JPH0198645A - Thermoplastic resin composition and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a thermoplastic resin composition with excellent heat resistance and rgI resistance, and the composition can be used for electrical/electronic mechanical parts, automobile parts, etc. It can be used in a wide range of fields.

[Prior Art] Polypropylene has excellent properties such as moldability and chemical resistance, and is inexpensive, so it is widely used in various molded products. However, polypropylene has problems with impact resistance, paintability, heat resistance, adhesion, etc., and has drawbacks that limit its uses.

On the other hand, polyphenylene oxide has excellent characteristics such as heat resistance and mechanical properties, but improvements in moldability, impact resistance, chemical resistance, etc. are desired.

[Problems to be solved by the invention] By compensating for the respective disadvantages of polypropylene and polyphenylene oxide with other advantages, a thermoplastic resin with extremely excellent properties can be obtained. It should work.

However, since polypropylene and polyphenylene oxide have different chemical structures, their compatibility is extremely poor, and the advantages of each can hardly be utilized.

[Means for Solving the Problems] As a result of intensive research to solve these problems, the present inventors have found that by using a thermoplastic resin having a specific multiphase structure, polypropylene and polyphenylene oxide can be combined. By improving compatibility, we have completed a thermoplastic resin composition that combines the excellent moldability, impact resistance, and chemical resistance of polypropylene with the excellent heat resistance and mechanical properties of polyphenylene oxide.

In other words, the first invention of the present invention comprises (I) polypropylene 99-1fflfi)%, (II
) from 1 to 990 M% of polyphenylene oxide, from 5 to 95 M% of a combination of (Ill) pyrene m, based on 100 parts by weight of the above (I) + (II), and at least one vinyl monomer. A multiphase thermoplastic resin (C ) 0.1 to 100 parts by weight, and (IV) 0 to 150 parts by weight of an inorganic filler based on 100 parts by weight of the above (I) + (I) + (III).

Furthermore, the second invention of the present invention includes adding at least one weight of a vinyl monomer, at least one radical (co)polymerizable organic peroxide, and a radical polymerization initiator to an aqueous suspension of a propylene polymer; The propylene polymer is impregnated with the vinyl monomer, the radical (co)polymerizable organic peroxide, and the radical polymerization initiator by heating under conditions in which decomposition of the radical polymerization initiator does not substantially occur. When the ratio reaches the initial 50% by weight or more, the hot water level of this aqueous suspension is raised, and the hinyl l-mer and the radical (co)polymerizable organic peroxide are copolymerized in the propylene polymer. Combined grafted precursors (A) 1-10
0%, propylene polymer (B) 0 to 99% by weight, and a vinyl (co)polymer (C) obtained by polymerizing at least one vinyl monomer 0 to 99% by weight, polypropylene ( I) and polyphenylene oxide (II), or melt and mix (A), (B) and (C) in advance at a temperature of 130 to 300°C to obtain a multiphase thermoplastic resin (III). This is a method for producing a thermoplastic resin composition, which comprises melting and mixing the above (I) and (II).

The polypropylene (I) used in the present invention is a crystalline polypropylene, which is not only a homopolymer of propylene but also a block or random copolymer made by copolymerizing propylene with an α-olefin such as ethylene or butene-1. Includes combinations, etc.

The polyphenylene oxide used in the present invention has the general formula [wherein R%R2, R3, R4, and R5 are selected from hydrogen, a halogen atom, a hydrocarbon group, or a substituted hydrocarbon group; One hydrogen atom is a hydrogen atom] This is a polymer obtained by oxidative polymerization of a phenol compound represented by the following formula with oxygen or M wood-containing gas using a coupling catalyst.

Specific examples of R1R2, R3, R4, and R5 in the above general formula include hydrogen, chlorine, fluorine, iodine, bromine,
Methyl, ethyl, propyl, butyl, chloroethyl, hydroxylethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl and the like.

Specific examples of the above general formula include phenol, 00, m or p-cresol, 2,6-12,5-12.4-1
or 3,5-dimethylphenol, 2-methyl-6-
phenylphenol, 2,6-diphenylphenol,
2.6-dimethylphenol, 2-methyl-6-ethylphenol, 2°3.5-12.3.6- and 2.4
．． Examples include 6-dorimedylphenol. Two or more types of these phenol compounds can also be used.

Further, a copolymer of a phenol compound having the above general formula and a dihydric phenol such as bisphenol A1 tetrabromo-sphenol A, resorcinol, hydroquinone, etc., and a phenol compound having the above general formula may also be used.

Specifically, the vinyl (co)polymer in the multiphase thermoplastic resin used in the present invention includes styrene, nuclear-substituted styrene such as methylstyrene, dimethylstyrene,
Ethylstyrene, isobrobylstyrene, chlorstyrene, α-substituted styrene such as α-methylstyrene, α-
Ethyl styrene is a (co)polymer obtained by polymerizing one or more vinyl aromatic monomers and (meth)acrylonitrile monomers.

Polyphase Ii in the present invention! 3. Thermoplastic resin is a resin in which a vinyl (co)polymer or propylene polymer, which is a different component, is uniformly dispersed in a spherical shape in a propylene polymer or vinyl (co)polymer matrix. means.

The particle size of the dispersed polymer is 0.001 to 10 μm1
Preferably it is 0.01 to 5 μm.

When the dispersed resin particle size is less than 0.001 μm or 1
If it exceeds 0 μm, the compatibilization of polypropylene and polyphenylene oxide becomes insufficient, resulting in a decrease in impact resistance and delamination.

The number average degree of polymerization of the vinyl (co)polymer in the multiphase thermoplastic resin of the present invention is 5 to io, ooo, preferably 10 to
It is in the range of 5.000.

If the number average degree of polymerization is less than 5, it is possible to improve the impact resistance of the thermoplastic resin composition of the present invention, but it is not preferable because the heat resistance decreases.

Moreover, if the number average degree of polymerization exceeds 10,000, the melt viscosity will be high, the moldability will be lowered, and the surface gloss will be lowered, which is not preferable.

The multiphase thermoplastic resin of the present invention comprises 5 to 95% by weight of propylene polymer, preferably 20 to 90fflf1%. Therefore, the vinyl (co)polymer content is 95 to 5% by weight, preferably 80 to 10% by weight.

When the propylene polymer content is less than 5% by weight, the compatibilization effect with polypropylene cannot be sufficiently exhibited, and when the propylene polymer content exceeds 95% by weight, the thermoplastic resin composition of the present invention has poor heat resistance and dimensional stability. It is not desirable because it impairs sexuality.

The grafting method for producing the multiphase structured thermoplastic resin of the present invention may be any of the generally well-known methods such as chain transfer method and ionizing radiation irradiation method, but the most preferred methods are as follows. This is based on the method shown in . The reason for this is that the grafting efficiency is high and secondary aggregation due to heat does not occur, so performance is more effectively expressed.

Hereinafter, the method for producing the thermoplastic resin composition of the present invention will be specifically explained.

That is, 100 parts by weight of a propylene polymer is suspended in water, and 5 to 400 parts by weight of at least one type of vinyl monomer is added with Radius 7J (compound) represented by the following general formula (a) or (b). ) One type or a mixture of two or more polymerizable organic peroxides at a rate of 0.1 per 1m of the vinyl and 100 sides of the vinyl.
~10 parts by weight of a radical polymerization initiator with a decomposition humidity of 40 to 90°C to obtain a half-life of 10 hours is combined with a vinyl monomer and a radical (co)polymerizable organic peroxide.
A solution in which 0.01 to 5 parts by weight of the vinyl monomer, radical A propylene polymer is impregnated with a polymerizable organic peroxide and a radical polymerization initiator, and when the impregnation rate reaches the initial 50% by weight or more, the temperature of this aqueous suspension is increased and the vinyl monomer is and a radical (co)polymerizable organic peroxide in a propylene polymer to obtain a grafting precursor (
A) is obtained.

This grafted precursor is also a multiphase thermoplastic.

Therefore, this grafting precursor (A) may be directly melted and mixed with polypropylene and polyphenylene oxide.

Moreover, the multiphase structure thermoplastic resin of the present invention can also be obtained by kneading the grafted precursor (A) while melting at 100 to 300°C. At this time, the grafting precursor (A
A multiphase thermoplastic resin can also be obtained by separately mixing a propylene polymer or a vinyl (co)polymer and kneading it while melting. Most preferred is a multiphase thermoplastic resin obtained by kneading a grafted precursor.

The radical (co)polymerizable organic peroxide represented by the general formula (a) is a radical (co)polymerizable organic peroxide represented by the general formula [wherein R11 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R2 is a hydrogen atom or a methyl group, R3 and R4
are each an alkyl group having 1 to 4 carbon atoms, and R5 is an alkyl group having 1 to 4 carbon atoms.
~12 alkyl group, phenyl group, alkyl-substituted phenyl group or cycloalkyl group having 3 to 12 carbon atoms,
m is 1 or 2. ] This is a compound represented by

In addition, the radical (co)polymerizable Isiso peroxide represented by the general formula (b) is a radical (co)polymerizable ion peroxide represented by the general formula [wherein R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R is a hydrogen atom or a methyl group, R8 and R9 are each an alkyl group having 1 to 4 carbon atoms, and R is an alkyl group having 1 to 12 carbon atoms.
represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, and n is 0.
, 1 or 2. ] This is a compound represented by

Examples of the radical (co)polymerizable organic peroxide represented by the general formula (a) include t-butylperoxyacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethyl carbonate, and t-butylperoxyacryloyloxyethyl carbonate. xylperoxyacryloyloxyethyl carbonate, 1,1
．． 3.3-Tetramethylbutylberoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isobu [i bicumylperoxyacryloyloxyethyl carbonate-1, t
-butylberoxymethacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethyl carbonate, t-hexylperoxymethacryloate, 1.1.3.3-tetramethylbutylperoxymethacryloyloxyethyl carbonate, cumylperoxymethacrylate carbonate, p-isoprobylcumylperoxymethacryloyloxyethyl carbonate, t-butylperoxyacryloyloxyethoxyethyl carbonateoxyethoxyethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate, 1
．． 1,3.3-Tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate, milperoxyacryloyloxyethoxyethyl carbonate, p
- Isoprovir cumylberoxyacryloyloxiche 1
-xyethyl carbonate, t-butylperoxymethacryloyl 0-oxyethoxyethyl carbonate, t-amylperoxymethacryloyl oxyethoxyethyl carbonate, t-hexylperoxymethacryloy 3,3-tetramethylbutylberoxymethacryloy 0
xyethoxyethyl carbonate, cumylperoxymethacryloyloxethoxyethyl carbonate, p-isoprobylcumylberoxymethacryloyloxyethoxyethyl carbonate, t-butylperoxyacryl 0
I0oxyisopropyl carbonate, t-amylberoxyacryloyloxyisopropyl carbonate, t-
Hexylperoxyacrybonate, 1.1,3.3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate, p-impovircumylperoxyacrybonate, t-butylberoxymethacryloyloxyisopropyl carbonate, t-amylberoxymethacryloyloxyisopropyl carbonate, t-hexylperoxymethacryloyloxyisopropyl carbonate, 1,1.3.3-te]-ramethylbutylperoxymethacryloyloxyisopropylcarbonate , cumylperoxymethacryloyloxyisobutylcarbonate, p-isobrobylcumylperoxymethacryloyloxyisopropyl carbonate, and the like.

Furthermore, as a compound represented by general formula (b), t
-Butyl peroxyallyl carbonate t-amyl peroxyallyl carbonate hexyl peroxyallyl carbonate, 1.1.

3, 3-tetramethylbutyl peroxyallyl carbonate, p-menthane peroxyallyl carbonate, cumyl peroxyallyl carbonate, t-butylperoxymethallyl carbonate-amyl peroxymethallyl carbonate hexylberoxymethallyl carbonate, 1.

1,3.3-Tetramethylbutylperoxymethallyl carbonate, p-menthane peroxymethallyl carbonate, cumylperoxymethallyl carbonate tyl carbonate, t-7 milberoxyallyloxyethyl carbonate, t-hexylperoxyallyloxyethyl carbonate carbonate, t-butylperoxyallyloxyethyl carbonate, 1-amylperoxymethallyloxyethyl carbonate, t-hexylberoxymethallyloxyethyl carbonate, t-butylperoxyallyloxyimpropyl carbonate, t-amylperoxyallyloxyisopropyl carbonate, t-hexylperoxy 7-lyloxyisopropyl carbonate, t-
Examples include butylberoxymetallyloxyisopropyl carbonate, t-amylberoxymetallyloxyisopropyl carbonate, t-hexylberoxymetallyloxyisopropyl carbonate, and the like.

Among these, preferred are t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-butylperoxyallyl carbonate, and t-butylperoxymethallyl carbonate.

In the present invention, the above (I) + (IF) + (I
II) 0 to 150 per 100 Jutabe of the resin component
Up to parts by weight of inorganic fillers (IV) can be included.

Examples of the above-mentioned inorganic fillers include granular, tabular, scaly, acicular, spherical or hollow, and fibrous fillers, and specific examples include calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, and silica sand. , glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, etc. Powder/granular fillers: mica, glass plate, sericite, pyrolite, aluminum flakes, etc. Flat or scaly fillers such as metal foil and graphite; Hollow fillers such as shirasu balloons, metal balloons, glass balloons, and pumice; glass fibers, carbon fibers, graphite 15 fibers, whiskers, metal fibers, silicon carbide tHIlf Examples include mineral fibers such as , asbestos, and wolstonite.

If the blending amount of filler exceeds 150 polymerization, the molded product's ma
This is not preferable because the strength decreases.

In addition, the surface of the inorganic filler is coated with stearic acid, oleic acid, palmitic acid or their metal salts, paraffin wax, polyethylene wax, or (modified products thereof, organic silane, organic borane, organic titanate, etc.). It is preferable to perform treatment.

The thermoplastic resin composition of the present invention comprises polypropylene, polyphenylene oxide resin, and multiphase thermoplastic resin at a temperature of 130 to 300°C, preferably 200 to 300°C.
By melting and mixing with 1! J is built.

The melting and mixing can be carried out using a commonly used kneading machine such as a mixing roll, a Banbury mixer-1 pressure kneader-1 kneading extrusion mill, a twin-screw extruder, or a roll.

Regarding the order of melting and mixing, all the components may be melted and mixed at the same time, or the polypropylene or polyphenylene oxide and the multiphase thermoplastic resin may be melted and mixed in advance, and then the other resin may be melted and mixed. You may.

In the present invention, other thermoplastic resins such as polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins,
Polycarbonate resin, polyamide resin, polyphenylene nalphide resin, porsulfone resin, natural rubber, synthetic rubber, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen type and phosphorus type, and antioxidants. Additives such as UV inhibitors, lubricants, dispersants, foaming agents, crosslinking agents, and coloring agents may be added.

[Example 1 Next, the present invention will be explained in more detail with reference to Examples.

Reference example 1 [Manufacture of multiphase structure thermoplastic resin (1)] Volume 5
Pure water 2,500 yen in fJ stainless steel autoclave
Add 2 g of polyvinyl alcohol as a suspending agent to a colander.
．． 59 was dissolved. Polypropylene (trade name: Nippon Seki Polypro J130GJ (manufactured by NOF Corporation) was stirred and dispersed in a nitrogen atmosphere.

Separately, benzoyl peroxide as a radical polymerization initiator [trade name: Niper BJ (manufactured by NOF Corporation) (1
0 hour half-life temperature 74°C) i, 5q, t-butylberoxymethacryloyloxyethyl carbonate 6q as a radical (co)polymerizable organic peroxide is dissolved in styrene 300Q as a vinyl monomer, and this solution is The mixture was placed in the autoclave and stirred.

Next, the autoclave was warmed to 60 to 65° C. and stirred for 2 hours to impregnate the vinyl monomer containing the radical polymerization initiator and the radical (co)polymerizable organic peroxide into the polypropylene.

Next, after confirming that the total amount of free vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator is at least 50% by weight, the temperature is increased to 80 to 85°C. The polymerization was completed by raising the temperature to 7 hours and washing with water and drying to obtain a grafted precursor.

This grafted precursor was heated at 180°C using a Labo Blast Mill B-75 mixer (manufactured by Toyo Seiki Seisakusho Co., Ltd.).
The grafting reaction was carried out by kneading for 10 minutes at a rotational speed of 5 rpm.

From this grafted product, the ungrafted copolymer was extracted with ethyl acetate using a Soxhlet extractor, and the grafting efficiency was determined. As a result, the grafting efficiency of styrene was 51% by weight. Furthermore, the xylene insoluble content was determined by extraction with xylene and was found to be 12.6% by weight.

Propylene homopolymer with a VFR of 4.0
J130GJ (manufactured by Nippon Petrochemicals), polyphenylene oxide, and the multiphase thermoplastic resin obtained in Reference Example were melted and mixed in the proportions shown in Table 1.

The melting/mixing method involved supplying the materials to a co-directional twin-screw extruder (manufactured by Plastic Engineering Research Institute Co., Ltd.) with a screw diameter of 3011 m set at a cylinder temperature of 250° C., and melting and mixing within the cylinder. After the mixed resin is granulated, 1
After drying at 50° C. for 3 hours, test pieces were prepared by injection molding.

The size of the test piece is as follows.

Izotsu impact test piece 13s-x 65 gardens x 6 seagulls- Load deflection temperature test piece 13ssx 130mm x 6sue For chemical resistance, the test piece was immersed in gasoline for 1.5 hours, and then its appearance was observed.

O: No change Δ: Part of the coating surface is eluted ×: Significant surface elution Examples 7 to 11 The grafted multiphase M4 thermoplastic resin of the above example was converted into a graph 1-formed precursor obtained in the reference example. Table 2 shows examples in which . This case also shows the same effect as the grafted multiphase thermoplastic resin.

Examples 12 to 16 In addition to the above examples, the average va rough length is 0.311I11
Table 3 shows an example in which glass fibers having a diameter of 10 μm were blended.

也ILL: 22 Apart from the above examples, Table 4 shows an example using an ethylene-glycidyl methacrylate copolymer and modified polypropylene (polypropylene graft-modified with 10.1% by weight of maleic anhydride). Ta. .

Table 1 Table 2 Table 3 Table 4 (*) Glycidyl methacrylate-1 - Content 15% by weight
[Effects of the Invention] The thermoplastic resin composition of the present invention is a resin composition that takes advantage of the respective advantages of polypropylene and polyphenylene oxide and has excellent heat resistance, impact resistance, and adhesiveness. Therefore, it can be used in a wide range of applications such as automobile parts, electrical/electronic parts, and industrial parts.

Patent applicant: Nippon Petrochemical Co., Ltd. Representative: Akimoto Tsuyoshi (7゛I) Akimoto Fuji Mie
: Procedural amendment 1, Indication of the case Patent Application No. 257682 of 1988 2, Name of the invention Thermoplastic resin composition and its manufacturing method 3, Person making the amendment Relationship with the case Patent applicant name Nippon Petrochemical Co., Ltd. 4. Agent address: 1-1-5 Minami-Aoyama-chome, Minato-ku, Tokyo, voluntary as of the date of the amendment order) (Date of dispatch) Month, Day, 7, 1939 Contents of the amendment (1) Scope of patent claims as shown in the attached sheet correct.

(2) Insert the following sentence between lines 12 and 13 on page 22 of the specification.

In the present invention, the amounts of (I) and (IF) are selected depending on the intended use of the composition.

That is, if the purpose is to maintain the characteristics of polypropylene while improving its disadvantages such as impact resistance, paintability, and adhesion, polypropylene should be used in an amount of 50 to 99% by weight, preferably 60 to 99% by weight.
95% by weight is required.

The reason for this is that if the polypropylene content is less than 50% by weight, the moldability and chemical resistance, which are characteristics of polypropylene, will be impaired, and if it exceeds 99% by weight, the impact resistance, paintability, and adhesion properties, which are one of the objectives of the present invention, will be impaired. This is because it has no effect on improving sex.

If the purpose is to maintain the characteristics of polyphenylene oxide resin while improving its disadvantageous chemical resistance, it is necessary to use 50 to 99 weight 1 L of polyphenylene oxide resin, preferably 60% to 95% by weight.

If the polyphenylene oxide resin is less than 50% by weight, the heat resistance, impact resistance, and adhesive properties of the polyphenylene oxide resin will not be improved, and if it exceeds 99% by weight, the moldability and chemical resistance, which are one of the objectives of the present invention, will be impaired. It is not preferable because it has no improvement effect.

The multiphase structure thermoplastic resin of the present invention has 0.1 to 10
0 parts by weight, preferably 1 to 50 parts by weight can be used.

If the multiphase structure thermoplastic resin is less than 0.1 parts by weight, it is not preferable because there is no compatibilizing effect and the W impact strength decreases, and delamination occurs in the molded product, deteriorating the appearance. Also, 100
If the amount exceeds 1 part by weight, the heat resistance of the composition decreases, which is not preferable. ” (3) Same, page 28, line 11, ro, 3jw+J is changed to “5
．． Correct it to 0 J.

(4) Table 1 on page 29 of the same is corrected as shown in the attached sheet.

(5) Table 2 on page 30 of the same is corrected as shown in the attached sheet.

(6) Table 3 on page 31 of the same is corrected as shown in the attached sheet.

(7) Table 4 on page 32 of the same is corrected as shown in the attached sheet.

Above 2, Claim (1) (I) 99 to 1% by weight of polypropylene, ([) 1 to 99% by weight of polyphenylene oxide, and (III) based on 100 parts by weight of the above (I) + (II). ) 5 to 95% by weight of a propylene polymer and 95 to 5% by weight of a vinyl-based (co)polymer obtained from at least one vinyl monomer, one of the (co)polymers having a particle size of 0.5% by weight. 0.1 to 100 parts by weight of a multiphase thermoplastic resin forming a dispersed phase of 0.001 to 10 um, and (IV) inorganic to 100 parts by weight of the above (I) + (IF) + (I [I) A thermoplastic resin composition containing 0 to 150 parts by weight of a filler.

(2) The thermoplastic resin with a multiphase structure is composed of at least one vinyl monomer and the following general formula (a) or (b) R1 [wherein R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms] , R2 and R7 are hydrogen atoms or methyl groups, R6 is hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, RR and R8
, R9 respectively represent an alkyl group having 1 to 4 carbon atoms, RR 5 and 1o represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms, m
is 1 or 2, and n is 0.1 or 2. ] Grafting precursor (A) obtained by copolymerizing at least one radical (co)polymerizable organic peroxide represented by in propylene polymer particles 1 to 100
weight R%, propylene polymer (B) 0-99% by weight, and vinyl-based (co)polymer (C) obtained by (co)polymerizing at least one vinyl monomer 0-99% weight The thermoplastic resin composition according to claim 1, which is a mixture consisting of and/or a grafted product obtained by melt-mixing them.

(3) The vinyl monomer is a vinyl aromatic monomer, (meth)
Claim 1 or 2 is one or more vinyl monomers selected from the group consisting of acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester 01 monomers. The thermoplastic resin composition described in .

(4) an aqueous suspension of propylene polymer containing at least one
A seed vinyl monomer, at least one radical (co)polymerizable organic peroxide, and a radical polymerization initiator are added, and the vinyl monomer is heated under conditions that substantially do not decompose the radical polymerization initiator. A propylene polymer is impregnated with a polymer, a radical (co)polymerizable organic peroxide, and a radical polymerization initiator, and when the impregnation rate reaches the initial 50% by weight or more, the temperature of this aqueous suspension is increased. A grafting precursor (A) in which a vinyl monomer and a radical (co)polymerizable organic peroxide are copolymerized in a propylene polymer.
1 to 100% by weight, propylene polymer (B) 0 to 99% by weight, and a vinyl (co)polymer (C) obtained by combining at least one vinyl single metal body 0 to 99% by weight. by melting and mixing with polypropylene (I) and polyphenylene oxide (n), or by melting and mixing (A), (B) and (C) in advance in the range of 130 to 300°C to obtain a multiphase thermoplastic resin. (IID), said (I) and (
II) A method for producing a thermoplastic resin composition, which comprises melting and mixing with the thermoplastic resin composition.

(5) The radical (co)polymerizable organic peroxide has the following general formula (a) or (b) R7 (wherein R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and RR is a hydrogen atom or methyl group, 2ゝ7 R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, RR
and RR each represent an alkyl group having 1 to 4 carbon atoms, R5 and Rlo each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, and m is 1 or 2, and n is 0, 1 or 2. ] The method for producing a thermoplastic resin composition according to claim 4, wherein the thermoplastic resin composition is one or a mixture of two or more peroxycarbonate compounds represented by:

(6) Vinyl monomer is vinyl aromatic monomer, (meth)
Claim 4 or 5 is one or more vinyl monomers selected from the group consisting of acrylic acid ester monomers, (meth)acrylonitrile monohangers, and vinyl ester monomers. A method for producing a thermoplastic resin composition as described in Section 1.

Table 1 Table 2 Table 3 Table 4

Claims (6)

[Claims] (1) (I) 99-1% by weight of polypropylene, (II)
1 to 99% by weight of polyphenylene oxide, 5 to 95% by weight of (III) propylene polymer based on 100 parts by weight of (I) + (II), and at least one vinyl monomer. 0.1 to 100 parts by weight of a thermoplastic resin with a multiphase structure, consisting of 95 to 5% by weight of a co)polymer, in which one of the (co)polymers forms a dispersed phase with a particle size of 0.001 to 10 μm; and a thermoplastic resin composition comprising 0 to 150 parts by weight of (IV) an inorganic filler per 100 parts by weight of the above (I) + (II) + (III). (2) A thermoplastic resin with a multi-phase structure contains at least one vinyl monomer and the following general formula (a) or (b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(a) ▲Mathematical formulas, chemical formulas, There are tables etc.▼(b) [In the formula, R_1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R_2 and R_7 are hydrogen atoms or a methyl group, R_
6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R_3
, R_4 and R_8, R_9 each have 1 to 4 carbon atoms.
The alkyl group, R_5, R_1_0 represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, m is 1 or 2, and n is 0, 1 Or 2. ] 1 to 100% by weight of a grafting precursor (A) in which at least one radical (co)polymerizable organic peroxide represented by is copolymerized in propylene polymer particles, propylene polymer (B) 0% -99% by weight, and a mixture and/or grafted product consisting of 0-99% by weight of a vinyl (co)polymer (C) obtained by (co)polymerizing at least one vinyl monomer The thermoplastic resin composition according to item 1. (3) The vinyl monomer is a vinyl aromatic monomer, (meth)
Claim 1 or 2 is one or more vinyl monomers selected from the group consisting of acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers. The thermoplastic resin composition described in . (4) an aqueous suspension of propylene polymer containing at least one
A seed vinyl monomer, at least one radical (co)polymerizable organic peroxide, and a radical polymerization initiator are added, and the vinyl monomer is heated under conditions that substantially do not decompose the radical polymerization initiator. A propylene polymer is impregnated with a polymer, a radical (co)polymerizable organic peroxide, and a radical polymerization initiator, and when the impregnation rate reaches the initial 50% by weight or more, the temperature of this aqueous suspension is increased. Grafting precursor (A) 1-1 in which a vinyl monomer and a radical (co)polymerizable organic peroxide are copolymerized in a propylene polymer.
Polypropylene (I ) and polyphenylene oxide (II), or melt and mix (A), (B) and (C) in advance at a temperature of 130 to 300°C to form a multiphase thermoplastic resin (IID). , a method for producing a thermoplastic resin composition comprising melting and mixing said (I) and (II). (5) The radical (co)polymerizable organic peroxide has the following general formula (a) or (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b ) (In the formula, R_1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R_2, R_7 is a hydrogen atom or a methyl group, R_
6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R_3
, R_4 and R_8, R_9 each have 1 to 4 carbon atoms.
The alkyl group, R_5, R_1_0 represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, m is 1 or 2, and n is 0, 1 Or 2. ] The method for producing a thermoplastic resin composition according to claim 4, wherein the thermoplastic resin composition is one or a mixture of two or more peroxycarbonate compounds represented by: (6) Vinyl monomer is vinyl aromatic monomer, (meth)
Claim 4 or 5 is one or more vinyl monomers selected from the group consisting of acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers. A method for producing a thermoplastic resin composition as described in Section 1.