JPH0725852B2 - Modified polyolefin resin composition - Google Patents

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a modified polyolefin resin that does not emit an odor during modification and has excellent adhesion to fillers, metals, and polymer resin substrates, and a thermoplastic resin composition that comprises the modified polyolefin resin and a thermoplastic resin and has good mechanical properties.

[Background technology]

Generally, polyolefin resins have excellent physical and chemical properties and are widely used as fibers, films, and other molding materials.
Reinforcement has been achieved using fillers such as glass fiber. However, because polyolefin resins lack reactive functional groups, they have poor adhesion to glass fiber, resulting in low reinforcing effects. To overcome this drawback, it has been proposed to use so-called modified polyolefin resins in which modifiers such as unsaturated carboxylic acids, glycidyl methacrylate (hereinafter abbreviated as GMA), or epoxy-containing vinyl monomers such as allyl glycidyl ether are copolymerized with olefins or grafted onto polyolefin resins (see, for example, JP 59-62613 A).

These methods form strong chemical bonds between carboxyl or epoxy groups and glass fibers, resulting in excellent adhesion between the modified polyolefin resin and the glass fibers. Systems using these modified polyolefin resins show improved glass fiber reinforcement. However, modification using unsaturated carboxylic acids can cause corrosion of metals, such as the extruder screw, during the manufacturing process. Furthermore, epoxy-containing vinyl monomers generally have low boiling points, which can lead to the generation of unpleasant odors at high temperatures during extrusion, making them difficult to work with.

Furthermore, because polyolefin resins are excellent in impact resistance, chemical resistance, low cost, etc., blends with polyester resins, polyphenylene sulfide resins, polycarbonate resins, and polyamide resins have been investigated. However, since polyolefin resins are inherently poorly compatible with these resins, the Izod impact strength, tensile strength, elongation, etc. are significantly reduced, making them far from practical use.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a graft-modified polyolefin resin which does not emit odors during modification and has excellent adhesion to fillers, metals and synthetic resin substrates.

Another object of the present invention is to provide a thermoplastic resin composition comprising a graft-modified polyolefin resin and another thermoplastic resin, which has excellent mechanical properties, particularly Izod impact strength, tensile strength, and elongation.

It is still another object of the present invention to provide a graft-modified polyolefin resin composition reinforced with a filler.

In accordance with the present invention, the polyolefin resin is provided with a compound having the following general formula I: (wherein Ar represents an aromatic hydrocarbon group having 6 to 24 carbon atoms substituted with at least one glycidyloxy group; R
The present invention provides a graft-modified polyolefin resin obtained by grafting an epoxy group-containing acrylamide monomer represented by the formula:

The modified polyolefin resin can be obtained by reacting the epoxy group-containing acrylamide monomer of the formula I with a polyolefin resin in the presence of a radical generator.

According to another aspect of the present invention, there is provided a thermoplastic resin composition comprising 5 to 95% by weight of the above modified polyolefin resin and 95 to 5% by weight of another thermoplastic resin.

According to yet another aspect of the present invention, there is provided a filler-reinforced polyolefin resin composition comprising 100 parts by weight of the above graft-modified polyolefin resin (hereinafter referred to as modified polyolefin resin) and 3 to 300 parts by weight of an inorganic or organic filler.

BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the polyolefin resins used in the present invention include polypropylene, polyethylene, propylene-ethylene block or random copolymers, ethylene-propylene elastomers, ethylene-propylene-diene elastomers, ethylene-propylene-dicyclopentadiene copolymers, ethylene-propylene-ethylidenenorbornene copolymers, poly(4-methyl-pentene-
1) and the like. In addition, the above resins may be used in combination.

The epoxy group-containing acrylamide monomer of the general formula I used as a modifier in the present invention can be prepared as disclosed in U.S. Pat. No. 4,709,066.
As disclosed in the specification of No. 2, for example, an aromatic hydrocarbon having at least one phenolic hydroxyl group,
N-methylolacrylamide, N-methylolmethacrylamide, an alkyl ether derivative of N-methylolacrylamide, or an alkyl ether derivative of N-methylolmethacrylamide is condensed in the presence of an acid catalyst, followed by
Specific examples of epoxy group-containing acrylamide monomers include N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide, N-
Examples thereof include [4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]methacrylamide and N-[4-(2,3-epoxypropoxy)-3-methylbenzyl]acrylamide.

As the radical generator, a compound known as a radical polymerization initiator is used, and specific examples thereof include t-butyl peroxybenzoate, dicumyl peroxide,
Examples of such organic peroxides include organic peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexene-3, azobisnitrile compounds such as azobisisobutyronitrile and azobisisovaleronitrile, and organic peroxides such as benzoin peroxide.

The modified polyolefin resin is produced using 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, of the epoxy group-containing acrylamide monomer of formula I and 0.005 to 5 parts by weight, preferably 0.01 to 1 part by weight, of a radical generator, per 100 parts by weight of polyolefin.

There are no particular limitations on the production method, and known methods can be used. For example, a mixture of an acrylamide monomer, a radical generator, and a polyolefin resin in an organic solvent can be reacted at the decomposition temperature of the radical generator while stirring.

Alternatively, these raw materials may be uniformly mixed using a high-speed mixer, and then melt-kneaded in a single-screw or multi-screw extruder having sufficient kneading capacity to carry out the reaction.

The reaction temperature is preferably 150 to 250° C. and the reaction time is preferably 0.5 to 30 minutes. From the viewpoint of economy, the production of modified polyolefin resins using an extruder is preferred.

The modified polyolefin resin of the present invention may be used in the form of a composition containing an unmodified polyolefin resin. The content of the unmodified polyolefin resin is 0 to 95% by weight, preferably 0 to 95% by weight.
80% by weight.

The preferred composition of the components of the filler-reinforced polyolefin resin composition of the present invention is 3 to 300 parts by weight, preferably 5 to 200 parts by weight, of filler per 100 parts by weight of the modified polyolefin resin and the resin composition comprising said modified polyolefin resin and polyolefin resin. If the amount of filler added is less than the above range, a sufficient effect of improving physical properties cannot be obtained, while if the amount is more than this range, discoloration of the resin and a decrease in impact strength occur, which is undesirable.

The filler used in the present invention is iron, aluminum,
Metals such as copper, lead, zinc, tin, and nickel, and alloys containing these as their main components (e.g., stainless steel,
In addition to metallic materials such as brass and various metal oxides, inorganic or organic materials include glass, carbon fiber, carbon black, silicon carbide fiber, carbon whiskers, asbestos, graphite, magnesium carbonate, calcium carbonate, clay, mica, talc, silica, barium sulfate, alumina, inorganic pigments, wood flour, pulp, and polyester fiber.

There are no particular limitations on the method for producing the filler-reinforced polyolefin resin composition of the present invention, and any commonly known method can be used. For example, the filler-reinforced polyolefin resin composition can be produced by uniformly mixing a polyolefin resin, an epoxy group-containing acrylamide monomer, a radical generator, and a filler using a high-speed mixer or the like, and then melt-kneading the mixture in a single-screw or multi-screw extruder with sufficient kneading capacity.

In this case, a method in which the polyolefin resin, the epoxy group-containing acrylamide monomer, the radical generator, and the filler are melt-kneaded simultaneously, a method in which only the filler is added later, or a method in which the filler is coated with a molten composition of the polyolefin resin, the epoxy group-containing acrylamide monomer, and the radical generator can be employed.

5 to 95 parts by weight of the modified polyolefin resin of the present invention,
In the thermoplastic resin composition preferably comprising 10 to 90 parts by weight of the hydroxybenzoate and 95 to 5 parts by weight, preferably 90 to 10 parts by weight of another thermoplastic resin, examples of the other thermoplastic resin include polyester resin, polyphenylene sulfide resin, polycarbonate resin, polyamide resin, polyacetal resin,
Polyphenylene oxide resin, polyarylate resin,
Polysulfone resins and the like.

The polyester resin is preferably a polymer or copolymer obtained by a condensation reaction of an aromatic dicarboxylic acid and a diol, which are polyesters having aromatic rings in their chain units. Examples of such polyester resins include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalate, and polybutylene terephthalate elastomers, such as Hytrel, a product name of DuPont-Toray Co., Ltd.

Polyphenylene sulfide resin (hereinafter referred to as PPS) is a cross-linked PPS that requires cross-linking after polymerization to achieve a high molecular weight.
Commercially available cross-linked PPS includes "Ryton P-6" (manufactured by Philips Petroleum), and linear PPS includes "FORTR
ON W-205" (manufactured by Kureha Chemical Industry Co., Ltd.)

Polycarbonate resins are prepared by reacting dihydric phenols with carbonate precursors such as phosgene, halogen formates (haloformates), or carbonate esters. Homopolymers derived from bisphenol A are preferably used.

Examples of polyamide resins include nylon 6, nylon 66, nylon 46, nylon 11, and nylon 12, with nylon 6 and nylon 66 being preferred from the standpoints of heat resistance and moldability.

The thermoplastic resin composition containing the modified polyolefin resin of the present invention can also be produced by simultaneously and uniformly mixing the polyolefin resin, other thermoplastic resin, epoxy group-containing acrylamide monomer, and radical generator, followed by melt-kneading in an extruder. Depending on the purpose, various elastomers, pigments, dyes, reinforcing materials such as glass fiber, metal, and carbon fiber, fillers such as talc and calcium carbonate, antioxidants, ultraviolet absorbers, lubricants, flame retardants, antistatic agents, conductive fillers such as carbon black, etc. can also be added.

The present invention will be described in more detail below with reference to examples. The physical properties described in the examples and comparative examples were evaluated according to the following methods.

(1) Odor when modifying polyolefin resin Unpleasant odor: An unpleasant odor is generated during extrusion.

Odorless: Almost no odor is emitted during extrusion.

(2) Izod impact strength Complies with JIS-K7110.

(3) Tensile strength and elongation Complies with JIS-K7113.

(4) Peel strength: Modified polyolefin resin is heated and pressed onto a degreased soft aluminum plate (abbreviated as A1 plate), a steel plate or an ethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH) sheet to adhere it, and the coating film is peeled from one end of a 10 mm wide strip test piece using a tensile tester at a temperature of 23°C and a peel angle of 180°C.
The interlayer peel strength was measured at this time.

(5) Deflection temperature under load (heat resistance) Measured in accordance with JIS-K7207 at a bending stress of 4.6 kgf/cm ² .

(6) Flexural modulus Complies with JIS-K7113.

Examples 1 to 4 Polypropylene resin (Mitsui Noblen JS-G, manufactured by Mitsui Toatsu Chemicals Co., Ltd.), N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide (Kaneka Chemical Co., Ltd.) and dicumyl peroxide were blended in the proportions shown in Table 1 and mixed in a Henschel mixer, and then extruded into pellets in a twin-screw extruder with a screw diameter of 30 mm and L/D = 30 at a melt temperature of 200°C and a screw rotation speed of 100 rpm to obtain modified polypropylene resins. These resins were subjected to Soxhlet extraction with chloroform for 8 hours, and then
When the infrared absorption spectrum was examined, it was found to have an absorption peak (1650 cm ⁻¹ ) of a carbonyl derived from an amide, confirming that the above monomer had undergone radical addition to the polypropylene resin.

The obtained modified polypropylene resin and A1 plate, steel plate, and
The peel strength with the EVOH sheet was measured. The results, along with the odor during extrusion, are shown in Table 1. There was almost no odor during extrusion, and the peel strength was sufficient, indicating good adhesion.

Comparative Examples 1 to 3 were the same as in Example 1, except that no radical generator or epoxy group-containing acrylamide monomer was added. This resin was subjected to Soxhlet extrusion in chloroform for 8 hours, and then its infrared absorption spectrum was examined. The carbonyl absorption peak (1650 cm ⁻¹ ) derived from the amide disappeared, confirming that no radical addition of the monomer to the polypropylene resin had occurred.

The peel strength of the obtained polypropylene resin was measured in the same manner as in Example 1. The results are shown in Table 1. Although almost no odor was generated during extrusion, the peel strength was low and the adhesiveness was poor.

Comparative Example 4 The procedure of Example 3 was repeated except that the epoxy group-containing acrylamide monomer was changed to allylglycidyl ether (AGE). The results are shown in Table 1. An unpleasant odor was generated during extrusion, and the peel strength was also low.

Examples 5 to 8 Polyethylene resin (manufactured by Mitsui Petrochemical Co., Ltd., trade name: Hi-Zex 2200J), N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl] methacrylamide (manufactured by Kanegafuchi Chemical Co., Ltd.), and 1,3-bis-(t-butylperoxyisopropyl)benzene were extruded and pelletized in the proportions shown in Table 2 in the same manner as in Example 1.
A modified polyethylene resin was obtained. The results of infrared absorption spectroscopy confirmed radical addition of the monomer to the polyethylene resin.

The resulting modified polyethylene resin was used to manufacture A1 plates, steel plates, and
The peel strength with EVOH was measured, and the results are shown in Table 2. There was almost no odor during extrusion, and the peel strength was also good.

Comparative Examples 5 to 7 were the same as in Example 5, except that no radical generator or epoxy group-containing acrylamide monomer was added. The results of infrared absorption spectroscopy after chloroform extraction confirmed that no addition of epoxy group-containing acrylamide monomer to polyethylene had occurred.

The resulting polyethylene resin was used to measure peel strength in the same manner as in Example 1. The results, along with the odor generated during extrusion, are shown in Table 2. Almost no odor was generated during extrusion, but the peel strength was low.

Comparative Example 8 The procedure of Example 7 was repeated except that the epoxy group-containing acrylamide monomer was changed to glycidyl methacrylate (GMA). The results are shown in Table 2. An unpleasant odor was generated during extrusion, and the peel strength was also low.

Examples 9 to 12 Polypropylene resin (trade name: Mitsui Noblen JS-G, manufactured by Mitsui Toatsu Chemicals Co., Ltd.) and N
4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide (manufactured by Kanegafuchi Chemical Co., Ltd.), dicumyl peroxide as a radical generator, and glass chopped strands having a length of 3 mm were charged and mixed in a tumbler in the proportions shown in Table 3, and then the mixture was mixed with a 30 mm screw diameter and
The mixture was extruded into pellets at a melt temperature of 240°C and a screw rotation speed of 100 rpm using a twin-screw extruder with an L/D ratio of 30. The pellets were injection molded, and the resulting test pieces were used to test their physical properties.
The results are shown in Table 3.

Comparative Examples 9 to 11 were the same as in Example 9 except that the amounts of acrylamide monomer or radical generator used were different from those specified in the present invention. The results are shown in Table 3. These were inferior in heat resistance or mechanical strength.

Comparative Example 12 The same procedure as in Example 11 was conducted except that maleic anhydride (MAH) was used instead of the acrylamide monomer. The results are shown in Table 3. Compared to the case where the acrylamide monomer was used, the physical properties were inferior and an unpleasant odor was generated during extrusion.

Examples 13 to 16: Polyethylene terephthalate (trade name J025, manufactured by Mitsui Pet Resin Co., Ltd.) was used as the polyester resin, ethylene-propylene-dicyclopentadiene elastomer resin (trade name EP86, manufactured by Japan Synthetic Rubber Co., Ltd.) was used as the polyolefin resin, and N-[4-(2,3-epoxypropyl)
[0043] Acrylamide (3,5-dimethylbenzyl) and dicumyl peroxide as a radical generator were mixed in the ratios shown in Table 4 using a Henschel mixer.
The mixture was extruded into pellets using a twin-screw extruder with a diameter of 1.5 mm and an L/D ratio of 30 mm at a melt temperature of 260°C and a screw rotation speed of 100 rpm. Test pieces were injection molded from the pellets and subjected to physical property tests, the results of which are shown in Table 4. An excellent balance of impact resistance, rigidity, and heat resistance was obtained.

Comparative Examples 13 to 15: The same as in Examples 13 to 15 except that the blending ratio of each raw material was changed as shown in Table 4.
The same test was conducted as in Example 13, and the results are shown in Table 4. The balance of impact resistance, rigidity, and heat resistance was poor, making it unsuitable for practical use.

Examples 17 to 22 Polybutylene terephthalate (manufactured by Teijin Chemicals Co., Ltd., product name TRB-H) and polybutylene terephthalate elastomer (manufactured by DuPont-Toray Co., Ltd., product name Hytrel 5557) were used as polyester resins, and propylene-ethylene block copolymer resin (manufactured by Mitsui Toatsu Chemicals Co., Ltd., product name Mitsui Noblen BJ) was used as polyolefin resin.
SG], N-[4-(2,3-epoxypropoxy)-3-methylbenzyl]acrylamide [manufactured by Kanegafuchi Chemical Co., Ltd.] as an epoxy group-containing acrylamide monomer,
After mixing 1,3-bis(t-butylperoxyisopropyl)benzene as a radical generator in a Henschel mixer, the mixture was extruded into pellets at a melt temperature of 250°C and a screw rotation speed of 100 rpm in a twin-screw extruder with a screw diameter of 30 mm and L/D = 30. Test pieces injection-molded from the pellets were used to conduct physical property tests, and the results are shown in Table 5.

Comparative Examples 16 to 19: Examples except that the blending ratio of each raw material was changed as shown in Table 5.
The same test was conducted as in Example 17, and the results are shown in Table 5. The balance of impact resistance, rigidity, and heat resistance was poor, making it unsuitable for practical use.

Examples 23 to 25 100 parts by weight of polypropylene resin (Mitsui Noblen JS-G, manufactured by Mitsui Toatsu Chemicals Co., Ltd.), 1 part by weight of N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide (Kaneka Chemical Co., Ltd.), and 0.1 part by weight of dicumyl peroxide were mixed in a Henschel mixer, and then extruded at a melt temperature of 200°C and a screw rotation speed of 100 rpm in a twin-screw extruder with a screw diameter of 30 mm and L/D = 30 to obtain a modified polypropylene resin. This modified polypropylene resin, the above polypropylene resin, and polybutylene terephthalate (TRB-H, manufactured by Teijin Chemicals Co., Ltd.) were mixed as shown in Table 6.
The mixture was extruded in the twin-screw extruder at a melt temperature of 250°C and a screw rotation speed of 100 rpm to give pellets. These pellets were injection molded into test pieces, which were then used to test the physical properties of the materials using the methods described above. The results are shown in Table 6. All of the materials had sufficient mechanical properties for practical use.

Comparative Examples 20 to 22 Physical property tests were carried out in the same manner as in Example 23, except that the modified polypropylene resin was not used, and the results are shown in Table 6. The mechanical properties were extremely low and the samples were not suitable for practical use.

Examples 26 to 28 100 parts by weight of polyethylene resin [manufactured by Mitsui Petrochemical Co., Ltd., trade name Mitsui Hi-Zex 2200J], N-[4-(2,3-
1 part by weight of 1,3-(epoxypropoxy)-3,5-dimethylbenzyl) methacrylamide (manufactured by Kanegafuchi Chemical Co., Ltd.),
After mixing 0.3 parts by weight of bis-(t-butylperoxyisopropyl)benzene in a Henschel mixer, the mixture was melted at a temperature of 200°C in a twin-screw extruder with a screw diameter of 30 mm and an L/D ratio of 30.
The modified polyethylene resin was extruded at 100° C. and a screw rotation speed of 100 rpm to obtain a deformed polyethylene resin.
Panlite L-1225 (manufactured by Panlite Corporation) in the proportions shown in Table 7.
The twin-screw extruder was used with a melt temperature of 250°C and a screw rotation speed of 1
The pellets were extruded at 100 rpm. Test pieces were injection molded from the pellets and the physical properties were tested using the methods described above.
The results are shown in Table 7. All of the samples have sufficient mechanical properties for practical use.

Comparative Examples 23 to 25 Physical property tests were carried out in the same manner as in Example 26, except that the modified polyethylene resin was not used. The results are shown in Table 7.
The mechanical properties are extremely poor and it is not suitable for practical use.

Examples 29 to 31: 100 parts by weight of propylene-ethylene block copolymer resin (manufactured by Mitsui Toatsu Chemicals Co., Ltd., trade name: Mitsui Noblen BEB-G), N-[4-(2,3-epoxypropoxy)-3-methylbenzyl]acrylamide (manufactured by Kanegafuchi Chemical Co., Ltd.).
After mixing 3 parts by weight of the mixture and 2 parts by weight of dicumyl peroxide in a Henschel mixer, the screw diameter was set to 30 mm and the L/D was set to 30
The melt temperature was 210°C and the screw rotation speed was 100.
The mixture was extruded at 1000 rpm into pellets to obtain a modified propylene-ethylene block copolymer resin. This modified polypropylene-ethylene block copolymer resin was mixed with polyphenylene sulfide resin (trade name FORTROM W-20, manufactured by Kureha Chemical Industry Co., Ltd.).
5] in the proportions shown in Table 8, and melted at a temperature of 310
The mixture was extruded into pellets at 100°C and a screw rotation speed of 100 rpm. Test pieces were injection molded from the pellets and subjected to the physical property tests using the methods described above. The results are shown in Table 8. The material has sufficient mechanical properties for practical use.

Comparative Examples 26 to 28 Physical property tests were carried out in the same manner as in Example 29, except that the modified propylene-ethylene block copolymer resin was not used, and the results are shown in Table 8. The mechanical properties were extremely low and the samples were not suitable for practical use.

Examples 32 to 34 100 parts by weight of polypropylene resin [manufactured by Mitsui Toatsu Chemicals Co., Ltd., trade name Mitsui Noblen BJH-G], N-[4-(2,3-
One part by weight of [epoxypropoxy]-3,5-dimethylbenzyl acrylamide [Kaneka Chemical Co., Ltd.] and 0.1 part by weight of dicumyl peroxide were mixed in a Henschel mixer and then extruded at a melt temperature of 200°C and a screw rotation speed of 100 rpm in a twin-screw extruder with a screw diameter of 30 mm and an L/D ratio of 30 to obtain a modified polypropylene resin. This modified polypropylene resin, the polypropylene resin described above, and nylon 6 resin [T-802, manufactured by Toyobo Co., Ltd.] were extruded in the twin-screw extruder at a melt temperature of 250°C and a screw rotation speed of 100 rpm in the proportions shown in Table 9 to obtain pellets. These pellets were injection molded into test specimens, which were then subjected to the physical property tests described above. The results are shown in Table 9. All specimens exhibited sufficient mechanical properties for practical use.

Comparative Examples 29 to 31 Physical property tests were carried out in the same manner as in Example 32, except that the modified polypropylene resin was not used, and the results are shown in Table 9. The mechanical properties were extremely low and the samples were not suitable for practical use.

Examples 35-37: 100 parts by weight of polypropylene resin (Mitsui Noblen JH-G, manufactured by Mitsui Toatsu Chemicals Co., Ltd.), 2 parts by weight of N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide (Kaneka Chemical Co., Ltd.), and 0.3 parts by weight of dicumyl peroxide were mixed in a Henschel mixer, and then modified polypropylene resin was obtained in the same manner as in Example 32. This modified polypropylene resin, polypropylene resin, polybutylene terephthalate (TRB-H, manufactured by Teijin Limited), and 3 mm long glass chopped strands as a filler were extruded in the proportions shown in Table 10 in a twin-screw extruder at a melt temperature of 260°C and a screw rotation speed of 100 rpm to obtain pellets. These pellets were injection-molded into test specimens, and the physical properties were tested using these specimens. The results are shown in Table 10.
10. Both have sufficient mechanical properties to withstand practical use.

Comparative Examples 30 to 32 Physical property tests were carried out in the same manner as in Example 35, except that the modified polypropylene resin was not used. The results are shown below.
10. The mechanical properties are extremely poor and it is not suitable for practical use.

Example 38 Polypropylene resin (same as in Example 1) 100 parts by weight, N
1 part by weight of 4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl!acrylamide and 0.05 part by weight of dicumyl peroxide were dry-blended in a Henschel mixer, and then a modified polypropylene resin was obtained in the same manner as in Example 23.

The epoxy group content and reaction rate of the modifier reacted with the polypropylene resin shown in Table 11 were determined as follows.

After modification, unreacted epoxy-containing acrylamide monomer, its oligomer, radical generator, and its decomposition products were removed by Soxhlet extraction with chloroform for 20 hours and washing. The epoxy group content (equivalent per 1g) was determined from the infrared absorption spectrum of the epoxy groups in the modified polyolefin resin from which the unreacted materials had been removed. Furthermore, the proportion of the modifier that actually reacted among the modifiers added as raw materials was calculated as the reaction rate (%) using the following formula:

30 parts by weight of 3 mm long glass chopped strands were added to 100 parts by weight of the modified polypropylene resin obtained above, and after mixing in a tumbler, the mixture was extruded and pelletized in the same manner as in Example 9. The pellets were injection molded, and the obtained test pieces were used for physical property tests. The results are shown in Table 11. Furthermore, a mixture of 70% by weight of the modified polypropylene resin and polybutylene terephthalate [trade name TRB-1, manufactured by Teijin Limited] was used.
The physical properties were tested in the same manner as in Example 23. The results are shown in Table 11.

Comparative Example 33: A modified polypropylene resin was obtained in the same manner as in Example 38, except that glycidyl methacrylate (GMA) was used in place of the modifying agent N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide used in Example 38 in an amount three times as much to maintain the same level of epoxy group content after modification.
Test pieces were prepared in the same manner as in the previous section and subjected to physical property tests. The results are shown in Table 11.

Comparative Example 34 In the case where no modifier was used, physical property tests were carried out in the same manner as in Example 38, and the results are shown in Table 11.

Based on the data in Table 11, instead of the modifier used in the present invention,
It can be seen that even when three times the amount of GMA was used to keep the epoxy group content after modification at the same level, the modified polypropylene resin of Comparative Example 33 emitted an unpleasant odor during extrusion, had reduced adhesive strength, and was inferior in mechanical properties.

[Industrial Applicability] The modified polyolefin resin composition of the present invention does not produce an unpleasant odor upon modification, has excellent adhesion to inorganic fillers, metals, and polymer resin substrates, and has good mechanical properties such as Izod impact strength, tensile strength, and elongation. Therefore, it can be used in the automotive field, home appliance field, industrial parts, etc., and its utility value is great.

──────────────────────────────────────────────────── Continued from the front page (31) Priority Number: Patent Application No. 207515 (32) Priority Date: August 7, 1990 (33) Priority Country: Japan (JP) (72) Inventor: Takashi Sato 2882 Iijima-cho, Sakae-ku, Yokohama, Kanagawa Prefecture Apartment 3-29, Mitsui Toatsu (72) Inventor: Minoru Takiguchi 4-5-45 Dai, Kamakura, Kanagawa Prefecture

Claims (13)

[Claims] Claim 1: A polyolefin resin containing a compound of general formula I (wherein Ar represents an aromatic hydrocarbon group having 6 to 24 carbon atoms substituted with at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group), in the presence of a radical generator. Claim 2: 0 to 95% by weight of unmodified polyolefin resin
2. The graft-modified polyolefin resin according to claim 1, wherein the graft-modified polyolefin resin contains the following: [Claim 3] A graft-modified polyolefin resin according to claim 1, wherein the polyolefin resin is selected from the group consisting of polypropylene, polyethylene, propylene-ethylene block or random copolymers, ethylene-propylene elastomers, ethylene-propylene-diene elastomers, ethylene-propylene-dicyclopentadiene copolymers, ethylene-propylene-ethylidenenorbornene copolymers, and poly(4-methyl-pentene-1). [Claim 4] A graft-modified polyolefin resin according to claim 1, wherein the epoxy group-containing acrylamide monomer is selected from the group consisting of N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]acrylamide, N-[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]methacrylamide, and N-[4-(2,3-epoxypropoxy)-3-methylbenzyl]acrylamide. 5. A polyolefin resin and a compound of general formula I (wherein Ar represents an aromatic hydrocarbon group having 6 to 24 carbon atoms substituted with at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group),
A method for producing a modified polyolefin resin, which comprises reacting in the presence of a radical generator. 6. A composition comprising 100 parts by weight of a polyolefin resin and 0.01 to 20 parts by weight of an epoxy group-containing acrylamide monomer of the above general formula I.
6. The method of claim 5, wherein 0.005 to 5 parts by weight of the radical generator are used. 7. The method of claim 5, wherein the reaction temperature is 150 to 250°C. Claim 8: Claim 5, wherein the reaction is carried out in an extruder.
The manufacturing method according to claim 1. 9. A thermoplastic resin composition comprising 5 to 95% by weight of a modified polyolefin resin obtained by reacting a polyolefin resin with an epoxy group-containing acrylamide monomer of the above general formula I in the presence of a radical generator, and 95 to 5% by weight of another thermoplastic resin. [Claim 10] A thermoplastic resin composition described in claim 8, wherein the other thermoplastic resin is selected from the group consisting of polyester resin, polyphenylene sulfide resin, polycarbonate resin, polyamide resin, polyacetal resin, polyphenylene oxide resin, polyarylate resin and polysulfone resin. 11. A filler-reinforced polyolefin resin composition comprising 100 parts by weight of a modified polyolefin resin obtained by reacting a polyolefin resin with an epoxy group-containing acrylamide monomer of the above general formula I in the presence of a radical generator, and 3 to 300 parts by weight of a filler. 12. (A) 10 to 90% by weight of a polyolefin resin, (B) 90 to 10% by weight of another thermoplastic resin, (A)
+ (B) a modified polyolefin resin composition obtained by melt-kneading 100 parts by weight of 0.01 to 20 parts by weight of an epoxy group-containing acrylamide monomer of the general formula I and 0.005 to 5 parts by weight of a radical generator. 13. A composition comprising 100 parts by weight of a polyolefin resin, 0.01 to 20 parts by weight of an epoxy group-containing acrylamide monomer of the above general formula I,
parts by weight, 0.005 to 5 parts by weight of a radical generator, and 3 parts by weight of a filler
A filler-reinforced polyolefin resin composition obtained by melt-kneading 300 parts by weight of a filler-reinforced polyolefin resin composition.