JP5791261B2 - Resin compatibilizer comprising polyoxazoline - Google Patents

Description

The present invention relates to a compatibilizer excellent in the mixing property of a polyester resin and a polyolefin resin. More specifically, the present invention blends an oxazoline-based aliphatic polymer, an oxazoline-modified polyolefin, an oxazoline-based aliphatic polymer and / or an oxazoline-modified polyolefin having an action of satisfactorily compatibilizing an aliphatic polyester resin and a general-purpose polyolefin resin. The present invention relates to a thermoplastic resin composition and a molded product of the resin composition.

Aliphatic polyesters such as polylactic acid and polybutylene succinate are biodegradable thermoplastic resins that can be produced from plant-derived raw materials, and thus are attracting attention in the plastics industry in terms of mitigating environmental problems such as global warming. It is expected to be used in various fields such as films, sheets, fibers, electronic equipment, and automobile parts. However, these biodegradable resins have high drawbacks such as high hygroscopicity and low hydrolysis resistance. In particular, hydrolysis of polylactic acid is a chain reaction, triggered by a carboxyl group at the end of the molecular chain, and proceeds markedly in a molten state of polylactic acid or in a high temperature / humid environment, resulting in molecular weight and melting. Physical properties such as viscosity and strength are reduced. Therefore, polylactic acid is not sufficiently stable as a plastic in the melt-molding stage, particularly in the product storage stage, and there is a problem that it is difficult to expand to general-purpose applications. In addition, molded products by injection molding of polylactic acid, etc. have high rigidity, but lack heat resistance, impact resistance and transparency, and do not have physical properties that can withstand the practical use of housings for home appliances, automobile parts, etc. It was.

In order to solve such problems, polymer blend methods widely used for improving the properties of general-purpose synthetic resins have been studied for improving biodegradable polyesters. The polymer blend is a method of incorporating a superior property of each polymer by mixing a plurality of polymers and imparting new properties. To compensate for the disadvantages of biodegradable resins, it has been proposed to blend with polyolefin resins that are lightweight and have excellent impact resistance, as well as good environmental properties such as chemical resistance, moldability, and water resistance. . However, because the polarities and crystal structures of the biodegradable resins such as polylactic acid and polyolefin resins are different, the miscibility (compatibility) of both resins is poor, and phase separation occurs even when blended. There was a problem that the performance improvement was not fully satisfactory.

Therefore, many attempts have been made to improve the compatibility between the aliphatic polyester and the polyolefin. For example, a method of blending polylactic acid and an epoxy group-containing olefin copolymer (Patent Document 1) has been proposed. Also, a method of blending an epoxy group-containing ethylene copolymer as a compatibilizing agent for a biodegradable resin and a polyolefin resin (Patent Document 2), a hydrogenated diene polymer and an olefin polymer each carrying a functional group that reacts with each other A method of simultaneously adding two components of a polymer (Patent Documents 3 and 4) and a method of using a polyolefin resin having an ester-forming functional group such as an acid anhydride (Patent Document 5) have been proposed. In these conventional technologies, compatibility with polyester resins such as polylactic acid is improved by using conventional modified polyolefins, but since the introduction rate of functional groups for modification is extremely low, impact resistance and heat resistance are still high. In terms of the improvement of moldability, the processability and long-term storage stability are not fully satisfactory, and there is room for further improvement by improving the modification rate (high functional group concentration).

However, it is not industrially easy to introduce a polar group such as a maleic anhydride group, a hydroxyl group, and an epoxy group or a reactive functional group uniformly at a high concentration at the terminal or side chain of the polyolefin. The most common method for producing modified polyolefins is graft polymerization of unsaturated compounds with specific functional groups on polyolefins, but usually the polyolefin is treated with radiation such as electron beams or ultraviolet rays or ozone to generate radicals. To react the unsaturated compound or to react the unsaturated compound in the presence of a radical generator such as an organic peroxide. For example, Patent Document 6 proposes a method of synthesizing an amide-modified polyolefin resin by melt-kneading a polyolefin resin and N-vinylalkylamide in the presence of an organic peroxide. In Patent Document 7, a polyolefin resin and a vinyl monomer having an oxazoline group such as 2- (4-N-acryloylaminophenyl) -2-oxazoline are melt-kneaded in the presence of an organic peroxide to synthesize an oxazoline-modified polyolefin resin. A method has been proposed. However, in these methods, since the polyolefin main chain is cleaved in the radical generation step, there is a problem that the molecular weight of the modified polyolefin is lowered and the strength of a molded product containing the modified polyolefin is also lowered.

Moreover, when the unsaturated compound monomer used for these radical grafting reactions has a high radical polymerizability, there are many by-products of homopolymer by homopolymerization of the monomer itself. On the other hand, when the radical polymerizability is low, problems such as odor and coloring due to unreacted residual monomers may occur.

In Patent Document 8, a resin having a terminal oxazoline group after reacting with a bifunctional organic carboxylic acid using a bisphenol A type epoxy resin to convert a terminal epoxy group into a carboxyl group and further reacting with bisoxazoline Is synthesized. In Patent Document 9, an oxazoline-modified polyolefin is synthesized by reacting polyethylene or polypropylene modified with maleic anhydride with bisoxazoline. However, in the products obtained by these methods, a large amount of raw materials or intermediates modified with unreacted carboxylic acid or acid anhydride remain, the manufacturing process is complicated, and much time and energy are consumed. There was a problem that productivity was low.

That is, in the conventional method of introducing a polar group or a reactive functional group into a polyolefin resin, the modification rate of the resulting modified polyolefin, that is, the introduction rate of a polar group or a reactive functional group is only a few weight percent, Further, when these modified polyolefins are used as compatibilizing agents, for example, when several weight percent of the modified polyolefin is added, the blending amount of polar groups and reactive functional groups is less than 1 weight percent in the target thermoplastic resin composition. (The functional group content in the final thermoplastic resin composition or molded article is 0.20% by weight when converted to the amide group monomer of Patent Document 6, and is 0.00 when converted to the oxazoline group monomer of Patent Document 7. 40% by weight), it cannot be said that satisfactory characteristics can be imparted.

In addition, a method has been reported in which a copolymer obtained from a vinyl monomer copolymerizable with a monomer having a reactive group is used as a polymer compatibilizing agent for blending a polyester resin and other types of resins (Patent Document 10). . Since this method can introduce 0.1 to 20% by weight of reactive groups, it is possible to increase the concentration of reactive groups (functional groups) compared to conventional modified polyolefins. A certain styrenic resin has poor compatibility with both polyester and polyolefin, and the reactive groups are likely to be locally concentrated. Especially when a high concentration is added, the moldability and processability of the friend resin due to a marked increase in melt viscosity are reduced. There is a problem that goes down.

From the viewpoint of improving the hydrolysis resistance of biodegradable resins such as polylactic acid among polyesters, the oxazoline group is most preferred as the reactive group used in the compatibilizing agent. This is because (1) when a carboxyl group is used, hydrolysis of polylactic acid is promoted. (2) when an acid anhydride is used, it reacts with the terminal hydroxyl group of polylactic acid to produce a carboxyl group. Similarly, hydrolysis of polylactic acid is promoted. (3) When an epoxy group is used, since the terminal carboxyl group and terminal hydroxyl group of polylactic acid react together, the effect of improving hydrolysis resistance is low, (4) When an isocyanate group is used, it mainly reacts with a terminal hydroxyl group of polylactic acid and cannot provide an improvement property of hydrolysis resistance by capping to a carboxyl group. ) Amide groups, hydroxyl groups, etc. have low reactivity with carboxyl groups at the molding temperature of polylactic acid around 200 ° C., while reactivity is improved at high temperatures above 280 ° C. (6) Oxazoline groups are characterized by high reactivity with carboxyl groups, sufficient reaction at the molding temperature of polylactic acid, and reaction with alcoholic hydroxyl groups. For example, the hydrolysis resistance of polylactic acid is improved by capping terminal carboxyl groups of polylactic acid intensively.

However, polyester resins and polyolefins that have a high concentration of oxazoline groups, exhibit excellent compatibility with both aliphatic polyester resins and polyolefin resins, and can impart good moldability, sufficient impact resistance, and hydrolysis resistance High performance compatibilizers used in resin blends have not been obtained by conventional techniques.

JP 9-316310 A JP 2007-277460 A WO2008 / 023758 JP 2009-227982 A JP 2007-326961 A Japanese Patent No. 3368651 JP-A-6-287222 Japanese Patent Laid-Open No. 3-269034 Japanese Patent Laid-Open No. 2008-19298 Japanese Patent Laid-Open No. 10-7922

The present invention solves the above problems, has excellent compatibility with various aliphatic polyester resins and general-purpose polyolefin resins, and improves the compatibility of both resins when blended with a polyester resin and a polyolefin resin by adding a small amount. It is an object of the present invention to provide a compatibilizing agent that is particularly excellent in the effect to be caused.
In addition, the present invention is formed from a blend of an aliphatic polyester resin and a polyolefin resin blended with such a compatibilizing agent, and has excellent mechanical properties such as impact resistance and strength, heat resistance, and hydrolysis resistance. It is an object of the present invention to provide a thermoplastic resin composition having good moldability and a molded product obtained from the resin composition.

As a result of intensive studies to solve these problems, the present inventors have found that a specific oxazoline-based aliphatic polymer and / or a modified polyolefin modified with the polymer can be used for aliphatic polyester resins and general-purpose polyolefin resins. It has been found that it has an excellent compatibility improvement effect. Specifically, in the general formula (1) (wherein R ₁ is a hydrogen atom or a methyl group, R _{2 to} R ₅ are the same or different and are a hydrogen atom or a linear or branched alkyl having 1 to 3 carbon atoms. R ₆ is a hydrogen atom or a methyl group, R ₇ is a linear, branched or cyclic alkyl or 2-alkenyl group having 1 to 20 carbon atoms, R ₈ is a hydrogen atom or a methyl group, R ₉ and R ₁₀ are the same or different and each represents a hydrogen atom, a linear, branched or cyclic alkyl group or a 2-alkenyl group having 1 to 20 carbon atoms, and the blending amount of the structural unit a is 5 to 100 mol%. The combined amount of the unit b and the structural unit c is 95 to 0 mol%.) The oxazoline-based aliphatic polymer represented by the formula (b) has an excellent compatibility improving effect on the aliphatic polyester resin and the general-purpose polyolefin resin. Heading was. In addition, a modified polyolefin having a high concentration of oxazoline groups can be obtained by reacting a polyolefin having a terminal or side chain modified with a functional group capable of reacting with an oxazoline such as a carboxyl group, and the polymer, It has been found that polyolefins also have an excellent compatibility improving effect on aliphatic polyester resins and general-purpose polyolefin resins. Furthermore, by mechanically blending the oxazoline-based aliphatic polymer and / or the oxazoline-modified polyolefin with an aliphatic polyester resin, a general-purpose polyolefin resin and then melt-kneading with an extruder or the like, mechanical properties such as impact resistance and strength, The present inventors have found that a thermoplastic resin composition having excellent heat resistance, hydrolysis resistance, and the like can be obtained, and have reached the present invention.

（２）前記オキサゾリン系脂肪族ポリマーの重量平均分子量が１，０００〜５００，０００であることを特徴とする前記（１）記載の相溶化剤、
（３）前記（１）または（２）に記載のオキサゾリン系脂肪族ポリマーと、末端または側鎖にカルボキシル基、酸無水物基、チオール基またはフェノール性水酸基を有するポリオレフィンとを反応させることによって得られた、オキサゾリン基を含有する変性ポリオレフィンからなる、脂肪族ポリエステル樹脂とポリオレフィン樹脂との相溶化剤、
（４）前記（１）または（２）に記載の相溶化剤、脂肪族ポリエステル樹脂、及びポリオレフィン樹脂を、該相溶化剤の含有量が０．１〜５０重量％となるように混合し、溶融混練して得られる熱可塑性樹脂組成物、
（５）前記（３）記載の相溶化剤、脂肪族ポリエステル樹脂、及びポリオレフィン樹脂を、該相溶化剤の含有量が１〜９０重量％となるように混合し、溶融混練して得られる熱可塑性樹脂組成物、
（６）前記（５）に記載の熱可塑性樹脂組成物からなる成型品
を提供するものである。 That is, the present invention
(1) General formula (1) (wherein R ₁ represents a hydrogen atom or a methyl group, and R _{2 to} R ₅ are the same or different and represent a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms. , R ₆ represents a hydrogen atom or a methyl group, R ₇ represents a linear, branched or cyclic alkyl group or 2-alkenyl group having 1 to 20 carbon atoms, R ₈ represents a hydrogen atom or a methyl group, R ₉ , R ₁₀ is the same or different and represents a hydrogen atom or a linear, branched or cyclic alkyl group or 2-alkenyl group having 1 to 20 carbon atoms, the amount of the structural unit a is 5 to 100 mol%, the structural unit b And a blending amount of the structural unit c is 95 to 0 mol%). A compatibilizer of an aliphatic polyester resin and a polyolefin resin, which comprises an oxazoline-based aliphatic polymer represented by A compatibilizer of an aliphatic polyester resin and a polyolefin resin, wherein the resin is a polymer containing L-lactic acid and / or D-lactic acid as a constituent component in a proportion exceeding 50 mol% ,

(2) The compatibilizer according to (1), wherein the oxazoline-based aliphatic polymer has a weight average molecular weight of 1,000 to 500,000.
(3) Obtained by reacting the oxazoline aliphatic polymer according to (1) or (2) above with a polyolefin having a carboxyl group, an acid anhydride group, a thiol group or a phenolic hydroxyl group at the terminal or side chain. A compatibilizer of an aliphatic polyester resin and a polyolefin resin, comprising a modified polyolefin containing an oxazoline group,
(4) The compatibilizer, aliphatic polyester resin, and polyolefin resin described in (1) or (2) above are mixed so that the content of the compatibilizer is 0.1 to 50% by weight, A thermoplastic resin composition obtained by melt-kneading,
(5) Heat obtained by mixing, melting and kneading the compatibilizer, aliphatic polyester resin, and polyolefin resin described in (3) so that the content of the compatibilizer is 1 to 90% by weight. A plastic resin composition,
(6) A molded article comprising the thermoplastic resin composition according to (5) is provided.

The oxazoline-based aliphatic polymer and oxazoline-modified polyolefin, which are the compatibilizers of the present invention, have an oxazoline group with excellent amphiphilic properties, and are excellent in phase with aliphatic polyester resins and general-purpose polyolefin resins. In order to show solubility, only by adding a small amount, the compatibility of both resins can be improved, and a uniform and stable mixed thermoplastic resin composition of aliphatic polyester / polyolefin can be formed. Therefore, no special modification treatment is required for the polyolefin resin, no special mixing equipment or purification technology is required, and only by melt kneading the aliphatic polyester, polyolefin resin and the compatibilizer of the present invention, the tensile strength In addition, a thermoplastic resin composition having good mechanical properties such as bending strength and impact resistance, heat resistance, and hydrolysis resistance can be obtained in high yield.

In addition, the addition of the compatibilizing agent of the present invention can suppress a decrease in molecular weight due to a heat history during processing of the resin composition, thereby suppressing a decrease in melt viscosity during processing, and can significantly improve moldability and workability. it can.
The oxazoline-based aliphatic polymer of the present invention can be produced simply and with high yield by a general-purpose radical polymerization method, and the oxazoline-modified polyolefin can also be easily produced by a general-purpose melt-kneading method.

Further, since the oxazoline group has abundant reactivity with the carboxyl group, the hydrolysis resistance of the thermoplastic resin composition can be improved by capping the carboxyl group derived from the aliphatic polyester resin in the thermoplastic resin composition. . In the molded article of the thermoplastic resin composition, the oxazoline-based aliphatic polymer and the oxazoline-modified polyolefin which are the compatibilizing agent of the present invention, which is a polymer, do not bleed and are stable and stable even after long-term use or storage. Excellent mixing and compatibility effects.

Furthermore, the reason why the heat resistance of the composite thermoplastic resin composition obtained in the present invention is particularly excellent is that it easily forms a hydrogen bond due to the presence of an oxazoline group, an amide group, and an ester group of an oxazoline-based aliphatic polymer. The present inventors have inferred.

Hereinafter, the present invention will be described in detail.
The compatibilizing agent of the present invention is an oxazoline-based aliphatic polymer described in the general formula (1) and a polyolefin resin containing an oxazoline group modified with the polymer, that is, an oxazoline-modified polyolefin.

The oxazoline-based aliphatic polymer is a homopolymer of alkenyl oxazoline or a copolymer of alkenyl oxazoline and a (meth) acrylamide monomer and / or a (meth) acrylic acid ester monomer.

The alkenyl oxazoline is a vinyl monomer having an oxazoline group represented by the general formula (2), in which R ₁ is a hydrogen atom or a methyl group, and R _{2 to} R ₅ are the same or different and have a hydrogen atom or a carbon number of 1 to 3 linear and branched alkyl groups are represented. Specifically, 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4-ethyl-2-vinyl-2-oxazoline, 5 -Ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline, 4,5-dimethyl-2-vinyl-2 -Oxazoline, 4,5-diethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl-2-isopropenyl-2- Oxazoline, 4-ethyl-2-isopropenyl-2-oxazoline, 5-ethyl-2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-iso Lopenyl-2-oxazoline, 4,4-diethyl-2-isopropenyl-2-oxazoline, 4,5-dimethyl-2-isopropenyl-2-oxazoline, 4,5-diethyl-2-isopropenyl-2-oxazoline Etc. Among these alkenyl oxazolines, 2-vinyl-2-oxazoline having a high reactivity with a reactive group such as a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, and a thiol group, 5-methyl-2-vinyl-2- Oxazoline and 4,4-dimethyl-2-vinyl-2-oxazoline are preferred, and 2-vinyl-2-oxazoline is most preferred. These alkenyl oxazolines can be used alone or in combination of two or more.

The (meth) acrylamide monomer is acrylamide, N-substituted acrylamide, N, N-disubstituted acrylamide, methacrylamide, N-substituted methacrylamide, N, N-disubstituted methacrylamide represented by the general formula (3), R ₈ in the formula represents a hydrogen atom or a methyl group, and R ₉ and R ₁₀ are the same or different and represent a hydrogen atom or a linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms. Specifically, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-pentyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-heptyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N -Decyl (meth) acrylamide, N-dodecyl (meth) acrylamide, N-tetradecyl (meth) acrylamide, N-hexadecyl (meth) acrylamide, N-oleyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-echo (Meth) acrylamide, N-docosyl (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-isobornyl (meth) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide N, N-dimethylaminoethylacrylamide, N, N-dimethylaminopropylacrylamide and the like. These (meth) acrylamide monomers can be used alone or in combination of two or more. In particular, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N, N-dimethylaminopropylacrylamide are preferable because industrial products are easily available.

The (meth) acrylic acid ester monomers are an acrylic acid alkyl ester and a methacrylic acid alkyl ester represented by the general formula (4), wherein R ₆ is a hydrogen atom or a methyl group, and R ₇ is a carbon number of 1-20. Represents a linear, branched, or cyclic alkyl group or alkenyl group. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, alkyl chain length of C8 to C20 Examples include (meth) acrylic acid ester monomers such as long chain aliphatic (meth) acrylates, allyl (meth) acrylates, cyclohexyl (meth) acrylates, and isobornyl (meth) acrylates. In these, 1 type (s) or 2 or more types can be used. In addition, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate and the like from which inexpensive industrial products can be easily obtained are preferable.

The alkenyl oxazoline used in the present invention can be produced by the method described in Patent Document 11 previously filed by the present inventors.

Patent Document 11: Japanese Patent Application Laid-Open No. 2001-058986,
JP 2002-275166 A,
JP 2004-250391 A,
JP 2004-238342 A,
JP 2004-238343 A,
JP 2004-238344 A

The homopolymerization of alkenyl oxazoline and the copolymerization method with (meth) acrylamide monomer and / or (meth) acrylic acid ester monomer are not particularly limited and can be carried out by a known radical polymerization method. For example, the method described in Patent Document 12 previously filed by the present inventors can be referred to. Examples thereof include solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization in an organic solvent such as alcohol and ethyl acetate. When the solution polymerization method in an organic solvent is employed, as a polymerization solvent, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl alcohol, ethyl alcohol, or the like can be used alone or in combination.

Patent Document 12: Japanese Patent Application Laid-Open No. 2007-246615,
JP 2009-120802 A

Examples of the polymerization initiator include generally known polymerization initiators such as azo series such as azobisisobutyronitrile, organic peroxide series, inorganic peroxide series, and redox series. As a usage-amount of a polymerization initiator, it is about 0.001 to 10 weight% normally with respect to the polymerizable monomer component total amount. Further, a normal radical polymerization technique such as adjustment of molecular weight by a chain transfer agent is applied.

The oxazoline-based aliphatic polymer is a homopolymer of alkenyl oxazoline or a copolymer of an alkenyl oxazoline and a (meth) acrylamide monomer and / or a (meth) acrylic acid ester monomer, and alkenyl oxazoline as a structural unit is 5 to 5 100 mol%, the preferable alkenyl oxazoline content is 10 mol% or more, more preferably 20 mol% or more. If it is less than 5 mol%, it is difficult to impart sufficient compatibility improvement effect and hydrolysis resistance improvement effect. Further, the blending ratio of the (meth) acrylamide monomer described later is desirably 1 mol% or more. In this case, the blending ratio of alkenyloxazoline is 99 mol% or less.

The molar ratio between the (meth) acrylamide monomer and the (meth) acrylic acid ester monomer is not particularly limited, but is 95 to 0 mol% in total. From the viewpoint of heat resistance, it is desirable that the (meth) acrylamide monomer is 1 mol% or more. Since the amide group is easier to form a hydrogen bond, the blending ratio of the (meth) acrylamide monomer may be increased in order to improve heat resistance.

The oxazoline aliphatic polymer has a weight average molecular weight of 1,000 to 500,000. Moreover, Preferably it is 2,000-300,000, More preferably, it is 5,000-100,000. When the weight average molecular weight is less than 1,000, when the blending amount in the polyolefin resin composition is large, for example, 10% by weight or more, the mechanical properties such as tensile strength and bending strength of the resin composition cannot be sufficiently satisfied. there is a possibility. On the other hand, if the weight average molecular weight exceeds 500,000, there may be a case where a sufficient compatibility improving effect cannot be obtained although it varies depending on the structure and molecular weight of the polyolefin.

The other compatibilizer of the present invention, the oxazoline-modified polyolefin, is obtained by reacting the oxazoline-based aliphatic polymer with a modified polyolefin having a reactive group capable of reacting with an oxazoline group at the terminal or side chain. . Examples of the modified polyolefin having a reactive group capable of reacting with an oxazoline group at the terminal or side chain include a modified polyolefin resin having a carboxyl group, an acid anhydride group, a thiol group, or a phenolic hydroxyl group at the terminal or side chain. The method for producing these modified polyolefins, that is, the method for introducing the reactive group into the polyolefin is not particularly limited, and conventionally known methods can be used. For example, a method in which a vinyl monomer having these reactive groups is copolymerized with an addition polymerizable monomer such as ethylene or propylene, and an olefin polymer and a vinyl monomer having these functional groups are grafted in the presence of a radical initiator. The method of making it include. Examples of the graft reaction include a solution method performed in an organic solvent and a kneading method using a melt kneading apparatus such as an extruder. These modified polyolefins may be used alone or in combination of two or more. Moreover, about the method of introducing a functional group, a combination of the above various methods, or the same or different methods may be performed a plurality of times.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, Itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, cinnamic acid and the like.

Examples of the vinyl monomer having an acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, cyclohexenedicarboxylic anhydride, and aconitic acid.

Examples of the vinyl monomer having a thiol group include vinyl-2-ethyl mercaptoethyl ether and allyl mercaptan.

Examples of the vinyl monomer having a phenolic hydroxyl group include o-, m- and p-hydroxystyrene, β-methyl o-, m- and p-hydroxystyrene, o-, m- and p-allylphenol, Examples include α-methyl-4-hydroxystyrene.

In the reaction between the oxazoline-based aliphatic polymer and the modified polyolefin having a reactive group capable of reacting with the oxazoline group at the terminal or side chain, the compounding ratio (charged weight ratio) can be arbitrarily adjusted according to the respective functional group concentration and molecular weight. The oxazoline-based polymer / modified polyolefin is preferably in the range of 1/99 to 99/1. This is because within this range, the function of providing each component and functional group can be clearly demonstrated.

The reaction between the oxazoline-based aliphatic polymer and the modified polyolefin having a carboxyl group, an acid anhydride group, a thiol group, or a phenolic hydroxyl group is performed by dissolving the oxazoline-based polymer and these modified polyolefins in a common solvent, and There is a melting method in which an oxazoline-based polymer and these modified polyolefins are dry-friended and used using a melt-kneading apparatus such as an extruder.

As a common solvent for the solution method, chlorobenzene, trichrene, benzene, toluene, xylene, dichlorobenzene, mesitylene and the like can be used. The reaction temperature is usually in the range of 20 ° C to 300 ° C, preferably 50 ° C to 250 ° C, more preferably 80 ° C to 200 ° C. If the reaction temperature is less than 20 ° C, the reaction may not occur easily. On the other hand, if the reaction temperature exceeds 300 ° C, the modified polyolefin may be deteriorated. The reaction time is in the range of 1 minute to 30 hours, preferably 5 minutes to 20 hours, more preferably 10 minutes to 10 hours. When the reaction time is shorter than 1 minute, a sufficient reaction rate may not be obtained. On the other hand, when the reaction time is longer than 30 hours, the efficiency deteriorates and the cost increases. A sufficient reaction rate can be obtained by combining the reaction temperature and the reaction time. For example, in the case of a low temperature reaction, the reaction time may be increased.

Examples of the reaction apparatus in the melting method include a plast mill, a Banbury mixer, and an extruder. Other devices may be any so-called high-viscosity stirrer or high-viscosity mixer, specifically, a horizontal twin-screw stirrer such as a multi-screw kneader, a horizontal twin-screw multi-disk device or a horizontal twin-screw surface renewal machine, and A vertical stirrer such as a double helical ribbon stirrer can also be used.

Furthermore, the solution method is composed of a dissolution process, a reaction process, a product purification process, a solvent recovery process, etc. of the raw material oxazoline-based polymer and modified polyolefin, and the work is complicated. High environmental addition. From these points of view, a simple melting method is preferable.

The above-mentioned melting method is a conventionally known melt-kneading method, but a single-screw or twin-screw extruder or the like is preferable because of the ease of pelletization of the oxazoline-modified polyolefin obtained after the reaction. Moreover, the temperature (for example, cylinder temperature of an extruder) of the part which knead | mixes is 50-300 degreeC normally, Preferably it is 100-250 degreeC. The temperature of the kneading part of the extruder may be set so that the kneading is divided into two stages, the first half and the second half, and the temperature in the second half is higher than the first half. If the kneading temperature is less than 50 ° C., the raw material oxazoline-based polymer and modified polyolefin may not be uniformly softened or melted, which may cause problems such as insufficient reaction or breakage of the extruder screw shaft. There is sex. On the other hand, when the kneading temperature exceeds 300 ° C., thermal decomposition and oxidation of various resin compositions easily occur, and problems such as a decrease in melt viscosity and coloring of the resin product occur. The kneading time is usually 0.1 to 30 minutes, preferably 0.5 to 5 minutes. In this time range, the reaction can be carried out sufficiently and efficiently.

The weight average molecular weight of the oxazoline-modified polyolefin resin obtained by the above production method is 2,000 to 1,000,000. Moreover, Preferably it is 5,000-500,000, More preferably, it is 10,000-200,000. When the weight average molecular weight is less than 2,000, when the blending amount of the oxazoline-modified polyolefin is large, for example, at 10% by weight or more, the tensile strength, bending strength, etc. of the target polyester resin and polyolefin resin composite thermoplastic resin composition There is a possibility that the mechanical properties of are not fully satisfied. On the other hand, when the weight average molecular weight exceeds 1,000,000, the melt viscosity of the oxazoline-modified polyolefin itself increases, and when added to a polyester resin or polyolefin resin and kneaded, the moldability is lowered and the compatibility is sufficiently improved. The effect may not be obtained.

The aliphatic polyester resin used in the present invention is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but is a copolymerized polylactic acid copolymerized with another monomer component having ester-forming ability. It may be. Other copolymer components include isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxyl group, 2,6-naphthalenedicarboxyl group, diphenyl dicarboxyl group, diphenoxyethane dicarboxyl group, diphenyl ether dicarboxyl group, diphenyl Aromatic dicarboxyl group such as sulfone dicarboxyl group, 1,3-cyclopentane dicarboxyl group, 1,3-cyclohexane dicarboxyl group, alicyclic dicarboxyl group such as 1,4-cyclohexane dicarboxyl group, malonic acid , Dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, azelaic acid, sebacic acid, suberin Aliphatic dicarboxylic acids such as acids, A dicarboxyl group derived from hydroxycarboxyl groups such as richolic acid, 3-hydroxybutyric acid, 4-hydroxyvaleric acid, hydroxypropionic acid, hydroxycaproic acid and hydroxybenzoic acid, and ester-forming derivatives thereof, ethylene glycol, Aliphatic diols such as propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglycol, 2,2-bis (4-β-hydroxyethoxyphenyl) ) Aromatic diols such as propane, 2,2-bis (4-β-hydroxyethoxyphenyl) sulfone, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol Diols derived from low molecular weight polyalkylene glycols such Lumpur, glycerin, compounds or derivatives thereof containing a plurality of hydroxyl groups in the molecule such as pentaerythritol. In addition, it is preferable that the ratio for which the polymer chain derived from another polymerizable monomer accounts for the total amount of the polymer is 50 mol% or less in terms of monomer. Furthermore, it is especially preferable that it is 20 mol% or less. Further, the arrangement pattern of the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer.

  The molecular weight and molecular weight distribution of the polylactic acid resin are not particularly limited as long as it can be practically processed, but the weight average molecular weight is usually 10,000 or more, preferably 50,000 or more, and further 100,000. The above is particularly preferable.

The raw material resin polyolefin used in the present invention is ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene. Homopolymers of α-olefins having 3 or more carbon atoms such as, copolymers of random or block or grafts of two or more monomers among these, main parts of ethylene or α-olefins having 3 or more carbon atoms and others Random, block, graft and other copolymers with these unsaturated monomers, or mixtures thereof.

Examples of the ethylene polymer include high pressure method low density polyethylene (LDPE), low pressure method high density polyethylene (HDPE), and linear low density polyethylene (LLDPE). Examples of propylene polymers include homo, block or random polypropylene.

Examples of the copolymer of two or more of α-olefin include rubber (EPDM), ethylene-propylene copolymer rubber (EPR) made of terpolymer of ethylene, propylene and diene, Examples thereof include ethylene-butene copolymer rubber (EBR).

The molecular weight of these polyolefin resins is preferably 10,000 to 1,000,000 in terms of weight average from the viewpoint of maintaining moldability and imparting impact resistance to the final target thermoplastic resin, and 20,000 to 800, 000 is particularly preferred.

The above various polyolefins may be used alone or in combination of two or more. Of these, polyethylene, polypropylene, ethylene / propylene copolymer, and propylene / unsaturated monomer copolymer are preferable from the viewpoint of imparting functionality by improving the dispersibility of the filler.

Furthermore, if necessary, a generally known modified polyolefin resin into which a polar group and / or a reactive group have been introduced can be appropriately added and used together with the above polyolefin resin. Here, the polar group and / or reactive group is a functional group such as a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, a thiol group, an epoxy group, an amino group, an amide group, or a hydroxyl group.

The blending ratio of the aliphatic polyester and the polyolefin, which is the raw material resin of the present invention, is not particularly limited, and the preferred range varies depending on the use. Usually, the polyester / polyolefin is 1/99 to 99/1 (weight ratio), preferably 10 / 90 to 80/20, more preferably 80/20 to 40/60.

The oxazoline-based aliphatic polymer and oxazoline-modified polyolefin of the present invention can be used as they are as they are as compatibilizers in a mixture of aliphatic polyester and polyolefin. Moreover, what mixed with other polymers, for example, a polyamide resin, a polyester resin, a polyacryl resin, etc. can also be used as a compatibilizing agent.

The compatibilizing agent of the present invention is preferably processed into a pellet or powder and added and mixed at the time of pellet production or molding of a resin mixture comprising an aliphatic polyester resin and a polyolefin resin. A method of mixing and using a masterbatch prepared by pelletizing an aliphatic polyester resin such as polylactic acid containing a high concentration of a compatibilizer and a polyolefin resin in order to uniformly mix the additive components, and a high concentration of the compatibilizer. A method of using a mixture of an aliphatic polyester resin and a master batch obtained by pelletizing the polyolefin resin contained in the above, or using a polyester resin master batch, a polyolefin resin master batch and a polyester resin, and a polyolefin resin simultaneously. The method is preferred.

The addition amount of the compatibilizer of the present invention varies depending on the concentration of the oxazoline group in the polymer, the molecular weight of the polymer, and the like.
In the oxazoline aliphatic polymer which is one form of the compatibilizing agent of the present invention, the oxazoline aliphatic polymer is usually 0% of the total amount of the aliphatic polyester resin, the polyolefin resin and the oxazoline aliphatic polymer. 0.1 to 50% by weight, preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight.
In the oxazoline-modified polyolefin which is the other form of the compatibilizing agent of the present invention, the total amount of the aliphatic polyester resin, the polyolefin resin and the oxazoline-modified polyolefin is 1 to 90% by weight, preferably Is added in an amount of 2 to 70% by weight, more preferably 5 to 50% by weight.
If the amount added is lower than these, sufficient compatibilizing effect may not be obtained, and the impact resistance and heat resistance of the resin composition comprising the aliphatic polyester resin and the polyolefin resin may be insufficient. When the amount exceeds these ranges, mechanical properties may be deteriorated.

In the present invention, the thermoplastic resin composition is obtained by mixing, melting and kneading an aliphatic polyester resin, a polyolefin resin, and the compatibilizing agent of the present invention.

As a raw material supply method in the melt-kneading process, a pellet-like aliphatic polyester, polyolefin, a powdery or pellet-like compatibilizer, or a masterbatch of a compatibilizer processed into a pellet-form and other additives are in a predetermined proportion. A method of dry blending and feeding the mixture directly to a melt kneader, or a quantitative apparatus for pelletized polyolefin, pelletized or powdered polyester, powdered or pelletized compatibilizer and other additives. There is a method of feeding directly to a melt kneader in a predetermined proportion, and in any method, good kneading is possible.

Examples of the melt-kneader used in the melt-kneading step include known melt-kneaders, such as a Banbury mixer, a plast mill, a Brabender plastograph, a single screw extruder, a twin screw extruder, and the like. From the viewpoint of satisfactorily dispersing the filler and improving the heat resistance and rigidity of the thermoplastic resin composition, it is preferably melt-kneaded by a single screw extruder or a twin screw extruder, and particularly preferably a twin screw extruder.

A twin-screw extruder is usually a raw material supply port, a vent port, a barrel with a jacket, two screws that are arranged in the barrel and rotate in the same direction, different directions, and a die attached to the tip of the extruder, Consists of screen mesh. Furthermore, the twin-screw extruder includes at least one melt-kneading section (kneading section) constituted by a plurality of kneading disks installed in the middle of the screw.

The number of kneading disks constituting one melt-kneading part (kneading part) is preferably from the viewpoint of dispersing the filler satisfactorily and preventing the resin from being decomposed by heat generated by shearing. The number is 3 to 200, and more preferably 5 to 50. Moreover, from the viewpoint of preventing one resin from being decomposed due to heat generated by shearing with one melt-kneading part (kneading part) as one unit, it is preferably 1 to 20 units, more preferably 1 to 15 units.

The screen mesh is preferably 10 to 500 mesh, more preferably 20 to 200 mesh, from the viewpoint of satisfactorily dispersing the filler and preventing the resin from being decomposed by heat generated by shearing.

The temperature of the melt-kneading part (cylinder part) of the extruder is from the viewpoint that the aliphatic polyester resin and the general-purpose polyolefin resin are compatibilized well to prevent decomposition of the raw material polyester resin and the produced thermoplastic resin composition. Usually, it is 100-280 degreeC, Preferably it is 150-250 degreeC.

The melt-kneading time is generally 0.1 to 30 minutes, preferably 0.5 to 15 minutes as a whole, from the viewpoint of preventing poor dispersion and decomposition of the produced thermoplastic resin composition.

In the production of the thermoplastic resin composition of the present invention, as long as the physical properties are not impaired, a stabilizer such as a crystal nucleating agent, an antioxidant or an ultraviolet absorber, an antistatic agent, a flame retardant, an antibacterial agent, Colorants such as dyes and pigments and additives for known thermoplastic resins such as lubricants, lubricants, waxes and inorganic substances for improving fluidity and releasability may be contained. The content of such an additive is preferably 20% by weight or less in the composite resin composition of the present invention. These additives may be used alone or in combination.

Applications of the thermoplastic resin composition of the present invention include injection molding materials, extrusion molding materials, press molding materials, blow molding materials, film molding materials, and the like. In particular, it is preferably an application that requires rigidity and impact resistance, and examples thereof include materials for automobiles and materials for household appliances.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In the following, parts and% indicate parts by weight and% by weight, respectively.

The materials used in Examples and Comparative Examples are as follows.
PLA: made by Mitsui Chemicals, Lacia H-100 (polylactic acid)
PP: manufactured by Sun Allomer, PM600A (polypropylene resin)
B-PP: manufactured by Mitsui Chemicals, B701WB (ethylene-propylene block polyolefin resin)
M-PP: manufactured by Mitsubishi Chemical Corporation, Modic AP-P502 (maleic anhydride-modified polypropylene)
A-PE: manufactured by Mitsui Chemicals, Excellex 15341PA (carboxylic acid-modified polyethylene)
E-PE: manufactured by Sumitomo Chemical Co., Ltd., Bond Fast E (epoxy-modified ethylene copolymer)
RPS: EPOCROS RPS (a copolymer of styrene and 2-isopropenyl-2-oxazoline) manufactured by Nippon Shokubai Co., Ltd.

The measurement methods and evaluation methods for various physical properties in the examples are as follows.
(1) Appearance moldability: The appearance of the resin composition pellets, press film, and injection-molded dumbbell test piece was visually observed, and the moldability was evaluated in the following four stages.
A: Unevenness and peeling cannot be visually recognized, and gloss is present.
○: Unevenness and peeling cannot be visually recognized, but there is no gloss.
Δ: Although there is slight unevenness, peeling cannot be visually recognized and there is no gloss.
X: Unevenness and peeling can be visually recognized, and there is no gloss.

(2) Processing stability: The processing stability of the kneading and extruding process of the resin composition was evaluated in the following three stages by fluctuations in the motor load value.
Comparative control: Motor load value when extruding a mixture of polylactic acid resin and polypropylene resin A: Almost no increase or decrease in load was observed, and it was possible to stably extrude into a strand shape.
○: A slight increase or decrease in load was observed, but kneading and extrusion could be performed almost stably.
Δ: Increase and decrease in load were observed and unstable, but kneading and extrusion were possible.
X: Rapid increase and decrease in load were observed, and kneading and extrusion could not be performed.

(3) Tensile strength: A tensile test was performed at a rate of 300 mm / min using five test pieces of a thermoplastic resin press film (100 mm × 15 mm, thickness 200 μm), and an average value of tensile strength at break was calculated.
The higher the tensile strength, the higher the mechanical strength of the thermoplastic resin composition.

(4) Impact resistance: An impact tester (Toyo Seiki Seisakusho) is used in accordance with JIS P-8134 using five test pieces of a thermoplastic resin press film (100 mm x 100 mm, thickness 200 µm). The average value of impact strength was calculated.
The higher the impact strength, the higher the impact resistance of the thermoplastic resin composition.

(5) Heat resistance: Using two thermoplastic resin injection-molded test pieces (thickness 4 mm), based on K7191, the deflection temperature under load was measured under the condition of 0.45 MPa, and the average value was calculated.
It shows that it is excellent in heat resistance, so that temperature is high.

(6) Compatibility: After the thermoplastic resin pellets were heated and melted, they were observed with a polarizing microscope at 100 ° C., and the compatibility of the polyester resin and the polyolefin resin was evaluated in the following four stages.
A: The interface cannot be visually recognized and is finely and uniformly dispersed.
○: The interface cannot be visually recognized and is uniformly dispersed.
Δ: A slight interface can be visually recognized.
X: Many clear interfaces can be visually recognized.

(7) Hydrolysis resistance: A press film (thickness: 200 μm) of a thermoplastic resin was prepared, and 10 test pieces of 100 mm × 15 mm were collected using the press film. The five test pieces were subjected to a tensile test at a speed of 300 mm / min, and an average value of tensile breaking strength was calculated to obtain an initial breaking strength value. The remaining five test pieces were placed in a high-temperature and high-humidity machine at 70 ° C. and a relative humidity of 95%, held for 60 hours, then taken out, cooled and dried to obtain test pieces after the high-temperature and high-humidity treatment. Using these test pieces, a tensile test was similarly performed at a speed of 300 mm / min, and an average value of tensile breaking strength was calculated to obtain a tensile strength value after the high temperature and high humidity treatment. The strength retention after the high-temperature and high-humidity treatment was calculated according to Equation (1).
The greater the strength retention, the higher the hydrolysis resistance of the thermoplastic resin.

Synthesis of Oxazoline Aliphatic Polymer <Synthesis Example 1-1>
Synthesis of 2-vinyl-2-oxazoline (VOZO) homopolymer (PolyVOZO) in a reaction vessel with a capacity of 500 mL equipped with a stirrer, thermometer, cooler and dry nitrogen inlet tube
100.0 g (1030.9 mmol), azobisisobutyronitrile (AIBN) 1.7 g (10.3 mmol), and ethyl acetate 200 mL were charged. The reaction solution was stirred at 30 ° C. for 60 minutes under a dry nitrogen stream, and then polymerized at 60 ° C. for 8 hours. After completion of the reaction, the reaction solution was returned to room temperature, the reaction solution having a high viscosity was poured into diisopropyl ether, and a polymer was precipitated to obtain a crude product. The crude product was dissolved in methanol, reprecipitated with diisopropyl ether, separated, and dried under reduced pressure at 50 ° C. to obtain 93.5 g of a white powdery solid (yield = 93.5%). The white powdery solid was detected by infrared absorption spectrum (IR) to detect the specific absorption derived from the cyclic structure of oxazoline, and the absorption of the monomer-derived vinyl group was not detected, confirming the formation of the homopolymer PolyVOZO. . Furthermore, the weight average molecular weight (Mw) of the homopolymer was analyzed by GPC method (standard polystyrene) and confirmed to be 23,000.

<Synthesis Example 1-2>
Synthesis of 2-vinyl-2-oxazoline (VOZO) and methyl methacrylate (MMA), N, N-dimethylacrylamide (DMAA) copolymer (PolyVOZO-MMA-DMAA) VOZO 25.0 g (257.7 mmol), MMA 25. Polymerization and purification were performed in the same manner as in Synthesis Example 1-1 using 8 g (257.7 mmol), DMAA 51.1 g (515.4 mmol), AIBN 1.7 g (10.3 mmol), and ethyl acetate 200 mL. 93.4 g of a solid was obtained (yield = 91.7%). From the infrared absorption spectrum (IR), the white powdery solid was detected to have a specific absorption derived from the cyclic structure of oxazoline, a specific absorption of MMA ester, and a specific absorption of amide of DMAA. Absorption was not detected, and formation of the copolymer PolyVOZO-MMA-DMAA was confirmed. The composition of the copolymer was analyzed by ¹ H-NMR (CDCl ₃ ), and it was confirmed that VOZO-derived unit / MMA-derived unit / DMAA-derived unit = 1.00 / 1.06 / 1.97. Furthermore, the weight average molecular weight (Mw) of the copolymer was analyzed by GPC method (standard polystyrene) and confirmed to be 30,000.

<Synthesis Example 1-3>
Synthesis of 2-Isopropenyl-2-oxazoline (IPOZO) Homopolymer (PolyIPOZO) Synthesis Example 1-1 using 100.0 g (899.6 mmol) of IPOZO, 1.5 g (9.0 mmol) of AIBN and 200 mL of ethyl acetate Polymerization and purification were carried out in the same manner as above to obtain 90.9 g of a white powdery solid (yield = 90.9%). The white powdery solid was detected by infrared absorption spectrum (IR) to detect the specific absorption derived from the cyclic structure of oxazoline, and the absorption of the vinyl group derived from the monomer was not detected, confirming the formation of the homopolymer PolyIPOZO. . Furthermore, the weight average molecular weight (Mw) of the homopolymer was analyzed by GPC method (standard polystyrene), and it was confirmed that it was 19,500.

<Synthesis Example 1-4>
Synthesis of 2-isopropenyl-2-oxazoline (IPOZO), 2-ethylhexyl acrylate (2EHA), N, N-diethylacrylamide (DEAA) copolymer (PolyIPOZO-2EHA-DEAA) IPOZO 50.0 g (449.8 mmol) 2EHA 41.4 g (224.9 mmol), DEAA 28.6 g (224.9 mmol), AIBN 1.5 g (9.0 mmol) and ethyl acetate 240 mL were polymerized and purified in the same manner as in Synthesis Example 1-1. 113.0 g of a white powdery solid was obtained (yield = 94.2%). From the infrared absorption spectrum (IR), the white powdery solid was detected to have a specific absorption derived from the cyclic structure of oxazoline, a specific absorption of the ester of 2EHA, and a specific absorption of the amide of DEAA, respectively, and the vinyl group derived from the monomer No absorption was detected, confirming the formation of the copolymer PolyIPOZO-2EHA-DEAA. The composition of the copolymer was analyzed by ¹ H-NMR (CDCl ₃ ), and it was confirmed that IPOZO-derived unit / 2EHA-derived unit / DEAA-derived unit = 1.00 / 0.53 / 0.48. Furthermore, the weight average molecular weight (Mw) of the copolymer was analyzed by GPC method (standard polystyrene) and confirmed to be 37,000.

<Synthesis Example 1-5>
Synthesis of 5-methyl-2-vinyl-2-oxazoline (MVOZO) homopolymer (PolyMVOZO) Synthesis example using 100.0 g (899.6 mmol) of MVOZO, 1.5 g (9.0 mmol) of AIBN and 200 mL of ethyl acetate Polymerization and purification were performed in the same manner as in 1-1 to obtain 91.9 g of a white powdery solid (yield = 91.9%). The white powdery solid was detected by infrared absorption spectrum (IR) to detect the specific absorption derived from the cyclic structure of oxazoline, and the absorption of the vinyl group derived from the monomer was not detected, confirming the formation of the homopolymer PolyMVOZO. . Furthermore, the weight average molecular weight (Mw) of the homopolymer was analyzed by GPC method (standard polystyrene) and confirmed to be 27,500.

<Synthesis Example 1-6>
Synthesis of 4,4′-dimethyl-2-vinyl-2-oxazoline (DMVOZO), a copolymer of methyl methacrylate (MMA) and N-isopropylacrylamide (NIPAM) (PolyDMVOZO-MMA-NIPAM) DMVOZO 50.0 g (400.0 mmol) ) Using MMA 20.0 g (200.0 mmol), NIPAM 22.7 g (200.0 mmol), AIBN 1.3 g (8.0 mmol) and ethyl acetate 200 mL, and polymerization and purification in the same manner as in Synthesis Example 1-1. To obtain 85.3 g of a white powdery solid (Yield = 92.0%). From the infrared absorption spectrum (IR), the white powdery solid was detected to have a specific absorption derived from the cyclic structure of oxazoline, a specific absorption of MMA ester, and a specific absorption of NIPAM amide. Was not detected, confirming the formation of the copolymer PolyMVOZO-MMA-NIPAM. The composition of the copolymer was analyzed by ¹ H-NMR (CDCl ₃ ), and it was confirmed that MVOZO-derived unit / MMA-derived unit / NIPAM-derived unit = 1.00 / 0.55 / 0.46. Furthermore, the weight average molecular weight (Mw) of the copolymer was analyzed by GPC method (standard polystyrene) and confirmed to be 28,500.

<Synthesis Example 1-7>
Synthesis of 2-vinyl-2-oxazoline (VOZO) and N-octylacrylamide (NOAM) copolymer (PolyVOZO-NOAM) VOZO 50.0 g (515.5 mmol), NOAM 47.3 g (257.7 mmol), AIBN Polymerization and purification were performed in the same manner as in Synthesis Example 1-1 using 1.3 g (7.7 mmol) and 200 mL of ethyl acetate to obtain 89.9 g of a white powdery solid (yield = 92.4%). From the infrared absorption spectrum (IR), the white powdery solid was detected to have a specific absorption derived from the cyclic structure of oxazoline and a specific absorption of amide of NOAM, respectively, and the absorption of the vinyl group derived from the monomer was not detected. Formation of the copolymer PolyVOZO-NOAM was confirmed. The composition of the copolymer was analyzed by ¹ H-NMR (CDCl ₃ ), and it was confirmed that VOZO-derived unit / NOAM-derived unit = 1.00 / 0.46. Furthermore, the weight average molecular weight (Mw) of the copolymer was analyzed by GPC method (standard polystyrene) and confirmed to be 29,500.

<Synthesis Example 1-8>
Synthesis of 2-vinyl-2-oxazoline (VOZO) and methyl methacrylate (MMA) copolymer (PolyVOZO-MMA) 25.0 g (257.7 mmol) of VOZO, 77.4 g (773.0 mmol) of MMA, azobisisobutyro Nitrile (AIBN) (1.7 g, 10.3 mmol) and ethyl acetate (200 mL) were charged, and polymerization and purification were carried out in the same manner as in Synthesis Example 1-1 to obtain 95.7 g of a white powdery solid (Yield = 93). .5%). From the infrared absorption spectrum (IR), the white powdery solid was detected to have a specific absorption derived from the cyclic structure of oxazoline and a specific absorption of the ester of MMA, respectively, and no absorption of the vinyl group derived from the monomer was detected. Formation of the copolymer PolyVOZO-MMA was confirmed. The composition of the copolymer was analyzed by ¹ H-NMR (CDCl ₃ ), and it was confirmed that VOZO-derived unit / MMA-derived unit = 1.00 / 3.16. Further, the weight average molecular weight (Mw) of the copolymer was analyzed by GPC method (standard polystyrene), and confirmed to be 33,000.

<Synthesis Example 1-9>
Synthesis of methyl methacrylate (MMA) and N, N-dimethylacrylamide (DMAA) copolymer (PolyMMA-DMAA) MMA 51.6 g (515.4 mmol), DMAA 51.1 g (515.4 mmol), AIBN 1.7 g (10 .3 mmol) and 200 mL of ethyl acetate were used for polymerization and purification in the same manner as in Synthesis Example 1-1 to obtain 94.5 g of a white powdery solid (yield = 92.0%). From the infrared absorption spectrum (IR), the white powdery solid was detected to have a specific absorption of the ester of MMA and a specific absorption of the amide of DMAA, and the absorption of the vinyl group derived from the monomer was not detected. -The production of DMAA was confirmed. The composition of the copolymer was analyzed by ¹ H-NMR (CDCl ₃ ), and it was confirmed that MMA-derived unit / DMAA-derived unit = 1.00 / 0.92. Furthermore, the weight average molecular weight (Mw) of the copolymer was analyzed by GPC method (standard polystyrene) and confirmed to be 34,500.

Synthesis of Oxazoline-Modified Polyolefin <Synthesis Examples 2-1 to 2-6>
Maleic anhydride-modified polypropylene (M-PP) or carboxylic acid-modified polyethylene (A-PE) and the oxazoline-based aliphatic polymer obtained in Synthesis Examples 1-1, 1-2, and 1-7 are shown in Table 1. Preliminarily mixed and supplied to a small biaxial kneading extruder (S1KRC kneader manufactured by Kurimoto Steel Works), and melt kneaded at 180 ° C. and 50 rpm to obtain oxazoline-modified polyolefin pellets.

Examples 1-10, Comparative Examples 1-8
Polyester resin, polyolefin resin, oxazoline-based aliphatic polymer and other additives are premixed in the proportions shown in Table 2, and supplied to a small biaxial kneading extruder (S1 KRC kneader manufactured by Kurimoto Steel Works). Melt kneading was performed at 50 rpm to obtain pellets of the target resin composition. The fluctuation of the motor load value was observed during the kneading extrusion, and the processing stability of the composition was evaluated. Further, pellets of various thermoplastic resin compositions were dried at 120 ° C. for 2 hours, and then a press film having a thickness of 200 μm was produced by a 180 ° C. hot press. The obtained press film was allowed to stand for 24 hours under the condition of 23 ° C. × 50% RH, and then used for various physical property evaluations. Furthermore, by using an injection molding machine (IS100GN manufactured by Toshiba Machine Co., Ltd.), a multi-purpose injection molding test piece was obtained under the conditions of an injection pressure of 55 kg / cm ² , an injection time of 5 seconds, a cylinder temperature of 170 ° C., a nozzle temperature of 180 ° C., and a mold temperature of 40 ° C. It was produced (JIS K7152). The various physical property measurements and evaluations were performed using the pellets, press films, and injection-molded test pieces of the various thermoplastic resin compositions obtained. The results are shown in Table 3 and Figs.

Examples 11-22
Polyester resin, polyolefin resin, oxazoline-modified polyolefin and other additives are premixed in the proportions shown in Table 4 and supplied to a small biaxial kneader-extruder (S1KRC kneader manufactured by Kurimoto Steel) and melt-kneaded at 200 ° C. After that, it was extruded into a strand (rotation speed: 30 rpm / min), cooled with water, cut into pellets, and pellets of the desired thermoplastic resin composition were obtained. The fluctuation of the motor load value was observed during the kneading extrusion, and the processing stability of the composition was evaluated. Moreover, the pellets of various thermoplastic resin compositions were dried at 120 ° C. for 2 hours, and then a multi-purpose injection-molded test piece was produced by a press film and an injection molding machine (IS100GN manufactured by Toshiba Machine) using a hot press machine (JIS K7152). The various physical property measurements and evaluations were performed using the pellets, press films, and injection-molded test pieces of the various thermoplastic resin compositions obtained. The results are shown in Table 5, FIG. 8 and FIG.

From the results of Examples and Comparative Examples, by blending the oxazoline-based aliphatic polymer or oxazoline-modified polyolefin of the present invention as a compatibilizing agent, an incompatible aliphatic polyester and a general-purpose polyolefin can be mixed uniformly and stably (phases). It can be seen that it is excellent in impact resistance and heat resistance while maintaining good mechanical properties, and the hydrolysis resistance is greatly improved. Moreover, the moldability and workability can be remarkably improved.

The compatibilizer of the present invention can satisfactorily compatibilize the aliphatic polyester resin and the general-purpose polyolefin resin by adding a small amount. Thereby, the thermal characteristics, impact resistance and hydrolysis resistance can be remarkably improved while maintaining the mechanical characteristics of the resulting thermoplastic resin composition high. Therefore, the thermoplastic resin composition of the present invention can be used for interior / exterior parts, electrical parts, home appliances, etc. in various industrial fields, particularly in the building material field and the automotive field. Specifically, as various engineering plastics, automobile / transport equipment-related interior / exterior parts such as bumpers, instrument panels, console boxes, roof sheets, panel covers, electrical parts, household appliances, furniture, miscellaneous goods such as sundries, medical care Suitable for molded materials of materials, food containers, food packaging, packaging materials such as general packaging, coating materials such as electric wires and cables, industrial materials such as construction and civil engineering, stationery and office supplies. The compatibilizing agent of the present invention can also be used as a compatibilizing agent for different types of thermoplastic resins other than polyester and polyolefin resins.

Claims (6)

General formula (1) (wherein R ₁ is a hydrogen atom or a methyl group, R _{2 to} R ₅ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, R ₆ Is a hydrogen atom or a methyl group, R ₇ is a linear, branched or cyclic alkyl group or 2-alkenyl group having 1 to 20 carbon atoms, R ₈ is a hydrogen atom or a methyl group, R ₉ and R ₁₀ are The same or different and represents a hydrogen atom or a linear, branched or cyclic alkyl group or 2-alkenyl group having 1 to 20 carbon atoms, the blending amount of the structural unit a is 5 to 100 mol%, the structural unit b and the structural unit c is a compatibilizer of an aliphatic polyester resin and a polyolefin resin, comprising the oxazoline-based aliphatic polymer represented by the formula: Is a polymer containing L-lactic acid and / or D-lactic acid as a constituent component in a proportion exceeding 50 mol% , a compatibilizing agent for an aliphatic polyester resin and a polyolefin resin.

The compatibilizer according to claim 1, wherein the oxazoline-based aliphatic polymer has a weight average molecular weight of 1,000 to 500,000. An oxazoline group obtained by reacting the oxazoline-based aliphatic polymer according to claim 1 or 2 with a polyolefin having a carboxyl group, an acid anhydride group, a thiol group or a phenolic hydroxyl group at a terminal or a side chain. A compatibilizing agent for an aliphatic polyester resin and a polyolefin resin, comprising the modified polyolefin. The compatibilizer according to claim 1, the aliphatic polyester resin, and the polyolefin resin are mixed and melt kneaded so that the content of the compatibilizer is 0.1 to 50% by weight. Thermoplastic resin composition. A thermoplastic resin composition obtained by mixing the compatibilizer according to claim 3, an aliphatic polyester resin, and a polyolefin resin so that the content of the compatibilizer is 1 to 90% by weight, and melt-kneading. object. A molded article comprising the thermoplastic resin composition according to claim 5.