JPH0867777A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic resin compsn. which gives a molding excellent in impact resistance, moldability, resistance to water absorption, heat resistance, appearance, etc. CONSTITUTION: This resin compsn. contains 100 pts.wt. resin components comprising an olefin resin and a satd. polyester and 2-40 pts.wt. modified olefinic elastomer obtd. by grafting 0.01-20 pts.wt. hydroxylated α, β-unsatd. carboxylic ester and 0-50 pts. wt. another vinyl monomer to 100 pts.wt. olefin elastomer having a flexural modulus (JIS K 7203, at 23 deg.C) of 500kg/cm<2> or lower. A modified olefinic elastomer obtd. by grafting 0.01-20 pts.wt. styrene, as the vinyl monomer, to 100 pts.wt. olefin elastomer is esp. pref.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having improved compatibility between an olefin resin and a saturated polyester and excellent mechanical strength such as impact strength.

This product is useful as a molding material for hollow containers, films, toys, wheel caps for automobiles, instrument panels, handles, door trims, housings for electric and electronic devices, knob dials and the like.

[0003]

2. Description of the Related Art Olefin resins represented by propylene resin and ethylene resin are excellent in molding processability, water absorption resistance, organic solvent resistance, etc., and have low specific gravity and are inexpensive.
It is widely used for manufacturing various molded products, but its heat resistance is not so high, which is an obstacle to its use for engineering plastics.

On the other hand, saturated polyesters typified by polybutylene terephthalate and polyethylene terephthalate are recognized as engineering plastics excellent in heat resistance, chemical resistance, electrical properties, etc. It has drawbacks in that it easily absorbs water during molding such as extrusion molding and during use under high temperature and high humidity conditions, and physical properties such as impact resistance are deteriorated.

As one of the attempts in the case where a single resin material cannot sufficiently satisfy the desired properties, a method of complementing the insufficient property by mixing other resin materials is often performed. ing. As a result, if a composition having good properties of both the saturated polyester and the olefin resin and complementing undesired points can be obtained, it is possible to provide an excellent resin material having a wide range of applications.

However, since the saturated polyester and the olefin resin are incompatible with each other and have no affinity, the adhesiveness at the interface of this two-phase structure is not good when both components are simply mixed. Therefore, the phase interface of the obtained molded product becomes a defective portion, and the mechanical strength is lowered. Further, the two phases are unlikely to be in a uniform and finely dispersed form, and when subjected to shear stress during molding such as injection molding, delamination is likely to occur.

In order to solve the above problems, it has been proposed to blend a modified olefin resin having a functional group which reacts with the saturated polyester with a modified olefin resin having poor reactivity into the saturated polyester.

For example, a resin composition of an unsaturated carboxylic acid-modified olefin resin and a saturated polyester is disclosed in JP-A-56.
Although disclosed in JP-A-74168 and JP-A-55-21430, the unsaturated carboxylic acid and the saturated polyester have insufficient dispersibility, are easily peeled off in layers, and a practically satisfactory resin composition has not been obtained. . Further, a resin composition of an epoxy-modified olefin resin and a saturated polyester,
JP-A-61-60746 and JP-A-1-213352
Although disclosed in each of the publications, although the compatibility is improved to some extent when using these methods, during melt-kneading in an extruder or the like, the fluidity is reduced due to the formation of a part of a gel, There are problems that the extruded strand is stable and cannot be taken off, and that the surface appearance of the extruded product is deteriorated.

Further, a hydroxyl group-modified olefin resin in which a hydroxyl group is introduced into a crystalline olefin copolymer consisting of at least one kind of ethylene or α-olefin having 3 to 8 carbon atoms and at least one kind of chain non-conjugated diene. JP-A-4-323239 discloses a resin composition of a saturated polyester.

Further, the present inventors have disclosed a resin composition of a saturated polyester and a hydroxyl group-modified polypropylene or a hydroxyl group-modified polyethylene obtained by graft-polymerizing an α, β-unsaturated carboxylic acid ester having a hydroxyl group (Japanese Patent Laid-Open Publication No. 6-58242).
-80843).

However, although the molded articles obtained from these resin compositions certainly have the effect of improving the compatibility, the effect of improving the impact strength is not yet sufficient.
Further improvements were desired.

[0012]

DISCLOSURE OF THE INVENTION The present invention improves the compatibility of saturated polyester and olefinic resin, and has a stable dispersion structure which cannot be achieved by the prior art, and has a mechanical strength such as impact resistance. The object is to provide a thermoplastic resin composition having excellent dynamic strength.

[0013]

As a result of intensive studies, the inventors of the present invention have found that it is extremely effective to blend a specific hydroxyl group-modified olefin elastomer with an olefin resin and a saturated polyester. The surprising facts have been found and the present invention has been completed.

That is, the present invention provides the following component (A),
A thermoplastic resin composition containing (B) and (C) and containing 2 to 40 parts by weight of the component (C) per 100 parts by weight of the components (A) and (B) in total.

(A) Olefin-based resin (B) Saturated polyester (C) Flexural modulus at 23 ° C. (JIS K 720
3) Olefin-based elastomer 1 of 500 kg / cm ² or less
Modified olefin obtained by subjecting 00 parts by weight of 0.01 to 20 parts by weight of an α, β-unsaturated carboxylic acid ester having a hydroxyl group and 0 to 50 parts by weight of another vinyl monomer to a graft copolymerization step Elastomer

Particularly, the modified olefin elastomer (C) is added to 100 parts by weight of the olefin elastomer,
Α, β-unsaturated carboxylic acid ester having a hydroxyl group 0.
The above thermoplastic resin composition is a modified olefin elastomer (C) obtained by subjecting 01 to 20 parts by weight and 0.01 to 20 parts by weight of styrene to a graft copolymerization step.

[0017]

By blending the hydroxyl group-modified olefinic elastomer of component (C) used in the present invention, good physical properties are exhibited by reacting the hydroxyl group of component (C) with the carboxyl group or ester group of component (B). It is presumed that this is because a graft copolymer, which serves as a compatibilizer for the olefin resin and the saturated polyester, is produced.

The present invention will be described in more detail below.

(1) Olefin Resin (A) The olefin resin (A) used in the present invention has 2 carbon atoms.
10 to at least one α-olefin, X
The crystallinity at room temperature by line diffraction is preferably 15% or more, more preferably 30 to 70%, and has a melting point of 60 ° C. or more. The decrease in crystallinity decreases the elastic modulus of the final composition. Further, this olefin resin needs to have a sufficient molecular weight as a molding resin at room temperature. For example, when propylene is the main component, J
Melt flow rate (hereinafter referred to as "MFR") measured according to IS K 6758 is 0.01 to 500 g /
It has a molecular weight corresponding to 10 minutes, preferably 0.05 to 100 g / 10 minutes, and a flexural modulus according to JIS K7203 of 500 kg / cm ² or more, preferably 5,000 to 28,
It is preferably 000 kg / cm ² .

Examples of the α-olefin forming the olefin resin include ethylene, propylene, butene-
1, pentene-1, hexene-1, 3-methylbutene-
1,4-methylpentene-1,3,3-dimethylpentene-1,3-methylhexene-1,4-methylhexene-1,4,4-dimethylhexene-1,5-methylhexene-1, allylcyclo Pentane, allylcyclohexane, allylbenzene, 3-cyclohexylbutene-1,
Examples thereof include vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo [2.2.1] heptane, heptene-1 and octene-1. These α-olefins may be used alone or in combination of two or more as a polymerization component.

Among the above, preferred examples are ethylene,
Propylene, butene-1, pentene-1, hexene-
1,3-methylbutene-1,4-methylpentene-1,
3-methylhexene-1 can be mentioned. Especially ethylene, propylene, butene-1,3-methylbutene-
1,4-methylpentene-1 is preferred.

(2) Saturated polyester (B) The saturated polyester (B) used in the present invention is a saturated polyester obtained by polycondensation of a dicarboxylic acid or a lower alkyl ester thereof, an acid halide or an acid anhydride derivative and a dihydroxy compound. Is.

Specific examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, sebacic acid, terephthalic acid, isophthalic acid, p-carboxyphenoxyacetic acid, 2,6-naphthalene dicarboxylic acid, 2,7- Examples thereof include naphthalene dicarboxylic acid.

Specific examples of the dihydroxy compound include linear alkylene glycols having 2 to 12 carbon atoms, such as ethylene glycol, 1,3-propylene glycol, 1,
4-butanediol, 1,6-hexanediol, etc .; aromatic diols such as pyrocatechol, resorcinol,
Hydroquinone and the like; cyclohexanedimethanol and the like as alicyclic glycol; and alkyl-substituted derivatives of these compounds.

Suitable saturated polyesters (B) include
Examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and poly (1,4-cyclohexanedimethylene terephthalate).
Liquid crystalline polyesters such as X7G manufactured by Eastman Kodak Co., Vectra manufactured by Hoechst Celanese Co., Ltd., and Econol manufactured by Sumitomo Chemical Co., Ltd. are also preferable. These may be used alone or in combination of two or more.

(3) Modified Olefin-based Elastomer (C) The modified olefin-based elastomer (C) has a hydroxyl group of α, β- in 100 parts by weight of the olefin-based elastomer.
A modified olefin elastomer obtained by subjecting an unsaturated carboxylic acid ester of 0.01 to 20 parts by weight and another vinyl monomer of 0 to 50 parts by weight to a graft copolymerization step.

Examples of the α, β-unsaturated carboxylic acid ester having a hydroxyl group for modifying the olefin elastomer include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl. Methacrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2
-Hydroxymethyl-3-hydroxypropyl methacrylate, 2-hydroxymethyl-3-hydroxypropyl acrylate, 2,2-dihydroxymethyl-3-hydroxypropyl methacrylate, 2,2-dihydroxymethyl-3-hydroxypropyl acrylate, carbon number 4 to 40 ethylene glycol or propylene glycol oligomer methacrylic ester acid or acrylic ester,

Bis (2-hydroxyethyl) malate,
Bis (2-hydroxyethyl) fumarate, bis (2-
Hydroxypropyl) malate, bis (2-hydroxypropyl) fumarate, bis (2,3-dihydroxypropyl) malate, bis (2,3-dihydroxypropyl) fumarate, bis (2-hydroxymethyl-3-hydroxypropyl) malate, Bis (2-hydroxymethyl-3-hydroxypropyl) fumarate, bis (2,2
2-dihydroxymethyl-3-hydroxypropyl) malate, bis (2,2-dihydroxymethyl-3-hydroxypropyl) fumarate, maleic acid or fumaric acid ester of an oligomer of ethylene glycol or propylene glycol having 4 to 40 carbon atoms, etc. Is mentioned. The maleic acid or fumaric acid ester is not limited to those in which two carboxyl groups are both esterified with a hydroxyalkyl group as described above, and those in which only one is esterified are similar monomers. Can be illustrated as

The above unsaturated carboxylic acid ester having a hydroxyl group can be used alone or in combination of two or more kinds. Among these, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, methacrylic acid or acrylic acid ester of an oligomer of ethylene glycol or propylene glycol having 4 to 40 carbon atoms, etc. preferable.

In order to enhance the grafting efficiency of the α, β-unsaturated carboxylic acid ester having a hydroxyl group onto an olefin elastomer, it is useful to use another vinyl monomer copolymerizable with the ester in combination. is there.

The reason for this is that α, β having a hydroxyl group
-When only unsaturated carboxylic acid ester is graft-copolymerized, interaction occurs between carboxylic acid ester groups having adjacent hydroxyl groups, and the hydroxyl groups are eliminated / disappeared. When used in combination with the vinyl-based monomer, the adjacent carboxylic acid ester groups are prevented from adjoining each other, the hydroxyl groups are less likely to disappear, and the saturated polyester effectively acts.

Other copolymerizable vinyl monomers include:
Styrene, α-methylstyrene, α-methoxystyrene, methylstyrene, dimethylstyrene, 2,4,6-
Aromatic vinyl monomers such as trimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, nitrostyrene, chloromethylstyrene, cyanostyrene, t-butylstyrene, vinylnaphthalene; ethyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid ester monomers such as methyl acrylate, propyl (meth) acrylate, octyl (meth) acrylate; N-methyl (meth)
(Meth) acrylamide monomers such as acrylamide and N-methylol (meth) acrylamide; cyanovinyl monomers such as acrylonitrile and methacrylonitrile;
Vinyl ester type monomers such as vinyl butyrate; Vinyl ether type monomers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; vinyl imidazole,
Heterocyclic ring-containing vinyl compounds such as vinyl oxazoline, vinyl pyridine and vinyl pyrrolidone can be exemplified. You may use these 2 or more types together.

Among them, styrene, α-methylstyrene, methylstyrene, vinyl butyrate, vinyloxazoline or vinylpyridine is used as the olefin elastomer 10
When 0.01 to 20 parts by weight is used with respect to 0 parts by weight, the compatibility is further improved, and styrene is most preferable.

The olefinic elastomer used in the present invention has a flexural modulus at 23 ° C. of not more than 500 kg / cm ² according to JIS K7203 and a glass transition temperature of -10 ° C.
The following rubber-like polymer.

Specific examples of these rubbery polymers include:
Homopolymers of olefins such as polybutadiene, polyisoprene and polyisobutylene, or ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), ethylene-isoprene copolymer, ethylene-chloroprene copolymer Different kinds of olefins or diolefins such as copolymers of ethylene and organic acid esters such as polymers, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers And the like.

These copolymers are random copolymers,
It may be a block copolymer, a graft copolymer or an alternating copolymer.

These olefin elastomers can be used alone or in combination of two or more.

Among these, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene -Methyl acrylate copolymer and the like are preferable, ethylene-
A propylene copolymer, an ethylene-propylene-diene copolymer, and an ethylene-butene-1 copolymer are more preferable.

The method for modifying the olefin elastomer with the above-mentioned α, β-unsaturated carboxylic acid ester having a hydroxyl group and another vinyl monomer is not particularly limited. β
-A method in which an unsaturated carboxylic acid ester and another vinyl-based monomer are allowed to coexist and reacted in the presence or absence of a radical generator such as an organic peroxide, a method of irradiating ultraviolet rays or radiation, oxygen or There is a method of contacting with ozone.

As the radical generator, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-
Dimethylhexane-2,5-dihydroperoxide, benzoyl peroxide, dicumyl peroxide, 1,3
-Organic and inorganic peroxides such as bis (t-butylperoxy-isopropyl) benzene, t-butylperoxybenzoate, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide, 2,
2'-azobisisobutyronitrile, 2,2'-azobis (isobutylamide) dihalide, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], azodi-t-butane An azo compound such as, a carbon radical generator such as dicumyl, and the like can be used. 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 in the range of 0 to 30 parts by weight, preferably 0 to 10 parts by weight, based on 100 parts by weight of the olefin elastomer.

The temperature during the graft copolymerization is usually 30 to 3
The temperature is 50 ° C., preferably 50 to 300 ° C., and the modification reaction time is 50 hours or less, preferably 0.5 minutes to 24 hours. The graft copolymerization reaction is carried out in a solution state, a molten state,
Any state of suspension may be adopted. Further, in the case of melt modification by an extruder or the like, for the purpose of improving the reaction efficiency, for example, an organic solvent such as xylene, a benzene system such as isopropylbenzene, a mercaptan system such as n-butyl mercaptan, a chlorination of carbon tetrachloride or the like. It is also possible to remove unreacted components and the like by adding a chain transfer agent such as a physical system or by kneading under reduced pressure.

The content of the α, β-unsaturated carboxylic acid ester having a hydroxyl group introduced into the olefin elastomer is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the olefin elastomer. It is a range of parts. If the content of the α, β-unsaturated carboxylic acid ester having a hydroxyl group is less than 0.01 parts by weight, the effect of improving the compatibility is small, and if it exceeds 20 parts by weight, molding processability may be deteriorated due to gelation or the like, or molding may occur. The appearance of the product may deteriorate, which is not preferable.

The content of the other vinyl-based monomer to be introduced into the olefin-based elastomer depends on the olefin-based elastomer 1
0 to 50 parts by weight, preferably 0.0
It is in the range of 1 to 20 parts by weight, more preferably 0.1 to 20 parts by weight. Even if the other vinyl-based monomer is not used in combination, the effect of improving the compatibility is observed to some extent, but the compatibility is further improved by using the combination. On the other hand, if it exceeds 50 parts by weight, the fluidity of the modified elastomer is remarkably lowered, the appearance of the molded product is deteriorated, and the mechanical strength is lowered due to the deterioration of rubber properties, which is not preferable.

Further, the ratio of the α, β-unsaturated carboxylic acid ester having a hydroxyl group to be introduced into the olefin-based elastomer and the other vinyl-based monomer may be any value, but the effect of improving the compatibility is recognized, but it is preferable. 5 to 1 in molar ratio
The range is 1 to 5.

The above-mentioned modified olefin elastomer is
MFR measured in accordance with JIS K 7210 (23
0 ℃, 2.16kg load) 0.001-200g / 10
Min, preferably 0.005 to 100 g / 10 min, more preferably 0.01 to 50 g / 10 min.

(3) Composition Ratio of Constituents The composition of the olefin resin as the component (A) and the saturated polyester as the component (B) in the thermoplastic resin composition of the present invention is 90 to 10 parts by weight of the component (A). %, Preferably 80
To 20% by weight, more preferably 70 to 30% by weight, and the component (B) is 10 to 90% by weight, preferably 20 to 30% by weight.
It is 80% by weight, more preferably 30 to 70% by weight.

When the content of the component (A) is less than 10% by weight, the effect of improving the moldability and water absorption resistance of the composition is small as compared with the saturated polyester, and when it exceeds 90% by weight, the heat resistance is improved as compared with the olefin resin. The effect is small.

The content of the modified olefinic elastomer as the component (C) is 2 to 40 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).
It is more preferably 10 to 25 parts by weight.

If the amount of the component (C) is less than 2 parts by weight, the effect of improving the impact strength is small, and if the amount of the component (C) exceeds 40 parts by weight, the elastic modulus is largely decreased, which is not preferable.

(4) Additional component The thermoplastic resin composition of the present invention comprises the above component (A),
Other components other than (B) and (C) can be contained. For example, a part (up to 90% by weight) of the modified olefin elastomer of the component (C) may be replaced with an unmodified olefin elastomer.

Further, a part (up to 90% by weight) of the olefin resin as the component (A) is a vinyl monomer such as α, β-unsaturated carboxylic acid ester having a hydroxyl group such as 2-hydroxymethyl methacrylate and styrene. May be replaced with a hydroxyl group-modified olefin resin obtained by graft copolymerization.

Furthermore, an impact resistance improver other than the modified olefin elastomer used in the present invention may be contained in the resin composition in an amount of 5 to 30% by weight. As such impact modifier, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber or hydrogenated products thereof, acrylic rubber, acrylic-styrene core shell rubber, ABS, AES and the like can be used.

In addition, organic / inorganic fillers and reinforcing agents, particularly glass fibers, carbon fibers, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica and the like are added to the resin composition in an amount of 5 to 40% by weight. That the rigidity,
It is effective in improving heat resistance, dimensional accuracy, and dimensional stability.
For practical use, various colorants and their dispersants are also included.
It can be used in a proportion of 10 to 10% by weight.

Further, a non-resinous additive may be added to improve chemical or physical properties, if necessary. For example, hindered phenol-based antioxidants, phosphorus-based antioxidants such as phosphite, amine-based antioxidants, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, aliphatic carboxylic ester-based lubricants, paraffin Examples include lubricants, flame retardants, release agents and antistatic agents.

Specific examples of the above hindered phenolic antioxidants include 2,6-di-t-butyl-p-cresol, Irganox 1076 (trade name of Ciba Geigy), Sumilizer GM (trade name of Sumitomo Chemical Co., Ltd.). ) Etc. Further, as the phosphorus-based antioxidant, Sumilizer TNP (trade name of Sumitomo Chemical Co., Ltd.), Mark PEP36
(Trade name of ADEKA ARGUS), IRGAFOSS 168 (trade name of Ciba-Geigy), and the like.

(5) Method for Preparing Composition and Molding Method The method for obtaining the thermoplastic resin composition of the present invention is not particularly limited, such as a melting method, a solution method and a suspension method. The method of kneading is preferable. As the melt-kneading method, a kneading method generally used for thermoplastic resins can be applied. For example, the powdery or granular components are uniformly mixed with the additives described in the section of additional components, if necessary, by a Henschel mixer, ribbon blender, V-type blender, etc., and then uniaxial or multiaxial kneading. Extruder,
It can be kneaded with a roll, a Banbury mixer or the like.

The melting and kneading temperature of each component is 100
In the range of ℃ to 400 ℃, preferably 120 ℃ to 300
It is in the range of ° C. Further, the kneading order and method of each component are not particularly limited, and examples thereof include a method of kneading an olefin resin, a modified olefin elastomer, a saturated polyester and an additional component at a time, and a partial or total amount of the modified olefin system. After kneading the elastomer and the saturated polyester, kneading the remaining components, kneading the olefin elastomer and the α, β-unsaturated carboxylic acid ester having a hydroxyl group, another vinyl monomer and the radical initiator. A method of kneading the remaining components after forming a modified olefin elastomer, an α, β-phenyl saturated carboxylic acid ester monomer having an olefin elastomer and a hydroxyl group, another vinyl monomer, a radical initiator, a saturated polyester Also, any method such as a method of kneading the additional components and the like at once and a method of kneading under reduced pressure may be used. Further, during the melt-kneading, an organic solvent such as chlorobenzene, trichlorobenzene, xylene or the like, or a catalyst such as tetrakis (2-ethylhexoxy) titanium or dibutyltin oxide can be added.

The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and the molding methods generally used for thermoplastic resins, that is, injection molding, blow molding, extrusion molding, thermoforming, and pressing. Various molding methods such as molding can be applied.

[0060]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

In the following, parts and percentages are based on weight.

The contents of 2-hydroxyethyl methacrylate and styrene, which are α, β-unsaturated carboxylic acid ester graft-polymerized on the modified olefin elastomer, were determined by the following method. 0.3 g of the modified olefin elastomer obtained by melt modification was dissolved by heating in 30 ml of xylene and then purified by reprecipitation in 250 ml of methanol. Then, the purified modified olefin elastomer is molded into a film by using a press, and an IR spectrum is measured by infrared spectroscopy (hereinafter referred to as “IR method”) to obtain an absorption of 1,724 cm ⁻¹ derived from carbonyl and The absorption at 700 cm ⁻¹ derived from the aromatic ring was quantified from a calibration curve prepared in advance.

Reference Example 1: Production of 2-hydroxyethyl methacrylate-styrene graft modified ethylene-propylene copolymer (modified EPR-1) Ethylene-propylene copolymer elastomer (manufactured by Japan Synthetic Rubber Co., Ltd., trade name: EP01, hereinafter) Called "EPR";
230 ° C MFR 3.5g / 10min, flexural modulus 200
kg / cm ² ) is a twin-screw extruder (manufactured by Japan Steel Works, trade name: T
EX-30), cylinder temperature 180 ° C, screw speed 300rpm, discharge rate 70g / min, 750mmHg
While kneading under reduced pressure conditions, 100 parts by weight of 2-hydroxyethyl methacrylate, 100 parts by weight of styrene and 2 parts by weight of bis (t-butylperoxyisopropyl) benzene were introduced from a front vent part provided in the middle of the extruder cylinder. The mixed solution was added under the condition of 14 g / min using a transport pump to obtain the target pellet.

The content of the constitutional unit based on 2-hydroxyethyl methacrylate of the obtained modified olefin elastomer (hereinafter referred to as "modified EPR-1") pellets was 0.42% by weight, and the constitutional unit based on styrene was determined by the IR method. The content was 0.56% by weight. Also, JIS
MFR of pellets measured according to K 7210
(230 ° C.) was 1.82 g / 10 minutes.

Reference Example 2: Production of 2-hydroxyethyl methacrylate-styrene graft modified ethylene-propylene copolymer (modified EPR-2) In Reference Example 1, 2-hydroxyethyl methacrylate, styrene and bis (t-butylperoxy) were used. Reference Example 1 except that the addition amount of the iropropyl) benzene mixed solution was changed to 28 g / min and the screw rotation speed was changed to 100 rpm.
Manufactured in the same manner as.

The modified elastomer thus obtained (hereinafter referred to as "modified E"
PR-2 ”) has a constitutional unit content based on 2-hydroxyethyl methacrylate of 1.20% by weight, a constitutional unit content based on styrene of 1.48% by weight, and an MFR of pellets of 0.33 g / 10 min. It was

Reference Example 3: Production of 2-hydroxyethyl methacrylate graft modified ethylene-propylene copolymer (modified EPR-3) Reference Example 1 except that styrene was not used and the screw rotation speed was changed to 100 rpm. Prepared as in 1.

The modified elastomer thus obtained (hereinafter referred to as "modified E"
The content of the constitutional unit based on 2-hydroxyethyl methacrylate in "PR-3") was 0.81% by weight, and the MFR of the pellet was 1.17 g / 10 minutes.

Reference Example 4: Production of 2-hydroxyethyl methacrylate graft modified polypropylene (modified PP) (for comparison) Propylene homopolymer powder (manufactured by Mitsubishi Yuka Co., Ltd., 230 ° C.)
MFR of 1 g / 10 min, melting point of about 164 ° C., flexural modulus: 12,000 kg / cm ² ) 2,000 g, 2-hydroxyethyl methacrylate 100 g and t-butyl peroxybenzoate 10 g were mixed with a super mixer, Using a twin-screw extruder (TEX-30 manufactured by Japan Steel Works, Ltd.), the cylinder temperature is 180 ° C. and the screw rotation speed is 250.
Melt kneading was performed under the conditions of rpm and discharge rate of 5 kg / hour to obtain pellets.

Obtained modified polypropylene (modified PP)
The content of the constitutional unit based on 2-hydroxymethyl methacrylate in the product was 1.94% by weight, and the MFR of the pellet was 40.
It was 3 g / 10 minutes.

Examples 1 to 8 and Comparative Examples 1 to 8 Modified EPR-1 to 3 and modified P obtained in Reference Examples 1 to 4
P and the following resins were used.

Olefin resin: propylene homopolymer [trade name: Mitsubishi Polypro MA6, MF, manufactured by Mitsubishi Petrochemical Co., Ltd.
R: 1.4g / 10 minutes (230 ° C, 2.16kg load),
Density: 0.90 g / cm ³ , abbreviated as "PP MA6" in the table]
And propylene-ethylene copolymer [manufactured by Mitsubishi Petrochemical Co., Ltd., trade name: Mitsubishi Polypro EC9, MFR: 0.5 g / 10
Min, density: 0.90 g / cm ³ , abbreviated as "PP EC9" in the table]

Saturated polyester: Porbutylene terephthalate (manufactured by Mitsubishi Kasei Co., trade name: Novador 5010,
(Abbreviated as "PBT" in the table) and polyethylene terephthalate (manufactured by Kanebo, trade name: PBK-1, abbreviated as "PET" in the table)

Maleic anhydride-modified ethylene-propylene copolymer elastomer: Maleized EPR (manufactured by Mitsubishi Petrochemical Co., Ltd., trade name: Modic, maleic anhydride content: 1.2
% By weight, MFR at 190 ° C .: 1.0 g / 10 minutes, abbreviated as “MAH-EPR” in the table)

Unmodified ethylene-propylene copolymer elastomer: EPR

Each of the components shown in Table 1 was blended in the composition shown in the same table with a Labo Plastomill kneader (manufactured by Toyo Seiki Seisakusho Ltd.) at a temperature of 250 ° C. and a screw rotation speed of 1
After kneading at 80 rpm for 5 minutes, it was pulverized to obtain a granular resin composition. In addition, about Example 8 and Comparative Example 8,
The kneading temperature was 280 ° C.

The characteristics of the obtained resin composition are measured by using an injection molding machine [Custom Scientifi
c), CS183MMX Minimax] at a temperature of 260 ° C., 2 for the compositions of Example 8 and Comparative Example 8.
The impact resistance of the test piece injection-molded at 80 ° C. was measured and evaluated by the following method. The results are shown in Table 1.

During the kneading and molding, the saturated polyester and the resin composition were vacuum dried at 120 ° C. for 5 hours until just before that.

Impact strength: length 31.5 mm, width 6.2 m
m, 3.2 mm thick test piece was injection molded and using an Izod impact tester (Nimimax CS-138TI type manufactured by Custom Scientific Co., Ltd.), the notched Izod impact strength at 23 ° C and the notch tip R Of 0.25 mm and depth of 1.2 mm was measured for notched Izod impact strength.

[0080]

[Table 1]

[0081]

As is clear from the examples and comparative examples,
The thermoplastic resin composition of the present invention gives a molded article having excellent impact resistance.

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Claims (2)

[Claims] 1. The following components (A), (B) and (C) are contained, and 2 to 40 parts by weight of the component (C) is contained per 100 parts by weight of the components (A) and (B) in total. Thermoplastic resin composition. (A) Olefin-based resin (B) Saturated polyester (C) Flexural modulus at 23 ° C. (JIS K 720
3) Olefin-based elastomer 1 of 500 kg / cm ² or less
Modified olefin obtained by subjecting 00 parts by weight of 0.01 to 20 parts by weight of an α, β-unsaturated carboxylic acid ester having a hydroxyl group and 0 to 50 parts by weight of another vinyl monomer to a graft copolymerization step Elastomer 2. A modified olefin elastomer (C)
Is an α, β-unsaturated carboxylic acid ester having a hydroxyl group in an amount of 0.01 to 100 parts by weight of the olefin elastomer.
The thermoplastic resin composition according to claim 1, which is a modified olefin elastomer (C) obtained by subjecting 20 parts by weight and 0.01 to 20 parts by weight of styrene to a graft copolymerization step.