WO2011062248A1

WO2011062248A1 - Epoxy-containing ethylene copolymer and resin composition

Info

Publication number: WO2011062248A1
Application number: PCT/JP2010/070638
Authority: WO
Inventors: 晃子関野
Original assignee: 住友化学株式会社
Priority date: 2009-11-17
Filing date: 2010-11-12
Publication date: 2011-05-26
Also published as: JP2011127101A

Abstract

Provided is an epoxy-containing ethylene copolymer that contains a monomer unit derived from ethylene and a monomer unit derived from glycidyl methacrylate. The monomer unit derived from glycidyl methacrylate constitutes between 15% and 25% of the mass of the copolymer, and the melt flow rate of the copolymer is 10-50 g/10 min at 190°C.

Description

Epoxy group-containing ethylene copolymer and resin composition

The present invention relates to an epoxy group-containing ethylene copolymer and a resin composition containing the same.

An epoxy group-containing ethylene copolymer comprising an ethylene-derived monomer unit and an epoxy group-containing olefin-derived monomer unit is, for example, a polyolefin as described in JP-A-52-32045. It is added to resins and polyester resins and used to improve mechanical properties such as impact resistance and tensile properties of these resins. In addition, the epoxy group-containing ethylene-based copolymer is used for bonding between dissimilar materials that are difficult to bond, such as polyester resins, metals, and fluororesins, as described in, for example, JP-A-55-40707. It is also used.
However, the epoxy group-containing ethylene copolymers described in JP-A-52-32045 and JP-A-55-40707 have monomer units derived from an epoxy group-containing olefin per molecule. Since the content is small, the physical properties of the resin composition obtained by adding the copolymer to other resins are not sufficiently improved in the properties compared to the properties of the original resin.

In view of the above problems, an object of the present invention is to provide an epoxy group-containing ethylene copolymer having a high resin modification effect and a resin composition containing the same.
The present invention is an epoxy group-containing ethylene copolymer containing a monomer unit derived from ethylene and a monomer unit derived from glycidyl methacrylate, and the mass of the copolymer is 100% by mass. A copolymer containing 15 to 25% by mass of the monomer unit derived from glycidyl methacrylate and having a melt flow rate at 190 ° C. of 10 to 50 g / 10 min, and a resin composition containing the copolymer provide.

[Epoxy group-containing ethylene copolymer]
The epoxy group-containing ethylene copolymer according to the present invention is a copolymer containing a monomer unit derived from ethylene and a monomer unit derived from glycidyl methacrylate.
From the viewpoint of the resin modification effect, this epoxy group-containing ethylene-based copolymer has a monomer unit derived from glycidyl methacrylate in an amount of 15 to 25% by mass when the mass of the copolymer is 100% by mass. Contained, preferably 15 to 20% by mass.
In addition, content of the monomer unit derived from glycidyl methacrylate is measured by infrared spectroscopy.
The epoxy group-containing ethylene copolymer in the present invention may be an epoxy group-containing ethylene copolymer consisting only of a monomer unit derived from ethylene and a monomer unit derived from glycidyl methacrylate, or ethylene. Derived from a monomer unit derived from, a monomer unit derived from glycidyl methacrylate, a compound represented by the following formula (1) and a compound represented by formula (2) An epoxy group-containing ethylene copolymer further containing a monomer unit may be used.
CH ₂ = CR ¹ R ² (1)
CHR ³ = CHR ⁴ (2)
Where
R ¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R ² represents a halogen atom or a group represented by —COOR ⁵ (R ⁵ represents an alkyl group having 1 to 8 carbon atoms);
R ³ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by —COOR ⁶ (R ⁶ represents an alkyl group having 1 to 8 carbon atoms);
R ⁴ represents an alkyl nitrile having 1 to 8 carbon atoms, an alkyl ether group, an alkylamide, a halogen atom, a phenyl group, or a group represented by —COOR ⁷ (R ⁷ represents an alkyl group having 1 to 8 carbon atoms). Or R ⁴ represents a group represented by —OCOR ⁸ (R ⁸ represents an alkyl group having 1 to 8 carbon atoms).
Examples of the compound represented by the formula (1) include propylene, 1-butene, vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl chloride, vinylidene chloride, and styrene. , Acrylonitrile, isobutyl vinyl ether, and acrylamide.
Examples of the compound represented by the formula (2) include dimethyl maleate, diethyl maleate, dimethyl fumarate, and diethyl fumarate.
The one or more compounds are preferably selected from the group consisting of vinyl acetate, methyl acrylate and methyl methacrylate.
The epoxy group-containing ethylene copolymer is a monomer unit derived from ethylene, a monomer unit derived from glycidyl methacrylate, and a monomer unit derived from the compound represented by formula (1) or formula (2) When the weight of the copolymer is 100% by mass, the content of the monomer unit derived from the compound represented by formula (1) or formula (2) is 40% by mass or less. Preferably, 30 mass% or less is more preferable. The content of the monomer unit derived from glycidyl methacrylate is 15 to 25% by mass.
Specific examples of the epoxy group-containing ethylene copolymer according to the present invention include an ethylene-glycidyl methacrylate copolymer, an ethylene-propylene-glycidyl methacrylate copolymer, and an ethylene-butene-1-glycidyl methacrylate copolymer. , Ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-acrylic acid-glycidyl methacrylate copolymer, ethylene-methacrylic acid-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, Ethylene-ethyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl methacrylate-glycidyl methacrylate copolymer, ethylene-ethyl methacrylate-glycidyl methacrylate copolymer, ethylene-methyl maleate-glycidyl methacrylate Copolymer, ethylene-ethyl maleate-glycidyl methacrylate copolymer, ethylene-methyl fumarate-glycidyl methacrylate copolymer, ethylene-ethyl fumarate-glycidyl methacrylate copolymer, ethylene-vinyl chloride-methacrylic acid Glycidyl acid copolymer, ethylene-vinylidene chloride-glycidyl methacrylate copolymer, ethylene-styrene-glycidyl methacrylate copolymer, ethylene-acrylonitrile-glycidyl methacrylate copolymer, ethylene-isobutyl vinyl ether-glycidyl methacrylate copolymer Examples thereof include ethylene and acrylamide-glycidyl methacrylate copolymers.
The epoxy group-containing ethylene copolymer according to the present invention can be synthesized by various methods. For example, it can be produced by bulk polymerization, emulsion polymerization, solution polymerization or the like using a free radical initiator. Representative polymerization methods include those described in JP-A-48-11388 and JP-A-61-127709, and in the presence of a polymerization initiator that generates free radicals, at a pressure of 500 kg / cm ^2. As mentioned above, a method of copolymerizing under the condition of a temperature of 40 to 300 ° C. can be mentioned.
In addition, an unsaturated epoxy compound and a radical generator are mixed with a polymer containing a monomer unit derived from ethylene and a monomer unit derived from the compound represented by the formula (1) or (2). , A method of melt graft copolymerization in an extruder, or ethylene and an unsaturated epoxy compound, and an optional component represented by the formula (1) or (2) in an inert medium such as water or an organic solvent And a method of copolymerizing in the presence of a radical generator.
The epoxy group-containing ethylene copolymer according to the present invention has a melt flow rate at 190 ° C. of 10 to 50 g / 10 minutes, preferably 10 to 30 g / 10 minutes, from the viewpoint of the effect of modifying the resin.
Further, the epoxy group-containing ethylene copolymer according to the present invention can be added to a resin such as a polyolefin resin or a polyester resin as described later and used as a modifier.
At that time, if necessary, for example, a nucleating agent, an anti-blocking agent, a heat stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, an ozone degradation inhibitor, a weather resistance stabilizer, a foaming agent, an inorganic filler, an antistatic agent. Various additives such as a colorant may be added to the resin together with the epoxy group-containing ethylene copolymer of the present invention.
(Resin composition)
The resin composition according to the present invention comprises the above epoxy group-containing ethylene copolymer (hereinafter referred to as component (A)) and an ester bond, carbonate bond, ether bond, sulfide bond and amide bond in the main chain. And a polymer having at least one bond selected from the group (hereinafter referred to as component (B)).
In this resin composition, the epoxy group-containing ethylene-based copolymer functions as a modifier. Therefore, the content of the component (A) in the resin composition is preferably 0.1 to 30% by mass when the total of the component (A) and the component (B) is 100% by mass, and preferably 1 to 25%. More preferably, it is more preferably 3 to 20% by mass.
When the total of the component (A) and the component (B) is 100% by mass, the content of the component (B) is preferably 70 to 99.9% by mass, and 75 to 99% by mass. Is more preferable and 80 to 97% by mass is even more preferable.
Examples of the component (B) include polyester, polyamide, polycarbonate, polyacetal, polyphenylene ether, polyphenylene sulfide and the like. You may use these individually or in combination of 2 or more types. The component (B) is preferably polyester.
Polyester is classified into unsaturated polyester and saturated polyester. Examples of the saturated polyester include aliphatic polyester and aromatic polyester.
The unsaturated polyester refers to a polyester polymer obtained by copolymerizing an unsaturated polybasic acid, a saturated polybasic acid and a glycol. Examples of unsaturated polyesters include polyethylene maleate / isophthalate, polypropylene maleate / isophthalate, polyethylene methacrylate / phthalate, polybisphenol A isophthalate.
The saturated polyester refers to a polyester polymer obtained by polymerizing a saturated polybasic acid and glycol.
The aliphatic polyester refers to a polyester polymer obtained by polymerizing an aliphatic hydroxycarboxylic acid, and a polyester polymer obtained by polymerizing an aliphatic diol and an aliphatic dicarboxylic acid.
Examples of polyester polymers obtained by polymerizing aliphatic hydroxycarboxylic acids include polylactic acid, polyglycolic acid, poly (3-hydroxybutyric acid), poly (4-hydroxybutyric acid), poly (4-hydroxyvaleric acid) ), Polycaprolactone and the like. Polyester polymers obtained by polymerizing aliphatic diols and aliphatic dicarboxylic acids include polyester carbonate, polyethylene succinate, polybutylene succinate, polyhexamethylene succinate, polyethylene adipate, polybutylene adipate, polyhexamethylene Examples include adipate, polybutylene succinate adipate, polyethylene oxalate, polybutylene oxalate, polyhexamethylene oxalate, polyethylene sebacate, polybutylene sebacate and the like.
As the aliphatic polyester, poly (α-hydroxy acid) such as polylactic acid and polyglycolic acid is preferably used, and polylactic acid is particularly preferably used.
The aliphatic polyester may be a homopolymer or a copolymer. Examples of the copolymer include a copolymer of lactic acid and a hydroxy acid other than lactic acid.
As the aliphatic polyester, one kind of polymer may be used, or two or more kinds of aliphatic polyester polymers may be blended and used. As a blend of the aliphatic polyester, for example, a blend of a polylactic acid-based resin based on polylactic acid and another aliphatic polyester is preferable. The content of the polylactic acid resin in the blended product of such a polylactic acid resin and another aliphatic polyester is preferably 60% by mass or more, and more preferably 70% by mass or more.
When polylactic acid is used as the aliphatic polyester, the synthesis method of polylactic acid may be direct polymerization of D-lactic acid or L-lactic acid, and D-lactide, L-lactide or meso which are cyclic dimers of lactic acid. -Ring-opening polymerization of lactide may be used. The polylactic acid may be composed of either one of a monomer unit derived from L-lactic acid and a monomer unit derived from D-lactic acid, or a co-polymer containing both monomer units. It may be a coalescence. Moreover, you may use what blended the polylactic acid from which the ratio of the monomer unit derived from L-lactic acid and the monomer unit derived from D-lactic acid differs by arbitrary ratios as aliphatic polyester.
The melt flow rate of the aliphatic polyester is preferably 0.5 to 50 g / 10 minutes, more preferably 1 to 30 g / 10 minutes, and most preferably 10 to 20 g / 10 minutes. The melt flow rate of the aliphatic polyester is measured at a test temperature of 190 ° C. and a test load of 21.18 N by the method defined in JIS K 7210 (1995).
Aromatic polyesters are polyesters obtained by polymerizing aromatic hydroxycarboxylic acids, polyesters obtained by polymerizing aromatic dicarboxylic acids and aromatic diols, and polymers obtained by polymerizing aromatic dicarboxylic acids and aliphatic diols. Polyester obtained by polymerizing an aliphatic carboxylic acid and an aromatic diol. Aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polybutylene naphthalate, poly1,4-cyclohexylenedimethylene terephthalate, polyethylene-1,2-bis (phenoxy) ethane. -4,4'-dicarboxylate, ethylene terephthalate-parahydroxybenzoic acid polycondensate, phenolphthalate-parahydroxybenzoic acid polycondensate, 2,6-hydroxynaphthoate-parahydroxybenzoic acid polycondensate. .
The component (B) is preferably polylactic acid, aromatic polyester, or a mixture thereof.
Examples of polyamides include ring-opening polymers of cyclic lactams, polycondensates of aminocarboxylic acids, and polycondensates of dicarboxylic acids and diamines. Specifically, Nylon 6, Nylon 4,6, Nylon 6,6, Nylon 6,10, Nylon 6,12, Nylon 11, Nylon 12, and other aliphatic polyamides, poly (metaxylene adipamide), poly (hexa Aliphatic-aromatic polyamides such as methylene terephthalamide), poly (hexamethylene isophthalamide), polynonanemethylene terephthalamide, poly (tetramethylene isophthalamide), poly (methylpentamethylene terephthalamide), and copolymers thereof Examples of the copolymer include nylon 6 / poly (hexamethylene terephthalamide), nylon 6/6 / poly (hexamethylene terephthalamide), nylon 6 / nylon 6/6 / poly (hexamethylene isophthalamide), poly (Hexamethylene isophthala Do) / poly (hexamethylene terephthalamide), nylon 6 / poly (hexamethylene isophthalamide) / poly (hexamethylene terephthalamide), nylon 12 / poly (hexamethylene terephthalamide), poly (methylpentamethylene terephthalamide) / And poly (hexamethylene terephthalamide).
<Other resins>
The resin composition according to the present invention may contain a polymer other than the component (A) and the component (B) (hereinafter referred to as the component (C)). For example, polyolefin resin, an elastomer, etc. are mentioned.
Here, the polyolefin-based resin is a polymer selected from an olefin homopolymer and a copolymer obtained by copolymerizing two or more olefins, and a polymer having a crystallinity of 25% or more. Means. The crystallinity of the polyolefin resin is preferably 35% or more, and more preferably 40% or more. Examples of polyolefin resins include polyethylene resins, polypropylene resins, polybutene resins, and the like, with polypropylene resins being preferred. As the polyolefin resin, one kind of resin may be used or two or more kinds of resins may be used in combination.
Here, the degree of crystallinity is measured by using a differential scanning calorimeter (DSC) by scanning twice at a heating / cooling rate of 10 ° C./min. Specifically, the crystallinity is a value calculated as a ratio of the heat of fusion measured in the second scan to the heat of fusion in the 100% crystal state.
The polyethylene resin used in the present invention is an ethylene homopolymer or an ethylene-α-olefin copolymer having an ethylene unit content of 50% by mass or more, but the ethylene-propylene copolymer is a polypropylene resin. Shall be included. Specific examples of the α-olefin constituting the ethylene-α-olefin copolymer include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-butene, Hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl- 1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, methyl-1-pentene, ethyl-1-hexene , Dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-none 1-decene, 1-undecene, and 1-dodecene. Of these, 1-butene, 1-pentene, and 1-hexene are preferable. The α-olefin constituting the ethylene-α-olefin copolymer preferably has 4 to 12 carbon atoms, and more preferably 4 to 6 carbon atoms.
When the polyolefin resin is a polyethylene resin, the melt flow rate is preferably 0.1 g / 10 min to 10 g / 10 min from the viewpoint of the mechanical strength of the molded product obtained from the resin composition of the present invention. More preferably, it is 0.3 g / 10 min to 8 g / 10 min, and particularly preferably 1.0 g / 10 min to 3 g / 10 min.
The melt flow rate of the polyethylene resin is measured under the conditions of a test load of 21.18 N and a test temperature of 190 ° C. by the method defined in JIS K 7210 (1995).
The polypropylene resin used in the present invention is a propylene homopolymer or a copolymer having a propylene unit content of 50% by mass or more, a propylene-ethylene random copolymer, a propylene-α-olefin random copolymer, A copolymer of propylene-ethylene-α-olefin copolymer, “propylene homopolymer component” and “one or more comonomers selected from the group consisting of propylene and ethylene and / or α-olefin having 4 or more carbon atoms”; Examples thereof include a copolymer composed of a “polymer component”. These polypropylene resins may be used alone or in combination of two or more.
When the polyolefin resin is a polypropylene resin, the melt flow rate is preferably 0.1 g / 10 min to 400 g / 10 min from the viewpoint of the mechanical strength of the molded product obtained from the resin composition of the present invention. More preferably, it is 1 g / 10 min to 400 g / 10 min, and particularly preferably 5 g / 10 min to 200 g / 10 min.
The melt flow rate of the polypropylene resin is measured under the conditions of a test load of 21.18 N and a test temperature of 230 ° C. by the method defined in JIS K 7210 (1995).
Moreover, the resin composition of this invention may contain the elastomer. As the elastomer, a copolymer other than the polyolefin-based resin can be used. Examples of the elastomer include natural rubber, polybutadiene rubber, polyisoprene rubber, butyl rubber, amorphous or low-crystalline ethylene elastomer, butadiene-styrene elastomer, butadiene-acrylonitrile elastomer, hydrogenated or non-hydrogenated styrene-conjugated. Examples include diene block elastomers, polyester rubbers, acrylic rubbers, and silicon rubbers. One type of elastomer may be used alone, or two or more types of elastomers may be used in combination.
The ethylene-based elastomer is an elastomer containing a monomer unit derived from ethylene as a main component, and examples thereof include an ethylene-α-olefin copolymer and an ethylene-ethylenically unsaturated ester copolymer.
The ethylene-based elastomer is preferably an ethylene-α-olefin copolymer which is a copolymer of ethylene and one or more α-olefins. The α-olefin is preferably an α-olefin having 3 to 12 carbon atoms. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4-methyl Examples include -1-hexene, vinylcyclohexane, vinylcyclohexene, styrene, norbornene, butadiene, and isoprene.
In the present invention, the “amorphous elastomer” refers to an elastomer in which a crystal melting peak having a heat of fusion of 1 J / g or more is not observed within a range of −100 ° C. to 200 ° C. by differential scanning calorimetry (DSC). . The “low crystalline elastomer” refers to an elastomer in which a crystal melting peak having a heat of fusion of 1 to 30 J / g is observed in the range of −100 ° C. to 200 ° C. by differential scanning calorimetry (DSC).
Examples of hydrogenated or non-hydrogenated styrene-conjugated diene block elastomers include styrene-isoprene copolymers, styrene-isoprene-styrene copolymers, styrene-ethylenebutene-styrene copolymers, styrene-butadiene copolymers, Examples thereof include styrene-butadiene-styrene copolymers.
The melt flow rate of the elastomer is preferably 0.1 g / 10 min to 100 g / 10 min from the viewpoint of the mechanical strength of the molded product obtained from the resin composition of the present invention. More preferably, it is 0.3 g / 10 min to 50 g / 10 min, and particularly preferably 0.5 g / 10 min to 40 g / 10 min. For example, the melt flow rate of the ethylene-α-olefin copolymer is preferably 0.1 g / 10 min or more, and is 100 g / 10 min or less from the viewpoint of increasing the mechanical strength of the obtained molded product. More preferably, it is 0.3 g / 10 min to 50 g / 10 min, and further preferably 0.5 g / 10 min to 40 g / 10 min.
The melt flow rate of the elastomer is measured under the conditions of a test load of 21.18 N and a test temperature of 190 ° C. by the method defined in JIS K 7210 (1995).
The content of each component in the resin composition according to the present invention is the component (A) when the total content of the components (A), (B), and (C) is 100% by mass. 1 to 40% by mass, component (B) 1 to 30% by mass, component (C) 40 to 98% by mass, component (A) 5 to 35% by mass, component (B) 5 More preferably, it contains ~ 25% by mass, 45-90% by mass of component (C), 10-30% by mass of component (A), 10-20% by mass of component (B), and 50 of component (C). It is more preferable to contain ~ 80% by mass.
[Method for producing resin composition]
The method for producing the resin composition of the present invention is not particularly limited, and a method used in the production of a conventional resin composition, for example, melt-heat kneading using a kneader, an extruder or the like. The method of manufacturing is mentioned. Examples of the kneader include a kneader, a Banbury mixer, and a roll. Examples of the extruder include a single screw extruder and a twin screw extruder.
The method for obtaining a molded product using the resin composition of the present invention is not particularly limited, and a molding method generally used for thermoplastic resin compositions, for example, injection molding, injection blow molding, injection compression molding. Any of blow molding, extrusion molding, thermoforming, rotational molding, vacuum molding, vacuum pressure forming and the like can be applied.
Examples of the molded product obtained using the resin composition of the present invention include films, sheets, foamed sheets, hollow containers, fibers such as nonwoven fabrics, and automobile parts such as interior materials.
The film or sheet obtained by molding the resin composition according to the present invention can also be used for applications requiring adhesiveness. Moreover, the laminated body by which the layer which consists of a resin composition containing the epoxy-group-containing ethylene-type copolymer based on this invention was laminated | stacked on the at least single side | surface of a base material can also be used for the use for which adhesiveness is calculated | required. As a method for producing a single layer or laminated film or sheet including a layer comprising a resin composition containing an epoxy group-containing ethylene copolymer according to the present invention, for example, a commonly used extrusion molding method, T-die method, Examples thereof include an inflation method, a calendar method, lamination molding, and press molding.
Moreover, two different articles | goods can also be adhere | attached with the epoxy group containing ethylene-type copolymer which concerns on this invention, or the resin composition containing this copolymer, and it can also be set as a laminated body. In this case, the article can be regarded as the substrate. Using a laminate in which layers of the resin composition are laminated on both surfaces of a base material, an article on one side of the laminate can be bonded to another article on the other side.
The materials constituting the two articles to be bonded may be the same or different. Examples of the material constituting the article include metals such as gold, silver, copper, iron, tin, lead, aluminum, and silicon, inorganic materials such as glass and ceramics, cellulosic polymers such as paper and cloth, Synthesis of melamine resin, acrylic / urethane resin, urethane resin, (meth) acrylic resin, styrene / acrylonitrile copolymer, polycarbonate resin, phenol resin, alkyd resin, epoxy resin, silicone resin, fluorine resin, etc. Examples thereof include polymers. Each article may be composed of two or more types of materials. The shape of the article is not particularly limited, and examples thereof include a film shape, a sheet shape, a plate shape, and a fiber shape. In addition, if necessary, the article has a surface such as a release agent, a coating such as plating, a coating film made of a resin composition other than the present invention, surface modification by plasma or laser, surface oxidation, etching, etc. Processing etc. may be given.

EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited by these.
1. Melt flow rate (MFR)
Melt flow rate was implemented based on JISK7210 (temperature 190 degreeC).
2. Glycidyl methacrylate content The content of monomer units derived from glycidyl methacrylate contained in the epoxy group-containing ethylene copolymer was measured by infrared spectroscopy.
3. Moldability When the resin composition was granulated using a uniaxial kneader, the case where the swell at the die outlet was small was marked as ◯, and the case where the swell was large and granulation was difficult was marked as x.
4). Appearance of strands The case where the strand surface obtained by granulating the resin composition using a uniaxial kneader was smooth was marked with ◯, and the case where there were obvious irregularities was marked with x.
5. Izod impact strength (unit: kJ / m ² )
The Izod impact strength of the molded product was measured according to the method defined in JIS K 7110 (1984). For this measurement, a test piece molded by injection molding and having a thickness of 6.4 mm and notched after molding was used. The measurement was performed at 23 ° C.
6). Tensile impact strength (unit: kJ / m ² )
The tensile impact strength of a 2 mm thick sheet compression molded under conditions of a molding temperature of 190 ° C., a preheating time of 10 minutes, a compression time of 5 minutes, and a compression pressure of 5 MPa was measured according to ASTM D1822-68.
7). Tensile properties Tensile properties of the molded bodies were measured according to the method defined in ASTM D638. As the test piece, a molded body having a thickness of 3.2 mm formed by injection molding was used. The test piece was previously marked with two marked lines and an interval of 50 mm. The test piece is pulled at a pulling speed of 50 mm / min. The stress (MPa) when the test piece breaks is taken as the breaking strength, and the difference between the distance between the marked lines and the initial value (= 50 mm) when the test piece breaks is extended. As evaluated. The measurement was performed at 23 ° C.
About the polymer used for the Example and the comparative example, a physical property etc. are shown below.
[Component (A)]
As the component (A), the following resins were used.
A-1: Ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate = 19% by mass), MFR at 190 ° C. = 13 g / 10 min
A-2: Ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate = 6 mass%), MFR at 190 ° C. = 3 g / 10 min
A-3: Ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate = 12% by mass), MFR at 190 ° C. = 3 g / 10 min
A-4: Ethylene-glycidyl methacrylate copolymer (glycidyl methacrylate = 19 mass%), MFR at 190 ° C. = 380 g / 10 min
[(B) component]
As the component (B), the following resins were used.
B-1: Polybutylene terephthalate (Torcon 1401-X06 manufactured by Toray Industries, Inc.)
B-2: Polylactic acid (Teramac TP-4000 manufactured by Unitika Ltd.)
[Component (C)]
As the component (C), the following resins were used.
C-1: ethylene-α-olefin copolymer (density 920 kg / cm ³ , MFR 1.9 g / 10 min at 190 ° C.)
C-2: Ethylene-α-olefin copolymer (Excellen FX CX4002 manufactured by Sumitomo Chemical Co., Ltd.)
Example 1
A mixture mixed at a mass ratio of A-1: B-1: C-2 = 10: 80: 10 was melt-kneaded using a single screw extruder to obtain a resin composition. Injection molding was performed using the obtained resin composition. The Izod impact strength and tensile properties of the injection molded product were measured. Table 1 shows the results.
(Comparative Example 1)
It carried out similarly to the Example except having used A-2 instead of A-1.
(Comparative Example 2)
The same procedure as in Example was performed except that A-3 was used instead of A-1.
(Comparative Example 3)
The same procedure as in Example was performed except that A-4 was used instead of A-1.

(Example 2)
A mixture mixed at a mass ratio of A-1: B-2: C-1 = 5: 30: 65 was melt-kneaded using a single screw extruder to obtain a resin composition. Press molding was performed using the obtained resin composition. The tensile properties and tensile impact of the press-formed product were measured. Table 1 shows the results.
(Comparative Example 4)
It carried out like Example 2 except having used A-2 instead of A-1.
(Comparative Example 5)
The same procedure as in Example 2 was performed except that A-3 was used instead of A-1.
(Comparative Example 6)
The same procedure as in Example 2 was performed except that A-4 was used instead of A-1.

According to the present invention, it is possible to provide an epoxy group-containing ethylene copolymer having a high resin modification effect and a resin composition containing the same.

Claims

An epoxy group-containing ethylene copolymer comprising a monomer unit derived from ethylene and a monomer unit derived from glycidyl methacrylate,
When the mass of the copolymer is 100% by mass, it contains 15 to 25% by mass of the monomer unit derived from the glycidyl methacrylate, and
A copolymer having a melt flow rate at 190 ° C. of 10 to 50 g / 10 min.
The copolymer according to claim 1, comprising only a monomer unit derived from ethylene and a monomer unit derived from glycidyl methacrylate.
The copolymer of Claim 1 which further contains the monomer unit derived from 1 or more types of compounds chosen from the compound represented by the following formula (1), and the compound represented by Formula (2).
CH 2 = CR 1 R 2 (1)
CHR 3 = CHR 4 (2)
Where
R 1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R 2 represents a halogen atom or a group represented by —COOR 5 (R 5 represents an alkyl group having 1 to 8 carbon atoms);
R 3 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by —COOR 6 (R 6 represents an alkyl group having 1 to 8 carbon atoms);
R 4 represents an alkyl nitrile having 1 to 8 carbon atoms, an alkyl ether group, an alkylamide, a halogen atom, a phenyl group, or a group represented by —COOR 7 (R 7 represents an alkyl group having 1 to 8 carbon atoms). Or R 4 represents a group represented by —OCOR 8 (R 8 represents an alkyl group having 1 to 8 carbon atoms).
The copolymer according to claim 3, wherein the one or more compounds are selected from the group consisting of vinyl acetate, methyl acrylate and methyl methacrylate.
An epoxy group-containing ethylene copolymer according to any one of claims 1 to 4,
A resin composition comprising a main chain and a polymer having at least one bond selected from the group consisting of an ester bond, a carbonic acid ester bond, an ether bond, a sulfide bond and an amide bond.
The resin composition according to claim 5, wherein the polymer is polylactic acid, aromatic polyester, or a mixture thereof.