JPH09157335A - Graft modified polyolefin resin and thermoplastic resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a graft modified polyolefin resin which gives a resin compsn. improved in flowability, weld characteristics, impact resistance, etc., and obtain a resin compsn. contg. the same. SOLUTION: This graft modified polyolefin resin is produced by polymerizing a water-base suspension which contains 100 pts.wt. polyolefin resin having a mol.wt. distribution defined by the ratio (Mw/Mn) of wt. average mol.wt. (Mw) to number average mol.wt. (Mn) of 1.5-2.5, 0.1-30 pts.wt. glycidyl component comprising a compd. represented by the formula (wherein Ar is a 6-23C arom. hydrocarbon group having at least one glycidyloxy group; and R is H or methyl) and/or an unsatd. glycidyl ester, 0.1-500 pts.wt. vinyl monomer, and a free-radical polymen. initiator.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a graft-modified polyolefin resin and a thermoplastic resin composition containing the same. More specifically, the present invention relates to a resin composition having improved fluidity, weld characteristics, impact resistance, etc., which can be suitably used for automobile parts, home electric appliance parts, industrial parts, sports equipment, furniture and the like.

[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. Among these, an olefin elastomer, for example, an ethylene-propylene copolymer or an ethylene-propylene-non-conjugated diene copolymer is blended with a thermoplastic resin such as a polyester resin, a polyamide resin or a polycarbonate resin to reduce the weight of the resin. Attempts have been made to improve mechanical properties such as impact resistance and impact properties. However, non-polar olefin elastomers have poor compatibility with these thermoplastic resins, so even if they are simply blended, they are not uniformly dispersed, and on the contrary, mechanical properties such as rigidity and impact resistance deteriorate,
A composition having the intended physical properties cannot be obtained. Further, there is a drawback that the weld characteristics are significantly impaired due to the decrease in interfacial adhesion strength.

Therefore, as a method for improving the compatibility between the thermoplastic resin and the olefin-based elastomer, Japanese Patent Laid-Open No. 5-2 / 1992 has been proposed.
No. 87138, a method of blending an olefinic elastomer modified with an unsaturated glycidyl compound and a polyester resin is disclosed in JP-A-1-144445 and JP-A-2-14445.
No. 160812 and JP-A No. 2-160813 disclose that
A method of blending an ethylene-propylene-non-conjugated diene copolymer modified with glycidyl methacrylate and a polyester resin has been proposed. However, although the impact resistance and the like can be improved by these methods, the weld characteristics are not always sufficient, and further improvement is desired. Further, the above-mentioned olefin-based elastomer does not have good fluidity, and further, since it is modified with a glycidyl compound having reactivity with a polyester-based resin or the like, the fluidity of the resin composition is deteriorated although the compatibility is improved. There is a problem that it will occur, and improvement is required.

On the other hand, polar olefin elastomers such as ethylene-vinyl acetate copolymer and ethylene-
Ethyl acrylate copolymer has a relatively good compatibility with a polar thermoplastic resin, but because of the large specific gravity of these ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer, Under the present circumstances, it has hardly contributed to the weight reduction of the thermoplastic resin. Further, since the above-mentioned copolymer has a high glass transition temperature (Tg), there is a problem that impact resistance at low temperature cannot be improved.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a graft-modified polyolefin resin obtained by adding a compound having a specific glycidyl group and a vinyl monomer to a specific polyolefin resin, and a thermoplastic resin and the graft modified polyolefin resin. The present invention provides a lightweight thermoplastic resin composition having a good balance of fluidity, weld characteristics, and impact resistance.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific polyolefin-based resin contains a modifier having a specific glycidyl group and a vinyl-based monomer as radicals. The inventors have found that a graft-modified polyolefin resin obtained by reacting in the presence of a polymerization initiator can achieve the above object, and have reached the present invention.

That is, the first aspect of the present invention is that the molecular weight distribution (Mw / Mn) represented by the ratio of (a-1) weight average molecular weight (Mw) to number average molecular weight (Mn) is 1.5 to 2. 100 parts by weight of a polyolefin resin in the range of (5), (a-2) the following general formula (I)

[0008]

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(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group bonded to at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). (A-2a) and / or unsaturated glycidyl ester (a-2b) of 0.1 to 30 parts by weight, (a-3) vinyl monomer of 0.1 to 500 parts by weight, and (a- 4) The radical polymerization initiator is added to the above (a-
An aqueous suspension containing 0.001 to 10 parts by weight per 100 parts by weight of the total amount of the component 2) and the component (a-3) was prepared, and (a-2) general in the aqueous suspension was prepared. The compound (a-2a) having a glycidyl group represented by the formula (I) and / or the unsaturated glycidyl ester (a-2b) and the vinyl monomer (a-3) are added to the above (a-1) polyolefin-based monomer. The resin is impregnated with the compound (a-2) having a glycidyl group represented by the general formula (I) (a-2a) and / or an unsaturated glycidyl ester (a-2b) and (a-3) vinyl type. It comprises a graft-modified polyolefin resin obtained by polymerizing the above-mentioned (a-1) polyolefin resin with a monomer.

A second aspect of the present invention is to use at least one thermoplastic resin selected from the group consisting of (A) 1 to 99% by weight of graft-modified polyolefin resin and (B) polyester resin, polyamide resin and polycarbonate resin. The content of the thermoplastic resin composition is 99 to 1% by weight.

The third aspect of the present invention is the second aspect of the present invention.
(D) 100 parts by weight of the thermoplastic resin composition,
(C) A thermoplastic resin composition containing 1 to 100 parts by weight of an unmodified polyolefin-based resin.

Still further, a fourth aspect of the present invention is, relative to 100 parts by weight of the above-mentioned first (A) graft-modified polyolefin resin and the second or third (D) thermoplastic resin composition of the present invention, The content of the thermoplastic resin composition is 1 to 100 parts by weight of a filler.

The polyolefin resin (a-1) used in the present invention has a molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of 1.5 to 2 It is in the range of 1.5, preferably 1.7.
The range is from to 2.3. If the amount is out of the above range, the fluidity and molding processability will be deteriorated, and the balance of mechanical properties will be deteriorated. This molecular weight distribution can be determined, for example, by the usual gel permeation chromatography method (GP
C) can be measured directly, or ASTM D-1
190 ° C./10 kgf as described in 238.
And the melt flow ratio (I ₁₀₎ which is the ratio of each melt index under the conditions of 190 ° C./2.16 kgf.
It can also be determined by measuring / I ₂ ).

It is preferable that the polyolefin resin (a-1) has a molecular weight distribution (Mw / Mn) of 1.5 to.
2.5 and the melt flow ratio (I ₁₀ /
I ₂ ) is 5.63 or more, more preferably 7.0 or more, and particularly preferably 8.0 or more. When the I ₁₀ / I ₂ value is smaller than the above range, the shear sensitivity becomes low, which may cause problems in molding and processability. As described above, the polyolefin resin (a-1) used in the present invention is characterized by having a narrow molecular weight distribution and high shear sensitivity, and as a result, has good fluidity, molding / workability, and thermoplasticity. A graft-modified polyolefin resin having good dispersibility in the resin can be obtained.

The monomer constituting the polyolefin resin (a-1) of the present invention is α-having 2 to 20 carbon atoms.
Olefins such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1
-Nonene, 1-decene, 1-undecene, 1-tridecene, 1-tetradecene, 3-methyl-1-butene and the like can be mentioned, and these can be used alone or in combination of two or more kinds. Examples of the ethylenically unsaturated monomer copolymerizable with the α-olefin include dienes, ethylenically unsaturated nitrile compounds, unsaturated aliphatic and aromatic vinyl compounds. A preferred combination of these monomers is ethylene and α having 3 to 10 carbon atoms.
-A copolymer with an olefin, more preferably ethylene and at least one α-olefin selected from the group consisting of 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. Is a copolymer of.
Further, a copolymer of ethylene and 1-octene is most preferable from the viewpoints of fluidity, moldability and weld characteristics of the resin composition. Polyolefin resins having the above-mentioned characteristics are disclosed, for example, in JP-A-4-279592 and JP-A-Hei-7-.
-500622, U.S. Pat. Nos. 5,194,532 and 531.
It can be produced by the catalyst and production method described in No. 2938. Specific examples of the (a-1) polyolefin resin having the above properties used in the present invention include ethylene-octene copolymers (trade names EG8100, EG8150, EG8200, etc.) commercially available from Dow Chemical Company. These can be used alone or in combination of two or more.

The compound (a-2) having a glycidyl group for modifying the polyolefin resin (a-1) is an important constituent element of the present invention and has the following general formula (I).

[0017]

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A glycidyl group represented by the formula (wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group bonded to at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). Having a compound (a-2a), the compound (a-2a) and an unsaturated glycidyl ester (a-2b)
Or a mixture of unsaturated glycidyl ester (a-2
b) is preferably used.

The compound (a-2a) having a glycidyl group represented by the general formula (I) is derived from a compound having at least one acrylamide group and glycidyl group in the molecule. The acrylamide group includes a methacrylamide group in addition to the acrylamide group. The compound (a-2a) having a glycidyl group, which is one of the components (a-2), can be produced, for example, by the method described in JP-A-60-130580. That is, an aromatic hydrocarbon having at least one phenolic hydroxyl group and N-methylol acrylamide or N
-The target compound is obtained by condensing methylol methacrylamide in the presence of an acidic catalyst and then glycidylating the hydroxyl group with epihalohydrin. 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, monohydric phenols having an alkyl substituent are preferred.

For example, when 2,6-xylenol and N-methylolacrylamide are used as starting materials, the following structural formula (II)

[0021]

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

[0023]

[Chemical 6]

The compound represented by can be obtained. Among these, the compound represented by the structural formula (II) is particularly preferably used.

As the unsaturated glycidyl ester (a-2b) which is another component (a-2) used in the present invention, glycidyl acrylate, glycidyl methacrylate, mono- and diglycidyl esters of itaconic acid,
Mono-, di- and triglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endo-cis-bicyclo (2,2,1) hept-
Mono- and diglycidyl esters of 5-ene-2,3-dicarboxylic acid, endo-cis-bicyclo (2,2,1)
Examples thereof include mono- and diglycidyl esters of hept-5-ene-2-methyl-2,3-dicarboxylic acid, mono- and diglycidyl esters of allyl succinic acid, glycidyl esters of p-styrenecarboxylic acid, and the like. Used in combination of two or more species. Among these, glycidyl methacrylate is preferable from the viewpoints of cost and impregnability with a polyolefin resin.

The amount of the compound (a-2a) represented by the general formula (I) and / or the unsaturated glycidyl ester (a-2b) which is the component (a-2) is (a-1) a polyolefin type. 0.1 to 30 parts by weight with respect to 100 parts by weight of resin,
It is preferably 0.5 to 30 parts by weight. If the amount is more than the above range, the mechanical properties of the resin composition, the flowability is deteriorated,
If the amount is small, the compatibilizing effect is poor. As the component (a-2), the compound (a-2a) having a glycidyl group represented by the general formula (I) and the unsaturated glycidyl ester (a-2)
When the mixture of b) is used, the sum of the two is 0.1 to 30 parts by weight, preferably 0.5 to 30 parts by weight. Moreover, the compounding ratio of the unsaturated glycidyl ester (a-2b) in this mixture is 0.1 to 100 parts by weight of the compound (a-2a) having a glycidyl group represented by the general formula (I). 700 parts by weight, preferably 1-500
Parts by weight, more preferably 5 to 500 parts by weight. When the amount is more than the above range, the fluidity of the resin composition is deteriorated, and when the amount is less than the above range, the balance of physical properties such as mechanical properties tends to deteriorate.

Examples of the vinyl monomer (a-3) used in the present invention include aromatic vinyl compounds such as styrene, o-methylstyrene, p-methylstyrene and m.
-Methyl styrene, α-methyl styrene, vinyltoluene, divinylbenzene and the like, as the methacrylic acid alkyl ester having 1 to 22 carbon atoms, methyl methacrylate, ethyl methacrylate, methacrylic acid-i-
Propyl, n-butyl methacrylate, methacrylic acid
t-butyl, allyl methacrylate, methacrylic acid-2-
Ethylhexyl, stearyl methacrylate, and the like are, as alkyl acrylates having 1 to 22 carbon atoms, methyl acrylate, ethyl acrylate, acrylic acid-i-propyl, acrylic acid-n-butyl, acrylic acid-t- Butyl, 2-ethylhexyl acrylate, stearyl acrylate, and the like, as the vinyl alkyl ether having 1 to 22 carbon atoms, vinyl methyl ether, vinyl ethyl ether, vinyl-n-propyl ether, vinyl-i-propyl ether. , Vinyl-i-butyl ether, vinyl-n-amyl ether, vinyl-
i-Amyl ether, vinyl-2-ethylhexyl ether, vinyl octadecyl ether and the like, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and unsaturated amino compounds such as acrylamide and methacrylamido, and maleic acid diester. Examples of the -alkyl ester include maleic acid di-n-amyl ester, maleic acid di-n-butyl ester, maleic acid di-i-amyl ester, maleic acid-i-butyl ester, maleic acid dimethyl ester and maleic acid di-ester. n-Propyl ester, maleic acid di-octyl ester, maleic acid dinonyl ester and the like, and as allyl alkyl ether having 1 to 8 carbon atoms, allyl ethyl ether, allyl-n-octyl ether and the like,
Examples of the diene compound include dicyclopentadiene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene,
1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclohexadiene, 1,3-cyclooctadiene, and the like, and other vinyl monomers include acrylic acid, methacrylic acid, maleic acid, Maleic anhydride, vinyl acetate, etc. are mentioned. These may be used alone or in combination of two or more.

Among these, the cost, the copolymerizability with the compound (a-2a) having a glycidyl group represented by the general formula (I) and / or the unsaturated glycidyl ester (a-2b), and the polyolefin resin Styrene, α-methylstyrene, butyl acrylate,
Methyl methacrylate, allyl methacrylate, vinyl acetate and acrylonitrile are preferable, and these are used alone or
Used in combination of more than one species.

(A-3) The mixing ratio of the vinyl monomer is
(A-1) 0.1 to 500 parts by weight, preferably 0.1 to 200 parts by weight, and more preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the polyolefin resin. When the amount is more than the above range, the polymerization of vinyl-based monomers becomes the main component, so that excessive aggregation, fusion bonding, agglomeration, etc. occur in the aqueous suspension during the polymerization. When the amount is less than the above range, the general formula (I) for polyolefin resin is
It becomes difficult to uniformly impregnate and graft-polymerize the compound (a-2a) having a glycidyl group represented by and / or the unsaturated glycidyl ester (a-2b).

Examples of the (a-4) lacal polymerization initiator used in the present invention include methyl ethyl ketone peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3,3. , 5-Trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,5-dimethylhexane-
2,5-dihydroperoxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2,5-di (t-
Butylperoxy) hexyne-3, organic peroxides such as 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, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-acetoxypropane), 2,2'-azobis (2- Azo compounds such as acetoxybutane) may be used, and these may be used alone or in combination of two or more. Further, as these radical polymerization initiators, desired ones can be appropriately selected depending on the impregnation and polymerization conditions.

The amount of the radical polymerization initiator (a-4) used is such that the component (a-2) is a compound (a-2a) having a glycidyl group represented by the general formula (I) and / or unsaturated. 0.001 to 100 parts by weight of the total amount of glycidyl ester (a-2b) and (a-3) vinyl-based monomer
It is 10 parts by weight, preferably 0.05 to 3 parts by weight. When it is more than the above range, thickening due to excessive crosslinking becomes remarkable, and when it is less than the above range, the polymerization becomes insufficient.

The (A) graft-modified olefin resin of the present invention is (a-1) a polyolefin resin, (a-2)
A compound (a-2a) having a glycidyl group represented by the general formula (I) and / or an unsaturated glycidyl ester (a
-2b), and (a-3) vinyl-based monomer, (a-
4) It is produced by polymerizing in an aqueous suspension in the presence of a radical polymerization initiator. The component (a-3) vinyl monomer is (a-1) a polyolefin resin (a).
-2) is an essential component for realizing uniform impregnation and polymerization of the compound (a-2a) having a glycidyl group represented by the general formula (I) and / or the unsaturated glycidyl ester (a-2b). By using the vinyl monomer (a-3), it is possible to obtain a resin composition having an excellent balance of fluidity, mechanical properties and the like.

When the (A) graft-modified polyolefin resin of the present invention is produced, for example, water, a suspending agent, an emulsifying agent, a dispersing agent, a stabilizer, a chain transfer agent, etc. may be appropriately used. There is no particular limitation as long as the aqueous suspension comprising the reaction mixture of each component is kept in a stable state to the extent that it does not excessively agglomerate or fuse under each condition such as type, pressure and stirring.

The (A) graft-modified polyolefin resin obtained as described above is blended with the (B) thermoplastic resin to provide a well-balanced thermoplastic resin composition having flowability, weld characteristics, impact resistance and the like. You can provide things.
The polyester resin, which is one of the thermoplastic resins (B) used in the present invention, is obtained by a condensation reaction containing an aromatic dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative as main components. Examples thereof include polymers and copolymers, ring-opening polymers of lactones, and the like, which may be used alone or in combination of two or more kinds.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid and the like, and ester-forming derivatives thereof and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

The above diol component is a C ₂ -C ₁₀ aliphatic diol, that is, ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6. -Hexanediol, 1,8-octanediol, cyclohexanediol, etc., or long-chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-
Examples thereof include 1,3-propylene glycol and polytetramethylene glycol, which are used alone or in combination of two or more.

Specific examples of the polyester resin of the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate and polyethylene-2,6-.
Naphthalate and the like are used, and these are used alone or in combination of two or more. Among these, polyethylene terephthalate, polybutylene terephthalate, or a mixture thereof is preferred from the balance of mechanical properties, heat resistance, and moldability.

The polyamide resin (B) used in the present invention, which is one of the thermoplastic resins, is usually called "nylon" and is not limited as long as it has an acid amide bond (-CONH-) as a repeating unit. Can be used. As specific examples, aliphatic amino acids, lactams, polymers obtained by a condensation reaction containing a diamine and a dicarboxylic acid as main components, or a small amount of an aromatic component or another aliphatic component is introduced into the aliphatic component. Examples thereof include copolyamide. Examples of the aliphatic amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, which may be used alone or in combination of two or more. Further, as the lactam, ε
-Caprolactam, ω-laurolactam and the like can be mentioned, and these can be used alone or in combination of two or more kinds. Examples of the diamine include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, and dodecamethylenediamine, which may be used alone or in combination of two or more. Examples of the dicarboxylic acid include adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and diglycolic acid, and these may be used alone or in combination of two or more.

Specific examples of the polyamide resin include polycaprolactam (nylon-6), polyhexamethyleneadipamide (nylon-66), nylon-610,
Polytetramethylene adipamide (nylon-46), polydodecanamide (nylon-12), nylon-9,
Nylon-11 etc. are mentioned. These may be copolymers of two or more kinds, or may be a mixture of two or more kinds.

As the polycarbonate resin which is one of the thermoplastic resins (B) used in the present invention, an aromatic polycarbonate resin, an aliphatic polycarbonate resin,
Examples thereof include aliphatic-aromatic polycarbonate-based resins, and among these, aromatic polycarbonate-based resins are preferably used. The aromatic polycarbonate-based resin is generally produced by reacting an aromatic dihydroxy compound and a carbonate precursor.

As the above aromatic dihydroxy compound,
For example, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxy-).
Bisphenols such as 3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane and 2,2-bis (4-hydroxy-3-methylphenyl) propane, Bis (4-hydroxyphenyl) ether, bis (3,5-dichloro-4)
-Hydroxyphenyl ethers and other dihydric phenol ethers, p, p'-dihydroxydiphenyl, 3,
Dihydroxydiphenyls such as 3'-dichloro-4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone, dihydroxyarylsulfones such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, resorcinol , Dihydroxybenzenes such as hydroquinone, 1,4-dihydroxy-2,5-dichlorobenzene, dihydroxybenzenes substituted with a halo or alkyl group such as 1,4-dihydroxy-3-methylbenzene, bis (4-hydroxy) Compounds such as dihydroxydiphenyl sulfides and dihydroxydiphenyl sulfoxides such as phenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide and the like can be mentioned. Is, they are used alone or in combination of two or more. Among these, bisphenol A is preferably used.

Examples of the carbonate precursor include carbonyl halides represented by phosgene and the like, carbonyl esters represented by diphenyl carbonate and the like, haloformate and the like, and these may be used alone or in combination of two or more kinds. To be The polycarbonate-based resin used in the present invention may be partially branched, and may be, for example, a thermoplastic random-branched polycarbonate resin obtained by reacting a polyfunctional aromatic compound with a dihydric phenol and a carbonate precursor. ,
Further, it may be a mixture of linear polycarbonate and branched polycarbonate.

As the polyfunctional aromatic compound, for example,
1,1,1-tri (4-hydroxyphenyl) ethane,
Trimellitic anhydride, trimellitic acid, trimellitoyl trichloride, 4-chloroformylphthalic anhydride, pyromellitic acid, pyromellitic dianhydride, mellitic acid, mellitic anhydride, trimesic acid, benzophenone tetracarboxylic acid, benzophenone tetra Examples thereof include carboxylic acid anhydrides, which may be used alone or in combination of two or more.

The resin composition comprises (A) 1 to 99% by weight of graft-modified polyolefin resin and (B) 99 to 1% by weight of thermoplastic resin. When the compounding ratio is out of the above range, a resin composition having the characteristics of both the component (A) and the component (B) cannot be obtained, and each component is substantially a single component. To the resin composition of the present invention, a catalyst that enhances the reactivity of (A) the graft-modified polyolefin resin and (B) the thermoplastic resin can be added. The catalyst is not particularly limited and is generally selected from a compound that promotes the reaction of a carboxylic acid group, a hydroxyl group or an ester group and a glycidyl group, or a combination of two or more thereof.
Preferred are amine compounds such as tertiary amine and quaternary ammonium salt, phosphorus compounds such as phosphonium salt and phosphine, and imidazoles.
(B) 0.001 with respect to 100 parts by weight of the thermoplastic resin
~ 2 parts by weight are used.

The method for producing the resin composition of the present invention includes:
There is no particular limitation as long as the reaction between the component (A) and the component (B) occurs. For example, the raw material is suitably produced by charging each raw material into a kneading apparatus and melt-kneading. As the kneading device, an extruder, a Banbury mixer, a mill, a kneader, a heating roll, or the like can be used, or a combination thereof can be used.As a method for inexpensively producing, a single-screw or multi-screw extruder is used. preferable.

An unmodified polyolefin resin (C) may be further added to the resin composition comprising (A) and (B). The unmodified polyolefin resin (C) used in the present invention is ethylene, propylene, 1-butene, 1-pentene, 1-octene, isobutene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,3-. Cyclohexadiene, 1,4-hexadiene, 1,3-octadiene,
1,5-cyclooctadiene, methylene norbornene,
1,5-norbornadiene, ethylidene norbornene,
A homopolymer consisting of one type selected from the group of α, ω-non-conjugated dienes, vinyl acetate and ethyl acrylate, or a copolymer consisting of two or more types, or two of them.
It may be a mixture of more than one species. Further, as the (C) unmodified polyolefin resin, the (a-1) molecular weight distribution (Mw / Mn) used in the production of the (A) graft modified polyolefin resin is in the range of 1.5 to 2.5. Using a polyolefin resin is also included.

Of these, preferred are specifically propylene homopolymer, propylene-ethylene copolymer, ethylene homopolymer, ethylene-octene copolymer, ethylene-propylene copolymer rubber, ethylene- Propylene-non-conjugated diene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer.

Specific examples of the non-conjugated diene in the ethylene-propylene-non-conjugated diene copolymer include dicyclopentadiene, 1,4-hexadiene, 1,4-heptadiene and 6-methyl-1,5-. Heptadiene, 1,5-
Cyclooctadiene, 2,5-norbornadiene, 2-
Methyl-2,5-norbornadiene, 5-methylidene-
2-norbornene, 5-ethylidene-2-norbornene, 5-n-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-n-butylidene-2-norbornene, 5-isobutylidene-2-norbornene, methyl Tetrahydroindene, limonene, etc. are mentioned, and these are used individually or in combination of 2 or more types.

The blending ratio of the (C) unmodified polyolefin resin is at least 1 selected from the group consisting of (A) 1 to 99% by weight of graft-modified polyolefin resin and (B) polyester resin, polyamide resin and polycarbonate resin. 1 to 100 parts by weight with respect to 100 parts by weight of a thermoplastic resin composition consisting of 99 to 1% by weight of a thermoplastic resin of a seed type.
Parts by weight, preferably 2 to 50 parts by weight. When the amount is more than the above range, the compatibility with the thermoplastic resin (B) decreases, and the balance of mechanical properties, surface properties, fluidity and the like of the resin composition deteriorates.

There are no particular restrictions on the mixing method and the mixing order of the (C) unmodified polyolefin resin, and various methods and orders can be adopted. As a compounding method, for example,
It is suitably manufactured by charging each raw material into a kneading device and melt-kneading. As a kneading device, an extruder, a Banbury mixer, a mill, a kneader, a heating roll, etc., or a combination thereof can be used, and as a method for producing at low cost, a single-screw or multi-screw extruder is used. Is preferred. The compounding order is, for example, a method in which the component (A), the component (B), and the component (C) are simultaneously charged into the above-mentioned kneading device and kneaded together, and (ii) the component (A)
And the component (B) are simultaneously charged into the extruder, and then the component (C) is charged from the middle of the barrel and kneaded, (ii)
i) A method in which the component (A) and the component (C) are simultaneously charged into the extruder, and then the component (B) is charged from the middle of the barrel and kneading, (iv) the component (B) and the component (C). Is added to the extruder at the same time, and then the component (A) is added from the middle of the barrel to knead. (V) The component (B) and the component (C) are simultaneously added to the kneading device and then this is a master batch. And kneading the masterbatch with the component (A),
(vi) A method of kneading a masterbatch composed of the components (A) and (B) and the component (C), and (vii) a masterbatch composed of the components (A) and (C) and the component (B). And the like.

The (A) graft-modified polyolefin-based resin of the present invention, or (A) the graft-modified polyolefin-based resin and (B) a thermoplastic resin, or these (A) and (B) and further (C) an unmodified polyolefin-based resin. The (E) filler can be added to the (D) thermoplastic resin composition comprising a resin. Examples of the (E) filler used in the present invention include silica, talc, mica, glass fibers, neutral clays, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, titanic acid fibers and the like. The filler is
(A) graft-modified polyolefin resin of the present invention,
(D) 1 to 1 relative to 100 parts by weight of the thermoplastic resin composition
It is used alone or in combination of two or more kinds in an amount of 00 parts by weight, preferably 5 to 50 parts by weight. When the amount is more than the above range, the balance of the mechanical properties and the molding fluidity of the resin composition becomes poor, and when the amount is less, the effect of addition is poor.

If necessary, the (A) graft-modified polyolefin resin or the (D) thermoplastic resin composition of the present invention contains a flame retardant, a pigment, a stabilizer, an antioxidant, an antistatic agent, a nucleating agent. , A lubricant and the like can be added.

Examples of the flame retardant include tetrabromobisphenol A, 2,2-bis (4-hydroxy-3,5-
Dibromophenyl) propane, hexabromobenzene,
Tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy-3,5-
Halogenated flame retardants such as dibromophenyl) propane, decabromodiphenyl oxide, brominated polyphosphate, chlorinated polyphosphate, chlorinated paraffin;
Ammonium phosphate, tricresyl phosphate, triethyl phosphate, trischloroethyl phosphate, tris (β-chloroethyl) phosphate,
Phosphorus flame retardants such as trisdichloropropyl phosphate, cresyl phenyl phosphate, xylenyl diphenyl phosphate, acidic phosphoric acid esters, nitrogen-containing phosphorus compounds; red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, meta Inorganic flame retardants such as barium borate, aluminum hydroxide, magnesium hydroxide, brominated polystyrene, brominated poly α-methylstyrene, brominated polycarbonate, brominated polyepoxy resin, chlorinated polyethylene, chlorinated poly α-methylstyrene Examples thereof include polymer flame retardants such as chlorinated polycarbonate and chlorinated polyepoxy resin.

The flame retardant is used in an amount of 1 to 50 parts by weight, preferably 3 to 100 parts by weight, based on 100 parts by weight of the (A) graft-modified polyolefin resin or the (D) thermoplastic resin composition of the present invention.
It is used alone or in combination of two or more at a ratio of 30 parts by weight. If the amount is more than the above range, the balance of mechanical properties, molding fluidity, etc. becomes poor, and if the amount is less than the above range, the effect of addition is poor.

[0055]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples, and can be changed as appropriate without departing from the scope of the invention. In the following description,
"Parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

(Production of Graft-Modified Polyolefin Resin) Example 1 In a pressure tight reaction vessel, 6000 parts of pure water was used to prepare an ethylene-octene copolymer (EG8200 manufactured by Dow).
Octene content 24%, Mooney viscosity 8) 1500 parts,
N- [4- (2,3-epoxypropoxy) -3,5-
Dimethylbenzyl] acrylamide 93.8 parts, glycidyl methacrylate 93.8 parts, styrene 187.6
Part, 1,1-bis (t-butylperoxy) 3,3,5
-Trimethylcyclohexane (4.56 parts), tricalcium phosphate (31.5 parts), and an emulsifier (Latemul PS: registered trademark manufactured by Kao Corporation) (0.945 parts) were mixed and stirred to obtain an aqueous suspension. The aqueous solution was stirred at 100 ° C. for 1 hour and then at 110 ° C. for 3 hours to complete the polymerization. The obtained particles were washed with water to remove residual monomers, tricalcium phosphate and latemur PS, and then dried to obtain a graft-modified polyolefin resin (GPO1).

Example 2 In a pressure-resistant closed reaction tank, an ethylene-octene copolymer (EG8200 manufactured by Dow) was added to 6000 parts of pure water.
Octene content 24%, Mooney viscosity 8) 1688 parts,
N- [4- (2,3-epoxypropoxy) -3,5-
Dimethylbenzyl] acrylamide 37.5 parts, glycidyl methacrylate 56.25 parts, styrene 93.8
Part, 1,1-bis (t-butylperoxy) 3,3,5
-Trimethylcyclohexane (4.56 parts), tricalcium phosphate (31.5 parts), and an emulsifier (Latemul PS: registered trademark manufactured by Kao Corporation) (0.945 parts) were mixed and stirred to obtain an aqueous suspension. The aqueous solution was stirred at 100 ° C. for 1 hour and then at 110 ° C. for 3 hours to complete the polymerization. The obtained particles were washed with water to remove residual monomers, tricalcium phosphate and latemul PS, and then dried to obtain a graft-modified polyolefin resin (GPO2).

Example 3 In a pressure-tight closed reaction tank, an ethylene-octene copolymer (EG8100 manufactured by Dow) was added to 6000 parts of pure water.
Octene content 24%, Mooney viscosity 23) 1500
Part, N- [4- (2,3-epoxypropoxy) -3,
5-dimethylbenzyl] acrylamide 93.8 parts, styrene 281.5 parts, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 4.56
Parts, 31.5 parts of tricalcium phosphate, and 0.945 parts of an emulsifier (Latemul PS: registered trademark, manufactured by Kao Corporation) were mixed and stirred to obtain an aqueous suspension. 1 of the aqueous solution
After stirring at 00 ° C for 1 hour, the mixture was further stirred at 110 ° C for 3 hours to complete the polymerization. The obtained particles were washed with water to remove residual monomers, tricalcium phosphate and latemul PS, and then dried to obtain a graft modified polyolefin resin (GPO3).

Example 4 In a pressure-tight closed reaction tank, an ethylene-octene copolymer (EG8200 manufactured by Dow) was added to 6000 parts of pure water.
Octene content 24%, Mooney viscosity 8) 1500 parts,
Glycidyl methacrylate 93.8 parts, styrene 28
1.5 parts, 1,1-bis (t-butylperoxy) 3,
4.55 parts of 3,5-trimethylcyclohexane, 31.5 parts of tricalcium phosphate, and 0.945 parts of an emulsifier (Latemul PS: registered trademark manufactured by Kao Corporation) were mixed and mixed with stirring to obtain an aqueous suspension. It was The aqueous solution is heated at 100 ° C for 1 hour.
After stirring for an hour, the mixture was further stirred at 110 ° C. for 3 hours to complete the polymerization. The obtained particles are washed with water to remove residual monomers, tricalcium phosphate and latemul PS,
Dry and graft-modified polyolefin resin (GPO
4) was obtained.

Comparative Example 1 In Example 1, instead of the ethylene-octene copolymer, an ethylene-propylene-non-conjugated diene copolymer (iodine value 12, propylene content 24%, diene component:
A graft modified polyolefin resin (GPO5) was obtained in the same manner as in Example 1 except that ethylidene norbornene and Mooney viscosity 26) were used.

Comparative Example 2 In Example 1, instead of the ethylene-octene copolymer, an ethylene-propylene-non-conjugated diene copolymer (iodine value 12.5, propylene content 24%, diene component: ethylidene norbornene, Mooney) A graft-modified polyolefin resin (GPO6) was obtained in the same manner as in Example 1 except that the viscosity of 60) was used.

Comparative Example 3 Grafting was carried out in the same manner as in Example 4 except that an ethylene-propylene copolymer (propylene content 26%, Mooney viscosity 24) was used in place of the ethylene-octene copolymer. Modified polyolefin resin (GPO
7) was obtained.

Comparative Example 4 Example 3 was repeated except that an ethylene-vinyl acetate copolymer (vinyl acetate content 28%, melt flow rate 6 g / 10 minutes) was used instead of the ethylene-octene copolymer. Graft-modified polyolefin resin (GPO8) was obtained in the same manner as in 3.

(Evaluation of Graft Modified Polyolefin Resin) Various physical properties of the graft modified polyolefin resins (GP01 to GP08) obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated by the following methods. (1) Capillary melt viscosity: The capillary melt viscosity at 250 ° C. was measured. As a measuring device, a Capillograph manufactured by Toyo Seiki was used. The residence time was 5 minutes and the shear rate was 1216 / sec.

(2) Melt flow rate: JIS K7
According to 210, the melt flow rate (g / 10 min) at 250 ° C. and a load of 10 kgf was measured.

(3) Specific gravity: According to JIS K7112,
A test piece with a thickness of 3 mm created by press molding has a temperature of 23 ° C.
Was measured.

The results of characteristic evaluation are shown in Table 1. From the results of Table 1, the graft-modified polyolefin resin of the present invention,
It can be seen that it is lightweight and has excellent fluidity.

[0068]

[Table 1]

(Production of Thermoplastic Resin Composition) Examples 5 to 11 and Comparative Examples 5 to 11 Polybutylene terephthalate resin (Duranex 2002 manufactured by Polyplastics Co., Ltd .: registered trademark, abbreviated as PBT in the table), Examples 1 to 4 and Comparative Example 1
To the graft-modified polyolefin resin (G
P01 to GP08), tetrabutylphosphonium bromide as a catalyst (manufactured by Aldrich, TBPB in the table)
Abbreviated. ) And glass fiber (NEC Electric Glass Co., Ltd. ECSO3T-19H / PS: registered trademark, G in the table)
Abbreviated as F. ) At a ratio shown in Table 2 and then mixed at 240 ° C.
Was supplied to a 45-mm twin-screw extruder (TEX44SS: registered trademark of Japan Steel Works, Ltd.) set at 15 rpm and melt-kneaded at a screw rotation speed of 100 rpm. The extrudate was cooled with water and pelletized, and then dried at 120 ° C. for 4 hours to produce a resin composition.

Examples 12 to 17, Comparative Examples 12 to 16 Polybutylene terephthalate resin (manufactured by Polyplastics Co., Ltd., Duranex 2000: registered trademark, abbreviated as PBT in the table), polypropylene resin (manufactured by Mitsui Petrochemical Co., Ltd.) Hypol J900: registered trademark, abbreviated as PP in the table), Examples 1 to 4 and Comparative Examples 1 to 4 above.
Graft-modified polyolefin resin (GP0
1 to GP08) and tetrabutylphosphonium bromide (manufactured by Aldrich, abbreviated as TBPB in the table) as a catalyst at a ratio shown in Table 3, and then set to 240 ° C. by a 45 mm twin-screw extruder (made by Japan Steel) Tosho Co., Ltd.
EX44SS: registered trademark) was fed 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 at 120 ° C. for 4 hours to produce a resin composition.

Examples 18-23, Comparative Examples 17-22 Nylon-6 resin (UBE101 manufactured by Ube Industries, Ltd.)
3B: registered trademark, abbreviated as Ny6 in the table. ), The graft modified polyolefin resins (GP01 to GP08) obtained in Example 14 and Comparative Examples 1 to 4 and tetrabutylphosphonium bromide (manufactured by Aldrich, abbreviated as TBPB in the table) as a catalyst. After being mixed at the ratio shown in Table 1, the mixture was fed to a 45 mm twin-screw extruder (TEX44SS: registered trademark of Japan Steel Works, Ltd.) set at 250 ° C. at a speed of 15 kg per hour, and the screw rotation speed was 100 rp.
Melt kneading at m. The extrudate was cooled with water and pelletized, and then dried under reduced pressure at 120 ° C. for 12 hours to produce a resin composition.

Examples 24 to 29, Comparative Examples 23 to 28 Polybutylene terephthalate resin (Duranex 800FP manufactured by Polyplastics Co., Ltd .: registered trademark, abbreviated as PBT in the table), nylon-66 resin (Ube Industries, Ltd.) UBE2020B: registered trademark, Ny in the table
Abbreviated as 66. ), The graft-modified polyolefin resins (GP01) obtained in Examples 1 to 4 and Comparative Examples 1 to 4 above.
To GP08) and tetrabutylphosphonium bromide (manufactured by Aldrich, abbreviated as TBPB in the table) as a catalyst at a ratio shown in Table 5, and then set to 250 ° C. by a 45 mm twin-screw extruder (Japan Steel Works). TE Corporation
X44SS: registered trademark) was fed at a rate of 15 kg per hour and melt-kneaded at a screw rotation speed of 100 rpm.
After cooling the extrudate with water and pelletizing,
A resin composition was produced by drying under reduced pressure for an hour.

Examples 30 to 35, Comparative Examples 29 to 34 Polycarbonate resin (Panlite L-1250 manufactured by Teijin Chemicals Ltd .: registered trademark, abbreviated as PC in the table), Examples 1 to 4 and Comparative Example 1 above. Table 6 shows the graft-modified polyolefin-based resins (GP01 to GP07) obtained in
After mixing at the ratio shown in, 45mm set to 280 ℃
Twin-screw extruder (TEX44SS:
(Registered trademark) at a rate of 15 kg per hour, 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 produce a resin composition.

(Evaluation of Thermoplastic Resin Composition) Various physical properties of the resin compositions obtained in Examples 5 to 35 and Comparative Examples 5 to 34 were evaluated by the following methods. (1) Tensile elongation at break: Examples 5 to 17 and Comparative examples 5-1
The resin composition obtained in Example 6 was set to a cylinder temperature of 240 ° C. and the mold temperature was set to 50 ° C., and the resin compositions obtained in Examples 18 to 29 and Comparative Examples 17 to 28 were prepared at a cylinder temperature of 25.
0 ° C., mold temperature 60 ° C., and Examples 30 to 3
5. The resin compositions obtained in Comparative Examples 29 to 34 were set to a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., respectively, injection-molded by an injection molding machine (TOSHIBA CORPORATION IS80EPN-2A: registered trademark), and dumbbelled. It was created. With respect to this test piece, the tensile elongation at break at 23 ° C. was evaluated according to the method specified in ASTM D638.

(2) Weld breaking elongation: A dumbbell test piece having a weld portion was prepared under the above injection molding conditions. With respect to this test piece, the weld tensile elongation at break at 23 ° C. was evaluated according to the method defined in ASTM D638.

(3) Izod impact strength: Izod bars having a thickness of 1/4 inch and 1/8 inch were prepared under the above injection molding conditions. Examples 5 to 29, Comparative Examples 5 to
Regarding the resin compositions (Table 2 to Table 5) obtained in No. 28,
Using the 1/4 inch bar, and for the resin compositions obtained in Examples 30-35 and Comparative Examples 29-34 (Table 6), 1/4 and 1/8 inch bars were used.
According to the method specified in D256, 23 ℃ and -30 ℃
The Izod impact strength with V notch was evaluated.

(4) Melt viscosity of capillaries: Examples 5 to 5
17, using the Capirograph manufactured by Toyo Seiki Co., Ltd. for the resin compositions (Tables 2 and 3) obtained in Comparative Examples 5 to 16,
The capillary melt viscosity at 250 ° C. was measured. At this time, the measurement was performed under the conditions of a residence time of 5 minutes and a shear rate of 1216 sec ^-1 .

(5) Molding fluidity: Under the above injection molding conditions, a rectangular spiral having a thickness of 3 mm was injection-molded, and the molding fluidity was evaluated by its length (mm).

(6) Surface releasability: Under the above injection molding conditions, a test piece was prepared with a mold having a pin gate diameter of 0.8 mm and a thickness of 2 mm. Examples 12-17, Comparative Examples 12-1
Regarding the resin composition (Table 3) obtained in No. 6, JIS-K
The surface release agent was evaluated according to the cross-cut test method described in 5400 (paint). The evaluation criteria for surface releasability are as follows. ⊚: Out of 100 grids, the number of grids remaining after the test is 96 or more. ◯: Out of 100 grids in total, the number of grids remaining after the test is 91 to 95. Δ: The number of grids remaining after the test is 86 to 90 out of 100 grids in total. X: The number of grids remaining after the test is 85 or less out of the total of 100 grids.

(7) Heat shock resistance: Under the above injection molding conditions, a mold having a thickness of 1 mm was used to prepare a test piece having a weld portion. Examples 5-11, Comparative Examples 5-
For the resin composition (Table 2) obtained in No. 11, 140 ° C
After annealing for 2 hours at 50 ° C., heat cycles were performed 50 times at temperatures of −30 ° C. and 140 ° C. At the end of 50 cycles, the heat shock resistance was evaluated from the number of cracks in the weld portion out of a total of 10 test pieces. The evaluation criteria are as follows. ◯: Out of 10 test pieces in total, the number of cracks in the weld portion was 2 or less. (Triangle | delta): The number which the crack generate | occur | produced in the weld part was 3-5 among the total of 10 test pieces. X: The number of cracks in the weld was 6 or more out of the total of 10 test pieces.

The results of characteristic evaluation are shown in Tables 2 to 6. Table 2
From the results, the resin compositions of the present invention obtained in Examples 5 to 11 exhibit extremely high tensile elongation at break regardless of the presence or absence of the weld portion, and also have good Izod impact strength. Furthermore, since it has excellent heat shock resistance, it can be seen that the weld characteristics in a wide temperature range are improved. On the other hand, in Comparative Example 8 or Comparative Example 11, the weld characteristics are relatively good, but there is a problem in fluidity or heat shock resistance. Therefore, it is clear that the resin composition of the present invention has an excellent balance of physical properties such as weld characteristics, impact resistance, fluidity, and heat shock resistance.

From the results shown in Table 3, the resin compositions of the present invention obtained in Examples 12 to 17 have excellent weld characteristics and good fluidity even when polypropylene, which is an unmodified polyolefin resin, is added. Is. Further, since the surface releasability is also excellent, it is understood that the graft-modified polyolefin resin (GPO1 to GPO4) of the present invention has a remarkable function as a compatibilizing agent for improving the compatibility of the resin composition.

From the results shown in Table 4, the resin compositions of the present invention obtained in Examples 18 to 23 have particularly excellent weld characteristics.
Further, it can be seen that the impact characteristics and the fluidity are also good.

From the results shown in Table 5, the resin compositions of the present invention obtained in Examples 24 to 29 have good weld characteristics, impact characteristics and fluidity even when a polyester and a polyamide, which originally have poor compatibility, are blended. It turns out that Particularly excellent weld characteristics and fluidity are remarkable.

From the results shown in Table 6, it is clear that the resin compositions of the present invention obtained in Examples 30 to 35 are excellent in weld characteristics, impact characteristics and fluidity. In particular, impact strength, which is a problem with polycarbonate resins, has little thickness dependency, and the resin composition of the present invention is suitable for thick parts and the like.

[0086]

[Table 2]

[0087]

[Table 3]

[0088]

[Table 4]

[0089]

[Table 5]

[0090]

[Table 6]

[0091]

As described above, the resin composition according to the present invention has significantly improved fluidity and weld characteristics, is lightweight, and has a good balance of impact resistance. Such a resin composition of the present invention is useful for various engineering plastics, particularly automobile parts, home electric appliances parts, industrial parts, sports equipment, furniture and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 69/00 LPN C08L 69/00 LPN 77/00 LQR 77/00 LQR

Claims (14)

[Claims] 1. A molecular weight distribution (Mw /) represented by the ratio of (a-1) weight average molecular weight (Mw) and number average molecular weight (Mn).
100 parts by weight of a polyolefin-based resin having a Mn) in the range of 1.5 to 2.5, (a-2) the following general formula (I): (In the formula, Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group bonded to at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) A compound having a glycidyl group 0.1 to 30 parts by weight of (a-2a) and / or unsaturated glycidyl ester (a-2b), (a-
3) 0.1 to 500 parts by weight of vinyl-based monomer, and (a-
4) The radical polymerization initiator is added to the component (a-2) and (a-
3) 0.001 to 100 parts by weight of the total amount of the components
An aqueous suspension containing 10 parts by weight was prepared, and (a-2) the compound (a-2a) having a glycidyl group represented by the general formula (I) and / or unsaturated glycidyl in the aqueous suspension. The above-mentioned (a-1) polyolefin resin is impregnated with the ester (a-2b) and (a-3) vinyl-based monomer, and has (a-2) a glycidyl group represented by the general formula (I). A graft-modified polyolefin resin obtained by polymerizing the compound (a-2a) and / or the unsaturated glycidyl ester (a-2b) and the vinyl monomer (a-3) with the polyolefin resin (a-1). 2. The polyolefin resin (a-1) has a molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of 1.5 to 2.5. And the melt flow ratio (I ₁₀ / I ₂ ) is 5.6.
The graft-modified polyolefin resin according to claim 1, which is a polyolefin resin having 3 or more. 3. The graft modified polyolefin resin according to claim 1, wherein the polyolefin resin (a-1) is a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. 4. The polyolefin resin (a-1) comprises ethylene, 1-butene, 1-hexene and 4-methyl-1.
The graft-modified polyolefin resin according to claim 3, which is a copolymer with at least one α-olefin selected from the group consisting of pentene and 1-octene. 5. The graft-modified polyolefin resin according to claim 4, wherein the polyolefin resin (a-1) is a copolymer of ethylene and 1-octene. 6. A compound (a-2a) having a glycidyl group represented by the general formula (I) of (a-2) is represented by the following structural formula (II): The graft-modified polyolefin resin according to any one of claims 1 to 5, which is a compound represented by: 7. The graft-modified polyolefin resin according to claim 1, wherein the unsaturated glycidyl ester (a-2b) of (a-2) is glycidyl methacrylate. 8. The vinyl monomer (a-3) is an aromatic vinyl compound, an alkyl acrylate having an alkyl group having 1 to 22 carbon atoms, and an alkyl group having 1 to 22 carbon atoms.
A methacrylic acid alkyl ester, a vinyl alkyl ether having an alkyl group having 1 to 22 carbon atoms, a vinyl alcohol, an unsaturated nitrile compound, an unsaturated amino compound, and a dialkyl maleic acid having an alkyl group having 1 to 9 carbon atoms. At least one selected from the group consisting of an ester, an allyl alkyl ether having an alkyl group having 1 to 8 carbon atoms, a diene compound, maleic anhydride, maleic acid, acrylic acid, methacrylic acid, and vinyl acetate. The graft-modified polyolefin resin according to any one of items 1 to 7. 9. The (a-3) vinyl monomer is styrene,
The graft modified polyolefin resin according to claim 8, which is at least one selected from the group consisting of α-methylstyrene, butyl acrylate, methyl methacrylate, allyl methacrylate, vinyl acetate and acrylonitrile. 10. A material selected from the group consisting of 1 to 99% by weight of (A) the graft-modified polyolefin resin according to any one of claims 1 to 9 and (B) a polyester resin, a polyamide resin and a polycarbonate resin. A resin composition comprising 99 to 1% by weight of at least one thermoplastic resin. 11. A thermoplastic resin composition comprising 100 parts by weight of the thermoplastic resin composition (D) according to claim 10 and 1 to 100 parts of the unmodified polyolefin resin (C). 12. The unmodified polyolefin resin is a propylene homopolymer, propylene-ethylene copolymer, ethylene homopolymer, ethylene-octene copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated. Diene copolymer, ethylene-butene copolymer,
The thermoplastic resin composition according to claim 11, which is at least one selected from the group consisting of an ethylene-vinyl acetate copolymer and an ethylene-ethyl acrylate copolymer. 13. (E) silica, talc, mica, glass fiber, neutral clays, relative to 100 parts by weight of the (A) graft-modified polyolefin resin according to any one of claims 1 to 9. A thermoplastic resin composition comprising 1 to 100 parts by weight of at least one filler selected from the group consisting of carbon fibers, aromatic polyamide fibers, silicon carbide fibers, and titanic acid fibers. 14. With respect to 100 parts by weight of the (D) thermoplastic resin composition according to any one of claims 10 to 12,
(E) silica, talc, mica, glass fiber, neutral clays, carbon fiber, aromatic polyamide fiber, silicon carbide fiber,
And at least one selected from the group consisting of titanic acid fibers
A thermoplastic resin composition comprising 1 to 100 parts by weight of a seed filler.