JPH07207078A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin compsn. excellent in moldability, chemical resistance, impact resistance, heat resistance, coatability, mechanical properties and appearance of a molded product thereof. CONSTITUTION:100 pts.wt. in total of (I) 99-1wt.% polypropylene and (II) 1-99wt.%, at least l resin selected from the group consisting of arom. polyester resins, polycarbonate resins, polyphenylene ether resins either alone or its mixture with a styrene polymer, and polyamide resins are blended with (III) 0.1-50 pts.wt. epoxy-modified block polymer comprising polymer block(s) of an arom. vinyl compd. and polymer block(s) of a partly epoxy-added hydrogenated conjugated diene compd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent chemical resistance, moldability, impact resistance, heat resistance, paintability, mechanical properties, and appearance of a molded article. The composition can be used in a wide variety of fields such as electric and electronic parts, mechanical parts, automobile parts and the like.

[0002]

2. Description of the Related Art So-called engineering plastics such as aromatic polyester resins, polycarbonate resins, polyamide resins and polyphenylene ether resins have excellent mechanical properties, heat resistance, rigidity and impact resistance.
S-based resins and polypropylene are widely used in various molded products because they have excellent chemical resistance, molding processability and the like and are inexpensive.

In recent years, not only engineering plastics but also ABS resins and polypropylenes are required to have new functions, and various attempts have been made. As one of them, a composition in which a plurality of plastics are combined and the respective advantages are utilized is known as a polymer alloy.
For example, a combination of engineering plastics such as aromatic polyester resin / polyphenylene ether resin and polycarbonate resin / ABS resin has been known for a long time, but there are very few examples of polymer alloys of polypropylene and engineering plastics. While maintaining the excellent properties of polypropylene such as moldability and chemical resistance, and the low cost, it has more mechanical properties.
If it is possible to impart heat resistance, rigidity, impact resistance, paintability, etc., it will be an industrially useful material.

However, polypropylene and the above plastics are difficult to mix with each other, and a polymer alloy cannot be obtained only by melt mixing. JP 61-
In Japanese Patent No. 62542 and Japanese Patent Laid-Open No. 61-64741, examples in which a polyamide resin is mixed with polypropylene are disclosed.
JP-A-61-60744, JP-A-61-6074
Japanese Patent No. 6 discloses an example in which an aromatic polyester resin is blended with polypropylene. In these examples, acid anhydride-modified polypropylene and an epoxy group-containing ethylene copolymer are used in order to facilitate mixing of the respective resins. In this case, the compatibility is improved as compared with the case where the two resins are simply mixed, but there is a defect that the melt viscosity is increased. In addition, almost no examples of improving the compatibility of resins other than polyamide resins and aromatic polyesters were found.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and includes moldability, chemical resistance, impact resistance, heat resistance, paintability, mechanical properties and molded articles. An object is to provide a thermoplastic resin composition having an excellent appearance.

[0006]

Means for Solving the Problems As a result of intensive studies to solve these problems, the present inventors have found that polypropylene, an aromatic polyester resin, and a polycarbonate are blended by blending a modified block copolymer having a specific structure. Improved compatibility with resin, polyamide resin, polyphenylene ether resin, etc., excellent moldability of polypropylene,
A thermoplastic resin composition having excellent heat resistance, mechanical properties, rigidity, impact resistance and paintability while maintaining chemical resistance has been completed.

That is, the present invention relates to "(I) polypropylene 99 to 1% by weight (II) aromatic polyester resin, polycarbonate resin,
1 to 99% by weight of at least one resin selected from the group consisting of a polyphenylene ether resin alone or a mixture thereof and a styrene polymer, and a polyamide resin.
And (I) + (II) 100 parts by weight of (III) a vinyl aromatic compound polymer block and a hydrogenated conjugated diene compound polymer block in which epoxy is partially added The present invention provides a thermoplastic resin composition containing 0.1 to 50 parts by weight of a block polymer.

The polypropylene (I) used in the present invention is
It is a crystalline polypropylene and includes a block or random copolymer obtained by copolymerizing propylene with an α-olefin such as ethylene or butene-1 in addition to a homopolymer of propylene.

Next, the component (II) used in the present invention will be described.

The aromatic polyester resin used in the present invention is a polyester having an aromatic ring as a chain unit of a polymer, and comprises an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). Is a polymer or copolymer obtained by a condensation reaction containing as a main component.

As the aromatic dicarboxylic acid mentioned here,
Terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4 ′ -Diphenyl ether dicarboxylic acid, 1,
Examples thereof include 2-bis (phenoxy) ethane 4,4′-dicarboxylic acid and their ester-forming derivatives. The diol component is an aliphatic diol having 2 to 10 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene. Examples thereof include diglycol, cyclohexanediol and the like, or long-chain glycol having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like and mixtures thereof.

The preferred thermoplastic aromatic polyester resin used in the present invention is specifically polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-1, 2-bis (phenoxy) ethane-4,4 '
-Dicarboxylate and the like. More preferred are polyethylene terephthalate and polybutylene terephthalate. The intrinsic viscosity of these thermoplastic aromatic polyester resins is measured at 25 ± 0.1 at a concentration of 0.32 g in 100 ml of trifluoroacid (25) / methylene chloride (75). If it is less than 0.4 deciliter / g, the thermoplastic aromatic polyester resin cannot find sufficient mechanical strength, which is not preferable. On the other hand, if it exceeds 4.0 deciliter / g, the fluidity at the time of melting is lowered and the surface gloss of the molded article is lowered, which is not preferable. The polyphenylene ether resin used in the present invention has the general formula

[Chemical 1] [Wherein 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 one of them is always a hydrogen atom. ]
Is a polymer obtained by oxidatively polymerizing the phenol compound represented by the formula (1) with oxygen or an oxygen-containing gas using a coupling catalyst. R ¹ , R ² , R ³ , R in the above general formula
⁴ , specific examples of R ⁵ are hydrogen, chlorine, fluorine, iodine, bromine, methyl, ethyl, propyl, butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, Examples thereof include phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl and the like.

Specific examples of the above general formula include phenol, o, m or p cresol, 2,6-, 2,5-,
2,4- or 3,5-dimethylphenol, 2 methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-dimethylphenol, 2-methyl-6-
Examples include ethylphenol, 2,3,5-, 2,3,6- and 2,4,6-trimethylphenol. Two or more kinds of these phenol compounds can be used. Further, a phenol compound other than the above general formula, for example, a dihydric phenol such as bisphenol A, tetrabromobisphenol A, resorcin, hydroquinone and the like, and a phenol compound of the above general formula may be copolymerized.

Examples of the styrene-based polymer used in the present invention include homopolymers of polystyrene, poly (α-methylstyrene), poly (p-methylstyrene) and the like, butadiene rubber, styrene-butadiene copolymer, ethylene-
High impact polystyrene modified with various rubbers such as propylene copolymer, ethylene-propylene-diene copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer , Styrene-methyl methacrylate copolymer and the like. These styrene polymers are mixed in the range of 0 to 95% by weight with respect to the polyphenylene ether resin.

The polycarbonate resin used in the present invention is 4,4-dihydroxydiphenyl-2,2-propane (commonly known as bisphenol A) and other 4,4-didioxyallyl alkane-based polycarbonates. 4,4-dihydroxydiphenyl-2,2
-Propane polycarbonate with a number average molecular weight of 15,
000-80,000 are preferable. These polycarbonate resins are manufactured by any method. For example, in the production of a polycarbonate of 4,4-dihydroxydiphenyl-2,2-propane, 4,4-dihydroxydiphenyl-2,2-propane is used as a dioxine compound, and phosgene is blown in the presence of an aqueous caustic alkali solution and a solvent. And the method of producing by transesterification with 4,4-dihydroxydiphenyl-2,2-propanecarbonic acid diester in the presence of a catalyst.

The polyamide resin used in the present invention means nylon 6, nylon 6.6, nylon 6.10, nylon 6.12, nylon 11, nylon 12, nylon 4.
6 include aliphatic polyamide resins such as: polyhexamethylenediamine terephthalamide, polyhexamethylenediamine isophthalamide, aromatic polyamide resins such as xylene group-containing polyamide, and modified products or mixtures thereof. Particularly preferred polyamide resins are nylon 6, nylon 6.6 and the like.

Examples of the vinyl aromatic compound constituting the epoxy-modified block polymer of the component (III) of the present invention include styrene, α-methylstyrene, vinyltoluene,
One or more of p-tertiary butyl styrene, divinyl benzene, p-methyl styrene and 1,1-diphenyl styrene can be selected, and styrene is preferred. Further, as the conjugated diene compound, for example,
Butadiene, isoprene, 1,3-pentadiene, 2,
3-dimethyl-1,3-butadiene, piperylene, 3-
Butyl-1,3-octadiene, phenyl-1,3-butadiene, etc. are selected from 1 type, or 2 or more types,
Of these, butadiene, isoprene and combinations thereof are preferable.

The block copolymer referred to herein is a block copolymer composed of a polymer block A mainly containing a vinyl aromatic compound and a polymer block B mainly containing a conjugated diene compound. The copolymerization ratio of the group compound and the conjugated diene compound is 5/95 to 70/30, and the polymerization ratio of 10/90 to 60/40 is particularly preferable. The block copolymer provided by the present invention has a number average molecular weight of 5,000.
~ 600,000, preferably 10,000 to 500,000
And the molecular weight distribution [ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn)] is 10 or less. The molecular structure of the block polymer is linear,
It may be branched, radial, or any combination thereof.

For example, A-B-A, B-A-B-A,
(A-B-) ₄ is a vinyl aromatic compound-conjugated diene compound block polymer having a structure such as Si and A-B-A-B-A. Further, the unsaturated bond of the conjugated diene compound of the block polymer is partially hydrogenated.

As the method for producing the block polymer used in the present invention, any method can be used as long as it has the above-mentioned structure. For example, Japanese Patent Publication No. 40-2
No. 3798, Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48-2
No. 423, Japanese Patent Application No. 49-105970, Japanese Patent Application No. 50-
27094, JP-B-46-32415, JP-A-59.
-166518, JP-B-49-36957, JP-B-43-17979, JP-B-46-32415, JP-B-56-28925 and the method described in JP-B-56-28925, in an inert solvent using a lithium catalyst and the like. A vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized.

Further, JP-B-42-8704, JP-B-43-6636, or JP-A-59-133.
According to the method described in JP-A-203, hydrogenation can be carried out in the presence of a hydrogenation catalyst in an inert solvent to synthesize the partially hydrogenated block copolymer used in the present invention. In the present invention, the epoxy-modified block copolymer used in the present invention can be obtained by epoxidizing the above block copolymer.

The epoxy-modified block copolymer in the present invention can be obtained by reacting the above block copolymer with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent. As peracids, a mixture of formic acid, peracetic acid, perbenzoic acid, and hydrogen peroxide,
Alternatively, a catalytic effect can be obtained by using an organic acid in combination with hydrogen peroxide or molybdenum hexacarbonyl in combination with tertiary butyl hydroperoxide.

There is no strict restriction on the amount of epoxidizing agent, and the optimum amount in each case is variable, such as the particular epoxidizing agent used, the desired degree of epoxidation, the individual block copolymer used, etc. Determined by factors.

Isolation of the obtained epoxy-modified copolymer is carried out by a suitable method, for example, a method of precipitating with a poor solvent, a method of adding the polymer to hot water under stirring and distilling off the solvent, or a direct desolvation method. It can be done by law.

To obtain the thermoplastic resin composition of the present invention,
Directly these modified block copolymers polypropylene and aromatic polyester resins, polycarbonate resins,
It may be melt mixed with at least one resin (II) selected from the group consisting of a polyamide resin, a polyphenylene ether resin alone or a mixture thereof and a styrene polymer, but the most preferable is modified block copolymer That is, the thermoplastic resin obtained by kneading the combined product (III) and polypropylene (I) is melt-mixed together with (II).

In the present invention, the above (I) and (I
The blending amount of I) is selected depending on the purpose of use of the composition.
That is, for the purpose of improving the rigidity, heat resistance and dimensional stability which are the weak points of polypropylene (I) while maintaining the characteristics of polypropylene (I), polypropylene of 50 to 99% by weight, preferably 60 to 95% by weight is required. . The reason is that if the polypropylene content is less than 50% by weight, the moldability and chemical resistance characteristic of polypropylene are impaired, and if it exceeds 99% by weight, the rigidity, heat resistance, and dimensional stability, which are one of the objects of the present invention, are achieved. This is because there is no improvement effect of.

On the other hand, if the purpose of improving the physical properties by polypropylene while maintaining the characteristics of (II), (II) is 50.
It is desirable that the content be ˜99% by weight. That is, for the purpose of improving the notched impact strength, which is a drawback thereof, while maintaining the characteristics of the aromatic polyester resin, the aromatic polyester resin is 50 to 99% by weight, preferably 60% to 95%.
Weight percent is required. The reason is that if the aromatic polyester resin is less than 50% by weight, the characteristics of the aromatic polyester resin such as rigidity and dimensional stability are impaired.

For the purpose of improving chemical resistance and moldability while maintaining the characteristics of the polycarbonate resin, the polycarbonate resin is 50 to 99% by weight, preferably 60% to 60% by weight.
95% by weight is required. 50 polycarbonate resin
If it is less than 10% by weight, the impact resistance, which is a characteristic of polycarbonate resin, is impaired, and if it exceeds 99% by weight, the effects of improving chemical resistance and moldability, which are one of the objects of the present invention, are not obtained.

For the purpose of improving the moldability and chemical resistance, which are the drawbacks of the polyphenylene ether resin while maintaining the characteristics of the polyphenylene ether resin, the polyphenylene ether resins 50 to 99 are used.
% By weight, preferably 60% to 95% by weight. If the polyphenylene ether resin is less than 50% by weight, the heat resistance and dimensional stability of the polyphenylene ether resin will be impaired, and if it exceeds 99% by weight, the effect of improving moldability and chemical resistance, which is one of the objects of the present invention, will be Absent.

For the purpose of improving the water absorption and the dimensional stability of the polyamide resin while maintaining the characteristics of the polyamide resin, the polyamide resin needs to be 50 to 99% by weight, preferably 60 to 95% by weight. When the content of the polyamide resin is less than 50% by weight, the characteristics of the polyamide resin are impaired, and when it exceeds 99% by weight, the effect of improving water absorption and dimensional stability, which is one of the objects of the present invention, cannot be expected.

The modified block copolymer used in the present invention is 0.1 to 5 with respect to 100 parts by weight of (I) + (II).
It is contained in an amount of 0 part by weight, preferably 0.5 to 30 parts by weight. If the amount of the graft copolymer resin is less than 0.1 parts by weight, there is no compatibilizing effect and the impact strength decreases, resulting in delamination of the molded product or deterioration of the appearance. Further, if it exceeds 50 parts by weight, the rigidity and heat resistance of the composition are deteriorated, which is not preferable.

In the present invention, the above (I) + (II) +
200 parts by weight or less of the inorganic filler (IV) can be added to 100 parts by weight of the resin component containing (III).
Examples of the inorganic filler include powdery, flat, scale-like, needle-like, spherical or hollow, and fibrous forms. Specifically, calcium sulfate, calcium silicate, clay,
Diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide,
Metal powder, graphite, silicon carbide, silicon nitride, silica,
Boron nitride, aluminum nitride, powder filler such as carbon black, mica, glass plate, sericite, pyroflight, metal foil such as aluminum flakes, flat plate-like or scale-like filler such as graphite, shirasu balloon, metal balloon, Examples include glass balloons, hollow fillers such as pumice, glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, silicon carbide fibers, asbestos, and mineral fibers such as wstonite. The compounding amount of the filler is 200 parts by weight or less, preferably 1 to 200 parts by weight. If the blending amount exceeds 200 parts by weight, the mechanical strength such as impact strength of the molded product will decrease, which is not preferable.

The surface of the inorganic filler is stearic acid, oleic acid, palmitic acid or metal salts thereof,
Surface treatment is preferably performed using paraffin wax, polyethylene wax or modified products thereof, organic silane, organic borane, organic titanate and the like.

In the present invention, 100 parts by weight of the thermoplastic resin composition (I) + (II) + (III)
(V) 150 parts by weight or less of flame retardant, preferably 5 to 150
Flame retardance can be easily achieved by adding parts by weight. Examples of the flame retardant include bromine-based and chlorinated paraffins such as tetrabromobisphenol (TBA), hexabromobenzene, decabromodiphenyl ether, tetrabromoethane (TBE), tetrabromobutane (TBB), and hexabromocyclodecane (HBCD). , Chlorine-based flame retardants such as chlorinated polyphenyl, chlorinated polyethylene, diphenyl chloride, perchloropentacyclodecane, chlorinated naphthalene, general halogen-based flame retardants such as halogenated diphenyl sulfides, brominated polystyrene,
Halogenated polystyrene or its derivative such as brominated poly-α-methylstyrene, halogenated polycarbonate such as brominated polycarbonate, halogenated polyester such as polyalkylene tetrabromoterephthalate, brominated terephthalic acid type polyester, halogenated bisphenol type epoxy resin Examples of the flame retardant include a halogenated epoxy compound such as the following, a halogenated polyphenylene oxide compound such as poly (dibromophenylene oxide), and a high-molecular halogen-containing polymer such as a cyanuric acid ester compound of a halogenated bisphenol. Of these, an oligomer or polymer type flame retardant composed of an aromatic halogen compound is particularly preferable.

As the phosphorus-based flame retardant, tricresyl phosphate, tri (β-chloroethyl) phosphate, tri (dibromopropyl) phosphate, 2,3-
Examples thereof include phosphoric acid esters such as dibromopropyl-2,3-chloropropyl phosphate, halogenated phosphoric acid esters, phosphonic acid compounds, and phosphinic acid derivatives. Examples of other flame retardants include guanidine compounds such as guanidine nitride. The organic flame retardants may be used alone or in combination of two or more.

The amount of the organic flame retardant compounded is 5 with respect to 100 parts by weight of the thermoplastic resin composition (I) + (II) + (III).
It is used in an amount of 0 parts by weight or less, preferably 5 to 50 parts by weight, more preferably 7 to 40 parts by weight. Compounded amount 5
Even if added in an amount of more than 0 parts by weight, the flame-retardant effect is not improved any more, and the cost is rather increased, which is not preferable.
When these organic flame retardants, especially halogen-based flame retardants, are used in combination with the flame retardant aid, a synergistic effect can be exhibited. Typical examples of the flame retardant aid include antimony compounds such as antimony trioxide, antimony pentaoxide, antimony trichloride, and other antimony halides, antimony trisulfide, antimony pentasulfide, sodium antimonate, antimony tartrate, and metal antimony. is there.

Further, as the inorganic flame retardant, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide,
Basic magnesium carbonate, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, tin oxide hydrate, hydrates of inorganic metal compounds such as borax, zinc borate, zinc metaborate, barium metaborate, carbonic acid zinc,
Examples thereof include magnesium carbonate-calcium carbonate, calcium carbonate, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide and red phosphorus. These may be used alone or in combination of two or more. Among these, particularly, a hydrate of at least one metal compound selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, and hydrotalcite, especially aluminum hydroxide, Magnesium hydroxide has a good flame retardant effect and is economically advantageous. The particle size of these inorganic flame retardants is
Although it depends on the type, in the above aluminum hydroxide, magnesium hydroxide, etc., the average particle size is preferably 20 μm or less, more preferably 10 μm or less.

The inorganic flame retardant is blended in an amount of 150 parts by weight or less, preferably 30 to 150 parts by weight, and further 100 parts by weight of the thermoplastic resin composition (I) + (II) + (III). It is preferably used in the range of 40 to 120 parts by weight. When the amount is more than 150 parts by weight, it causes deterioration of mechanical strength such as reduction of impact strength. Further, in the present invention, by using the inorganic filler and the flame retardant in combination, the blending amount of the flame retardant can be reduced and other characteristics can be imparted.

The thermoplastic resin composition of the present invention is produced by melt-mixing the above (I) + (II) + (III) at a temperature of 150 to 350 ° C, preferably 180 to 320 ° C. When the temperature is lower than 150 ° C., the melting is incomplete, the melt viscosity is high, the mixing is insufficient, and the layered peeling occurs, which is not preferable. Again 350
If the temperature exceeds ℃, the resin is decomposed or gelled, which is not preferable.

As a method of melt mixing, a kneading machine which is usually used, such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin-screw extruder, or a roll can be used.

In the present invention, other thermoplastic resins such as polyolefin resin, ABS resin, polyvinyl chloride resin, and the like, without departing from the scope of the present invention,
Addition of additives such as polyvinylidene chloride resin, polyphenylene sulfide resin, polysulfone resin, natural rubber, synthetic rubber, antioxidants, UV inhibitors, lubricants, dispersants, foaming agents, crosslinking agents, colorants, etc. It doesn't matter.

[0042]

Industrial Applicability The thermoplastic resin composition of the present invention is a composition that takes advantage of the advantages of resins having different properties, and has moldability, chemical resistance, impact resistance, heat resistance, paintability, and mechanical properties. And excellent appearance of molded products. By changing the resin to be mixed and the mixing ratio thereof, the degree of impact resistance, heat resistance and mechanical properties can be changed, and various requirements can be met. From the above points, the thermoplastic resin composition of the present invention can be used in a wide range of fields such as automobile parts, electric and electronic machine parts, and industrial parts. <Examples> Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In addition, in Tables 1 to 13, the compounding amounts (parts by weight) of the component (III) and components corresponding thereto are the same as those of the component (I) and (I
The total amount of the component (I) is 100 parts by weight, and the blending amount (parts by weight) of the other components such as the inorganic filler is from (I) to
The amount is based on 100 parts by weight of the component (II) in total.

<Preparation Example 1> 400 g of hydrogenated styrene-butadiene block copolymer [manufactured by Asahi Kasei Corp., Tuftec H-1041] and 1500 g of cyclohexane in a jacketed reactor equipped with a stirrer, a reflux condenser and a thermometer.
, And then a 30% by weight solution of peracetic acid in ethyl acetate 3
9 g was continuously added dropwise, and an epoxidation reaction was carried out at 50 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out from the reactor, washed with water, and the solvent was removed by steam stripping to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer A (epoxy equivalent of polymer 5340).

<Preparation Example 2> In a reactor equipped with a stirrer and a thermometer, 300 g of polystyrene-polybutadiene-polystyrene block copolymer [Nippon Synthetic Rubber Co., Ltd., trade name: TR2000] and 3000 g of cyclohexane were added. Charged and dissolved, temperature 60 ℃, di-P-tolyl bis (1-cyclopentadienyl) titanium / cyclohexane solution as hydrogenation catalyst (concentration 1 mmol
40 ml / n) and 8 ml of n-butyl lithium solution (concentration 5 mmol / l) at 0 ° C., 2. The mixture mixed under a hydrogen pressure of 0 kg / cm ² was added, and the mixture was reacted at a hydrogen partial pressure of 2.5 kg / cm ^{2 for} 30 minutes.
The obtained partially hydrogenated polymer solution was dried under reduced pressure to remove the solvent (hydrogenation rate of the entire butadiene portion was 30%). 300 g of this partially hydrogenated polymer and 1500 g of cyclohexane were charged and dissolved. Then, 300 g of a 30 wt% ethyl acetate solution of peracetic acid was continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours while stirring. The reaction solution was returned to room temperature and taken out from the reactor, a large amount of methanol was added to precipitate a polymer, which was filtered, washed with water and dried to obtain an epoxy-modified polymer. The obtained epoxy-modified polymer is referred to as polymer B (epoxy equivalent of polymer: 275).

[Examples 1 to 8] Polypropylene [trade name: Noprene D501, manufactured by Sumitomo Chemical Co., Ltd.] Polybutylene terephthalate as an aromatic polyester resin [hereinafter P
BT and indication in the table, DURANEX 400FP, made of polyplastics] and the modified block copolymer obtained in Preparation Example 1 or Preparation Example 2 were melt mixed at the ratio shown in Table 1. The melt-mixing method was performed by melt-mixing with a twin-screw extruder and granulating the obtained resin. Further, the granulated product was dried and then a test piece was prepared by injection molding.

Table 1 Example No. 1 2 3 4 5 6 7 8 Polypropylene 90 90 70 70 40 30 30 10 (% by weight) PBT 10 10 30 30 60 70 70 90 (% by weight) Modified block A B A B B B B B B Copolymer 10 10 10 10 10 5 10 10 (part by weight) Izod 9 12 13 14 18 21 24 22 Impact value (kg ・ cm / cm) Deflection temperature under load 70 71 73 72 84 86 85 87 18.6 kg / cm ² (℃) Bending strength kg / cm ² 410 420 480 450 590 610 600 650 Delamination state ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ The size of the test piece and the test method are as follows.

Izod impact value (with notch) 13 mm × 65 mm × 6 mm (JIS K7110) Deflection temperature under load 13 mm × 130 mm × 6 mm (JIS K7207) Bending strength 10 mm × 130 mm × 4 mm (JIS K7203) Furthermore, the compatibility of resins is checked. Therefore, the fracture surface of the molded product was visually inspected to determine whether or not delamination had occurred. Delamination state: In the delamination state, the fracture surface of the molded product was observed and ranked as follows.

⊚: No peeling was observed. ○: There was slight peeling. ×: No peeling. [Examples 9 to 17] The resins used in the above Examples had an average fiber length of 5.0 mm and a diameter of 10 μm as an inorganic filler. Table 2 shows an example in which the above glass fiber is blended.

Table 2 Example No. 9 10 11 12 13 14 15 16 17 Polypropylene 80 70 70 70 30 30 20 20 20 (% by weight) PBT 20 30 30 30 70 70 80 80 80 (% by weight) Modified block B B B B B B B B B B B Copolymer 10 10 5 15 10 5 10 5 15 (part by weight) Glass fiber 30 30 30 30 30 30 30 30 30 (part by weight) Izod 13 17 15 15 17 16 18 17 20 Impact value ( (kg ・ cm / cm) Deflection temperature under load 132 136 139 138 139 143 153 160 158 18.6 kg / cm ² (℃) [Examples 18 to 23] Combustion test pieces (1/4 "x 1/2" x 1/5 "having the composition shown in Table 3 were prepared by further adding a flame retardant and an auxiliary agent to the compositions of Examples 9 and 15. ) Was prepared and a vertical combustion test was performed according to the UL-94 standard, and the results are shown in Table 3.

Table 3 Example No. 18 19 20 21 22 22 23 Polypropylene 80 80 80 80 80 20 20 (wt%) PBT 20 20 20 20 80 80 (wt%) Modified block 10 10 10 10 10 10 Copolymer (parts by weight) ) fiberglass 30 30 30 30 30 30 (parts by weight) brominated polystyrene 5 10 25 - 10 - (parts by weight) of magnesium hydroxide - - - 50 - 100 (parts by weight) of antimony trioxide 2 2 10 - 4 - (wt Part) UL-94 flammability V-0 V-0 V-0 V-2 V-0 V-2 [Comparative Examples 1 to 5] Separately from the above examples, an ethylene-glycidyl methacrylate copolymer [Bondfast 2C Manufactured by Sumitomo Chemical Co., Ltd.] or modified polypropylene (0.15% by weight of maleic anhydride added) is shown in Table 4.

Table 4 Comparative Example No. 1 2 3 4 5 Polypropylene (wt%) 40 40 40 40 40 PBT (wt%) 60 60 60 60 60 Ethylene- glycidyl methacrylate copolymer (parts by weight) -5 10-10 Modified polypropylene (parts by weight) − − − 25 25 Izod impact value (kg ・ cm / cm) 3 6 8 5 8 18.6 kg / cm ² / Deflection temperature under load 61 62 60 59 63 (℃) Bending strength (kg / cm ² ) 510 630 500 520 490 Delaminated state × × × × ○ [Examples 24 to 29] In Example 1, polybutylene terephthalate was used as a polycarbonate resin [Panlite L].
1225, manufactured by Teijin Kasei Co., Ltd.], and melt-mixed at a ratio shown in Table 5. Regarding the chemical resistance, Table 5 shows the results obtained by immersing the test piece in methanol at 75 ° C. for 30 days and then drying it at room temperature to observe the rate of decrease in tensile strength and the appearance.

Table 5 Example No. 24 25 26 27 28 29 Polypropylene 25 25 50 50 80 80 (wt%) Polycarbonate 75 75 50 50 20 20 (wt%) Modified block A B A B A B B Polymer (parts by weight) 10 10 10 10 10 10 Izod impact value 70 75 60 65 45 53 Notched ( kgcm / cm) Deflection temperature under load 128 129 125 127 120 123 (℃) 18.6 kg / cm ² Chemical resistance Appearance ○ ○ ○ ○ ○ O Tensile strength decrease rate (%) 8 6 4 4 2 2 o: No change x: Cracks were formed on the surface or were eluted.

[Examples 30 to 33] Table 6 shows an example in which glass fibers having an average fiber length of 3.0 mm and a diameter of 10 μm were further added to the compositions of the above examples.

Table 6 Example No. 30 31 32 32 33 Polypropylene (% by weight) 25 25 50 80 Polycarbonate (% by weight) 75 75 50 50 20 Modified block copolymer A B B B (Parts by weight) 20 20 20 20 Glass Fiber (weight part) 30 30 30 30 Izod impact value Notched 80 85 82 62 (kg ・ cm / cm) Deflection temperature under load (℃) 140 143 138 134 18.6 kg / cm ² [Examples 34 to 41] In Example 1, polybutylene terephthalate was added to nylon 6 [UBE nylon 1013].
B, manufactured by Ube Industries, Ltd.], and the properties were measured by melt-mixing with the formulations shown in Table 7. The results are shown in Table 7. In addition, the water absorption test was conducted at 23 ° C. for 24 hours with the test piece
After soaking in water, the mixture was allowed to stand for 1 day at 23 ° C. and 65% relative temperature, and the water absorption was calculated from the weight increase rate. In addition, the coating film adhesion was measured by applying an acrylic paint to the test piece, attaching a cellophane tape to the application surface, removing this, and observing the state of the coating film. The results are shown in Table 7.

Table 7 Example No. 34 35 36 37 38 39 40 41 Polypropylene 80 80 60 60 50 30 30 20 (wt%) Nylon 6 20 20 40 40 50 70 70 80 (wt%) Modified block A B A B B B A B B copolymer (parts by weight) 15 15 15 15 15 15 15 15 15 15 Izod 16 20 15 18 18 15 16 20 22 Impact value Notched (kg / cm / cm) Deflection temperature under load 70 71 74 74 76 79 80 79 81 ( ℃) 18.6 kg / cm ² Coating film adhesion ○ ○ ○ ○ ○ ○ ○ ○ Water absorption 2.6 2.3 3.8 3.5 4.0 5.9 5.8 6.2 ○: No paint peeling △: Partial peeling ×: Almost peeling [Examples 42 to 49] Further, Table 8 shows an example in which glass fibers having a fiber length of 7.0 mm and a diameter of 10 μm were mixed.

Table 8 Example number 42 43 44 44 45 46 47 48 48 49 Polypropylene 80 60 60 50 50 50 30 30 20 (wt%) Nylon 6 20 40 40 50 50 50 70 70 80 (wt%) Modified block B A B A B A B A B B copolymer (parts by weight) 15 15 15 15 15 20 15 15 15 15 glass fiber 35 35 35 35 35 35 35 35 35 35 (parts by weight) Izod impact value 37 35 35 39 32 32 34 30 35 37 with notch (kgcm / cm) Deflection temperature under load 118 125 132 130 128 140 145 150 (℃) 18.6 kg / cm ² [Examples 50 to 56] In Examples 42 and 49, the same flame retardant and auxiliary agent as in Example 18 were further compounded as shown in Table 9, and a combustion test was conducted. The test method is described in Example 18.
Is the same as. The results are shown in Table 9.

Table 9 Example No. 50 51 52 53 53 54 55 56 Polypropylene 80 80 80 80 80 80 20 20 (wt%) Nylon 6 20 20 20 20 20 20 80 80 (wt%) Modified block A B A B A B B B Polymer (parts by weight) 20 20 20 20 20 20 20 20 Glass fiber (parts by weight) 35 35 35 35 35 35 35 35 35 Bromination 10 10 15 15 -20- Polystyrene (parts by weight) Hydroxyl --- 100 -100 Magnesium (Parts by weight) 5 5 5 5 10-10- antimony trioxide (parts by weight) UL-94 V-0 V-0 V-0 V-0 V-2 V-0 V-2 flammability [Comparative Examples 6 to 11] Table 10 shows an example in which modified polypropylene was used in the same manner as in Comparative Examples 1 to 5 instead of the modified block copolymer in Example 35.

Table 10 Comparative Example No. 6 7 8 9 10 11 11 Polypropylene 80 80 80 80 50 40 30 (wt%) Nylon 6 20 20 20 50 60 70 70 (wt%) Modified polypropylene 10 15 25 20 20 20 20 (wt% ) Izod Impact value 5 6 12 14 15 20 Notched (kg ・ cm / cm) Deflection temperature under load 60 62 67 67 77 77 79 (℃) 18.6 kg / cm ² Coating Adhesion × × △ ○ ○ ○ Water Absorption 3.2 3.4 3.0 5.0 5.4 6.8 [Examples 57 to 64] Poly-2,6 having an intrinsic viscosity of 0.31 in place of polybutylene terephthalate in Example 1
-Dimethyl-1,4-phenylene ether (hereinafter PPE
In the table) and modified PPE [Zylon 500
H, manufactured by Asahi Dow Co., Ltd.] and an example using the modified block copolymer obtained in Preparation Example 1 is shown in Table 11. Regarding the chemical resistance, the appearance of the test piece was observed after the test piece was immersed in gasoline for 1.5 hours.

Table 11 Example No. 57 58 59 60 61 62 63 64 Polypropylene 30 30 50 50 80 80 30 80 (wt%) PPE 70 70 50 50 20 20 − − (wt%) Modified PPE − − − − − − 70 20 (% by weight) Modified block Copolymer BBBBBBBBBB (parts by weight) 10 20 10 20 10 20 10 20 Izod 24 34 25 30 15 23 29 20 Impact value (kgcm / cm) Load Deflection temperature 126 124 120 119 120 120 129 122 18.6 kg / cm ² (℃) Chemical resistance ○ ○ ○ ○ ○ ○ ○ ○ ○: No change △: Part of the surface is eluted ×: Elution of the surface is remarkable [Examples 65 to 71] In addition to the composition of Example 57, the average fiber length Table 12 shows an example in which glass fibers having a diameter of 5.0 mm and a diameter of 10 μm were mixed.

Table 12 Example No. 65 66 67 68 69 70 71 Polypropylene 25 25 25 50 80 25 80 (wt%) PPE 75 75 75 50 20 --- (wt%) Modified PPE --- --- 75 20 (wt %) %) Modified block copolymer BBBBBBBBB Polymer (part by weight) 15 20 25 20 20 20 20 Glass fiber 30 30 30 30 30 30 30 (part by weight) Izod impact value 45 50 53 47 39 40 30 With notch (Kg ・ cm / cm) Deflection temperature under load 149 143 130 135 120 130 125 (℃) 18.6 kg / cm ² [Comparative Examples 12-18] Separately from the above-mentioned examples, ethylene /
Table 13 shows an example using a glycidyl methacrylate copolymer and a modified polypropylene (obtained by adding 0.15% by weight of maleic anhydride to polypropylene).

Table 13 Comparative Example No. 12 13 14 15 16 17 17 18 Polypropylene 30 30 50 50 50 75 30 30 (wt%) PPE (wt%) 70 70 50 50 50 25 70 70 Ethylene / glycidyl methacrylate copolymer (parts by weight) ) 10 15 20 − − − − Modified polypropylene (parts by weight) − − − − − − 15 Izod impact value 9 5 11 7 4 24 Notched (kg ・ cm / cm) Deflection temperature under load 115 111 97 98 91 88 90 (℃) 18.6 kg / cm ² Chemical resistance △ △ △ × × × ×

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 23/10 LCV C08G 59/34 NHV C08L 25/02 LDS LDX LED 53/02 LLY LLZ 63/00 NJM 67/02 LNZ 69/00 LPN 71/12 LQP 77/00 LQS

Claims (1)

[Claims] (I) Polypropylene 99 to 1% by weight (II) Aromatic polyester resin, polycarbonate resin,
1 to 99% by weight of at least one resin selected from the group consisting of a polyphenylene ether resin alone or a mixture thereof and a styrene polymer, and a polyamide resin.
And epoxy modified with (III) a vinyl aromatic compound polymer block and a hydrogenated conjugated diene compound polymer block partially having epoxy added to 100 parts by weight of (I) + (II). A thermoplastic resin composition containing 0.1 to 50 parts by weight of a block polymer.