JP2009185085A - High rigidity and high impact resistance resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefinic resin composition having high rigidity and high impact resistance to serve as a POM replacement. <P>SOLUTION: The high rigidity and high impact resistance resin composition comprises an olefinic thermoplastic resin, which has a bending elasticity modulus of 1,600-1,950 MPa and Charpy impact strength of ≥6.0 KJ/m<SP>2</SP>(at 23°C), and an organic modified laminar silicate. The resin composition may have a bending elasticity modulus of ≥2,200 MPa and Charpy impact strength ≥5.0 KJ/m<SP>2</SP>(23°C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an olefin-based resin composition, and particularly to an olefin-based resin composition that has both high rigidity and high impact resistance and can exhibit practical properties equivalent to those of polyoxymethylene (polyacetal) resin (POM).

  POM parts by injection molding have a relatively balanced mechanical property (strength property, etc.) and thermal property (temperature change, etc.). in use.

  On the other hand, olefinic thermoplastic resins, particularly polypropylene (PP), are used in large quantities in automobiles, home appliances, etc. as general-purpose resins because of their properties (strength, heat, chemical resistance, price, etc.). However, since mechanical characteristics, thermal characteristics, and the like are fundamentally different from those of POM, they are used in a field different from the field of use of POM parts.

In POM, both the flexural modulus and the Charpy impact strength are relatively high. In the standard grade, the flexural modulus is 2350 MPa or more and the Charpy impact strength is 5.0 KJ / m ² or more. For example, in the standard polyoxymethylene resins (POM) M25-44 and M90-44 (both made of polyplastics), the flexural modulus is 2350 MPa and 2500 MPa (catalog values), and the Charpy impact strength is 8 KJ, respectively. / M ² and 6 KJ / m ² (catalog values).
On the other hand, in olefin-based thermoplastic resins such as PP, generally, a high elastic polymer having a high flexural modulus has a low impact strength, and a high impact polymer having a high impact strength has a low flexural modulus. It is difficult to combine high rigidity and high impact resistance like POM.

  In recent years, due to the growing interest in the treatment of waste plastics and environmental hormones, the automobile-related and consumer electronics industries are required to reflect new values with consideration for the environment in their business activities. Regarding automobiles, environmental regulations called “European ELV Directive” have been issued, and domestic automobile manufacturers have set their own production start targets for products that comply with them. ELV is an abbreviation for End of Life Vehicle. This regulation is established with the aim of giving consideration to the environment in which used vehicles do not affect the environment. It is divided into two regulations regarding the recycling rate. This regulation will apply to new cars sold after July 1, 2003, and automakers will be obliged to comply with this regulation. Against this background, there is a demand for automobile manufacturers to share the materials used in plastic parts from the viewpoint of improving the recyclability of used parts. For example, POM parts are to be replaced with polypropylene parts. A request exists.

  In the automobile industry, there is an increasing interest in VOC (VOC is an acronym for Volatiles Organic Compound, which is called a volatile organic compound in Japanese). In POM parts, formaldehyde derived from polyoxymethylene is present in the resin, and is scattered in the air over time. A very small number of chemical substances such as formaldehyde are considered as sick house causative substances, and the understanding that many of the causative chemical substances of sick houses are VOCs is advancing. Against this background, there is a demand for alternatives or low formaldehyde for POM parts.

  Furthermore, automobiles, home appliances, and information-related machines using POM parts are rapidly becoming lighter and smaller, and plastic parts used for them are also required to be lighter and smaller. However, with POM parts, even if the physical properties of polyoxymethylene are improved, it is difficult to achieve lighter weight than ever.

Therefore, if an olefinic thermoplastic resin can be used as a POM substitute, it is very useful in terms of lightness and environmental compatibility.
However, there is only a proposal for improving the olefin-based thermoplastic resin as a substitute for POM parts by incorporating a solid lubricant or the like into polypropylene and making the wear resistance close to POM (Patent Document 1). .

On the other hand, in Patent Document 2, an organically modified layered silicate having an amphoteric surfactant and a nonionic polar organic compound between layers of a swellable layered silicate is finely dispersed in a thermoplastic resin such as a polyolefin resin. It has been reported that the rigidity such as tensile strength, bending strength, and flexural modulus is improved.
However, when the flexural modulus is improved by blending the organically modified layered silicate, the impact resistance is lowered, and it is very difficult to obtain a product having both a high flexural modulus and high impact resistance.
JP 2002-363305 A JP 2006-56932 A

  This invention is made | formed in view of the said background art, The objective is to provide the olefin resin composition which has high rigidity and impact resistance which can become a POM substitute.

In order to solve the above-mentioned problems, the present inventors have intensively studied with a flexural modulus of 2200 MPa or more and a Charpy impact strength of 5.0 KJ / m ² or more as target values. As a result, it is found that the above target value can be achieved by finely dispersing the organically modified layered silicate in an olefinic thermoplastic resin having a specific flexural modulus and Charpy impact strength, and the present invention is completed. It came to.

That is, the highly rigid and high impact resin composition according to the present invention comprises an olefinic thermoplastic resin having a flexural modulus of 1600 MPa or more and less than 1950 MPa and a Charpy impact strength of 6.0 KJ / m ² (23 ° C.) or more. And an organically modified layered silicate.
The resin composition of the present invention can be a high rigidity and high impact resistance resin composition having a flexural modulus of 2200 MPa or more and a Charpy impact strength of 5.0 KJ / m ² or more (23 ° C.).
In the resin composition of the present invention, it is preferable that the organically modified layered silicate is 3 to 20% by mass in the resin composition.
In the resin composition of the present invention, it is preferable that the organically modified layered silicate has an amphoteric surfactant and a nonionic polar organic compound between the layers of the swellable layered silicate.

In the resin composition of the present invention, the amphoteric surfactant is preferably 0.4 to 1.5 times equivalent to the cation exchange capacity (CEC) of the swellable layered silicate.
In the resin composition of the present invention, it is preferable that the swellable layered silicate is a synthetic clay mineral.
In the resin composition of the present invention, it is preferable that the olefin-based thermoplastic resin is a polypropylene resin.
Moreover, the resin composition of this invention WHEREIN: It is suitable that 0.01-20 mass% of acid-modified resins are contained in the said olefin type thermoplastic resin.
Moreover, in the resin composition of this invention, it is suitable that metal soap is further contained 20 mass% or less with respect to organic modified layered silicate.

  The resin composition of the present invention exhibits excellent mechanical performance such as high rigidity and high impact resistance of a certain level or more while being based on an olefinic thermoplastic resin. Therefore, for example, it can be suitably used for parts such as fasteners as an alternative to POM, and the lightness and environmental compatibility of POM parts can be greatly improved.

  The resin composition of the present invention is produced using an olefinic thermoplastic resin having a specific flexural modulus and impact strength and an organically modified layered silicate.

The organically modified layered silicate used in the present invention is one in which an organic modifier is inserted between the layers of the swellable layered silicate.
In the present invention, the layered silicate means a silicate mineral having an exchangeable cation between the layers of the layered crystal, for example, although not particularly limited thereto, such as montmorillonite, saponite, hectorite, etc. Smectite group, vermiculite group, mica group clay mineral and the like. Among these, swellable layered silicate is preferred. These may be natural or synthetic, but in the case of natural, synthetic clay minerals are preferably used because they may contain toxic substances such as heavy metals and need to be used with care. . The swellable layered silicate preferably has a high purity with a cation exchange capacity of 80 meq / 100 g or more. Synthetic clay minerals are advantageous in that they are easy to obtain in high purity. Synthetic clay minerals include, but are not limited to, synthetic tetralithic mica and synthetic sodium teniolite.

  The layered silicate increases the affinity between the layered silicate and the thermoplastic resin by cation exchange between the layered crystals in advance with a cationic surfactant, amphoteric surfactant, etc. to make it hydrophobic. And can be uniformly finely dispersed in the olefin-based thermoplastic resin. Here, the surfactant is more preferably an amphoteric surfactant.

  The reaction between the layered silicate and the cationic surfactant is usually carried out by a liquid phase method, and salts containing halogen are by-produced by ion exchange. When used as a material, a washing process is performed in which the by-product ions and salts are removed by repeated washing with water, but this significantly deteriorates cost and productivity, which is not practical. On the other hand, when an amphoteric surfactant is used, there is an advantage that an organic treatment can be performed at low cost without generation of extra salts.

  Although it does not specifically limit as a cationic surfactant, For example, a quaternary ammonium salt, a quaternary phosphonium salt, etc. are mentioned. Among them, a quaternary ammonium salt having an alkyl chain having 6 or more carbon atoms, that is, an alkylammonium salt is preferably used because it can sufficiently depolarize the layered crystal of the layered silicate. Examples of the quaternary ammonium salt include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl ammonium salt, distearyl dimethyl ammonium salt and the like. Examples of the quaternary phosphonium salt include dodecyltriphenylphosphonium salt, stearyltrimethylphosphonium salt, trioctylphosphonium salt, distearyldimethylphosphonium salt, and the like.

An amphoteric surfactant is a compound having both a cationic group and an anionic group in the molecule. As such amphoteric surfactants, known amphoteric surfactants such as amino acid type, betaine type, imidazolinium derivative type and the like can be applied, but betaine type amphoteric surfactants are preferred. Examples include lauryldimethylaminoacetic acid betaine, lauric acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine, myristic acid amidopropyl betaine, palm kernel oil fatty acid amidopropyl betaine, lauryl hydroxysulfobetaine, lauric acid amidopropyl hydroxylsulfobetaine, etc. It is done.
In the present invention, any one or more of these amphoteric surfactants can be used.

  Moreover, the dispersibility of a layered silicate and a thermoplastic resin can also be improved by enlarging an interlayer with a nonionic polar organic compound. The nonionic polar organic compound is more preferably used in combination with an amphoteric surfactant.

  Nonionic polar organic compounds are those having polar groups such as alcoholic hydroxyl groups, phenolic hydroxyl groups, ether bonds (-O-), amide bonds (-CONH-), ester bonds (-COO-). . Here, nonionic means that an ionic group such as an amino group or a sulfo group is not included, and therefore, an onium ion compound (onium salt) is not included in the nonionic polar organic compound of the present invention. Absent.

  The nonionic polar organic compound is not particularly limited as long as it is basically adsorbed between the layers of the swellable layered silicate and can expand the layer, but melt kneading with a resin matrix described later In the case of using for the above, a compound that weakens the interlaminar bonding force to facilitate the delamination in the resin, and makes the dispersibility of the layered silicate in the resin favorable is suitable.

  The nonionic polar organic compound is preferably a water-soluble compound. In the case of oil-soluble organic compounds, coordination to interlayer ions or adsorption to interlayers does not easily occur. In addition, oil-soluble organic compounds are difficult to be treated simultaneously with amphoteric surfactants during organic modification of the swellable layered silicate, and a solvent is required for simultaneous treatment, increasing the cost of the treatment. Will be forced.

  More preferably, the nonionic polar organic compound is a water-soluble compound having a boiling point of 105 to 300 ° C. In the organically modified layered silicate, if there is an excessive nonionic polar organic compound that cannot be adsorbed between the layers of the swellable layered silicate and adsorbed on the surface, it may cause a decrease in physical properties of the resin composition. However, if the boiling point is 300 ° C. or less, the nonionic polar organic compound adsorbed on the surface when melt-kneading with the thermoplastic resin described later (usually the melt-kneading temperature is 300 ° C. or less) can be volatilized and removed. It is possible to suppress a decrease in resin physical properties. However, if the boiling point is too low, it may volatilize during mixing with the swellable layered silicate, so the boiling point is preferably 105 ° C or higher. Accordingly, the nonionic polar organic compound preferably has a boiling point of 105 ° C. or higher and lower than the melting temperature of the thermoplastic resin, more preferably 105 to 300 ° C., particularly preferably 110 to 200 ° C. is there.

  Examples of the nonionic polar organic compound include divalent or trivalent polyhydric alcohols such as ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; ethylene glycol monoethyl ether, ethylene Polyhydric alcohol alkyl ethers such as glycol diethyl ether; Polyhydric alcohol alkyl esters such as ethylene glycol monoacetate and ethylene glycol diacetate; Water-soluble polymers such as polyvinyl pyrrolidone, polyacrylamide, and polyvinyl alcohol. It can also be selected from those used as plasticizers and surface modifiers. Of these, divalent or trivalent polyhydric alcohols are particularly preferable. In the present invention, one or more nonionic polar organic compounds can be used as the organic modifier.

  The method of inserting the organic modifier between the layers of the swellable layered silicate is not particularly limited, but the liquid phase method in which the organic modifier and the swellable layered silicate are contacted in water, dispersion Examples thereof include a solid phase method in which mixing is performed by mechanical shearing force in the presence or absence of a medium, and a vapor phase method in which a vapor of an organic modifier is brought into contact with a layered silicate. Among them, the liquid phase method is generally used, but when an amphoteric surfactant and / or a nonionic organic compound is used as the organic modifier, the swellable layered silicate and the organic modifier are dispersed. A method of mixing with a mechanical shear force in the absence of a medium is preferred.

  In the above mixing, the swellable layered silicate, the nonionic organic compound, and the amphoteric surfactant may be mixed at the same time, or one of the organic modifiers may be mixed with the swellable layered silicate. The other organic modifier may be further mixed. However, it is preferable to mix while considering the manufacturing cost. The organic modifier may be added to the swellable layered silicate all at once or a little at a time.

For the mixing, it is desirable to use an apparatus of a method that requires a share, and examples include, but are not limited to, a planetary mixer, a kneader mixer, a Henschel mixer, a coffee mill, and a juicer mixer.
The degree of the share may be an extent that can not be splinted, and may be processed usually at a rotational speed of 100 to 2000 rpm.
The stirring time may be appropriately set so that the reaction is sufficiently performed, but is usually 1 minute to 2 hours.

  Although the swellable layered silicate self-heats by high-speed stirring, the temperature of the reaction system is preferably 100 ° C. or lower. This is because if the temperature becomes too high, the raw material may be altered or evaporated.

The amount of amphoteric surfactant and nonionic polar organic compound added to the swellable layered silicate can be appropriately determined depending on the type of raw material used, the intended performance, and the like. However, if the amount of the organic modifier is too small relative to the swellable layered silicate, an unreacted phase of the swellable layered silicate may be generated, and if used excessively, the unreacted organic modifier may be used as a plasticizer. The desired performance may not be obtained.
In the present invention, the amount of amphoteric surfactant added to the swellable layered silicate is 0.4 to 1.5 times equivalent to the cation exchange capacity (CEC) of the swellable layered silicate, more preferably, 0.9-1.2 times equivalent. The addition amount of the nonionic polar organic compound is preferably 1 to 50% by mass, more preferably 5 to 20% by mass.
The organically modified layered silicate thus obtained has a larger interlayer distance than the raw material swellable layered silicate due to the insertion of the organic modifier. The interlayer distance is preferably 13 angstroms or more.

  The resin composition of the present invention can be obtained by using the above-mentioned organically modified layered silicate and melt-kneading it with a resin at a temperature equal to or higher than the melting point of the olefin-based thermoplastic resin.

For melt-kneading, it is desirable to use a device having a high kneading ability, and any device having such ability is not particularly limited. For example, since a general-purpose twin screw extruder, a disk type extruder, a kneader, or the like can be used, it is not necessary to prepare a special apparatus.
The ratio of the organically modified layered silicate to the thermoplastic resin is 3 to 20% by mass, preferably 5 to 15% by mass. If the amount is too small, the effect of adding the organically modified layered silicate will not be sufficiently exhibited, and if it is added excessively, the layered silicate may not be sufficiently dispersed, workability may be reduced, or the effect commensurate with the addition may not be exhibited. There are things to do.

  Examples of the olefinic thermoplastic resin in the present invention include polyolefins such as polyethylene and polypropylene. In particular, polypropylene has a good balance of physical properties and is suitable. In order to improve the impact resistance of polyethylene, polypropylene, etc., natural rubber, isoprene rubber, chloroprene rubber, styrene rubber, nitrile rubber, ethylene-propylene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, epichlorohydrin rubber, acrylic Rubber components such as rubber, urethane rubber, fluorine rubber, and silicone rubber may be added, and these may be used alone or in combination of two or more. The olefin-based thermoplastic resin may be a small amount (for example, about 0.5 to 7.0 mol%) of a copolymer component (for example, ethylene, 1-butene, 1-pentene, linear olefins such as 1-hexene, etc.) may be contained, and these may be used alone or in combination of two or more.

The high rigidity / high impact resistance resin composition of the present invention is an olefinic thermoplastic resin, but has a flexural modulus of 2200 MPa or more, more than 2250 MPa, and Charpy impact strength (23 ° C.) of 5.0 KJ / m ² or more. Furthermore, it can be set to 6.0 KJ / m ² or more, which is promising as a POM substitute.
Further, when the Charpy impact strength is less than 5.0 KJ / m ^2, cracks are more likely to occur than POM when plastic parts are used.

In the present invention, an acid-modified resin can be used in combination in order to improve the compatibility between the olefinic thermoplastic resin and the organically modified layered silicate. In the olefinic thermoplastic resin of the present invention, the acid-modified resin is preferably 0.01 to 20% by mass in the resin composition.
An acid-modified resin is a resin obtained by modifying a base resin with an acid. Examples of such a base resin include low density polyethylene, medium density polyethylene, high density polyethylene, ultrahigh molecular weight polyethylene, and ethylene-vinyl acetate copolymer. Resin, ethylene acetate-ethyl acrylate copolymer resin, polypropylene and the like.

Among these, polyolefin resins such as polyethylene and polypropylene are preferable. The molecular weight of the polyolefin serving as the main chain in the acid-modified polyolefin resin is usually preferably 10 × 10 ^{4 to} 100 × 10 ⁴ , and more preferably 20 × 10 ⁴ to 80 × 10 ⁴ . Examples of acids that modify these polyolefin resins include low molecular weight organic acids containing carboxyl groups such as maleic acid, maleic anhydride, acrylic acid, and methacrylic acid, low molecular weight organic sulfonic acids containing sulfo groups, phosphonic acids, etc. The low molecular-weight organic acid etc. which contain these phospho groups are mentioned, What modified | denatured by these 1 type (s) or 2 or more types can be used.

  The acid addition amount in the acid-modified resin is usually 0.01 to 20% by mass, preferably 0.05 to 15% by mass in the acid-modified resin. By adding the acid-modified resin, the compatibility between the resin composition and the organically modified layered silicate can be increased, and the dispersibility can be further improved.

In the olefinic thermoplastic resin of the present invention, for example, aliphatic hydrocarbons, higher fatty acids, higher aliphatic alcohols are used in order to further improve the dispersibility of the organically modified layered silicate or improve the moldability. -You may mix | blend a metal, a metal soap, a higher fatty acid ester, etc. Of these, metal soap is preferably used because of its good balance of thermal stability and slipperiness. When the metal soap is blended with the olefinic thermoplastic resin, it is preferably blended in an amount of 0.3% by mass or more, more preferably 0.5% by mass or more based on 100% by mass of the resin composition.
Further, in order to improve the flexural modulus of the resin composition, it is preferable to blend in an amount of 20% by mass or less with respect to the organically modified layered silicate. Even if it mixes excessively, the improvement corresponding to it cannot be obtained.

As the metal soap, known ones can be used, for example, (RCOO) nX (where R is a hydrocarbon residue having 10 to 40 carbon atoms, X is Li, Na, K, Mg, Zn, A metal component of Ca, Ba or Al, and n is 1, 2, or 3 corresponding to the ionic valence of X.).
Specifically, lithium stearate, sodium stearate, magnesium stearate, zinc stearate, calcium stearate, aluminum stearate, and similar lauric acid metal salts, behenic acid metal salts, montanic acid metal salts, hydroxystearic acid metal Examples include salts. Among these, metal soaps such as lithium stearate, magnesium stearate, zinc stearate, calcium stearate, aluminum stearate, magnesium behenate, zinc behenate, calcium behenate are preferably used because of performance and availability. It is done.

  The metal soap may be added at the time of melt kneading, but it is preferable that the organically modified layered silicate and the metal soap are mixed in advance and then subjected to melt kneading. The mixing of the metal soap and the organically modified layered silicate is not particularly limited as long as both can be made homogeneous, and can be performed by a known mixer such as a container rotating type or a container fixing type. More preferably, metal soap is mixed at the time of finely pulverizing the organically modified layered silicate. In this case, the metal soap and the organically modified layered silicate can be pulverized and mixed at the same time, which is advantageous in terms of economy. In that case, it can carry out with well-known grinders, such as a ball mill, a hammer mill, a jet mill, for example.

  Furthermore, the olefin-based thermoplastic resin of the present invention includes pigments, dyes, thermal stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, flame retardants, and antistatic agents as necessary. Additives such as can be added.

  The resin composition of the present invention can be molded into various forms such as pellets, films, sheets, and the like depending on applications. The resin composition is a concept including even a molded product.

  The resin composition of the present invention can be made into plastic parts for various devices and apparatuses by, for example, injection molding. The component may be either a single component or an assembly component, and there is no particular restriction on the type of device / device to be used, but the component can be used for a device in which a POM component is used. Since the plastic part of the present invention is an injection-molded product based on an olefinic thermoplastic resin, it can be formed into any shape and can be shaped according to the purpose of the equipment. It is.

  For example, industrial fastener parts are parts that are joined to other parts or members when used, and there are various types and forms. POM is the mainstream plastic fastener material. Since the olefin-based resin composition of the present invention has rigidity and impact resistance equivalent to those of POM, it can be used for fastener parts as an alternative to POM. For example, when it is a fastener part for automobiles, it can be recycled together with the polyolefin interior material, and the effect of the present invention can be enjoyed to the maximum.

  The following examples further illustrate the invention. However, the present invention is not limited to the following examples without departing from the gist thereof. In addition, the used material and the evaluation method of a physical property are as follows. CEC represents the theoretical cation exchange capacity (theoretical cation exchange capacity per 100 g of layered silicate).

I. Material <Layered silicate>
Synthetic sodium tetrasilicon mica (CEC: 98meq / 100g)
Synthetic sodium hectorite (CEC: 85meq / 100g)
Natural montmorillonite (CEC: 115meq / 100g)

<Cationic surfactant>
Distearyl dimethyl ammonium chloride (Lion Akzo's Arcard 2HT-75)

<Amphoteric surfactant>
2000HG: Palm oil fatty acid amidopropyl betaine, molecular weight ≈ 370
(Sanyo Chemical Industries Levon 2000HG (30.4% aqueous solution))
LD-36: lauryldimethylaminoacetic acid betaine, molecular weight = 272
(Sanyo Chemical Industries Levon LD-36 (40.5% aqueous solution))

<Nonionic polar organic compound>
EG: Ethylene glycol (Reagent grade 1, Wako Pure Chemical Industries, Boiling point: 197.6 ° C)
PEG200: Polyethylene glycol (molecular weight 200, reagent grade 1, manufactured by Wako Pure Chemical Industries)

<Olefin-based thermoplastic resin>
(I) High elasticity PP
MA3AH: crystalline polypropylene
(Nippon Polypro MA3AH, MFR12g / 10min)
PM900: crystalline polypropylene
(PM900 made by Sun Allomer, MFR30g / 10min)

(Ii) High impact resistance PP
BC4ASW: crystalline ethylene / propylene copolymer
(Nippon Polypro BC4ASW, MFR 5g / 10min)
BC6C: Crystalline ethylene / propylene copolymer
(Nippon Polypro BC6C, MFR 2.5g / 10min)
(Iii) Acid-modified PP
PPMA: PP-based maleic anhydride graft polymer
(ER320P made by Nippon Polyolefin)
Flexural modulus: 1350 MPa, Charpy impact strength: ² KJ / m ² (actual value)

<Metal soap>
Calcium stearate (Wako Pure Chemical Industries)

II. Test method <ash content>
Place the weighed sample in a crucible and heat on a gas burner. After removing the volatile decomposition products, put the crucible in a muffle furnace heated to 550 ° C ± 25 ° C, heat until all the carbonaceous material burns to a constant weight, and measure the remaining amount after cooling. . The ratio of the remaining amount to the initial weight was calculated and used as ash (%).

<Bending elastic modulus>
Measured according to JIS K 7171.
<Charpy impact strength>
It was measured according to JIS K 7111 (23 ° C.).

Production Example 1 Organically modified layered silicate (treated mica 1)
An organically modified layered silicate (treated mica 1) was produced using the following components. Organically modified layered silicate in which layered silicate and organic modifier (amphoteric surfactant and nonionic polar organic compound) are reacted at high speed with a juicer mixer and the organic modifier is inserted between the layers of the layered silicate. The acid salt was obtained. In addition, the amphoteric surfactant and the nonionic polar organic compound were added to the reaction several times so that the powder state could be maintained, and drying was repeated. All reaction times were 5 minutes. About the obtained organic modified layered silicate, it confirmed that the interlayer distance was expanded compared with untreated layered silicate (raw layered silicate).
The organically modified layered silicate used in the present invention is manufactured according to the above Production Example 1 unless otherwise specified.

(Processed mica 1)
――――――――――――――――――――――――――――――――――――
Ingredient Amount used ――――――――――――――――――――――――――――――――――――
Synthetic sodium tetrasilicon mica 100g
Amphoteric surfactant (Levon 2000HG) 119g *
Nonionic polar organic compound (EG) 20g
――――――――――――――――――――――――――――――――――――
* 1.0 equivalent to CEC of synthetic sodium tetrasilicon mica

Production Example 2 Production of Resin Composition The material of the resin composition was dry blended with a V-blender, melt-mixed at 180 to 210 ° C. using a same-direction twin screw extruder, and then pelletized. The pellet was dried with hot air at 100 ° C. and injection molded to prepare a test piece. The test piece is a multi-purpose test piece mold (JIS K 7139) under the conditions of a molding temperature of 205 ° C., a mold temperature of 30 ° C., an injection time of 10 sec, and a cooling time of 25 sec by a hydraulic injection molding machine (clamping pressure 80T). This was produced by injection molding and used for the test.
In addition, the test piece of the resin composition used by this invention is manufactured according to the said manufacture example 2 unless there is particular description.

Test example 1
First, an attempt was made to achieve a flexural modulus of 2200 MPa or more and a Charpy impact strength of 5.0 or more by mixing high impact resistance PP and high elasticity PP. In addition, the test piece was manufactured with the following composition A, and the test piece of high impact-resistant PP and high elastic PP single was similarly manufactured as control.

(Composition A)
――――――――――――――――――――――――――――
Component Amount used (% by mass)
――――――――――――――――――――――――――――
Processing mica 1 9.5
PP 76.5
PPMA 14.0
――――――――――――――――――――――――――――
Total 100.0
――――――――――――――――――――――――――――

As in Table 1, bending modulus 2200MPa greater than the high modulus PP (MA3AH), with only Charpy impact strength simply mixing the 6.0KJ / ^{m 2} greater than high impact PP (BC4ASW), target It was difficult to satisfy both the values of bending elastic modulus of 2200 MPa or more and Charpy impact strength of 5.0 KJ / m ² or more.
On the other hand, when the organically modified layered silicate was blended, the flexural modulus improved and the Charpy impact strength tended to decrease, but mixed PP (high impact resistance PP and high elasticity PP). It has been suggested that if the flexural modulus and Charpy impact strength of the mixture are within a certain range, it is possible to achieve a flexural modulus of 2200 MPa or more and a Charpy impact strength of 5.0 KJ / m ² or more.

Therefore, the high impact resistance PP shown in Table 1 was examined using BC6C instead of BC4ASW. The results are shown in Table 2.
Similar to Table 1, it was difficult to satisfy both the target values of flexural modulus of 2200 MPa or more and Charpy impact strength of 5.0 KJ / m ² or more only by mixing high impact resistance PP and high elasticity PP. However, by blending the organically modified layered silicate, the target values could be achieved within a certain range of the flexural modulus and Charpy impact strength of PP alone or mixed PP.

From Tables 1 and 2 above, by blending an organically modified layered silicate with a specific mixed PP having a flexural modulus of less than 1950 MPa and a Charpy impact strength of 6.0 or greater, the flexural modulus is improved to 2200 MPa or greater. In addition, it is considered that the Charpy impact strength can be maintained at 5.0 KJ / m ² or more.

Test example 2
As PP, a mixture of BC6C, which is high impact-resistant PP, and MA3AH, which is high-elastic PP, was used, and the case where the blending amount of the treated mica 1 was changed with the following composition B was examined.

(Composition B)
――――――――――――――――――――――――――――――――――
Component Amount used (% by mass)
――――――――――――――――――――――――――――――――――
Processed mica 1-20
PP (BC6C / MA3AH = 62.5 / 37.5) Remaining PPMA 14
――――――――――――――――――――――――――――――――――
Total 100
――――――――――――――――――――――――――――――――――

As shown in Table 3, if the amount of the organically modified layered silicate is too small, the flexural modulus may not be sufficiently improved. On the other hand, if the amount is too large, the Charpy impact strength may decrease too much.
Therefore, the blending amount of the organically modified layered silicate is preferably 3 to 20% by mass in the resin composition.

Test example 3
Next, the type of treated mica 1 was changed and examined. The resin composition was manufactured with the following composition C.

(Composition C)
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Component Amount used (% by mass)
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Processing mica 7-11
PP (BC6C / MA3AH = 50/50) Remaining PPMA 14
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Total 100
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Table 4 shows the case where the amount of the organic modifier is changed in the treated mica 1.
When the amount of the amphoteric surfactant is small, the effect of improving the flexural modulus is low. Therefore, it is preferable that the amphoteric surfactant is 0.4 times or more equivalent to the CEC in the swellable layered silicate.
On the other hand, even if the amphoteric surfactant is used in excess of 1.5 times equivalent, the improvement effect of the flexural modulus corresponding to the increase is not recognized. Therefore, it is preferable that the amphoteric surfactant is not more than 1.5 times equivalent, more preferably not more than 1.2 times equivalent to CEC in the swellable layered silicate.
In addition, when a nonionic polar compound is used together with an amphoteric surfactant as an organic modifier, Charpy impact strength can be improved together with the flexural modulus compared to when each is used alone. Is preferred. In order to exhibit such an effect, the nonionic polar compound is preferably 1 to 50% by mass, more preferably 5 to 20% by mass with respect to the swellable layered silicate.

Table 5 shows the case where the kind of the layered silicate and the organic modifier is changed in the treated mica 1.
In any case, the target values of a flexural modulus of 2200 MPa and a Charpy impact strength of 5.0 KJ / m ² or more were achieved.

Test example 4
Metal soap (calcium stearate) was added to treated mica 4 (organic modified layered silicate prepared with Na tetrasilicon mica 100 g / EG 20 g / 2000 HG 1.1 eq), 2, 5, 10 and 20 mass based on the organic modified layered silicate. % Was added and mixed uniformly. Using this mixture as a treated mica, a resin composition was produced with the composition C. The results are shown in Table 6.
As shown in Table 6, by using metal soap together with the organically modified layer silicate, the flexural modulus can be increased without reducing the Charpy impact strength. In order to obtain such an effect, the metal soap was preferably 20% by mass or less based on the organically modified layered silicate. Even when blended in excess of 20% by mass, an improvement corresponding to that was not obtained.

Claims (9)

High rigidity, characterized by comprising an olefinic thermoplastic resin having a flexural modulus of 1600 MPa or more and less than 1950 MPa and a Charpy impact strength of 6.0 KJ / m ² (23 ° C.) or more, and an organically modified layered silicate. High impact resistance resin composition. 2. The resin composition according to claim 1, wherein the resin composition has a flexural modulus of 2200 MPa or more and a Charpy impact strength of 5.0 KJ / m ² or more (23 ° C.). Resin composition. 3. The resin composition according to claim 1, wherein the organically modified layered silicate is 3 to 20% by mass in the resin composition. 4. The resin composition according to claim 1, wherein the organically modified layered silicate has an amphoteric surfactant and a nonionic polar organic compound between the layers of the swellable layered silicate. A high-rigidity, high-impact resin composition characterized by that. 5. The resin composition according to claim 4, wherein the amphoteric surfactant is 0.4 to 1.5 times equivalent to the cation exchange capacity (CEC) of the swellable layered silicate.・ High impact resistance resin composition. The resin composition according to any one of claims 1 to 5, wherein the swellable layered silicate is a synthetic clay mineral. The resin composition according to any one of claims 1 to 6, wherein the olefinic thermoplastic resin is a polypropylene resin. The resin composition according to any one of claims 1 to 7, wherein 0.01 to 20% by mass of an acid-modified resin is contained in the olefin-based thermoplastic resin. object. The resin composition according to any one of claims 1 to 8, further comprising 20% by mass or less of metal soap with respect to the organically modified layered silicate.