JP2711988B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition.
More specifically, it relates to a polypropylene resin composition having excellent permanent antistatic properties, mechanical strength and heat resistance.

[0002]

2. Description of the Related Art Hitherto, as a method for imparting permanent antistatic properties to polypropylene, there has been proposed (1) a method of adding polyetheresteramide to polypropylene (Japanese Patent Publication No. 4-5691). However, this method has a problem in that the compatibility between polypropylene and polyetheresteramide is poor, so that phase separation occurs and the resin strength is reduced. Further, since polyoxyalkylene glycol such as polyethylene glycol is used for the polyether component, heat resistance is low, and there is a problem in molding at high temperature. Furthermore, because polypropylene is a crystalline resin, at the time of molding, the molded product surface preferentially becomes a polypropylene phase, and since polyetheresteramide is hardly exposed on the surface, in order to impart substantial antistatic properties,
A large amount of polyetheresteramide had to be added. In order to improve this, there has been proposed a method (2) in which a modified polyolefin is used in combination for the purpose of improving the compatibility between polypropylene and polyetheresteramide (JP-A-1-163234, JP-A-3-290).
No. 464). In this method, the problem of phase separation has been solved by using a modified polyolefin having a high molecular weight, but the problem of molding at a high temperature and polyetheresteramide hardly appear on the surface of a crystalline polypropylene molded product. The problem has not been solved.

[0003]

Accordingly, there is a strong demand for a polypropylene resin composition having permanent antistatic properties and excellent mechanical strength and heat resistance.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a mixture of a polypropylene resin and an aromatic ring-containing polyetheresteramide has a
By adding polyamide resin and modified low-molecular-weight polypropylene, polyetheresteramide is more likely to appear on the surface of the molded product. Addition of a small amount of polyetheresteramide has permanent antistatic properties, as well as mechanical strength and heat resistance. It has been found that a polypropylene-based resin composition excellent in the above can be obtained, and the present invention has been achieved.

That is, the present invention relates to a polyamide (b) having 55 to 90% by weight of a polypropylene resin (A) and a carboxyl group at both ends and having a number average molecular weight of 200 to 5,000.
An aromatic ring-containing polyetheresteramide (B) derived from 1) and an alkylene oxide adduct (b2) of a bisphenol having a number average molecular weight of 300 to 5,000 using zirconyl acetate as a catalyst; 3-20% by weight of polyamide resin (C) and the following (D1)-(D
(D1) a number average molecular weight of 800 to 25,000, wherein the resin composition comprises 1 to 20% by weight of one or more modified low molecular weight polypropylenes (D) selected from 3).
Modified low molecular weight polypropylene having an acid value of 5-150. (D2): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polypropylene having a hydroxyl value of 5 to 150. (D3); a part or all of (D1) is esterified with a polyoxyalkylene compound, and has a number average molecular weight of 1,
2,000 to 28,000 modified low molecular weight polypropylene. And 55 to 90% by weight of a polypropylene resin (A) having a number average molecular weight of 20 having carboxyl groups at both terminals.
Aromatic ring-containing polyetheresteramide (B) derived from polyamide (b1) having a molecular weight of 0 to 5,000 and an ethylene oxide adduct (b2 ′) of a bisphenol having a number average molecular weight of 1,600 to 5,000 (B) 5 to 40 % By weight, 3 to 20% by weight of polyamide resin (C) and the following (D1)
A resin composition (second invention) comprising 1 to 20% by weight of one or more modified low molecular weight polypropylenes (D) selected from (D3) to (D3). (D1): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polypropylene having an acid value of 5-150. (D2): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polypropylene having a hydroxyl value of 5 to 150. (D3); a part or all of (D1) is esterified with a polyoxyalkylene compound, and has a number average molecular weight of 1,
2,000 to 28,000 modified low molecular weight polypropylene.

In the present invention, examples of the polypropylene resin (A) include a propylene homopolymer and a copolymer (random or block) of propylene with one or more other α-olefins. Other α-olefins include, for example, ethylene, 1-butene, 4-methyl-
Examples thereof include 1-pentene, 1-pentene, 1-octene, 1-decene, and 1-dodecene. The melt flow rate (MFR) of (A) is generally 0.5 to 150, preferably 1
~ 100. Melt flow rate is JIS K6
758 (temperature 230 ° C., load 2.16 kgf). The crystallinity of (A) is usually 25%
Or more, preferably 30% or more. The crystallinity can be measured by a method such as X-ray diffraction or infrared absorption spectrum analysis.

[0007] The amount of (A) in the resin composition of the present invention is usually 55 to 90% by weight, preferably 60 to 85% by weight. When the amount of (A) is less than 55% by weight, the mechanical strength of the resin composition is poor, and when it exceeds 90% by weight, the antistatic property is reduced.

In the present invention, the polyamide (b1) having a carboxyl group at both ends which constitutes the aromatic ring-containing polyetheresteramide (B) comprises (1) a lactam ring-opened polymer and (2) a polycondensation of an aminocarboxylic acid. Or a polycondensate of (3) a dicarboxylic acid and a diamine,
Examples of the lactam (1) include caprolactam, enantholactam, laurolactam, undecanolactam and the like. Examples of the aminocarboxylic acid (2) include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Is mentioned. Examples of the dicarboxylic acid (3) include adipic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, and isophthalic acid. Diamines include hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and decamethylene. Diamines and the like can be mentioned. Two or more of those exemplified as the amide-forming monomers may be used. Preferred among these are caprolactam, 12-aminododecanoic acid, and adipic acid-hexamethylenediamine, and particularly preferred is caprolactam.

(B1) can be obtained by using a dicarboxylic acid component having 4 to 20 carbon atoms as a molecular weight modifier and subjecting the amide-forming monomer to ring-opening polymerization or polycondensation in a conventional manner in the presence of the dicarboxylic acid component. . Examples of the dicarboxylic acids having 4 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, terephthalic acid, and isophthalic acid. , Phthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, and 1,
4-cyclohexanedicarboxylic acid, dicyclohexyl-
Aliphatic dicarboxylic acids such as 4,4-dicarboxylic acid and 3
Alkali metal salts of 3-sulfoisophthalic acid, such as sodium sulfoisophthalate and potassium 3-sulfoisophthalate, of which aliphatic dicarboxylic acid, aromatic dicarboxylic acid and alkali metal salt of 3-sulfoisophthalic acid are preferred. Particularly preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate.

The number average molecular weight of (b1) is from 200 to
It is 5,000, preferably 500-3,000.
If the number average molecular weight of (b1) is less than 200, the heat resistance of the polyetheresteramide itself will decrease, and if it exceeds 5,000, the reactivity will decrease, and a great amount of time will be required during the production of the polyetheresteramide.

The bisphenols of the alkylene oxide adduct (b2) of bisphenols, which is the other component constituting (B), include bisphenol A (4,
4'-dihydroxydiphenyl-2,2-propane),
Bisphenol F (4,4'-dihydroxydiphenylmethane), bisphenol S (4,4'-dihydroxydiphenylsulfone), 4,4'-dihydroxydiphenyl-2,2-butane and the like are listed, and among these, particularly preferable ones are Bisphenol A. Also, (b
Examples of the alkylene oxide 2) include ethylene oxide, propylene oxide, 1,2- or 1,4-butylene oxide, and a mixture of two or more thereof. Preferred among these is ethylene oxide.

The number average molecular weight of (b2) is usually 30
0-5,000, preferably 1,000-3,000,
Particularly preferably, it is from 1,600 to 3,000. If the number average molecular weight is less than 300, the antistatic property becomes insufficient,
If it exceeds 5,000, the reactivity decreases, so that a great amount of time is required for producing the polyetheresteramide.

The amount of (b2) in (B) is the same as that of (b1)
It is usually in the range of 20 to 80% by weight, preferably 25 to 75% by weight, based on the total weight of (b2) and (b2). (B
If the amount of 2) is less than 20% by weight, the antistatic property of (B) is inferior, and if it exceeds 80% by weight, the heat resistance of (B) itself is undesirably reduced.

The production method of (B) is not particularly limited, and examples thereof include the following production methods or production methods. Production method: A method in which (b1) is formed by reacting an amide-forming monomer and a dicarboxylic acid, and (b2) is added thereto, and a polymerization reaction is carried out at high temperature and under reduced pressure. Production method: The amide-forming monomer and the dicarboxylic acid and (b2) are simultaneously charged into a reaction vessel, and a pressure reaction is performed at a high temperature in the presence or absence of water to generate (b1) as an intermediate, and then the pressure is reduced. A method of performing a polymerization reaction of (b1) and (b2) below.

In the above-mentioned polymerization reaction according to the first aspect of the present invention, zirconyl acetate is used as a catalyst. The polymerization reaction in the invention of claim 2 includes a known esterification catalyst, for example, an antimony catalyst such as antimony trioxide, a tin catalyst such as monobutyltin oxide, a titanium catalyst such as tetrabutyl titanate, A zirconium-based catalyst such as butyl zirconate or a metal acetate-based catalyst such as zinc acetate may be used. The use amount of these catalysts is usually 0.1 to 5% by weight based on the total weight of (b1) and (b2).

The reduced viscosity of (B) (0.5% by weight, m-cresol solution, 25 ° C.) is not particularly limited, but is usually 0.1%.
It is 5 to 4.0, preferably 0.6 to 3.0. If the reduced viscosity is less than 0.5, heat resistance is poor, and if it exceeds 4.0, moldability may be reduced.

The amount of (B) in the resin composition of the present invention is usually 5 to 40% by weight, preferably 5 to 30% by weight.
If it is less than 5% by weight, the antistatic property is insufficient, and if it exceeds 40% by weight, the mechanical strength decreases.

In the present invention, the polyamide resin (C) includes (1) a ring-opening polymer of lactam, (2) a polycondensate of aminocarboxylic acid, or (3) a polycondensate of dicarboxylic acid and diamine. Specific examples include nylon 66, nylon 69, nylon 610, nylon 6
12, nylon 6, nylon 11, nylon 12, nylon 46 and the like. Also, nylon 6/66,
Nylon 6/10, Nylon 6/12, Nylon 6/6
Copolyamides such as 6/12 can also be used. Further, there may be mentioned aromatic-containing polyamides obtained from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and meta-xylenediamine or aliphatic diamine.
Of these, particularly preferred are nylon 66, nylon 6 and nylon 12.

Relative viscosity of (C) (97% sulfuric acid, concentration 1 g
/ 100 ml, 30 ° C) is usually 0.8 to 5, preferably 1 to 4. If it is less than 0.8, heat resistance is poor, and if it exceeds 5, moldability may be reduced.

The amount of (C) in the resin composition of the present invention is usually 3 to 20% by weight, preferably 3 to 15% by weight.
If the amount of (C) is less than 3% by weight, the antistatic property becomes insufficient, and if it exceeds 20% by weight, the mechanical strength decreases.

The modified low molecular weight polyolefin (D) in the present invention is at least one selected from the following (D1) to (D3). (D1): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polypropylene having an acid value of 5-150. (D2): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polypropylene having a hydroxyl value of 5 to 150. (D3); a part or all of (D1) is esterified with a polyoxyalkylene compound, and has a number average molecular weight of 1,
2,000 to 28,000 modified low molecular weight polypropylene.

The (D1) has a number average molecular weight of 7 obtained by a polymerization method or a thermal degradation method of high molecular weight polypropylene.
Α, β to low molecular weight polyolefins of 00-20,000
-It can be obtained by reacting an unsaturated carboxylic acid and / or an anhydride thereof, if necessary, in the presence of an organic peroxide by a solution method or a melting method to modify. From the viewpoint of easy modification, a low molecular weight polypropylene obtained by a thermal degradation method is preferred. Low molecular weight polypropylene produced by the thermal degradation method is disclosed in, for example,
It can be obtained according to the method described in Japanese Patent No. 62804.

The α, β-unsaturated carboxylic acids and / or anhydrides used for the modification include (meth) acrylic acid, (maleic anhydride) maleic acid, fumaric acid, (anhydride) itaconic acid and citraconic anhydride. And the like. Among these, maleic acid (anhydride) is preferred. These amounts used during the modification are usually 1 to 25% by weight, preferably 3 to 2% by weight, based on the weight of the low molecular weight polypropylene.
0% by weight. (D1) obtained by the above method
Has a number average molecular weight of usually 800 to 25,000, preferably 1,000 to 20,000. If the number average molecular weight is less than 800, the heat resistance is poor, and if it exceeds 25,000, the effect as a compatibilizer is poor, and the mechanical properties of the resin composition deteriorate. The acid value of (D1) is usually 5 to 15
0, preferably 10 to 100. If the acid value is less than 5, the effect as a compatibilizer is poor, and if it exceeds 150, the hue deteriorates, which causes coloring of the resin composition.

The (D2) can be obtained by subjecting the above (D1) to secondary modification with an alkanolamine or the like. Examples of the alkanolamine include monoethanolamine, monoisopropanolamine, diethanolamine and diisopropanolamine. Of these, particularly preferred is monoethanolamine. The hydroxyl value of (D1) is from 5 to 150, preferably from 10 to 100.

The (D3) can be obtained by esterifying a part or all of the (anhydride) carboxylic acid unit of the above (D1) with a polyoxyalkylene compound. Examples of the polyoxyalkylene compound used for the esterification include a compound having a hydroxyl group at both terminals such as polyethylene glycol and polypropylene glycol, and a compound in which the above hydroxyl group is replaced with an amino group or an epoxy group. Further, compounds having active hydrogen such as alcohols (methanol, ethanol, butanol, octanol, lauryl alcohol, 2-ethylhexyl alcohol, etc.) and phenols (phenol, alkylphenol, naphthol, phenylphenol, benzylphenol, etc.) have alkylene oxides. In addition, a polyalkylene compound having a hydroxyl group at one terminal is basically mentioned. The molecular weight of these polyoxyalkylene compounds is usually from 300 to 5,000. Although the esterification ratio is not particularly limited, it is preferable that 10 to 100 mol% of the (anhydrous) carboxylic acid unit of (D1) is esterified. The number average molecular weight of (D3) is generally 1,000-28,000, preferably 1,200-2.
5,000. When the number average molecular weight is less than 1,000, the heat resistance decreases, and when it exceeds 28,000, the effect as a compatibilizer is poor.

The modified low molecular weight polypropylenes (D1) to (D3) exemplified above may be used in combination of two or more. Note that a modified low-molecular-weight polypropylene having a carboxyl group, a hydroxyl group, and a polyoxyalkylene group in the molecule may be used.

The amount of (D) in the resin composition of the present invention is usually 1 to 20% by weight, preferably 3 to 15% by weight.
When the amount of (D) is less than 1% by weight, the compatibilizing effect is reduced and the phase separation of the resin composition tends to occur, and when it exceeds 20% by weight, the mechanical strength is reduced.

The resin composition of the present invention may contain a metal salt (E) comprising a halide of an alkali metal and / or an alkaline earth metal for the purpose of further improving the antistatic property. Examples of (E) include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, and magnesium bromide. Preferred among these are sodium chloride and potassium chloride.

The amount of (E) used is (A), (B),
Usually 0.01 to the total weight of (C) and (D)
It is 3% by weight, preferably 0.05 to 2% by weight. 0.
If the amount is less than 01% by weight, no effect is exhibited. If the amount is more than 3% by weight, it precipitates on the resin surface and may impair the appearance of the resin, which is not preferable.

There is no particular limitation on the method of adding (E), but from the viewpoint of easy dispersion in the composition,
It is preferable to disperse in advance in the polyetheresteramide (B). When (E) is dispersed in (B), a method in which (E) is previously added and dispersed during polymerization of (B) is particularly preferable.

The resin composition of the present invention may contain a nonionic, anionic, cationic or amphoteric surfactant (F) to further improve the antistatic property. As nonionic surfactants, higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polyethylene glycol type nonionic surfactants such as polypropylene glycol ethylene oxide adducts, polyethylene oxide, Glycerin fatty acid ester, pentaerythrit fatty acid ester, sorbit and sorbitan fatty acid ester, polyhydric alcohol alkyl ether,
Examples include polyhydric alcohol type nonionic surfactants such as aliphatic amides of alkanolamines. Examples of the anionic surfactant include carboxylate salts such as alkali metal salts of higher fatty acids, sulfate salts such as higher alcohol sulfate salts and higher alkyl ether sulfate salts, alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfones. Sulfonates such as acid salts, and phosphate salts such as higher alcohol phosphates, and the like. Examples of the cationic surfactant include quaternary ammonium salts such as an alkyltrimethylammonium salt. Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as higher alkylaminopropionate, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine. These may be used alone or in combination of two or more. Of these, preferred are anionic surfactants, and particularly preferred are sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates.

The amount of (F) used is (A), (B),
Usually 0.1 to 5 based on the total weight of (C) and (D)
%, Preferably 0.4 to 3% by weight. 5% by weight
If it exceeds, it is not preferred because it precipitates on the resin surface, impairs the appearance of the resin, and impairs the resin properties.

Although there is no particular limitation on the method of adding (F), in order to effectively disperse it in the composition,
It is preferable to disperse in (A) or (B) in advance.

The resin composition of the present invention can be obtained by kneading the above components using various known mixers. Examples of the mixer include an extruder, a Brabender, a kneader, and a Banbury mixer.

The order of addition of each component at the time of kneading is not particularly limited. For example, (A) to (D) may be blended and kneaded at once, a small amount of (A) and a small amount of (B) to (B).
A method of blending and kneading (D) and then kneading the remaining (A), a method of previously blending and kneading (B) to (D), and kneading (A) are exemplified. The above methods are methods called master batch or master pellet. Among them, the method is particularly preferable in that a resin having good dispersibility, excellent antistatic property and excellent mechanical strength can be obtained.

The method for obtaining the composition of the present invention via a masterbatch includes, for example, (A) 0 to 50 parts by weight,
Preferably 5 to 20 parts by weight, (B) 5 to 40 parts by weight,
(C) 3 to 20 parts by weight and (D) 1 to 20 parts by weight are blended and kneaded to form a master batch, and this master batch and (A) are further blended and kneaded to obtain the composition of the present invention. Method. This method has the advantage that a small amount of (B) to (D) can be uniformly dispersed in a large amount of (A), and is particularly preferable as a method for producing the resin composition of the present invention.

The resin composition of the present invention may optionally contain other known resin additives within a range that does not impair the properties of the composition according to various uses. Examples of the additives include pigments, dyes, fillers, nucleating agents, glass fibers, lubricants, plasticizers, release agents, antioxidants, flame retardants, and ultraviolet absorbers.

[0038]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the examples, "parts" indicates parts by weight, and "%" indicates% by weight. After the resin composition finally obtained was molded by an injection molding method, various physical properties were measured based on the following test methods. (1) Impact strength: Conforms to ASTM D256 (notched, 3.2 mm thick). (2) Flexural modulus: according to ASTM D790. (3) Surface specific resistance value: A 3 mm thick disk-shaped test piece injection molded was measured by a super insulation meter (manufactured by Advantest) in an atmosphere of 20 ° C. and 50% RH. (4) Compatibility: Evaluated by bending the molded product and observing the fracture surface. Evaluation criteria ○: good, ×: poor compatibility, laminar exfoliation (5) Thermal loss initiation temperature: measured by TG-DTA in air.

[Production of Aromatic Ring-Containing Polyetheresteramide (B)] Production Example 1 In a 3 L stainless steel autoclave, 112 parts of ε-caprolactam, 105 parts of a bisphenol A ethylene oxide adduct having a number average molecular weight of 1,000, and adipic acid Fifteen
Parts, 0.3 parts of "Irganox 1010" (antioxidant manufactured by Ciba-Gaiky), 0.5 parts of zirconyl acetate and 7 parts of water. 245 ° C, 1
Polymerization was performed for 3.5 hours under reduced pressure of not more than mmHg to obtain a viscous polymer. The polymer was taken out in a strand form on a belt and pelletized to obtain a polyetheresteramide. The reduced viscosity (η
_sp / C, m-cresol solvent, 25 ° C., C = 0.5% by weight, the same applies hereinafter) was 1.80. This polyetheresteramide is abbreviated as [B-1] below.

Production Example 2 A 3 L stainless steel autoclave was charged with 105 parts of ε-caprolactam, 17.1 parts of adipic acid, 0.3 parts of “Irganox 1010” and 7 parts of water. The mixture was heated and stirred for 4 hours in a sealed state to obtain 117 parts of a polyamide oligomer having a carboxyl group at both terminals and having an acid value of 100. Next, 225 parts of a bisphenol A ethylene oxide adduct having a number average molecular weight of 2,000 and 0.5 part of zirconyl acetate were added, and the mixture was polymerized at 245 ° C. under a reduced pressure of 1 mmHg or less for 5 hours to obtain a viscous polymer. . Hereinafter, the same operation as in Production Example 1 was performed to obtain a polyetheresteramide. Its reduced viscosity is 2.10
Met. This polyetheresteramide is referred to below as [B
-2].

[Production of Comparative Polyetheresteramide] Production Example 3 105 parts of ε-caprolactam, 17.1 parts of adipic acid, 0.3 parts of “Irganox 1010” and 6 parts of water were charged into a 3 L stainless steel autoclave. After purging with nitrogen, the mixture was heated and stirred at 220 ° C. for 4 hours while sealing under pressure to obtain 117 parts of a polyamide oligomer having an acid value of 110 and having carboxyl groups at both ends. Then, 175 parts of polyoxyethylene glycol having a number average molecular weight of 1,500 and 0.5 parts of zirconyl acetate were added, and the mixture was polymerized at 245 ° C. under a reduced pressure of 1 mmHg or less for 5 hours to obtain a viscous polymer. Hereinafter, the same operation as in Production Example 1 was performed to obtain a polyetheresteramide. This had a reduced viscosity of 2.30. This polyetheresteramide was used in the following [B-3]
Abbreviated.

[Production of Modified Low-Molecular-Weight Polyolefin] Production Example 4 95 parts of low-molecular-weight polypropylene having a number average molecular weight of 12,000 and a density of 0.89, obtained by thermal degradation, and 5 parts of maleic anhydride were mixed under a nitrogen stream for 180 minutes. Xylene 5 in which 1.5 parts of dicumyl peroxide was dissolved.
A 0% solution was added dropwise over 15 minutes, and after the reaction was carried out for 1 hour, the solvent was distilled off to obtain an acid-modified low molecular weight polypropylene. It has an acid value of 25.7 and a number average molecular weight of 1
It was 5,000. This modified product is abbreviated as [D-1] below.

Production Example 5 The acid-modified low molecular weight polypropylene 95 obtained in Production Example 4
Was dissolved in 100 parts of xylene at 120 ° C. under a nitrogen stream,
Then, 5 parts of monoethanolamine was added dropwise thereto over 15 minutes, and the mixture was reacted for 1 hour. Thereafter, the solvent and unreacted monoethanolamine were distilled off to obtain a modified low molecular weight polypropylene having a hydroxyl group. This had a hydroxyl value of 25.2 and a number average molecular weight of 16,000. This modified product is abbreviated as [D-2] below.

Production Example 6 The acid-modified low molecular weight polypropylene 95 obtained in Production Example 4
And 50 parts of an adduct of 24 mol of ethylene oxide of lauryl alcohol were melted at 180 ° C. in a nitrogen stream,
The esterification reaction was performed under reduced pressure of 0 mmHg for 5 hours,
A polyoxyalkylene-modified low molecular weight polypropylene was obtained. This had a hydroxyl value of 0.5 and a number average molecular weight of 18,000. From NMR analysis,
It was confirmed that the esterification reaction was performed quantitatively.
This modified product is abbreviated as [D-3] below.

Production Example 7 After blending (A) to (D) at the ratios shown in Table 1 for 3 minutes using a Henschel mixer, the mixture was subjected to a vented twin screw extruder at 240 ° C., 30 rpm, and a residence time of 5 minutes. To obtain masterbatches (M-1) to (M-4).

[0046]

[Table 1] (Note) [A-1]: “UBE Polypropylene J” manufactured by Ube Industries, Ltd.
609H "[C-1]: UBE Nylon 6 manufactured by Ube Industries, Ltd.
1013B "

Examples 1 to 4 Masterbatches (M-1) to (M-4) obtained in Production Example 7
And a polypropylene resin [A-1] were blended and kneaded under the same conditions as in Production Example 7 to obtain a composition of the present invention. (A) in the composition of the present invention via the masterbatch
(E) The final ratio of each component is shown in Table 2.

[0048]

[Table 2] (Note) [E-1]: Sodium chloride (added during kneading in a twin-screw extruder) [E-2]: Potassium chloride (added during production of polyetheresteramide) * 1): The proportion of metal salt (E) is ( Ratio of A) to (D) based on the total weight

Examples 5 to 11 and Comparative Examples 1 to 6 (A) to (E) or (A) to (D)
Under the same conditions as in Production Example 7, blending and kneading were performed to obtain a composition of the present invention and a comparative composition.

[0050]

[Table 3] (Note) [A-2]: “UBE Polypropylene J” manufactured by Ube Industries, Ltd.
385 "[C-2]: UBE nylon 66 manufactured by Ube Industries, Ltd.
2020B "[E-1]: Sodium chloride (added during kneading in twin-screw extruder) [E-2]: Potassium chloride (added during manufacturing of polyetheresteramide) [E-3]: Potassium chloride (kneaded in twin-screw extruder) * 2): The ratio of the metal salt (E) is the ratio to the total weight of (A) to (D).

Performance Test The compositions of the present invention of Examples 1 to 11 and the comparative compositions of Comparative Examples 1 to 6 were subjected to an injection molding machine at a cylinder temperature of 24.
A test piece was prepared by molding at 0 ° C. and a mold temperature of 60 ° C., and the resin properties and antistatic properties were evaluated. Table 4 shows the results. The antistatic property was evaluated by subjecting the test piece to the treatment and conditioning described below and measuring the surface specific resistance. (A) After molding, the test piece is kept at 20 ° C. and humidity 50% R
Leave for 24 hours under H atmosphere. (B) After molding, test specimens were washed with detergent (mama lemon; lion
After washing with an aqueous solution and then sufficiently washing with ion-exchanged water, the water on the surface was dried and removed, and then at 20 ° C.
Left in a 50% RH atmosphere for 24 hours.

[0052]

[Table 4]

As is clear from Table 4, the composition of the present invention is superior in permanent antistatic property as compared with Comparative Examples 1, 2, 4 and 5, and superior in mechanical properties as compared with Comparative Examples 1-3. Compared with Comparative Examples 2 and 6, it is superior in heat resistance. That is,
It is a polypropylene resin composition having excellent permanent antistatic properties, mechanical properties, and heat resistance that could not be achieved conventionally.
In particular, the composition via the masterbatch (Examples 1 to 4) is superior to the performance of the composition not via the corresponding masterbatch, or reduces the amount of polyetheresteramide or metal salt added. However, they have the same permanent antistatic properties. This indicates that the small components are uniformly dispersed and contribute to the performance.

[0054]

The resin composition of the present invention has excellent permanent antistatic properties, mechanical properties and heat resistance, which cannot be achieved by the prior art, in a well-balanced manner. Due to the above effects, the resin composition of the present invention is extremely useful as various molding materials that require antistatic properties of housing products for home appliances and OA equipment, various plastic containers, and automobile parts.

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Claims (3)

(57) [Claims] 1. A polypropylene resin (A) 55 to 90.
Zirconyl acetate is used as a catalyst from a polyamide (b1) having a carboxyl group at both terminals and a number average molecular weight of 200 to 5,000 and a bisphenol alkylene oxide adduct (b2) having a number average molecular weight of 300 to 5,000 by weight. 5 to 40% by weight of an aromatic ring-containing polyetheresteramide (B) derived using the same, and a polyamide resin (C) 3 to 2
A resin composition comprising 0% by weight and 1 to 20% by weight of one or more modified low molecular weight polypropylenes (D) selected from the following (D1) to (D3). (D1): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polypropylene having an acid value of 5-150. (D2): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polypropylene having a hydroxyl value of 5 to 150. (D3); a part or all of (D1) is esterified with a polyoxyalkylene compound, and has a number average molecular weight of 1,
2,000 to 28,000 modified low molecular weight polypropylene. 2. A polypropylene resin (A) 55 to 90.
% By weight, derived from a polyamide (b1) having carboxyl groups at both terminals and having a number average molecular weight of 200 to 5,000 and an ethylene oxide adduct of a bisphenol having a number average molecular weight of 1,600 to 5,000 (b2 '). 5 to 40% by weight of an aromatic ring-containing polyetheresteramide (B), 3 to 20% by weight of a polyamide resin (C) and one or more modified low molecular weight polypropylenes (D) 1 selected from the following (D1) to (D3) A resin composition comprising up to 20% by weight. (D1): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polypropylene having an acid value of 5-150. (D2): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polypropylene having a hydroxyl value of 5 to 150. (D3); a part or all of (D1) is esterified with a polyoxyalkylene compound, and has a number average molecular weight of 1,
2,000 to 28,000 modified low molecular weight polypropylene. 3. A process according to claim 1 or 2, which is carried out via a small amount of (A), (B), (C) and (D) or a master batch consisting of (B), (C) and (D). The resin composition as described in the above. Further, a metal salt (E) comprising a halide of an alkali metal and / or an alkaline earth metal and / or a nonionic, anionic, cationic or amphoteric surfactant (F) is used. The resin composition according to any one of claims 1 to 3, which is contained.