JP2009046316A - Organized layered silicate and resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To formulate an organized layered silicate with high dispersibility for a resin having a furan ring in its molecular chain, and to improve the durability and stiffness of the resin. <P>SOLUTION: The resin composition is obtained by mixing the layered silicate organized with an organizing agent having a furan ring and a resin having a furan ring in its molecular chain. The resin composition is excellent in heat resistance and stiffness. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a layered silicate organized by an organic agent having a furan ring and a resin composition containing the organized layered silicate.

  In recent years, in order to suppress the use of fossil resources as much as possible from the viewpoint of environmental protection and reduce the emission of greenhouse effect gas, resins synthesized using renewable resources have attracted attention. Currently, many of the biopolymers are aliphatic polyesters. However, the physical properties are inferior to those of general-purpose resins and engineering plastics synthesized from fossil resources. At present, physical properties are improved by mixing. However, when a resin made from fossil fuel is mixed, the environmental load reducing effect is reduced. On the other hand, since a furan ring can be synthesized from a sugar compound, a resin having a furan ring in the molecular chain can be synthesized not using fossil resources but using renewable resources.

  Here, in general, thermoplastic resins are used in a wide variety of fields such as films and shaping materials by utilizing excellent properties such as mechanical strength, heat resistance, weather resistance, and chemical resistance. Furthermore, since the strength and heat resistance of the resin are improved by blending a reinforcing filler with these thermoplastic resins, the reinforcing composition thus obtained is suitable as a material for machine parts. One example of such a reinforcing filler is inorganic powder such as talc, glass fiber, and layered silicate. When such a powdery filler is used, when a resin composition is obtained by melt kneading or the like, addition at a high mixing ratio is necessary, and there are problems in workability and dispersibility.

Therefore, by exchanging exchangeable cations existing between the layers of the layered silicate with organic onium ions to form an organicated layered silicate, the layer is easily peeled off and the affinity with the resin is increased. Ingenuity has been made. Patent Document 1 discloses a technique in which a polyester resin and an organically modified layered silicate produced by bonding an organic onium ion having a benzene ring in the structure to a layered silicate are disclosed.
JP 2001-261947 A

  However, the dispersibility for a specific resin is improved by using an organic onium ion having a benzene ring in its structure bonded to a layered silicate, but the dispersibility for a resin having a furan ring in the molecular chain is improved Sex was not satisfactory.

  When the dispersibility of the layered silicate is insufficient and unevenly distributed, not only the strength and heat resistance of the resin composition are not improved, but also the stress applied to the resin composition is concentrated on a specific part. Accordingly, it is an object of the present invention to formulate an organically modified layered silicate having high dispersibility with respect to a resin having a furan ring in the molecular chain.

  The organically modified layered silicate according to the present invention has a specific organic onium ion between the layers. By melt-kneading this with a resin having a furan ring in the molecular chain, it is possible to easily disperse the layered silicate into the resin uniformly at the nano level. Nano-level dispersion refers to a state in which layers having a thickness of about 1 nanometer forming a layered silicate are separated in a single layer and dispersed in a resin.

  That is, the organically modified layered silicate according to the present invention is a layered silicate that is organized with an organic agent having a furan ring.

  The resin composition according to the present invention is characterized in that the organically modified layered silicate is mixed with a resin having a furan ring in a molecular chain.

  The present invention relates to a novel resin composition. The resin composition has good physical properties such as mechanical strength and heat resistance, and is also effective for recycling.

  Hereinafter, embodiments of the present invention will be described.

  The resin composition according to the present invention is a mixture of a layered silicate organized with an organic agent having a furan ring, that is, an organic layered silicate according to the present invention into a resin having a furan ring in the molecular chain. The resin composition is excellent in heat resistance and rigidity.

  The resin constituting the resin composition according to the present invention is not particularly limited as long as it has a furan ring in its molecular chain. For example, a dicarboxylic acid having a furan ring in its molecule or an ester-forming derivative thereof and a diol Or the thermoplastic polyester resin which has the ester formation derivative as a main component and has a furan ring in the molecular chain which is a polymer or copolymer obtained by those polymerization reaction can be used. Further, for example, a thermoplastic polyester resin having a furan ring in the molecular chain, which is a polymer or copolymer obtained mainly by a compound having a furan ring, a carboxyl group and an alcohol group in the molecule, and a polymerization reaction thereof. Can be used. In addition, for example, a dicarboxylic acid having a furan ring in the molecule or an ester-forming derivative thereof and a diamine or an ester-forming derivative thereof as main components, and in a molecular chain that is a polymer or copolymer obtained by a polymerization reaction thereof. A resin such as a thermoplastic polyamide resin having a furan ring can be used.

Specific examples of the resin having a furan ring in the molecular chain include polybutylene furandicarboxylate (Chemical Formula 1), polyalkylene furandicarboxylate such as polypropylene furandicarboxylate and polyethylene furandicarboxylate, polybutylene furan carboxamide, and polypropylene furan. Carboxamide, polyethylene furan carboxamide, polybutylene furanamide, polypropylene furanamide, polyethylene furanamide, etc. are preferably used. Among these, in the present invention, polybutylene flange carboxylate (chemical formula 1), polypropylene flange carboxylate, and polyethylene flange carboxylate are preferably used, and polybutylene flange carboxylate (chemical formula 1) is particularly preferably used.

ポリブチレンフランジカルボキシレート（式中Ｒは（ＣＨ₂）₄を表す。）

Polybutylene furandicarboxylate (wherein R represents (CH ₂ ) ₄ )

  In the resin composition according to the present invention, other resin components may be copolymerized or mixed as necessary, as long as the mechanical properties and heat resistance are not significantly impaired. Specific examples of other resins include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polyethylene terephthalate, polylactic acid, polycaproic acid, polycarbonate, polyamide 6, polyethylene, polypropylene, polystyrene, polyvinyl alcohol, polybutadiene, and ABS resin. Can be mentioned.

  The layered silicate used in the present invention is a swellable layered silicate. For example, a general nanocomposite material such as smectite such as montmorillonite or saponite, swellable synthetic mica, graphite, or imogolite should be used. Can do. Among these, montmorillonite and synthetic mica are preferable.

  The organic agent having a furan ring for organicizing these layered silicates is an onium cation having a furan ring, and is not limited as long as the effect of the present invention is exhibited. A compound in which a compound having a furan ring is bonded to the cation atom of the onium cation can be used.

  A preferred embodiment of the organic agent having a furan ring in the present invention is an onium cation represented by the following general formula (I).

The general formula (I) satisfies the following conditions. That is, M is a nitrogen atom or a phosphorus atom. R ¹ is an alkyl group having 1 to 24 carbon atoms. R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms having a linear or branched structure (the alkyl group may have a hydroxy group as a substituent). R ⁴ is furan or a carbon chain having 1 to 6 carbon atoms and having furan as a substituent (the carbon chain may contain carbonyl, ether or ester. The furan is It may have at least one alkyl group having 1 to 4 carbon atoms as a substituent, and the furan may have a condensed ring.

R ¹ is more preferably an alkyl group having 6 to 20 carbon atoms, and further preferably 8 to 18 carbon atoms, from the viewpoint of the effect of increasing the interlayer distance of the layered silicate.

R ² and R ³ are each independently more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms.

R ⁴ is more preferably furan or an alkyl group having 1 to 4 carbon atoms and having furan as a substituent, and more preferably furan.

Therefore, the general formula (I) more preferably satisfies the following conditions. That is, M is a nitrogen atom or a phosphorus atom. R ¹ is an alkyl group having 6 to 20 carbon atoms. R ² and R ³ are alkyl groups having 1 to 6 carbon atoms. R ⁴ is furan or an alkyl group having 1 to 4 carbon atoms and has furan as a substituent.

Further, the general formula (I) particularly preferably satisfies the following conditions. That is, M is a nitrogen atom or a phosphorus atom. R ¹ is an alkyl group having 8 to 18 carbon atoms. R ² and R ³ are alkyl groups having 1 to ³ carbon atoms. R ⁴ is franc.

  Specific examples of the organic agent having a furan ring include the following compounds. Examples of the quaternary phosphonium having a furan ring include dimethylstearylfuranphosphonium, 2-furancarboxydimethylstearylphosphonium, dodecyldibutylfuranphosphonium, hexadecyldibutylfuranphosphonium, and octadecyldibutylfuranphosphonium. Nium, dodecyldimethylfuranphosphonium, hexadecyldimethylfuranphosphonium, octadecyldimethylfuranphosphonium, didodecylbutylfuranphosphonium, dodecyldibutylfuranphosphonium, dihexadecylbutylfuranphosphonium, hexadecyl Dibutylfuranphosphonium, dioctadecylbutylfuranphosphonium, octadecyldibutylfuranphosphonium, di Decyl methyl furan phosphonium, dodecyl dimethyl furan phosphonium, dihexadecyl methylfuran phosphonium, hexadecyl dimethyl furan phosphonium, dioctadecyl methyl furan phosphonium, octadecyl dimethyl furan phosphonium and the like.

  Examples of the quaternary ammonium having a furan ring include dimethyl stearyl furan ammonium, 2-furancarboxydimethyl stearyl ammonium, dodecyl dibutyl furan ammonium, hexadecyl dibutyl furan ammonium, octadecyl dibutyl furan ammonium, dodecyl dimethyl furan ammonium, hexadecyl dimethyl. Furan ammonium, octadecyl dimethyl furan ammonium, didodecyl butyl furan ammonium, dodecyl dibutyl furan ammonium, dihexadecyl butyl furan ammonium, hexadecyl dibutyl furan ammonium, dioctadecyl butyl furan ammonium, octadecyl dibutyl furan ammonium, didodecyl methyl furan ammonium, dodecyl Dimethylfuran Moniumu, dihexadecyl methylfuran ammonium, hexadecyl dimethyl furan ammonium, dioctadecyl methyl furan ammonium, octadecyl dimethyl furan ammonium and the like. In addition, for example, trimethylfuran ammonium, dimethylhydroxyethyl furan ammonium, 2-acetoxyethyl dimethyl furan ammonium, dioctyl methyl furan ammonium, polyoxypropylene methyl ethyl furan ammonium, methyl / tallowbis (2-hydroxyethyl) furan ammonium Dimethylbenzyl hydrogenated tallow furan ammonium, dimethyl hydrogenated tallow-2-ethylhexyl furan ammonium, methyl dihydrogenated tallow furan ammonium, and the like.

  Among these organic agents having a furan ring, dimethyl stearyl furan ammonium and dimethyl stearyl furan phosphonium are particularly preferable.

  These organic agents having a furan ring may be used alone, or may be used as a mixture of two or more compounds.

  The organic agent having a furan ring can be produced by a known method. For example, a quaternary ammonium having a furan ring is obtained by reacting a compound having a halogenated furan ring as shown in Chemical Formula 3 to Chemical Formula 11 with, for example, dimethylstearylamine (Chemical Formula 12). Specifically, dimethylstearylfuran ammonium can be obtained by reacting dimethylstearylamine (Chemical Formula 12) with 3-chlorofuran (Chemical Formula 3). The reaction is a nucleophilic substitution reaction.

３−クロロフラン

3-chlorofuran

３−ブロモフラン

3-Bromofuran

フラン−２−カルボニルクロライド

Furan-2-carbonyl chloride

３−メチルフラン−２−カルボニルクロライド

3-methylfuran-2-carbonyl chloride

５−メチルフラン−２−カルボニルクロライド

5-methylfuran-2-carbonyl chloride

２−メチルフラン−３−カルボニルクロライド

2-Methylfuran-3-carbonyl chloride

５−ｔ−ブチル−２−メチルフラン−３−カルボニルクロライド

5-t-butyl-2-methylfuran-3-carbonyl chloride

３−メチルベンゾフラン−２−カルボニルクロライド

3-methylbenzofuran-2-carbonyl chloride

２−クロロメチレン−５−メチルフラン

2-chloromethylene-5-methylfuran

ジメチルステアリルアミン

Dimethylstearylamine

  Subsequently, the organic layered silicate manufacturing method according to the present invention will be described, in particular, the organic layered silicate. First, a smectite of a layered silicate is dispersed while being swollen in warm water of 60 ° C. to 90 ° C. To this, an organic agent having a furan ring is gradually added and stirred in warm water for about 20 to 30 hours to exchange exchangeable ions existing between layers of the layered silicate with those ionized by the organic agent. The suspension is filtered, and the resulting solid is washed repeatedly with warm water to remove residual sodium ions and excess organic agent. Finally, it is dried in an oven and pulverized by a pulverizer to obtain a powdered organic layered silicate according to the present invention.

  At this time, the addition amount of the organic agent having a furan ring can be, for example, 0.5 equivalent to 1.5 equivalent with respect to 1 equivalent of the ion exchange capacity of the layered silicate, 0.7 equivalent To 1.2 equivalents.

  Next, the layered silicate according to the present invention is dispersed in the resin using a biaxial kneader. First, a resin having a furan ring in the molecular chain is put into a biaxial kneader that is temperature-controlled at a temperature equal to or higher than the melting point of the resin, and then the organically modified layered silicate according to the present invention is added using a quantitative feeder. While kneading. The organically modified layered silicate is gradually peeled off by the shear stress generated by the screw of the kneading machine, and the layers of about 1 nanometer in thickness forming the layered silicate are dispersed in the resin in a state where each layer is peeled off. . At this time, it is considered that the organic agent having a furan ring is ionically bonded to the surface of the layer forming the organically modified layered silicate. Since the organic agent having a furan ring has a furan ring, it has high affinity with a resin having a furan ring in the molecular chain. Therefore, the organically modified layered silicate according to the present invention is easily dispersed in a resin having a furan ring in the molecular chain.

  The addition amount of the organic layered silicate according to the present invention can be 0.1 to 30 parts by weight with respect to a total of 100 parts by weight of the resin and the organic layered silicate. The amount is preferably 15 parts by weight, and more preferably 1 to 10 parts by weight. This is because when the addition amount of the organic layered silicate is less than 0.1 parts by weight, the resin composition may not be significantly improved in strength and heat resistance. On the other hand, when the amount exceeds 30 parts by weight, deterioration of the matrix resin is promoted by the influence of the quaternary ammonium ion component in the intercalation compound, which may hinder molding. In addition, the organically modified layered silicate may be used alone, or a plurality of types may be used in combination.

  The produced resin composition can be pelletized with a pelletizer.

  In addition, the resin composition of the present invention includes various additives within a range that does not impair the object of the present invention, such as impact modifiers, anti-coloring agents, thermal stabilizers, lubricants, flame retardants, release agents, nucleating agents, A hydrolysis inhibitor or the like can be added.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and it goes without saying that various modifications can be made without departing from the spirit of the present invention.

[Example 1]
A 1 liter induction rotating autoclave was charged with 300 g of dimethyl 12 (dimethylstearylamine), 100 g of isopropyl alcohol and 10 g of water. A compound having a furan ring represented by Chemical Formula 3 (3-chlorofuran) (Wako Pure Chemical Industries, Ltd.) as a quaternizing agent was used, and the reaction temperature was maintained at 90 ° C. while being introduced into the reactor. When the reaction was carried out for 4 hours, a dimethylstearylfuran ammonium chloride represented by Chemical formula 13 was obtained.
Dimethylstearylamine

ジメチルステアリルフランアンモニウム

Dimethylstearylfuran ammonium

[Example 2]
A phosphonium chloride having a furan ring represented by chemical formula 14 was obtained in the same manner as in Example 1 except that dimethylstearyl phosphate was used instead of dimethylstearylamine (chemical formula 12).

ジメチルステアリルフランフォスフォニウム

Dimethylstearylfuran phosphonium

Example 3
A quaternary ammonium salt having a furan ring was obtained by the same method except that Chemical Formula 4 was used instead of Chemical Formula 3 in Example 1.

Example 4
A phosphonium salt having a furan ring was obtained by the same method except that Chemical Formula 4 was used instead of Chemical Formula 3 in Example 2.

Example 5
A quaternary ammonium salt having a furan ring was obtained by the same method except that Chemical Formula 5 was used instead of Chemical Formula 3 in Example 1.

Example 6
A phosphonium salt having a furan ring was obtained by the same method except that Chemical Formula 5 was used instead of Chemical Formula 3 in Example 2.

Example 7
0.99 liters of 60 ° C. warm water was added to 100 g of stratified silicate montmorillonite (sodium type) (Bengel E, Hojun Co., Ltd.) and dispersed while swelling. Next, 1 liter of an aqueous solution containing 5 parts by weight of the quaternary ammonium salt represented by Chemical Formula 13 obtained in Example 1 was gradually added, and the mixture was stirred at 24 ° C. for 24 hours. Exchange reaction was performed. Thereafter, the precipitate was separated by filtration, washed with ultrapure water repeatedly to remove residual sodium ions, dried, and pulverized to obtain a powdered organic layered silicate.

Example 8
An organically modified layered silicate was obtained in the same manner as in Example 7 except that the phosphonium salt having the furan ring represented by Chemical Formula 14 obtained in Example 2 was used instead of Chemical Formula 13.

Example 9
An organically modified layered silicate was obtained in the same manner as in Example 7 except that the quaternary ammonium salt having a furan ring obtained in Example 3 was used instead of Chemical Example 13.

Example 10
An organically modified layered silicate was obtained in the same manner as in Example 7 except that the phosphonium salt having a furan ring obtained in Example 4 was used instead of Chemical Formula 13.

Example 11
An organically modified layered silicate was obtained in the same manner as in Example 7 except that the quaternary ammonium salt having a furan ring obtained in Example 5 was used instead of Chemical Example 13.

Example 12
An organically modified layered silicate was obtained in the same manner as in Example 7 except that the phosphonium salt having a furan ring obtained in Example 6 was used instead of Chemical Formula 13.

Example 13
Using a biaxial kneader TEM-26SS (Toshiba Machine Co., Ltd.), the organic layered layer obtained in Example 7 was added to 95 parts by weight of the resin of Chemical Formula 1 at a temperature condition of 180 ° C., biaxial rotation in the same direction and rotation speed of 800 rpm. A resin composition was prepared by melt-kneading while adding a fixed amount of 5 parts by weight of silicate.

  The obtained resin composition was pelletized, and a strip test piece (80 mm × 10 mm × t 4.0 mm) was prepared using the pellet with an injection molding machine FN1000-5ADN (Nissei Resin Industry Co., Ltd.).

  About the obtained strip test piece, the surface distance of the organically modified layered silicate was measured at each n = 1 using an X-ray diffraction measurement device (XRD): X'Pert Pro (trade name, manufactured by Philips). Since the diffraction peak of the organic layered silicate was shifted to the low angle side and the peak was small, it was confirmed that the interplanar spacing of the organic layered silicate was widened. That is, it was found that a resin having high affinity with the organic agent was intercalated between the layers of the organically modified layered silicic acid.

  Moreover, the obtained pellet was sliced into thin pieces using an ultramicrotome, and the dispersion state of the organic layered silicate was confirmed with a transmission electron microscope and a scanning transmission electron microscope. As shown in the conceptual diagram in FIG. 1, it was confirmed that the flakes were dispersed in the resin composition in a state where the layer having a thickness of about 1 nanometer forming the layered silicate was separated by a single layer.

Example 14
In Example 13, the resin and the organically modified layered silicate were used in the same manner except that the organically modified layered silicate obtained in Example 8 was used instead of the organically modified layered silicate obtained in Example 7. Was melt-kneaded to prepare a resin composition. Further, it was confirmed that the organically modified layered silicate was dispersed in the resin composition.

Example 15
The resin and the organically modified layered silicate were used in the same manner as in Example 13 except that the organically modified layered silicate obtained in Example 9 was used instead of the organically modified layered silicate obtained in Example 7. Was melt-kneaded to prepare a resin composition. Further, it was confirmed that the organically modified layered silicate was dispersed in the resin composition.

Example 16
In Example 13, the resin and the organically modified layered silicate were used in the same manner except that the organically modified layered silicate obtained in Example 10 was used instead of the organically modified layered silicate obtained in Example 7. Was melt-kneaded to prepare a resin composition. Further, it was confirmed that the organically modified layered silicate was dispersed in the resin composition.

Example 17
In Example 13, the resin and the organically modified layered silicate were used in the same manner except that the organically modified layered silicate obtained in Example 11 was used instead of the organically modified layered silicate obtained in Example 7. Was melt-kneaded to prepare a resin composition. Further, it was confirmed that the organically modified layered silicate was dispersed in the resin composition.

Example 18
The resin and the organically modified layered silicate were used in the same manner as in Example 13 except that the organically modified layered silicate obtained in Example 12 was used instead of the organically modified layered silicate obtained in Example 7. Was melt-kneaded to prepare a resin composition. Further, it was confirmed that the organically modified layered silicate was dispersed in the resin composition.

[Comparative Example 1]
In Example 13, instead of the organically modified layered silicate obtained in Example 7, a commercially available organically modified layered silicate (Esven E, Hojun Co., Ltd.) that is organicized with the organic agent represented by Chemical Formula 15 A resin composition was prepared by melt-kneading the resin and the organically modified layered silicate in the same manner except that was used. However, the organically modified layered silicate was localized while maintaining the layered structure in the resin composition, and it could not be confirmed that it was dispersed in a delaminated state.

トリメチルステアリルアンモニウム

Trimethylstearylammonium

[Comparative Example 2]
In Example 13, instead of the organically modified layered silicate obtained in Example 7, a commercially available organically modified layered silicate (Esven NZ, Hojun Co., Ltd.) that has been organicized with the organic agent represented by Chemical Formula 16 A resin composition was prepared by melt-kneading the resin and the organically modified layered silicate in the same manner except that was used. However, the organically modified layered silicate was localized while maintaining the layered structure in the resin composition, and it could not be confirmed that it was dispersed in a delaminated state.

ジメチルステアリルベンジルアンモニウム

Dimethylstearylbenzylammonium

[Comparative Example 3]
In Example 13, a resin was used in the same manner except that a commercially available non-organized layered silicate (Wenger FW, Hojun Co., Ltd.) was used instead of the organically modified layered silicate obtained in Example 7. And a layered silicate were melt-kneaded to prepare a resin composition. However, it was confirmed that the layered silicate was not dispersed at all in the resin and existed as an aggregate.

[Comparison 1]
About the quaternary ammonium salt (Chemical Formula 13, Chemical Formula 15, and Chemical Formula 16) supported on the organically modified layered silicate used in Example 13 and Comparative Examples 1 and 2, and the resin having a furan ring (Chemical Formula 1) The polarity term δp of the solubility parameter (SP value) was calculated by Hansen's method, and the data in Table 1 were obtained. The SP value is a value used as a scale representing intermolecular force, and a method of calculating from the molecular composition has been proposed. The closer the value is, the easier it is to dissolve. In particular, in the case where the organic layered silicate is dispersed in a resin having polarity, it has been found that the closer the value of the polar term of the organic agent of the layered silicate to the value of the resin, the better the dispersibility. Yes. From Table 1, it was confirmed that Chemical formula 13 is the value closest to Chemical formula 1.

[Comparison 2]
Dispersibility evaluation of the organically modified layered silicate in the resin compositions obtained in Examples 13 to 18 and Comparative Examples 1 to 3 was performed, and the results shown in Table 2 were obtained. In Table 2, “O” indicates that the layered structure of the organically modified layered silicate was broken by the transmission electron microscope and the scanning light electron microscope, and was peeled to a single layer, and XRD was used. This is the result of confirming the expansion of the surface spacing and the reduction of the peak. On the other hand, x is the result of confirming that the layered structure is maintained or in an aggregated state.

[Comparison 3]
The resin pellets of Chemical Formula 1, the pellets of the resin compositions obtained in Example 13, Comparative Example 1 and Comparative Example 3 were used in a strip test piece formed by using an injection molding machine, and heat resistance was measured by the following physical property test. And the rigidity was evaluated.

(1) Heat resistance evaluation The heat resistance of the resin composition of the said Example and a comparative example was evaluated by load deflection temperature (DTUL) using the produced strip test piece. The heat resistance evaluation conforms to ISO 75, flatwise, stress: 0.45 MPa, temperature increase rate: 2 ° C./min, measuring device: HDT / VSPT test device TM-4126 (trade name, manufactured by Ueshima Seisakusho Co., Ltd.) ) And each n = 2.

(2) Bending physical properties The bending elastic modulus of the thermoplastic resin composition of the present example was evaluated by a three-point bending test using the prepared strip test piece. In addition, based on ISO 178, it measured by measuring apparatus: Precision universal testing machine Autograph AG-IS (trade name, manufactured by Shimadzu Corporation), each n = 4.

  As a result of the physical property test, the test piece of the resin composition obtained in Example 13 had a DTUL of 130 ° C. and a flexural modulus of 5500 MPa. On the other hand, in the test piece of the resin composition obtained in Comparative Example 1 and Comparative Example 3, the DTUL was 105 ° C. and 90 ° C., respectively, and the flexural modulus was 4000 MPa and 3500 MPa, respectively. In the virgin material of Chemical 1 to which no layered silicate is added, since DTUL is 105 ° C. and the flexural modulus is 3200 MPa, the layered silicate organized with an organic agent having a furan ring is added. It was confirmed that the heat resistance and rigidity of the resin composition were improved.

Example 19
Using the resin composition obtained in Example 13, the casing of a printer or copier was molded with an injection molding machine, and it was confirmed that it could be used as a product.

  Moreover, when this casing component (molded product) was crushed and remolded assuming recycling, it was confirmed that it could be used as the same molded product without problems such as heat resistance.

  The present invention relates to the dispersion of reinforcing additives when improving the physical properties of resins such as plastics, and is very useful in a wide range of industrial fields using resins that require heat resistance and rigidity.

Schematic diagram of observation results of a scanning transmission electron microscope

Explanation of symbols

1 layered silicate 2 resin

Claims (7)

  Layered silicate organically treated with an organic agent having a furan ring. The layered silicate according to claim 1, wherein the organic agent is an onium cation represented by the following general formula (I).

(M is a nitrogen atom or a phosphorus atom. R ¹ is an alkyl group having 1 to 24 carbon atoms. R ² and R ³ are each independently a hydrogen atom or a carbon atom having a linear or branched structure. (The alkyl group may have a hydroxy group as a substituent.) R ⁴ is furan or a carbon chain having 1 to 6 carbon atoms and has furan as a substituent. (The carbon chain may contain carbonyl, ether or ester. The furan may have at least one alkyl group having 1 to 4 carbon atoms as a substituent. The furan may have a condensed ring.)   A resin composition comprising a resin having a furan ring in a molecular chain and the layered silicate according to claim 1 or 2 mixed therein.   The resin composition according to claim 3, wherein the resin is a polyalkylene furandicarboxylate.   The resin composition according to claim 3 or 4, wherein the layered silicate is 0.1 to 30 parts by weight with respect to 100 parts by weight of the total of the layered silicate and the resin. .   The resin composition according to any one of claims 3 to 5, wherein each layer of the layered silicate is dispersed in the resin in a peeled state.   A molded product molded using the resin composition according to any one of claims 3 to 6.

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