JP3482262B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] 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 parts, 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, polyolefin has low specific gravity and excellent impact resistance.
And good environmental properties such as moldability, water resistance and chemical resistance.
It has the advantage of being favorable. So polyester and po
Combined with polyolefin, resin set with both advantages
Attempts have been made to produce products. However, Polje
Because stel and polyolefin are incompatible with each other,
In a thermoplastic resin composition containing both, impact resistance and
And the mechanical strength is reduced. [0003] The compatibility between polyester and polyolefin
As an attempt to improve the
Acid or derivatives thereof, especially maleic anhydride (MAH)
Polyolefins with Unsaturated Dicarboxylic Anhydrides
There is known a method of mixing and melting and kneading. This one
The method improves the compatibility and dispersibility of the two, and
Is excellent, and the composition is prevented from deteriorating due to water absorption.
You. However, in this method, the dicarboxylic anhydride is
When added to olefin,
Deterioration and deterioration caused by polyolefin
Because a specific part of the resin cannot be denatured,
Reaction, intramolecular association, etc. of
Is not enough to improve the physical properties. Also, polyolefin
Unreacted acid remaining after denaturation reacts with polyester
There was also a problem of coloring and impairing the appearance. Therefore, the applicant of the present application has already made polyester and
And polyolefins are converted to heavy glycidyloxy groups.
Method of melt-kneading with a compound and a polymerization initiator
(JP-A-5-39329). [0005] The present invention relates to polyesters and polyolefins.
Good impact resistance, tensile strength, peeling resistance
Table of mechanical properties such as releasability, thermal properties such as heat resistance, and appearance
Excellent surface characteristics and environmental characteristics such as water resistance and chemical resistance
An object is to provide a thermoplastic resin composition. [0006] DISCLOSURE OF THE INVENTION The present inventors have made a
Intensive study on compatibilization of ter and polyolefin
As a result, styrene-based compound residues
If polypropylene is used at the end, compatibilization of both can be achieved.
Good, excellent properties without coloring
Have been obtained, and have reached the present invention.
Reached. That is, the present inventionAccording to, (A) POLYS
Ter 0.1-99% by weight, (B) polyolefin 0.1
To 99% by weight, and at the (C) end, the following formula (I): [0
008] Embedded image (In the above formula, Ra and Rb are each independently hydrogen
X represents an atom or a methyl group;Halogen atom, al
Kill group, alkoxy group, alkoxyalkyl group, haloa
Alkyl group, ester group, dialkylaminoalkyl group,
Bistrialkylsilylamino group or trialkylsilyl group
Selected from a roxy group,Substituents not containing active hydrogen
M is an integer of 0 to 5 representing the number of substituents X;
n is an average value,0.5-100In the range)
Terminal-modified polypropylene 0.01 having the structure
Thermoplastic resin composition containing -99% by weightIs provided. [0008] Embedded image (In the above formula, R^aAnd R^bAre each independently hydrogen
X represents an atom or a methyl group;
M is an integer of 0 to 5 representing the number of substituents X
N is an average value and is in the range of 0.1 to 500)
Terminal-modified polypropylene having a structure represented by the formula:
It is a thermoplastic resin composition containing from 01 to 99% by weight. Preferred embodiments include the following.
You can: In the formula (I), X is a chlorine atom, a methyl group,
Methoxy group, t-butoxy group, methoxymethyl group,
Romethyl group, methoxycarbonyl group, ethoxycarbonyl
Group, dimethylaminomethyl group, bistrimethylsilyl
Amino groupOrBefore being selected from trimethylsiloxy group
The thermoplastic resin composition described above. (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 thermoplastic resin composition. A method for producing a thermoplastic resin composition according to any one of the above.
A method in which each component is melt-kneaded at 200 to 350 ° 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
And 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 and 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 weight of α-olefin (including ethylene)
Copolymer; copolymer of two or more α-olefins (lander
This includes all copolymers such as
Or olefin-based compounds.
Lastmer. 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)
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 with ethylene content of 20% by weight or less
Propylene copolymer.
Wren 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 or polypropylene mentioned above
Len is about 40% by weight of olefin elastomer.
May be included. Here, the olefin elastomer is
Ethylene and one or more α-
Olefins (eg propylene, 1-butene, 1-hexene
, 4-methyl-1-pentene)
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
Diene in copolymer rubber (EPDM)
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) or one or more
Lock copolymer or random copolymer or copolymer
Includes body rubber. The terminal structure represented by the formula (I) is
Having different degrees of end group polymerization
A composition of end-modified polypropylene, where n is the average
Value. n is 0.1 to 500, preferably 0.5 to 1
00. In the above formula (I), active hydrogen is contained.
Substituents such as halogen atoms, alkyl groups
(Methyl, ethyl, propyl, butyl, etc.), haloalkyl
(Chloromethyl, dichloromethyl, chloroethyl
Etc.), alkoxy groups (methoxy, ethoxy, propoxy)
, T-butoxy, etc.), alkoxyalkyl groups (Methoxy
Cimethyl, ethoxymethyl, ethoxyethyl, etc.), S
Ter group (methoxycarbonyl, ethoxycarbonyl
Etc.), dialkylaminoalkyl groups (dimethylaminomethyl
Chill, dimethylaminoethyl, methylethylaminomethyl
), Bistrialkylsilylamino group (bistrime
Tylsilylamino, etc.), trialkylsiloxy groups (tri
Methylsiloxy, etc.). Above all, haloge
Heteroatoms such as oxygen, oxygen, nitrogen, silicon, etc.
Groups containing an atom are preferred. Preferred X is a halogen atom
Child, alkyl group, alkoxy group, alkoxyalkyl
Group, haloalkyl group, ester group, dialkylamino
Alkyl group, bistrialkylsilylamino groupOrbird
Selected from alkylsiloxy groups. Particularly preferably,
Chlorine atom, methyl group, methoxy group, t-butoxy group,
Toximethyl group, chloromethyl group, methoxycarbonyl
Group, ethoxycarbonyl group, dimethylaminomethyl group,
Bistrimethylsilylamino groupOrTrimethylsiloxy
Selected from the group The substitution position of X is ortho (O-)
Position, meta (m-) positionOrAny of the para (p-) positions
You may. In the case of the chlorine atom, O-, m-, p-
All are preferred, and a methoxy group, a t-butoxy group,
Toximethyl group, methoxycarbonyl group, dimethylamido
Nomethyl group, bistrimethylsilylamino groupOrbird
In the case of a methylsiloxy group, p- is preferred, and
In the case of a tyl group, m-Orp- is preferred. Polypropylene having the above terminal structure (I)
Pyrene can be produced as follows. That is,
(II): [0017] 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
With the following formula (III): [0018] Embedded image (In the above formula, R^a, R^b, X and m are as defined above.
Produced by reacting the compound with
You. Here, vanadium represented by the above formula (II)
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
BA 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 compound represented by the following formula (IV)
Compound, ie, V (acetylacetonato)_Three;under
The compound represented by the formula (V), that is, V (2-methyl-
1,3-butanedionato)_ThreeA compound represented by the following formula (VI):
Object, ie V (1,3-butanedionato)_ThreeIs preferred. [0021] Embedded image [0022] Embedded image[0023] Embedded image Next, the organic aluminum used as the above-mentioned catalyst
The compound has the general formula: [0024] [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 organoaluminum 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.
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.
And an organoaluminum compound in an amount of 1 to 1,000 moles 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. Amount of polymerization catalyst used in the polymerization of propylene
Is 1 mole equivalent of propylene (and other α-olefins)
Or vanadium compound 1 × 10^-Four~ 0.1 mol, preferred
Ha 5 × 10^-Four~ 5 × 10^-2Mole, organoaluminum compound
The thing is 1 × 10^-Four~ 0.5 mol, preferably 1 × 10^-3~ 0.1 m
It is. It should be noted that per mole of the vanadium compound,
Aluminum compound is preferably used in 4 to 100 mol.
New The 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 yields 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. During 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 the amount of the vanadium compound 1
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 (III)
Is reacted. As the compound (III), styrene, α-
Methylstyrene, β-methylstyrene and α, β-di
Methylstyrene and a compound having the above-mentioned substituent X
These derivatives can be used. Converted to living polypropylene
Reaction with compound (III) is due to the presence of living polypropylene
To react by supplying compound (III) to the reaction system
Is preferred. The reaction is usually carried out at a temperature between -100 ° C and 150 ° C.
For 5 minutes to 50 hours. Increase the reaction temperature or react
By increasing the time, the compound (III) unit
Can increase the modification rate of the polypropylene end
You. Normal compound per mole of living polypropylene
Use 1 to 1,000 mol of product (III). Living polypropylene and compound (III)
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 terminal-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 of said terminal structures
You. In addition, the end-modified poly-
Ripropylene has a syndiotactic dyad fraction
One feature 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 includes:
Commercially available engineering plastics impact resistance
Up to about 50% by weight of an improving agent may be contained. That
Examples of such impact modifiers include staphyloid
(Manufactured by Takeda Pharmaceutical Co., Ltd.). The 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 the kneading method, for example, a single-screw or twin-screw extruder,
Burr mixer, kneading roll, brabender, kneader
-Any known method such as a batch kneader can be used.
You. The kneading temperature is preferably 200 to 350 ° 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
May be added in any order.
Moreover, it can also be manufactured by a solution method. [0041] In the resin composition of the present invention, each component is good.
It is said that it has high impact resistance and high MFR.
Demonstrate excellent characteristics. The reason is not always obvious
Although it does not have a styrene compound residue-containing terminal structure,
Polyester and polyester through the end-modified polypropylene
It is presumed that this is due to compatibilization with the polyolefin.
In other words, when melt-kneaded, the end-modified polyolefin changes.
The functional moiety binds to the end of the polyester, while the
The polypropylene part of polypropylene is polyolefin
Because they are compatible, it is thought that each component will be compatible.
available. In particular, it has been used as a compatibilizer in the conventional method.
Modified polypropylene changes onto the polypropylene main chain.
Conductive agent (MAH, epoxy functional group, etc.)
On the other hand, in the present invention,
Compound residue containing structure is introduced only at the molecular chain end,
Excellent effect due to the true block shape
It is thought that it is possible. Furthermore, 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. Also, the components are kneaded together to form a resin composition.
Can be obtained industrially and easily.
The cost associated with kneading is low and the utility is extremely high. [0043] 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, (manufactured by Tonen Chemical Co., Ltd., J20
9), melt flow rate (MFR) (230 ° C, 2.16kg)
Measured by load) 9 dg / min EPR: ethylene-propylene copolymer rubber (Nihon Gosei
Rubber Co., Ltd., EP912P), MFR (230 ° C, 2.
Measured with 16kg load) 7.5 dg / min (C) Terminal-modified polypropylene synPP-St-1: end-modified with p-chlorostyrene
Syndiotactic polypropylene (R^a= R^b=
H, m = 1, X = p-Cl), prepared as follows; (1) Living polymerization of propylene 1-liter stainless steel
Put 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 30 mmol of Al (C_TwoH_Five)_TwoN- of Cl
Heptane solution and 3 mmol of V (2-methyl-1,3-butane)
Tandionato)_ThreeToluene solution and add weight with stirring.
Started the match. Propylene polymerization at -60 ° C for 30 minutes
Was. (2) Reaction with p-chlorostyrene 100 ml of p-chlorostyrene is added to the above reaction system at -60 ° C.
The mixture was added and reacted at the same temperature for 1 hour. Then this reaction
The solution is poured into one liter of methanol and the polymer
Was precipitated. The polymer obtained is washed 5 times with methanol
After washing, it was dried under reduced pressure at room temperature. 2.56 g of polymer
-Was obtained. The molecular weight and molecular weight of the obtained polymer
The cloth is subjected to 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 calibration curve of polystyrene, and
A calibration curve of polypropylene was prepared by the toluene method. Obtained
The GPC runoff curve of the polymer was unimodal. this
Mn of the polymer is 2.9 × 10^ThreeAnd Mw / Mn is
1.18, a value close to monodispersion. (3) Determination of polymer structure¹ H-NMR: JSX-400 (product of JEOL Ltd.)
Name), using a Fourier transform type NMR spectrometer
Measured under conditions of 400 MHz, 30 ° C, pulse interval 15 seconds
did. The sample was prepared by dissolving in deuterated chloroform. Po
Peaks attributed to protons of propylene (δ = 0.7 to
1.7 ppm), and the peak consisting of the chemical shift values shown in Table 1.
A peak was observed. The proton sig of the polypropylene part
Null (δ = 0.7 to 1.7 ppm) and the benzene ring
From the area ratio of the ton signal (δ = 7.1 to 7.3 ppm),
The resulting polymer has 12 p-
A lorostyrene unit has been introduced (n = 1
2) It turned out. [0046] [Table 1] [0047] Embedded image synPP-St-2: Terminal modification with p-methoxystyrene
Syndiotactic polypropylene (R^a= R^b
= H, m = 1, X = p-OCH_Three). The above synPP-S
In place of p-chlorostyrene, according to the production method of t-1
Using p-methoxystyrene. Poly obtained
Weigh 2.44 g, Mn = 2.6 × 10^Three, Mw / M
n = 1.16.¹The results of H-NMR analysis are shown in Table 2.
You. Further, n = 14. [0048] [Table 2] [0049] Embedded image synPP-St-3: 4-vinylbenzyldimethylami
Syndiotactic polypropylene end-modified with
(R^a= R^b= H, m = 1, X = p-CH_TwoN (CH_Three)
_Two. According to the method for producing synPP-St-1, p-
4-vinylbenzyldimethylamine instead of chlorostyrene
Manufactured using min. 1.99 g of polymer obtained
And Mn = 1.6 × 10^Three, Mw / Mn = 1.14
Was.¹Table 3 shows the H-NMR analysis results. Also, n =
It was 13. [0050] [Table 3][0051] Embedded image synPP-St-4: terminal-modified with p-methylstyrene
Syndiotactic polypropylene (R^a= R^b=
H, m = 1, X = p-CH_Three). The above synPP-St-
According to the production method of 1, p-chlorostyrene is replaced with p-chlorostyrene.
Manufactured using methylstyrene. The resulting polymer is
2.33 g, Mn = 2.2 × 10^Three, Mw / Mn = 1.
It was 19.¹Table 4 shows the results of H-NMR analysis. Ma
Further, n = 12. [0052] [Table 4] [0053] Embedded image synPP-St-5: terminated with p-chloromethylstyrene
Modified syndiotactic polypropylene (R^a=
R^b= H, m = 1, X = p-CH_TwoCl). The above synP
According to the method for producing P-St-1, p-chlorostyrene was
Produced using p-chloromethylstyrene instead. Profit
The obtained polymer weighed 3.12 g, and Mn = 3.6 × 1
0^Three, Mw / Mn = 1.20.¹H-NMR analysis
Table 5 shows the results. Further, n = 14. [0054] [Table 5] [0055] Embedded image synPP-St-6-1: with methyl 4-vinylbenzoate
End-modified syndiotactic polypropylene (R
^a= R^b= H, m = 1, X = p-CO_TwoCH_Three). The above s
According to the method for producing ynPP-St-1, p-chlorostyrene
Manufactured using methyl 4-vinylbenzoate instead of
Was. The obtained polymer weighed 2.11 g and Mn = 1.8
× 10^Three, Mw / Mn = 1.09.¹H-NMR fraction
The results of the analysis are shown in Table 6. Further, n = 15. [0056] [Table 6] [0057] Embedded image synPP-St-6-2: methyl 4-vinylbenzoate
End-modified syndiotactic polypropylene (R
^a= R^b= H, m = 1, X = p-CO_TwoCH_Three). The above s
As in ynPP-St-6-1, except that at the time of reaction
Produced in 15 hours. The resulting polymer is 32
g, Mn = 6.0 × 10^Four, Mw / Mn = 1.21
Was.¹The analysis result of H-NMR was synPP-St-6-
Same as 1 and n = 14. SynPP-St-7: β-methylstyre
Syndiotactic polypropylene end-modified with
(R^a= CH_Three, R^b= H, m = 0). The above synPP
-In place of p-chlorostyrene,
Instead, it was prepared using β-methylstyrene. Got
The polymer weighs 2.49 g and Mn = 2.8 × 10^Three, Mw
/Mn=1.13.¹Table 7 shows the H-NMR analysis results.
Shown in Further, n = 11. [0059] [Table 7] [0060] Embedded image synPP-St-8: terminal modification with α-methylstyrene
Syndiotactic polypropylene (R^a= H,
R^b= CH_Three, M = 0). Of the above synPP-St-1
According to the manufacturing method, α-meth
Manufactured using chill styrene. The resulting polymer is
2.55 g, Mn = 2.8 × 10^Three, Mw / Mn = 1.
It was 16.¹Table 8 shows the H-NMR analysis results. Ma
Further, n = 12. [0061] [Table 8] [0062] Embedded image synPP-St-9: Terminal modification with p-divinylbenzene
Syndiotactic polypropylene (R^a= R^b
= H, m = 1, X = p-CH = CH_Two). The above synPP
-In place of p-chlorostyrene,
Instead, it was produced using p-divinylbenzene. Got
The polymer weighs 2.88 g and Mn = 3.1 × 10^Three, Mw
/Mn=1.18.¹Table 9 shows the H-NMR analysis results.
Shown in Further, n = 13. [0063] [Table 9] [0064] Embedded image synPP-St-H: Syndi terminated with styrene
Tactical polypropylene (R^a= R^b= H, m =
0). According to the method for producing synPP-St-1,
Manufactured using styrene instead of p-chlorostyrene
Was. The amount of the obtained polymer was 2.84 g, and Mn = 3.0 × 10
^Three, Mw / Mn = 1.17.¹H-NMR analysis results
From the results, n = 16. Note that, in place of the component (C), the following comparative examples
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 Industries, Ltd.) IG
ETABOND, grade E, glycidyl methacrylate (G
MA) copolymer of ethylene with GMA content of 12% by weight
%, MFR 3 g / 10 min. In addition, tests performed in Examples and Comparative Examples
Was measured as follows. 1) Melt flow rate (MFR): JIS K7210
Measurement was performed at 275 ° C and 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 square on all four squares
Use 100 scotch tape (Nichiban Co., Ltd.)
And the degree of peeling was observed. Peeling per 100 pieces
The number was calculated in%. [0067]Examples 1 to 15 Using Labo Plastomill, each component shown in Table 10,
5 minutes at 280 ° C and 80 rpm under a nitrogen blanket
It was kneaded and crushed by a crusher. Product obtained
After drying in a drying oven, test specimens are created by injection molding
MFR, tensile rigidity, elongation at break, Izod impact strength
The degree of surface peeling was measured, and the presence or absence of coloring was observed. result
Are shown in Table 10.In Table 10, Example 2 is a reference example.
It is. [0068] [Table 10] In Table 10 above, the terminally modified PP is represented by an abbreviation.
However, the meaning of each symbol is as follows: C1 synPP-St-1 (terminal modification with p-chlorostyrene
Sex PP) C2 synPP-St-2 (terminal with p-methoxystyrene
Denatured PP) C3 synPP-St-3 (4-vinylbenzyldimethyl
Amine terminal-modified PP) C4 synPP-St-4 (terminal modification with p-methylstyrene
Sex PP) C5 synPP-St-5 (with p-chloromethylstyrene
Terminally modified PP) C6-1 synPP-St-6-1 (4-vinylbenzoic acid
Cyl-terminal-modified PP, Mn = 1.8 × 10^Three) C6-2 synPP-St-6-2 (4-vinylbenzoic acid
Cyl-terminal-modified PP, Mn = 6.0 × 10^Four) C7 synPP-St-7 (terminal with β-methylstyrene
Denatured PP) C8 synPP-St-8 (terminal with α-methylstyrene
Denatured PP) C9 synPP-St-9 (terminal with p-divinylbenzene
Denatured PP) C10 synPP-St-H (terminally modified with styrene
PP)Comparative Example 1 (A) 80 parts by weight of polyester and (B) polyolefin
Only 20 parts by weight of the resin and component (C)
Was. A composition was prepared as in Example 1 and then sprayed.
Out-molding was performed and each evaluation was performed. Table 11 shows the results. [0069]Comparative Example 2 Other than adding 0.4 part by weight of PP-MAH
Prepared a composition in the same manner as in Comparative Example 1, and then performed injection molding.
And each evaluation was performed. Table 11 shows the results. [0070]Comparative Example 3 (A) 80 parts by weight of polyester and (B) polyolefin
15 parts by weight of BF was mixed with 5 parts by weight of the resin. Comparison
The composition was prepared by melt-kneading in the same manner as in Example 1 and then
Each evaluation was performed by injection molding. Table 11 shows the results. [0071] [Table 11] Comparison with Example 12 in which the composition ratio of components (A) and (B) is close
Comparing with Examples 1 and 2, the compatibilizer component (C) was added.
In Comparative Example 1 where no addition was performed, the compatibility was poor,
Low elongation and Izod impact strength, plus surface peeling
The rates are also very high. Also, instead of the compatibilizer component (C),
In Comparative Example 2 using MAH-modified polypropylene
Has high tensile stiffness and elongation at break,
The impact strength is slightly lower and the surface peeling rate is also higher.
Coloring has occurred. Bond Firth, an impact resistant agent
In the comparative example 3 using the Izod, the Izod impact strength was high.
Has very poor flowability (MFR) and surface peeling
You. [0072] 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 characteristics and environmental characteristics 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 Sachi Usui 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. Research Institute (56) References JP-A-6-122711 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/00-23/36 C08L 67/00-67/02

Claims (1)

(57) [Claims 1] (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 and Rb each independently represent a hydrogen atom or a methyl group; X represents a halogen atom,
Kill group, alkoxy group, alkoxyalkyl group, haloa
Alkyl group, ester group, dialkylaminoalkyl group,
Bistrialkylsilylamino group or trialkylsilyl group
An active hydrogen-free substituent selected from loxy groups ; m is an integer of 0 to 5 representing the number of substituents X;
n is an average value and is in the range of 0.5 to 100).
A thermoplastic resin composition comprising -99% by weight.