JPH0790144A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To improve the affinity between blended polymers and mechanical strength by mixing an acid-anhydride-modified polyolefin resin with an unmodified polyolefin resin, a polyacetal resin, an esterification catalyst, and a filler. CONSTITUTION:100 pts.wt. resin ingredient consisting of 100-10wt.% polyolefin resin modified with an unsaturated carboxylic anhydride (or a derivative thereof) and 0-90wt.% unmodified polyolefin resin is mixed with 1-99 pts.wt. polyacetal resin having a hydroxyl content of 30mmol/kg or higher, 0.01-5 pts.wt. one or more esterification catalysts selected from pyridine, tertiary amines, quaternary ammonium salts, derivatives thereof, etc., and 0-150 pts.wt. one or more fillers selected from fibrous, particulate, and hollow fillers.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin having improved mechanical strength while maintaining the properties of the polyolefin resin by improving the affinity between the resins of a polymer blend comprising the polyolefin resin and a thermoplastic polyacetal resin. It relates to a composition.

[0002]

2. Description of the Related Art Polyolefin resins typified by polyethylene and polypropylene are inexpensive and lightweight and have excellent electrical properties, chemical properties, moldability, etc. It is widely used in various fields as containers, various films, sheets, tapes, insulating parts, coating materials and the like. However, since it is relatively soft and has low rigidity and elastic modulus, it cannot be used in a portion requiring mechanical strength. In order to improve this point, a method of blending various fillers such as glass fiber has been attempted, but there is a problem that molding becomes impossible in the case of use requiring fluidity such as a thin molded product. . Therefore, blending with a tough resin represented by a polyacetal resin or a polyester resin has been attempted. However, the mixing of the polyolefin resin and these blended resins is poor, dispersion failure occurs simply by melt-kneading, and toughness cannot be obtained, and also the appearance of the surface of the molded product due to surface layer peeling or flow marks It was damaged. In order to overcome this point, for example, a copolymer obtained by introducing a polar comonomer component such as methyl methacrylate into a polyolefin resin or an improvement such as blending a polyolefin resin containing a reactive glycidyl group in its molecular structure has been improved. Although it was carried out, it is still insufficient and has not been put to practical use.

[0003]

The inventors of the present invention have made diligent studies on such points, and as a result, accelerate the esterification reaction of a polyacetal resin with a polyolefin resin having an acid anhydride group having high reactivity. By compounding the catalyst, the affinity between the polyolefin resin and the polyacetal resin was improved, and a tough polyolefin resin was successfully obtained, and the present invention was completed.

That is, the present invention is based on 100 parts by weight of the total amount of (A) 100 to 10% by weight of acid anhydride-modified polyolefin resin (a) and 90 to 0% by weight of unmodified polyolefin resin (b). (B) 1 to 99 parts by weight of polyacetal resin, (C) 0.01 to 5 parts by weight of esterification reaction catalyst, and (D) selected from fibrous filler, powdered and granular filler, plate-shaped filler and hollow filler 1 A polyolefin resin composition comprising 0 to 150 parts by weight of one or more fillers.

The constituent components of the present invention will be described below. The component (A) of the present invention is an acid anhydride-modified polyolefin resin (a) of 100 to 10% by weight and an unmodified polyolefin resin.
(b) 90 to 0% by weight. The polyolefin-based resin used here is a homopolymer of α-olefin such as ethylene, propylene, butene, hexene, octene, nonene, decene, and dodecene, or a random, block, or graft copolymer composed of two or more of these. Polymer,
Alternatively, non-conjugated dienes such as 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 2,5-norbonadiene, conjugated diene components such as butadiene, isoprene and piperylene, acrylic acid and methacrylic acid Derivatives of α, β-unsaturated acids or their esters, aromatic vinyl compounds such as acrylonitrile, styrene, α-methylstyrene, vinyl esters such as vinyl acetate, vinyl ethers such as vinyl methyl ether and vinyl compounds thereof. Examples thereof include random, block, or graft copolymers containing one or more of comonomer components such as derivatives. The degree of polymerization, presence or absence of side chains or branches, degree, copolymer composition ratio, etc. It doesn't matter.
Further, as the acid anhydride used for modification, unsaturated carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, nadic acid anhydride, methyl nadic acid anhydride, and allyl succinic anhydride. ,
Alternatively, one or more selected from derivatives thereof may be used. As a modification method, a polyolefin resin and an unsaturated carboxylic acid anhydride such as maleic anhydride or a derivative thereof are heated and reacted with a radical initiator such as an appropriate organic peroxide in a solution state or a molten state. The method and the like are suitable, but the manufacturing method thereof is not particularly limited. Here, the blending amount of both components is the polyolefin resin.
0.1 to 30 parts by weight of acid anhydride is suitable for 100 parts by weight. When the amount of the effective acid anhydride in the acid anhydride-modified polyolefin resin is too small, the affinity between the polyolefin resin and the polyacetal resin is not sufficiently improved, so the effect of the present invention cannot be obtained, and the amount is too large. If it does, gelation may occur, resulting in poor dispersibility and poor molding. In addition, the acid anhydride-modified polyolefin resin used in the present invention is a non-modified polyolefin resin such as 90
It may contain less than or equal to wt%.

Next, the polyacetal resin in the present invention is a thermoplastic resin containing as a main component a polymer compound having an oxymethylene unit (-CH ₂ O-) as a main repeating constitutional unit, such as formaldehyde, trioxane or tetraoxane. Etc. homopolymerized by a conventional method, or a copolymer composed of two or more of these, or a monomer and a cyclic ether such as ethylene oxide, propylene oxide, oxacyclobutane, or 1,3-dioxolane, β- Cyclic ester such as propiolactone, γ-butyrolactone,
Alternatively, a copolymer with a certain vinyl compound or the like is used as the component (B). Further, the polyacetal resin may have a part of its molecular terminal converted to an ether bond, an ester bond, or the like. Further, a part or all of the polyacetal resin may be a polyacetal resin having a large amount of hydroxyl groups produced by the method as shown below (hereinafter referred to as a hydroxyl-rich polyacetal resin), in which case the effect of the present invention is obtained. Is more remarkable, but more preferable results can be obtained when the concentration of hydroxyl groups in the polyacetal resin is 30 mmol / kg or more. As a method of producing the hydroxyl group-rich polyacetal resin, for example,
When polymerizing trioxane with a cationic initiator such as BF _3, there is a method of adding a small amount of a compound having a hydroxyl group such as water, ethylene glycol, glycerin, and glycidol, but the production method is not particularly limited. Absent. Further, the degree of polymerization, the presence or absence of branching, homopolymer or copolymer, or copolymer type such as random, block or graft may be used. Also, the binding site of the hydroxyl group is not particularly limited.

The component (B) is compounded in an amount of 1 to 99 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the component (A). If the blending amount of the component (B) is too low, the effects of the present invention will not be sufficiently exhibited, and if it is too large, the properties of the polyolefin resin will be impaired.

As the esterification reaction catalyst of the component (C),
Pyridine, 4-dimethylaminopyridine, pyridine derivatives such as 4-pyrrolidinopyridine and salts thereof, triethylamine, trimethylamine, triethylenediamine, N,
Tertiary amines such as N'-dimethylpiperidine, benzylmethylamine, dimethylaniline and their derivatives, quaternary ammonium salts such as trimethylbenzylammonium chloride and its derivatives, aliphatic and aromatic organic acids such as acetic acid and benzoic acid, Salts of organic acids such as sodium acetate, sodium lauryl sulfate, sodium paratoluene sulfonate, tetrabutyl zirconate, zirconium naphthate, tetrabutyl titanate, tetraoctyl titanate, tetraphenyl tin, zinc acetate, stannous oxalate, naphthene Zinc acid, iron acetylacetate, manganese naphthenate, triphenylantimony, tributylantimony, triphenylbismuth, organic metal compounds such as dibutyltin dichloride, zinc chloride, magnesium titanate, magnesium dichloride Examples include various metal compounds of luconate, and one or more of them can be added. Particularly preferred catalysts include pyridines or their derivatives or salts thereof and tertiary amines or their derivatives from the viewpoints of thermal stability, hue and the like. (C)
The amount of the component added is appropriately 5 parts by weight or less, preferably 0.01 to 2 parts by weight, relative to 100 parts by weight of the component (A). If the amount of the catalyst is too small, the reaction does not proceed sufficiently and the effect of the present invention cannot be obtained.

The filler of the component (D) used in the present invention is not always an essential component, but in order to obtain a molded article excellent in performance such as mechanical strength, heat resistance, dimensional stability and electrical properties. It is preferable to mix them. As the component (D), a fibrous, powdery, tabular or hollow filler is used depending on the purpose. As the fibrous filler, glass fiber, asbestos fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber,
Examples thereof include boron fibers, potassium titanate fibers, and inorganic fibrous substances such as metal fibrous substances such as stainless steel, aluminum, titanium, copper, and brass. Particularly, glass fibers or carbon fibers are often used. In addition, high melting point organic fibrous fibrous substances such as aromatic polyamide resin, fluororesin and acrylic resin can also be used. As a granular filler,
Carbon black, silica, quartz powder, glass beads,
Glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, metal oxides such as iron oxide, titanium oxide and alumina, metals such as calcium sulfate and barium sulfate. Examples thereof include sulfates, calcium carbonate, magnesium carbonate, carbonates such as dolomite, and other silicon carbide, silicon nitride, boron nitride, various metal powders, and the like. Examples of the plate-like filler include mica, glass flakes, various metal foils, and the like, and examples of the hollow filler include shirasu balloon, metal balloons, glass balloons, and the like. Further, as these fillers, those whose surface is treated with organic silane, organic borane, organic titanate, urethane or the like can also be preferably used. These fillers can be used alone or in combination of two or more. The combined use of a fibrous filler, particularly glass fiber or carbon fiber, with a powdery or plate-like filler is a preferable combination particularly in terms of having both mechanical strength, dimensional accuracy and electrical properties. The blending amount of the component (D) is 150 parts by weight or less with respect to 100 parts by weight of the component (A),
If the amount of addition is too large, the molding processability and toughness may be impaired, which may be undesirable.

The composition of the present invention is prepared by melt mixing the above-mentioned components by various methods. For example, a method of melt-kneading a predetermined amount of an acid anhydride-modified polyolefin-based resin and a polyacetal resin, and cooling and cutting into pellets may be mentioned, but the mixing timing of each component and its method are not particularly limited. . At this time, if necessary, antioxidants, ultraviolet absorbers, photoprotectors, phosphite stabilizers, peroxide decomposers, basic auxiliaries, nucleating agents, plasticizers, lubricants, antistatic agents. Additives such as flame retardants and colorants may be added in any amount within the range that does not impair the physical properties of the present invention. Further, the polymer of the present invention can be appropriately blended with other polymers as long as the physical properties thereof are not impaired. The composition obtained by the present invention can be molded by a usual method.

[0011]

EFFECT OF THE INVENTION The composition obtained by the present invention improves the affinity between the polyolefin resin and the polyacetal resin, whereby the mechanical strength of the composition is remarkably improved while maintaining the excellent properties of the polyolefin resin. Furthermore, there is no appearance defect or surface peeling of the molded product due to poor dispersion of the dispersed resin, and it can be expected to be applied to many uses.

[0012]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 100 parts by weight of a polypropylene resin (manufactured by Mitsui Petrochemical Industry Co., Ltd., Hypol J400) was modified with 10 parts by weight of maleic anhydride (A) Maleic anhydride modified polypropylene I 1
00 parts by weight, (B) 30 parts by weight of polyacetal resin (DURACON M90-44, manufactured by Polyplastics Co., Ltd.), and
(C) Mix 0.2 parts by weight of dimethylaminopyridine and add 30 mm
Twin screw extruder, set temperature 190 ℃, screw speed 80
The mixture was melt-kneaded at rpm and pelletized. Next, the pellets were molded into test pieces by an injection molding machine, and the following evaluations were performed. [Flexural Modulus] The flexural modulus (kgf / cm ² ) of the test piece was measured according to ASTM D790. [Surface Layer Peeling Test] Cellophane tape was attached to the surface of the test piece and peeled off, and then the peeling condition was visually evaluated. Examples 2-3 As shown in Table 1, test pieces were prepared and evaluated in the same manner as in Example 1 except that the compounding amounts of the (B) polyacetal resin and the catalyst were changed. The composition and the evaluation results are shown in Table 1. Comparative Example 1 (A) A test piece was prepared and evaluated in the same manner as in Example 1 except that maleic anhydride-modified polypropylene I was blended alone.
The composition and the evaluation results are shown in Table 1. Comparative Example 2 A test piece was prepared and evaluated in the same manner as in Example 1 except that unmodified polypropylene was used alone. The composition and the evaluation results are shown in Table 1. Comparative Example 3 (A) In place of the maleic anhydride-modified polypropylene I, 100 parts by weight of polypropylene resin (manufactured by Mitsui Petrochemical Co., Ltd., Hypol J400) was modified with 10 parts by weight of maleic acid. A test piece was prepared and evaluated in the same manner as in Example 2 except for the above. The composition and the evaluation results are shown in Table 1. Comparative Example 4 A test piece was prepared and evaluated in the same manner as in Comparative Example 3 except that unmodified polypropylene was used as the component (A). The composition and the evaluation results are shown in Table 1. Comparative Example 5 A test piece was prepared and evaluated in the same manner as in Example 2 except that the component (C) was not added. The composition and the evaluation results are shown in Table 1. Example 4 A test piece was prepared and evaluated in the same manner as in Example 2 except that the amount of the component (C) was changed to 2.0 parts by weight. The composition and the evaluation results are shown in Table 1.

Example 5 (A) The above-mentioned Example except that maleic anhydride modified polypropylene II was used in place of maleic anhydride modified polypropylene I with a maleic anhydride modification rate of 5 parts by weight per 100 parts by weight of polypropylene. Test pieces were prepared and evaluated in the same manner as in 2. The composition and the evaluation results are shown in Table 2. Example 6 (A) Maleic anhydride modified polypropylene II was used instead of the maleic anhydride modified polypropylene II, and the modification rate was 100% by weight of polypropylene.
25 parts by weight of maleic anhydride modified polypropylene III
Test pieces were prepared and evaluated in the same manner as in Example 5 except that was used. The composition and the evaluation results are shown in Table 2.

Example 7 (C) A test piece was prepared and evaluated in the same manner as in Example 2 except that 0.3 part by weight of triethylenediamine was added instead of dimethylaminopyridine. Table 3 shows the composition and the evaluation results. Example 8 (C) Sodium acetate instead of dimethylaminopyridine
Test pieces were prepared and evaluated in the same manner as in Example 2 except that 0.2 part by weight was blended. Table 3 shows the composition and the evaluation results. Example 9 (C) A test piece was prepared and evaluated in the same manner as in Example 2 except that 0.2 part by weight of tetraphenyltin was added instead of dimethylaminopyridine. Table 3 shows the composition and the evaluation results.

Examples 10 and 11 Glass fibers were further added as a component (D) to Example 7, and test pieces were prepared and evaluated in the same manner as in Example 7.
Table 4 shows the composition and the evaluation results. Comparative Example 6 A test piece was prepared and evaluated in the same manner as in Example 10 except that (A) unmodified polypropylene and (D) glass fiber were blended together. Table 4 shows the composition and the evaluation results. Examples 12 to 14 Test pieces were prepared and evaluated in the same manner as in Example 10 except that talc, mica or glass balloon was used as the component (D). Table 4 shows the composition and the evaluation results. Example 15 A test piece was prepared and evaluated in the same manner as in Example 10 except that glass fiber and talc were used in combination as the component (D). Table 4 shows the composition and the evaluation results.

Example 16 A test piece was prepared and evaluated in the same manner as in Example 1 except that a hydroxyl group-rich polyacetal resin having a hydroxyl group content of 80 mmol / kg was used as the component (B). Table 5 shows the composition and the evaluation results. The hydroxyl group content of the component (B) was measured by the method described below. [Hydroxyl group content] The hydroxyl groups of the polyacetal resin were acetylated with acetic anhydride and the amount of the terminal groups was determined by NMR measurement to determine the amount of hydroxyl groups per kg of the polyacetal resin. Comparative Example 7 A test piece was prepared and evaluated in the same manner as in Example 16 except that unmodified polypropylene was used as the component (A). Table 5 shows the composition and the evaluation results. Example 17 A test piece was prepared and evaluated in the same manner as in Example 2 except that a polyacetal rich in hydroxyl group and a general polyacetal resin were used in combination as the component (B). Table 5 shows the composition and evaluation results.
Shown in. Examples 18 to 20 Test pieces were prepared and evaluated in the same manner as in Example 2 except that maleic anhydride modified polypropylene I and unmodified polypropylene were used in combination as the component (A). Table 5 shows the composition and the evaluation results.

Example 21 (A) Instead of the maleic anhydride-modified polypropylene I, 100 parts by weight of high-density polyethylene (Hipol 1300J, manufactured by Mitsui Petrochemical Co., Ltd.) was modified with 10 parts by weight of maleic anhydride. Test pieces were prepared and evaluated in the same manner as in Example 2 except that acid-modified polyethylene was used.
Table 6 shows the composition and the evaluation results. Comparative Example 8 (C) A test piece was prepared and evaluated in the same manner as in Example 21 except that dimethylaminopyridine was not added. Table 6 shows the composition and the evaluation results. Comparative Example 9 (A) A test piece was prepared and evaluated in the same manner as in Example 21 except that unmodified polyethylene was used in place of the maleic anhydride modified polyethylene. Table 6 shows the composition and the evaluation results.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

[0022]

[Table 5]

[0023]

[Table 6]

Claims (5)

[Claims] 1. (A) Acid anhydride-modified polyolefin resin
(a) 100 to 10 wt% and unmodified polyolefin resin (b) 90
(B) 1 to 99 parts by weight of a polyacetal resin, (C) 0.01 to 5 parts by weight of an esterification reaction catalyst, and (D) a fibrous filler, a granular filler A polyolefin resin composition comprising 0 to 150 parts by weight of one or more fillers selected from plate-like fillers and hollow fillers. 2. The (A) acid anhydride-modified polyolefin-based resin comprises 100 parts by weight of the polyolefin-based resin and 0.1 to 0.1 of the acid anhydride.
The polyolefin resin composition according to claim 1, which has been modified with 30 parts by weight. 3. The (C) esterification reaction catalyst is one or more selected from the group consisting of pyridines or derivatives thereof or salts thereof and tertiary amines or derivatives thereof. The polyolefin resin composition of. 4. (C) The esterification reaction catalyst comprises a quaternary ammonium salt or its derivative, an aliphatic organic acid, an aromatic organic acid or a salt thereof, an organometallic compound, zinc chloride, magnesium titanate and magnesium zirconate. The polyolefin resin composition according to claim 1 or 2, which is one or more selected from the group consisting of: 5. The polyolefin resin composition according to claim 1, wherein the polyacetal resin (B) has a hydroxyl group content of 30 mmol / kg or more in the resin.