JPH06287309A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Structure] A thermoplastic resin composition containing a graft copolymer of an olefin resin and a saturated polyester, which is obtained by reacting the following component (A) and component (B). (A) 0.01 to 20 parts by weight of an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group is the olefin resin 1
Modified olefin resin (B) saturated polyester having a hydroxyl group residual ratio of 0.3 to 1.0 graft-polymerized to 00 parts by weight. [Effect] The compatibility of the olefin resin and the saturated polyester is remarkably improved. The composition has a good appearance of a molded product and an excellent balance of mechanical properties such as impact strength and tensile strength.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has an improved compatibility between olefinic resins and saturated polyesters, an excellent balance of heat resistance and mechanical strength, and excellent moldability, hygroscopicity and appearance of molded articles. It relates to an excellent thermoplastic resin composition.

[0002]

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 in the production of various molded products, but its heat resistance is not so high, which is an obstacle to its use in 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.

[0004] As one of the attempts in the case where a single resin material cannot sufficiently satisfy desired properties, it is often practiced to mix other resin materials to complement the insufficient properties. It is being appreciated. 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 reduced. 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 propylene resin and a saturated polyester is disclosed in JP-A-56-
As disclosed in Japanese Patent No. 74168, 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 is disclosed in JP-A-61-60746 and JP-A-1-213352. However, even if these methods are used, Although the solubility is improved to some extent, during melt-kneading with an extruder or the like, the formation of a part of a gelled product reduces the fluidity of the extruded strand,
There are problems that it cannot be stably collected and that the surface appearance of the extrusion molded product is deteriorated.

[0008]

DISCLOSURE OF THE INVENTION The present invention has improved the compatibility of an olefin resin and a saturated polyester, and has a stable dispersion structure which cannot be achieved by the prior art. It is an object of the present invention to provide a thermoplastic resin composition having an excellent appearance.

[0009]

[Means for Solving the Problems] As a result of intensive studies, the present inventors have found that a composition of a specific hydroxyl group-modified olefin resin and a saturated polyester shows extremely good affinity. The present invention has been completed.

That is, the present invention is a thermoplastic resin composition containing a graft copolymer of an olefin resin and a saturated polyester, which is obtained by reacting the following components (A) and (B). .

(A) 0.01 to 20 parts by weight of an α, β-unsaturated carboxylic acid ester monomer containing a hydroxyl group is graft-polymerized with 100 parts by weight of an olefin resin, and
Modified olefin resin (B) saturated polyester having a hydroxyl group residual ratio of 0.3 to 1.0

[0012]

The specific hydroxyl group-modified olefin resin used in the present invention and the saturated polyester show good affinity.
This is because the hydroxyl group of component (A) reacts with the carboxyl group or ester group of component (B) to form a graft copolymer that serves as a compatibilizer for the olefin resin and the saturated polyester.

The present invention will be described in more detail below. <Modified olefin resin (A)> The modified olefin resin (A) used in the present invention is a modified olefin resin modified by graft-polymerizing an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group. The proportion of the hydroxyl groups contained in the grafted α, β-unsaturated carboxylic acid ester-based monomer with respect to the total amount of the hydroxyl groups, that is, the hydroxyl group residual rate is in the range of 0.3 to 1.0. . A specific method for measuring the residual ratio of hydroxyl groups will be described in the section of Examples below.

Examples of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group for modifying the olefin resin include, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxy. Propyl acrylate, 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 Methacrylic acid or acrylic acid ester of oligomer of ethylene glycol or propylene glycol of ~ 40,

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-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, and the like. The maleic acid or fumaric acid ester is not limited to those in which two carboxyl groups are esterified with two co-hydroxyalkyl groups as described above, and those in which only one is esterified are similar monomers. Can be illustrated as

The above unsaturated carboxylic acid esters 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.

A method for producing a modified olefin resin in which the residual ratio of the hydroxyl group of the α, β-unsaturated carboxylic acid ester having a hydroxyl group graft-polymerized to the olefin resin is in the range of 0.3 to 1.0 is Any method may be used as long as it is a method in which a hydroxyl group having a hydroxyl group having an α, β-unsaturated carboxylic acid ester graft-polymerized with an olefin resin and capable of effectively reacting with a saturated polyester does not disappear. . The mechanism of the disappearance of hydroxyl groups will be described below, but this is for clarifying the idea of the present invention, and the present invention is not limited thereto.

Examples of the modified resin obtained by graft-polymerizing an α, β-unsaturated carboxylic acid ester having a hydroxyl group on polypropylene (PP) are as follows. 1) Chain hydrolysis

[0019]

[Chemical 1]

2) Cyclization reaction

[0021]

[Chemical 2]

However, R represents an alkylene group. That is, since the hydroxyl group-containing methacrylic acid ester-based monomers are adjacent to each other, an interaction occurs and the ester portion to which the hydroxyl group is bonded disappears, so that the adjacent effect is hindered,
Any method may be used as long as it improves the residual ratio of hydroxyl groups. Specifically, for example, α, β- having an olefin resin and a hydroxyl group
A method in which an unsaturated carboxylic acid ester-based monomer is intercalated with another monomer and is modified by melt-kneading in the presence or absence of a radical generator such as an organic peroxide is used. Can be mentioned.

Other copolymerizable monomers include styrene, α-methylstyrene, α-methoxystyrene, methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene and nitro. Styrene, chloromethylstyrene,
Aromatic vinyl monomers such as cyanostyrene, t-butylstyrene and vinylnaphthalene; ethyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate, octyl (meth) acrylate and the like ( (Meth) acrylic acid ester-based monomer; (meth) acrylamide-based monomer such as N-methyl (meth) acrylamide, N-methylol (meth) acrylamide; acrylonitrile,
Cyanovinyl monomers such as methacrylonitrile; vinyl ester monomers such as vinyl butyrate; vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; vinyl imidazole, vinyl oxazoline, vinyl pyridine, vinyl pyrrolidone, etc. And the heterocyclic ring-containing vinyl compound. Among these, styrene, α-methylstyrene, methylstyrene, vinyl butyrate, vinyloxazoline and vinylpyridine are preferable. These may be used alone or in combination of two or more.

The olefin resin used in the present invention is composed of at least one of α-olefins having 2 to 10 carbon atoms, and the crystallinity at room temperature by X-ray diffraction is preferably 10% or more, more preferably 20%. % Or more, and has a melting point of 40 ° 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, JI
Melt flow rate measured according to SK 6758 is 0.01 to 500 g / 10 minutes, preferably 0.05.
It has a molecular weight equivalent to 100 g / 10 min.
It is preferable that the flexural modulus according to K 7203 is 500 kg / cm ² or more.

The above α which is a constituent component of the olefin resin
-Examples of olefins 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, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexylbutene-1, vinylcyclopropane, vinylcyclohexane,
2-vinyl-bicyclo [2.2.1] heptane, heptene-1, octene-1, and the like can be mentioned, and one or more of these α-olefins can be used 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. In addition, as other components, 4-methyl-1,4-hexadiene, 5
-Methyl-1,4-hexadiene, 7-methyl-1,6
Non-conjugated dienes such as -octadiene and 1,9-decadiene may be used as a part of the polymerization component.

The method of modifying the olefin resin with another monomer copolymerizable with the above-mentioned α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group is not particularly limited.
For example, in the presence of a radical generator such as an organic peroxide, an olefin resin and an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group are allowed to coexist with another copolymerizable monomer. There are a method of reacting in the absence, a method of irradiating ultraviolet rays and radiation, a method of contacting with oxygen and ozone, and the like.

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 (isobutylamido) 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 resin.

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 1 minute to 24 hours. The graft reaction may be carried out in any of a solution state, a molten state and a suspension state. Furthermore, at the time of melt modification by an extruder or the like, for the purpose of improving reaction efficiency, by adding an organic solvent such as xylene or kneading under reduced pressure,
Unreacted components and the like can also be removed.

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

The content of the other copolymerizable monomer to be introduced into the olefin resin is 0.01 to 50 parts by weight, preferably 0.05 to 2 parts by weight based on 100 parts by weight of the olefin resin.
It is in the range of 0 parts by weight. If the content of the other copolymerizable monomer is less than 0.01 part by weight, the effect of improving the compatibility is small,
If it exceeds 50 parts by weight, the appearance of the molded product may be deteriorated or the mechanical strength may be deteriorated, which is not preferable.

The weight ratio of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group to the other monomer copolymerizable is preferably 1:99 to 99: 1.
More preferably, it is in the range of 10:90 to 90:10.
If these ratios are out of the range, α having a hydroxyl group,
The random or alternating copolymerization ratio of the other monomer copolymerizable with the β-unsaturated carboxylic acid ester-based monomer becomes unbalanced, and the effect of improving the compatibility becomes small, which is not preferable.

The hydroxyl group residual ratio of the α, β-unsaturated carboxylic acid ester having a hydroxyl group graft-polymerized to the olefin resin is in the range of 0.3 to 1.0, preferably 0.4.
The range is from 1.0 to 1.0. If the residual ratio of hydroxyl groups is less than 0.3, the effect of improving the compatibility becomes small, which is not preferable. The modified olefin resin has a melt flow rate (MFR) of 0.0 measured according to JIS K 7210.
It is preferably 1 to 200 g / 10 minutes, more preferably 0.
It is 1 to 100 g / 10 minutes.

<Saturated Polyester (B)> The saturated polyester (B) used in the present invention includes thermoplastic saturated obtained by polycondensation of dicarboxylic acid or its lower alkyl ester, acid halide or acid anhydride derivative and dihydroxy compound. It is polyester. 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-naphthalene dicarboxylic acid and the like. Specific examples of the dihydroxy compound include 2 carbon atoms.
~ 12 straight chain alkylene glycols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc .; aromatic diols such as pyrocatechol, resorcinol, hydroquinone; alicyclic glycols Examples thereof include cyclohexanedimethanol and the like; or alkyl-substituted derivatives of these compounds. Suitable saturated polyesters (B) include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly (1,4-).
Cyclohexane dimethylene 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.

<Composition Ratio of Constituent Components> The composition ratio of the modified olefin resin of the component (A) and the saturated polyester of the component (B) in the present invention is good even if they are mixed in any value, but generally the modified olefin is used. When the resin (A) is the main component, the heat resistance of the olefin resin is improved by mixing the saturated polyester (B). On the other hand, when the saturated polyester (B) is the main component, the water absorption resistance and molding processability are improved by mixing the component (A). The component (A) and the component (B) obtained by harmonizing the characteristics of these two constituent components
In the case of a two-component system, the composition ratio of is preferably 90 by weight.
10 to 10 to 90, more preferably 70 to 30 to 30
The range is 70 pairs. When the amount of the component (A) is less than 10% by weight, the effect of improving the moldability and water absorption of the composition is smaller than that of the saturated polyester, and when it exceeds 90% by weight, the effect of improving the heat resistance is less than that of the olefin resin.

<Additional component> The thermoplastic resin composition of the present invention may contain a component other than the components (A) and (B). For example, a part (up to 90% by weight) of the modified olefin resin of the component (A) may be replaced with an unmodified olefin resin.

Further, 0.5 to 3% by weight of antioxidants, weather resistance improvers, nucleating agents, flame retardants, slip agents, etc .; 3 to 15% by weight of plasticizers, fluidity improvers, release agents, etc. % Can be used as an additional component. Furthermore, organic / inorganic fillers, reinforcing agents,
In particular, adding 5 to 40% by weight of glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc. to the resin composition improves rigidity, heat resistance, dimensional accuracy, dimensional stability, etc. Is effective for. For practical use, various colorants and their dispersants can be used in a proportion of 1 to 10% by weight.

Further, addition of a rubber component, particularly styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber or hydrogenated products thereof; ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber. Further, those α, β-unsaturated carboxylic acid anhydride modified products, unsaturated glycidyl ester or unsaturated glycidyl ether modified products; copolymers of unsaturated epoxy compounds and ethylene or unsaturated epoxy compounds, ethylene and ethylene series A copolymer or the like composed of an unsaturated compound is effective in improving the impact strength of the composition. The compounding amount of the rubber varies depending on the target physical property value, but in the case of improving the balance between the rigidity and the impact strength of the composition, it is 5 to 30% by weight in 100% by weight of the composition.

Further, polyphenylene ether, hydroxyalkylated polyphenylene ether, nylon 6,
Nylon 6,6, Nylon 6,10, Nylon
6,12, 1 to 7 in the resin composition such as polycarbonate
You may contain 0 weight%.

<Preparation Method and Molding Method of Composition> 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, but it is practically a melt kneading method. Is preferred. 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, roll,
It can be kneaded with a Banbury mixer or the like.

The temperature of the melt-kneading 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 for example, a method of kneading the modified olefin resin and the saturated polyester and the additional component at once, a part or the whole amount of the modified olefin resin and the saturated polyester. After kneading, the method of kneading the remaining components,
After kneading the olefin resin, an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group, another copolymerizable monomer and a radical initiator to prepare a modified olefin resin, the remaining components Method of kneading, olefin resin and α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group, other copolymerizable monomer, radical initiator, saturated polyester and additional components are kneaded together Any method such as a method of kneading and a method of kneading under reduced pressure may be used. Furthermore,
At the time of melt-kneading, an organic solvent such as chlorobenzene, trichlorobenzene or xylene, 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 are used. Various molding methods such as molding can be applied.

[0043]

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 content of 2-hydroxyethyl methacrylate, which is an α, β-unsaturated carboxylic acid ester graft-polymerized on the modified olefin resin, was determined by the following method.

(1) Infrared spectroscopy (hereinafter referred to as "IR method"): A purified modified olefin resin was formed into a film by using a press, and the IR spectrum was measured to absorb carbonyl-derived 1724 cm ^-1 . Was quantified from a calibration curve prepared in advance. (2) Proton Nuclear Magnetic Resonance Spectroscopy (hereinafter referred to as "NMR method"): 50 mg of purified modified olefin resin was dissolved in about 2 ml of o-dichlorobenzene by heating at 130 ° C, and a sample was prepared using deuterated benzene as a standard substance. ¹ H-
The NMR spectrum was measured and quantified using the absorption of methylene having a hydroxyl group bonded (chemical shift: 3.7 ppm) and methylene bonded to it (chemical shift: 4.2 ppm).

Using the ratio of the contents obtained by these two kinds of measuring methods, the residual ratio of hydroxyl groups was calculated from the following formula. Hydroxyl group residual rate = [content (%) determined by NMR method] /
[Content (%) determined by IR method]

Reference Example 1: Preparation of 2-hydroxyethyl methacrylate-styrene graft modified propylene resin-1 (modified PP-1) Homopolymer powder of propylene (MFR at 230 ° C: 1
g / 10 minutes, melting point about 164 ° C.) 2,000 g, 2-hydroxyethyl methacrylate 60 g, styrene 40 g and t-butyl peroxybenzoate 20 g were mixed with a super mixer, and then a twin-screw extruder (manufactured by Japan Steel Works, Ltd., (Product name: TEX-30 type), cylinder temperature 180 ° C, screw rotation speed 250 rpm, discharge amount 5 kg
The pellets were obtained by kneading under a reduced pressure for 1 hour. 0.3 g of the obtained pellets was added to 20 ml of xylene at a temperature of 110 ° C.
Completely dissolved in 150 ml of methanol, the product was precipitated, filtered and washed twice, and then dried under reduced pressure for purification.
1 (modified PP-1) was obtained. The content of 2-hydroxyethyl methacrylate of this purified product was 1.31 by IR method.
% And 0.94% by the NMR method. Similarly, the styrene content of this purified product was found to be 0.80 by the IR method using a peak at 700 cm ^-1 derived from monosubstituted benzene.
%Met. Further, the MFR at 230 ° C. of the pellet measured according to JIS K 7210 is 33.4 g / 10.
It was a minute.

Reference Example 2: Production of 2-hydroxyethylmethacrylate-styrene graft modified propylene resin-2 (modified PP-2) Production and analysis were carried out under the same conditions as in Reference Example 1 except that 200 g of styrene was used. Obtained modified resin (modified PP-2)
The content of 2-hydroxyethylmethacrylate of IR is IR
It was 1.10% by the method and 1.06% by the NMR method. Similarly, the styrene content was 2.85%. MF of pellet
R was 0.3 g / 10 minutes.

Reference Example 3: Preparation of 2-hydroxyethyl methacrylate-styrene graft modified propylene resin-3 (modified PP-3) The same conditions as in Reference Example 1 except that 100 g of 2-hydroxyethyl methacrylate and 100 g of styrene were used. Manufactured and analyzed. The content of 2-hydroxyethyl methacrylate was 1.91% by IR method and 1.23% by NMR method. Similarly, the styrene content was 1.38% and the pellet MFR was 5.1 g / 10 min.

Reference Example 4: 2-hydroxyethyl methacrylate-vinyl butyrate graft-modified propylene resin-4
Production of (Modified PP-4) Production and analysis were carried out in the same manner as in Reference Example 3 except that vinyl butyrate was used instead of styrene in Reference Example 3. Two
The content of -hydroxyethyl methacrylate was 0.38% by IR method and 0.26% by NMR method. Similarly, the content of vinyl butyrate is 0.02% and the MFR of pellets is 97.
It was g / 10 minutes.

Reference Example 5: 2-hydroxyethyl methacrylate-vinyl pyridine graft-modified propylene resin-
Production of 5 (modified PP-5) In Reference Example 3, except that vinyl pyridine was used in place of styrene, it was produced and analyzed in the same manner as in Reference Example 3. The content of 2-hydroxyethyl methacrylate is I
It was 1.97% by the R method and 1.23% by the NMR method. Similarly, the content of vinyl pyridine is 1.89%, M of the pellet is
FR was 3.40 g / 10 minutes.

Reference Example 6: 2-hydroxyethyl methacrylate graft modified propylene resin-6 (modified PP-
6) Production (for comparison) Propylene homopolymer powder 2,000 used in Reference Example 1
After mixing 0 g, 100 g of 2-hydroxyethylmethacrylate and 10 g of t-butylperoxybenzoate with a super mixer, they were produced under the same conditions as in Reference Example 1 and analyzed. The content of 2-hydroxyethyl methacrylate was 1.94% by IR method and 0.40% by NMR method. The MFR of the pellet was 40.3 g / 10 minutes.

Reference Example 7: Production of 2-hydroxyethyl methacrylate-styrene graft modified propylene resin-7 (modified PP-7) Production was carried out in the same manner as in Reference Example 3 except that 40 g of styrene was used. And analyzed. The content of 2-hydroxyethyl methacrylate is 2.26% by IR method,
It was 0.88% by the NMR method. Similarly, the styrene content was 0.81% and the pellet MFR was 32.8 g / 10 min.

Examples 1 to 8 and Comparative Examples 1 to 4 Modified PP-1 to 7 and unmodified propylene resin obtained in Reference Examples 1 to 7 (manufactured by Mitsubishi Yuka Co., Ltd., trade name: Mitsubishi Polypro M)
A8, MFR: 1.2g / 10 minutes, "PP MA 8"
Abbreviated) and saturated polyester (polybutylene terephthalate manufactured by Mitsubishi Kasei, trade name: Novador 5010,
Abbreviated as "PBT 5010", and polyethylene terephthalate manufactured by Kanebo, trade name: PBK-1, "PET P
(Abbreviated as "BK-1") in accordance with the composition ratio shown in Table 1 using a Labo Plastomill kneader (manufactured by Toyo Seiki Seisakusho) at 250 ° C and 180 rpm for 5 minutes, and then pulverized. To obtain a granular resin composition.

The characteristics of the obtained resin composition are measured by using an injection molding machine (Custom Scientifi
c), CS183MMX Minimax] manufactured by injection molding at a temperature of 260 ° C. was used to measure and evaluate the test pieces by the following methods. The measurement results are shown in Table 1.

[0055]

[Table 1]

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

(1) Impact resistance 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 an Izod impact tester [made by Custom Scientific Co., Minimax CS was used. -138TI type]
The Izod impact strength without notch at ℃ was measured.

(2) Tensile strength: Tensile test pieces having a parallel part length of 7 mm and a parallel part diameter of 1.5 mm were injection-molded, and a tensile tester [manufactured by Custom Scientific Co., CS-183 was used.
TE type] was used to perform a tensile test at a tensile rate of 1 cm / min, and the tensile yield stress and elongation at break were measured.

(3) Appearance of molded product (layered peeling): Cellophane tape (manufactured by Nitto Denko Corp., trade name: Jim Pack NO. 1) was sufficiently crimped on the surface of the test piece molded in (1) above,
Keep the surface of the test piece at about 30 degrees and pull it off at once in front,
The area of the part which was not peeled off was determined by a gravimetric method, and the area of the part which was not peeled off was shown as a delamination retention rate by the following formula. Delamination retention rate (%) = (area of non-peeled portion) x
100 / (area of test piece surface)

(4) Content of saturated polyester-olefin resin graft copolymer: 20 g of trichlorobenzene was added to 1 g of the resin composition, and the mixture was dissolved and swollen by stirring at 180 ° C. for 30 minutes. Then, 40 ml of xylene was added, and the temperature was lowered to 130 ° C. with stirring to prepare a solution in which unreacted olefin resin was dissolved, unreacted saturated polyester which was insoluble, and saturated polyester-olefin resin graft copolymer. A mixed solution was obtained. This mixed solution was centrifuged at 130 ° C., 10,000 rpm for 30 minutes using a centrifuge to recover a precipitate of unreacted saturated polyester and saturated polyester-olefin resin graft copolymer. It was filtered, washed and dried under reduced pressure. The supernatant liquid was poured into 150 ml of methanol to precipitate unreacted olefin resin, which was washed by filtration, and then dried under reduced pressure to isolate unreacted olefin resin, and the weight of this component (W _A ) Was measured.

Next, 30 ml of hexafluoroisopropanol was added to the unreacted saturated polyester and saturated polyester-olefin resin graft copolymer mixture,
The mixture was stirred at room temperature for 5 hours to dissolve unreacted saturated polyester. The insoluble matter in this solution was filtered under reduced pressure using a 0.45 μm filter, and then dried under reduced pressure to isolate a saturated polyester-olefin resin graft copolymer, and the weight (W _g ) of this component was measured. . Further, the filtrate was poured recovered and in methanol 150 ml, to precipitate a saturated polyester unreacted was filtered and washed, dried under reduced pressure to a saturated polyester unreacted isolated by weight of the component (W _B
And) was measured. As a result of analyzing each component isolated by the above method by the infrared spectroscopic analysis method, it was confirmed that they were respectively an olefin resin alone, a saturated polyester-olefin graft copolymer and a saturated polyester alone. Based on the weight of each of the isolated components, the content of the saturated polyester-olefin resin graft copolymer ( _Cg )
Was calculated from the following formula. C _g (%) = 100 W _g / (W _A + W _g + W _B ).

[0062]

As is apparent from the results of the above-mentioned Examples and Comparative Examples, the specific hydroxyl group residual ratio of the α, β-unsaturated carboxylic acid ester group having a hydroxyl group is in the range of 0.3 to 1.0. The resin composition containing the modified olefin resin (A) and the saturated polyester (B) has a remarkably high content of the saturated polyester-olefin resin graft copolymer produced by the reaction between the two, and therefore is saturated with the olefin resin. It is possible to obtain a thermoplastic resin composition in which the compatibility of polyester is remarkably improved, the appearance of molded products is good, and the mechanical properties such as impact strength and tensile strength are well balanced.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display location C08L 67/02 LPA 8933-4J (72) Inventor Aritomi Mitsuri Toho-cho, Yokkaichi-shi, Mie Prefecture Mitsubishi Yuka Co., Ltd. Yokkaichi Research Institute

Claims (1)

[Claims] 1. A thermoplastic resin composition containing a graft copolymer of an olefin resin and a saturated polyester, which is obtained by reacting the following component (A) and component (B). (A) 0.01 to 20 parts by weight of an α, β-unsaturated carboxylic acid ester-based monomer containing a hydroxyl group is graft-polymerized with 100 parts by weight of an olefin resin, and the residual ratio of the hydroxyl group is 0.3 to. Modified Olefin Resin (B) Saturated Polyester with 1.0