JPS60170643A - Production of polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having improved impact resistance, particularly falling weight impact strength in simple steps, by melt kneading a polyolefin with a treated filler prepared by applying an epoxy resin, etc. to an inorganic or organic filler. CONSTITUTION:(A) 20-90pts.wt. polyolefin resin, preferably crystalline polypropylene (PP) or crystalline ethylene-propylene copolymer is melt kneaded with (B) 10-80pts.wt. treated filler prepared by applying (i) an epoxy resin and (ii) a treating material consisting of an organic compound having functional groups having binding property to an epoxy resin and ethylenically unsaturated bond in the molecule preferably at 1:0.2-5 weight ratio between the epoxy resin (i) and the treating material (ii) to an inorganic or organic filler. Preferably, 0.5- 10pts.wt. treating material is applied to 100pts.wt. filler, and the component (i) is first applied to the filler. The component (ii) is then applied thereto while or after curing the component (i).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized in that the mechanical properties, especially the falling weight rljl bombardment, are excellent.
The present invention relates to a method for economically producing a ζ polyolefin resin composition in just 16J steps.

It is well known that properties such as rigidity, heat resistance, and dimensional stability can be improved by blending various inorganic fillers with polyolefin resin, and it is widely used in parts for automobiles, light electrical appliances, etc. .

However, simply blending inorganic filler and polyolefin resin improves rigidity and heat resistance, but
The impact resistance decreases, and the decrease is particularly significant in the region where the inorganic filler concentration is high.

In terms of impact resistance, recent polyolefin resin compositions containing inorganic fillers have improved not only the isot impact strength for protrusions and small parts, but also the falling weight impact strength, which is important for large parts with many flat parts. It is becoming highly desired as the technology expands into large parts applications.

Various proposals have been made to counter this problem, and some of the present inventors have already proposed a method of using an active inorganic filler treated with a polymerizable organic acid as the inorganic filler. (Japanese Patent Publication No. 51-11653, Japanese Patent Publication No. 51-983, Samurai Publication No. 52-38581, Japanese Unexamined Patent Publication No. 50-151237) However, although this method improves impact strength while maintaining high strength and rigidity, The improvement in falling weight impact strength was not fully satisfactory.

This method also has the disadvantage that the inorganic filler is limited to substances that have binding properties with polymerizable organic acids.

! , a method using an inorganic filler treated with an epoxy resin and an olefinic polymer grafted with an unsaturated carboxylic acid (for example, If!
No. 842) has also been disclosed, but the olefinic polymer grafted with unsaturated carboxylic acid must be separately produced, and the process is complicated.

Therefore, the present inventors aimed to improve the moldability of a wide range of fillers.
As a result of intensive research to develop a method for easily producing inorganic filler-containing polyolefin with even higher impact resistance, especially drop weight impact strength, without deterioration in rigidity and heat resistance, the present invention was achieved. The present invention comprises (I) a polyolefin resin of 20 to 90 parts and (II)
A treated filler made by attaching (4) an epoxy resin (B) a treatment substance consisting of an organic compound containing a functional group that has bonding properties with the epoxy resin and an ethylenic double bond in its molecule to an inorganic or organic filler. 10-80
The present invention relates to a method for producing a polyolefin resin composition, which comprises melt-kneading parts by weight.

The polyolefin resin used in the present invention is mainly composed of polymers and copolymers of monoolefins such as ethylene, propylene/butene, etc., such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, etc. , crystalline polypropylene, crystalline ethylene-propylene block copolymer, crystalline ethylene-propylene random copolymer, polybutene-1, poly-methylpentene-1, ethylene-vinyl acetate copolymer mainly composed of ethylene These may be used alone or as a mixture of two or more of them, such as a combination or an ethylene-acrylic acid ester copolymer.

Particularly suitable are crystalline polypropylene and crystalline ethylene-propylene block copolymers.

The epoxy resin used in the present invention is a general term for a polymer having two or more oxirane rings in the molecule, a prepolymer, and a composition containing a curing agent, a modifier, a diluent, etc. in addition to these. Generally, bisphenol A type epoxy resins are useful, and resorcin type, bisphenol FW, novolac type, polyglycol type, polyolefin type, etc. are possible. One embodiment of the epoxy resin has an epoxy equivalent of 150 to 3000, and 9 parts 17
A system containing a so-called epoxy resin curing agent such as amines, acid anhydrides, polyamides, phenol resin, butylated urea formaldehyde resin, etc. in an epoxy resin with a molecular weight of 0 to 2,000 and a molecular weight of 300 to 3,000 is possible. In addition to the above-mentioned curing agent, a deflection imparting agent or a diluent may be added. Another embodiment of the epoxy resin has a molecular weight of 1
00 or more, preferably in the range of 100 to 1000, and a thermoplastic epoxy resin system containing no curing agent is possible.

Examples of compounds containing a functional group having bonding properties with the epoxy resin and an ethylenic weight bond in the molecule used in the present invention include acrylic acid, methacrylic acid, mabiine, maleic anhydride, fumaric acid, itaconic anhydride, itaconic acid,
Mesaconic acid, citraconic acid, crotonic acid, sorbic acid,
unsaturated carboxylic acids or their acid anhydrides such as hymic acid, himic anhydride, vinyl acetic acid, isocrotonic acid, and angelic acid; unsaturated amines such as allylamine, 2-methylallylamine, and 1-amino-4-pentene; Unsaturated ratio 2 amines such as diallylamine, allylmethylamine, niethylamino-3-butene, allyl alcohol, crotyl alcohol, methylvinylalpinol, allyl carbinol, 4-penten-1-ol, 4-pentene -2-ol, 2-methyl-4-penten-2-ol, and other unsaturated alcohols ethylene glycol monoacrylate, polyethylene glycol monoacrylate, glycerin dimethacrylate, sorbitol dimethacrylate, and other polyhydric alcohols (
Epoxy group-containing monomers such as methacrylic) ester, glycidyl acrylate, and chrycidyl methacrylate,
Terminal carboxy 1,2-polybutadiene, maleic anhydride grafted 1,2-polybutadiene, epoxidation modification 1
, 2-polybutadiene, maleic anhydride, kraft styrene-diene block copolymer, and other liquid rubbers or entomers containing functional groups can be used.

These may be used alone or as a mixture of two or more, and may be used in combination with monomers that do not contain functional groups that are reactive with epoxy groups, such as polymers, styrene, divinylbenzene, acrylic esters, and triallyl cyanurates. It's okay.

Inorganic fillers used in the present invention include inorganic substances commonly used as fillers for plastics, such as calcium carbonate, basic magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum oxide, zinc oxide,
Calcium silicate, wollastonite, heptium silicate, talc, sodium aluminosilicate, nepheline, karuma,
Carbonates and hydroxides of metals of Groups 1, 2 or 2 of the periodic table, such as calcium aluminosilicate, magnesium aluminosilicate, dolomite, mixed crystals and mixtures thereof;
Oxides, silicates, etc., quartz powder, silica, glass powder, glass flakes, glass fiber, carbon fiber, carbon black, graphite, clay, titanium oxide, barium sulfate, calcium sulfate, calcium sulfite, ceramic powder, aluminum powder. A wide range of materials can be mentioned, including metal oxides and salts, metal powders, and metal-plated fillers. Further, examples of the organic filler include wood flour, strength paper, and rice husk powder.

These inorganic and organic fillers may be used alone or in combination.
More than one species may be mixed and used. Moreover, you may use a mixture of an inorganic filler and an organic filler.

The shape of such inorganic or organic fillers may be granular, plate-like,
It can be used in any shape: acicular, irregular, or fibrous. In the case of granular non-fibrous inorganic or organic fillers, the average particle size is preferably 0.01 to 100μ, more preferably 0.
．． It is in the range of 1 to 20μ.

In the present invention, adhesion includes coating, compounding, and infiltration, and various methods are possible for adhering the treatment substance to the inorganic or organic filler. For example, the inorganic or organic filler is stirred in a high-speed fluid mixer with a heating jacket, such as a Henschel mixer, while adding the treated substance, or the inorganic filler is suspended in an inert solvent and mixed with the treated substance. A method of mixing, a method of stirring and mixing the inorganic filler and the treatment substance in a heated and pressurized container, etc. are possible.

It is desirable to purify and remove impurities such as inert solvents and unreacted substances in the treated filler by solvent washing, filtration, heating, distillation under reduced pressure, etc. Also, secondary aggregates generated in the treated filler should be removed. It is desirable to remove it by sieving, crushing, etc.

Regarding the treatment order of the treatment substance used in the present invention, a mixture of an epoxy resin and an unsaturated compound containing a functional group that has binding properties to the epoxy resin may be used, or one of the two may be used as the treatment substance first. The remaining treated filler thus obtained may be further treated as a treatment substance, but after adhering an epoxy resin to the filler and partially or completely curing it, or after allowing it to be partially or completely cured, the filler containing the functional group may be treated. Further deposition treatment of unsaturated compounds is desirable.

At this time, if the viscosity of the treated substance is relatively high, it may be used after being dissolved in an inert solvent.

Further, a usual epoxy modifier and epoxy curing agent may be added to this solution.

(4) The blending ratio of the epoxy resin and (B) the unsaturated compound containing a functional group capable of bonding to the epoxy resin is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 10 parts by weight of the latter to 1 part by weight of the former. .2 to 5M parts. (B) component is 0.
If the amount is more than 1 part by weight, the strength and rigidity of the resulting polyolefin resin composition will be affected, and if the amount of component (J3) is less than 10 parts by weight, the falling weight impact strength of the resulting polyolefin resin composition will be affected. This is preferable in this respect.

In the present invention, the blending ratio of the treatment substance to the inorganic or organic filler varies depending on the purpose of modifying the composition, manufacturing conditions, specific surface area of the filler, etc., but ranges from 0.1 to 0.1 to 100 parts by weight of the treatment substance to 100 parts by weight of the filler. 20 overlapping parts, preferably 0
．． 5 to 10 parts by weight.

When the amount of the treated substance is more than 0.1 parts by weight, it is preferable from the viewpoint of reinforcing effect of the obtained resin composition, and when it is less than 20 parts by weight, it is preferable from the point of view of agglomeration between the treated fillers.

In the composition of the present invention, the blending ratio of the treated filler is in the range of 10 to 80 parts by weight based on 20 to 90 parts by weight of the polyolefin resin. If the amount of treated filler is less than the above range, the reinforcing effect of the treated filler will be small; if it is more than the above range, manufacturing and molding will be difficult, the reinforcing effect will be saturated, and the appearance of the molded product will deteriorate.

The composition of the present invention can be produced by melt-kneading a polyolefin resin composition, a treated filler, and, if necessary, a radical generator.

In addition to the above-mentioned composition, the composition may contain a heat stabilizer, an ultraviolet absorber, a crystal nucleating agent, a lubricant, a pigment, a flame retardant, an antistatic agent, a thickener, a foaming agent, a bile agent, and other additives.

Melt-kneading methods include mixing rolls, kneaders, and Banbury mixers, which are generally used when producing polyolefin compositions. - Single-screw and multi-screw extruders are generally melt-kneaded using a mixer such as a multi-screw extruder, but they may also be directly molded by being fed to a mild molding machine that has a melt-mixing function. .

Although not an essential requirement in the present invention, radical generators preferably used during the production of the composition include tetravalent tin compounds such as diptyltin oxide, 2.5-dimethy/l
/-2,5-di(t-butylno(-oxy)hexane,
2.5-dimethyl-2,5-di(1-butylperoxy)hexyne-3, dicumyl, < -oxide, t-butyl-peroxymaleic acid, lauroyl peroxide, penzoylmonoxide, t-butyl peroxide Commonly used organic peroxides such as benzony), t-7'' methyl hydroperoxide, isoprobylno(-carbonate), azo compounds such as azobisisobutyronitrile, and inorganic peroxides such as ammonium persulfate. It is a radical generator, and one of these or a combination of more than one can be used.

The preferable amount of the radical generator used is in the range of 0.001 to 10 parts by weight per 100 parts by weight of the polyolefin, and it may not be used under conditions where sufficient polymer radicals are generated during melt mixing.

The polyolefin resin composition produced by the method of the present invention has excellent mechanical strength, rigidity, and heat resistance, and particularly has improved falling weight impact strength. Further, the above composition can be used in various molding applications such as compression molding, extrusion molding, blow molding, and injection molding, but is suitable for use in large-sized molded products by slit injection molding.

EXAMPLES The present invention will be specifically explained below with reference to Examples.

In the Examples, the tensile strength, mechanical strength and falling weight impact strength of the molded products were measured according to the following methods.

Tensile strength □ ASTM D-638 Bend strength □ ASTM D-790 Falling weight impact strength □ 5 oz injection molding machine (molding temperature 230℃
) to form a flat plate (180 x 180 x 2 tugs direct gate) at a metal temperature of 40°C.

A hemispherical weight with a tip diameter of 1.5 crn was dropped onto the above injection molded flat plate to a height of tm while changing the weight. A falling weight test was performed on more than 10 hemispherical weights of the same weight, and 50 pieces cracked and 5
The falling weight impact strength is calculated by multiplying the weight (chest) of the hemispherical weight when 0% does not break by the height (1771).

[Production method of treated filler]

Production Example 1 100 parts by weight of calcium bicarbonate with an average particle size of 3 microns was placed in a Henschel mixer, stirred, and then mixed with epoxy resin (bisphenol A type, epoxy equivalent: 300) 1.
0 parts by weight of acrylic acid and 0.1 parts by weight of diethylenetriamine (hereinafter referred to as DETA) dissolved in thinner were sprayed. After the spraying was completed, the mixture was heated to about 140° C. while stirring to completely volatilize the thinner, and the epoxy resin and acrylic acid were reacted to obtain treated filler A.

Production Example 2 A treated filler Cf was obtained in the same manner as Production Example 1 except that DETA in Production Example IK was not used.

Production Example 3 100 parts by weight of the calcium carbonate used in Production Example 1 was placed in a Henschel mixer, and while stirring, Production Example I was added.
1.0 parts by weight of epoxy resin and DETA
A solution of 1 part by weight of O in thinner was sprayed. After the spraying was completed, the mixture was heated to about 80° C. while stirring to completely volatilize the thinner and obtain a treated filler. Further, 100 parts by weight of this treated filler was placed in a Henschel mixer, and 1.0 parts by weight of acrylic acid was sprayed thereon while stirring. After the spraying was completed, the mixture was heated to about 140°C to react the acrylic acid and the epoxy resin to obtain a treated filler.

Production Example 4 1.0 parts by weight of the epoxy resin in Production Example 1, DETA
A treated filler E was obtained in the same manner as in Production Example 1 except that 1 part by weight of O was used and acrylic acid was not used.

Production Example 5 A treated filler F was obtained in the same manner as in Production Example 4, except that parts by weight of acrylic acid were used for the epoxy resin and DETA.

Production Example 6 A treated filler G was obtained in the same manner as in Production Example 3 except that 1.0 parts by weight of maleic anhydride was used instead of acrylic acid in Production Example 3.

Production Example 7 2.5-dimethyl-2 was added to the thinner solution in Production Example IK.
Production Example 1 except that 0.06 parts by weight of ,5 di(1-butylperoxy)hexane was dissolved and sprayed in the same manner as in Production Example 1.
Processed filler H was obtained in the same manner as in Production Example 8. A treated filler material was obtained in the same manner as in Production Example 3 except that talc (average particle size 2 microns) was used instead of calcium carbonate in Production Example 3. .

Production Example 9 A treated filler J was obtained in the same manner as in Production Example 3 except that mica (average particle size: 12 microns) was used as a base for calcium carbonate.

Production Example 10 A treated filler K was obtained in the same manner as in Production Example 3, except that sieving barium sulfate (average particle size: 4 microns) was used instead of the calcium carbonate used in Production Example 3.

Examples 1 to 4, Comparative Examples 1 to 3 Crystalline ethylene-propylene block copolymer (ethylene content 3%, FIIIFI 1.5 y/1o mix
) 50 parts by weight of various fillers shown in Table 1, and 2,5-dimethyl-2,5-di(t-butyl)-
0.03 parts by weight of oxy)hexane was melt-kneaded with the composition shown in Table 1 at a temperature of 230°C in a non-bury mixer to obtain a polyolefin resin composition.These compositions were tested by injection molding. Table 1 shows the pieces of dried fruit that were prepared and evaluated.

Example 5 50 parts by weight of the crystalline ethylene-propylene block copolymer of Example 1 and 50 parts by weight of treated filler H were melt-kneaded at 260°C to obtain a polyolefin resin composition. The evaluation results for this composition are shown in Table 1. Example 6, Comparative Example, Treated Filler It or Treated Filler I as filler.

40 parts by weight of talc, crystalline polypropylene (M
A polyolefin resin composition was obtained in the same manner as in Example 1 using 60 parts of FI (3.3 t/io s*).

Table 2 shows the evaluation results for these compositions.

Example 7, Comparative Example 5 In the same manner as in Example 1, using treated filler J or 30 parts by weight of mica used in treated filler J and 70 parts by weight of crystalline polypropylene used in Example 6 as fillers. Table 2 shows the evaluation results for these polyolefin resin compositions.

Example 8, Comparative Example 6 Example using treated filler K as a filler or 30 parts by weight of barium sulfate used as a treated filler and 70 parts by weight of the crystalline ethylene-propylene copolymer used in Example 1. 1
A polyolefin resin composition was obtained in the same manner as above. The evaluation results for these are shown in Table 2.

Example 9, Comparative Example 7 High density polyethylene (density 0.96 y/cx, MI
13t/1o = )so parts by weight, 50 parts by weight of treated filler A or the same calcium carbonate as used in Production Example 1 and 2,5-dimethyl-2,5di(t-
Butylperoxy)hexane o, o3! (Part i was melt-kneaded in the same manner as in Example 1 to obtain a polyolefin 4iLJ resin composition. Table 3 shows the evaluation results for these compositions.

Margin below Table 1 Table 2 Table 3 Procedural correction! ! (spontaneous) Show 1 LI 59 March 121” Commissioner of the Patent Office Wakasugi Wainu ■、Small incident display 1981 Patent Application No. 25'249 2. Name of the invention Manufacturing method for polyolefin resin compositions 3. Person who makes corrections 4. Subject of correction “Detailed description of the invention” column in the detailed description 5. Contents of correction ! ,, 59.3121 S! .

Contents of the amendment fil In the 5th line of page 3 of the detailed text, ``uboxy resin'' is corrected to ``epoxy (b) resin.''

(3) In the 6th line of page 3, "Unsaturated when collapsing A" is corrected to "Unsaturated when filling J is unsaturated."

(4) `` rloooo'' on page 5, line 18, r1000.
I am corrected.

(5) Correct the first line of the 6th summer [ethylenic weight bond] to "ethylenic double bond."

(6) Page 8, line 11, “/l jujube], waste paper” was replaced with “wood flour,
"Used paper," he corrected.

that's all

Claims (1)

[Claims] (I) 20 to 90 parts by weight of polyolefin resin and (I[)
A treated filler made by attaching (4) an epoxy resin (B) a treatment substance consisting of an organic compound containing a functional group that has bonding properties with the epoxy resin and an ethylenic double bond in its molecule to an inorganic or organic filler. 10-80
A method for producing a polyolefin resin composition, characterized by bath melting and mixing parts by weight.