JPH06299020A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition improved in impact resistance, rigidity and heat resistance by mixing a carboxylated propylene resin and a specified copolymer. CONSTITUTION:0.5-8wt.% epoxidized vinyl monomer is copolymerized with 52-89.5wt.% aromatic vinyl monomer, 10-40wt.% vinyl cyanide monomer and 0,40wt.% other vinyl monomer to give a copolymer containing 0-15wt.% material insoluble in a solvent mixture (a) consisting of 10vol.% dimethylacetamide, 9vol.% toluene and 21vol.% 1-propanol, 50-100wt.% material soluble in the solvent mixture (a) and insoluble in a solvent mixture (b) consisting of 5vol.% dimethylacetamide, 6vol.% toluene and 14vol.% 1-propanol, and 0-45wt.% material soluble in the solvent mixture (b). 60-5wt.% of the obtained copolymer is mixed with 40-95wt.% carboxylated propylene resin obtained by the addition reaction of a propylene resin with an alpha,beta-unsaturated carboxylic acid and having a melt flow rate of 0.01-100g/10min.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article having excellent impact resistance, rigidity and heat resistance, for example, automobile wheel caps, instrument panels, handles, door trims, housings for electronic / electrical devices, knobs, etc. , A dial, and the like.

[0002]

2. Description of the Related Art Propylene-based resins are excellent in moldability, water resistance,
Excellent chemical resistance and light weight (density 0.890-0.910g
It is used for blow containers, TV packers, toys, trays, etc. because it is cheap at / cm ³ ). However, since it is a non-polar crystalline olefin resin, the injection-molded molded product has drawbacks of low impact resistance and low dimensional accuracy. In addition, special surface oxidation treatment such as corona discharge treatment and plasma treatment is required for painting and plating.

On the other hand, ABS, SAN, AAS containing an aromatic vinyl monomer and a vinyl cyanide monomer as copolymerization components,
AES and other aromatic hydrocarbon copolymers are amorphous, have excellent impact resistance, molding processability and paintability, and have good dimensional accuracy, and are widely used in wheel caps, instrument panels, etc. ing. However, the chemical resistance is not sufficient,
Limited use under harsh conditions.

Therefore, a method of blending the two resins can be considered for the purpose of providing a molding material having complementary defects without impairing the advantages of the two resins, but in this case, the compatibility between the two is very poor. is there. Various methods have been proposed as methods for improving compatibility between polymers having poor compatibility. For example, in JP-A-4-18441, 10 to 95% by weight of a carboxyl group-modified olefin resin (A) obtained by graft-reacting an unsaturated carboxylic acid (including an acid anhydride) on an olefin resin, and epoxy A single aromatic vinyl polymer containing a group, or a mixture of the same and an aromatic vinyl polymer containing no epoxy group, wherein the epoxy group content is 50 to 1,000 mmol /
A resin composition has been proposed which comprises 90 to 5% by weight of a mixture (B) having an MFR (230 ° C.) of 15 to 200 g / 10 min.

As the aromatic vinyl polymer (B) containing an epoxy group in JP-A-4-18441, Blemmer CP-510 used in Examples.
SA and Bremmer CP-20SA are soluble in a mixed solvent of 10 parts by volume of dimethylacetamide, 9 parts by volume of toluene, and 21 parts by volume of 1-propanol, and 5 parts by volume of dimethylacetamide, 6 parts by volume of toluene, 1- The proportion of the copolymer obtained as an insoluble component in the mixed solvent of 14 parts by volume of propanol was less than 50% by weight, and since it was a very low molecular weight substance, it was considered as an olefin resin (B) having a carboxyl group. In the additional tests conducted by us on the blended resin composition, the weld strength and rigidity are improved, but the impact strength is not practically sufficient.

[0006]

SUMMARY OF THE INVENTION The present invention provides impact resistance,
It is intended to provide a thermoplastic resin composition which gives a molded product in which mechanical strength such as tensile strength, dimensional accuracy, and heat resistance are balanced.

[0007]

[However, the fraction, the fraction, and the total of the fractions are 100% by weight. ]

The present invention provides a thermoplastic resin composition containing the above component (A) and component (B) in the above proportions.

[0008]

By melt-kneading the carboxyl group (including the acid anhydride group) of the propylene polymer as the component (A) and the epoxy group of the vinyl polymer having the specific structure as the component (B), React to improve compatibility between both polymers. At this time, the component (B) has a relatively high molecular weight (100,
000 to 250,000) and a structure in which epoxy groups are evenly distributed throughout the molecule of the copolymer (fraction), the reaction between the two polymers is It occurs evenly, the effect of improving compatibility is further increased, and mechanical strength such as impact resistance, tensile strength, and rigidity,
Gives molded products with excellent dimensional accuracy and heat resistance.

[0009]

SUMMARY OF THE INVENTION (A) Component Carboxyl Group-Containing Propylene Resin (A) Component Carboxyl Group-Containing Propylene Resin
It is obtained by addition-reacting an α, β-unsaturated carboxylic acid with a propylene resin. The propylene-based resin is a crystalline resin obtained by copolymerizing 70 to 100% by weight of propylene, 0 to 10% by weight of ethylene, other α-olefin, and 0 to 30% by weight of a carbon / carbon unsaturated compound, if necessary. Is.

Examples of the α-olefin include 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3.
-Dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene , Allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-
Examples thereof include butene, vinylcyclopropane, vinylcyclohexane, and 2-vinylbicyclo [2,2,1] -heptane. These may be used alone or in combination of two or more.

As the polycarbon / carbon unsaturated compound, the following dienes and unsaturated styrene derivatives can be used. (1) 2-methyl-1,4-pentadiene, 4-methylidene-1-hexene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,4 -Heptadiene, 4-ethyl-1,4
-Hexadiene, 4,5-dimethyl-1,4-hexadiene, 4-methyl-1,4-heptadiene, 4-ethyl-1,4-heptadiene, 5-methyl-1,4-heptadiene, 5-methyl-1 , 1,4-dienes such as 4-octadiene,

(2) 1,5-heptadiene, 1,5-octadiene, 5-ethyl-1,5-heptadiene, 6-
Methyl-1,5-heptadiene, 2-methyl-1,5-
Chain-like 1,5-dienes such as heptadiene, (3) 1,
6-octadiene, 6-ethyl-1,6-octadiene, 7-methyl-1,6-octadiene, 2-ethyl-
1,6-heptadiene, 6-methylidene-1-octene, 6-ethyl-1,6-octadiene, 6,7-dimethyl-1,6-octadiene, 1,6-nonadiene, 6
-Ethyl-1,6-nonadiene, 7-methyl-1,6-
Chain 1,6-dienes such as nonadiene and 7-methyl-1,6-decadiene,

(4) 1,7-nonadiene, 7-methyl-
Chain-like 1,7-nonadiene, 8-methyl-1,7-nonadiene, 2-methyl-1,7-octadiene, etc.
Chain 1,8 such as 7-dienes, (5) 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene
Α, ω-dienes such as dienes, (6) 1,9-decadiene and 1,13-tetradecadiene. (7) Unsaturated styrene derivatives such as divinylbenzene and isopropenylstyrene,

Of these, preferred are 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadioene, 1,9-decadiene,
1,13-tetradecadiene and divinylbenzene, particularly preferably 6-methyl-1,6-octadiene and 7-methyl-1,6, from the viewpoint of increasing the addition reaction density of α, β-unsaturated carboxylic acid. -Octadiene, 1,9-decadiene, divinylbenzene.

These diene compounds may be used alone or in combination of two or more. Further, these diene compounds may be randomly distributed in the propylene-based resin, or may be distributed in blocks.
In order to increase the graft ratio of α, β-unsaturated carboxylic acid, the propylene-based resin is a crystalline propylene-based resin having an unsaturated bond which is a copolymer of propylene and a polycarbon / carbon unsaturated compound. It is preferable.

The content of the structural unit based on the diene compound in the propylene resin having an unsaturated bond is 1 to 30% by weight, preferably 1 to 15% by weight. If it is less than 1% by weight, there is a small amount of unsaturated groups in the propylene-based resin, so that there is a drawback that the effect of improving compatibility due to the copolymerization of the diene compound cannot be seen. On the other hand, if it exceeds 30% by weight, the copolymerization rate is slow during the production of the propylene-based resin, and in the case of slurry polymerization, the solvent-soluble by-product polymer increases and the viscosity of the polymerization system increases, resulting in poor productivity. However, there are drawbacks such that the resulting unsaturated copolymer becomes sticky and the resinous state cannot be maintained.

The molecular weight of the propylene-based resin having an unsaturated bond is not particularly limited as long as it maintains the above-mentioned resin state, but for example, the crystallinity at room temperature by X-ray diffraction is 1
It is preferably 0% or more, more preferably 20% or more, and has a melting point of 40 ° C or more. The decrease in crystallinity results in a decrease in the elastic modulus of the final composition. Further, this propylene-based resin should have a molecular weight sufficient to be called a resin at room temperature. For example, JIS-K-675
Melt flow rate (MFR) measured according to 8
Is 0.01 to 100 g / 10 minutes, preferably 0.05
It has a molecular weight corresponding to -50 g / 10 min, and is JIS-K
-7203 has an elastic modulus of 500 to 28,000 kg /
cm ² , preferably 1,200 to 25,000 kg / c
m ² .

This propylene-based resin is obtained by copolymerizing these propylene, α-olefin and diene with a Ziegler-Natta catalyst for propylene polymerization using the same method and apparatus as those used for producing propylene polymer. Can be manufactured by. The α, β-unsaturated carboxylic acid to be added to the propylene resin is acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, their anhydrides or alkali metal salts, preferably acrylic acid and methacrylic acid. , Maleic anhydride, and particularly preferably maleic anhydride.

When the α, β-unsaturated carboxylic acid is added, a monomer other than the above α, β-unsaturated carboxylic acid, such as styrene, methyl acrylate, methyl methacrylate or vinyl acetate is used. It is also possible to copolymerize within a range not exceeding a majority. The reaction between the propylene resin and the α, β-unsaturated carboxylic acid can be carried out under radical reaction conditions.

As radical reaction conditions, a method of irradiating radiation such as γ-ray or electron beam in the coexistence of the propylene-based resin and the polymerizable monomer, and the propylene-based resin are
Any method such as a method of coexisting a polymerizable monomer after irradiation with radiation, a method of coexisting a propylene-based resin and a polymerizable monomer and heating in the presence or absence of a radical generator may be used. Any of a solution state, a molten state and a suspension state may be adopted.

As radical generators, benzoyl peroxide, t-butyl peroxybenzoate, t-butyl hydroperoxide, t-butyl peroxyacetate, diisopropyl peroxydicarbonate,
Organic and inorganic peroxides such as 2,2-bis (t-butylperoxy) octane, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide, and azo compounds such as α, α′-azobisisobutyronitrile Is used. The peroxide can be used as a redox system in combination with a reducing agent. For example, there is a combination of hydrogen peroxide and ferrous salts. These radical generators can be appropriately selected in relation to the modifier and the reaction form. Further, two or more kinds can be used in combination.

The amount of the radical generator used is 0 based on 100 parts by weight of the propylene resin having an unsaturated bond.
-100 parts by weight, preferably 0-30 parts by weight. The temperature at the time of graft copolymerization is usually 30 to 350.
C., preferably 50 to 300.degree. C., and the modification reaction time is 50 hours or less, preferably 1 minute to 24 hours.

0 to 90% by weight of the modified propylene-based resin (A) component having a carboxyl group may be replaced with an olefin resin having no carboxyl group. Such olefin resins are ethylene, propylene, butene-1,3-methylbutene-1,4-methylpentene-1.
Etc., homopolymers or copolymers thereof, or a majority of these olefins, vinyl acetate, acrylic acid, methacrylic acid, acrylic acid alkyl ester, methacrylic acid alkyl ester (where the carbon number of the alkyl group is 1 to
It is a copolymer with 4). Among them, crystalline propylene polymer, that is, crystalline propylene homopolymer, crystalline propylene / ethylene copolymer or propylene / butene-1 random copolymer, or crystalline propylene / ethylene block copolymer or propylene. Butene-1 block copolymers are preferred.

Component (B) Epoxy Group-Containing Vinyl Polymer (B) Component Copolymer is (a) Epoxy Group-Containing Vinyl Monomer 0.5-8% by Weight, (b) Aromatic Vinyl Monomer 52 to 89.5% by weight, (c) Vinyl cyanide monomer 10 to 40% by weight, and (d) Other vinyl monomer 0
-40% by weight of the copolymer, and each of the fractions obtained by the following mixed solvent fractionation of the copolymer has the following proportions.

(Fraction) Insoluble content of mixed solvent of 10 parts by volume of dimethylacetamide, 9 parts by volume of toluene and 21 parts by volume of 1-propanol 0 to 15% by weight (fraction) 10 parts by volume of dimethylacetamide, 9 parts of toluene 50 to 100 parts by weight which are soluble in a mixed solvent of 1 part by volume and 21 parts by volume of 1-propanol and insoluble in a mixed solvent of 5 parts by volume of dimethylacetamide, 6 parts by volume of toluene and 14 parts by volume of 1-propanol. % (Fraction) 5 parts by volume of dimethylacetamide, toluene 6
Soluble in a mixed solvent of 1 part by volume and 14 parts by volume of 1-propanol 0 to 45% by weight [however, the fractions, the fractions and the total of the fractions are 100% by weight. Here, as the vinyl monomer (a) having an epoxy group, for example, glycidyl methacrylate, butyl glycidyl malate, butyl glycidyl fumarate, propyl glycidyl malate, glycidyl acrylate and the like can be mentioned.

As the aromatic vinyl monomer (b), styrene, α-methylstyrene, p-methylstyrene and the like can be used. Examples of the vinyl cyanide monomer (c) include acrylonitrile and methacrylonitrile. Other monomers (d) include methyl methacrylate and acrylic acid lower alkyl ester (wherein the alkyl group has 1 carbon atom).
.About.6), N-substituted maleic imides such as N-methyl maleic imide, N-butyl maleic imide, N-cyclohexyl maleic imide, N-phenyl maleic imide and the like.

The vinyl polymer having an epoxy group, which is the component (B), is an aromatic vinyl monomer (b), a vinyl cyanide monomer (c), and other vinyl monomers (d). )
And the solvent in which the radical generator is dissolved are heated to the polymerization temperature, and then the solution is added while adding the vinyl monomer (a) having an epoxy group in the solvent over 40 to 90% of the total polymerization time. It is obtained by polymerization.

As the solvent, benzene, toluene, ethylbenzene, xylene, methyl ethyl ketone, dioxane, dimethylacetamide, dimethylformamide and the like can be used. These may be used alone or as a mixed solvent. The amount of the solvent is a vinyl monomer having an epoxy group, an aromatic vinyl monomer, a cyanated vinyl monomer,
And the total amount of other monomers is 100 parts by weight.
To 10,000 parts by weight, preferably 5 to 5,000 parts by weight, more preferably 5 to 2,000 parts by weight.

As radical generators, benzoyl peroxide, t-butyl peroxybenzoate, t-butyl hydroperoxide, t-butyl peroxyacetate, diisopropyl peroxydicarbonate,
Organic and inorganic peroxides such as 2,2-bis (t-butylperoxy) octane, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide, and azo compounds such as α, α′-azobisisobutyronitrile Is used. The peroxide can be used as a redox system in combination with a reducing agent. For example, there is a combination of hydrogen peroxide and ferrous salts. These radical generators can be appropriately selected in relation to the modifier and the reaction form. Further, two or more kinds can be used in combination.

The amount of the radical generator used is 0.1 with respect to 100 parts by weight of the total amount of the vinyl monomers (a) to (d).
-100 parts by weight, preferably 0.1-30 parts by weight. Regarding the method of adding the radical generator, the entire amount thereof may be added at the start of the polymerization, or a part thereof may be mixed with the vinyl monomer having an epoxy group and added.

The optimum polymerization temperature is selected depending on the type of solvent and / or radical generator used. Usually, it is 0 to 200 ° C, preferably 20 to 150 ° C.
The addition time of the vinyl monomer having an epoxy group is 40 to 90% of the total polymerization time, preferably 50 to 90%, and more preferably 60 to 90%. Here, the total polymerization time means the polymerization initiation point when the solvent containing the aromatic vinyl monomer, the vinyl cyanide monomer and the other vinyl monomer and the radical generator reaches the polymerization temperature. In the above, the time required for adding the vinyl monomer having an epoxy group is added thereto, and further, heating is continued after the addition is completed, until the polymerization can be completed.

Regarding the addition amount of the vinyl monomer having an epoxy group per unit time during continuous addition, it is preferable to add it in consideration of the decomposition amount of the radical generator. The vinyl monomer having an epoxy group may be mixed with a part of the solvent and added. The conversion rate of the total amount of the vinyl monomer having an epoxy group, the aromatic vinyl monomer, the vinyl cyanide monomer, and the other vinyl monomer into the copolymer is 70%.
Or more, preferably 80% or more, more preferably 8
It is preferable that the content is 5% or more because the fraction copolymer is contained in a larger amount.

The polymerization time is not particularly limited, but is usually 60 minutes to 100 hours, preferably 2 hours to 5 hours.
It's 0 hours. Specific examples of the copolymer of the component (B) include styrene / acrylonitrile / glycidyl methacrylate copolymer, styrene / α-methylstyrene / acrylonitrile / glycidyl methacrylate copolymer, and styrene / methacrylonitrile / glycicyl methacrylate copolymer. Examples thereof include polymers and styrene / acrylonitrile / glycidyl acrylate copolymers.

In the copolymer of the component (B), the ratio of the fractions in the mixed solvent is from 0 to 1 as described above.
5 parts by weight, preferably 0-10% by weight, fractions 50-
The proportion is 100% by weight, preferably 50 to 80% by weight, and the fraction is 0 to 45% by weight, preferably 0 to 40% by weight. When the molecular weight of the copolymer is Mw and the weight% of the constitutional unit based on the vinyl monomer having an epoxy group in the copolymer is [Ex],

[0035]

## EQU1 ## 5.70 <log Mw + 0.040 [Ex] (1) A high molecular weight copolymer represented by (1) or a high molecular weight copolymer having a high epoxy group concentration. If the proportion of the polymer (B) in the polymer exceeds 15% by weight, the resulting molded article will have a low impact strength, or the intermolecular reaction with the propylene resin having a carboxyl group as the component (A) will be excessive. A gel-like inhomogeneous component is produced, resulting in poor appearance and brittle molding. The fraction is the formula (2)

[0036]

## EQU2 ## 5.30 <log Mw + 0.040 [Ex] <5.70 (2) is satisfied, and it is a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). It is a copolymer having a narrow Q value of 2 or less and a narrow molecular weight distribution. This one is
By increasing the reaction density of the component (A) and the component (B), it contributes to the improvement of the impact resistance of the molded body. The fraction is the formula (3)

[0037]

## EQU00003 ## log Mw + 0.040 [Ex] <5.30 (3), and (b) is a copolymer segment whose molecular weight distribution is not defined, and is a low molecular weight copolymer and / or low epoxy group content. It is a copolymer. If the proportion of this fraction is large, the impact strength improving effect is small. It is presumed that the decrease in the mechanical strength due to the decrease in the molecular weight or the decrease in the reactivity due to the low epoxy group content.

The epoxy-containing vinyl monomer used to form the copolymer (B) is 0.5 to 8% by weight,
It is preferably 1 to 7% by weight, more preferably 2 to 7% by weight. When the copolymerization ratio of the epoxy group is high, a large amount of the high epoxy content copolymer of the fraction is formed, which hinders the effect of improving the impact strength. Further, when the epoxy group content is low, the compatibility between the component (A) and the component (B) is low and the impact improving effect is small.

The amount of vinyl cyanide monomer used is from 10 to 10.
It is 40% by weight, preferably 20 to 35% by weight. When the content of the vinyl cyanide monomer is low, the heat resistance rigidity of the obtained molded article decreases. When the content of the vinyl cyanide monomer is high, it causes difficulties in producing the copolymer, and the heat resistance of the obtained molded product is improved, but the molded product is colored, and the molded product is fragile. Become.

The component (B) may be a vinyl copolymer containing an epoxy group alone or a mixture with a vinyl polymer containing no epoxy group. Vinyl, which does not contain epoxy groups, includes polystyrene and styrene.
Other than acrylonitrile copolymer, polybutadiene, butadiene copolymer, ethylene / propylene copolymer rubber, ethylene / propylene / diene copolymer rubber, acrylic acid alkyl ester polymer elastomer, acrylic acid alkyl ester polymer elastomer, ethylene -Styrene copolymerized in the presence of an elastomer such as a vinyl acetate copolymer can also be used.

The group formed components (A) and the resin composition of the present invention the composition ratio of (B) the mechanical strength, moldability from the viewpoint of harmony such as heat resistance, component (A) and component (B) In the weight ratio of 40:60 to 95: 5, preferably 40:60 to 80: 2.
0 range, more preferably 40:60 to 70:30
Is the range. [Propylene-based resin as the component (A) exhibits a matrix. When the content of the component (A) is less than 40% by weight, the effect of improving impact resistance, dimensional accuracy, etc. is small as compared with the propylene-based resin.
When the content is more than 5% by weight, the effect of improving organic solvent resistance, heat resistance, etc. is smaller than that of, for example, styrene / acrylonitrile copolymer, ABS resin and the like.

Optional components In the thermoplastic resin composition of the present invention, if necessary, 0.05 to 5 parts by weight of an antioxidant, a weather resistance improver, a nucleating agent, and a flame retardant are added to 100 parts by weight of the resin composition. 5 to 20 parts by weight of a plasticizer and a fluidity improver, 5 to 50 parts by weight of organic and inorganic fillers such as glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate and silica, and The colorant dispersant may be added in an amount of 0.5 to 50 parts by weight. Furthermore, addition of impact strength improvers, for example, styrene-butadiene copolymer rubber and its hydride, ethylene-propylene copolymer rubber, ethylene-
Propylene-diene copolymer rubber, and their α, β
-Unsaturated carboxylic acid anhydride modified product, polybutadiene, silicone rubber, and modified products thereof may be added in an amount of 8 to 50 parts by weight.

Preparation of Composition As a melt-kneading method for obtaining a resin composition, a kneading method generally used for thermoplastic resins can be applied. For example, powdery or powdery components, if necessary together with the additives described in the section of additional components, are uniformly mixed by a Henschel mixer, ribbon blender, V-type blender, etc., and then uniaxially or It can be kneaded with a multi-screw kneading extruder, roll, Banbury mixer or the like.
The thermoplastic resin composition of the present invention, injection molding, blow molding,
It is applied to various molded products by molding methods such as extrusion molding and press molding.

[0044]

【Example】

(Production Example-1) Styrene / acrylonitrile / glycidy
Synthesis of Lumethacrylate Copolymer In a round-bottomed flask having an inner volume of 500 ml which was sufficiently replaced with nitrogen gas, 70.0 g of styrene, 25.0 g of acrylonitrile, 0.6 g of 2,2-azobis (isobutyronitrile) and After adding 100 ml of xylene and stirring under a nitrogen stream to confirm that 2,2-azobis (isobutyronitrile) was completely dissolved, 60 ° C.
At the same time as starting the polymerization, a solution of 5 g of glycidyl methacrylate (GMA) dissolved in 20 ml of xylene was added dropwise at 6.25 ml / hour for 4 hours. Then, polymerization was further performed at the same temperature for 1 hour (GM
The addition time of A accounts for 80% of the total polymerization time).

After the polymerization, the temperature was lowered to room temperature, 200 ml of chloroform was placed in the flask, the polymer was completely dissolved, and then poured into 2 liter of methanol to precipitate the polymer, which was then filtered and dried to obtain the polymer 9
2.5 g was recovered (conversion rate 92.5%). Infrared spectroscopic analysis and proton nuclear magnetic resonance spectroscopic analysis revealed that the polymer composition was 72.6 based on the styrene component.
% By weight, 22.2 based on acrylonitrile components
% By weight, based on the glycidyl methacrylate component was 5.2% by weight, and the number average molecular weight (Mn) in terms of polystyrene was 73, as determined by gel permeation chromatography.
000, the weight average molecular weight (Mw) was 168,000, and the molecular weight distribution (Mw / Mn) was 2.3. (Resin A)

The mixed solvent fractionation of this polymer was carried out by the following method. First, the polymer was dissolved in dimethylacetamide, and a mixed solvent of 3 parts by volume of toluene and 7 parts by volume of 1-propanol was added dropwise to this solution to prepare 10 parts by volume of dimethylacetamide, 9 parts by volume of toluene, and 21 parts by volume of 1-propanol. The polymer deposited with the solvent composition was precipitated by the centrifugal separation method and collected. (Fraction)
A mixed solvent consisting of 3 parts by volume of toluene and 7 parts by volume of 1-propanol was added dropwise to the supernatant, and dimethylacetamide 5 was added.
A polymer deposited with a solvent composition of 1 part by volume, 6 parts by volume of toluene and 14 parts by volume of 1-propanol was precipitated by a centrifugal separation method and collected. (Fraction) The remaining supernatant was concentrated and dried. (Fraction) For each fraction
The weight was measured, the composition was determined by infrared spectroscopic analysis and proton nuclear magnetic resonance spectral analysis, and the molecular weight in terms of polystyrene was determined by gel permeation chromatography measurement. The results of solvent fractionation of this polymer are shown in Table 1.

(Production Example-2) Styrene / acrylonitri
Synthesis of Le-Glycidyl Methacrylate Copolymer In a round-bottomed flask having a content of 500 ml, which had been sufficiently replaced with nitrogen gas, 70.0 g of styrene, 25.0 g of acrylonitrile, and 2,2-azobis (isobutyronitrile) After adding 3 g and 200 ml of methyl ethyl ketone and stirring under a nitrogen stream to confirm that 2,2-azobis (isobutyronitrile) was completely dissolved, the temperature was raised to 60 ° C. and glycidyl was started at the same time when the polymerization was started. A solution prepared by dissolving 5 g of methacrylate and 0.3 g of 2,2-azobis (isobutyronitrile) in 20 ml of methyl ethyl ketone was added dropwise at 5.0 ml / hour for 5 hours. Then, the polymerization was further performed at the same temperature for 1 hour (the addition time of GMA accounts for 83% of the total polymerization time).

After the polymerization, the temperature was lowered to room temperature, 200 ml of chloroform was placed in the flask, the polymer was completely dissolved, and then poured into 2 liters of methanol to precipitate the polymer, which was then filtered and dried to obtain the polymer 9
4.3 g was recovered (conversion rate 94.3%). Infrared spectroscopic analysis and proton nuclear magnetic resonance spectroscopic analysis revealed that the polymer composition was 7 based on the styrene component.
0.9% by weight, 2 based on acrylonitrile component
4.8% by weight, 4.3% by weight based on the glycidyl methacrylate component, polystyrene conversion number average molecular weight (Mn) of 51,300, weight average molecular weight (Mw) of 128, 00
0, the molecular weight distribution (Mw / Mn) was 2.5. (Resin B) Mixed solvent fractionation of this polymer was performed in the same manner as in Production Example-1. The results of solvent fractionation are shown in Table 1.

(Production Example-3) Styrene / acrylonitri
Synthesis of le-glycidyl methacrylate copolymer (comparison
(For use) In a round-bottomed flask having a content of 500 ml, which had been sufficiently replaced with nitrogen gas, 70.0 g of styrene, 25.0 g of acrylonitrile, 5.5 g of glycidyl methacrylate,
After adding 0.6 g of 2,2-azobis (isobutyronitrile) and 100 ml of xylene and stirring under a nitrogen stream to confirm that 2,2-azobis (isobutyronitrile) was completely dissolved, The temperature was raised to 60 ° C. and polymerization was carried out for 5 hours.

After the polymerization, the temperature was lowered to room temperature, 200 ml of chloroform was placed in the flask, the polymer was completely dissolved, and then poured into 2 liters of methanol to precipitate the polymer, which was then filtered and dried to obtain the polymer 7.
0.4 g was recovered (70.4% conversion). Infrared spectroscopic analysis and proton nuclear magnetic resonance spectroscopic analysis revealed that the polymer composition was 6 based on the styrene component.
8.4% by weight, 2 based on acrylonitrile component
6.1% by weight, 5.5% by weight based on the glycidyl methacrylate component, the number average molecular weight (Mn) in terms of polystyrene was 45,500, and the weight average molecular weight (Mw) was 129, by gel permeation chromatography measurement. 00
0, the molecular weight distribution (Mw / Mn) was 2.9. (Resin C) The mixed solvent fractionation of this polymer was performed in the same manner as in Production Example-1. The results of solvent fractionation are shown in Table 1.

(Production Example-4) Styrene-acrylonitri
Synthesis of le-glycidyl methacrylate copolymer (comparison
(For use) In a round-bottomed flask having a content of 500 ml that had been sufficiently replaced with nitrogen gas, 70.0 g of styrene, 25.0 g of acrylonitrile, 5 g of glycidyl methacrylate, 2,
Add 0.6 g of 2-azobis (isobutyronitrile),
After confirming that 2,2-azobis (isobutyronitrile) was completely dissolved while performing nitrogen bubbling, 6
The temperature was raised to 0 ° C. and polymerization was carried out for 5 hours.

After the polymerization, the temperature was lowered to room temperature, 200 ml of chloroform was placed in the flask, the polymer was completely dissolved, and then poured into 2 liter of methanol to precipitate the polymer, which was then filtered and dried to obtain the polymer 6.
5.7 g was recovered (conversion rate 65.7%). Infrared spectroscopic analysis and proton nuclear magnetic resonance spectroscopic analysis revealed that the polymer composition was 7 based on the styrene component.
4.1% by weight, 1 based on the acrylonitrile component
9.1% by weight, 6.8% by weight based on the glycidyl methacrylate component, polystyrene conversion number average molecular weight (Mn) of 30,100, weight average molecular weight (Mw) of 124, 00
0, the molecular weight distribution (Mw / Mn) was 4.1. (Resin D) The mixed solvent fractionation of this polymer was performed in the same manner as in Production Example-1. The results of solvent fractionation are shown in Table 1.

(Production Example-5) Polyester containing maleic anhydride
250 g of propylene homopolymer "MA8" (trade name) manufactured by Ropylene Mitsubishi Petrochemical Co., Ltd. and 50 g of maleic anhydride were placed in a 10-liter glass flask equipped with a stirrer, which had been previously replaced with nitrogen, and 5 liters of chlorobenzene were added, 1
It heated at 10 degreeC and stirred, and it melt | dissolved.

To this solution, 25 g of benzoyl peroxide dissolved in 500 ml of chlorobenzene was added dropwise over 2 hours, and after completion of the addition, the reaction was continued at 110 ° C. for 3 hours. The reaction product obtained was poured into 15 liters of acetone to precipitate the product, which was filtered and washed in 3
After repeating once, it was dried under reduced pressure to obtain a maleic anhydride graft-modified polypropylene. The content of the constitutional unit based on maleic anhydride was 0.98% by weight by infrared spectroscopic analysis. MRF is 5.7g / 1
It was 0 minutes. (Resin E)

(Production Example-6) Maleic anhydride graft
Ropylene-7-methyl-1,6-octadiene copolymer Copolymer of propylene and 7-methyl-1,6-octadiene [Constituent unit content based on 7-methyl-1,6-octadiene 0.9 mol% , Crystallinity by X-ray diffraction method 4
8.5%, MF measured according to ASTM D1238
R (230 ° C., 2.16 kg load) 1.5 g / 10 minutes,
Elastic modulus of 8,750 kg / cm ² ] 250 g and maleic anhydride 250 g were put into a 10-liter glass flask equipped with a stirrer, which had been previously replaced with nitrogen, 5 liters of chlorobenzene was added, and the mixture was heated to 110 ° C. and stirred. Dissolved.

To this solution, 25 g of benzoyl peroxide dissolved in 500 ml of chlorobenzene was added dropwise over 2 hours, and after completion of the addition, the reaction was continued at 110 ° C. for 3 hours. The reaction product obtained was poured into 15 liters of acetone to precipitate the product, which was filtered and washed in 3
After being carried out once, it was then dried under reduced pressure to obtain a maleic anhydride graft-modified unsaturated propylene-based copolymer. The content of the structural unit based on maleic anhydride in this product was 5.0% by weight by infrared spectroscopic analysis. In addition, the maleic anhydride graft-modified unsaturated propylene copolymer MR
F was 0.3 g / 10 minutes. (Resin F)

Examples 1 to 6 and Comparative Examples 1 to 8 Resins A to F obtained in Production Examples 1 to 6 and polybutadiene "Blendex 33" manufactured by GE Plastics Co., Ltd.
6 "(trade name), propylene homopolymer" MA8 "(trade name) manufactured by Mitsubishi Yuka, ABS" Toughlex 410 "(trade name) manufactured by Mitsubishi Kasei, and styrene manufactured by NOF Corporation.
Acrylonitrile / glycidyl methacrylate copolymers “Blenmer CP-510SA” and “Blenmer CP-20SA” (both are trade names) were mixed in the composition shown in Table 2 and the content was 60 ml, and the temperature was 230 ° C. with a Toyo Seiki Plastomill. , 6 minutes, 180 rpm
It was melt-kneaded.

After the completion of kneading, the sample was crushed with a crusher to give a granule. Granular sample is CS-1 manufactured by Custom Scientific (Custom Scientific)
Using an 83MMX Minimax injection molding machine, a temperature of 23
A test piece for physical property evaluation was molded at 0 ° C., and the following physical property evaluation was performed. (1) Storage elastic modulus A test piece having a length of 47 mm, a width of 5.3 mm, and a thickness of 2.0 mm was injection-molded, and a storage elastic modulus at a frequency of 1 Hertz and 30 ° C. was used using a solid analyzer RSA2 type manufactured by Rheometrics. (E ') was calculated.

(2) Izod impact strength A test piece having a length of 31.5 mm, a width of 6.2 mm, and a thickness of 3.2 mm was injection-molded, and a mini-max Izod impact tester CS-138TI manufactured by Custom Scientific.
Notch Izod impact strength JIS K
It was measured according to 7110-1984. The results are shown in Table 2.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Effect] A molded article having excellent heat resistance, rigidity and impact strength is provided.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yusuke Arashiro 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (2)

[Claims] 1. A propylene-based resin (A) having an α, β-unsaturated carboxylic acid added thereto and having a carboxyl group-containing propylene-based resin of 40 to 95% by weight (B) (a) having an epoxy group. Pinyl monomer 0.5
-8% by weight, (b) aromatic vinyl monomer 52-89.
5% by weight, (c) 10 to 40% by weight of vinyl cyanide monomer, and (d) 0 to 40% by weight of other vinyl monomer, which is the following mixture. Each fraction obtained by solvent fractionation has the following proportions (fraction) Insoluble matter of mixed solvent of 10 parts by volume of dimethylacetamide, 9 parts by volume of toluene and 21 parts by volume of 1-propanol 0 to 15% by weight (Fraction) Soluble in a mixed solvent of 10 parts by volume of dimethylacetamide, 9 parts by volume of toluene and 21 parts by volume of 1-propanol, and contained 5 parts by volume of dimethylacetamide, 6 parts by volume of toluene and 14 parts by volume of 1-propanol. Insoluble mixed solvent 50 to 100% by weight (fraction) 5 parts by volume of dimethylacetamide, 6 parts of toluene
What is soluble in a mixed solvent of 1 part by volume and 14 parts by volume of 1-propanol 0-45% by weight A thermoplastic resin composition containing the above components (A) and (B) in the above ratio. 2. The copolymer of the component (B) dissolves the preliminarily aromatic vinyl compound (b), vinyl cyanide compound (c), other vinyl monomer (d) and a radical generator. After the temperature of the solvent is raised to the polymerization temperature, the vinyl monomer having an epoxy group is added to the solvent at a total polymerization time of 40 to 90.
The thermoplastic resin composition according to claim 1, which is obtained by solution polymerization while being added over a period of%.