JPS59215351A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having improved mechanical characteristics such as resistance to impact and water, tensile strength, flexural strength, rigidity, etc., by blending a polyester and an olefin polymer with an olefin polymer/polyester copolymer. CONSTITUTION:A thermoplastic resin compsn. is obtd. by blending 0.1-90pts.wt. olefin polymer/polyester copolymer (A) [e.g. a copolymer wherein a polyester linkage of formula I (wherein R<1>, R<2> are each H, lower alkyl; m is 2-12; x is 0-1,000) or an amide linkage of formula II is interposed between the olefin polymer segment and the polyester segment], 5-95pts.wt. polyester (B) and 0-95pts.wt. olefin polymer (C) (A+B+C=100pts.wt.). When component B is used as the main ingredient and only component A is added thereto, impact strength, boiling water resistance and elongation are improved. When further component C is added thereto, a compsn. having improved impact strength and high crystallization velocity can be obtd. When component C is used as the main ingredient, tensile strength and rigidity are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition containing an olefin polymer/polyester copolymer, and more particularly to a thermoplastic resin composition with improved mechanical properties.

Thermoplastic polyesters such as polyethylene terephthalate are used in fibers, films, bottles, electrical and electronic parts, etc., but they may not be able to meet the required characteristics for each molded product. For this reason, the balance of physical properties is adjusted by blending other polymers or adding inorganic fillers.

For example, attempts have been made to blend elastomers and polyolefins to improve the impact resistance of polyester, but these polymers do not necessarily have good compatibility with polyester, resulting in poor dispersibility. Non-uniformity and separation between different phases are likely to occur, and the purpose of modification is often not achieved.

On the other hand, polyolefins are used in a wide range of fields because they are relatively inexpensive, chemically stable, have excellent moldability, and have low density. Furthermore, as the development of applications has progressed in recent years, the required performance has become stricter, and in order to cope with this, it is also being done to achieve the same physical properties by blending with other polymers or adding inorganic fillers.

For example, attempts have been made to blend polyethylene terephthalate or the like into polyolefins such as polyethylene, but the purpose of the modification is often not realized for the same reasons as mentioned above.

The present inventors discovered a method of adding other polymers to the polyester of polyethylene terephthalate to improve its mechanical properties such as impact resistance and water resistance.
In addition, as a result of testing methods for adding other polymers to polyolefins to improve their mechanical properties such as tensile strength, bending strength, and rigidity, we found that olefin-based polymers have an affinity for both polyester and olefin-based polymers. By utilizing polyester copolymer orientation,
Roll ↓-1 for those objectives to be achieved. That is, Ministry of the Invention et al. (: 11), the olefin polymer/polynisdel copolymer (B) should have excellent dispersibility when blended with polyester (5) or olefin polymer (C2), and the polyester (N It is reported that the mechanical properties of olefinic polymers (Q) are improved.

1) In addition to blending this copolymer (B) into a blend system containing polyester color) and olefin polymer (q), Nagisa et al. The inventors have discovered that the solubility is significantly improved and that various properties such as the water resistance of polyester (A) are improved, leading to the present invention.

That is, in the present invention, polyester color) 5 to 95 parts by weight, olefin polymer/polyester copolymer 60 parts by weight
．． 1 to 90 parts by weight, and olefinic polymer Ω
The present invention relates to a thermoplastic resin composition comprising 95 parts by weight of O to 95 parts by weight (total of 100 parts by weight of (B) 10C+).

[Composition of polyester prisoner]

The polyester (2) used in the present invention can be melt-molded,
It is not particularly limited as long as it is a polyester that can be molded by solution molding or the like. Usually polyesters composed of aromatic, cycloaliphatic and/or aliphatic dicarboxylic acids and aromatic, cycloaliphatic and/or aliphatic diols, or aromatic, cycloaliphatic and/or aromatic oxycarboxylic/ You can choose from polyesters composed of acids.

Among them, the polyester (2) that is preferably used is a polyester composed of a dicarboxylic acid whose main component is an aromatic dicarboxylic acid and a diol whose main component is an aliphatic or alicyclic diol. Aromatic dicarboxylic acids constituting the compound include terephthalic acid,
Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis(1)-
carboxyphenyl)methane, anthracenedicarboni*, 4.4'-diphenyldicarvone g, 4.4'
-Cyphenyl ether cycarpho/acid, etc. or ester-forming derivatives thereof.

In addition, if the proportion of the dicarboxylic acid component consisting of these aromatic dicarboxylic acids is about 40 mol% or less, adipine, aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, dodecane dicarboxylic acid, and 1,6-cyclo It may be substituted with dicarboxylic acids other than aromatic dicarboxylic acids such as alicyclic dicarboxylic acids such as gisanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and their ester-forming derivatives, but usually aromatic The lower the proportion of acid components other than group dicarboxylic acids, the better.

Still aliphatic or cycloaliphatic diols include ethylene glycol, fluorene glycol, 1,4-butanediol, neopentylglycol/l/, 1,5-penp
aliphatic glycols such as diol, 1,6-hexanediol, and decamethylene glycol; alicyclic glycols such as cyclohexanediol and tricyclodecane dimethylol; and diethylene glycol, triethylene glycol, or those having a molecular weight of about io or oo.

The following polyethylene glycol, poly-1,3=glopylene glycol, polytetramethylene glycol, etc.
and mixtures thereof.

A part of the diol component consisting of these aliphatic or alicyclic diols is hydroquinone, resorcinol, 4.
4'-dihydroxyphenylmethane, 2. Goobis (4
-hydroxy-6,5-dimethylphenyl)propane,
Although it may be substituted with an aromatic diol such as bis(4-hydroquine-3,5-dimethylphenyl)methane, it is usually preferable to have a small proportion of aromatic diol.

More specifically, preferred polyesters used in the present invention include polyethylene terephthalate,
Examples include polypropylene terephthalate, polybutylene prephthalate, polyhexamethylene terephthalate-1, polycyclohexylene symethylene terephthalate, polyethylene-2,6-naphthalate, and polyarylate. Among them, polyethylene has moderate mechanical strength.
Nterephthalate, or polybutylene terephthalate
Particularly suitable is

The polyester (2) usually has an intrinsic viscosity [η] (o-chlorophenol solvent, 25°C) of 0.3 and 10, preferably about 0.4 and about 5.0. be. When it is smaller than about 0.3, tensile strength and elongation tend to be low, and when it exceeds about 10, moldability tends to decrease.

[Structure of olefin polymer/polyester copolymer 0] Olefin polymer/polyester copolymer () 3)
U, a copolymer having an olefin polymer segment and a polyester segment. Examples of olefinic polymer segments include olefinic polymers (where q has the same repeating unit as the polymers exemplified later) that may be used as a component of the present invention. The type of segment does not necessarily have to be the same as the type of the olefin polymer C) that may be used in combination, but it is preferable that they are compatible with each other.

Among these, α-olefin-based elastic polymers or diene-based polymers are preferred, and hydrogenated diene polymers are particularly preferred.

Examples of the polyester segment constituting the copolymer (B) include those having the same repeating units as the polymer exemplified as the polyester (2) above.

Another embodiment of the polyester segment is a polylactone segment, which is a segment obtained by polymerizing the following general formula (where n is a positive integer of 2 to 12, and R1 and R2 are hydrogenated or lower alkyl groups). Examples of these lactones include β
Examples include polymers such as -propiolactone, β-butyrolactone, δ-valerolactone, and C-caprolactone. Of these 9, preferred is a segment made of a polymer of ε-caprolactone, which is industrially produced in large quantities and is economically advantageous.

Among these polyester segments, as long as they are compatible with the polyester used in polyester (polyester), the type thereof does not necessarily have to be the same as polyester (3), but it is particularly suitable for polyester (2). It is preferable to use the same type of polyester as used.

Copolymer 0 is a block copolymer or graft copolymer in which an olefin polymer segment and a polyester segment are connected to each other by a divalent group, and the connecting portion of each segment is an ester bond, an amide bond, It is preferable that the bond is formed by a bond selected from an imide bond, a urethane bond, a urea bond, or a carbonyl bond.

The number average molecular weight of the olefinic polymer segment in copolymer β) is usually about 300 to about 700.0
00, about 500 to about 500,000 is preferred.

The number average molecular weight of the polyester segment in the copolymer (c) is generally about 500 to about 100,000, preferably about 800 to about 50.00 [.1]. In the copolymer 0, one or more such polyester segments are connected to the reed or olefinic polymer segment at one end or both ends.

The composition of the copolymer (I3) is approximately 2.5/97 as a ratio of the total weight of the olefinic polymer segments to the total weight of the polyester segments (including polylactone segments, if any). A range of 5 to about 9515, particularly about 5/95 to about 90/10, is preferred. Weight ratio is approximately 2.5/97.5
If it is smaller than this, even if this copolymer (B) is mixed with polyester (Al), the mechanical properties such as impact strength will not be sufficiently improved. (Even if blended with polyester (2) together with C1, polynisdel (8 and olefin polymer C)
The improvement in compatibility between
If it is larger than 5, the copolymer (c) and polyester (
The compatibility with 2) is not sufficient.

゛If copolymer 0 is still soluble in 0-chlorophenol or decalin, its limiting viscosity (0-chlorophenol solvent, 25°C, or a solvent with a large difference from the limiting viscosity is preferably avoided; from about 0.6 to about 10 are used.

[Production method of olefin polymer/polyester copolymer (B)]

Copolymer 0) is a copolymer in which the connecting portion between an olefin polymer segment and a polyester segment is usually a bond selected from ester bonds, amide bonds, imide bonds, urethane bonds, urea bonds, or carbonyl bonds. It is manufactured by various methods.

Among the copolymers (1B), a preferred method for producing a copolymer in which the connecting portions of the segments are constituted by ester bonds is as follows. There is a method of manufacturing by reacting an olefin-based polymer having an aromatic dicarboxylic acid (or a lower alkyl group) with a polyester or an oligomer thereof composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol. The olefinic polymer 7 having an aromatic ester group represented by the general formula α) in the terminal and/or side chain used as a raw material can be obtained by introducing an aromatic ester group into the olefinic polymer by various methods. Manufactured by Examples of the olefin polymer used as a raw material include diene-containing polymers and hydrides thereof. As the diene-containing polymer, 1,
At least one hexamer selected from 6-butadiene, 1,6-pentadiene, chloroprene, isoprene, etc.
Among pomopolymers or copolymers obtained by polymerizing more than one type, conjugated diene polymers, particularly polybutadiene and polyisoprene, are preferably used.

These diene-containing polymers contain radicals, cations,
There are polymers using catalysts such as anions and coordinating anions, which can be used without particular limitation in the present invention. For example, it can be produced by a living anionic polymerization method using an initiator such as organic lithium, or by radical polymerization using a peroxide as an initiator. It is also possible to employ a method of copolymerizing a small amount of Ike's monomer together with the diene monomer. In this case, the proportion of other monomers copolymerized with the diene monomer is about 40 mol% or less, preferably about 60 mol% or less of the total monomers. Other copolymerizable monomers include styrene, α-methylstyrene, o- or p-vinyltoluene, vinylxylene, acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, vinylpyridine, etc. Examples of vinyl monomers include:

In addition, in the presence of the initiator, the same or different living polymers are coupled with a polyfunctional coupling agent such as methylene chloride, xylylene dibromide, terephthalic acid dichloride, silicon tetrachloride, etc. Although branched and radial diene-containing polymers are also exemplified, linear ones are usually preferably used.

When these diene-containing polymers were further hydrogenated and used, their average degree of unsaturation (11 unsaturated bonds calculated from the iodine value) was reduced to about 60% or less of its original value. Particularly preferred are those in which the average degree of unsaturation is reduced to about 20% or less of the original value.

To hydrogenate diene-containing polymers, methods well known in the art can be employed.

Examples of the method for introducing the aromatic ester group represented by the above general formula (1v) to the end of the diene-containing polymer include the following method.

A method of introducing phenoxycarbonyl groups by reacting phenoxycarbonyl halide, etc. with a living polymer of diene monomer. Examples of phenoxycarbonylhalite include phenylchloroformate, 2-methylphenylchloroformate, 6-methylphenylchloroformate, 4-methylphenylchloroformate, and the like.

A living polymer of diene monomer is reacted with ethylene oxide to form a terminal hydroxyl, and then reacted with a compound having multiple acyl halide groups such as terephthalic acid dichloride or Q or phosgene to introduce an acyl halide group at the end. A method in which a phenoxycarbonyl group is introduced by reacting this with phenol, etc. Compounds with multiple acylno-ride groups that are used include oxalic acid cybalide, malonic acid cybalide, succinic acid cybalide,
Glutaric acid civalide, adipic acid civalide, sebacic acid civalide, cyclohexanedicarboxylic acid civalide, terephthalic acid dino-ride, isophthalic acid civalide, xylylene dicarboxylic acid civalide, 2,6-
Examples include cybaride of naphthalene dicarboxylic acid and cybaride of bis(4-carboxyphenyl) ether.

Terminal and /-! preferably used in the present invention! or a diene-containing polymer having an aromatic ester group in the side chain, or a hydride thereof, having a molecular weight of about 300 to about 7.
00,000, particularly preferably from about 500 to about 50
0,000, and the diene-containing polymers still have a carbon number of 1, [100,1] in the proportion of aromatic ester groups of about 0.02 to about 95,
Particularly preferably, the number is about 0.03 to about 601.

If the molecular weight is less than about OO, the excellent properties of diene-containing polymers or their hydrides will develop and disappear, but if the molecular weight exceeds about 700,000, the polyester will be incompatible with its oligomers. '' and the copolymerization efficiency is lowered, so both are unfavorable.

The number of aromatic ester groups is approximately 0 per carbon number i, ooo
．． If it is less than 02, the copolymerizability with polyester or its oligomer will decrease, and if it exceeds about 95, gelation may proceed during the copolymerization reaction with the polyester component, both of which are unfavorable. Further, it is particularly preferable that the aromatic ester group is introduced at at least one end, particularly two ends, of a chain of a diene-containing polymer or a hydride thereof.

Commercially available polybutadiene homopolymers or copolymers having hydroxyl or carboxyl groups at the terminals, as well as hydrogenated polymers thereof, can be used as diene-containing polymers that serve as raw materials for introducing aromatic ester groups. For example, the following are exemplified.

N15so PB C, -1000 Nippon Soda G200
0 tt G-300On CI-1OLIO// CI-2000// Cl-3000tt C-1000// Cl-1000// Polytail H Mitsubishi Kasei tt HA Poly-BD Ayosha Butare
z HT 7 I+) Sofussha Hy
car HTB Guttrich Te
The other component used in the copolymerization, the polyester straddling oligomer, is appropriately selected from the polyesters mentioned above. There is no particular restriction on the molecular weight of the oligomer.

In particular, the polyester used in the copolymerization, the oligomer of which is the polyester (A) which is the other component of the composition.
A substance similar to the above is preferable because it has good compatibility.

By mixing a diene-containing polymer into which an aromatic ester group has been introduced, or a hydride thereof and a polyester or its oligomer under heating, and reducing the pressure of the reaction system as necessary, the aromatic ester group and the polynitride are combined. The terminals of are connected by an ester bond by transesterification reaction.

Although the mixing under heating may be performed in the absence of a catalyst, it is preferably performed in the presence of a catalyst. As polymerization catalysts, all those commonly used for polyester production can be used, including metal acetates such as manganese acetate and zinc acetate, metal oxides such as germanium oxide and antimony trioxide, and organic titanates such as tetrabutyl titanate. Examples include. During the reaction, other additives such as coloring agents, fillers, fillers, etc. may be added as necessary.

The charging ratio of the diene-containing polymer having an aromatic ester group or its hydride and the polyester or its oligomer depends on the type, molecular weight, and molecular weight of both components used.
The ratio of aromatic ester groups and other reaction conditions, such as heating temperature, can be changed as appropriate. Usually, the weight ratio of the polyester or its oligomer to the diene-containing polymer or its hydride is approximately 0,
5/99.5fr, or approximately 98/2.

Conventionally known equipment can be used to mix the mixture containing both components while heating. For example, devices such as a reaction tank with stirring blades, a screw or twin-screw extractor, a Niegoo mixer, a Banbury mixer, a mixing roll, a Henschel mixer, etc. can be used alone or in combination. It is also possible to complete the reaction in the solid phase of the reaction system melt-mixed by these devices.

The heating temperature is about 150°C to about 650°C, preferably about 180°C to about 300°C. If the temperature is less than about 150°C, the reaction rate of both components is slow, and if it exceeds about 650°C, deterioration of the diene-containing polymer or its hydride is likely to occur, which is not preferable. Still, it is preferable to keep the reaction system under reduced pressure conditions, with a constant pressure of 5 mynHg.
It is desirable to carry out the reaction for about 0.2 hours to about 50 hours at a pressure below, preferably for about 0.5 hours to about 20 hours at a pressure below about 2 mm Hg.

Among the copolymers still used in the present invention, the segment linkage) 1 has the general formula (1) (wherein H1 and R2 are each hydrogen or a lower alkyl group, and m is a positive integer of 2 to 12. and X
is a positive integer from 1 to 1000. ) A preferred method for producing a copolymer (P;I) composed of a divalent group having a lactone or polylactone segment shown in An example is a method of using an olefin polymer into which a polylactone segment is introduced instead of the olefin polymer. Examples of such an olefin polymer include a diene-containing polymer having a polylactone segment at the terminal and/or side chain, or a diene-containing polymer having a polylactone segment at the terminal and/or side chain. There are hydrides, which can be produced, for example, by the following method.

A method of open fJAM synthesis of lactones in the coexistence of a living polymer of a diene monomer.

A living polymer of a diene monomer is reacted with ethylene oxide or the like to form a terminal hydroxyl, and then reacted with a compound having multiple, preferably two acyl halide groups such as terephthaloyl dichloride, or phosgene to form an acyl hashide at the end. A method in which a group is introduced and then reacted with polylactones.

A method of reacting a diene-containing polymer with a hydroxyl group introduced at its terminal or a hydride thereof with a base such as sodium hydride to activate the terminal, and then ring-opening polymerizing lactones from these terminals.

Diene-containing polymer with carboxyl group introduced at the end=-
A method in which 1 or its hydride is treated with a halogenating agent such as thionyl chloride to convert the terminal into an acyl halide group, and then reacted with polylactones.

A method of ring-opening polymerization of lactone in the presence of a diene-containing polymer or its hydride, which has a carboxyl group or hydroxyl group introduced at the end.

diene-containing polymers used in these methods,
and their hydrides or lactones are the same as those mentioned above.

Suitable diene-containing polymers having polylactone segments at the terminal and/or side chains, or their hydrides, have a molecular weight of about 300 to about 7 (
] O, U 00, particularly preferably a molecular weight of about -, or a hydride segment thereof with a molecular weight of about 300
From about 200,000. Particularly preferred are those in which from about 500 to about 100,000 polylactone segments are introduced, the total weight of the polylactone segments being 100 M parts by weight of the geno-containing polymer or its hydride. , about 1 to about 200 weight■l・
parts, particularly preferably from about 1.5 to about 150 parts heavy.

If the molecular weight of the polylactone segment is less than about 300, the compatibility between the diene-containing polymer into which the polylactone segment has been introduced, or its hydride, and the polyester or its oligomer will deteriorate, resulting in a decrease in copolymerization efficiency; If the molecular weight exceeds about 200,000', the heat resistance of the resulting copolymer will decrease, which is not preferred.

Similarly, if the total weight of the polylactone segments is less than about 1 part by weight per 100 parts by weight of the diene-containing polymer or their hydride, the efficiency of copolymerization will decrease; If the amount is more than 200 parts by weight, it is not preferable because the heat resistance of the resulting copolymer decreases.

These diene-containing polymers in which polylactone segments have been introduced, or among their hydrides, diene-containing polymers, or diene-containing polymers in which polylactone segments have been introduced at one or both ends of their hydrogen components; or hydrides thereof are particularly preferred.

Among the copolymers used in the present invention, a method for producing a copolymer in which the connecting portion of the segments is composed of an amide bond represented by the general formula (U) -C1 In the production of the above copolymer, Examples of the olefinic polymer include a similar production method using an olefinic polymer in which an amine group is introduced into the terminal and/or side chain.

As the olefin polymer, for example, terminal and/or
Alternatively, there are diene-containing polymers having amine groups in side chains or hydrides thereof, which are produced, for example, by the method described below.

A living polymer of a diene monomer is reacted with ethylene oxide to terminally hydroxylate it, and then reacted with ammonia, and the hydroxyl group is converted into a compound having a plurality of, particularly preferably two, acyl halide groups, such as terephthalic acid dichloride. , or by reacting with phosgene or the like to introduce an acyl halide group at the end, and then reacting this with a diamino compound such as ethylenediamine, or by amidating the acyl halide group with liquid ammonia, an amidide of an alkali metal, etc. After that, hydrogenation and amination are performed.

A method of cyanoethylating the terminal hydroxylated diene-containing polymer with acrylonitrile and then hydrogenating it. Alternatively, it is treated with a halogenating agent such as thionyl chloride to form a halide, which is further amidated with liquid ammonia or an alkali metal amidide, and then hydrogenated.

A method in which a living polymer of diene monomer is reacted with p-bromomethylnitrobenzene, etc. to introduce a nitro group at the end, and then hydrogenated.

A method in which a living polymer, which is still a diene monomer, is reacted with carbon dioxide to introduce a carboxyl group at the end, and this is then reacted with a diaminated material such as hexamethylene diamine.

The terminal carboxylated diene-containing polymer is reacted with a halogenating agent such as thionyl chloride to convert the terminal to an acyl halide group, and then reacted with a diamino compound such as ethylenediamine, or the acyl halide group is converted to liquid ammonia or an alkali. A method of amidation with a metal amidide, etc., and then hydrogenation.

In the method exemplified above, when a hydride of a diene-containing polymer is used, the diene-containing polymer may be hydrogenated in advance, or, if possible, hydrogenated when introducing an amine group.

As a diene-containing polymer having an amine group at the terminal and/or side chain, or its hydride, the molecule! 1t is about 300 to about 7 Q O,000, particularly preferably about 500 to about 500,000, and the proportion of amine groups is about U,02 to about 95 per 1,000 carbon atoms. about 0.03 to about 60
These are preferably used. If the molecular weight is less than about 300, it is not preferred because the excellent properties of diene-containing polymers and their hydrides, such as low-temperature flexibility, are no longer exhibited.

Moreover, if the molecular weight exceeds about 700,000, the compatibility with the polyester or its oligomer to be copolymerized with the diene-containing polymer or their hydride becomes poor, and the efficiency of copolymerization decreases, which is not preferable.

Also, the number of amine groups is approximately 0.0 per 1,000 carbon atoms.
If the number is less than 2, the copolymerizability of the polyester with the oligomer is lowered, which is not preferable.

If it exceeds about 95, it is not preferable because it tends to cause gelation during copolymerization with polyester or its oligomer.

Among these diene-containing polymers or hydrides thereof into which amine groups have been introduced, particularly preferred are diene-containing polymers or hydrides thereof in which amino groups have been introduced at one or both ends of the diene-containing polymers or hydrides thereof. It is.

[Configuration of olefin polymer (C)] The olefin polymer (C) includes an α-olefin elastomer,
Preferred examples include α-olefin crystalline polymers and diene-containing polymers. Among these, the low-crystalline α-olefin-based elastic polymer is a low-crystalline elastic polymer whose main component is an α-olefin component unit, which has two or more α-olefin component units. In some cases, it may consist solely of the α-olefin component, or it may contain a small amount of diene component units in addition to the α-olefin component. α constituting the base α-olefin elastic polymer
- The content of olefin component units is usually 80 mol% or more,
Preferably, the content is 85 mol% or more, and the content of the diene component is usually O to 20 mol%, preferably 0 to 15 mol%. Other physical properties of the base α-olefin elastomer include crystallinity of usually 20% or less, preferably in the range of 19 to 1%, and a M/L/17 o-rate at 190°C [MFR19o- c] is usually 0.01 to 50y/10, preferably 0.05
The glass transition temperature is generally -10°C or lower, preferably -20°C or lower. Here, the α-olefin component units of the constituent components include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, etc. can be exemplified, and the diene component unit is 1,4-hexadiene,
Examples include non-conjugated diene components such as dicyclobentadiene, 5-:r-f')f, 2-norbornene, and 2,5-turbonasiene, and conjugated diene components such as butadiene, isoprene, and piperylene. The base α-
Examples of olefin-based elastic polymers include ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/4-methyl-1-pentene copolymer, ethylene/propylene copolymer,
1-hexene copolymer, ethylene/1-octene copolymer, ethylene/1-decene copolymer, propylene/ethylene copolymer, propylene/1-butene copolymer, propylene/4-methyl-1-pentene α-copolymers, propylene/1-octene copolymers, propylene/1-decene copolymers, propylene/1-dodecene copolymers, etc.
Olefin elastic copolymer, ethylene/propylene/1.
4-hexadiene copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene/
5-ethylidene-2-norbornene-1-14 copolymer, ethylene liflopylene-2,5-turbonasiene copolymer, ethylene/1-butene/dicyclopentadiene copolymer, ethylene/1-butene/1,4- Examples include hexadiene copolymers and α-olefin/non-conjugated diene elastic copolymers such as ethylene/1-butene/5-ethylidene-2-norbornene copolymers.

Among these α-olefin elastic polymers, ethylene/propylene copolymer, propylene/ethylene copolymer, ethylene/1-butene copolymer, and propylene/1-butene copolymer are particularly preferably used. .

A modified α-olefin elastomeric polymer obtained by further modifying part or all of the sweet α-olefin elastomeric polymer with an unsaturated carboxylic acid or its derivative can be used together with an α-olefin polymer. can.

Such modified α-olefin elastomeric polymers contain unsaturated carboxylic acid or its derivative component units per 100 parts of the base α-olefin elastomer containing α-olefin component units as a main component. is usually graft copolymerized in a proportion of about 0.01 to about 10 parts by weight,
Further, its crystallinity is usually within a range of about 20% or less. These polymers have a melt flow rate at 190°C [14FR1? o℃] is about 0.01 to about 501/
It is preferable that it is in the range of 10 mn, and furthermore, α-
Grafting an unsaturated carboxylic acid monomer or its derivative component unit in a range of about 0.05 to about 5 parts by weight to 100 parts by weight of a base α-olefin elastomer containing an olefin component unit as a product component. Must not be copolymerized, have a crystallinity of 19% or less, and have a melt flow rate (MFR19o-c) of 0.05 at 190°C.
Or 21J! It is preferable to be in the range of i'/10m1M. Furthermore, other physical properties of the modified α-olefin-based elastic polymer include that the molecular weight distribution (Mw/jJn) is usually 1.
in the range of 5 to 50, preferably 2 to 30,
Glass transition temperature is usually -10°C or lower, preferably -20°C
The range is below ℃.

When the grafting ratio of unsaturated carboxylic acid or its derivative component units in the modified α-olefin elastomeric polymer increases beyond 10 g, the degree of crosslinking of the graft modified product increases, and even when blended into polyester, the degree of crosslinking increases. The effect of improving the impact resistance of the composition tends to be poor. When the melt flow rate at 190°C of the modified α-olefin elastic polymer is less than 0.01y/1omtπ, the impact resistance and melt viscosity of the polyester decrease, and when it exceeds 50f/10mm, the The effect of improving the impact resistance tends to be smaller.

The α-olefin crystalline polymer, which is another example of the olefin polymer (C), is a crystalline polymer containing α-olefin component units as a main component, and contains one or more α-olefin units. It may be composed only of olefin component units, or may contain a small amount of polar vinyl monomer component units in addition to α-olefin component units. α constituting the base crystalline α-olefin polymer
- The content of olefin component units is usually 6 [ ] mol % or more, preferably in the range of 70 to 100 mol %, and when polar vinyl monomer component units are included, the content is usually 0 to 40 mol %, preferably ranges from 0 to 30 mol%. The physical properties of the α-olefin crystalline polymer are that the degree of crystallinity is usually 6o% or more, preferably in the range of 88 to 65%, and the melt flow rate (MFR + 9o-c) at 190°C
'l 50! / i Q +n#+1goodt(
, l: in the range of 0.05 to 20g710m, and the melting point is usually 6° to 600°C, preferably 80 to 2
It is in the range of 80°C. Here, the constituent α-olefin component units include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-totenane, etc. can be expressed as I+11, and the polar vinyl monomer component units include vinyl acetate, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester,
Examples include fm/metal salts of acrylic acid and various metal salts of methacrylic acid. These α-olefin crystalline polymers include polyethylene, polypropylene/, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-1-
Butene copolymer, ethylene/1-pentene copolymer, ethylene/4-methyl-1-pentene copolymer, ethylene/1-ocdene copolymer, ethylene/1-f-cen-
144i combination, ethylene/1-dodecene copolymer, ethylene/vinyl acetate copolymer, ethylene/methyl (meth)acrylate copolymer, ethylene/(meth)acrylic acid copolymer, ethylene/(meth)acrylic acid Examples include salt copolymers. A modified α-olefin crystalline polymer obtained by further modifying part or all of the α-olefin crystalline polymer with an unsaturated carboxylic acid or a derivative thereof is an α-olefin crystalline polymer. It can be used instead of coalescence or together with an α-olefin crystalline polymer.

The modified α-olefin crystalline polymer usually contains about 0.01 to about 10 parts by weight per 100 parts by weight of the base α-olefin crystalline polymer containing α-olefin component units as a main component. The crystallinity is usually in the range of 30% or more, and the crystallinity is 19% or more.
Melt flow rate CMFRno=c at 0°C)
is usually in the range of about 0.01 to 50 g/10M.

Further, it is obtained by graft copolymerizing in a range of about 0.05 to about 7 parts by weight with respect to 100 parts by weight of a base α-olefin crystalline polymer containing α-olefin component units as a main component. The melt flow rate at 190°C is from about 0.05 to about 2.
Preferably, it is in the range of 0f/10m. The modified α-
Other physical properties of the olefin crystalline polymer are as follows:
(Mw/Mn) is preferably in the range of 1.5 to 50, particularly 2 to 30, and the melting point is generally
A temperature range of 60 to 00°C, particularly 80 to 280°C is preferred.

The base α-olefin crystalline polymer and the following Section 111
A modified crystalline α-olefin polymer can be obtained by reacting the No. 11 carboxylic acid or its derivative according to the method described below. Examples of the unsaturated carboxylic acid or its derivative component unit of the craft monomer component constituting the modified α-olefin elastic polymer and the modified α-olefin crystalline polymer include acrylic acid, methacrylic acid, and α-edyl acrylic acid. , maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydro-7-acetic acid, endocys-bicyclo(2
, 2, 1) Heb [・-5-ene-2,6-dicarboxylic acid (Nadic acid), Methyl-endocytosis bi/liguch [2
,2,1]hept-5-ene-2,3-dicarboxylic acid (
Examples include unsaturated dicarboxylic acids such as methylnadic acid, and derivatives of unsaturated dicarboxylic acids such as acid norides, amides, imides, acid anhydrides, and esters of 1+1+ dicarboxylic acids. Examples include maleyl, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Among these, unsaturated dicarboxylic acids and their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are particularly preferred.

A graft monomer selected from the unsaturated carboxylic acid derivatives is added to an α-olefin elastomer.
Various conventionally known methods can be employed to produce the modified α-olefin elastomeric polymer or modified α-olefin crystalline polymer by graft copolymerization with the olefin crystalline polymer. . For example, for the α-olefin elastomeric polymer, the α-olefin crystalline polymer is melted in a bath and graft copolymerized by adding a kraft monomer, or alternatively, the α-olefin crystalline polymer is dissolved in a solvent and a graft monomer is added. There is a method of graft copolymerization. In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator. The grafting reaction is usually carried out at a temperature of 60 to 650°C. The ratio of the radical initiator used is usually about 0.01 parts by weight per 100 parts by weight of the elastomeric α-olefin polymer or the crystalline α-olefin polymer.
and 20xc parts. As the radical initiator, organic peroxides, organic bere esters, azo compounds, etc. can be used.

In the thermoplastic resin composition of the present invention, the unmodified or
is the ratio of the melt flow rate (MFR+9o-c) of both at 190°C when blending a modified α-olefin elastomeric polymer and the unmodified or modified α-olefin crystalline polymer 't91'. , (MF'R elasticity t
, o'c) / CMFR crystallinity 190. It is generally desirable to adjust the value of U, U to a value in the range of 1 to 100, particularly in the range of about 0.5 to 50.

Other examples of olefinic polymers (C)O include diene-containing polymers and hydrides thereof. Examples of the polymer include homopolymers or copolymers obtained by polymerizing at least one monomer selected from 1,3-butadiene, 1,3-pentadiene, chloroprene, and isoprene, or hydrides thereof. Diene-containing polymers include polymers using catalysts such as radicals, cations, anions, and coordinating anions.
In the present invention, it can be used without particular limitation. For example, it can be prepared by a living anion polymerization method using an initiator such as organic lithium, or by radical polymerization using a peroxide as an initiator. It is also possible to employ a method of copolymerizing a small amount of other monomers together with the diene monomer.

In this case, the proportion of other monomers copolymerized with the diene monomer is about 40 mol% or less, preferably about 60 mol% or less of the total monomers. Other copolymerizable monomers include styrene, α-methylstyrene,
O- or p-vinyltoluene, vinylxylene, acrylonitrile, methyl acrylate, ethyl acrylate,
Examples include vinyl monomers such as butyl acrylate, methyl methacrylate, and vinylpyridine.

As these diene-containing polymers and hydrogenated diene-containing polymers, polybutadiene, polyisoprene, and hydrides thereof are particularly suitable.

[Thermoplastic resin composition]

The composition of the present invention comprises polyester (A) 5 to 95M
itl part Olefin polymer/polyester copolymer (B) 0.1 to 90 parts by weight and olefin polymer (C) 0 to 95 parts by weight (A) +
(B) + (C) totaling 100 parts by weight).

Among them, compositions containing polynisder (A) as the main component include 55 to 95 parts by weight of polyester (A), 0.1 to 90 parts by weight of olefin polymer/polyester copolymer (B), and olefin polymer (C) O. A composition comprising from 45 parts by weight (with a total of 100 parts by weight of A) + (B) + (C)) is suitable.

Among compositions containing polyester (A) as a main component, in embodiments in which only copolymer (B) is blended, properties such as impact strength, boiling water resistance, and elongation properties of polyester (A) are improved. Furthermore, in an embodiment in which the olefin polymer (C) is blended with the copolymer (B), in addition to the above effects, the compatibility between the polyester (A) and the olefin polymer (C) is improved; Impact strength is improved and crystallization speed is also faster.

On the other hand, as a composition containing an olefin polymer (C) as a main component, 5 to 45 parts by weight of polyester (A) olefin polymer/polyester copolymer 1 (B)
0.1 to 90 parts by weight and an olefinic polymer (
C) 55 to 95 parts by weight (Tatashiku A) + (B) -
Particularly preferred are compositions comprising a total of 100 parts by weight of 4-(C). In a composition containing the olefin polymer (C) as a main component, the tensile strength and rigidity of the olefin polymer (C) are improved.

In addition to the above-mentioned essential components, the thermoplastic resin composition of the present invention may optionally contain antioxidants, ultraviolet absorbers, photoprotectants,
It is also possible to incorporate phosphite stabilizers, peroxide decomposers, basic adjuvants, nucleating agents, plasticizers, lubricants, antistatic agents, flame retardants, pigments, dyes, and the like. In addition, other polymers such as polyamides such as nylon 6, polycarbonates, polyacetals, polysulfones, polyphenylene oxides, fluororesins, silicone resins, epoxy resins, etc. may be blended into the composition of the present invention to the extent that their physical properties are not impaired. You can also do it.

It may be preferable to use a filler in combination with the composition of the present invention, and fillers include carbon black, carbon fiber, asbestos, glass fiber, potassium titanate whisker, mica, kaolin, talc, silica, etc. , inorganic fillers such as silica alumina, fluororesins such as Teflon,
Suitable fillers include fully aromatic polyamide fibers such as Kevlar, and phenolic resin fibers.

When blending these fillers, the above (A) + (B)
+ (c) It is preferable to mix the filler in a proportion of about 1 to about 200M, 1 part by weight, particularly about 2 to about 150 parts by weight, per 100 parts by weight of (c).

The thermoplastic resin compositions of the present invention are prepared by melt-mixing in a variety of ways. Examples include a method in which two optional components are premixed and then mixed with the remaining other components, or a method in which two essential components are simultaneously mixed with other remaining components added as needed. Moreover, the above-mentioned additives, such as antioxidants, can be added at any of these stages as necessary.

The thermoplastic resin composition of the present invention can be molded into various shapes by various conventionally known melt molding methods depending on the intended use. Examples include injection molding, extrusion molding, compression molding, foam molding, and casting molding, and are used for a wide range of applications including automobile parts, electrical appliances, electrical parts, and packaging materials. Next, the present invention will be explained in more detail with reference to Examples.

In the Examples, the thermoplastic resin composition and its constituent units, polyester (A), olefin polymer/polyester copolymer (B), and olefin polymer (C), were evaluated by the following method.

Molding: The dried thermoplastic resin composition was molded at 15cnx in a nitrogen atmosphere using a press molding machine (molding temperature = 290°C).
15cmxO, 05crrL(A) and 15mx
A sheet having a shape of 15 m x O, 2 cfnc B) was produced. The thermoplastic resin composition blended with glass fiber was molded using an injection molding machine (L5-35P manufactured by Toshiba Machinery Co., Ltd.) under conditions of a resin temperature of 260°C, a mold temperature of 60°C, and a curing time of 60 seconds. A JIS No. 2 dumbbell test piece with a thickness of 2 mm and a notched Izot test piece were prepared.

Tensile test: A dumbbell-shaped test piece with a length of 5α and a width of parallel part of 0.5 art punched from the sheet (A) or a JI 82 dumbbell test piece molded with an injection molding machine was used with an Instron tensile tester model. 26℃ using 1122
The crosshead speed was 50 mm/min.

Izot impact strength: Measured at 23° C. according to JIS K7110 using Test 1, which is a stack of two sheets of (B) or Izot test pieces molded with an injection molding machine.

Compatibility: Microtome (Ivansono (Lesha GMT2)
B) After cutting the sheet of (A) using f:, the microstructure of the cross section of the sample was photographed using a scanning microscope (JSM-2583 manufactured by JEOL Ltd.). From this photograph, the average diameter of the olefin polymer or polyester particles dispersed in the sample was measured.

Molecular weights other than the niolefin polymer (C) were measured using GPC, model 150C (o-chlorophenol solvent, 70°C) manufactured by Waters. Regarding polyethylene terephthalate and the olefin polymer/polyethylene terephthalate copolymer, which are the s acid units of the composition, the number average molecular weight in terms of polyethylene terephthalate was calculated. That is, various polyethylene terephthalates having different intrinsic viscosities were measured by GPC=i, and the number average molecular weight Mn in terms of standard polystyrene was calculated. On the other hand, [η]=3.
Calculate the number average molecular weight Mn of these polyethylene terephthalates using the viscosity formula 0xlOMn, and calculate Mn and M
Conversion formula for n % Formula % (7) The number average molecular weight in terms of polyethylene terephthalate was calculated using the formula.

Boiling water resistance: A dumbbell-shaped test piece with the same shape as that used in the tensile test was punched out from the sheet (A), and it was
The molecular weight retention rate after being immersed for one day (weight average molecular weight after submerged immersion/weight average molecular weight before boiling water immersion zx100) was evaluated.

Crystallization rate' PerkinElmer DSC model ll
The crystallization rate was measured using a mold. In other words, Trial Testament 5
ntf/ was placed in a Zangle pan, held at 280°C for 6 minutes, and then lowered to 220°C at a rate of 80°C/min and held at that temperature. From the obtained crystallization curve, t 1/
2 (time required for crystallization to progress to half of the saturated crystallinity) was calculated.

Example 1 (Production of polyester oligomer) Terephthal y54os, 242 parts of ethylene glycol,
] - 0.164 parts of ethylamine was stirred in an autoclave at 240°C and 2.7 ky/c4 gauge pressure, and the reaction was carried out for 8 hours while removing the water produced. At the end of the reaction, phosphoric acid was added. 0.15 part of trimethyl was added.

In this way, a polyethylene terephthalate oligomer with an esterification rate of 92% was produced. (Production of polyolefin with amine group at the end) Cooler, dropping funnel,
A three-necked flask (1) equipped with a stirrer was charged with 63 parts of terephmeric acid dichloride and 600 parts of toluene under a nitrogen atmosphere, and stirred at 1 to make the solution uniform. Actually,”
Hydrogenated polybutadiene CI-3000 with hydroxyl groups at both ends (Nippon Soda Membrane, KOH value: 28) 20
A solution of 0 parts of pyridine and 54 parts of pyridine dissolved in 700 parts of toluene was charged into a dropping funnel, and the mixture was added dropwise into the flask with strong stirring using a stirrer, and the reaction was carried out at 50°C for 2 hours. In a separate flask sealed with nitrogen, add hexamethylene diamine 2.
After preparing and dissolving 10 parts and 1100 parts of I. Chef,
The reaction solution in the flask←) was added dropwise, and the reaction was carried out at 50°C for 2 hours. After the reaction solution was passed through Δ4 to remove most of the pyridine hydrochloride, the solvent was evaporated. The obtained product was dissolved in hexanoate, and the operations of washing with water, filtration, and removing the solvent were repeated until the product became transparent. This product was dried in a vacuum dryer for a day and night to obtain hydrogenated polybutadiene having an amine group at the end. 0.5 g of this hydrogenated polybutadiene was dissolved in 25 mlK of I.luene, and 0.5 g of this hydrogenated polybutadiene was dissolved using thymol blue as an indicator. As a result of titration of IN p-)luenesulfonic acid with an In-cresol bath solution, the amount of terminal amino groups was 0.16 meq/g polymer. As a result, the ratio of amino groups (e) corresponds to about 2 per 10[]O carbon atoms in the hydrogenated polybutadiene.

Note that substantially anhydrous reagents and solvents were used in the above reactions.

(Synthesis of copolymer of polyester and polyolefin) 510 parts of polyethylene terephthalate oligomer synthesized by the above method, 90 parts of hydrogenated polybutadiene having amino groups at both ends, and 0.12 parts of antimony trioxide were charged into a reactor. The mixture was reacted at 27 parts C. for 1 hour with stirring under a nitrogen atmosphere. Next, the pressure of the system was gradually reduced over 15 minutes, and the reaction was finally carried out for 4 hours at a reduced pressure of 0.7 mmHg or less. As a result of measuring the molecular weight of the produced polymer using GPC (0-chlorophenol solvent, 70°C, manufactured by Waters, model 150G), the number average molecular weight in terms of polyethylene terephthalate was 32,900. Intrinsic viscosity (0 - 1: I lua / -ru, 25℃)
LtO was 93 dl/g. The produced polymer was processed using a rotor speed mill (manufactured by FrltSCh, Pu1uv).
After pulverizing using erisette 14), the mixture was placed in a Soxhlet extractor and extracted with toluene for 8 hours.

The ratio of the extracted polymer to the hydrogenated polyfridiene used in the reaction (hereinafter referred to as toluene extraction rate) is 27
% by weight. The copolymer composition ratio (weight ratio of hydrogenated polybutadiene to polyethylene terephthalate) calculated from the toluene extraction rate was 11/89.

(Manufacture of thermoplastic resin composition) Polyethylene terephthalate resin (Kanegu Gosen Co., Ltd.)
manufactured by Velvet EFG-7, intrinsic viscosity: 0.80dl/
g) 169.2 parts, propylene/ethylene copolymer, (propylene composition: 59 mo1%, intrinsic viscosity measured using decalin at 165°C: 2.90 d#/g)
30.8 parts, 20 parts of hydrogenated polybutadiene/polyethylene terephthalate copolymer synthesized by the above method, and 20 m
Using a ml extruder (L/D=28, Dalmage type screw), the resin temperature was 260°C and the screw rotation speed was 60r.
Melt blending was carried out under the conditions of pln. The physical properties were investigated and the results are shown in Table 1.

Examples 2 to 4 When producing the thermoplastic resin composition in Example 1,
A blend sample was prepared under the same conditions as in Example 1 except that the blend ratios of polyethylene terephthalate resin, propylene/ethylene copolymer, and hydrogenated polybutadiene/polyethylene terephthalate copolymer were changed. The results of measuring the physical properties are shown in Table 1.

Example 5 When producing the thermoplastic resin composition in Example 1,
Ethylene-propylene copolymer (ethylene composition: 3 inlo/%,
Intrinsic viscosity measured using decalin at 135°C: 2.1
A polyester composition was produced in the same manner as in Example 1, except that 60.8 parts of 9 dl/g) were used. Table 1 shows the results of measuring the physical properties.

Example 6 (Production of polyolefin having a polylactone segment at the end) Anionic polymerization of ε-caprolactone was carried out in a toluene solvent using n-butyllithium as an initiator to obtain a molecular weight of 20.
00 poly-ε-caprolactone was synthesized. A dropping funnel containing 200 parts of hydrogenated polybutadiene GI-3000 having hydroxyl groups at both ends and 52 parts of pyridine dissolved in 1500 parts of toluene was added to a reactor containing 61 parts of terephthalic acid dichloride in 500 parts of L-shelf. The reaction mixture was added dropwise using a nitrogen atmosphere at 50° C. for 2 hours.

Then 600 parts of the above poly-ε-caprolactone
A solution dissolved in 1,000 parts of l-toluene was added dropwise, and the mixture was reacted at 50° C. for 2 hours in a nitrogen atmosphere. After the reaction solution was passed through the mouth to remove most of the pyridine hydrochloride, it was precipitated into methanol. The precipitate was dissolved in hexanoate and washed with water, then precipitated in acetone and the insoluble portion was collected. Repeat the above purification operation until this insoluble part becomes transparent, and add poly-ε-
Hydrogenated polybutadiene with caprolactone segments was isolated.

As a result of elemental analysis (quantification of oxygen) of the hydrogenated polybutadiene whose terminals were modified in this way, it was found that it contained about 51% poly-ε-caprolactone. This result shows that poly-ε per 100 parts by weight of hydrogenated polybutadiene
- corresponding to 104 parts by weight of caprolactone segment.

(Manufacture of olefin polymer/polyester copolymer) 85 parts of polyethylene terephthalate oligomer synthesized by the same method as in Example 1, 15 parts of hydrogenated polybutadiene having poly-ε-caprolactone segments at both ends synthesized by the above method. part and antimony trioxide 0.0
A reaction was carried out under the same conditions as in Example 1 except that 2 parts were used to synthesize a hydrogenated polybutadiene/polyethylene terephthalate copolymer. The number average molecular weight of the produced polymer was 29,300 in terms of polyethylene terephthalate.

Moreover, the toluene extraction rate was 26%. The copolymer composition ratio (weight ratio of hydrogenated polybutadiene and polyethylene terephthalate) calculated from the toluene extraction rate is 12/88.
Met.

(Manufacture of thermoplastic resin composition) The same conditions as in Example 1 were performed as shown in Table 1 except that the copolymer synthesized by the above method was used instead of the hydrogenated polybutadiene/polyethylene terephthalate copolymer used in Example 1. A sample with the blend ratio shown was prepared. Table 1 shows the results of measuring the physical properties.

Example 7 (Production of polyolefin having a poly-ε-caprolactone segment at the end) Anhydrous Be/Zen 700 was placed in a reactor equipped with a cooler and a stirrer.
130 parts of isoprene and stirred vigorously for 5 ec.
A bexane solution containing 0.64 parts of -butyllithium was added dropwise, and the mixture was reacted for 5 hours at room temperature under an argon atmosphere. The reactor was then cooled in a water bath to convert the engineered ethylene oxide to 16
The mixture was added dropwise and reacted at 5° C. for 2 hours, and then at room temperature for 12 hours. The reaction solution was precipitated into a large excess of methanol to isolate polyisoprene having hydroxyl groups at its terminals. As a result of GPC measurement using THF solvent, the number average molecular weight was approximately 10,000 in terms of polyisoprene. The concentration of the ester group produced by reacting this polyisoprene with acetyl chloride was determined by IR (using the absorption intensity ratio of IR absorption due to the double bond between the carbonyl of 1740crIL and the carbon of 1640cIn), and the result was 0.013 mol%. I failed. 0 parts of this polyinoprene filter, 700 parts of cyclohexane, and 15 parts of palladium on a carbon carrier (5% palladium supported) were charged into an autoclave and the hydrogen pressure was 100 ky/cr.
A reaction was carried out at 140°C for 4 hours. The reaction solution was filtered, washed with water, and then precipitated into methanol to obtain hydrogenated polyimprene having hydroxyl groups at the terminals. The iodine value of this hydrogenated polyimrene was 11. In Example 6, hydrogenated polybutadiene GI-
The same reaction as in Example 6 was carried out except that the thus synthesized hydrogenated polyisoprene having a hydroxyl group at the end was used instead of 6000, and a hydrogenated polyisoprene having a poly-ε-caprolactone segment at the end was synthesized. .

(Manufacture of olefin polymer/polyester copolymer) The same procedure was carried out as in Example 6 except that 15 parts of hydrogenated polyisoprene synthesized by the above method was used instead of hydrogenated polybutadiene having poly-ε-caprolactone segments at both ends. A polycondensation reaction was carried out under the same conditions as in Example 6 to synthesize a hydrogenated polyisoprene/polyethylene terephthalate copolymer.

As a result of toluene extraction, the extraction rate was 40%, and the copolymer composition ratio (weight ratio of hydrogenated polyisoprene and polyethylene terephthalate) was U9/91.

(Production of thermoplastic resin composition) Example 5 was repeated except that the hydrogenated polyisoprene/polyethylene terephthalate copolymer synthesized by the above method was used instead of the hydrogenated polybutadiene/polyethylene terephthalate copolymer. Blend samples having the blend ratios shown in Table 1 were prepared in the same manner. Table 1 shows the results of measuring the physical properties.

Example 8 (Production of olefin polymer/polyester copolymer) 10.2 parts of terephthalic acid dichloride and 6 parts of toluene were placed in a three-bottle flask equipped with a condenser, dropping funnel, and stirrer.
00 parts were charged and dissolved. A solution prepared by dissolving 100 parts of hydrogenated polybutadiene GI-3000 having hydroxyl groups at both ends and 95 parts of pyridine in 600 parts of toluene was added dropwise into a funnel via a dropping funnel, and the mixture was heated at 50°C under a nitrogen atmosphere for 2 hours.
Allowed time to react.

Poly-ε-caprolactone (Placcel H manufactured by Daicel Chemical Industries, Ltd.) with a molecular weight of about 10,000 was added to this reaction solution.
-1) and 600 parts of toluene were added, and the mixture was heated to 60°C.
After reacting for 2 hours, 5 parts of phenol was added and the reaction mixture was reacted for 60 minutes.
A copolymer having a polybutadiene segment was obtained by hydrogenating the ε-cabrolactone segment (Production of thermoplastic resin composition) In Example 1, in place of the hydrogenated polybutadiene/polyethylene terephthalate copolymer, Samples having the blend ratios shown in Table 1 were exploded under the same conditions as in Example 1 except that the hydrogenated polybutadiene/poly-C-caprolactone copolymer synthesized in the above reaction was used. Table 1 shows the results of measuring the physical properties.

Example 9 (Production of polyolefin having a phenyl ester group at the end) A reactor containing 61 parts of terephthalic dichloride and 500 parts of toluene was charged with 200 parts of hydrogenated polybutadiene Cl-3000 having hydroxyl groups at both ends, and 5 parts of pyridine.
A solution of 2 parts dissolved in 1500 parts of toluene was added dropwise using a dropping funnel, and the mixture was reacted for 2 hours at 50°C in a nitrogen atmosphere. Next, phenol 101 was added dropwise and reacted at 50° C. for 2 hours in a nitrogen atmosphere. After the reaction solution was passed through the mouth to remove most of the pyridine hydrochloride, it was precipitated in tutanol. The precipitate was dissolved in hexane, passed through the mouth, washed with alkaline water, and then precipitated in acetone to recover insoluble matter.

The above purification operation was repeated using a strainer in which the insoluble portion became transparent, and hydrogenated polybutadiene having phenyl ester groups at both ends was isolated.

(Production of olefin polymer/polyester copolymer) In Example B, hydrogenated polybutadiene having phenyl ester groups at the ends synthesized by the above method was used instead of hydrogenated polybutadiene having poly-ε-caprolactone segments at both ends. A polycondensation reaction was carried out in the same manner as in Example 6 except that a hydrogenated polybutadiene/polyethylene terephthalate copolymer was synthesized. However, instead of 0.02 parts of antimony trioxide, 0.0 parts of tetrabutyl titanate is added.
One copy was used. As a result of toluene extraction, the extraction rate was 26%,
Copolymer composition (hydrogenated polybutadiene and polyethylene).

(Manufacture of thermoplastic resin composition) In Example 1, the same conditions as in Example 1 were used as shown in Table 1, except that the copolymer synthesized by the above method was used instead of the hydrogenated polybutadiene/polyethylene terephthalate copolymer. Blend ratio samples were prepared. Table 1 shows the results of measuring the physical properties.

Example 10 (Manufacture of polyester oligomer) 100 parts of polyethylene terephthalate resin (EFC, -7 manufactured by Kanebo Gosen Co., Ltd.) with an intrinsic viscosity of 0.80 d/l'/g and 4 parts of terephthalic acid were placed in a flask with branches. The mixture was reacted at 275° C. for 2 hours with stirring under a nitrogen atmosphere. Next, the pressure of the reaction solution was gradually reduced over 20 minutes, and finally the reaction was carried out at a pressure of 0.3 mmHg or less for 5 hours.

Precisely weigh 0.5 g of the reaction product, add benzyl alcohol 6
After dissolving in a mixed solvent of 0 ml and 10 ml of tonitrobenzene, titration was performed with benzyl alcoholic KOH using phenol red as an indicator.

As a result, it was found that the amount of terminal carboxyl groups in this polyester oligomer was 0.59 milliequivalents/g polymer.

(Manufacture of olefin polymer/polyester copolymer) 94 parts of the hydrogenated polybutadiene having an amino group at the end synthesized in Example 1 and 25.6 parts of the polyester oligomer synthesized by the method described in 2 were charged into a flask with a side arm, and nitrogen was added. The reaction was carried out at 270° C. for 2 hours under strong stirring in an atmosphere.

In step V), gradually reduce the pressure of the reaction system to a final pressure of 0.3 mm.
The reaction was carried out for 8 hours at a pressure below Hg. The obtained rubbery product was freeze-pulverized under liquid nitrogen, then placed in a Soxhlet extractor and extracted with hexane for 8 hours. Hexane extraction rate [(weight of polymer extracted with hexane)/(weight of charged hydrogenated polybutadiene) xloo:] is 20.0%
Met. The copolymer composition ratio (weight ratio of hydrogenated polybutadiene to polyester) calculated as the hexane extraction rate was 75/25.

(Manufacture of thermoplastic resin composition) Table 1 was prepared under the same conditions as in Example 1 except that the copolymer synthesized by the above method was used instead of the hydrogenated polybutadiene/polyethylene terephthalate copolymer used in Example 1. Samples with the blend ratio shown in were prepared. Table 1 shows the results of measuring the physical properties.

Example 11 Polyethylene terephthalate resin (Kanebo Gosen Co., Ltd.)
manufactured by EGG-7 > 1692 parts, 304 parts of the propylene-ethylene copolymer used in Example 1, 200 parts of the hydrogenated polybutadiene-polyethylene terephthalate copolymer with the same composition as that used in Example 1, and the average length of 6-hole glass fiber (Nitto Boseki (manufactured by Sakaki, chip strand cs 6PE)
-231) 94' 5 parts were melt-mixed under the same conditions as in Example 1. The thus prepared blend sample was molded into a 2-thickness molding machine using an injection molding machine (Toshiba Machine Co., Ltd. MIS-35P).
A JIS No. 2 dumbbell test piece with a thickness of 2 mm and a notched Izot test piece with a thickness of 2 mm were prepared.

Table 1 shows the results of measuring the physical properties.

Comparative Examples 1 to 6 Polyethylene terephthalate (EFC-7) alone 1
Blend samples of EFG, -7 and the propylene/ethylene copolymer used in Example 1 or the ethylene/propylene copolymer used in Example 5 were prepared under the same conditions as Example 1, and the physical properties were determined. It was measured.

The results are shown in Table 2.

2-3-19 Minamiei, Otake City 0 shots Akira Honda Narimichi Waki 2-chome, Waki-machi, Kuga-gun, Yamaro Prefecture 4 number 8 0 shots Akira Nakano Misono-chome 2-3, Otake City

Claims (1)

[Scope of Claims] 0) 5 to 95 parts by weight of polynisdel (c), orene/fon-based polymer/polyester copolymer (13)
0.1 to 90 1 part of heavy weight and olefin polymer (QO to 95 part of heavy weight h1 part (self) + (U + ()
Kishi characterized by consisting of 004 old and loLI heavy 1st generation). Plastic resin composition. (2) Typical olefin polymer/polyester 4
([31] In [31], the connecting portion between the orange-based polymer segment and the polyester segment constituting the copolymer is formed by a bond selected from an ester bond, an amide bond, an imide bond, a urethane bond, a urea bond, or a carbonyl bond) The composition according to item il+ of the desired range of science WFMn, whose characteristic characteristic is that it is a copolymer having a structure of: (3) an olefinic polymer segment and a polyester
The connecting portion of the chill segment is represented by the following general formula (wherein R1
and R2 are hydrogen or lower alkyl group, m
must be a positive integer between 2 and 12, and X is between 0 and 1,00
It is an integer of 0. ) or an amide bond represented by H -C-N-(II) Olefinic polymer - polyester copolymer (6) is used. The composition according to item (2). (4) The total weight of the olein-based polymer segment: polyester segment (if the copolymer has a positive lactone segment, the polylactone segment is included). Claim (1) characterized in that a copolymer β) having a total weight ratio of 2.5/97.5 to 9515 is used.
The composition according to any one of items 1 to 3. (5) Olefin-based polymer/polyester copolymer (Claim No.
The composition according to any one of Items to Items (4). (6) A patent characterized in that the olefin polymer segment in the olefin polymer/polyester copolymer (2+) is a diene-containing polymer, an α-olefin elastic polymer, or an α-olefin crystalline polymer. A composition according to any one of claims (2) to (5). (Olefin polymer/polyester copolymer (
The polyester segment at θ can contain aromatic, cycloaliphatic and/or aliphatic dicarboxylic acids and aromatic, cycloaliphatic and/-! or aliphatic diol, polyester consisting of aromatic, alicyclic and/or aromatic oxycarboxylic acid, or polylactone (claim 2) The composition according to any one of Items to Items (6). (8) Polyester polyester or aromatic, alicyclic diol in which the polyester (A) is composed of an aromatic, alicyclic and/or aliphatic dicarboxylic acid and an aromatic, alicyclic and/or aliphatic diol The composition according to claim 1, wherein the composition is a polyester selected from the group consisting of polyesters composed of and/or aromatic oxycarboxylic acids. +91 When polyester (2) is soluble in 0-chlorophenol, the intrinsic viscosity [η] measured at 25°C using 0-chlorophenol as a solvent is 0.3 to 1.
0. The composition according to claim 1 or claim 8, wherein (IQ) The composition according to claim (1), wherein the olefin polymer (C) is an elastomeric α-olefin polymer, a crystalline α-olefin polymer, or a diene-containing polymer. 0υ Polyester (A) 55 to 95 parts, Olefin polymer/polyester copolymer 00.1; j
: 50 parts by weight of stone and olefin polymer (QO
to 45 parts by weight ((2) + (B) + IC
), and further contains 1 to 200 parts by weight of filler powder, according to claim (1). Composition of.