JPH05295188A - Polypropylene resin composition - Google Patents

Abstract

PURPOSE:To provide the objective compsn. light in wt. and having improved impact resistance and stiffness by compounding a PP resin, an inorg. filler, and a specific water-sol. vinyl polymer. CONSTITUTION:A water-sol. vinyl polymer having a wt.-average mol.wt. of 1,000-100,000 is prepd. by polymerizing at least one monomer selected from the group consisting of (meth)acrylamide, (a salt of) vinylpyridine, (a salt of) vinylimidazole, vinylpyrrolidone, and monomers of formulas I to IV [wherein R<1>, R<3>, R<7>, and R<9> are each H or a 1-4C alkyl; R<2> is H, Na, or K; R<4>, R<5>, and R<6> are each H, an alkyl, or an aralkyl; A and Y are each 0 or NH; B is a 1-4C alkylene, 2-4C hydroxyalkylene, or phenylene; X is a counterion; R<8> is a di- or trivalent (substd.) hydrocarbon group; M is H or one equivalent of the cation; a is 1 or 2; R<10> is a 2-4C alkylene; and R<11> and R<12> are each H, an alkyl, or an aralkyl]. 100 pts.wt. compsn. comprising 45-95wt.% PP resin having an MI of 1-80g/10min and 55-5wt.% inorg. filler is compounded with 0.05-10 pts.wt. the water-sol. vinyl polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polypropylene resin composition.

[0002]

2. Description of the Related Art Conventionally, polypropylene resin compositions have been manufactured by injection molding or the like for automobile parts such as instrument panels, trims, fenders, bumpers, spoilers, home electric appliances such as TV / VTR housings, and OA for personal computer housings. Molded into equipment parts, containers, pallets, etc., and used in many industrial applications.
In the above-mentioned applications, the rigidity of the molded product of the polypropylene resin alone is insufficient, so various attempts have been made to improve the rigidity of the molded product.

As a means for improving the rigidity of a polypropylene resin molded product, for example, Japanese Patent Laid-Open No. 57-8235 discloses a technique of blending talc with a polypropylene resin. Also, for example, Japanese Patent Laid-Open No. 56-884.
Japanese Patent Publication No. 47 discloses a technique in which a polypropylene resin is mixed with a filler such as talc, calcium carbonate or mica.

However, the addition of these fillers generally improves the rigidity, but on the other hand, there is a problem that the impact resistance is significantly lowered. Further, it is known that the effect of improving rigidity differs depending on the type of filler.

Further, for example, Japanese Examined Patent Publication No. 64-2616 discloses a technique of blending ethylene-propylene copolymer with Wallacenite as a filler. However, since the above technique uses wollastonite having a small aspect ratio (about 10), there is a problem that impact resistance is lowered even if the rigidity can be improved to some extent.

[0006] Generally, when a filler that enhances rigidity is used, impact resistance decreases, and a filler that enhances impact resistance tends to decrease rigidity. Therefore, in order to enhance rigidity and impact resistance, If the compounding amount is increased, there is a drawback that the weight of the molded product becomes heavy.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and its object is impact resistance and rigidity without impairing the chemical properties and mechanical properties of polypropylene resins. And to provide a polypropylene-based resin composition having an excellent balance of performance between the two.

[0008]

The polypropylene-based resin composition of the present invention is (meth) based on 100 parts by weight of a mixture comprising 45-95% by weight of a polypropylene-based resin and 55-5% by weight of an inorganic filler. Water-soluble vinyl obtained by polymerizing at least one selected from the group consisting of acrylamide, vinyl pyridine and salts thereof, vinyl imidazole and salts thereof, vinyl pyrrolidone and monomers represented by the general formulas (I) to (IV). System polymer 0.05-10
It is characterized by containing parts by weight, whereby the above object is achieved.

The present invention will be described in detail below. The polypropylene resin used in the present invention, propylene homopolymer, ethylene-propylene random copolymer,
Examples thereof include ethylene / propylene block copolymers. The ethylene content of the ethylene / propylene random copolymer and the ethylene / propylene block copolymer is preferably in the range of 0.2 to 30% by weight.

The polypropylene-based resin has a melt index of 1 to 80 g / for the reason of molding.
10 minutes (JIS K-7210, 230 ° C, 2.16k
The range of gf) is preferred.

In the present invention, in order to improve the rigidity of the polypropylene resin, an inorganic filler is added to form a blend. Examples of the inorganic filler used in the present invention include glass fiber, talc, mica, whiskers, carbon fiber and boron fiber. These fillers may be used alone or in combination of two or more. May be used. Further, as the above-mentioned inorganic filler, one whose surface is treated with silicon, titanate, phosphoric acid ester, surfactant or the like may be used. Such surface treatment may be performed in advance before adding the inorganic filler to the resin, or may be performed in a compounding step of kneading the inorganic filler with the resin.

If the amount of the inorganic filler added to the above-mentioned compound is small, there is no effect of improving the rigidity, and if it is too large, the impact resistance is lowered.
Is.

The polypropylene resin composition of the present invention is
It is composed of the above-mentioned compound and a water-soluble vinyl polymer. The water-soluble vinyl polymer is (meth) acrylamide, vinyl pyridine and salts thereof, vinyl imidazole and salts thereof,
It is obtained by polymerizing at least one selected from the group consisting of vinylpyrrolidone and monomers represented by the general formulas (I) to (IV). For example, poly (meth) acrylamide is preferably used.

[0014]

[Chemical 5]

In the formula, R ¹ represents H or an alkyl group having 1 to 4 carbon atoms, and R ² represents H, Na or K atom.

[0016]

[Chemical 6]

In the formula, R ³ is H or an alkyl group having 1 to 4 carbon atoms; R ⁴ , R ⁵ and R ⁶ are each independently H, an alkyl group or an aralkyl group; A is O or NH; B is carbon. Number 1
~ 4 alkylene group; C2-4 hydroxyalkylene group or phenyl group; X represents a counter anion.

[0018]

[Chemical 7]

In the formula, R ⁷ is H or an alkyl group having 1 to 4 carbon atoms; R ⁸ is a divalent or trivalent hydrocarbon group or a substituted hydrocarbon group; M is hydrogen or one equivalent of a cation; Y is O Or NH respectively, and a is 1 or 2.

[0020]

[Chemical 8]

In the formula, R ⁹ is H or an alkyl group having 1 to 4 carbon atoms; R ¹⁰ is an alkylene group having 2 to 4 carbon atoms,
R ¹¹ and R ¹² each independently represent H, an alkyl group or an aralkyl group.

In the present invention, when the content of the water-soluble vinyl polymer in the polypropylene resin composition is small, the effect of improving the rigidity of the molded article does not appear, and when the content is large, the rigidity decreases, so that the polypropylene The water-soluble vinyl polymer is contained in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the blend of the resin and the inorganic filler.

In the present invention, the above water-soluble vinyl polymer is
Monomers other than the above may be copolymerized as long as the water solubility is maintained. As such a monomer, for example,
Alkyl esters of (meth) acrylic acid such as methyl methacrylate, ethyl acrylate, and 2-ethylhexyl acrylate; hydroxyalkyl esters of (meth) acrylic acid such as hydroxyethyl methacrylate and hydroxypropyl acrylate; (meth) acrylonitrile; styrene; vinyl acetate; Butadiene; isoprene and the like are preferable, and those having one vinyl group in the molecule are preferable so that the obtained vinyl copolymer maintains water solubility.

The proportion of the comonomer in the copolymer is not particularly limited as long as it maintains the water solubility, but it is preferably 50% by weight or less of the total monomers constituting the copolymer, and more preferably. It is 20% by weight or less.

When the weight average molecular weight of the water-soluble vinyl polymer is small, the rigidity of the polypropylene resin composition is low, and when it is large, the dispersibility is poor and the effect is not exhibited. It is more preferably 5000 to 100,000.

In the present invention, the above water-soluble vinyl polymer is added to the following general formula (V) (in the formula, R ¹³ and R ¹⁴ are each independently H, a hydroxy compound residue or a carboxylic acid residue,
OA is an oxyalkylene group, and n is an integer of 1-40. The compound represented by) may be added.

R ¹³ (OA) _n OR ¹⁴ ... (V)

The term "residue" as used herein means a hydroxy compound or carboxylic acid from which an OH group has been removed. The hydroxy compound residue has 1 to 20 carbon atoms (preferably 1 to 20 carbon atoms).
7) Saturated or unsaturated aliphatic alcohol residues, C1-C20 aromatic nucleus-containing hydroxy compound residues (residues such as phenol, alkylphenol, and benzylacol). Further, as the carboxylic acid residue,
Saturated or unsaturated fatty acid residues having 1 to 20 carbon atoms (preferably 1 to 7), aromatic nucleus-containing carboxylic acid residues having 1 to 25 carbon atoms (residues such as benzoic acid, alkylbenzoic acid, cinnamic acid)
Etc.

Examples of the oxylene group represented by OA in the general formula (V) include oxyethylene group, oxypropylene group, oxybutylene group, oxytetramethylene group, oxidodecamethylene group, and the like. In the case of a plurality, the number (n) of the same type of groups is 1 to 4
It is 0, preferably 2 to 20.

Specific examples of the compound represented by the above general formula (V) include ethylene glycol, ethyl cellosolve,
Butyl cellosolve, diethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, trioxyethylene nonylphenyl ether, dodecaoxyethylene nonylphenyl ether, hydroxyethyl bezoate, 2-hydroxypropyl acetate and the like can be mentioned.

In addition to the compounds represented by the general formula (V), aliphatic and alicyclic alcohols having 4 or more carbon atoms,
At least one selected from the group consisting of cationic surfactants, amphoteric surfactants and polyamines may be added. The addition amount of these components is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the water-soluble vinyl polymer.

Specific examples of the aliphatic alcohol having 4 or more carbon atoms include butanol, 2-ethylhexanol, decyl alcohol, stearyl alcohol, oleyl alcohol and the like.

Specific examples of the alicyclic alcohol having 4 or more carbon atoms include cyclohexanol and the like, and the aliphatic or alicyclic alcohol having 4 to 12 carbon atoms is preferable.

The above-mentioned cationic surfactant and amphoteric surfactant are not particularly limited. For example, aliphatic amine salts such as stearylamine acetate, tetramethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, Examples include quaternary ammonium salts such as cetyltrimethylammonium saccharate and distearyldimethylammonium chloride (above cationic surfactants), lauryldimethylbetaine, sodium laurylaminopropionate (above amphoteric surfactants) and the like. Quaternary ammonium salt type cationic surfactants and amphoteric surfactants are preferred.

The polyamine salt is composed of a polyamine component and an acid component, and examples of the polyamine component include polyalkylene polyamines represented by the general formula (VI) (wherein R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are
H, an alkyl group, an aryl group, an aralkyl group, and a hydroxyalkyl group are shown, n is an integer of 1 to 6, and m is an integer of 1 or more. );

[0036]

[Chemical 9]

Piperazine, dimethylpiperazine, 1,3
-Dipiperidyl propane, 4-aminopiperidine, aliphatic polyamines having a heterocycle such as dimethylaminopiperidine; aliphatic polyamines having an aromatic ring such as xylenediamine; aromatic polyamines such as diphenylmethanediamine; A polyalkylene polyamine represented by the general formula (VI) is preferable.

As the acid component constituting the polyamine, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, ammonium bisulfate,
Examples thereof include inorganic acids such as first sodium phosphate and second sodium phosphate; organic acids such as acetic acid, oxalic acid, and chloroacetic acid.

These polyamine salts may be salts in which all the amino groups are in the form of salts or salts in which a part of the amino groups are in the form of salts. These polyamines may be used alone or in combination of two or more.

As the quaternary compound of polyamine, N, N-
Tetramethyl xylene diamine, N ', N'- tetramethyl xylene diamine, etc. are mentioned. Of the polyamine salts and the quaternary compounds of polyamines, polyamine salts with inorganic acids are preferable.

In the polypropylene resin composition of the present invention, other various resins, fillers, rubber substances, pigments, antioxidants, ultraviolet absorbers, flame retardants, plasticizers, lubricants, electrification agents, etc. An inhibitor or the like can be added.

As a method for pelletizing the polypropylene resin composition of the present invention, any method can be adopted.
A melt-kneading device such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll, a Brabender plastograph, and a kneader can be used in the same manner as in the conventional method.

[0043]

In the present invention, the polypropylene resin is blended with the poly (meth) acrylamide or the water-soluble vinyl polymer in addition to the inorganic filler, so that the impact resistance of the resin molding is not lowered. The rigidity can be improved with a small amount of filler.

The poly (meth) acrylamide or the water-soluble vinyl polymer has a polar group and a non-polar group in its molecular structure, the polar group has an affinity with the inorganic filler, and the non-polar group is It is considered that by exhibiting the affinity with the polypropylene resin, the adhesion and the dispersibility of the polypropylene resin and the inorganic filler are improved, and as a result, the impact resistance and rigidity of the molded product are improved.

[0045]

EXAMPLES Examples of the present invention will be described below.

(Example 1) 1) Preparation of test piece Polypropylene resin ("MS540" manufactured by Tokuyama Soda Co., Ltd.,
Ethylene / propylene block copolymer, MI = 10,
Ethylene content 2% by weight, hereinafter referred to as block PP) 80
To a mixture of 20 parts by weight and 20 parts by weight of talc (“K-1” manufactured by Nippon Talc Co., Ltd., average particle size: 3.5 mμ), polyacrylamide (A) (“Safrock N-50” manufactured by Sanyo Kasei Co., Ltd.
5P ") 1 part by weight was added and the mixture was extruded with a twin-screw extruder [" PCM302 "manufactured by Ikegai Tekko KK] to produce pellets. Injection molding machine [TOSHIBA CORPORATION's "IS
-30 EP "], and a test sample was prepared.

2) Measurement of physical properties (1) Rigidity Flexural modulus was selected as an index of stiffness, and the flexural modulus of the sample prepared in 1) was measured by an autograph manufactured by Shimadzu Corporation in accordance with JISK-7203. ,
It was 3.2 × 10 ³ kgf / cm ² . (2) Impact resistance Izod impact value was selected as an index of impact resistance, and the sample produced in 1) was subjected to Izod impact test (with notch) according to JIS K-7110. It was cm / cm 2. (3) Density The density was measured according to JIS K7112 (A method).

(Examples 2 to 10, Comparative Examples 1 to 9) A polypropylene resin, an inorganic filler and polyacrylamide were blended in the proportions shown in Tables 1 and 2, and biaxially treated in the same manner as in Example 1. After being extruded with an extruder to fabricate a test sample, the physical properties of the same items as in Example 1 were measured. The results are shown in Table 1 for Examples and Table 2 for Comparative Examples.

[0049]

[Table 1]

[0050]

[Table 2]

(Examples 11 to 14, Comparative Examples 10 to 13)
A polypropylene resin, an inorganic filler, and poly (meth) acrylamide were mixed in the proportions shown in Table 3, and extruded with a twin-screw extruder in the same manner as in Example 1 to prepare a test sample, and then Example 1 Physical properties are measured for the same items as
The results are shown in Table 3.

[0052]

[Table 3]

Note] Homo PP: polypropylene homopolymer (“ME240”, MI = 9 manufactured by Tokuyama Soda Co., Ltd.) Calcium carbonate: “Softon 260 manufactured by Shiraishi Calcium”
0 "Polyacrylamide (B): Sanyo Chemical Co., Ltd." Sunflock AH-210P "Polyacrylamide (C): Sanyo Chemical Co., Ltd." Sunfloc CH-509P "

[0054]

EFFECTS OF THE INVENTION According to the present invention, by blending a polypropylene resin with an inorganic filler, poly (meth) acrylamide or a water-soluble vinyl polymer, polypropylene having an excellent performance balance of impact resistance and rigidity is obtained. A resin composition can be provided. Further, according to the present invention, impact resistance and rigidity can be improved with a small amount of an inorganic filler, so that a lightweight molded product can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 33:14 7921-4J 33:26) 7921-4J

Claims (1)

[Claims] 1. A (meth) acrylamide, a vinylpyridine and a salt thereof, a vinylimidazole and a salt thereof, with respect to 100 parts by weight of a blend consisting of 45 to 95% by weight of a polypropylene resin and 55 to 5% by weight of an inorganic filler. Containing 0.05 to 10 parts by weight of a water-soluble vinyl polymer obtained by polymerizing at least one selected from the group consisting of vinylpyrrolidone and monomers represented by the general formulas (I) to (IV). A polypropylene-based resin composition comprising: [Chemical 1] (In the formula, R ¹ represents H or an alkyl group having 1 to 4 carbon atoms, and R ² represents H, Na or K atom.) (In the formula, R ³ is H or an alkyl group having 1 to 4 carbon atoms;
R ⁴ , R ⁵ and R ⁶ are each independently H, an alkyl group or an aralkyl group; A is O or NH; B is an alkylene group having 1 to 4 carbon atoms, a hydroxyalkylene group having 2 to 4 carbon atoms or a phenyl group. X represents a counter anion, respectively. ) [Chemical 3] (In the formula, R ⁷ is H or an alkyl group having 1 to 4 carbon atoms; R ⁸
Is a divalent or trivalent hydrocarbon group or a substituted hydrocarbon group;
M is 1 equivalent of hydrogen or cation; Y is O or NH, respectively, and a is 1 or 2. ) [Chemical 4] (In the formula, R ⁹ is H or an alkyl group having 1 to 4 carbon atoms; R ¹⁰
Represents an alkylene group having 2 to 4 carbon atoms; R ¹¹ and R ¹² each independently represent H, an alkyl group or an aralkyl group. )