JPH07118353A - Modified polyolefin resin, its production and thermoplastic resin composition containing same - Google Patents

Abstract

PURPOSE:To obtain the modified polyolefin resin which very scarcely suffers from a change in hue and has excellent mechanical properties by mixing a specified resin with a specified modifier, a vinyl monomer and a radical initiator. CONSTITUTION:100 pts.wt. resin component comprising 90-10 pts.wt. PP resin (e.g. PP) and 10-90 pts.wt. diene copolymer (e.g. ethylene/propylene/diene copolymer) is mixed with 0.1-30 pts.wt. glycidyl-containing modifier of the formula (wherein Ar is a 6-23C aromatic hydrocarbon group having at least one glycidyl group; and R is H or CH3), 0.1-30 pts.wt. vinyl monomer (e.g. styrene) and 0.01-5 pts. wt. radical initiator [e.g. 2,5-dimethyl-2,5-di(t-butylperoxy)-hexine-3].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified polyolefin resin, a method for producing the same, and a thermoplastic resin composition containing the modified polyolefin resin and having excellent mechanical properties. More specifically, a modified polyolefin-based resin having an improved hue change before and after modification, a method for producing the same, and a thermoplastic resin composition containing the modified polyolefin-based resin and having an extremely small hue change and excellent mechanical properties Regarding things.

[0002]

2. Description of the Related Art Polyolefin resins have excellent mechanical properties, chemical properties, physical properties and moldability and are used as inexpensive plastic materials. However, since polyolefin resin is non-polar, it has poor affinity with metals, glass, polar polymer materials, etc., and it is difficult to form a composite with these materials. Among them, by introducing a functional group into polypropylene, the conventional drawback is the adhesiveness,
Graft-polymerize an unsaturated compound having maleic anhydride or a glycidyl group in the presence of an organic radical generator for the purpose of improving chemical properties such as paintability and printability, or improving compatibility with other polymers. The method is used (for example, Japanese Patent Publication No. 3-290418).

However, in these conventional methods, there is a large change in fluidity before and after graft modification of the polyolefin resin, and as a result, the physical properties of the graft modified product or the resin composition containing the same deteriorates. Have Further, the polyolefin resin before modification is colorless, whereas the modified polyolefin resin after modification usually exhibits a yellow hue, which is not preferable when the modified polyolefin is used alone as a product. Further, even when it is used as a product body by mixing with another thermoplastic resin, it is not preferable in terms of appearance to have a yellowish hue, particularly in a white or transparent thermoplastic resin.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a modified polyolefin resin having improved heat resistance, dyeability, paintability, adhesiveness, etc. without impairing the hue and mechanical properties inherent to the polyolefin resin, and the production thereof. Provided is a thermoplastic resin composition which has a very small change in hue and is excellent in mechanical properties, which is obtained by blending the method.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a polypropylene resin, a diene copolymer, a modifier having a specific glycidyl group, and a vinyl monomer. The inventors have found that a modified polypropylene resin obtained by reacting the above in the presence of a radical initiator can achieve the above object, and reached the present invention. That is, the first aspect of the present invention is (C) the following general formula (C) with respect to 100 parts by weight of a resin composed of 90 to 10 parts by weight of (A) polypropylene resin and 10 to 90 parts by weight of (B) diene copolymer. I)

[0006]

[Chemical 3]

(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). 0.1 to 30 parts by weight of modifier,
(D) 0.1 to 30 parts by weight of vinyl-based monomer, and (E)
A modified polyolefin-based resin obtained by blending 0.01 to 5 parts by weight of a radical initiator is a second aspect of the present invention. (A) At least 1% by weight of the polypropylene-based resin is in a powder form, (E) The radical initiator is preblended into the resin and uniformly dispersed, and then the remaining polypropylene resin, (B) diene copolymer, (C) glycidyl group-containing modifier and (D) vinyl monomer. A method for producing a modified polyolefin-based resin, characterized in that the monomers are mixed and melt-kneaded. The third aspect of the present invention is (F) the modified polyolefin-based resin or the first aspect of the present invention. 1 to 99% by weight of the modified polyolefin resin produced by 2 and (G) polyester resin,
A thermoplastic resin composition having excellent mechanical properties, which comprises 99 to 1% by weight of at least one kind selected from the group consisting of a polyamide resin and a polycarbonate resin, is included.

The polypropylene resin (A) of the present invention is not particularly limited, and homopolypropylene resin, polypropylene resin having an unsaturated group, other α-olefins such as ethylene and butene, and propylene random or block copolymers. A polymer is preferably used, but it is preferable that 60% or more of the repeating units of the polypropylene resin is propylene because of high rigidity, heat resistance and mechanical strength.

Examples of the (B) diene copolymer of the present invention include ethylene-propylene-non-conjugated diene rubber, ethylene-butene 1-non-conjugated diene rubber, methylmethacrylate-butadiene-styrene rubber, styrene- Examples thereof include a butadiene rubber and a styrene-butadiene-ethylene-styrene copolymer. Among these, an ethylene-propylene-non-conjugated diene copolymer is particularly preferable. As the diene component, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,3-cyclohexadiene, 1,4-
There are cyclohexadiene, methylene norbornene, ethylidene norbornene, 1,3-octadiene, 1,5-cyclooctadiene and the like, and single or a combination of two or more thereof, but ethylidene norbornene is particularly preferable.

In the present invention, (C) the following general formula (I)

[0011]

[Chemical 4]

(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). The modifier is derived from a modifier having at least one acrylamide group and one glycidyl group in the molecule. The acrylamide group includes a methacrylamide group in addition to the acrylamide group.

Such a compound is disclosed, for example, in Japanese Patent Laid-Open No. Sho 60/1985.
It can be manufactured by the method described in No. 130580. That is, the target compound is obtained by condensing an aromatic hydrocarbon having at least one phenolic hydroxyl group and N-methylolacrylamide or N-methylolmethacrylamide in the presence of an acidic catalyst, and then glycidylating the hydroxyl group with epihalohydrin. Is obtained. As the aromatic hydrocarbon having at least one phenolic hydroxyl group, a phenol compound having 6 to 23 carbon atoms is used. Specific examples of the phenol compound include phenol, cresol, xylenol, carvacrol, thymol, naphthol, resorcin, hydroquinone, pyrogallol, phenanthrol and the like. Among them, 1 having an alkyl substituent
Polyhydric phenols are preferred. For example, when 2,6-xylenol and N-methylolacrylamide are used as starting materials, the following structural formula (II)

[0014]

[Chemical 5]

A compound represented by can be obtained. When orthocresol and N-methylolacrylamide are used as starting materials, the following structural formula (III)

[0016]

[Chemical 6]

It is possible to obtain the compound represented by:

The amount of the modifier having a glycidyl group used is in the range of 0.1 to 30 parts by weight based on 100 parts by weight of the total of (A) polypropylene resin and (B) diene copolymer. . When the amount is more than this range, the original mechanical properties and fluidity of the polyolefin resin are impaired, and when the amount is less than this range, the effect of improving the dyeability, paintability and adhesiveness is poor.

Examples of the vinyl monomer (D) used in the present invention include aromatic vinyl compounds such as styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, Examples of the alkyl methacrylate having 1 to 22 carbon atoms such as vinyltoluene and vinylbenzene include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, t-butyl methacrylate, and methacrylic acid. 2-ethylhexyl acid and stearyl methacrylate are alkyl acrylates having 1 to 22 carbon atoms, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-acrylate. Butyl, 2-ethylhexyl acrylate and stearic acrylate Examples of vinyl alkyl ethers having 1 to 22 carbon atoms include vinyl methyl ether, vinyl ethyl ether, vinyl i-propyl ether, vinyl n-propyl ether, vinyl i-butyl ether, vinyl n-amyl ether, and vinyl. i-amyl ether, vinyl 2-ethylhexyl ether, vinyl octadecyl ether, etc., and the unsaturated nitrile compound includes acrylonitrile, methacrylonitrile, etc.
Examples of unsaturated amino compounds include acrylamide and methacrylamide, and examples of maleic acid di-alkyl esters include maleic acid di-n-amyl ester, maleic acid di-n-butyl ester, and maleic acid di-i-amyl ester. Maleic acid di-i-butyl ester, maleic acid dimethyl ester, maleic acid di-n-propyl ester, maleic acid di-octyl ester, maleic acid di-nonyl ester and the like are allyl alkyl ethers having 1 to 8 carbon atoms. Is allyl ethyl ether, allyl n
-Octyl ether and the like, as the diene compound, dicyclopentadiene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene,
1,5-norbonadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclohexadiene, 1,3-cyclooctadiene and the like,
Other vinyl monomers include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, vinyl acetate and the like. These are used alone or in combination of two or more.

The vinyl monomer is used in a total amount of 1 (A) polypropylene resin and (B) diene copolymer.
It is used in the range of 0.1 to 30 parts by weight with respect to 00 parts by weight. When it is more than this range, the original mechanical properties and fluidity of the polyolefin resin are impaired, and when it is less than this range, it is not sufficient to reduce the hue.

The radical initiator (E) used in the present invention is, for example, methyl ethyl ketone peroxide, 1,1-bis (t-butylperoxy) -3,3,3.
5-trimethylcyclohexane, n-butyl-4,4-
Bis (t-butylperoxy) valerate, 2,5-dimethylhexane-2,5-dihydroperoxide,
Dicumyl peroxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl- Organic peroxides such as 2,5-di (t-butylperoxy) hexyne-3 and benzoyl peroxide, or, for example, 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1
-Cyano-1-methylethyl) azo] formamide, 2
-Phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile,
Examples of the azo compound include 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-acetoxypropane), and 2,2'-azobis (2-acetoxybutane). , And these are used alone or in combination of two or more kinds.

The amount of radical initiator used is (A)
It is 0.01 to 5 parts by weight based on 100 parts by weight of the total of the polypropylene resin and the (B) diene copolymer. When the radical polymerization initiator is less than 0.01, (C) a modifier,
(D) the polymerization of vinyl monomers and (A) the formation of radical initiation points for polyolefin resins become insufficient,
On the other hand, if the amount exceeds 10 parts by weight, a crosslinking reaction by radicals of the polyolefin resin or a molecular weight reduction due to main chain scission is caused, resulting in deterioration of mechanical properties of the resin.

As the method for producing the modified polyolefin resin of the present invention, at least 1% by weight or more of the polypropylene resin (A) is in a powder form, and the radical initiator (E) is added to the powder polypropylene resin. After blending and uniformly dispersing, the remaining polypropylene resin, (B) diene copolymer, (C) glycidyl group-containing modifier and (D) vinyl monomer are mixed and melt-kneaded. Is preferably used. As a method of dispersing the radical initiator in the powdery polypropylene,
A method of simply dry blending powdery polypropylene and a radical initiator with a mixer or the like, or a wet blending method in which the radical initiator solution dissolved in an appropriate organic solvent is thoroughly blended with the powdery polypropylene and then the organic solvent is distilled off. Law etc. are mentioned. As the kneading device, an extruder, a Banbury mixer, a mill, a kneader, a heating roll or the like can be used, and a method using a single-screw or twin-screw extruder is particularly preferable because of high productivity.

Further, if necessary, the modified polyolefin resin of the present invention may contain stabilizers, antioxidants, flame retardants, ultraviolet absorbers, antistatic agents, nucleating agents, inorganic and organic reinforcing agents, fillers and the like. You may add it.

Since the modified polyolefin resin obtained as described above has improved affinity with other resins, it is generally a thermoplastic or thermosetting resin instead of a polyolefin resin which is difficult to be blended / alloyed. It is possible to provide a resin composition which is blended with the resin composition and has a better balance of mechanical properties. As such a resin, a polyester resin, a polyamide resin, and a polycarbonate resin are particularly preferable, and the mixing ratio thereof is modified polyolefin resin 1 to 99.
At least one kind selected from the group consisting of polyester resins, polyamide resins and polycarbonate resins is 99 to 1% by weight based on the weight%.

The polyester resin used in the present invention is a polymer or copolymer obtained by a condensation reaction containing an aromatic dicarboxylic acid or its ester-forming derivative and a diol or its ester derivative as main components, or a lactone. Is a ring-opening polymer. Examples of the aromatic dicarboxylic acid as used herein include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenylcarboxylic acid, 4 ，
4'-diphenyl ether dicarboxylic acid, an ester-forming derivative thereof, a mixture thereof, or the like. The diol component is C _{2 to} C ₁₀
Aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octadiol, cyclohexanediol, etc. Or a long-chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-
1,3-polypropylene glycol, polytetramethylene glycol, etc., and mixtures thereof can be mentioned.

Specific examples of the polyester resin of the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-1,2-bis (phenoxy) ethane-. 4,4'-dicarboxylate and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

The polyamide resin used in the present invention is usually called "nylon" and has an acid amide bond (-CONH).
Any compound having (-) as a repeating unit can be used without particular limitation. Depending on the type of polymerization reaction, (1) reaction by ring-opening polymerization of lactam, (2) reaction of aliphatic diamine with at least one compound selected from aliphatic carboxylic acid, acid anhydride thereof and acid halide thereof. Due to the
(3) Examples thereof include those obtained by polycondensation of aminocarboxylic acids. Specific examples include polycaprolactam (nylon-6), polyhexamethylene adipamide (nylon-).
66), nylon 610, nylon-12, nylon-
9, nylon-11 and the like. Further, it may be a copolymer of two or more kinds, or a mixture of two or more kinds.

The polycarbonate resin used in the present invention generally comprises divalent phenols as a carbonate precursor,
For example, it is produced by reacting with phosgene, halogen formate (haloformate) or carbonate ester. In the present invention, a homopolymer derived from bisphenol A is preferably used.

[0030]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

(Synthesis of Denaturing Agent) Reference Example A mixture of 102.6 parts of 4-acrylamidomethyl-2,6-dimethylphenol, 181 parts of epichlorohydrin and 2.27 parts of benzyltriethylammonium chloride was stirred at 100 ° C. for 30 minutes. The reaction mixture was cooled to room temperature, 147 parts of 5N sodium hydroxide was added dropwise with stirring for 10 minutes, and then the mixture was stirred at 45 to 50 ° C for 1 hour. The obtained reaction mixture was cooled to room temperature, 120 parts of methyl isobutyl ketone and 500 parts of water were added, and the layers were separated. The organic layer was washed with 300 parts of water three times and dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain N-[(2,
3-Epoxypropoxy) -3,5-dimethylphenylmethyl] acrylamide was obtained. The epoxy equivalent measured by the method of JIS K 7236 is 271, and the melting point is 90-9.
It was 2 ° C.

(Production of Modified Polyolefin Resin) Example 1 Powdered Polypropylene (J manufactured by Mitsui Petrochemical Co., Ltd.)
300P) to 9 parts of radical initiator [2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 manufactured by NOF Corporation] 0.07 part of a radical dissolved in 5 parts of chloroform. After adding the initiator solution and thoroughly stirring and mixing, it was dried at 30 ° C. under reduced pressure for 15 hours and chloroform was distilled off to obtain a blend of powdery polypropylene and a radical initiator. To this, 5 parts of the modifier obtained in Reference Example and 5 parts of styrene were added and mixed, and then 36 parts of propylene-ethylene copolymer (BJ500 manufactured by Tonen Corporation) and ethylene-propylene-diene copolymer (JSR Corporation). Manufactured by EP181SP) and mixed with 20 parts of 20 parts
Twin screw extruder set at 0 ° C (TEX44 manufactured by Japan Steel Works)
Is supplied at a speed of 15 kg per hour, and the screw rotation speed is 100
Melt kneading at rpm. The extrudate was cooled with water to be pelletized, and then dried under reduced pressure at 50 ° C. for 12 hours to obtain a modified polyolefin resin. The dried pellets thus obtained were dissolved in chlorobenzene heated to 100 ° C., and the chlorobenzene solution was added dropwise to acetone to reprecipitate the modified resin, whereby the unmodified modifier contained in the modified resin, styrene and the modifier. The styrene homopolymer and the copolymer of styrene and the modifier were removed. After the reprecipitation, the epoxy equivalent of the modified resin was determined from the analysis value of the epoxy group by titration of the modified resin.

Example 2 Synthesis was performed in the same manner as in Example 1 except that n-butyl acrylate was used instead of styrene.

Example 3 Synthesis was performed in the same manner as in Example 1 except that styrene was changed to methyl methacrylate.

Example 4 Synthesis was performed in the same manner as in Example 1 except that styrene was changed to octadecyl ether in Example 1.

Example 5 Synthesis was performed in the same manner as in Example 1 except that styrene was changed to allyl ethyl ether.

Example 6 Synthesis was performed in the same manner as in Example 1 except that styrene was changed to maleic acid.

Example 7 Synthesis was carried out in the same manner as in Example 1 except that styrene was changed to acrylamide.

Example 8 Synthesis was performed in the same manner as in Example 1 except that styrene was changed to acrylonitrile.

Example 9 Synthesis was performed in the same manner as in Example 1 except that styrene was changed to vinyl acetate.

Example 10 Synthesis was performed in the same manner as in Example 1 except that styrene was changed to dicyclopentadiene.

Comparative Example 1 Synthesis was carried out in the same manner as in Example 1 except that styrene was not used and the modifier was changed to 10 parts.

Comparative Example 2 Synthesis was carried out in the same manner as in Example 1 except that the modifier and styrene were not used.

(Evaluation of Modified Polyolefin Resin) Evaluation of Grafting Efficiency: Based on the epoxy equivalents of the modified polyolefin resins obtained in Examples 1 to 9 and Comparative Example 1, the grafting amount (wt%) of the modifier to the polyolefin resin.
Was calculated, and the grafting efficiency of the modifier was calculated by taking the ratio of the grafted amount of the modifier and the blending amount (wt%) of the modifier based on the following formula. The results are shown in Table 1. Grafting efficiency (%) = (amount of grafted modifier / amount of modifier blended) × 100 For the vinyl-based monomer, the modified polyolefin after reprecipitation of the modified polyolefin obtained in Examples 1 to 9 was used.
Using a compression molding machine (manufactured by Shindo Metal Industry Co., Ltd.), a film having a thickness of about 20 μm was formed. The grafting efficiency of the polymer was calculated. The results are shown in Table 1. Evaluation of coloring degree: The yellowing degree (YI) of the dried pellets was measured according to JIS K7103, and the coloring degree was evaluated by Comparative Example 2.
The difference (ΔYI) in the degree of yellowing with the pellets prepared in Step 1 was determined. As a measuring device, a color difference meter Z-Σ manufactured by Nippon Denshoku Industries Co., Ltd.
80 was used. The results are shown in Table 1. Evaluation of tensile properties: The modified polyolefin-based resin or the polyolefin-based resin obtained in Examples 1 to 9 and Comparative Examples 1 and 2 had a cylinder temperature of 230 to 240 ° C and a mold temperature of 50.
Injection molding machine set to ℃ (IS80EP manufactured by Toshiba Corporation
N-2A) was injection molded, and the tensile elongation at break at 23 ° C. was evaluated according to the method specified in ASTM D638. The results are shown in Table 1. Evaluation of Izod impact strength: An injection molding machine in which the modified polyolefin resin obtained in Examples 1 to 9 and Comparative Examples 1 and 2 was set to a cylinder temperature of 230 to 240 ° C and a mold temperature of 50 ° C (Toshiba stock Company-made IS80EPN-2
After injection molding according to A), the Izod impact strength with V-notch at 23 ° C. was evaluated according to the method specified in ASTM D256. The results are shown in Table 1.

[0045]

[Table 1]

(Production of Thermoplastic Resin Composition) Examples 11 to 20 and Comparative Examples 3, 4, 5 With respect to 75 parts of polybutylene terephthalate resin (S2002 manufactured by Polyplastics Co., Ltd.), the above Examples 1 to
10 and the modified polyolefin resins and polyolefin resins (A-1 to A-10 and a-) obtained in Comparative Examples 1 and 2.
1, a-2) 25 parts and 0.075 parts of tetrabutylphosphonium bromide (TBPB) [manufactured by Aldrich Chemical Company] as a catalyst were mixed, and then the mixture was set to 240 ° C. The mixture was fed to a twin-screw extruder (TEX44 manufactured by Japan Steel Works) at a rate of 15 kg / h and melt-kneaded at a screw rotation speed of 100 rpm. The extrudate was cooled with water and pelletized, and then dried under reduced pressure at 120 ° C. for 12 hours to obtain a resin composition. The obtained resin composition (Examples 11 to 20,
With respect to Comparative Examples 3 and 4) and the polybutylene terephthalate resin alone (Comparative Example 5), the physical properties described below were evaluated.

Examples 21 to 30 and Comparative Examples 6, 7, and 8 Nylon-6 resin (UBE101 manufactured by Ube Industries, Ltd.)
3) For 75 parts, Examples 1 to 10 and Comparative Example 1,
25 parts of the modified polyolefin resin and polyolefin resin (A-1 to A-10 and a-1, a-2) obtained in 2 and tetrabutylphosphonium bromide (TBPB) as a catalyst [Aldrich Chemical Company Company)], and then the mixture is supplied to a twin-screw extruder (TEX44 manufactured by Japan Steel Works) set at 250 ° C. at a speed of 15 kg / hour and melted at a screw rotation speed of 100 rpm. Kneaded
After cooling the extrudate with water and pelletizing,
A resin composition was obtained by drying under reduced pressure for an hour. The physical properties shown below were evaluated for the obtained resin compositions (Examples 21 to 30, Comparative Examples 6 and 7) and nylon-6 resin alone (Comparative Example 8).

Examples 31 to 40, Comparative Examples 9, 10 and 11 Obtained in Examples 1 to 10 and Comparative Examples 1 and 2 with respect to 75 parts of polycarbonate resin (Panlite L-1250 manufactured by Teijin Chemicals Ltd.). Modified polyolefin resin and polyolefin resin (A-1 to A-10 and a-1, a-
2) 25 parts and 0.075 tetrabutylphosphonium bromide (TBPB) [manufactured by Aldrich Chemical Company] as a catalyst.
After mixing the parts, the mixture was set to 280 ° C. 2
It was supplied to a shaft extruder (TEX44 manufactured by Japan Steel Works) at a rate of 15 kg / h, and melt-kneaded at a screw rotation speed of 100 rpm. 120 ° C. after cooling the extrudate with water and pelletizing
A resin composition was obtained by drying under reduced pressure for 12 hours.
The obtained resin composition (Examples 31 to 40, Comparative Examples 9 and 1)
0) and the polycarbonate resin alone (Comparative Example 11) were evaluated for the following physical properties.

(Evaluation of Thermoplastic Resin Composition) Evaluation of Coloring Degree: The evaluation of the coloring degree was carried out according to JIS K7103 in accordance with JIS K7103.
I) was measured and the difference in yellowing degree (ΔYI) from the pellets produced in Comparative Examples 4, 7, and 10 was determined. As a measuring device, a color difference meter Z-Σ80 manufactured by Nippon Denshoku Industries Co., Ltd. was used. The results are shown in Tables 2, 3, and 4. Evaluation of tensile properties: The resin compositions obtained in Examples 11 to 20 and Comparative Examples 3 to 5 were set to a cylinder temperature of 240 ° C and a mold temperature of 50 ° C, and Examples 21 to 30 and Comparative Example 6 were used.
Cylinder temperature of 250 ° C.,
The mold temperature was set to 60 ° C., and the resin compositions obtained in Examples 31 to 40 and Comparative Examples 9 to 11 were used at a cylinder temperature of 2
The temperature is set to 80 ° C. and the mold temperature is set to 80 ° C., injection-molded by an injection molding machine (TOSHIBA CORPORATION IS80EPN-2A), and in accordance with the method specified in ASTM D638, 2
The tensile elongation at break at 3 ° C was evaluated. The results are shown in Tables 2, 3, 4
Shown in. Evaluation of Izod impact strength: The resin compositions obtained in Examples 11 to 20 and Comparative Examples 3 to 5 were used at a cylinder temperature of 240.
C., the mold temperature is set to 50.degree. C., the resin compositions obtained in Examples 21 to 30 and Comparative Examples 6 to 8 are set to a cylinder temperature of 250.degree. C. and a mold temperature of 60.degree.
40 and the resin compositions obtained in Comparative Examples 9 to 11 were set to a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., respectively.
Injection molding was performed with an injection molding machine (IS80EPN-2A manufactured by Toshiba Corporation), and the Izod impact strength with V notch at 23 ° C was evaluated according to the method specified in ASTM D256. The results are shown in Tables 2, 3, and 4.

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

As described above in detail, the modified polyolefin resin of the present invention can improve dyeability, paintability, adhesiveness, etc. without impairing the original hue of polypropylene and good mechanical properties. Is. Taking advantage of such characteristics, the modified polyolefin resin of the present invention is a fiber,
In addition to films and the like, it can be widely used for molded articles, and also widely used for structural materials such as adhesives and pressure-sensitive adhesives. Further, since the affinity with other resin components is improved, it can be used in place of the polyolefin resin, which is generally difficult to blend / alloy. In this case, it is possible to obtain a resin composition having a small change in hue of the blended product and an excellent balance of mechanical properties, and can be widely used for molded articles and structural materials.

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Claims (8)

[Claims] 1. (A) Polypropylene resin 90 to 10
With respect to 100 parts by weight of a resin composed of 10 parts by weight and (B) 10 to 90 parts by weight of a diene copolymer, (C) the following general formula (I): (In the formula, Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) A modifier having a glycidyl group 0 1 to 30 parts by weight, (D) vinyl monomer to 0.1 to 30 parts by weight, and (E) radical initiator 0.1.
Modified polyolefin resin obtained by blending 01 to 5 parts by weight. 2. The modified polyolefin resin according to claim 1, wherein 60% by weight or more of the repeating unit of the polypropylene resin (A) is propylene. 3. The repeating unit of the diene of the diene copolymer (B) is cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, methylene norbornene, ethylidene norbornene, 1,3-octadiene, 1, The modified polyolefin resin composition according to claim 1, which comprises 5-cyclooctadiene, butadiene, isoprene, chloroprene, phenylpropadiene, or a combination of two or more thereof. 4. The modified polyolefin resin according to claim 1, wherein the diene copolymer is an ethylene-propylene-non-conjugated diene copolymer. 5. A structural unit having a glycidyl group (C) has the following formula (II): The modified polyolefin resin according to claim 1, which is represented by: 6. The vinyl monomer (D) is an aromatic vinyl compound, a methacrylic acid alkyl ester having an alkyl group having 1 to 22 carbon atoms, and an alkyl group having 1 to 22 carbon atoms.
An acrylic acid alkyl ester, a vinyl alkyl ether having an alkyl group having 1 to 22 carbon atoms, an unsaturated nitrile compound, an unsaturated amino compound, a maleic acid dialkyl ester having an alkyl group having 1 to 9 carbon atoms, an alkyl group 6. The modification according to claim 1, which is at least one selected from the group consisting of an allylalkyl ether having 1 to 8 carbon atoms, a diene compound, maleic anhydride, maleic acid, acrylic acid, methacrylic acid, and vinyl acetate. Polyolefin resin. 7. At least 1% by weight of the (A) polypropylene-based resin is in powder form, and (E) the radical initiator is preblended into the polypropylene-based resin in a powder form and uniformly dispersed, and then the remaining polypropylene-based resin is used. resin,
A method for producing a modified polyolefin resin, which comprises mixing (B) a diene-based copolymer, (C) a modifier having a glycidyl group, and (D) a vinyl-based monomer and melt-kneading the mixture. 8. (F) 1 to 99% by weight of the modified polyolefin resin according to claim 1 or the modified polyolefin resin produced according to claim 7, and (G) a polyester resin, a polyamide resin and a polycarbonate resin. A thermoplastic resin composition having excellent mechanical properties, which comprises at least 99% by weight of at least one selected from the group.