JPH0570529A - Modified polypropylene and thermoplastic resin composition comprising modified polypropylene and polyphenylene ether - Google Patents

Abstract

PURPOSE:To provide a modified polypropylene excellent in coatability, antistatic properties and mechanical properties and useful for a molding or a high- molecular alloying agent and a thermoplastic resin composition excellent in strengths and heat resistance. CONSTITUTION:A modified polypropylene prepared by grafting a specified amount of a specified combination of monomers selected from among a styrene monomer, an amine monomer and an aminostyrene monomer onto a polypropylene wherein the number of grafts is 1-10 on the average per polypropylene molecule, the weight-average degree of polymerization of the graft is 1-100, and the weight-average molecular weight is 1000-500000; and a thermoplastic resin composition comprising the above modified polypropylene and a polyphenylene ether modified with a compound having an amino-reactive functiuonal group in the molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel modified propylene polymer which can be used for producing a molded article by injection molding, extrusion molding or the like. Further, the present invention is
The present invention relates to a thermoplastic resin composition containing a modified propylene polymer as one component. The thermoplastic resin composition can be used as a molded product by injection molding or extrusion molding.

[0002]

2. Description of the Related Art Propylene polymers are excellent in molding processability, toughness, water resistance, chemical resistance, etc., and have low specific gravity and are inexpensive. Widely used. However, the propylene polymer has drawbacks in heat resistance, rigidity, impact resistance, paintability, antistatic property, adhesiveness, or the like, or needs improvement, which prevents development of new applications. In particular, improvements in coating properties, antistatic properties and mechanical properties are strongly desired.

Also, polyphenylene ether is heat resistant,
Although it is a resin with excellent properties such as hot water resistance, dimensional stability, and mechanical and electrical properties, it has drawbacks such as high melt viscosity, poor moldability, poor chemical resistance, and low impact resistance. Have If a resin composition containing a polyphenylene ether and a propylene polymer and having the characteristics of both, molding processability, and impact resistance is obtained, a wide range of potential new applications are expected. is there. However, in reality, even if a propylene polymer is blended with the polyphenylene ether, the compatibility is poor, and the molded product obtained by injection molding or the like has a phase separation between the polyphenylene ether and the propylene polymer, and only a remarkably poor appearance is obtained. However, the mechanical properties are inferior, and it is not practically usable. However, in the market, a resin composition having high impact resistance and excellent weather resistance while maintaining the excellent heat resistance of polyphenylene ether is required.

As a method for improving the compatibility of polyphenylene ether and propylene polymer, JP-A-1-207
As described in Japanese Patent No. 349, there is a method of blending a propylene polymer obtained by graft-copolymerizing a styrene-based monomer with polyphenylene ether. It is possible to obtain a composition excellent in heat resistance and mechanical properties by blending polyphenylene ether with a propylene polymer obtained by graft-copolymerizing styrene or a mixture of styrene and a monomer copolymerizable with styrene, and rubber, etc. Is Japanese Patent Laid-Open No. 1-2073
49, No. 1-234462, etc. A resin composition containing an amino group-containing polyolefin and a polar group-containing polyphenylene ether is disclosed in JP-A-2-173137.

However, in some cases, a molded article using the resin composition does not have sufficient impact resistance, heat resistance, molding processability or the like, or has insufficient elongation, tensile strength or chemical resistance. In some cases, it may be difficult to use the resin composition depending on the application due to insufficient mechanical properties of the welded part of the injection molded product, or it may be expensive. There has been a strong demand from the market for improved and cheap resin compositions.

[0006]

The object of the present invention is to provide a modified propylene polymer having excellent coating properties, antistatic properties and mechanical properties, and a modified propylene polymer and polyphenylene ether, which have heat resistance and melt flowability. Another object of the present invention is to provide a thermoplastic resin composition having excellent processability, chemical resistance, impact resistance, appearance and gloss.

[0007]

The inventor of the present invention has completed the present invention as a result of extensive studies to solve the above problems.

That is, the present invention provides a propylene polymer 1
1 to 200 parts by weight of at least one monomer or a combination of monomers selected from the group consisting of the following monomers (a) to (d) and a combination of monomers to 100 parts by weight: Copolymerized, the average number of graft chains per propylene polymer molecule is 1 to 10, the weight average degree of polymerization of the graft chains is 1 to 100, and the weight average molecular weight is 1000 to
The present invention relates to 500,000 modified propylene polymer and a thermoplastic resin composition containing the modified propylene polymer as one component. (A) Amino group-containing styrene-based monomer (b) Styrene-based monomer and amino group-containing monomer, and the weight ratio of the styrene-based monomer and the amino group-containing monomer is 0.01. In the range of up to 100. (C) Amino group-containing styrene-based monomer and styrene-based monomer, the weight ratio of the amino group-containing styrene-based monomer and the styrene-based monomer being in the range of 0.01 to 100 .. (D) Amino group-containing styrene monomer and amino group-containing monomer, wherein the weight ratio of the amino group-containing styrene monomer and the amino group-containing monomer is within the range of 0.01 to 100. What is. (However, the above-mentioned styrene-based monomer and amino group-containing monomer exclude amino group-containing styrene-based monomers.)

When the amount of the monomer constituting the graft chain of the modified propylene polymer exceeds 200 parts by weight or the weight average degree of polymerization of the graft chain exceeds 100, the moldability of the modified propylene polymer is deteriorated. Is not preferable.
When the weight average molecular weight of the modified propylene polymer is less than 1000, the mechanical properties of the modified propylene polymer are insufficient, and when the weight average molecular weight exceeds 500,000, the moldability of the modified propylene polymer decreases. Is not preferable.

The propylene polymer which is a raw material of the modified propylene polymer of the present invention is a propylene homopolymer or a significant amount of propylene and other α having a carbon number of 2 to 18 in the range.
-Means random or block copolymers with olefins. Specific examples of the propylene polymer include ethylene-propylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene- 1
-Octen copolymer etc. can be mentioned.

If necessary, the propylene polymer may be blended with an ethylene-α-olefin copolymer and / or a styrene-modified product of the copolymer.
As the ethylene-α-olefin copolymer to be blended,
Those having a density of 0.82 to 0.92 g / cm ³ are preferably used.

As the propylene polymer, a highly crystalline propylene polymer can be used if necessary.
The high crystallinity propylene polymer referred to herein is, for example, as described in JP-A-1-247457.
The homopolymer or block copolymer of propylene, which is the first segment polymerized in the first step, has the isotactic pentad fraction of the boiling heptane-insoluble portion of the propylene homopolymer portion of 0.970 or more. Further, in the field where high rigidity is required, it is preferable to add a known nucleating agent to the propylene polymer.

Besides, it is known that a vinylcycloalkane polymer having 6 or more carbon atoms also effectively acts as a nucleating agent. That is, a composition obtained by blending a propylene polymer with a vinylcycloalkane polymer having 6 or more carbon atoms, which is described in JP-A-1-234462, wherein vinylcycloalkane units are contained in the composition. A propylene polymer composition containing 0.05 to 10000 wtppm is preferable because it has higher crystallinity.

Further, a highly rigid propylene polymer can be obtained by blending the vinylcycloalkane polymer with the above-mentioned highly crystalline propylene polymer. The propylene polymers (propylene homopolymer and propylene copolymer) can be used alone or in combination of two or more kinds.

In the modified propylene polymer of the present invention,
As the monomer to be graft-copolymerized with the propylene polymer, at least one monomer or a monomer selected from the group consisting of the following monomers (a) to (d) and a combination of monomers: Combinations can be mentioned. (A) Amino group-containing styrene-based monomer. (B) A styrene-based monomer and an amino group-containing monomer, wherein the weight ratio of the styrene-based monomer and the amino group-containing monomer is in the range of 0.01 to 100. (C) Amino group-containing styrene-based monomer and styrene-based monomer, the weight ratio of the amino group-containing styrene-based monomer and the styrene-based monomer being in the range of 0.01 to 100 .. (D) Amino group-containing styrene monomer and amino group-containing monomer, wherein the weight ratio of the styrene monomer and the amino group-containing monomer is within the range of 0.01 to 100. .. (However, the above-mentioned styrene-based monomer and amino group-containing monomer exclude amino group-containing styrene-based monomers.)

The amino group-containing styrene-based monomer means an amino group-containing styrene-based monomer which can be graft-copolymerized with a propylene polymer. As the monomer, a styrene-based monomer having a primary or secondary amino group in the molecule is preferably used. Specifically, aminostyrene, aminomethylstyrene and the like are preferably used.
All include various isomers. The amino group-containing styrene-based monomer can be used alone or as a mixture of two or more kinds.

Next, the styrene-based monomer means a compound represented by the general formula 1 excluding the amino group-containing styrene-based monomer.

[0018]

[Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are the same or different and each is a hydrogen atom, a halogen atom, a hydrocarbon or a substituted hydrocarbon group, a hydrocarbon oxy or a substituted hydrocarbon oxy group. And R ₆ represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms).

R ₁ , R ₂ , R ₃ , R _{4 in the} above general formula
And specific examples of R ₅ include a hydrogen atom; chlorine, bromine,
Halogen atom such as iodine; Hydrocarbon group such as methyl, ethyl, propyl, vinyl, allyl, benzyl, methylbenzyl; Substituted hydrocarbon group such as chloromethyl, bromomethyl; Hydrocarbon oxy such as methoxy, ethoxy, phenoxy, monochloromethoxy Groups or substituted hydrocarbonoxy groups and the like. Further, specific examples of R ₆ include a hydrogen atom, a lower alkyl group such as methyl and ethyl, and the like.

Specific examples of the styrene type monomer include styrene, 2,4-dichlorostyrene, p-methoxystyrene, p-methylstyrene, p-phenylstyrene and p-.
Divinylbenzene, p- (chloromethoxy) -styrene, α-methylstyrene, o-methyl-α-methylstyrene, m-methyl-α-methylstyrene, p-methyl-
Examples include α-methylstyrene and p-methoxy-α-methylstyrene. These can be used alone or as a mixture of two or more kinds. Of these, styrene is preferably used.

The term "amino group-containing monomer" means a monomer containing an amino group and capable of being graft-copolymerized with a propylene polymer, excluding amino group-containing styrene-based monomers. To do. As the monomer, a monomer having a primary or secondary amino group and a carbon-carbon double bond or triple bond in the molecule is preferably used. Specifically, allylamine, diallylamine, vinylimidazole, allylaniline, acrylamide, methacrylamide, N
-Phenylmethacrylamide and the like are preferably used. The amino group-containing monomer can be used alone or as a mixture of two or more kinds.

As the graft copolymer component for preparing the modified propylene polymer of the present invention, the above-mentioned (a) to
In addition to the monomer (d) or a combination of monomers, a monomer copolymerizable with the styrene-based monomer may be used together.

Specific examples of the monomer copolymerizable with such a styrene-based monomer include acrylonitrile, methacrylonitrile, fumaric acid and maleic acid,
Vinyl ketone, maleic anhydride, acrylic acid, methacrylic acid, vinylidene chloride, maleic acid ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, glycidyl acrylate, glycidyl methacrylate, butyl methacrylate, methyl acrylate, 2-hydroxyethyl methacrylate , Ethyl acrylate, propyl acrylate, butyl acrylate, vinyl chloride, vinyl acetate, divinylbenzene, ethylene oxide, vinylidene chloride, maleic acid ester, isobutene, alkyl vinyl ether, anethole, indene, coumarone, benzofuran, 1,2-dihydro Naphthalene, acenaphthylene, isoprene, chloroprene, trioxane, 1,3
-Dioxolane, propylene oxide, β-propiolactone, vinylbiphenyl, 1,1-diphenylethylene, 1-vinylnaphthalene, 2-vinylnaphthalene,
2,3-dimethylbutadiene, ethylene, propylene,
Allyltrimethylsilane, 3-butenyltrimethylsilane, vinylcarbazole, fumarnitrile and the like can be mentioned. Further, derivatives of these monomers can also be used. These can be used alone or as a mixture of two or more kinds.

Examples of the method for producing the modified propylene polymer of the present invention include a suspension graft copolymerization method, an emulsion graft copolymerization method, a solution graft copolymerization method and a melt graft copolymerization method. Among these, the suspension graft copolymerization method and the melt graft copolymerization method are preferable.

Specifically, a propylene polymer in the aqueous phase,
At least one monomer or combination of monomers selected from the group consisting of the above-mentioned monomers (a) to (d) and a combination of monomers, a dispersant, a radical initiator and the like are added. By increasing the temperature with stirring, at least one monomer or a monomer selected from the group consisting of the above-mentioned monomers (a) to (d) and a combination of monomers is added to the propylene polymer. Mention may be made of a suspension graft copolymerization method in which the combination is graft copolymerized.

As a concretely preferred suspension graft copolymerization method, at a temperature of 10 to 50 ° C., a system in which water, a dispersant and propylene polymer particles are dispersed is added to the above (a) to (d). At least one monomer or combination of monomers selected from the group consisting of monomers and combinations of monomers, and a radical initiator such as an organic peroxide are introduced and then the system is charged with 20- 100-13 over 80 minutes
After the temperature is raised to a temperature range of 0 ° C., the temperature range is 30 to 1
Examples include a method of holding and reacting for 20 minutes.

At this time, at least one monomer or monomer selected from the group consisting of the above-mentioned monomers (a) to (d) and a combination of monomers with respect to 100 parts by weight of the propylene polymer. 1 to 200 parts by weight, and 50 parts of water to 100 parts by weight of the total amount of the propylene polymer and the above-mentioned monomers.
It is suitable to use ˜1000 parts by weight, 0.05 to 10 parts by weight of dispersant and 0.01 to 10 parts by weight of radical initiator.

As the dispersant, known dispersants can be used, but it is particularly preferable that 50% by weight or more of the compound used as the dispersant is a compound represented by the general formulas (2) and (3).

[0029]

[Chemical 2] (Here, a to h each represent a number of 5 to 1000, and R represents a hydrocarbon group having 1 to 10 carbon atoms.)

[0030]

[Chemical 3] (Here, i, j, and k represent numbers of 10 to 1000, respectively.)

Next, as a preferable melt graft copolymerization method, at least one monomer selected from the group consisting of a propylene polymer, the above-mentioned monomers (a) to (d) and a combination of monomers is used. Examples thereof include a method in which a body or a combination of monomers and a radical initiator are mixed and melt-kneaded in a temperature range of 180 to 280 ° C.

The blending ratio of the raw materials in the melt graft copolymerization method is 100 parts by weight of the propylene polymer,
1 to 50 parts by weight of at least one monomer or combination of monomers selected from the group consisting of the above-mentioned monomers (a) to (d) and combinations of monomers is preferable. here,
If the kneading temperature does not reach 180 ° C., it is difficult to uniformly knead each component, and if the kneading temperature exceeds 280 ° C., the propylene polymer is decomposed during kneading, which is not preferable.

The kneading device is not particularly limited, and a usual kneading device can be used. For melt kneading, generally used kneading devices such as a single-screw or twin-screw extruder and various kneaders can be used. A biaxial high kneader is particularly preferable.

The modified propylene polymer as referred to in the present invention is at least one selected from the group consisting of the above-mentioned monomers (a) to (d) and a combination of monomers in one molecule of the propylene polymer. It means a monomer having a graft chain formed from one monomer or a combination of monomers, but actually, the raw material propylene in which the polymer is not modified even after the above-mentioned copolymerization reaction is carried out. It may also include a polymer. In practical use, the polymer may be provided as it is,
Alternatively, a raw material propylene polymer which has not been modified may be removed from the polymer by using a solvent.

A copolymer of styrene monomer and glycidyl acrylate is first prepared by anionic polymerization, and then the copolymer and propylene polymer are combined with a radical initiator and an amino group-containing styrene as shown below. A method of obtaining a modified propylene polymer by melt-kneading with a system monomer or the like, and in the same manner, first a copolymer of a styrene monomer and acrylonitrile is produced, and then this copolymer and a propylene polymer And a styrene-based monomer, an amino group-containing styrene-based monomer, and a radical initiator as shown below are melt-kneaded to obtain a modified propylene polymer.

Here, the radical initiator used in the production of the modified propylene polymer is not particularly limited, and for example, a radical initiator as described in JP-A-2-160856 may be appropriately selected and used. You can

In the modified propylene polymer of the present invention, if necessary, a flame retardant, an antioxidant, a heat stabilizer, a light stabilizer, a nucleating agent, an antistatic agent, an inorganic or organic colorant, a rust preventive agent, Various additives such as a cross-linking agent, a foaming agent, a lubricant, a plasticizer, a fluorescent agent, a surface smoothing agent and a surface gloss improving agent can be added.

To describe the flame retardants in more detail, the flame retardants useful in the present invention include a group of compounds well known to those skilled in the art. Generally, more important compounds among them, such as bromine, chlorine, antimony, phosphorus and nitrogen which can impart flame retardancy such as those described in JP-A-2-160856. A compound containing an element is used. For example, halogenated organic compounds, antimony oxide, antimony oxide and halogenated organic compounds, antimony oxide and phosphorus compounds, simple phosphorus or phosphorus compounds, phosphorus compounds or compounds having a phosphorus-nitrogen bond and halogen-containing compounds, or 2 of these.
A mixture of two or more species is used.

Next, the present invention relates to a thermoplastic resin composition comprising the modified propylene polymer and modified polyphenylene ether. That is, the present invention provides (A) a polyphenylene ether modified with a compound having a functional group capable of reacting with an amino group in the molecule, (B) a propylene polymer 100.
1 to 200 parts by weight of a graft copolymer containing at least one monomer or a combination of monomers selected from the group consisting of the following monomers (a) to (d) and combinations of monomers in parts by weight: Polymerized, the average number of graft chains per molecule of the propylene polymer is 1 to 10, the weight average degree of polymerization of the graft chains is 1 to 100, and the weight average molecular weight is 1000 to 50.
Consisting of 50,000 modified propylene polymers, 99-1% by weight of component (A) and 1-99% by weight of component (B)
Which relates to the thermoplastic resin composition. (A) Amino group-containing styrene-based monomer. (B) A styrene-based monomer and an amino group-containing monomer, wherein the weight ratio of the styrene-based monomer and the amino group-containing monomer is in the range of 0.01 to 100. (C) Amino group-containing styrene-based monomer and styrene-based monomer, the weight ratio of the amino group-containing styrene-based monomer and the styrene-based monomer being in the range of 0.01 to 100 .. (D) Amino group-containing styrene monomer and amino group-containing monomer, wherein the weight ratio of the styrene monomer and the amino group-containing monomer is within the range of 0.01 to 100. .. (However, the above-mentioned styrene-based monomer and amino group-containing monomer exclude amino group-containing styrene-based monomers.)

The polyphenylene ether as a raw material of the modified polyphenylene ether of the component (A) in the present invention is represented by the general formula 4

[0041]

[Chemical 4] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are selected from hydrogen, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and at least one of them is a hydrogen atom. The polymer obtained by oxidatively polymerizing at least one of the phenol compounds represented by the formula (1)) with oxygen or an oxygen-containing gas using an oxidative coupling catalyst.

R ₁ , R ₂ , R ₃ , R in the above general formula
Specific examples of ₄ and R ₅ are hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n- or iso-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl. , Hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl, allyl groups and the like.

Specific examples of the above general formula include phenol, o-, m- and p-cresol, 2,6-, 2,
5-, 2,4-, and 3,5-dimethylphenol,
2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2,3.
6- and 2,4,6-trimethylphenol, 3-methyl-6-t-butylphenol, thymol, 2-methyl-6-allylphenol and the like can be mentioned. further,
A copolymer of a phenol compound other than the above general formula, for example, a polyvalent hydroxyaromatic compound such as bisphenol-A, tetrabromobisphenol-A, resorcin, hydroquinone, and novolak resin with the above general formula may be used. Among these compounds, preferred are 2,
Homopolymer of 6-dimethylphenol and 2,6-diphenylphenol and copolymer of a large amount of 2,6-xylenol and a small amount of 3-methyl-6-t-butylphenol or 2,3,6-trimethylphenol Is mentioned.

The oxidative coupling catalyst used for oxidative polymerization of the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used. For example, typical examples thereof include cupric chloride-trimethylamine chloride and JP-A-2-1608.
Examples thereof include catalysts described in Japanese Patent Publication No. 56 and the like.

It is known that there are differences in the physical properties of the polymer obtained when the oxidative polymerization for obtaining polyphenylene ether is carried out at a temperature higher than 40 ° C. (high temperature polymerization) and when it is carried out at 40 ° C. or lower (low temperature polymerization). However, either high-temperature polymerization or low-temperature polymerization can be employed in the present invention.

The polyphenylene ether modified with the compound having a functional group capable of reacting with the amino group of the component (A) in the present invention is specifically the following compounds (a) to (c). Examples thereof include those obtained by reacting one or more compounds selected from the group with polyphenylene ether.

(A) A compound having at least one group selected from the following group (I) and at least one group selected from a group (II) in the molecule at the same time. (I) Carbon-carbon double and triple bonds. (II) A carboxyl group, an acid anhydride group, an acid amide group, an imide group, an epoxy group, a carboxylic acid ester group, an isocyanate group, a methylol group, a group having an oxazoline ring, and a hydroxyl group.

Specific examples include maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, and reaction products of maleic anhydride and diamine, for example,

[0049]

[Chemical 5]

[0050]

[Chemical 6] (Wherein R represents an aliphatic or aromatic group), etc., methylnadic acid anhydride, dichloromaleic anhydride, maleic acid amide, soybean oil, tung oil, castor oil, linseed oil , Natural oils and fats such as hemp oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil and sardine oil, epoxidized natural oils and fats such as epoxidized soybean oil, acrylic acid, butenoic acid, crotonic acid, vinyl Acetic acid, methacrylic acid, bentenoic acid, angelic acid, tiglic acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl- 2-Bentenoic acid, 3
-Methyl-2-pentenoic acid, α-ethyl crotonic acid,
2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2
-Octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10-
Undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-
Tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, mycoribene acid,
2,4-pentadienoic acid, 2,4-hexadienoic acid, diallylacetic acid, geranium acid, 2,4-decadienoic acid,
2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, octadecatrienoic acid, eicosadienic acid, eicosatrienoic acid, eicos Satetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid,
Unsaturated carboxylic acids such as hexacodienoic acid, octacocenoic acid and traacontenoic acid, or esters of these unsaturated carboxylic acids, acid amides, anhydrides, or allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methyl propenyl carbyl Nole, 4-penten-1-ol, 10-undecene-
1-ol, propargyl alcohol, 1,4-pentadiene-3-ol, 1,4-hexadiene-3-ol, 3,5-hexadiene-2-ol, 2,4-hexadiene-1-ol, 3-butene -1,2-diol, 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-3,4-diol, 2,6
- unsaturated alcohols such as octadiene-4,5-diol, or the OH group of such unsaturated alcohols, unsaturated amines or glycidyl acrylates Tsu replace the -NH ₂ group, glycidyl methacrylate, allyl glycidyl ether Can be mentioned. Among them, maleic anhydride, fumaric acid, itaconic acid, hymic acid anhydride,
Glycidyl acrylate, glycidyl methacrylate,
Allyl glycidyl ether is preferred.

Further, two or more functional groups of the (I) group, (I
It is also possible to use a compound containing two or more (same or different) functional groups of group I), and it is also possible to use two or more of these compounds.

(B) General formula (R ¹ O) _m R (COOR ² ) _n (CONR ³ R ⁴ ) _s [wherein R is an alkyl group (carbon number: 2 to 20, preferably 2 to 10) R ¹ : Hydrogen, alkyl group, acyl group or carbonyldioxy group (carbon number: 1 to 10, preferably 1 to 6, more preferably 1 to 4, particularly preferably hydrogen), or aryl group (carbon number: 6 to 6) 20) R ² : hydrogen, an alkyl group (carbon number: 1 to 20, preferably 1 to 10), or an aryl group (carbon number: 6 to 20) R ³ and R ⁴ : hydrogen, an alkyl group (carbon number: 1 ~Ten,
Preferably 1 to 6, more preferably 1 to 4), or an aryl group (carbon number: 6 to 20) m = 1 n + s ≧ 2, preferably 2 or 3 n ≧ 0 s ≧ 0 (R ¹ O) is carbonyl Located at the α or β position of the group,
There are 2-6 carbon atoms in a set of adjacent carbonyl groups. ] The saturated aliphatic polycarboxylic acid represented by these and its derivative compound.

Specific examples thereof include ester compounds, amide compounds, anhydrides, hydrates and salts of saturated aliphatic polycarboxylic acid. Examples of the saturated aliphatic polycarboxylic acid include citric acid, malic acid, agaric acid and the like. Examples of the acid ester compound include acetyl ester of citric acid, mono- or distearyl ester and the like. As the acid amide compound, citric acid N, N′-diethylamide,
N, N'-dipropylamide, N-phenylamide,
N-dodecylamide, N, N'-di dodecylamide,
Further, N-dodecylamide of malic acid and the like can be mentioned.

(C) General formula X-Z-Y [wherein X is a formula:

[0055]

[Chemical 7] (In the formula, X ′ is F, Cl, Br, I, OH, OR ⁵ , or —O—CO—R ⁵ , and R ⁵ is H, an alkyl group or an aryl group). , Y is a carboxyl group, an acid anhydride group, an acid amide group, an imide group, a carboxylic acid ester group or a hydroxyl group, and X and Y
Are covalently bonded via a bond Z which is a hydrocarbon]. Specific examples thereof include chloroformyl succinic anhydride, chloroethanoyl succinic anhydride, trimellitic anhydride, acetic anhydride, terephthalic acid chloride and the like. Among the compounds listed in (a) to (c) containing these functional groups in the molecule, unsaturated dicarboxylic acid anhydrides are particularly preferable.

In the present invention, the amount of the compounds (a) to (c) having at least one functional group in the molecule used for modification is 100 parts by weight of polyphenylene ether.
0.01 to 20 parts by weight, preferably 0.1 to 1
0 parts by weight. When the amount of the compound used is less than 0.01 part by weight, the mechanical strength of the thermoplastic resin composition according to the present invention is not sufficient, and when it exceeds 20 parts by weight, the resin composition is colored or the fluidity is deteriorated. It is not preferable because

Regarding the method of reacting the polyphenylene ether with the modifying compound, a well-known solvent is used in the presence or absence of a radical generator, or a method of reacting the polyphenylene ether in the absence of a solvent is used. There is a method of efficiently performing the reaction by melt-kneading at a melting temperature, and any method may be used. If necessary, the modified polyphenylene ether of the component (A) in the thermoplastic resin composition of the present invention may be blended with an unmodified polyphenylene ether.

The (A) polyphenylene ether modified with a compound having a functional group capable of reacting with an amino group in the molecule of the present invention, and (B) at least one monomer or monomer selected from a specific group A thermoplastic resin composition composed of a modified propylene polymer in which a combination of polymers is graft-copolymerized is a thermoplastic resin composition of only a modified polyphenylene ether and a propylene polymer in various aspects such as heat resistance, mechanical properties, and appearance. Or a thermoplastic resin composition in which an interface is formed only by the intermolecular force of the styrene chain in the modified propylene polymer and the modified polyphenylene ether. This action in the present invention is combined with the reaction of the functional group in the modified polyphenylene ether and the amino group in the modified propylene polymer and the intermolecular force of the styrene chain in the modified polyphenylene ether and the modified propylene polymer, and the thermoplasticity according to the present invention This is considered to significantly improve the binding force at the interface between the modified propylene polymer and the modified polyphenylene ether in the resin composition and the dispersibility of the modified polyphenylene ether.

In the present invention, the intended thermoplastic resin composition can be obtained by setting the composition ratio of the component (A) and the component (B) within a specific range. The ratio of the component (A) to the component (B) in the present invention is preferably 99 to 1% by weight for the component (A) and 1 to 99% by weight for the component (B). Regarding the proportion of the component (A) and the component (B), if the component (A) is less than 1% by weight, the heat resistance of the composition is insufficient, and if it exceeds 99% by weight, the processability and the resistance of the composition are high. The chemical properties become insufficient.

In the resin composition of the present invention, it is more preferable that the component (A) is the dispersed phase and the component (B) is the continuous phase. In this case, the chemical resistance and moldability of the composition are excellent, and the molded article of the composition has a good appearance, which is preferable. In order to realize such a form in the composition, the ratio of the component (A) to the component (B) is 8
It is preferable that the content is 0 to 1% by weight and the component (B) is 20 to 99% by weight. More preferably, the component (A) is 70-
1% by weight, and the component (B) is preferably 30 to 99% by weight.

In the resin composition of the present invention, if necessary, an unmodified polyphenylene ether can be blended with the modified polyphenylene ether of the component (A), and the unmodified polyphenylene ether of the component (B) can be unmodified. A propylene polymer can be blended. Particularly, when an unmodified propylene polymer is blended, it is preferable in that the elongation rate is improved. Here, the modified polyphenylene ether and the unmodified polyphenylene ether are sufficiently compatible with each other, and the modified propylene polymer and the unmodified propylene polymer are sufficiently compatible with each other. Also in these cases, it is preferable that the compatible polyphenylene ether portion is the dispersed phase and the compatible propylene polymer portion is the continuous phase for the same reason as described above.

When an unmodified propylene polymer is further added to the modified propylene polymer of the component (B) in the thermoplastic resin composition of the present invention, each of the component (A), the component (B) and the unmodified propylene polymer is The ratio of
It is preferable that the component (A) is 1 to 90% by weight, the component (B) is 94 to 1% by weight, and the propylene polymer is 5 to 98% by weight. More preferably, the component (A) is 1 to 80% by weight, the component (B) is 94 to 10% by weight, and the propylene polymer is 10 to 89% by weight.

In the resin composition of the present invention, a rubber-like substance is optionally used as the component (C) for the purpose of improving impact resistance. The term "rubber-like substance" as used herein refers to a natural or synthetic polymer material that is elastic at room temperature.

Specific examples thereof include natural rubber, butadiene polymers, butadiene-styrene copolymers (including all random copolymers, block copolymers, graft copolymers, etc.), or hydrogenated products thereof. Isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, acrylic ester copolymer, ethylene-α-olefin copolymer, Styrene-isoprene copolymer or hydrogenated product thereof, styrene-ethylene-butylene copolymer, styrene-butylene copolymer, styrene-ethylene-propylene-copolymer, perfluoro rubber, fluororubber, chloroprene rubber, butyl rubber, Silicone rubber, ethylene-α-o Reffin-non-conjugated diene copolymer, thiochol rubber, polysulfide rubber, polyurethane rubber,
Examples thereof include polyether rubber (eg, propylene oxide), epichlorohydrin rubber, polyester elastomer, polyamide elastomer, and epoxy group-containing copolymer. The epoxy group-containing copolymer referred to here is a copolymer composed of an unsaturated epoxy compound and an ethylenically unsaturated compound.

The composition ratio of the component (C) to the sum of the component (A) and the component (B) is 0 to 100 parts by weight of the total weight of the component (A) and the component (B). 60 parts by weight is preferred. When the amount of the component (C) exceeds 60 parts by weight with respect to 100 parts by weight of the total weight of the components (A) and (B), the heat resistance of the composition is significantly lowered, which is not preferable.

In the thermoplastic resin composition used in the present invention, an inorganic filler is optionally used for the purpose of improving the rigidity, dimensional stability and the like of the molded product. Examples of such an inorganic filler include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, and the like. Among them, talc,
Calcium carbonate is preferably used. The inorganic filler having an average particle size of 0.05 to 10 μm is preferably used. If the particle size is less than 0.05 μm, the effect of improving the dimensional stability and rigidity of the molded product becomes small, and if it exceeds 10 μm, the surface gloss of the molded product is significantly impaired, and the object of the present invention cannot be achieved. Glass fibers can also be used as the inorganic filler.

In the thermoplastic resin composition used in the present invention, a melt fluidity improver can be used, if necessary, in addition to the above components. As the melt fluidity improver, known ones can be used, but preferred examples include white oil, liquid paraffin, low molecular weight hydrocarbon resin, low molecular weight polyolefin and the like, and modified products thereof are also used. can do. As the white oil here, those described in JP-A-2-238051 are used.

Liquid paraffin is obtained by distilling crude oil under atmospheric pressure and vacuum and then removing unsaturated components, aromatic components, sulfur components and the like. As the low molecular weight hydrocarbon resin referred to herein, those described in JP-A-2-160858 can be used. As the melt fluidity improver, the ones exemplified above can be used alone or in combination of two or more kinds.

If necessary, the thermoplastic resin composition of the present invention further contains an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, an inorganic or organic colorant, and an antirust agent. Various additives such as an agent, a cross-linking agent, a foaming agent, a fluorescent agent, a surface smoothing agent and a surface gloss improving agent can be added during the manufacturing process or in the subsequent processing process. To describe the flame retardants in more detail, the flame retardants useful in the present invention include the class of compounds well known to those skilled in the art. Generally, more important compounds among them, such as bromine, chlorine, antimony, phosphorus and nitrogen, which can impart flame retardancy such as those described in JP-A-2-160856, etc. A compound containing an element is used. For example, a halogenated organic compound, antimony oxide, antimony oxide and a halogenated organic compound, antimony oxide and a phosphorus compound, phosphorus alone or a phosphorus compound, a phosphorus compound or a compound having a phosphorus-nitrogen bond and a halogen-containing compound, or two kinds thereof. A mixture of the above is used.

The method for producing the thermoplastic resin composition according to the present invention is not particularly limited, and a commonly known method can be used. For example, a method of mixing in a solution state and evaporating a solvent or precipitating in a non-solvent is effective, but from an industrial point of view, a method of actually kneading in a molten state is preferable. For melt kneading, generally used kneading devices such as a single-screw or twin-screw extruder and various kneaders can be used. A biaxial high kneader is particularly preferable. Upon kneading, it is preferable that the respective components are uniformly mixed in advance with a device such as a tumbler or a Henschel mixer, but if necessary, the mixing may be omitted, and a method of separately supplying a fixed amount to the kneading device may also be used. it can. The kneaded resin composition is molded by injection molding, extrusion molding, and various other molding methods, but without undergoing the kneading process in advance, it is dry-blended during injection molding or extrusion molding and kneaded during the melt processing operation. Alternatively, the resin composition of the present invention can be used to directly obtain a molded product.

In the present invention, the kneading order is not particularly limited, and the components (A), (B) and (C) may be kneaded together, or the components (A) and (B) may be kneaded in advance. After that, the component (C) may then be kneaded. further,
Other kneading orders are possible.

[0072]

The modified propylene polymer of the present invention is excellent in coating properties, antistatic properties and mechanical properties,
By utilizing such characteristics, it is used for molded articles, sheets, tubes, films, fibers, laminates, coating materials and the like by injection molding or extrusion molding. It can also be used as a polymer alloying agent. The thermoplastic resin composition of the present invention is a resin composition excellent in heat resistance, melt fluidity, processability, chemical resistance, impact resistance, appearance and gloss, and by utilizing such characteristics, injection molding or It is used for molded articles, sheets, tubes, films, fibers, laminates, coating materials and the like by extrusion molding.

The modified propylene polymers and thermoplastic resin compositions of the present invention are especially useful for automobile parts such as bumpers,
Glove box, console box, brake oil tank, radiator grill, cooling fan, lamp housing, air cleaner, instrument panel, door trim, rear end trim, door panel,
It is also used for interior / exterior materials such as side protectors, air intakes, garnishes, trunk lids, sirocco fans, and roofs, as well as machine parts. Further, it is used as a motorcycle component, for example, a covering material, a muffler cover, a leg shield and the like. Further, it is used as an optical fiber cable covering material, and also as a housing for electrical, electronic parts, a chassis, a connector, a printed circuit board, a pulley and the like. In particular, the modified propylene polymer is used for parts requiring strength and antistatic properties. Further, particularly, the thermoplastic resin composition comprising the modified propylene polymer and polyphenylene ether is used for parts requiring strength and heat resistance.

[0074]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto. In addition, polyphenylene ether is PPE,
The propylene polymer is sometimes abbreviated as PP.

(I) Method for measuring physical properties of propylene polymer [Weight average molecular weight] All propylene polymers used were those produced in a laboratory. The weight average molecular weight (hereinafter sometimes referred to as Mw) of the propylene polymer and the modified propylene polymer was determined by a gel permeation chromatography method (hereinafter sometimes referred to as GPC method) according to a conventional method. [Styrene content] The styrene content in the modified propylene polymer was determined by changing the amount ratio of the homopropylene polymer and polystyrene and mixing them to prepare an infrared absorption spectrum (IR) calibration curve using a standard sample. Was measured by IR measurement. [Amino Group-Containing Monomer Content] The amino group-containing monomer content in the modified propylene polymer was obtained by determining the nitrogen content in the modified propylene polymer by an atomic absorption method and then converting the content.

[Amino Group-Containing Styrenic Monomer Content] The amino group-containing styrene-based monomer content was determined in the same manner as in the case of determining the styrene content. When both the amino group-containing styrene monomer and the amino group-containing monomer are graft-copolymerized with the modified propylene polymer, the nitrogen content in the modified propylene polymer is determined by atomic absorption spectrometry, and then I
The amino group-containing monomer content was determined by subtracting the amino group-containing styrene-based monomer content determined by R measurement.

[Flexural Modulus] Flexural modulus of propylene polymer and modified propylene polymer is IS1 manufactured by Toshiba Machine Co., Ltd.
Molding temperature of 250-2 using a 50E-V type injection molding machine
A molded article injection-molded at 30 ° C. and a mold cooling temperature of 70 ° C. was measured according to ASTM D790.

[Paintability] The coatability was measured as follows. Preparation of coating test plate sample: 150 mm (L) x 90 mm (W) x 2 mm (T) by controlling the resin composition of the present invention to a resin temperature of 230 ° C by the above injection molding machine.
A plate-shaped sample of was obtained. Paintability test: The above plate sample was surface-cleaned in 1,1,1-trichloroethane vapor (74 ° C) for 30 seconds and dried at room temperature, and then directly applied with a urethane-based paint (Nippon Bee Chemical Co., Flexen 101). ) Is spray painted and 120
A baking finish was performed for 30 minutes in an oven at ℃.

Next, after leaving this coating sample for 24 hours, 100 pieces of 2 mm squares (length 10 × width 10) were cut on the coating film of the coating sample with a razor blade, and a 24 mm wide cellophane tape was placed on it. (Product name, manufactured by Nichiban Co., Ltd.)
After being crimped with a finger, the end face was grasped and peeled off at a stretch, and the number of streaks left was evaluated as the residual rate (%).

[Surface Resistance] The antistatic property of the modified propylene polymer was evaluated by its surface resistance value. The surface resistance of the sample was 10 × 10 × 0.
The measurement was performed on a sheet of 2 (mm). At that time, an insulation resistance meter was used to measure the surface resistance value after 1 minute at a measurement temperature of 23 ° C. and an applied voltage of 500V.

(II) Method for measuring physical properties of thermoplastic resin composition Physical properties are measured by using a twin-screw extruder at a cylinder temperature of 260 to 33.
After kneading the composition at 0 ° C, use IS 150 manufactured by Toshiba Machine Co., Ltd.
Molding temperature 260 ℃ ～ 330 using EV type injection molding machine
C., mold temperature 70 to 140.degree. Deflection temperature test under load (HDT) is JIS K72
07, Izod impact strength (thickness 3.2 mm) is JIS K
Measured according to 7110. The reduced viscosity (η _SP / c) of polyphenylene ether is a value measured at 25 ° C. with a chloroform solution of 0.5 g / dl solution. The melt flow index (MI) of the propylene polymer was measured according to JIS K6758 at a temperature of 230 ° C. and a load of 2.16 kg.

The appearance of the injection-molded product was evaluated according to the following criteria. ◯: The appearance is beautiful, and no flow mark or color tone change is observed. X: Flow marks and color tone changes are observed on the surface of the molded product. The morphology of the composition was observed as follows. The injection molded product is cut with a microtome and etched with carbon tetrachloride. It was observed using a scanning electron microscope and classified as follows. A: Polyphenylene ether part (modified PPE and unmodified PPE) is dispersed phase, propylene polymer part (modified PPE)
P and unmodified PP) are continuous phases. B: The polyphenylene ether portion is a continuous phase and the propylene polymer is a dispersed phase.

The flexural modulus is according to ASTM D790
The measurement was performed on each of the welded portion and non-welded portion of the injection molded product. Surface impact strength is made by Rheometrics (USA)
3 mm using High Rate Impact Tester (RIT-8000 type)
Fix the thick flat plate tester piece with a 2-inch circular holder, and
/ 8 inch (spherical tip 5/16 inch R) impact probe at 23 ° C. and speed 1.5
The test piece was evaluated at m / sec. The energy value required for the material to break is expressed in joules (J).

(III) Raw Material of Thermoplastic Resin Composition (1) Component (A) Modified Polyphenylene Ether (i) η _SP /c=0.35 Polyphenylene Ether manufactured by Nippon Polyether Co., Ltd. 100 parts by weight of maleic anhydride is added. After blending 6.1 parts by weight and 2.9 parts by weight of styrene together with a radical initiator (trade name: Perbutyl PV, manufactured by NOF CORPORATION) and a stabilizer (trade name: Irganox 1010, manufactured by Ciba Geigy), and mixing with a Henschel mixer, Toshiba Machine Co., Ltd.
Using a twin-screw extruder, granulation was performed at a cylinder temperature of 265 ° C. to obtain modified polyphenylene ether. Hereinafter, the modified polyphenylene ether is abbreviated as A-1. (Ii) Maleic anhydride was added to 100 parts by weight of polyphenylene ether manufactured by Nippon Polyether Co., Ltd. with η _SP /c=0.4.
Parts by weight, styrene 5 parts by weight, radical initiator (trade name perbutyl PV), stabilizer (trade name Irganox 101)
0) and blended using a Henschel mixer,
Cylinder temperature using a twin-screw extruder manufactured by Toshiba Machine Co., Ltd.
Granulation was performed at 270 ° C. to obtain modified polyphenylene ether. Hereinafter, the modified polyphenylene ether is abbreviated as A-2.

(2) Modified propylene polymer of component (B) (i) 100 parts by weight of homopolypropylene (MI = 4.9),
3.9 parts by weight of p-aminostyrene (manufactured by Tokyo Kasei Co., Ltd.) was put into a twin-screw extruder together with a radical initiator (t-butylperoxy-2-ethylhexanoate) and a stabilizer,
Under a nitrogen atmosphere, kneading is performed at a cylinder temperature of 270 ° C,
A modified propylene polymer was obtained. Hereinafter, the modified propylene polymer is abbreviated as B-1. (Ii) p-aminostyrene (manufactured by Tokyo Kasei Co., Ltd.) 3.9
A modified propylene polymer was obtained in the same manner as in B-1 except that 2.3 parts by weight of aminomethylstyrene and 5.9 parts by weight of styrene were used instead of the parts by weight. Hereinafter, the modified propylene polymer is abbreviated as B-2. (Iii) Block polypropylene (MI = 6.2) 100
Parts by weight, p-aminostyrene (manufactured by Tokyo Chemical Industry Co., Ltd.) 12 parts by weight, styrene 6 parts by weight, glycidyl methacrylate 3
By weight, a radical initiator (trade name: perbutyl PV), a dispersant (trade name: Pluronic F68, manufactured by Asahi Denka Co., Ltd.),
Put it in an autoclave with water and put it under a nitrogen atmosphere.
A modified propylene polymer was obtained by reacting at about 1 hour for 1 hour.
Hereinafter, the modified propylene polymer is abbreviated as B-3.

(Iv) As a propylene polymer, 100 parts by weight of pellets of homopolypropylene (MI = 3.8) were added.
12 parts by weight of styrene monomer, 1 part by weight of glycidyl methacrylate and 14 parts by weight of diallylamine are used as a dispersant (Metroses 90SH-100, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.),
A radical initiator (trade name: Perbutyl PV) and water were put into an autoclave, and the mixture was reacted at 100 ° C. for about 1 hour while blowing nitrogen and then cooled to recover a modified propylene polymer. Hereinafter, this modified propylene polymer is abbreviated as B-4. (V) A modified propylene polymer was produced in the same manner as in B-4 except that diallylamine was not used. Hereinafter, this modified propylene polymer is abbreviated as B-5. (Vi) 100 parts by weight of pellets of block propylene polymer (MI = 7.4) as propylene polymer, styrene 27
Parts by weight, allylaniline 5 parts by weight, diallylamine 4 parts by weight, a dispersant (trade name Pluronic F68), a radical initiator (1,1-bis (t-butylperoxy) 3,3,5-
(Trimethylsiloxane) and water were put into an autoclave, reacted at 90 ° C. for about 1 hour while blowing nitrogen, and then cooled to recover a modified propylene polymer. Hereinafter, this modified propylene polymer is abbreviated as B-6. (3) Component (C) rubber-like substance Abbreviation Content C-1: ethylene-propylene-diene copolymer rubber modified with maleic anhydride and styrene C-2: ethylene-propylene-non-conjugated diene copolymer Combined rubber Trade name Esplen E301 (Sumitomo Chemical Co., Ltd., ML _{1 + 4} 100 ° C. = 55) C-3: Ethylene-epoxy acrylate copolymer Trade name Bondfast 2C (Sumitomo Chemical Co., Ltd.)

Example 1 Raw material homopropylene polymer (Mw = 12600) 100
Parts by weight, styrene 11 parts by weight, diallylamine 28 parts by weight, water 500 parts by weight, dispersant (Metroses 90SH-1
00 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) 1.6 parts by weight of a radical initiator t-butyl peroxypivalate 1.
It was put into an autoclave together with 2 parts by weight and reacted at 102 ° C. for about 1 hour in a nitrogen atmosphere. From the polymer obtained by this polymerization reaction, an ungrafted styrene-diallylamine copolymer produced simultaneously with the modified propylene polymer was extracted by the treatment with methyl ethyl ketone. Next, a modified propylene polymer was obtained by extracting and removing the homopropylene polymer by treatment with xylene. The graft efficiency at this time was 83%. Hereinafter, the modified propylene polymer may be abbreviated as P-1.

The Mw of the ungrafted styrene-diallylamine copolymer extracted by the treatment with methyl ethyl ketone was measured by the GPC method to determine the Mw of the grafted chain. Also, this Mw and M of the propylene polymer before and after modification
The average number of graft chains in one molecule of the modified propylene polymer (A-1) was calculated by converting from w. The results are shown in Table 1. The average number of graft chains was similarly determined for the following modified propylene polymers. Table 2 shows the physical properties of the obtained modified propylene polymer.

The modified propylene polymer (A
1) and IR spectra of the starting homopropylene polymer. In addition, FIG. 2 shows the IR spectrum of polystyrene (infrared absorption diagram Sozo, Sankyo Publishing), FIG. 3 shows the IR spectra of styrene monomer, and FIG. 4 shows the IR spectra of diallylamine monomer (Aldrich diagram of IR spectrum, THE A
LDRICH LIBRARY OF INFARERE
D SPECTRA). It is found from the IR spectrum of the modified propylene polymer (A-1) that these free monomers do not exist. As shown by the arrows in FIG. 1, at about 700, 755 and 890 cm ⁻¹ , the modified propylene polymer has an IR absorption not found in the homopropylene polymer, which is based on the graft copolymerized styrene and diallylamine. I know there is.

Comparative Example 1 Table 2 shows the physical properties of the homopropylene polymer (Mw = 12600).

Example 2 100 parts by weight of a homopropylene polymer (Mw = 18000), 9 parts by weight of styrene, 46 parts by weight of vinylimidazole, 12 parts by weight of glycidyl methacrylate were added to 400 parts by weight of water, and a dispersant (Metroze 90SH-100 (commercial product)). Name), manufactured by Shin-Etsu Chemical Co., Ltd.), 3.1 parts by weight, and 0.8 parts by weight of a radical initiator t-butylperoxypivalate were charged into an autoclave and reacted at 96 ° C. for about 1 hour. The united body was collected and vacuum dried. Further, the same treatment as in Example 1 was performed to obtain a modified propylene polymer. The graft efficiency at this time was 72%. Hereinafter, the modified propylene polymer may be abbreviated as P-2. The number of graft chains of the resulting modified propylene polymer is shown in Table 1.
Table 2 shows the physical properties.

Comparative Example 2 Table 2 shows the physical properties of the homopropylene polymer (Mw = 18000).

Example 3 100 parts by weight of a random propylene polymer (ethylene content 2.1% by weight, Mw = 45100), 7 parts by weight of allylaniline, and 9 parts by weight of p-aminostyrene were used as stabilizers (Irganox 1010 (trade name). ), Manufactured by Ciba Geigy)
0.1 part by weight and 1.2 parts by weight of a radical initiator t-butylperoxypivalate were charged into a twin-screw extruder and melt-kneaded at a cylinder temperature of 230 ° C. The obtained polymer was treated in the same manner as in Example 1 to obtain a modified propylene polymer. The graft efficiency at this time was 52%. Hereinafter, the modified propylene polymer may be abbreviated as P-3. The number of graft chains and the like of the obtained modified propylene polymer are shown in Table 1 and various physical properties are shown in Table 2.

Comparative Example 3 Various physical properties of the homopropylene polymer (Mw = 45100) are shown in Table 2.

Example 4 Modified propylene polymer (P-2) 7 obtained in Example 2
5 parts by weight and homopropylene polymer (Mw = 18000)
25 parts by weight of t-butyl peracetate as a radical initiator, 0.4 parts by weight of stabilizer and 0.3 part by weight of stabilizer (Irganox 1010 (trade name), manufactured by Ciba-Geigy) were charged into a twin-screw extruder, and the cylinder temperature was changed. Melt kneading at 230 ° C. to obtain a modified propylene polymer composition. Table 2 shows the physical properties of the obtained modified propylene polymer composition. From the above Examples and Comparative Examples, it can be seen that the modified propylene polymer of the present invention exhibits excellent coating properties, antistatic properties and mechanical properties.

Examples 5 to 12 and Comparative Examples 4 to 12 Each component was blended and kneaded with the compositions shown in Tables 3 to 6 and the physical properties were measured. The obtained results are shown in Tables 3-6.

[0097]

[Table 1]

[0098]

[Table 2]

[0099]

[Table 3]

[0100]

[Table 4]

[0101]

[Table 5]

[0102]

[Table 6]

[Brief description of drawings]

FIG. 1 is an IR spectrum of the modified polypropylene of the present invention of Example 1 and a homopolypropylene as a raw material. (Modified polypropylene--solid line, homopolypropylene--dotted line)

FIG. 2 is an IR spectrum of polystyrene.

FIG. 3 is an IR spectrum of styrene.

FIG. 4 is an IR spectrum of diallylamine.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masashi Yamamoto 5-1 Anezaki Kaigan, Ichihara City, Chiba Sumitomo Chemical Co., Ltd.

Claims (2)

[Claims] 1. To 100 parts by weight of a propylene polymer, at least one monomer or a monomer selected from the group consisting of the following monomers (a) to (d) and a combination of monomers: 1 to 200 parts by weight of the combination is graft-copolymerized, and the average number of graft chains per propylene polymer molecule is 1 to 10
A modified propylene polymer having a graft chain weight average degree of polymerization of 1 to 100 and a weight average molecular weight of 1,000 to 500,000. (A) Amino group-containing styrene-based monomer. (B) A styrene-based monomer and an amino group-containing monomer, wherein the weight ratio of the styrene-based monomer and the amino group-containing monomer is in the range of 0.01 to 100. (C) Amino group-containing styrene-based monomer and styrene-based monomer, the weight ratio of the amino group-containing styrene-based monomer and the styrene-based monomer being in the range of 0.01 to 100 .. (D) Amino group-containing styrene monomer and amino group-containing monomer, wherein the weight ratio of the styrene monomer and the amino group-containing monomer is within the range of 0.01 to 100. .. (However, the above-mentioned styrene-based monomer and amino group-containing monomer exclude amino group-containing styrene-based monomers.) 2. A polyphenylene ether modified with a compound (A) having a functional group capable of reacting with an amino group in the molecule, and (B) a modified propylene polymer according to claim 1, wherein the component (A) is 99. ~ 1 wt%, component (B) 1-9
A thermoplastic resin composition which is 9% by weight.