JP3352548B2 - Thermoplastic resin composition - Google Patents

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 excellent heat resistance, impact resistance, moldability, solvent resistance and color. This is suitably used as a molding material in a wide range of fields such as automobile parts and electric or electronic equipment parts, for example, switches, housings and hollow containers.

[0002]

2. Description of the Related Art Crystalline olefin resins represented by polypropylene and polyethylene (hereinafter referred to as "PO").
Is widely used in the production of various molded products because of its excellent moldability, water resistance, solvent resistance, etc., as well as low cost and low specific gravity. Is an obstacle to the use of

On the other hand, saturated polyesters (hereinafter referred to as “PEs”) represented by polyethylene terephthalate and polybutylene terephthalate are recognized as engineering plastics having excellent heat resistance, chemical resistance, electric properties, etc. It has the disadvantages of poor water resistance, easy water absorption during molding processing such as injection molding and extrusion molding, and use under high-temperature and high-humidity conditions, and lowering of mechanical properties such as impact resistance.

Attempts have been made to blend PO and PEs to provide a material that combines the advantages of both and complements the drawbacks. However, simply blending the two results in low impact strength. Only an unsatisfactory composition.

[0005] In order to improve the impact resistance, there is known a method of modifying PO to improve compatibility with PEs or blending a small amount of a thermoplastic elastomer. PO
As a method for denaturing, a case where various functional groups such as an acid group and an epoxy group are introduced has been studied. However, these effects are small but their effects are small. As for the method of compounding the elastomer, specifically, a method of adding a styrene-butadiene block copolymer or a hydrogenated product thereof (hereinafter referred to as “hydrogenated product”) (JP-A-53-12455).
No. 9) shows an excellent effect of improving impact resistance,
Because of low compatibility, delamination is apt to occur, and impact resistance at low temperature (for example, −30 ° C.) is low. Further improvement of compatibility is required to further improve performance.

[0006] To improve the compatibility, Japanese Patent Application Laid-Open No. 5-78526 discloses a method in which a carboxylic acid group is introduced into an elastomer to be compounded, and a glycidyl group is also introduced into PO. According to this, although the impact strength is improved, it is not only insufficient, but also for example, maleic anhydride, which is often used for introducing an acid group, is used. Further, adverse effects such as yellowing of the composition are observed, which are not preferable.

[0007]

SUMMARY OF THE INVENTION The present invention relates to PO and P
It is an object of the present invention to provide a thermoplastic resin composition having improved mechanical properties such as impact strength by improving the compatibility of Es and having less corrosion of equipment and less coloring of the composition.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies, and as a result, have found that a modified aromatic vinyl compound-conjugated compound containing a hydroxyl group-containing unsaturated compound or an aromatic vinyl compound in combination with the unsaturated compound is used. The inventors have found that the above object can be achieved by blending a hydrogenated diene block copolymer with a composition of PO and PEs, and have reached the present invention.

That is, the present invention provides the following component (A):
The thermoplastic resin composition contains (B) and (C), and contains 2 to 40 parts by weight of the component (C) based on 100 parts by weight of the total of the components (A) and (B). (A) crystalline olefin resin (B) saturated polyester (C) aromatic vinyl compound-conjugated diene block copolymer 100 parts by weight of hydrogenated unsaturated compound having 0.05 to 100 parts by weight and aromatic compound Aromatic vinyl compounds 0 to 50
Modified resin obtained by graft modification with parts by weight

Hereinafter, the present invention will be described in detail.

(1) Crystalline olefin-based resin (A) The crystalline olefin-based resin (A) has an α of 2 to 10 carbon atoms.
A polymer or copolymer comprising at least one olefin, having a crystallinity of 1 at room temperature by X-ray diffraction.
It is preferably at least 5%, more preferably from 30 to 70%, having a melting point of 85 to 230 ° C, and JIS K 720
3 has a flexural modulus at 23 ° C. of 5,000 to 40,0.
00 kg / cm ² . Reduced crystallinity reduces the modulus of the final composition. Further, this olefin-based resin requires a sufficient molecular weight as a molding resin having a necessary strength at ordinary temperature. For example, when propylene is the main component, the melt flow rate (hereinafter, referred to as “MFR”) measured based on JIS K 6758 is 0.01 to 500 g / 10 min, preferably 0.1 to 50 g.
The molecular weight is equivalent to g / 10 minutes.

Examples of the above-mentioned α-olefin which is a component of the crystalline olefin resin include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, and 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-vinylbicyclo [2.2.1] heptane, heptene-1 or octene-1 And the like.

Preferred examples of the α-olefin include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, and 3-methylhexene-1. Can be mentioned. In particular, ethylene, propylene, butene-1,
4-Methylpentene-1 is preferred.

As another component, 4-methyl-
Non-conjugated dienes such as 1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and 1,9-decadiene may be used as a part of the polymer component.

Specific examples of the crystalline olefin resin include propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-butene-1 copolymer, propylene-butene-1 copolymer, and propylene-4-polymer. Methylpentene-1 copolymer, poly (4-methylpentene-
1), propylene-3-methylpentene-1 copolymer,
Examples include high-density polyethylene, linear medium-density polyethylene, linear low-density polyethylene, and propylene-1,9-decadiene copolymer.

Among these, the most preferred are isotactic polypropylene and propylene-ethylene block copolymer. The higher the tacticity of isotactic polypropylene, the higher the tacticity.

These crystalline olefin resins can be used after being modified in the presence or absence of a radical initiator.

The modification can be carried out by a general method as exemplified in the section of the modified resin of the component (C). Examples of the modifier used for the modification include α, β-unsaturated carboxylic acids and derivatives thereof, and vinyl monomers. α, β-
Specific examples of unsaturated carboxylic acids and derivatives thereof include acrylic acid, methacrylic acid, maleic acid, itaconic anhydride, maleic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, glycidyl methacrylate,
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate,
Examples include 2-hydroxypropyl methacrylate and the like, and specific examples of the vinyl monomer include styrene, methylstyrene, and vinyl acetate.

(2) Saturated Polyester (B) As the saturated polyester (B), various saturated polyesters can be used. For example, it is a thermoplastic saturated polyester obtained by polycondensation of a dicarboxylic acid or a lower alkyl ester, an acid halide or an acid anhydride derivative thereof with a dihydroxy compound according to an ordinary method.

Specific examples of aromatic or aliphatic dicarboxylic acids suitable for producing the saturated polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, sebacic acid, terephthalic acid, isophthalic acid, p-carboxy acid. Phenoxyacetic acid, 2,6-naphthalene dicarboxylic acid, 2,7
-Naphthalene dicarboxylic acid and the like.

Specific examples of the dihydroxy compound include linear alkylene glycols having 2 to 12 carbon atoms, for example, ethylene glycol, 1,3-propylene glycol,
4-butanediol, 1,6-hexanediol and the like;
Aromatic diols include, for example, pyrocatechol, resonosinol, hydroquinone and the like; alicyclic glycols, for example, cyclohexanedimethanol and the like; or alkyl-substituted derivatives of these compounds.

Preferred saturated polyesters (B) include:
Examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and poly (1,4-cyclohexane dimethylene terephthalate).
Liquid crystalline polyesters, for example, those commercially available under the trade names such as X7G of Eastman Kodak Co., Vectra of Hoechst Celanese Co., and Econol of Sumitomo Chemical Co., Ltd. can also be desirably used. These can be used alone or 2
More than one species can be used in combination.

(3) Modified Resin (C) The modified resin (C) used in the present invention is prepared by adding 100 parts by weight of a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene in the presence of a radical initiator. And an elastomer type modified resin obtained by graft-modifying 0.05 to 100 parts by weight of an unsaturated compound having a hydroxyl group and 0 to 50 parts by weight of an aromatic vinyl compound.

I) Hydrogenated aromatic vinyl compound-conjugated diene block copolymer The hydrogenated aromatic vinyl compound-conjugated diene block copolymer used in the present invention is, specifically, at least one aromatic compound. A polymer block mainly composed of a vinyl compound and at least 80% of an aliphatic double bond based on a conjugated diene of a block copolymer composed of a polymer block mainly composed of at least one conjugated diene, which is obtained by hydrogenating the polymer. It is a block copolymer hydrogenated product.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, α-methoxystyrene,
Methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, chlorostyrene, dichlorostyrene,
Bromostyrene, nitrostyrene, chloromethylstyrene, cyanostyrene, t-butylstyrene, vinylnaphthalene and the like can be mentioned, among which styrene is preferred. These can be used alone or in combination of two or more.

The conjugated dienes include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,
One or two or more of 3-butadiene are selected, and among them, butadiene, isoprene or a combination thereof is preferable.

The method for producing these block copolymers is as follows:
For example, the compound can be synthesized in an inert solvent using a lithium catalyst by a method described in Japanese Patent Publication No. 40-23798.

The polymer block mainly composed of a conjugated diene can arbitrarily select a microstructure in the block. For example, in a polybutadiene block,
5-65% of 1,2-vinyl bond structure, preferably 10%
５０50%. The molecular structure of the block copolymer may be linear, branched, radial, radial teleblock, or any combination thereof.

A preferred block copolymer is styrene-
Butadiene block copolymer, styrene-butadiene-
Styrene block copolymer, butadiene-styrene-butadiene block copolymer, styrene-isoprene block copolymer, and styrene-isoprene-styrene block copolymer.

The method for producing the hydrogenated block copolymer is described, for example, in JP-B-42-8704 and JP-B-43-663.
No. 6 can be obtained by the method described in each gazette. In particular, the hydrogenated block copolymer obtained is most preferably a hydrogenated block copolymer synthesized using a titanium-based hydrogenation catalyst exhibiting excellent performance in heat resistance and heat deterioration. Nos. 59-133203 and 60-79005
The block copolymer having the above structure can be obtained by hydrogenation in an inert solvent in the presence of a titanium-based hydrogenation catalyst by the methods described in the above publications. At this time, the aliphatic double bond based on the conjugated diene of the aromatic vinyl compound-conjugated diene block copolymer is hydrogenated by at least 80%, and the polymer block mainly composed of the conjugated diene compound is morphologically converted into an olefin type compound. It needs to be converted into a union. The amount of non-hydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily determined by infrared spectroscopy, nuclear magnetic resonance, or the like. The content of the aromatic vinyl compound block is 10 to 50% by weight, preferably 20 to 40% by weight.

The hydrogenated block copolymer has a number average molecular weight of 10,000 to 200,000, preferably 20,000 to 150,000, more preferably 30,000 to 100,000.

The block copolymer hydrogenated product is available from Shell Chemical Company under the grade name of Creton G1652 or the like.
It can also be obtained from Kuraray under the grade name such as Septon 2007.

Ii) Unsaturated Compound Having Hydroxyl Group As the unsaturated compound having a hydroxyl group used for modifying the hydrogenated block copolymer, for example, α, β-unsaturated carboxylic acid ester, specifically 2-hydroxyethyl ester (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxymethyl-3-hydroxypropyl (meth) acrylate, 2,2-bishydroxymethyl-3-hydroxy Examples thereof include propyl (meth) acrylate and oligomer (meth) acrylates of ethylene glycol having 4 to 40 carbon atoms. Here, (meth) acrylate means acrylate and methacrylate.

Further, bis (2-hydroxyethyl) malate, bis (2-hydroxypropyl) malate, bis (2,3-dihydroxypropyl) malate, bis (2
-Hydroxymethyl-2-hydroxypropyl) malate, bis (2,2-bishydroxymethyl-3-hydroxypropyl) malate and the like, and isomers thereof, fumarate, ethylene glycol or propylene glycol having 4 to 40 carbon atoms, As described above, the maleic acid or fumaric acid ester of the oligomer is not an ester of a hydroxyalkyl group in both carboxylic acids, and one of them can also be exemplified as an effective compound. Further, allyl alcohol, crotyl alcohol, phenols and the like can be used. Specific examples of these include:
4- (2-hydroxyethyl) styrene, 3- (2-hydroxyethyl) styrene, 4- (hydroxymethyl)
Examples include styrene, 3- (hydroxymethyl) styrene, 4-hydroxystyrene, and 3-hydroxystyrene.

The above unsaturated compounds having a hydroxyl group can be used alone or in combination of two or more. Of these, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferred. The graft amount of the unsaturated compound having a hydroxyl group onto the hydrogenated aromatic vinyl compound-conjugated diene block copolymer is 0.05 to 10% by weight, preferably 0.2 to 5% by weight.
%, More preferably 0.5 to 3% by weight. 0.
If it is less than 05% by weight, the effect of improving the impact strength and appearance of the molded product is small, and if it exceeds 10% by weight, the molecular breakage of the polyester becomes remarkable, and the mechanical properties tend to deteriorate.

The amount of the unsaturated compound having a hydroxyl group used in the graft modification step is based on the amount of the block copolymer hydrogenated product 1
It is used in an amount of 0.05 to 100 parts by weight, preferably 1 to 50 parts by weight based on 00 parts by weight. Further, particularly when the graft modification is performed by melt kneading, preferably 0.03
5 to 30 parts by weight, more preferably 1 to 20 parts by weight. If the amount is less than 0.05 part by weight, the necessary graft amount cannot be obtained, so that the effect of improving the impact strength and appearance of the molded article is small, and if the amount exceeds 100 parts by weight, the unsaturated compound having a hydroxyl group or the homopolymer thereof remains. The amount tends to be large, and the molding processability of the composition becomes difficult, or the mechanical properties of the molded product deteriorate.

Iii) Aromatic vinyl compound In order to increase the amount of the unsaturated compound having a hydroxyl group grafted onto the hydrogenated block copolymer, an aromatic vinyl compound is used in the graft modification step, especially in the graft modification step by melt-kneading. Combinations of compounds are effective. Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, α-methoxystyrene, methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, nitrostyrene, and chlorostyrene. Methyl styrene, cyano styrene,
Examples thereof include t-butylstyrene and vinylnaphthalene, among which styrene, α-methylstyrene and methylstyrene are preferable. These can be used alone or in combination of two or more.

The addition amount of the aromatic vinyl compound to 100 parts by weight of the hydrogenated block copolymer is 0 to 50 parts by weight, preferably 1 to 20 parts by weight. By adding the aromatic vinyl compound, the effect of improving the graft amount of the unsaturated compound having a hydroxyl group onto the hydrogenated block copolymer is increased. On the other hand, if it exceeds 50 parts by weight, the impact resistance of the obtained molded article is impaired.

The weight ratio of the unsaturated compound having a hydroxyl group to the aromatic vinyl compound is 1:99 to 90:
It is possible in the range of 10 but preferably 20:80 to 8
The range is 0:20.

Iv) Radical initiators Radical initiators include t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, t-butylperoxybenzoate, benzoylperoxide Organic and inorganic peroxides such as oxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, and hydrogen peroxide; -Azobisisobutyronitrile, 2,2'-azobis (isobutylamide) dihalide, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide],
Azo compounds such as azodi-t-butane and carbon radical generators such as dicumyl can also be used. These radical initiators can be appropriately selected in relation to a modifying agent and reaction conditions, and two or more kinds can be used in combination.

The amount of the radical initiator used is in the range of 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the hydrogenated block copolymer.
In particular, when the graft modification is performed by melt kneading, the content is preferably in the range of 0.05 to 5 parts by weight.

V) Graft modification method The graft modification of the unsaturated compound having a hydroxyl group or the aromatic vinyl compound with the hydrogenated block copolymer is carried out by swelling, dissolving, melting or solid state of the block copolymer. The heating is carried out in a state in which the additive is impregnated with an unsaturated compound having a hydroxyl group or an aromatic vinyl compound, and a dissolution or melting reaction is particularly preferable.

The solvent used for the reaction in the dissolved state is appropriately selected depending on the type of the reaction.
Often selected from alicyclic and aromatic hydrocarbons and their halides, esters, ketones, ethers having 6 or more carbon atoms, carbon disulfide and the like. These are 2
It is also possible to use as a mixed solvent of more than one kind. Since the reaction in melting does not require the use of a solvent or uses only a small amount, it has advantages such as saving production costs and avoiding emission of solvent vapor to the environment.

Hereinafter, a radical graft modification method by melt-kneading will be specifically described. For the reaction in the molten state, a usual melt-kneading apparatus, for example, an extruder or a stirrer can be used. Specific examples include a lab plast mill, a single-screw or twin-screw kneader, a horizontal twin-screw multi-disc device, a horizontal twin-screw surface updater, and a double helical ribbon stirrer. The kneading temperature at this time may be any temperature as long as the aromatic vinyl compound-conjugated diene compound block copolymer hydrogenated product is in a molten state. 250 ° C. is desirable. The kneading time is 0.0
It is between 1 and 10 minutes, preferably between 0.1 and 5 minutes.

In order to remove unreacted unsaturated compounds having a hydroxyl group, etc., and to prevent the resulting modified resin from deteriorating, it is desirable to carry out melt kneading and granulation under reduced pressure. An unsaturated compound having a hydroxyl group or an aromatic vinyl compound which is a graft modifier is dry-blended with a block copolymer hydrogenated product and kneaded together, and a modifier is added to the molten block copolymer hydrogenated product. Examples thereof include a method of adding a radical initiator. At this time, a small amount of an organic solvent may be added to improve the reaction efficiency.

(4) Additional Component The thermoplastic resin composition of the present invention comprises the above component (A),
Other components can be contained in addition to (B) and (C). For example, a part of the modified resin of the component (C) may be replaced with an elastomer such as an unmodified styrene-butadiene block copolymer, styrene-isoprene block copolymer or ethylene-propylene copolymer.

Further, a resin composition such as polycarbonate, polyphenylene ether, polyamide, ABS, AES, acrylic rubber, acryl-styrene core shell rubber or a mixture thereof may be contained.

Further, the addition of organic / inorganic fillers and reinforcing agents, especially glass fiber, carbon fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc., can reduce rigidity, heat resistance, etc. It is effective for improvement. For practical use, various colorants and their dispersants can also be used.

[0049] If necessary, a non-resinous additive may be contained in order to improve the chemical and physical properties. For example, hindered phenol-based antioxidants, phosphite-based antioxidants, amine-based antioxidants, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, aliphatic carboxylic acid ester-based lubricants, paraffin-based lubricants, Flame retardants, release agents, antistatic agents, coloring agents and the like.

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.) And so on. Examples of the phosphorus-based antioxidant include Sumilizer TNP (trade name of Sumitomo Chemical Co., Ltd.) and Mark PEP36.
(Trade name of Adeka Ardes), Irgafoss 168 (trade name of Ciba Geigy) and the like.

(5) Composition Ratio of Constituent Components In the thermoplastic resin composition of the present invention, the total composition of the crystalline olefin resin of the component (A) and the saturated polyester of the component (B) is 100% by weight. As part, component (A) is 90 to 10 parts by weight, preferably 80 to 20 parts by weight, and component (B) is 10 to 90 parts by weight, preferably 20 to 80 parts by weight. If component (A) exceeds 90 parts by weight, the heat resistance and impact resistance are greatly reduced, and component (B)
Exceeds 90 parts by weight, the effect of improving the water absorption resistance is small.

The amount of the modified resin of the component (C) is from 2 to 4 based on 100 parts by weight of the total of the components (A) and (B).
0 parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 20 parts by weight. If the amount of the component (C) is less than 2 parts by weight, the effect of improving the impact resistance is small, and if it exceeds 40 parts by weight, the elastic modulus is greatly reduced.

(6) Production method and molding method of the 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. The method is preferred. As a method of melt kneading, a method generally used for thermoplastic resins can be applied. For example, after the powdery or granular components are uniformly mixed with the additional components, if necessary, using a Henschel mixer, ribbon blender, V-type blender, etc., a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, etc. Can be kneaded.

The melting and kneading temperature of each component is 180
To 350 ° C, preferably 200 to 300 ° C. The kneading order and method of each component are not particularly limited, for example, a method of kneading each component collectively,
After kneading a part or all of the modified resin and PEs, any method such as a method of kneading the remaining components or a method of kneading under reduced pressure may be employed. Further, at the time of melt-kneading, an organic solvent such as chlorobenzene, trichlorobenzene and xylene, or a catalyst such as tetrakis (2-ethylhexoxy) titanium and dibutyltin oxide can also be added.

The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and general molding methods for the thermoplastic resin, namely, injection molding, extrusion molding, hollow molding, thermoforming, press molding, and the like. Various molding methods such as molding can be applied.

[0056]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

In the following, parts and percentages are by weight.

Reference Example 1 Preparation of Modified Resin- (1) Styrene-butadiene block copolymer hydrogenated product (manufactured by Shell Chemical Company, trade name: Creton G1652, hereinafter referred to as "G1652") 3 kg, 2-hydroxyethyl 300 g of methacrylate (hereinafter referred to as "HEMA"), 600 g of styrene (hereinafter referred to as "SM") and 1,3-bis (t-butylperoxyisopropyl) benzene (manufactured by Kayaku Akzo Co., Ltd., trade name: Percadox 14, hereinafter referred to as " P
14 "), and then using a twin-screw extruder (trade name: TEX-30, manufactured by Nippon Steel Works, Ltd.) at a cylinder temperature of 160 ° C and a screw speed of 20.
The mixture was kneaded under reduced pressure at 0 rpm, a discharge rate of 2 kg / hr, and a vent pressure of 50 mmHg to obtain a modified resin (1).

0.3 g of the resulting modified resin (1) was dissolved in 50 ml of chloroform at normal temperature, and 300 ml of methanol was dissolved.
And precipitated. The precipitate was separated by filtration and dried under reduced pressure (normal temperature) to obtain a purified resin. The HEMA content of this purified resin was determined by the following method.

Method for quantifying HEMA Infrared spectroscopy (hereinafter referred to as “IR method”): A sample resin was press-molded to form a film, and the IR spectrum was measured. The quantification was made from the characteristic absorption of carbonyl at 1,724 cm ^-1 and a calibration curve was used.

Proton nuclear magnetic resonance spectroscopy (hereinafter “HN”)
MR method): 30 to 50 mg of a sample resin was dissolved in about 1 ml of o-dichlorobenzene at 130 ° C., a small amount of deuterated benzene was added to prepare a sample, and the H-NMR spectrum was measured. For quantification, absorption of methylene bound to a hydroxyl group (chemical shift: 3.9 ppm) and methylene bound to an ester group (chemical shift: 4.2 ppm) were used.

The value determined by the IR method indicates the amount of HEMA added to the graft, and the value determined by the H-NMR method indicates the amount of HEMA holding hydroxyl groups. Therefore, the residual ratio of hydroxyl groups can be defined by the following equation.

[0063]

(Equation 1)

Table 1 shows the results.

Reference Example 2: Production of Modified Resin- (2) In Reference Example 1, 600 g of SM was added to 300 g and P14
A modified resin (2) was obtained in the same manner as in Reference Example 1, except that 15 g was changed to 30 g. Table 1 shows the results.

Reference Example 3 Production of Modified Resin- (3) Styrene-isoprene diblock copolymer hydrogenated product (manufactured by Shell Chemical Company, trade name: Clayton G1701, hereinafter referred to as "G
1701 ") 3kg, HEMA 600g, SM30
After dry-blending 0 g and P14 15 g, the same procedure as in Reference Example 1 was carried out to obtain a modified resin- (3). Table 1 shows the results
Shown in

Reference Example 4: Production of modified resin (4) 20 g of G1652 in 400 ml of chlorobenzene, HEM
A8.3 g was dissolved. While stirring at 110 ° C. under a nitrogen atmosphere, benzoyl peroxide (water content: 25% by weight) dissolved in 20 ml of chlorobenzene was added to the solution.
g was added dropwise over 2 hours, and stirring was continued for another 3 hours. After allowing to cool to room temperature, the mixture was poured into a large amount of methanol to precipitate a polymer component, which was separated by filtration, washed with methanol, and dried under reduced pressure to obtain a modified resin- (4). Table 1 shows the results.

Reference Example 5 (Comparative): Modified resin- (5) Hydrogenated styrene-butadi entry block copolymer modified with maleic anhydride (trade name: Tuftec M1913 (Asahi Kasei Corporation) (hereinafter referred to as "M1913") ) Was designated as Modified Resin- (5), which is shown in Table 1.

[0069]

[Table 1]

Reference Example 6 Production of Modified PP-1 2 kg of polypropylene (pulverized product of MA8, manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as "MA8"), 100 g of glycidyl methacrylate (hereinafter, referred to as "GMA"), SM100
g and t-butyl peroxybenzoate (manufactured by NOF CORPORATION, trade name: Perbutyl Z, hereinafter referred to as “PBZ”) 2
After dry blending 0 g, a cylinder temperature of 180 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 5 were measured using a twin-screw extruder (trade name: TEX-30, manufactured by Nippon Steel Works, Ltd.).
kg / hr, kneading under reduced pressure under the condition of vent pressure 50mmHg,
Modified PP-1 was obtained.

0.3 g of the resulting modified PP-1 was placed in 50 ml of xylene, dissolved at 140 ° C., and poured into 300 ml of methanol for precipitation. The precipitate was separated by filtration and dried under reduced pressure (normal temperature) to obtain a purified resin. This purified denatured PP-
The GMA content of No. 1 was determined by IR in the same manner as in the modified resin- (1).
And H-NMR methods. GMA for H-NMR
The absorption peaks were measured for methine, methylene bound to the oxygen of the epoxy group (chemical shift 3.1 ppm and 2.5 and 2.6
ppm) and methylene bound to the ester (chemical shift 4.
3 and 4.1 ppm). Table 2 shows the results.

[0072]

[Table 2]

Reference Example 7: Production of modified PP-2 A modified PP-2 was obtained in the same manner as in Reference Example 6, except that GMA was changed to HEMA. Table 2 shows the results.

Examples 1 to 9 and Comparative Examples 1 to 4 Modified resins (1) to (5), modified PP-1 and 2, G1
652, G1701, unmodified PP (manufactured by Mitsubishi Chemical Corporation, trade names: MA8 and MA3) and polybutylene terephthalate (manufactured by Mitsubishi Chemical Corporation, trade name: Novador 5010, hereinafter referred to as “PBT”), respectively, in the composition shown in Table 3. Depending on the ratio, each component was kneaded with a Labo Plastomill kneader (manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 250 ° C. and 180 rpm for 5 minutes, and then pulverized to obtain a powdery composition. During melt kneading, 0.2 parts by weight of 4-methyl-2,6-di-t-butylphenol and 0.2 parts by weight of Irganox 1010 were added to 100 parts by weight of these resin components in total.
(Manufactured by Ciba Geigy) was added.

The obtained resin composition was injected into an injection molding machine [Custom Scientific,
CS183MMX Minimax] at 250 ° C.
A test piece was injection molded at a mold cooling temperature of 50 ° C., and its characteristics were measured and evaluated by the following methods. Table 3 shows the results. In addition, at the time of kneading and molding, the resin composition was dried at 120 ° C. for 5 hours in advance.

(1) Izod impact strength: length 31.5
Injection molding of a test piece having a width of 6.2 mm, a width of 6.2 mm, and a thickness of 3 mm, and using an Izod impact tester (Minimax CS183TI type manufactured by Custom Scientific), the tip R
A notched Izod impact strength of 0.25 mm and 1.2 mm depth was measured at 23 ° C.

(2) Flexural modulus: length 45 mm, width 5 mm,
A test piece having a thickness of 2 mm is injection molded, and a solid viscoelasticity measuring device (Rheometrics First East Co., Ltd., RSAI
Using I), storage elastic modulus (E ') under the condition of frequency 1 Hz
Was measured to determine the flexural modulus at 23 ° C.

(3) MFR: Using a melt flow rate measuring device (manufactured by Toyo Seiki Seisaku-sho, Ltd.) at a load of 250 ° C.
MFR was measured under the condition of 16 kg.

(4) Appearance of molded article: The appearance of the molded test piece was evaluated. Those which have no practical problems were indicated by 〇, those in which delamination and pearl luster were observed, etc. requiring improvement, and those which were extremely poor were indicated by x.

(5) Yellowness: From a granular resin composition produced by melt-kneading and pulverization, a compression molding machine (manufactured by Toyo Seiki Seisaku-sho, Ltd.) was used to preheat at 250 ° C. for 3 minutes and at 17.6 MPa.
A compression under the pressure of a for 3 minutes and then cooling at 19.6 MPa for 4 minutes to produce a compression molded sheet having a length of 5 cm, a width of 5 cm and a thickness of 2 mm. The yellowness of this sheet was measured according to JIS K 7103.
And according to the following method according to ASTM D1925.

That is, using a spectrophotometer (trade name: Karacom B, manufactured by Dainichi Seika Kogyo Co., Ltd.) according to the method standardized by the International Commission on Illumination (CIE) (CIE1931 standard color system), The three stimulus values (X, Y, Z) of the hue of the molded sheet were measured, and the yellowness (YI) was calculated by the following equation.

[0082]

(Equation 2)

The larger the YI value, the deeper the yellowness and the more likely it is to cause problems due to coloring, which is not preferable in practical use.

[0084]

[Table 3]

[0085]

Industrial Applicability The thermoplastic resin composition of the present invention has excellent moldability and provides a molded article having excellent impact strength, coloring resistance and appearance without deteriorating other mechanical properties.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (1)

(57) [Claims] 1. It contains the following components (A), (B) and (C), and contains 2 to 40 parts by weight of the component (C) based on 100 parts by weight of the total of the components (A) and (B). Thermoplastic resin composition. (A) crystalline olefin resin (B) saturated polyester (C) aromatic vinyl compound-conjugated diene block copolymer 100 parts by weight of hydrogenated unsaturated compound having 0.05 to 100 parts by weight per 100 parts by weight Aromatic vinyl compound 0
Modified resin obtained by graft modification with 50 parts by weight