JP3496991B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION This invention relates to polyester and polio.
Further details on thermoplastic resin compositions containing refining
In other words, polyester and poly
The present invention relates to a thermoplastic resin composition containing an olefin. The present invention
Especially for automotive interior and exterior products, electrical components, home appliances,
Useful in applications such as art supplies, furniture, and office supplies
The present invention relates to the resin composition. [0002] BACKGROUND OF THE INVENTION Polyester is heat resistant
It is a resin with excellent properties, mechanical strength and insulating properties. one
On the other hand, polyolefins are lightweight and have excellent impact resistance,
In addition, good environmental properties such as moldability, water resistance, chemical resistance, etc.
There is a feature that there is. So polyester and polio
A resin composition that has the advantages of both by blending with refin
Attempts have been made to manufacture. However, Polyester
And polyolefins have poor compatibility with each other.
The thermoplastic resin composition containing
There is a problem that mechanical strength is reduced. [0003] The compatibility between polyester and polyolefin
As an attempt to improve, unsaturated polyesters
Acid or derivatives thereof, especially maleic anhydride (MAH)
Polyolefins with unsaturated dicarboxylic anhydrides
There is known a method of blending and melting and kneading. This one
The method improves the compatibility and dispersibility of the two, and
The composition is excellent and the deterioration by water absorption is prevented.
You. However, in this method, the dicarboxylic anhydride is
When added to olefins, it can be used to crosslink polyolefins.
Deterioration and deterioration caused by polyolefin
Because a specific part of the resin cannot be denatured,
Reaction, intramolecular association, etc.
Is not enough to improve the physical properties. Also, polyolefin
Unreacted acid remaining after modification reacts with polyester
There was also a problem of coloring and impairing the appearance. Accordingly, the present invention relates to polyester and polyol
Good impact resistance and tensile strength with good compatibility with fins
Temperature, mechanical properties such as peeling resistance, thermal properties such as heat resistance,
Surface characteristics such as appearance and environmental characteristics such as water resistance and chemical resistance
The purpose is to provide a thermoplastic resin composition excellent in
You. [0005] DISCLOSURE OF THE INVENTION The present inventors have made a
Intensive study on compatibilization of ter and polyolefin
As a result, a specific epoxy group-containing structure was used as a compatibilizer.
Compatibility of both with polypropylene at the end
Is excellent, and the above-mentioned characteristics are excellent without causing coloring.
It is found that a resin composition having
Reached. That is, the present invention relates to (A) polyester
0.1 to 99% by weight, (B) polyolefin 0.1 to 9
9% by weight, and (C) at the end, the following formula (I): [0007] Embedded image (In the above formula, R^aRepresents a hydrogen atom or 1 to 8 carbon atoms
X comprises an epoxy group; and
A hydrocarbon group having 2 to 20 carbon atoms; n is an average
Value, which is in the range of 0.1 to 500)
Having terminal-modified polypropylene 0.01 to 99% by weight
It is a thermoplastic resin composition containing. [0008] Preferred embodiments include the following.
You can: (C) The terminal-modified polypropylene has the following formula (I
I): [0009] Embedded image (In the above formula, R^aAnd n are as defined above)
The above-mentioned thermoplastic resin composition having a structure as described above. (C) Terminal structural formula in terminal-modified polypropylene
In (I) or (II), n is in the range of 0.5 to 100.
Any of the above thermoplastic resin compositions. (C) The terminal-modified polypropylene is a vanadium compound
In the presence of a catalyst consisting of
The propylene is obtained by living polymerization
The thermoplastic resin composition of any one of the above. The amount of each component is (A) 1 to 95% by weight, (B) 1 to 9
5% by weight and (C) 0.1-95% by weight.
Any of the thermoplastic resin compositions. A method for producing a thermoplastic resin composition according to any one of the above.
A method of melt-kneading the components at 200 to 300 ° C. Next, the present invention will be described. First, (A)
The ester is not particularly limited.
Known polyesters obtained by polycondensation with
You. Dicarboxylic acids include phthalic acid, terephthalic acid,
And aromatic dicarboxylic acids such as isophthalic acid. This
They have aromatic rings substituted with alkyl groups, halogen atoms, etc.
May be. As the diol, ethylene glycol
, Propylene glycol, tetramethylene glycol
, Neopentyl glycol, hexamethylene glycol
Saturated dihydric alcohols such as alkylene glycols
And the like. These dicarboxylic acids or diols
May be used alone or in combination of two or more.
You can also. Preferred polyesters include, for example,
Polyethylene terephthalate (PET), polypropylene
Renterephthalate, polytetramethylene terephthale
(Polybutylene terephthalate, PBT), polyhexene
Samethylene terephthalate, polycyclohexane-1,4-
Dimethylol terephthalate, neopentyl terephthale
And the like. Among these, polyethylene
Terephthalate (PET) and polybutylene terephthalate
Rate (PBT) is preferred. The glycol component
Is the main glycol, up to about 50% by weight,
It may contain a glycol. For example, polyethylene
1,4-butylene for terephthalate (PET)
Recall, propylene glycol, hexamethylene glycol
Coal, polybutylene terephthalate (PB
In the case of T), ethylene glycol, propylene glycol
About 50% by weight of coal, hexamethylene glycol, etc.
Can be contained up to a degree. (B) Polyolefin used in the present invention
Is not particularly limited, and known polyolefins can be used.
You. For example, the sole weight of α-olefin (including ethylene)
Copolymer; copolymer of two or more α-olefins (lander
Including all copolymers such as
Or olefin-based compounds.
Lastmer is mentioned. Examples of α-olefins
For example, ethylene, propylene, 1-butene, 1-hexene, 3-
Methyl-1-butene, 4-methyl-1-pentene, 1-hepte
, 1-octene, 1-decene and the like. As the ethylene homopolymer, low density poly
Ethylene (LDPE), high density polyethylene (HDP
E) and linear low density polyethylene (LLDPE) etc.
Can be used. As polypropylene, professional
Not only pyrene homopolymer but also propylene and ethylene
It includes a block copolymer or a random copolymer. Shared weight
In the case of coalescence, ethylene content of 20% by weight or less
Propylene copolymer.
Len is usually a melt flower of about 0.1 to 200 g / 10 min.
(In accordance with MFR, JIS K7210, load 2.16kg, 230 ℃
Measurement). The polyethylene and polypropylene described above
Rene is an olefin elastomer up to about 40% by weight.
May be included. Here, the olefin-based elastomer is
Ethylene and one or more α-
Olefins (eg, propylene, 1-butene, 1-hexene
, 4-methyl-1-pentene, etc.)
I do. Typically, ethylene-propylene copolymer rubber
(EPR), ethylene-butene copolymer rubber (EB
R), ethylene-propylene-diene copolymer rubber (E
PDM) and the like. Ethylene-propylene-die
Dienes in copolymer rubber (EPDM) include, for example,
Dicyclopentadiene, 1,4-hexadiene, cyclo
Non-conjugated dienes such as kutadiene and methylene norbornene
Or use conjugated dienes such as butadiene and isoprene
be able to. These EPR, EBR and EP
DM is another repeating unit such as 4-methyl-1-pentene
Repeating units derived from other α-olefins such as
May be contained up to a ratio of 10 mol% or less. Preferred polyolefins are ethylene or
Is a homopolymer of propylene,
Copolymers, ethylene or propylene and other α-olefins
And olefin-based elastomers. Next, (C) the terminal-modified polypropylene is
Polypropylene having a terminal structure represented by the above formula (I)
It is. Here, as polypropylene, propylene
Propylene and other α-olefins
(Eg, ethylene, 1-butene, 1-hexene, 4-methyl
-1-pentene, etc.) and one or more blocks
Polymer or random copolymer or copolymer rubber
Include. A port having a terminal structure represented by the formula (I)
Lipropylene is end-modified with various degrees of end group polymerization
A polypropylene composition, where n is the average value
You. n is from 0.1 to 500, preferably from 0.5 to 100. Previous
In the formula (I), R^aHas 1 to 8 carbon atoms
In the case of a hydrocarbon group, for example, a methyl group, an ethyl group,
Ropyl, butyl, pentyl, hexyl, hepti
A straight-chain or branched alkyl group such as an alkyl group or an octyl group;
Alkenyl groups such as vinyl group, propenyl group and allyl group;
Cycloalkyl such as cyclopentyl group and cyclohexyl group
Groups; aryl groups such as a phenyl group and a toluyl group
You. R^aIs preferably a hydrogen atom or a methyl group.
X is, for example, an epoxy group, glycidyl (or
2,3-epoxypropyl) group, 3,4-epoxybutyl group, 1,
2-epoxybutyl group, 4,5-epoxypentyl group, 5,6-d
Oxyhexyl group, 2-methyl-3,4-epoxybutyl group,
3,4-epoxycyclohexyl group and the like. X is good
Preferably, it is a glycidyl group. Preferred terminal structures include, for example, R^aBut
A hydrogen atom or a methyl group and X is a glycidyl group
And represented by the following formula (II). [0017] Embedded image (In the above formula, R^aAnd n are as defined above. The polypropylene having the above terminal structure (I) is as follows:
It can be manufactured as follows. That is, the following equation (III): [0018] Embedded image(In the above formula, R¹, R^TwoAnd R^ThreeAre independent
A hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms
Represents Where R¹~ R^ThreeAt least one is a hydrogen source
Must be a child, but R¹~ R^ThreeAre all hydrogen atoms
There must not be. ) And vanadium compounds
Propium in the presence of a catalyst consisting of organic aluminum compounds
Living polypropylene obtained by living polymerization of ren
And the following equation (IV): [0019] Embedded image (In the above formula, R^aAnd X are as defined above)
By reacting with the compound to be prepared. Here, vanadium represented by the above formula (III)
Specific examples of the compound will be described. (1) R^TwoIs a hydrogen atom, and R¹And R^ThreeAre carbonized together
When it is a hydrogen group. R¹/ R^ThreeAs a combination of
If CH_Three/ CH_Three, CH_Three/ C_TwoH_Five, C_TwoH_Five/ C_Two
H_Five, CH_Three/ C₆H_Five, C_TwoH_Five/ C₆H_Five, C₆H
_Five/ C₆H_Five, CH_Three/ C₆H_FiveCH_Two, C₆H_FiveCH
_Two/ C₆H_FiveCH_Two, C_TwoH_Five/ C₆H_FiveCH_Two, C₆
H_Five/ C₆H_FiveCH_TwoIs mentioned. (2) R^TwoIs a hydrocarbon group, and R¹And R^ThreeAny of
When one is a hydrogen atom and the other is a hydrocarbon group. R^Two
/ R¹(Or R^Three) Is, for example, CH
_Three/ CH_Three, C_TwoH_Five/ CH_Three, CH_Three/ C_TwoH_Five, C
_TwoH_Five/ C_TwoH_Five, C₆H_Five/ CH_Three, CH_Three/ C₆H
_Five, C₆H_Five/ C_TwoH_Five, C_TwoH_Five/ C₆H_Five, C₆H
_Five/ C₆H_Five, C₆H_FiveCH_Two/ CH_Three, CH_Three/ C₆
H_FiveCH_Two, C₆H_FiveCH_Two/ C₆H_FiveCH_Two, C₆H
_FiveCH_Two/ C_TwoH_Five, C_TwoH_Five/ C₆H_FiveCH_Two, C₆
H_FiveCH_Two/ C₆H_Five, C₆H_Five/ C₆H_FiveCH_TwoIs raised
I can do it. (3) R^TwoIs a hydrogen atom, and R¹And R^ThreeAny of
When one is a hydrogen atom and the other is a hydrocarbon group. R¹Ma
Or R^ThreeAs, for example, CH_Three, C_TwoH_Five, C
₆H_Five, C₆H_FiveCH_TwoAnd the like. Among them, the following formula (V) is particularly preferred.
Compound, ie, V (acetylacetonate)_Three;under
The compound represented by the formula (VI), that is, V (2-methyl-1,3
-Butandionato)_ThreeA compound represented by the following formula (VII):
Object, ie V (1,3-butanedionato)_ThreeIs preferred. [0022] Embedded image [0023] Embedded image [0024] Embedded image Next, the organic aluminum used as the above-mentioned catalyst
The compound has the general formula: [0025] [Image Omitted] R_mAlY_3-m (In the above formula, R is an alkyl group or an aryl group,
Y is a halogen atom or a hydrogen atom, and m is 1 ≦ m <
Is an arbitrary number that satisfies 3)
Wear. Preferred organic aluminum compounds have 1 to 1 carbon atoms.
Organic aluminum having 18 carbon atoms, preferably 2 to 6 carbon atoms
Compounds or mixtures or complex compounds thereof, for example
For example, dialkyl aluminum monohalide, monoalkyl
Aluminum dihalide, alkyl aluminum ses
Kihalide and the like. Dialkyl aluminum
Monohalides include, for example, dimethyl aluminum
Chloride, diethylaluminum chloride, diethylal
Minium bromide, diethyl aluminum iodide
And diisobutylaluminum chloride
Examples of monoalkylaluminum dihalides
For example, methyl aluminum dichloride, ethyl aluminum
Mudichloride, methylaluminum dibromide, ethyl
Aluminum dibromide, ethyl aluminum diio
Dyed, isobutylaluminum dichloride, etc.
Alkyl aluminum sesquihalides
For example, ethyl aluminum sesquichloride and the like.
It is. Vanadium compound and organic alcohol in catalyst
The ratio of the minium compound was 1 mole of the vanadium compound.
1 to 1,000 moles of the organoaluminum compound is preferred.
No. In the living polymerization of propylene, propylene is used.
In addition to homopolymerization of propylene, ethylene, 1-butene,
Α-olefins such as 1-hexene and 4-methyl-1-pentene
It is also possible to carry out polymerization in the presence of The polymerization reaction is inert to the polymerization reaction,
It is preferable to carry out the reaction in a solvent which is liquid at the time of polymerization. So
Examples of the solvent such as propane, butane, and pen
Saturated aliphatic hydrocarbons such as tan, hexane and heptane;
Saturated alicyclic hydrocarbons such as clopropane and cyclohexane
Element: aromatic hydrocarbons such as benzene, toluene and xylene
And the like. The amount of polymerization catalyst used in the polymerization of propylene
Is 1 mole equivalent of propylene (and other α-olefins)
Or 1 × 10 of vanadium compound^-Four~ 0.01 mol, preferred
Ha 5 × 10^-Four~ 5 × 10^-3Mole, organoaluminum compound
Things are 1 × 10^-3~ 0.1 mol, preferably 5 x 10^-3~ 0.01 m
It is. In addition, per mole of the vanadium compound,
The aluminum compound is preferably used in an amount of 5 to 25 mol.
No. Living polymerization is usually carried out at a temperature between -100 ° C and 100 ° C.
C. for 0.5 to 50 hours. The molecular weight of the obtained living polypropylene
And yield can be varied by changing the reaction temperature and reaction time.
Can be adjusted. Keep the polymerization temperature low, especially below -30 ° C.
Polymer with a molecular weight distribution close to monodispersion
It can be. Mw (weight average)
(Molecular weight) / Mn (number average molecular weight) of 1.05 to 1.40
Polymer. At the time of the polymerization reaction, a reaction accelerator may be used.
it can. Reaction accelerators include anisole, water, oxygen,
Alcohol (methanol, ethanol, isopropanol
And esters (ethyl benzoate, ethyl acetate, etc.)
No. The amount of the accelerator used is determined by the amount of the vanadium compound
It is usually 0.1 to 2 moles per mole. As described above, the number of about 800 to 400,000
Living polypropylene with average molecular weight and close to monodisperse
Can be manufactured. Next, in order to introduce a terminal structure,
And a compound represented by the formula (IV)
Is reacted. As the compound (IV), glycidyl aqua
Preferred are lylate and glycidyl methacrylate. Livi
The reaction of polypropylene with compound (IV)
Compound (IV) is added to the reaction system in which
The method of supplying and reacting is preferable. The reaction is usually -1
It is performed at a temperature of 00 ° C to 150 ° C for 5 minutes to 50 hours. reaction
By increasing the temperature or increasing the reaction time,
Increase the rate of modification of polypropylene ends with one unit of compound
Can be great. 1 mole of living polypropylene
On the other hand, the compound (IV) is usually used in an amount of 1 to 1,000 mol. Living polypropylene and compound (IV)
Is then contacted with a proton donor. Professional
Ton donors include, for example, methanol, ethanol, etc.
Alcohols; phenols; mineral acids such as hydrochloric acid and sulfuric acid
No. Alcohols, phenols and mineral acids
You may use simultaneously. Proton donors are usually in large excess
Used. Contact with the proton donor is usually -100.
C. to 100.degree. C. for 1 minute to 10 hours. The end-modified polyp obtained as described above
Lopylene has a number average molecular weight (Mn) of about 800-500,000
And the living polypropylene itself is
Following a very narrow molecular weight distribution (Mw / Mn = 1.05-1.
40). Moreover, at the end, 0.1 to 50 on average
0, preferably 0.5 to 100 terminal structures
You. In addition, the end-modified polyprotein thus produced
Ripropylene has a syndiotactic dyad fraction
One characteristic is that it is 0.6 or more. The thermoplastic resin composition of the present invention has the above-described composition.
Each component is contained in the following ratio. That is, (A) 0.1
-99% by weight, (B) 0.1-99% by weight and (C)
0.01 to 99% by weight, preferably (A) 1 to 9
5% by weight, (B) 1-95% by weight and (C) 0.1-%
95% by weight. The thermoplastic resin composition of the present invention contains
Components, as well as customary additives such as fillers and reinforcements
(Glass fiber, carbon fiber, carbon black, silica,
Titanium oxide, etc.), heat stabilizer, light stabilizer, oxidation deterioration prevention
Agent, flame retardant, plasticizer, antistatic agent, nucleating agent, foaming agent, weather resistance
Agents, lubricants, release agents, flow improvers, etc.
Good. Further, the thermoplastic resin composition of the present invention comprises:
Commercially available engineering plastics shock resistant
Up to about 50% by weight of an improver may be contained. That
Such impact modifiers include, for example, Stafloid (Takefuji).
Tadaku Co., Ltd.). A method for producing the thermoplastic resin composition of the present invention
The method is not particularly limited, but a melt kneading method is preferred. Melting
As a kneading method, for example, a single-screw or twin-screw extruder,
Burr mixer, kneading roll, brabender, kneader
-Any known method such as a batch type kneader can be used.
You. The kneading temperature is preferably 200 to 300 ° C,
The kneading time is usually 0.5 to 15 minutes. Melt kneading
At this time, the kneading order of each component is not particularly limited, and each component is simultaneously mixed.
May be added in any order.
Moreover, it can also be manufactured by a solution method. [0042] In the resin composition of the present invention, each component is good.
It is said that it is compatibilized, has excellent impact resistance, and has a high MFR
Demonstrates excellent characteristics. The reason is always obvious
Not terminally modified with epoxy group-containing terminal structure
Polyester and polyolefin via polypropylene
Is presumed to be compatible. That is,
When melt kneading, the modified part of the terminally modified polyolefin
Bonded to the end of the ester, while the end modified polypropylene
Polypropylene part is compatible with polyolefin
Therefore, it is considered that each component becomes compatible. Special
The modified polyp used as a compatibilizer in the conventional method
Lopylene has a modifier (MA) on the polypropylene backbone.
H, epoxy functionality, etc.) in a branched form
In contrast, in the present invention, the epoxy group-containing structure has a molecular structure.
Introduced only at the chain ends, forming a true block
Therefore, it is considered that excellent effects can be obtained. Further, in the present invention, an acid is used as a compatibilizing component.
Use of the resin composition by coloring as in the conventional method.
Does not cause appearance deterioration. In addition, polypropylene
The molecular weight can be controlled by using
It is possible to freely change the amount of introduced terminal functional groups.
Can be. In addition, the components are kneaded together to form a resin composition.
Can be industrially easily implemented and can be mixed.
The cost associated with kneading is low and the utility is extremely high. [0044] The present invention will be described in more detail with reference to the following examples.
I will tell. In Examples and Comparative Examples, the following
Material used. (A) Polyester PBT: Polybutylene terephthalate (Teijin Corporation)
Manufactured by TRB-K), intrinsic viscosity [η] 1.0, PET: polyethylene terephthalate (Teijin Corporation)
Manufactured by TR 4500), intrinsic viscosity [η] 0.7 (B) Polyolefin PP: polypropylene (J209 manufactured by Tonen Chemical Co., Ltd.)
 ), Melt flow rate (MFR) (230 ° C, 2.16kg)
9g / 10min. EPR: Ethylene-propylene copolymer rubber (Nihon Gosei
Rubber Company, EP912P), MFR (230 ° C, 2.
Measured at 16kg load) 7.5g / 10min (C) Terminal-modified polypropylene synPP-GMA: glycidyl methacrylate (G
MA) end-modified syndiotactic polypropylene
Wren, manufactured as follows; (1) Living polymerization of propylene 1 liter stainless steel well purged with nitrogen gas
Place 600 ml of n-heptane in a toclave and bring to -60 ° C.
Cool. At this temperature, add 200 ml of liquefied propylene
Was. Then, 150 mmol of Al (C_TwoH_Five)_TwoCl
n-Heptane solution and 30 mmol of V (2-methyl-1,3-
Butandionate)_ThreeOf toluene, and with stirring
The polymerization was started. Propylene polymerization at -60 ° C for 2 hours
Performed for 30 minutes. (2) Reaction with glycidyl methacrylate Glycidyl methacrylate (GMA) 10
0 ml was added at -60 ° C, and the temperature in the system was increased over 1 hour.
After the temperature was raised to 25 ° C., the mixture was stirred at the same temperature and mixed with GMA.
The reaction was performed. After 5 hours, 3 liters of the reaction solution was added.
The polymer was precipitated by pouring into ethanol. Profit
Redissolved polymer in n-heptane and centrifuged
To obtain a supernatant. 3 liters of this supernatant
Pour into methanol to precipitate the polymer again
Was. The obtained polymer was washed five times with methanol.
Thereafter, the resultant was dried under reduced pressure at room temperature. 58 g of polymer are obtained
Was. Molecular weight and molecular weight of the obtained polymer
The cloth is separated by GPC (gel permeation chromatography).
-) Using Model 150 (Waters)
I asked. Using o-dichlorobenzene as the solvent,
At 135 ° C. and a solvent flow rate of 1.0 ml / min. The column is
GMH6HT (trade name, manufactured by Tosoh Corporation) was used. Measurement
Using a Tosoh monodispersed polystyrene standard sample
Calculate the polystyrene calibration curve,
A calibration curve of polypropylene was prepared by the Lewis method. Obtained
The GPC runoff curve of the polymer was unimodal. this
Mn of the polymer is 1.03 × 10^FourAnd Mw / Mn is
It was a value close to monodispersion of 1.12. (3) Determination of polymer structure IR: Model IR-810 (trade name) manufactured by JASCO Corporation
Measured by liquid film method (KBr plate) using infrared spectrophotometer
Specified. 1740cm^-1(Absorption based on carbonyl stretching vibration)
Income). [0046]¹H-NMR: JSX-40 manufactured by JEOL Ltd.
0 (trade name), Fourier transform type NMR spectrometer
At 400 MHz, 30 ° C, pulse interval 15 seconds
Was measured. Samples were prepared by dissolving in deuterated chloroform.
Was. Peaks due to polypropylene protons (δ =
0.7 to 1.7 ppm)
A peak was observed. [0047] [Table 1] [0048] Embedded image Proton signal of the polypropylene part (δ = 0.7 to 1.
7 ppm) and the area ratio of the above signal (D).
The polymer has one end at the end of polypropylene as shown below.
Three GMA units are introduced (n = 1
3) It turned out. [0049] Embedded image (4) Measurement of dyad fraction Next, the obtained polypropylene syndiotactic
Separately, the same procedure as above is used to measure the Iad fraction.
After the living polymerization of propylene was performed, the reaction solution was
In ethanol-hydrochloric acid solution (500 ml) cooled to 78 ° C
Quickly stop the polymerization by adding
Wash 5 times with 0 ml ethanol, dry at room temperature
Propylene was obtained. The obtained polypropylene is¹³C-NMR component
Was analyzed. Varian PFT pulse Foury
D) Using XL-200 type (product name) with conversion device, 50M
Hz, 120 ° C, pulse width 8.2 μs π / 3, pulse interval
The measurement was performed under the conditions of 4 seconds and the number of accumulations was 5,000. The sample is
Dissolved in a mixed solvent of Lichlorobenzene and Benzene (2: 1)
Prepared by disassembly. The ratio of the multiple line intensity of methyl carbon in the spectrum
The stereoregularity of the polypropylene calculated from this is shown below. [0052] [Table 2]Triad fraction Dyad fraction ^a) [rr] [rm] [mm] [r]0.625 0.320 0.055 0.785 a) Calculated from triad fraction synPP-GMA: glycidyl methacrylate (G
MA) end-modified polypropylene, propylene resin
Except that the reaction time was 15 hours during bing polymerization
It was manufactured in the same manner. Terminal structure similar to the above (the above formula
(VIII)) (n = 13), but Mn = 6.04 × 10^Four
Met. In place of component (C), the following comparative examples were used.
The following materials were used: PP-MAH: Group of maleic anhydride and polypropylene
Raft copolymer, maleic anhydride content 0.25 mol%, weight
Weight average molecular weight 133,000. The weight average molecular weight is GP
Measured by the C method and converted to polypropylene
Asked. BF: Bond First (Sumitomo Chemical Co., Ltd.) IG
ETABOND, grade E, glycidyl methacrylate (G
MA) copolymer of ethylene with GMA content of 12% by weight
%, MFR 3 g / 10 min. Further, tests performed in Examples and Comparative Examples
Was measured as follows. 1) Melt flow rate (MFR): JIS K7210
Measured at 230 ° C under a load of 2.16 kg in accordance with. 2) Tensile rigidity: Measured according to JIS K7113
Was. 3) Breaking strength (elongation at break): Based on JIS K7113
And measured. 4) Izod impact strength: based on JIS K7110
At 23 ° C. with a notch. 5) Surface peeling rate: 1mm for No. 2 dumbbell^TwoGo grid on all four sides
Put 100 pieces in an eye, and use an adhesive tape to measure the degree of peeling.
Was observed. Calculate the number of peeled per 100 pieces by%
Was. [0055]Examples 1 to 7 Each component shown in Table 3 was nitrided using a Labo Plastomill.
Under a blanket seal, knead at 280 ° C and 80 rpm for 5 minutes,
Crushed by Brabender. Dry the resulting product in a drying oven
After drying, a test piece is prepared by injection molding, and MF
R, tensile rigidity, elongation at break, Izod impact strength, surface
The peeling rate was measured, and the presence or absence of coloring was observed. Table 3 shows the results
Show. (C) Reaction rate of synPP-GMA
Made a 200 μm thick film from the composition and
Extraction with m-cresol for 2 hours, followed by tetrachloroethane
(TCE) After washing, the film is made again and FT
It was determined quantitatively by IR. [0057] [Table 3] Comparative Example 1 (A) 80 parts by weight of polyester and (B) polyolefin
(C) synPP-GM
A was not blended. A composition was prepared in the same manner as in Example 1.
And then injection molded to evaluate each. Table of results
It is shown in FIG. [0058]Comparative Example 2 0.4 parts by weight of PP-MAH is further blended,
As in Comparative Example 1 except that the weight of the resin was 19.6 parts by weight.
To produce a composition, and then injection molding, each evaluation
went. Table 4 shows the results. [0059]Comparative Example 3 (A) 15 parts by weight of BF with respect to 80 parts by weight of polyester
And (B) 5 parts by weight of polyolefin.
A composition was prepared in the same manner as in Example 1 and then injection molded
Then, each evaluation was performed. Table 4 shows the results. [0060] [Table 4]Comparison with Example 4 in which the composition ratio of components (A) and (B) is close
Then, Comparative Example 1 in which the compatibilizer component (C) was not added.
In this case, the elongation at break is extremely low due to poor compatibility.
Izod impact strength is also quite low. Furthermore, the surface peeling rate
Very high. Also, instead of the compatibilizer component (C), MA
In Comparative Example 2 using H-modified polypropylene,
Poor flowability (MFR) and low Izod impact strength
Coloration and surface peeling rate
I have. Comparison using Bondfast, an impact resistant agent
In Example 3, the Izod impact strength was high, but the flowability (MF
R) is very poor, has low tensile rigidity, and has surface peeling
Be looked at. [0061] According to the composition of the present invention, each component is well compatible.
And therefore impact resistance, tensile strength, and peel resistance
Mechanical properties such as heat resistance, thermal properties such as heat resistance, appearance and other surfaces
Excellent environmental properties such as water resistance and chemical resistance
You. Therefore, various engineering plastics
In particular, automotive interior and exterior products, electrical components, home appliances,
Industrial material parts, sporting goods, furniture, office supplies, packaging materials
It is suitable for use in applications such as food.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Satoshi Ueki 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Pref. Tonen Co., Ltd. JP-A-5-247119 (JP, A) JP-A-5-17646 (JP, A) JP-A-4-275363 (JP, A) JP-A-6-65486 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (1)

(57) Claims: (A) 0.1 to 99% by weight of a polyester, (B) 0.1 to 99% by weight of a polyolefin, and (C) a terminal represented by the following formula (I) : (Wherein ^Ra is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; X is a hydrocarbon group containing an epoxy group and having 2 to 20 carbon atoms; n is an average 0.01 to 99% by weight of a terminal-modified polypropylene having a structure represented by the following formula:
A thermoplastic resin composition comprising: