mineral is also improved. I do. Furthermore, in a layered clay mineral that has been organized with such an organic onium compound, polymer intercalation is likely to occur, so that the layered clay mineral tends to be more finely dispersed.

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in more detail.

The polymer composition of the present invention comprises a polymer having a solubility parameter of 9 to 14 (cal / cm ³ ) ^1/2 and a layered clay mineral dispersed in the polymer. Minerals
A hydroxyl group, a mercapto group, an amide group, and at least one functional group selected from the group consisting of an ester group,
It is a layered clay mineral which is organically treated with an organic agent having a number average molecular weight of 800 or less.

In the present invention, the solubility parameter of the polymer being 9 to 14 (cal / cm ³ ) ^1/2 means that the solubility parameter calculated by the Fedors method is 9 to 14 (cal / cm ³ ).
/ cm ³ ) ^1/2 (18.4 to 28.7 (MJ / m ³ ) ^1/2 ). The method of Fedors is that the evaporation energy of each atomic group constituting the chemical structure of a polymer is Δe.
When i and the molar volume are Δvi, the value of δ calculated by the following equation (1) is used as the solubility parameter.

[0017]

(Equation 1)

For a specific example of this calculation method, see, for example, 193, p. 9-11 (1
993) “Calculation of solubility parameter” can be referred to. Regarding the evaporation energy Δei and the molar volume Δvi, the same coating time signal or RF F
edors, Polym. Eng. Sci., 14, 147 (1974).

In the present invention, the value of the solubility parameter of the polymer is 9 to 13 (cal / cm ³ ) ^1/2 (18.4 to 26.6).
(MJ / m ³ ) ^1/2 ), more preferably 9 to 12 (cal
/ cm ³ ) ^1/2 (18.4 to 24.6 (MJ / m ³ ) ^1/2 ). The solubility parameter of the polymer is 9-1.
0 (cal / cm ³ ) ^1/2 (18.4 to 20.5 (MJ / m ³ ) ^1/2 ) is particularly preferable.

Examples of the polymer having such a solubility parameter include a polymer having a polar group in a side chain, a polymer having a polar bond in a main chain, and a combination of these polymers.

The polymer having a polar group in the side chain is 1 or 2
Any type may be used as long as it contains at least one kind of polar group in the side chain. A polymer having a nitrile group on the side chain such as an acrylonitrile- (meth) acrylate copolymer; a compound having a hydroxyl group on the side chain such as a phenol resin; a polymer having an amide group on the side chain such as polyacrylamide; (Meth) acrylate, ethylene-
Polymers having an ester group in the side chain such as (meth) acrylate copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer; polymers having an ether group in the side chain such as polyvinyl ether; styrene-anhydride Polymers having a carboxyl group in the side chain such as maleic acid copolymer, acrylic acid- (meth) acrylate copolymer, ethylene-acrylic acid copolymer; chlorinated polypropylene, polyvinyl chloride, polyvinylidene chloride, etc. And a halogen atom-containing polymer.

The polymer having a polar bond in the main chain may be one having one or more polar bonds in the main chain.
Examples include polyamide, polyimide, polyester, polythioester, polyether, polythioether, polysulfide, polyimidazole, polysulfone, polycarbonate, polyurethane, and polyurea.
Examples of those having two or more polar bonds in the main chain include polyamide imide, polyether sulfone, polyether ketone, polyether imide, polyether-based polyurethane, polyester-based polyurethane, and ether-based polyester.

Further, crosslinked or vulcanized products of the above-mentioned polymers can also be used, and examples thereof include chloroprene rubber, nitrile rubber, epichlorohydrin rubber, styrene butadiene rubber, acrylic rubber, acrylonitrile-butadiene rubber, and natural rubber. And the like.

In the present invention, it is preferable to use a polymer containing a nitrile group among the above-mentioned polymers. This is because the polymer containing a nitrile group is particularly excellent in compatibility with the layered clay mineral that has been organically treated with the organic agent used in the present invention, so that the dispersibility of the layered clay mineral is further improved.

As the polymer containing a nitrile group, a acrylonitrile-butadiene copolymer and a hydrogenated acrylonitrile-butadiene copolymer are preferably used since a polymer composition having particularly excellent gas barrier properties and strength can be obtained. preferable.

The nitrile group content in the polymer containing a nitrile group is preferably from 5 to 75% by weight, more preferably from 10 to 50% by weight. When the nitrile group content is less than 5% by weight, physical properties such as gas barrier properties of the obtained polymer composition tend to be insufficient, and when the nitrile group content exceeds 75% by weight,
The viscosity of the polymer tends to be high, and long-time stirring or high shearing force may be required for dispersing the layered clay mineral.

The polymer used in the present invention has a number average molecular weight of 5,000 to 10,000,000.
00 is preferred. Number average molecular weight is 5,000
When the amount is less than the above, the mechanical properties of the obtained polymer composition tend to be inferior. On the other hand, when it exceeds 10,000,000, the dispersion of the layered clay mineral tends to be difficult.

In the present invention, the above polymer is
A hydroxyl group, a mercapto group, an amide group, and at least one functional group selected from the group consisting of an ester group,
Further, a layered clay mineral that has been organically treated with an organic agent having a number average molecular weight of 800 or less is added.

Examples of the layered clay mineral include a kaolinite group such as kaolinite and halosite; a smectite group such as montmorillonite, beidellite, saponite, hectorite and mica; and a layered clay mineral such as a vermiculite group. The layered clay mineral may be derived from a natural product, a processed product of a natural product, or a synthetic product such as swellable fluorinated mica. The above layered clay minerals may be used alone or in combination of two or more. The total cation exchange capacity is 10 to 300 meq / 100.
g, preferably 50 to 200 meq / 100.
g is more preferable.

In the present invention, the term "organization" means that an organic substance is adsorbed and / or bound between the surface and / or the interlayer of the above-mentioned layered clay mineral by a physical or chemical method.
The term “organizing agent” refers to an organic substance capable of such adsorption and / or binding, and an organic compound having a polar group that generates an ion in a solvent is usually used.

In the present invention, there is no limitation on the reaction ratio between the layered clay mineral and the organic agent, but it is preferable that 100% of the total cation exchange capacity of the layered clay mineral is organized by the organic agent.

The organic agent used in the present invention has at least one functional group selected from the group consisting of a hydroxyl group, a mercapto group, an amide group and an ester group and has a number average molecular weight of 800 or less. There is no particular limitation, but an organic onium compound having the above functional group and molecular weight is preferable from the viewpoint of excellent reactivity with the layered clay mineral. In the present invention, a hydroxyl group is preferably used as the functional group of the organic agent, and the number average molecular weight of the organic agent is preferably 50 to 800. The number average molecular weight is more preferably from 50 to 600, and particularly preferably from 50 to 500.

Examples of the organic onium compound include an organic ammonium compound, an organic phosphonium compound, an organic pyridinium compound, an organic sulfonium compound, and the like. Among them, organic ammonium compounds and organic sulfonium compounds are preferable because of the good reactivity of the generated organic onium ions. More preferably, a phosphonium compound is used.

The number of carbon atoms of an organic group bonded to an atom having a lone pair of electrons in the above-mentioned organic onium compound (for example, a nitrogen atom in an organic ammonium compound) is not particularly limited, but the number of carbon atoms of the longest chain organic group is 6 It is preferably from 30 to 30, more preferably from 10 to 30. When the carbon number of the longest chain is less than 6, the effect of organizing the layered clay mineral tends to be insufficient, and when it exceeds 30, the dispersion of the layered clay mineral in the polymer tends to be insufficient. It is in. Further, the number of organic groups bonded to the atom having a lone electron pair in the organic onium compound is 1 or more, and is equal to or less than the maximum number that allows bonding.

The organic group must have at least one functional group selected from the group consisting of a hydroxyl group, a mercapto group, an amide group, and an ester group. Further, the number average molecular weight must be 800 or less. Here, the number average molecular weight of the organic onium compound means the number average molecular weight of organic onium ions (organic onium ions not containing a counter ion) generated from the organic onium compound. This is because when an organic onium compound is used, the layered clay mineral is organized by replacing inorganic ions in the layered clay mineral with organic onium ions generated from the organic onium compound.

The organic ammonium compound used as the organic agent in the present invention includes primary and secondary compounds having at least one functional group selected from the group consisting of a hydroxyl group, a mercapto group, an amide group and an ester group. ,
Both tertiary and quaternary organic ammonium compounds can be used. The organic group in this organic ammonium compound may be any of aliphatic, alicyclic and aromatic.

The primary organic ammonium compounds include:
For example, hydroxyalkylammonium salts, hydroxyarylammonium salts, hydroxyaralkylammonium salts, mercaptoalkylammonium salts, mercaptoarylammonium salts, mercaptoaralkylammonium salts and the like can be mentioned. In these ammonium salts, the number of hydroxyl groups and the number of mercapto groups are 1
However, it may be two or more. The longest chain organic group bonded to the nitrogen atom of these ammonium salts has 6 carbon atoms.
It is preferably from 30 to 30.

Examples of the hydroxyalkyl ammonium salt include hydroxyhexyl ammonium salt, hydroxyoctyl ammonium salt, hydroxydecyl ammonium salt, hydroxydodecyl ammonium salt, hydroxytetradecyl ammonium salt, hydroxyhexadecyl ammonium salt, hydroxyoctadecyl ammonium salt and the like. As the mercaptoalkyl ammonium salt, mercaptohexyl ammonium salt, mercaptooctyl ammonium salt, mercaptodecyl ammonium salt, mercaptododecyl ammonium salt, mercaptotetradecyl ammonium salt, mercaptohexadecyl ammonium salt, mercaptooctadecyl ammonium salt, and the like. Can be.

The primary organic ammonium compounds include:
A primary organic ammonium salt to which an organic group having an amide group is bonded, and a primary organic ammonium salt to which an organic group having an ester group is bonded can also be used. The organic group of such a primary organic ammonium salt preferably has 6 to 30 carbon atoms.

As the secondary organic ammonium compound,
Ammonium salts such as hydroxyalkylalkylammonium salt, hydroxyalkylarylammonium salt, hydroxyalkylaralkylammonium salt, bis (hydroxyalkyl) ammonium salt, bis (hydroxyaryl) ammonium salt and bis (hydroxyaralkyl) ammonium salt; Ammonium salts having a structure in which a hydroxyl group is replaced with a mercapto group are exemplified. In these ammonium salts,
The number of hydroxyl groups and the number of mercapto groups may be one or two or more. The longest chain organic group bonded to the nitrogen atom of these ammonium salts preferably has 6 to 30 carbon atoms.

Examples of such a compound include hydroxyethyl decyl ammonium salt, hydroxyethyl dodecyl ammonium salt, hydroxyethyl octadecyl ammonium salt, bis (hydroxyoctadecyl) ammonium salt, mercaptoethyl decyl ammonium salt, mercaptoethyl dodecyl ammonium salt, Mercaptoethyl octadecyl ammonium salt, bis (mercaptooctadecyl) ammonium salt and the like can be mentioned.

The secondary organic ammonium compounds include:
A secondary organic ammonium salt to which an organic group having an amide group is bonded, and a secondary organic ammonium salt to which an organic group having an ester group is bonded can also be used. The organic group of such a secondary organic ammonium salt preferably has 6 to 30 carbon atoms.

The tertiary organic ammonium compounds include
Hydroxyalkyldialkylammonium salt, bis (hydroxyalkyl) alkylammonium salt, bis (hydroxyaryl) alkylammonium salt, bis (hydroxyaralkyl) alkylammonium salt, tris (hydroxyalkyl) ammonium salt, tris (hydroxyaryl) ammonium salt, tris Examples include ammonium salts such as (hydroxyaralkyl) ammonium salts, and ammonium salts having a structure in which a hydroxyl group of the ammonium salt is replaced with a mercapto group. The number of hydroxyl groups and the number of mercapto groups in these ammonium salts may be one or two or more. The longest chain organic group bonded to the nitrogen atom of these ammonium salts preferably has 6 to 30 carbon atoms.

Among these ammonium salts, those having a hydroxyl group include hydroxyethyl dioctyl ammonium salt, hydroxyethyl didecyl ammonium salt, hydroxyethyl didodecyl ammonium salt, hydroxyethyl dioctadecyl ammonium salt, hydroxyethyl methyl octadecyl ammonium salt. , Bis (hydroxymethyl) dodecyl ammonium salt, bis (hydroxyethyl) octadecyl ammonium salt and the like.

As the tertiary organic ammonium compound,
A tertiary organic ammonium salt having an organic group having an amide group bonded thereto and a tertiary organic ammonium salt having an organic group having an ester group bonded can also be used. The organic group of such a tertiary organic ammonium salt preferably has 6 to 30 carbon atoms.

As the quaternary organic ammonium compound,
Hydroxyalkyltrialkylammonium salts, bis (hydroxyalkyl) dialkylammonium salts, bis (hydroxyalkyl) diarylammonium salts,
Bis (hydroxyalkyl) diaralkylammonium salt, bis (hydroxyaryl) dialkylammonium salt, bis (hydroxyaralkyl) dialkylammonium salt, tris (hydroxyalkyl) alkylammonium salt, tris (hydroxyaryl) alkylammonium salt, tris (hydroxyaralkyl) ) Alkylammonium salts, tetrakis (hydroxyalkyl)
Examples thereof include ammonium salts such as ammonium salts, and ammonium salts having a structure in which a hydroxyl group of the ammonium salt is replaced with a mercapto group. The number of hydroxyl groups and the number of mercapto groups in these ammonium salts may be one or two or more. The longest chain of the organic group bonded to the nitrogen atom of these ammonium salts preferably has 6 to 30 carbon atoms.

Among these ammonium salts, those having a hydroxyl group include hydroxyethyltrioctylammonium salt, hydroxyethyltridecylammonium salt, hydroxyethyltrioctadecylammonium salt, bis (hydroxyethyl) dioctylammonium salt, bis (hydroxy Ethyl) didecyl ammonium salt, bis (hydroxyethyl) dioctadecyl ammonium salt, bis (hydroxymethyl) methyloctyl ammonium salt, bis (hydroxyethyl) methyloctyl ammonium salt, bis (hydroxymethyl) methyloctadecyl ammonium salt, bis (hydroxy Ethyl) methyloctadecyl ammonium salt, bis (hydroxymethyl) ethyloctadecyl ammonium salt, bis (hydroxyethyl) ethyl Ammonium salts, tris (hydroxyethyl) octadecyl ammonium salts, tetrakis (hydroxy octadecyl) ammonium salts.

As the quaternary organic ammonium compound,
A quaternary organic ammonium salt having an organic group having an amide group bonded thereto and a quaternary organic ammonium salt having an organic group having an ester group bonded thereto can also be used. The organic group of such a quaternary organic ammonium salt preferably has 6 to 30 carbon atoms.

The organic agent used in the present invention is particularly preferably a compound containing an ammonium ion having a structure represented by the following general formula (1).

[0050]

Embedded image (Wherein m, n, and x may be the same or different,
Represents an integer of 5. y represents an integer of 6 to 30)

Among the ammonium ions represented by the general formula (1), it is preferable to use a compound containing an ammonium ion (bis (hydroxyethyl) methyloctadecyl ammonium ion) represented by the following formula (2).

[0052]

Embedded image

The organic treatment of the layered clay mineral using the above-mentioned organic agent is described, for example, in Japanese Patent No. 262719 by the present applicant.
The method can be carried out by the method disclosed in Japanese Patent Publication No. That is, it can be performed by ion-exchanging inorganic ions such as sodium ions in the layered clay mineral with organic onium ions generated from the above-mentioned organic onium compounds (for example, organic ammonium ions in the case of organic ammonium compounds).

When an organic ammonium compound is used as the organic onium compound, for example, the organic method can be performed by the following method. That is, when the layered clay mineral is in a lump, it is first pulverized by a ball mill or the like and powdered. Next, this powder is dispersed in water using a mixer or the like to obtain an aqueous dispersion of the layered clay mineral.
Separately, an aqueous solution of an organic ammonium compound having at least one functional group selected from the group consisting of a hydroxyl group, a mercapto group, an amide group, and an ester group and having a number average molecular weight of 800 or less is prepared. By adding and mixing this aqueous solution with the aqueous dispersion of the layered clay mineral, inorganic ions in the layered clay mineral are ion-exchanged with organic ammonium ions generated from an organic ammonium compound. Then, by removing water from the mixture, an organic layered clay mineral can be obtained. As a dispersion medium of the organic ammonium compound and the layered clay mineral, in addition to water, methanol, ethanol, propanol, isopropanol, ethylene glycol, a mixture thereof, a mixture thereof, and a water can also be used.

The method for producing the polymer composition of the present invention is not particularly limited. For example, it can be obtained by dispersing or dissolving the above-described polymer and the organized layered clay mineral in a solvent such as water or an organic solvent, and then removing the solvent.

Further, it can also be obtained by heating and mixing the polymer and the organic layered clay mineral at a temperature higher than the melting point or softening point of the polymer. At the time of heating, it is preferable to apply a shearing force to uniformly disperse the organic layered clay mineral, and it is preferable to use an extruder as a means for applying the shearing force while heating. At this time, an organic solvent, oil, or the like can be added, and after or during the dispersion of the layered clay mineral, crosslinking of the polymer and / or
Alternatively, vulcanization may be performed.

In addition to the above-mentioned method, for example, an organic layered clay mineral is added to a monomer to be converted into a polymer having a solubility parameter of 9 to 14 (cal / cm ³ ) ^1/2 , and the organic layered clay mineral is added. It is possible to obtain a polymer composition by polymerizing the monomer in the presence of a clay mineral. In the case where a polymer is formed by mixing and reacting two or more components such as polyurethane, polyester, polyurea, etc., at least one of the two or more components before the reaction is pre-organized. By adding a layered clay mineral in advance, a polymer composition can be obtained.

In the present invention, the mixing ratio of the polymer and the organically modified layered clay mineral is preferably 0.1 to 200 parts by weight, more preferably 0 to 200 parts by weight, with respect to 100 parts by weight of the former. 0.1 to 30 parts by weight, particularly preferably 0.5 to 10 parts by weight. When the weight part of the layered clay mineral is less than 0.1 part by weight, the strength and gas barrier properties of the obtained polymer composition tend to be insufficient,
On the other hand, when the amount exceeds 200 parts by weight, the polymer tends to be unable to form a continuous layer, the strength and the like of the polymer composition are reduced, and the viscosity is increased and the processability tends to be impaired.

In the present invention, a pigment, a heat stabilizer, a flame retardant, an antioxidant, a weathering agent, a release agent, a plasticizer, a reinforcing agent, etc. are used as long as the properties of the polymer composition are not significantly impaired. Can be added.

In the present invention, a polymer having a solubility parameter of 9 to 14 (cal / cm ³ ) ^1/2 is used because the layered clay mineral organically treated with the above-mentioned organic agent is used. Intercalation between the mineral layers is facilitated. Therefore, the interlayer distance of the layered clay mineral increases, but the interlayer distance at this time is preferably 10 Å or more, more preferably 30 Å or more than the interlayer distance before intercalation occurs. The interlayer distance is more preferably expanded to 100 Å or more, and most preferably the interlayer distance is expanded to such an extent that the regular layer structure of the layered clay mineral disappears.

The interlayer distance can be measured by X-ray diffraction, and the increase in interlayer distance can be confirmed by the occurrence of a peak in a smaller diffraction angle region in the X-ray diffraction pattern. The loss of the regularity of the layer structure can be confirmed from the fact that the peak is not clear or the peak does not appear.

As described above, in the present invention,
Since the layered clay mineral is organized with an organic agent having a number average molecular weight of 800 or less, the organic agent easily penetrates between the layers of the layered clay mineral, and the interlayer distance of the layered clay mineral increases. Further, since the organic agent has at least one functional group selected from the group consisting of a hydroxyl group, a mercapto group, an amide group, and an ester group, the polarity of the layered clay mineral having an increased interlayer distance is determined by a solubility parameter. Can be close to the polarity of the polymer of 9 to 14 (cal / cm ³ ) ^1/2 , and the intercalation of the polymer into the layered clay mineral becomes easy. Therefore, the layered clay mineral is very finely dispersed in the polymer. Therefore, the polymer composition of the present invention has improved properties such as strength and gas barrier properties, and can be suitably used in fields requiring high strength and gas barrier properties.

[0063]

Hereinafter, preferred embodiments of the present invention will be described in more detail, but the present invention is not limited to these embodiments.

(Example 1) Sodium montmorillonite (layered clay mineral manufactured by Kunimine Industries Co., Ltd., trade name: Knipia F, total cation exchange capacity: 119 meq / 100 g) 80
g was dispersed in 5000 ml of water at 80 ° C. Next, a compound containing an ammonium ion (organizing agent) represented by the following formula (2), Sapone GL-2218-Br (manufactured by Nippon Fine Chemical Co., Ltd., number average molecular weight: 372.6) 50
g was dissolved in 2000 ml of water at 80 ° C., and this solution was added to the above montmorillonite dispersion to obtain a precipitate. The precipitate was filtered, washed with water at 80 ° C. three times, and freeze-dried to obtain an organized montmorillonite (hereinafter, referred to as C18 (OH) -Mt).

[0065]

Embedded image

C18 (OH) -Mt and an acrylonitrile-butadiene copolymer (Nipol DN401, manufactured by Zeon Corporation) having an acrylonitrile content of 17% were mixed at 80 ° C. using a mill to obtain a polymer composition. I got something. The acrylonitrile-butadiene copolymer and C
The mixing ratio with 18 (OH) -Mt was 100 parts by weight of the former and 10 parts by weight of the latter.

(Comparative Example 1) Sodium montmorillonite (layered clay mineral manufactured by Kunimine Industries Co., Ltd., trade name: Knipia F, total cation exchange capacity: 119 meq / 100 g) 80
g was dispersed in 5000 ml of water at 80 ° C. 31.1 g of octadecylamine and 9.5 ml of concentrated hydrochloric acid were added to 80 ° C. water 2
000 ml, and this solution was added to the montmorillonite dispersion to obtain a precipitate. The precipitate was filtered, washed three times with water at 80 ° C., and then freeze-dried to give an organized montmorillonite (hereinafter referred to as C18-
Mt). C18-Mt and an acrylonitrile-butadiene copolymer (Nipol DN401, manufactured by Zeon Corporation) having an acrylonitrile content of 17% were mixed at 80 ° C using a mill to obtain a polymer composition. The acrylonitrile-butadiene copolymer and C
The mixing ratio with 18-Mt was 100 parts by weight of the former and 10 parts by weight of the latter.

Comparative Example 2 Methyl acrylate (20 mol
1%), 2-hydroxyethyl acrylate (70 mol
%), 2- (dimethylamino) ethyl acrylate (10%
mol%) to obtain a polymer having a number average molecular weight of 1550. 80 g of sodium montmorillonite (layered clay mineral manufactured by Kunimine Industries Co., Ltd., trade name: Kunipia F, total cation exchange capacity: 119 meq / 100 g) was added to 80 ° C. water 5
000 ml. 60 g of the above polymer and 12 ml of concentrated hydrochloric acid were dissolved in 2000 ml of water at 80 ° C., and this solution was added to the above montmorillonite dispersion to obtain a precipitate. The precipitate is filtered and washed three times with 80 ° C. water,
After removing the excess organic agent (hydrochloride of the polymer), it was freeze-dried to obtain an organized montmorillonite. This organized montmorillonite and an acrylonitrile-butadiene copolymer (Nipol DN401, manufactured by Nippon Zeon Co., Ltd.) having an acrylonitrile content of 17% were mixed at 80 ° C. using a mill to obtain a polymer composition. The mixing ratio of the acrylonitrile-butadiene copolymer and the organized montmorillonite was 100 parts by weight of the former and 10 parts by weight of the latter.

X-ray diffraction was performed using the polymer compositions obtained in Example 1 and Comparative Examples 1 and 2. The obtained X-ray diffraction patterns are shown in FIGS. The peak in FIG. 1 is broad, and in Example 1, the layered clay mineral was dispersed in a single layer in the acrylonitrile-butadiene copolymer, indicating that the dispersibility of the layered clay mineral was very good. Was. On the other hand, a clear peak appears in FIG. 2, and in Comparative Example 1, acrylonitrile-
Although the layered clay mineral is dispersed in the butadiene copolymer, the layered clay mineral has a certain layer structure,
It was found that the dispersibility was inferior to that of Example 1.
In Comparative Example 2, as can be seen from the X-ray diffraction pattern in FIG. 3, the layered clay mineral maintained a clear layered structure in the acrylonitrile-butadiene copolymer, and acrylonitrile-butadiene was compared to the layered clay mineral. No or little intercalation of the copolymer has occurred. Therefore, it was found that the dispersibility of Comparative Example 2 was considerably inferior to that of Example 1.

[0070]

As described above, according to the present invention,
A polymer composition comprising a polymer having a solubility parameter of 9 to 14 (cal / cm ³ ) ^1/2 medium polarity and a layered clay mineral, wherein the layered clay mineral is finely dispersed. It is possible to provide a molecular composition.

[Brief description of the drawings]

FIG. 1 is a view showing an X-ray diffraction pattern of a polymer composition obtained in Example 1.

FIG. 2 is a view showing an X-ray diffraction pattern of a polymer composition obtained in Comparative Example 1.

FIG. 3 is a view showing an X-ray diffraction pattern of a polymer composition obtained in Comparative Example 2.

Continuation of the front page (72) Inventor Usumi Atsuki Usuki Aichi, Aichi-gun, Nagakute-cho, Oku-cho, 41-cho, Yokomichi Yokomichi F-term (reference) 4J002 AA001 AC011 AC071 AC081 AC091 BB061 BB071 BB081 BB241 BC051 BC061 BD041 BD101 BE041 BF021 BF031 BG011 BG031 BG041 BG101 BG131 BH011 BN151 CC071 CF001 CF101 CF141 CG001 CH001 CH041 CK011 CK021 CK031 CK041 CL001 CM031 CM041 CN011 CN021 CN031 DJ006 DJ0DJ0

Claims (3)

[Claims] (1) a solubility parameter of 9 to 14 (cal / cm ³ );
^1/2 of a polymer and a layered clay mineral dispersed in the polymer, wherein the layered clay mineral is at least one functional group selected from the group consisting of a hydroxyl group, a mercapto group, an amide group, and an ester group. A polymer composition comprising a layered clay mineral having a group and having a number-average molecular weight of 800 or less, which is organized by an organic agent. 2. The polymer composition according to claim 1, wherein the polymer is a polymer containing a nitrile group. 3. The polymer composition according to claim 1, wherein the organic agent is an organic onium compound.