WO2013099921A1 - 酸素吸収性樹脂組成物 - Google Patents
酸素吸収性樹脂組成物 Download PDFInfo
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- WO2013099921A1 WO2013099921A1 PCT/JP2012/083601 JP2012083601W WO2013099921A1 WO 2013099921 A1 WO2013099921 A1 WO 2013099921A1 JP 2012083601 W JP2012083601 W JP 2012083601W WO 2013099921 A1 WO2013099921 A1 WO 2013099921A1
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- oxygen
- resin composition
- absorbing
- resin
- absorbing component
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- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7248—Odour barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/738—Thermoformability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/46—Bags
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/60—Bottles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/008—Additives improving gas barrier properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/012—Additives improving oxygen scavenging properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
Definitions
- the present invention relates to a resin composition excellent in oxygen absorption, which contains a thermoplastic resin, particularly a polyester resin as a base resin, and further contains an oxygen absorbing component.
- the present invention also relates to a packaging container including a layer formed from the resin composition.
- Thermoplastic resins such as polyester resins such as polyethylene terephthalate (PET) are excellent in properties such as moldability, transparency, mechanical strength and chemical resistance, and have a relatively high gas barrier property such as oxygen. For this reason, polyester resins are used in various fields as packaging materials for films, sheets, bottles and the like. Further, in order to improve the gas barrier property of such a packaging material, a layer made of a gas barrier resin having an excellent gas barrier property such as a saponified ethylene-vinyl acetate copolymer or polyamide is interposed through an appropriate adhesive resin layer. A multilayer structure provided as an intermediate layer between inner and outer layers made of a polyester resin is also known.
- an inorganic oxygen absorbent such as iron powder as a means for improving the oxygen barrier property.
- Such an oxygen absorbent exhibits a barrier property by absorbing oxygen by being oxidized and blocking oxygen permeation through oxygen absorption.
- the inorganic oxygen absorbent colors the resin, it is not applied to the field of packaging that requires transparency. Accordingly, in the field of packaging, it is common to use an organic oxygen absorbent that does not cause resin coloring.
- Patent Document 1 proposes an oxygen-absorbing resin composition containing an oxidizing organic component (organic oxygen absorbent) such as unmodified polybutadiene and maleic anhydride-modified polybutadiene.
- Patent Document 2 proposes an oxygen scavenging composition containing a compound having an unsaturated alicyclic structure (cyclohexene structure) as an organic oxygen absorbent.
- the organic oxygen absorbent as described above requires a transition metal catalyst (for example, cobalt or the like) in order to oxidize it, and the use of the transition metal catalyst causes various disadvantages.
- a transition metal catalyst for example, cobalt or the like
- the base resin is also oxidized and deteriorated together with the oxygen absorbent, oxygen permeation through the base wall of the base resin occurs, and the barrier property against oxygen is not so improved.
- the oxidative deterioration of the base resin may cause a decrease in strength.
- many low molecular weight decomposition by-products such as aldehydes and ketones are generated, which causes problems such as generation of malodor and deterioration of flavor of contents.
- the reduction of the flavor of the contents is a big problem.
- a resin composition containing a resin that exhibits excellent oxygen absorption even under the condition where no transition metal catalyst is present includes, for example, a polymer containing a structural unit derived from a compound having an unsaturated alicyclic structure such as a ⁇ 3 -tetrahydrophthalic acid derivative obtained by Diels-Alder reaction of maleic anhydride and a diene. Contains as an absorbent resin.
- This type of oxygen-absorbing resin is extremely reactive with oxygen and not only exhibits excellent oxygen absorption even in the absence of a transition catalyst, but does not produce low molecular weight decomposition by-products that cause off-flavors. . Therefore, the oxygen-absorbing resin has an advantage that an excellent container that does not impair the flavor property of the contents can be formed.
- the oxygen-absorbing resin used in Patent Document 3 has a problem that the oxygen-absorbing property cannot be sufficiently improved when used in combination with a polyester resin such as PET. That is, the above oxygen-absorbing resin has a glass transition temperature of ⁇ 8 ° C. to 15 ° C., and has extremely high molecular mobility at room temperature. This mobility is one of the factors that show excellent oxygen absorption.
- the glass transition temperature of a polyester resin such as PET used in the field of packaging containers is about 70 ° C., and the mobility of the polyester resin at room temperature is extremely low. For this reason, even if the above-described oxygen-absorbing resin is simply coexisted with the polyester resin, the mobility of the molecules at room temperature is suppressed, and as a result, it is difficult to sufficiently exhibit the oxygen-absorbing property. It will end up.
- transition is made from a resin (B) that triggers oxidation of the resin (A) to a polyolefin resin (A) obtained by polymerizing an olefin having 2 to 8 carbon atoms.
- An oxygen-absorbing resin composition blended with the metal catalyst (C) has been proposed, and it is described that a styrene polymer is used as the resin (B).
- the resin composition is used for imparting oxygen absorbability to the polyolefin resin, and is not applied to a polyester resin.
- an oxygen absorbent that does not use a transition metal catalyst and is blended in a polyester resin (particularly a packaging grade polyester resin) and exhibits excellent oxygen absorption properties has not yet been known.
- the object of the present invention is excellent in oxygen absorption even in the absence of a transition metal catalyst, and is not particularly desired in the field of packaging containers without accompanying deterioration of a thermoplastic resin used as a base resin.
- Another object of the present invention is to provide an oxygen-absorbing resin composition exhibiting sufficient oxygen absorbability to ensure the gas barrier property.
- Another object of the present invention is to produce a low-molecular-weight decomposition product that causes a strange odor during oxygen absorption, and thus can form a single-layer container, which is extremely useful for realizing a thin container.
- the object is to provide a resin composition.
- Still another object of the present invention is to provide a packaging container including a layer formed from the oxygen-absorbing resin composition.
- an acid anhydride containing a certain unsaturated alicyclic structure and a derivative of the acid anhydride are used as a transition metal catalyst.
- a compound containing benzyl hydrogen as an oxidation promoting component, it was found that it exhibits excellent oxygen absorption capacity without causing oxidative degradation of the polyester, and a patent application was filed (Japanese Patent Application No. 2011-2011). 014844).
- the present inventors have found that, among these, the acid anhydride derivatives are used in combination with a compound containing benzyl hydrogen as an oxidation promoting component. At least, it has been found that an appropriate oxygen absorbing ability is exhibited and the oxygen barrier property required in the field of packaging containers can be secured, and the present invention has been completed.
- a base resin composed of a thermoplastic resin as well as, (B) the following formula (1);
- ring X is an aliphatic ring having one unsaturated bond
- n represents the number of substituents Y bonded to the ring X, and is an integer of 0 or 1
- Y is an alkyl group
- An oxygen-absorbing component comprising at least one selected from the group consisting of an ester, an amide, an imide or a dicarboxylic acid derived from an acid anhydride represented by: and a polymer having a structural unit derived from the acid anhydride, It is possible to provide an oxygen-absorbing resin composition comprising
- n 1.
- ring X is a cyclohexene ring
- the ring X is a bicyclo ring having one unsaturated bond
- the oxygen-absorbing component (B) is an imide obtained by heat-treating an amide formed by a reaction between the acid anhydride of the formula (1) and an amine
- the base resin (A) is a polyester resin, Is preferred.
- a packaging container characterized in that at least one layer comprising the above oxygen-absorbing resin composition is formed in the vessel wall.
- this packaging container it is possible to adopt a mode in which the layer made of the oxygen-absorbing resin composition is formed at a position in contact with the contents of the container, particularly only the layer made of the oxygen-absorbing resin composition.
- an acid anhydride derivative having an unsaturated alicyclic structure represented by the above formula (1) is used as the oxygen-absorbing component (B) (that is, an oxidizing component). It is a remarkable feature that it contains. That is, such an oxygen-absorbing component (B) can be used at room temperature to 50-50, as shown in Examples described later, even if an oxidation promoting component such as a transition metal catalyst or a compound having benzyl hydrogen is not used in combination. It exhibits a sufficiently high oxygen absorption capacity in an atmosphere of about 0 ° C., and can ensure oxygen barrier properties that are practically no problem when applied to packaging containers such as bottles.
- an oxygen-absorbing component (B) has a very high thermal decomposition starting temperature measured by TGA (about 200 ° C. or higher). For this reason, this oxygen-absorbing component (B) does not deteriorate even when exposed to molding conditions such as a bottle of polyester such as polyethylene terephthalate, and can sufficiently exhibit its oxygen-absorbing ability.
- the oxygen absorbing ability of the oxygen absorbing component (B) is that it absorbs oxygen by auto-oxidation, and this oxidation cleaves the unsaturated bond portion in the aliphatic ring. Therefore, when the oxygen absorbing component (B) absorbs oxygen, low molecular weight oxidative decomposition products such as aldehydes and ketones are not by-produced.
- such auto-oxidation exhibits oxygen absorption ability even in the absence of a transition metal catalyst, so that not only by-products of low molecular weight decomposition products due to the use of the transition metal catalyst are suppressed, but also the substrate A decrease in strength and gas barrier properties due to oxidative deterioration of the thermoplastic resin used as the resin (A), for example, a polyester resin, can be effectively avoided.
- the oxygen-absorbing resin composition of the present invention can be used to form a packaging container excellent in oxygen barrier properties using this, and also has a low molecular weight that causes a bad odor and reduced flavor during oxygen absorption (oxidation). Therefore, a layer formed from the resin composition can be provided at a position where it comes into contact with the contents of the container. That is, since the by-product of the low molecular weight oxidative decomposition product is suppressed, even if such a layer comes into contact with the container contents, the flavor of the container contents is not impaired. Therefore, when the packaging container is formed using the oxygen-absorbing resin composition of the present invention and its oxygen barrier property is increased, the degree of freedom in designing the vessel wall is increased, and the layer of the oxygen-absorbing resin composition is arbitrarily formed.
- the oxygen barrier property of the present invention can be ensured by excellent oxygen absorption even when a container having a single layer structure is used without using a transition metal catalyst or a special oxidation accelerator.
- the absorbent resin composition is extremely advantageous for reducing the thickness and weight of the container and realizing cost reduction.
- thermogravimetric analysis TGA
- thermogravimetric analysis TGA
- the base resin (A) (that is, the resin component serving as a matrix) is a thermoplastic resin, most preferably a polyester resin, and a predetermined oxygen-absorbing component (B) is added thereto.
- a known compounding agent blended into this type of resin composition if necessary.
- any thermoplastic resin can be used as long as it can be molded.
- Olefin resins such as low density polyethylene, high density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene or ⁇ -olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene Random or block copolymers, cyclic olefin copolymers, etc .
- Ethylene / vinyl copolymers such as ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / vinyl chloride copolymer, etc .
- Styrenic resin such as polystyrene, acrylonitrile / styrene copolymer, ABS, ⁇ -methylstyrene / styrene copolymer, etc .
- Vinyl resins such as polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvin
- polyester resins and olefin-based resins are suitable, can be molded at a relatively low molding temperature, can reduce thermal deterioration of oxygen-absorbing components described later, and can ensure high gas barrier properties. In this respect, polyester resin is most suitable.
- any polyester resin having at least a molecular weight sufficient to form a film may be used.
- the intrinsic viscosity (IV) is 0.6 to 1.40 dl / g
- a polyester resin in the range of 0.63 to 1.30 dl / g is preferably used as the base resin (A).
- thermoplastic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate, these polyesters and polycarbonate, Blends such as arylate resins can be used.
- a packaging grade PET polyester in which 60 mol% or more, more preferably 80 mol% or more of the ester repeating units are ethylene terephthalate units is particularly preferably used.
- Such a packaging grade PET-based polyester has a glass transition point (Tg) as high as 50 to 90 ° C., particularly 55 to 80 ° C. as described above, and a melting point (Tm) of 200 to 275 ° C. It is in the range of the degree.
- a copolymerized polyester having an ethylene terephthalate unit content within the above range can also be suitably used.
- Aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc .; Alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; Aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, dodecanedioic acid and the like; 1 type, or 2 or more types of combinations, such as these, can be illustrated.
- diol components other than ethylene glycol Propylene glycol, 1,4-butanediol, Diethylene glycol, 1,6-hexylene glycol, Cyclohexanedimethanol, 1 type, or 2 or more types, such as an ethylene oxide adduct of bisphenol A, may be mentioned.
- the dibasic acid component originating in the acid anhydride etc. which comprise the oxygen absorption component (B) described below may be introduce
- ⁇ Oxygen absorbing component (B)> As the oxygen-absorbing component (B) that absorbs oxygen, the following formula (1): Wherein ring X is an aliphatic ring having one unsaturated bond, n represents the number of substituents Y bonded to the ring X, and is an integer of 0 or 1, Y is an alkyl group, And at least one selected from the group consisting of an ester, an amide, an imide or a dicarboxylic acid derived from an acid anhydride represented by formula (I) and a polymer having a structural unit derived from the acid anhydride.
- formula (1) wherein ring X is an aliphatic ring having one unsaturated bond, n represents the number of substituents Y bonded to the ring X, and is an integer of 0 or 1, Y is an alkyl group, And at least one selected from the group consisting of an ester, an amide, an imide or a dicarboxylic acid derived from an acid
- the unsaturated bond portion in the unsaturated aliphatic ring X is easily oxidized, whereby oxygen is absorbed and oxygen absorption is improved. Demonstrate.
- an unsaturated bond in an aromatic ring does not show such oxidizability.
- a packaging container molded from a resin composition containing such a compound has an advantage of not reducing the flavor properties of the container contents.
- the layer made of this composition can be disposed on the side in contact with the contents of the container, and further, only the layer made of this composition.
- the container can be formed with (that is, a single layer structure).
- this layer exhibits excellent oxygen barrier properties due to excellent oxygen absorption, so that the wall of the container can be made thin, and from the viewpoint of weight reduction and resource saving of the container. It will be advantageous.
- the acid anhydride itself represented by the general formula (1) cannot be used as the oxygen absorbing component (B), and the oxygen absorbing component (B) Polymers in which structural units derived from esters, amides, imides, dicarboxylic acids or acid anhydrides obtained by reacting reactive species are incorporated (hereinafter sometimes referred to as “acid anhydride derivatives”) )Must. That is, the acid anhydride itself represented by the general formula (1) itself has insufficient oxygen absorption capacity, for example, at room temperature to 50 ° C., and therefore prevents oxidative deterioration of the contents when applied to a packaging container. This is because sufficient oxygen barrier properties cannot be obtained.
- the acid anhydride itself represented by the general formula (1) itself has insufficient oxygen absorption capacity, whereas the reason why the acid anhydride derivative derived from this acid anhydride exhibits high oxygen absorption capacity is clear.
- the present inventors presume as follows. That is, as understood from the thermogravimetric analysis (TGA) measurement results shown in FIGS. 1 and 2, acid anhydride has a considerably low thermal decomposition onset temperature at which weight loss starts, but acid anhydride derivatives. It is presumed that this thermal decomposition starting temperature is as high as about 200 ° C. or higher, sufficiently withstands the heat history when molded into a container such as a bottle, and the thermal deterioration is effectively suppressed.
- TGA thermogravimetric analysis
- the ring X is an aliphatic ring having one unsaturated bond, for example, cyclohexene A ring, bicyclo [2.2.1] hept-2-ene represented by the following formula, Tricyclo [4.4.0.1 2.5 ] -3-undecene, Tetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, Pentacyclo [8.4.0.1 2.5 . 1 9.12 . 0 8.13 ] -3-hexadecene, Pentacyclo [6.6.1.1 3.6 . 0 2.7 .
- a cyclohexene ring or one unsaturated bond A bicyclo ring having a ring is preferred, and a cyclohexene ring or bicyclo [2.2.1] hept-2-ene is particularly preferred.
- the position of the unsaturated bond may be either the 3-position or the 4-position, but the 3-position is particularly preferred from the viewpoint of oxidizability.
- the position of the unsaturated bond when the aliphatic ring X is bicyclo [2.2.1] hept-2-ene is preferably the 3rd position from the viewpoint of stability.
- Y represents an alkyl group.
- the alkyl group is not particularly limited, but in general, from the viewpoint of synthesis and oxidizability, a lower alkyl group having 3 or less carbon atoms, particularly a methyl group is preferable, and the bonding position is generally aliphatic.
- ring X is a cyclohexene ring, it may be either the 3-position or the 4-position, and when it is bicyclo [2.2.1] hept-2-ene, the 3-position is preferred.
- n represents the number of substituents Y bonded to the ring X, and is an integer of 0 or 1, and it has been experimentally clarified that it exhibits particularly high oxygen absorption ability. Therefore, n is preferably 1.
- the acid anhydride represented by the formula (1) is alkyltetrahydrophthalic anhydride, which is obtained by Diels-Alder reaction of maleic anhydride and diene, each obtained in the form of a mixture of isomers. It can be used as an absorption component (B).
- the acid anhydride that is the raw material for forming the acid anhydride derivative include 3-methyl- ⁇ 4 -tetrahydrophthalic acid anhydride represented by the following formula (2), 4-methyl- ⁇ 3 -tetrahydrophthalic anhydride represented by the following formula, 5-norbornene-2,3-dicarboxylic anhydride represented by the following formula (4) and methyl represented by the following formula (5) -5-norbornene-2,3 -Dicarboxylic anhydrides may be mentioned. (Four) (5)
- an ester, amide, imide, or dicarboxylic acid derived from the above acid anhydride is used as the oxygen-absorbing component (B).
- a polymer in which the above acid anhydride is incorporated as a structural unit is also used as the oxygen-absorbing component (B).
- the ester is an ester obtained by reacting an acid anhydride such as alkyltetrahydrophthalic anhydride with various alcohols.
- the alcohol used for esterification is not particularly limited, and any of aliphatic alcohols such as methyl alcohol and ethyl alcohol, and aromatic alcohols such as phenol can be used.
- polyhydric alcohols such as glycols can also be used. When a polyhydric alcohol is used, a number of unsaturated alicyclic structures corresponding to the number of alcohols in one molecule can be introduced.
- Such an ester may be a partial ester of the above acid anhydride.
- Such an ester is represented by the following formula, for example. R—O—OC—Z—CO—O—R HOOC-Z-CO-O-R Or HOOC-Z—CO—O—R—O—CO—Z—COOH
- Z is an unsaturated aliphatic ring possessed by the acid anhydride
- R is an organic group derived from the alcohol used in the reaction.
- Amides in the above derivatives are obtained by reacting acid anhydrides such as alkyltetrahydrophthalic anhydride with various amine compounds.
- the amine to be used is not particularly limited, and any of aliphatic amines such as methylamine, ethylamine and propylamine, and aromatic amines such as phenylamine can be used.
- One of the two carbonyl groups forming the acid anhydride group may be amidated, or both may be amidated.
- an amine it is not limited to a monoamine, Polyvalent amines, such as diamine and a triamine, can also be used. When a polyvalent amine is used, the number of unsaturated alicyclic structures corresponding to the number of amines in one molecule can be introduced.
- the imide among the above derivatives is obtained by heat-treating the above amide, for example, the following formula: HOOC-Z-CONH-R Or HOOC-Z-CONH-R-CONH-Z-COOH
- Z is an unsaturated aliphatic ring possessed by the acid anhydride
- R is an organic group derived from the amine used in the reaction.
- Z and R are the same as above. It is represented by
- imide when ring Z is bicyclo [2.2.1] hept-2-ene include compounds represented by the following formulae.
- imide is most suitable as the oxygen-absorbing component (B).
- the dicarboxylic acid is one obtained by hydrolysis of the acid anhydride and cleavage of the acid anhydride group, and the following formula: HOOC-Z-COOH
- Z and R are the same as above. It is represented by
- a polymer having a structural unit derived from the above-described acid anhydride can be obtained by using the acid anhydride as a dibasic acid component forming a polyester.
- Such a copolyester has an unsaturated alicyclic structure in the molecular chain, and therefore exhibits a predetermined oxygen absorptivity (oxidation property), so that it can be used as an oxygen-absorbing component (B). It is possible.
- such a copolyester has an extremely high affinity with the polyester resin used as the base resin (A), and is very suitable for uniformly dispersing the oxygen-absorbing component (B).
- dibasic acids used in the production of copolymer polyesters that can be used as such oxygen-absorbing component (B) include terephthalic acid, isophthalic acid, succinic acid, and adipic acid. These dibasic acids can be polycondensed with the diol component together with the above acid anhydride to produce a copolyester.
- diol component include 1,4-butanediol, ethylene glycol, 1,6-hexanediol, neopentyl glycol, and the like.
- the amount of the acid anhydride is preferably in the range of 30 to 90 mol%, particularly 50 to 80 mol%, based on the total dibasic acid. That is, if the amount of the structural unit derived from the acid anhydride in the copolymer is small, the oxygen absorbability is low, so that it is necessary to add a large amount to the polyester resin composition. As a result, it is necessary to add a large amount of an oxidation promoting component (C) to be described later, and the excellent properties of the thermoplastic resin (particularly polyester resin) used as the base resin (A) are impaired, for example, blow molding is difficult. Therefore, there is a possibility that it cannot be formed into a container.
- the advantage that the copolymer polyester obtained shows high affinity with respect to the polyester resin which can be used as base resin (A) is impaired. That is, the physical properties of the obtained copolymer polyester and the polyester resin (eg, PET) used as the base resin (A) are greatly different, and the copolymer polyester ⁇ oxygen absorbing component (B) ⁇ is uniformly dispersed. It becomes difficult to make it, or it becomes easy to produce a molding defect.
- the number average molecular weight of the copolymerized polyester that can be suitably used as the oxygen-absorbing component (B) is generally about 1,000 to 1,000,000.
- various acid anhydride derivatives those having a low molecular weight are suitable.
- various derivatives having a molecular weight of 2000 or less are suitably used.
- the amount of the oxygen-absorbing component (B) used is set so that sufficient oxygen-absorbing properties can be obtained and properties such as moldability of a thermoplastic resin used as the base resin (A), for example, a polyester resin, are not impaired. Is done. Although the specific amount cannot be strictly defined because of various forms, it is generally 0. 0 on the resin composition basis in terms of acid anhydride represented by the formula (1). A range of 1 to 20% by weight, particularly 0.5 to 10% by weight is preferred.
- the oxygen-absorbing resin composition of the present invention containing the components (A) and (B) described above is used in combination with a compound having benzyl hydrogen typified by a styrene polymer such as polystyrene, if necessary.
- Oxygen absorption can be further increased. That is, benzyl hydrogen is easily extracted, for example, is extracted during melt kneading and the like to generate a stable radical that does not easily react with oxygen, and this serves as a radical supply source to generate the radical of the oxygen-absorbing component (B) described above. Promotes oxidation of the oxygen-absorbing component (B) when in contact with oxygen. Therefore, the combined use of such oxidation promoting components can further enhance the oxygen absorption performance.
- a transition metal catalyst commonly used in this type of composition can also be used.
- Typical transition metals in such a transition metal catalyst are iron, cobalt, nickel, copper, silver, tin, titanium, zirconium, vanadium, chromium, manganese, and the like, and in particular, the oxygen-absorbing component (B) described above. Cobalt is optimal from the viewpoint of promoting oxidation and enhancing oxygen absorption.
- Such transition metal catalysts are generally used in the form of low-valent inorganic, organic or complex salts of these transition metals. The specific form is known and is described in detail in, for example, Japanese Patent Application Laid-Open No. 2004-161796.
- the use of the above transition metal catalyst causes inconveniences such as oxidative degradation of the base resin (A), a decrease in strength based thereon and a decrease in oxygen barrier properties, and a low molecular weight decomposition product that causes a strange odor as a by-product. There are things to do. Therefore, its use should be limited to applications where such inconvenience can be ignored, and even when used, its amount should be limited as much as possible.
- the transition metal catalyst may be in an amount of 1000 ppm or less, particularly 400 ppm or less in terms of metal based on the resin composition, and it is needless to say that it is optimal that it is not blended at all.
- the resin composition of the present invention can contain a gas barrier resin known per se.
- the resin composition containing the oxygen-absorbing component (B) described above has a function of increasing the barrier property against oxygen by absorbing oxygen by oxidation, but the barrier property against oxygen decreases with time. Go. From the viewpoint of effectively avoiding such inconvenience and improving the life against oxygen barrier properties, it is preferable to use a gas barrier resin known per se.
- the use of a gas barrier resin also has an advantage of improving barrier properties against other gases (for example, water vapor and carbon dioxide gas).
- Nylon 6, Nylon 6,6, Nylon 6/6 ⁇ 6 copolymer, Polymetaxylylene adipamide (MXD6), Nylon 6,10, Nylon 11, Nylon 12, Nylon 13 And the like are typical.
- amount of terminal amino groups is 40 eq / 10 6 g or more, particularly 50 eq / 10 poly meta xylylene adipamide exceeding 6 g, because resistance is high with respect to oxidative degradation, which is preferable.
- a typical gas barrier resin other than the polyamide resin is an ethylene-vinyl alcohol copolymer.
- the gas barrier resin as described above may have a molecular weight sufficient to form a film.
- a known N-hydroxyphthalimide compound that functions as an oxidation catalyst can be blended in order to enhance oxygen absorption.
- the N-hydroxyphthalimide compound easily extracts a hydrogen atom from an N-hydroxyimide group by molecular oxygen to generate a radical, and the radical abstracts a hydrogen atom from the oxygen-absorbing component (B) to generate an alkyl radical.
- the radical abstracts a hydrogen atom from the oxygen-absorbing component (B) to generate an alkyl radical.
- it functions as an oxidation catalyst.
- N-hydroxyphthalimide compounds include: N-hydroxyphthalimide, N-hydroxytetrachlorophthalimide, N-hydroxytetrabromophthalimide, N-hydroxyhexahydrophthalimide, 3-sulfonyl-N-hydroxyphthalimide, 3-methoxycarbonyl-N-hydroxyphthalimide, 3-methyl-N-hydroxyphthalimide, 3-hydroxy-N-hydroxyphthalimide, 4-nitro-N-hydroxyphthalimide, 4-chloro-N-hydroxyphthalimide, 4-methoxy-N-hydroxyphthalimide, 4-dimethylamino-N-hydroxyphthalimide, 4-carboxy-N-hydroxyhexahydrophthalimide, 4-methyl-N-hydroxyhexahydrophthalimide, Can be mentioned.
- the blending amount of the N-hydroxyphthalimide compound is preferably 0.001 to 1% by weight based on the resin composition of the present invention.
- various compounding agents such as a filler, a colorant, a heat stabilizer, a weather stabilizer, an antioxidant, as long as the properties such as excellent oxygen absorption and moldability of the resin composition of the present invention are not impaired.
- Anti-aging agents, light stabilizers, ultraviolet absorbers, antistatic agents, lubricants such as metal soaps and waxes, modifying resins or rubbers can be appropriately blended.
- the above-described oxygen-absorbing resin composition is generally prepared by kneading each of the above-described components using an extruder or the like in a non-oxidizing atmosphere.
- a master is obtained by melt-kneading a part of the thermoplastic resin of the base resin (A) and the oxygen-absorbing component (B) and other compounding agents appropriately blended while degassing using a twin screw extruder. Batch pellets can be prepared, and the remaining thermoplastic resin can be kneaded and used for molding immediately before use.
- the thermoplastic resin used for preparing the masterbatch and the thermoplastic resin kneaded later may have different physical properties. By adopting such means, the physical properties can be adjusted according to the application.
- a solution in which the transition metal catalyst is dissolved in an appropriate organic solvent for example, an organic solvent such as an alcohol, ether, ketone, or hydrocarbon is used. It is preferred to prepare and mix this solution with other ingredients in a kneader such as an extruder.
- the oxygen-absorbing polyester resin composition of the present invention exhibits an oxygen-absorbing ability that can sufficiently ensure the gas barrier properties required in the field of packaging containers without using special components such as transition metal catalysts and oxidation accelerators. . Therefore, the resin composition of the present invention is not only extremely advantageous in terms of cost, but also can effectively avoid deterioration of the base resin (A). In addition, since oxygen is not accompanied by by-product of low molecular weight decomposition products that cause off-flavors, it is extremely suitable in the field of packaging materials from the viewpoint of preventing oxidative deterioration of contents and not losing flavor. Therefore, the resin composition of the present invention is suitably used as a packaging material in the form of a film, sheet, cup, tray, bottle, tube, lid or the like. Moreover, it can also be used for the purpose of absorbing oxygen in a hermetically sealed container in the form of powder, film, sheet or the like.
- the oxygen-absorbing resin composition of the present invention does not involve the by-product of a low molecular weight decomposition product that causes a strange odor during oxygen absorption, when used for molding packaging containers such as bags, cups, bottles, and tubes.
- the layer made of this resin composition can be positioned on the side in contact with the container contents. Therefore, a packaging container can be formed only with the layer which consists of this resin composition.
- the oxygen barrier property due to the excellent oxygen absorption of the layer composed of the resin composition can be utilized to reduce the thickness of the container wall, thereby reducing the weight and resources of the container. Cost reduction can be realized.
- the molding into the packaging container as described above may be performed by a publicly known means.
- a film is formed by extrusion molding using the above resin composition, and the obtained film is bonded by heat sealing.
- a bag-like container can be obtained.
- a sheet-like or test-tube preform is formed by extrusion molding, injection molding, etc., and is used for secondary molding such as vacuum molding, stretch molding, pressure forming, plug assist molding, blow stretch molding, etc.
- a cup-shaped, tray-shaped or bottle-shaped packaging container can be obtained.
- a tube-shaped packaging container can be directly formed by extrusion molding, injection molding, direct blow molding, or the like.
- the oxygen-absorbing resin composition of the present invention can also be made into a multi-layered packaging container in combination with other resins or resin compositions.
- the barrier property against oxygen can be further improved, but also the barrier property against gas other than oxygen (for example, carbon dioxide gas or water vapor) can be enhanced, and further, the oxygen absorption property can be maintained for a long time.
- Examples of such a multilayer structure include the following layer configurations. In the following layer structure, the following abbreviations were used.
- OAR oxygen-absorbing layer formed using the oxygen-absorbing resin composition of the present invention
- PET polyethylene terephthalate layer
- PE made of low, medium or high-density polyethylene, linear low-density polyethylene or linear ultra-low-density polyethylene
- Layer PP Layer made of polypropylene
- COC Cyclic olefin resin
- GBAR Gas barrier layer made of aromatic polyamide or ethylene / vinyl alcohol copolymer
- an embodiment including a gas barrier resin layer is suitable for maintaining the oxygen absorption of the oxygen absorption layer (OAR) for a long period of time.
- any side may be formed on the inner surface side or the outer surface side of the container. If the adhesiveness between the layers is insufficient, a layer of an adhesive resin such as an olefin resin modified with an unsaturated carboxylic acid may be interposed as appropriate.
- a packaging container having such a multilayer structure is manufactured by molding in the same manner as in the case of the single-layer structure described above, utilizing multilayering by coextrusion, co-injection, or the like.
- the packaging container provided with the layer made of the oxygen-absorbing resin composition of the present invention exhibits excellent oxygen barrier properties due to its excellent oxygen-absorbing property, beer, Beverages such as wine, fruit juice, carbonated soft drink, fruits, nuts, vegetables, meat products, infant foods, coffee, jam, mayonnaise, ketchup, cooking oil, dressing, sauces, boiled dairy products, dairy products, other pharmaceuticals, It is extremely suitable as a container for filling various contents that deteriorate in the presence of oxygen, such as cosmetics and gasoline. Moreover, since it is excellent also in transparency, it can be suitably used for applications requiring transparency.
- BX Methyltetrahydrophthalic anhydride mixture containing 45% by weight of 4-methyl- ⁇ 3 -tetrahydrophthalic anhydride and 21% by weight of cis-3-methyl- ⁇ 4 -tetrahydrophthalic anhydride (HN-2200, manufactured by Hitachi Chemical) was used as a raw material for oxygen-absorbing components and used in the following synthesis examples.
- HN-2200 cis-3-methyl- ⁇ 4 -tetrahydrophthalic anhydride
- Comparative Examples 1 and 2 the methyltetrahydrophthalic anhydride mixture was used as an oxygen-absorbing component (BX) as it was.
- the TGA curve of this oxygen-absorbing component raw material is indicated by BX in FIG.
- BY 5-Norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a raw material for the oxygen-absorbing component. In Comparative Example 3, this was used as it was as an oxygen-absorbing component (BY).
- BZ Methyl-5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a raw material for the oxygen absorbing component. In Comparative Example 4, this was used as it was as an oxygen-absorbing component (BZ).
- Transition metal catalyst Cobalt neodecanoate (DICnate 5000: manufactured by Dainippon Ink and Chemicals)
- Organic radical catalyst NHPI (N-hydroxyphthalimide) (manufactured by Tokyo Chemical Industry Co., Ltd.)
- the organic layer was dehydrated with sodium sulfate and then heated under reduced pressure to obtain an oxygen-absorbing component (B1). From the IR spectrum, the disappearance of the 1780 cm ⁇ 1 peak derived from methyltetrahydrophthalic anhydride and the appearance of the 1708 cm ⁇ 1 peak derived from imide were confirmed. The TGA curve of this oxygen absorption component is indicated by B1 in FIG.
- the structural formulas of main components of the obtained oxygen-absorbing component are as follows.
- Synthesis Example 2 Synthesis was performed in the same manner as in Synthesis Example 1 except that 13 g of laurylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the amine component to obtain an oxygen-absorbing component (B2).
- the TGA curve of this oxygen absorption component is indicated by B2 in FIG.
- the structural formulas of main components of the obtained oxygen-absorbing component are as follows.
- Synthesis Example 3 Synthesis was performed in the same manner as in Synthesis Example 1 except that 3.1 g of hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the amine component, to obtain an oxygen-absorbing component (B3).
- the TGA curve of this oxygen absorbing component is indicated by B3 in FIG.
- the structural formulas of main components of the obtained oxygen-absorbing component are as follows.
- Synthesis Example 4 Synthesis was performed in the same manner as in Synthesis Example 1 except that 3.7 g of metaxylylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the amine component, to obtain an oxygen-absorbing component (B4).
- the TGA curve of this oxygen absorbing component is indicated by B4 in FIG.
- the structural formulas of main components of the obtained oxygen-absorbing component are as follows.
- Synthesis Example 5 Synthesis was performed in the same manner as in Synthesis Example 1 except that 3.7 g of paraxylylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the amine component, to obtain an oxygen-absorbing component (B5).
- the TGA curve of this oxygen-absorbing component is indicated by B5 in FIG.
- the structural formulas of main components of the obtained oxygen-absorbing component are as follows.
- Synthesis Example 6 Synthesis was performed in the same manner as in Synthesis Example 1 except that 3.85 g of 1,3-bis (aminomethyl) cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the amine component, to obtain an oxygen-absorbing component (B6).
- the TGA curve of this oxygen absorption component is indicated by B6 in FIG.
- the structural formulas of main components of the obtained oxygen-absorbing component are as follows.
- Synthesis Example 9 Synthesis was performed in the same manner as in Synthesis Example 8 except that 26.6 g of oxygen-absorbing component raw material BX and 20.0 g of BHET were used, and consisted of a copolyester having terephthalic acid-ethylene glycol-oxygen-absorbing component raw material BX as a constituent monomer. An oxygen absorbing component (B9) was obtained.
- the reaction solution was added to 200 mL of 2-propanol, and the resulting slurry was subjected to suction filtration and washed with 25 mL of 2-propanol. Then, oxygen-absorbing component (B12) was obtained by vacuum drying at 40 ° C. for 12 hours.
- the structural formula of the obtained oxygen-absorbing component is as follows.
- Oxygen-absorbing component raw material BY 25 g, 24.6 g of stearylamine, 20 g of xylene (manufactured by Wako Pure Chemical Industries) and 13.6 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries) was reacted in a nitrogen atmosphere at 120 to 160 ° C. for about 4 hours while removing generated water.
- the reaction solution was added to 200 mL of distilled water, and the resulting slurry was suction filtered and washed with 25 mL of distilled water.
- oxygen-absorbing component (B13) was obtained by vacuum drying at 40 ° C. for 12 hours.
- the structural formula of the obtained oxygen-absorbing component is as follows.
- Synthesis Example 14 Synthesis was performed in the same manner as in Synthesis Example 12 except that 25 g of BZ and 9.55 g of metaxylenediamine were used as the oxygen-absorbing component raw material to obtain an oxygen-absorbing component (B14).
- the structural formula of the obtained oxygen-absorbing component is as follows.
- Oxygen absorption measurement Various resin composition pellets were quantified after pulverization with a freeze pulverizer, and an oxygen-impermeable container with an internal volume of 58 ml ⁇ High Leto Flex: polypropylene / steel foil / polypropylene cups made by Toyo Seikan Co., Ltd. Laminated container ⁇ , heat-sealed with a lid ⁇ polypropylene (inner layer) / aluminum foil / polyester (outer layer) ⁇ , and stored under conditions of 23 and 50 ° C. After 7 days, the oxygen concentration in the container was measured with a micro gas chromatograph (manufactured by Agilent Technologies; M200), and the oxygen absorption (cc / g) was calculated.
- thermogravimetric analysis Each oxygen-absorbing component was tested using a thermogravimetric analyzer (TGA7: manufactured by Perkin-Elmer) at a heating rate of 10 ° C / min. The results are shown in FIGS.
- Example 1 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B1 was added to the base resin A1 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 2 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B2 was added to the base resin A1 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 3 A resin composition pellet in which 10% by weight of the oxygen absorbing component B3 was added to the base resin A1 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 4 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B4 was added to the base resin A1 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 5 Resin composition pellets obtained by adding 10% by weight of the oxygen-absorbing component B1 to the base resin A1 based on the resin composition and 0.035% by weight (350 ppm) of the transition metal catalyst in terms of metal based on the resin composition are as described above. The oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 6 Resin composition pellets obtained by adding 10% by weight of the oxygen-absorbing component B2 to the base resin A1 on the basis of the resin composition and 0.035% by weight (350 ppm) of the transition metal catalyst in terms of metal on the basis of the resin composition are as described above. The oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 7 Resin composition pellets obtained by adding 10% by weight of the oxygen-absorbing component B3 to the base resin A1 based on the resin composition and 0.035% by weight (350 ppm) of the transition metal catalyst in terms of metal based on the resin composition are as described above. The oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 8 Resin composition pellets obtained by adding 10% by weight of the oxygen-absorbing component B4 to the base resin A1 based on the resin composition and 0.035% by weight (350 ppm) of the transition metal catalyst in terms of metal based on the resin composition are as described above. The oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 9 A resin composition pellet obtained by adding 10% by weight of the oxygen absorbing component B1 to the base resin A2 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 10 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B4 was added to the base resin A2 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 11 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B1 was added to the base resin A3 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 12 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B4 was added to the base resin A3 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 13 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B1 was added to the base resin A4 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 14 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B4 was added to the base resin A4 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 15 A resin composition pellet obtained by adding 10% by weight of the oxygen-absorbing component B5 to the base resin A1 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 16 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B6 was added to the base resin A1 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 17 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B7 was added to the base resin A1 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 18 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B1 was added to the base resin A5 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 19 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B4 was added to the base resin A5 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 20 A resin composition pellet obtained by adding 10% by weight of the oxygen absorbing component B1 to the base resin A6 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 21 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B4 was added to the base resin A6 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 22 A resin composition pellet in which 5% by weight of the oxygen-absorbing component B1 was added to the base resin A1 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 23 A resin composition pellet in which 5% by weight of the oxygen-absorbing component B4 was added to the base resin A1 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 24 A resin composition pellet in which 5% by weight of oxygen-absorbing component B1 and 0.5% by weight of NHPI as an organic radical catalyst are added to base resin A1 based on the resin composition is prepared by the above-described method. The amount of oxygen absorbed (cc / g) was calculated. The results are shown in Table 1.
- Example 25 A resin composition pellet in which 5% by weight of oxygen-absorbing component B4 and 0.5% by weight of NHPI as an organic radical catalyst are added to base resin A1 based on the resin composition is prepared by the above method. The amount of oxygen absorbed (cc / g) was calculated. The results are shown in Table 1.
- Example 26 A resin composition pellet in which 10% by weight of the oxygen absorbing component B8 was added to the base resin A1 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 27 A resin composition pellet in which 10% by weight of the oxygen-absorbing component B9 was added to the base resin A1 based on the resin composition was prepared by the above method, and the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 29 A resin composition pellet in which 10% by weight of oxygen-absorbing component B13 and 0.5% by weight of NHPI as an organic radical catalyst are added to the base resin A1 based on the resin composition is prepared by the above method. The amount of oxygen absorbed (cc / g) was calculated. The results are shown in Table 1.
- Example 30 A resin composition pellet in which 10% by weight of the oxygen absorbing component B14 and 0.5% by weight of NHPI as an organic radical catalyst are added to the base resin A1 based on the resin composition is prepared by the above method. The amount of oxygen absorbed (cc / g) was calculated. The results are shown in Table 1.
- Example 31 A resin composition pellet in which 10% by weight of oxygen absorbing component B15 and 0.5% by weight of NHPI as an organic radical catalyst are added to the base resin A1 based on the resin composition is prepared by the above method. The amount of oxygen absorbed (cc / g) was calculated. The results are shown in Table 1.
- Example 32 A resin composition pellet prepared by adding 10% by weight of the oxygen-absorbing component B13 and 0.035% by weight (350 ppm) of the transition metal catalyst in terms of metal to the base resin A5 based on the resin composition is prepared by the above method.
- the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
- Example 33 A resin composition pellet prepared by adding 10% by weight of the oxygen-absorbing component B15 and 0.035% by weight (350 ppm) of the transition metal catalyst in terms of metal to the base resin A5 based on the resin composition is prepared by the above method.
- the oxygen absorption amount (cc / g) of the resin composition was calculated. The results are shown in Table 1.
Abstract
Description
また、特許文献2には、不飽和脂環構造(シクロヘキセン構造)を有する化合物を有機系酸素吸収剤として含む酸素捕集組成物が提案されている。
しかしながら、かかる樹脂組成物も、遷移金属触媒を使用することが必須である。さらに、該樹脂組成物は、ポリオレフィン系樹脂に酸素吸収性を付与するために使用されるものであり、ポリエステル樹脂に適用されるものではない。
本発明の他の目的は、酸素吸収に際して異臭の要因となる低分子量分解物を生ぜず、従って単層構造の容器を形成することができ、容器の薄肉化の実現に極めて有用な酸素吸収性樹脂組成物を提供することにある。
本発明のさらに他の目的は、上記の酸素吸収性樹脂組成物から形成された層を含む包装容器を提供することにある。
(A)熱可塑性樹脂からなる基材樹脂、
及び、
(B)下記式(1);
nは、前記環Xに結合した置換基Yの数を示し、0又は1の整
数であり、
Yはアルキル基である、
で表わされる酸無水物から誘導されるエステル、アミド、イミド又はジカルボン酸、及び該酸無水物に由来する構成単位を有する重合体からなる群より選択された少なくとも一種からなる酸素吸収成分、
を含有していることを特徴とする酸素吸収性樹脂組成物が提供される。
(1)前記式(1)において、n=1であること、
(2)更に、環Xが、シクロヘキセン環であること、
(3)前記式(1)において、環Xが、一つの不飽和結合を有するビシクロ環であること、
(4)前記酸素吸収成分(B)が、前記式(1)の酸無水物とアミンとの反応により形成されるアミドを熱処理して得られるイミドであること、
(5)基材樹脂(A)がポリエステル樹脂であること、
が好ましい。
この包装容器においては、前記酸素吸収性樹脂組成物からなる層が、容器内容物と接する位置に形成されているという態様を採用することができ、特に前記酸素吸収性樹脂組成物からなる層のみから容器壁が形成されている単層構造の包装容器とすることができる。
従って、本発明の酸素吸収性樹脂組成物を用いて包装容器を成形し、その酸素バリア性を高めるときには、器壁の設計の自由度が高められ、酸素吸収性樹脂組成物の層を任意の位置に設けた多層構造とすることが可能となるばかりか、この酸素吸収性樹脂組成物の層のみにより器壁が形成された単層構造とすることもできる。特に、遷移金属触媒や格別の酸化促進剤を併用せずに単層構造の容器とした場合であっても、優れた酸素吸収性により酸素バリア性を確保することができるため、本発明の酸素吸収性樹脂組成物は、容器の薄肉化や軽量化、コスト削減の実現に極めて有利である。
基材樹脂(A)としては、成形可能である限り、任意の熱可塑性樹脂を使用することができる。例えば、
オレフィン系樹脂、例えば、低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、ポリ1-ブテン、ポリ4-メチル-1-ペンテンあるいはエチレン、プロピレン、1-ブテン、4-メチル-1-ペンテン等のα-オレフィン同士のランダムあるいはブロック共重合体、環状オレフィン共重合体など;
エチレン・ビニル系共重合体、例えば、エチレン・酢酸ビニル共重合体、エチレン・ビニルアルコール共重合体、エチレン・塩化ビニル共重合体等;
スチレン系樹脂、例えば、ポリスチレン、アクリロニトリル・スチレン共重合体、ABS、α-メチルスチレン・スチレン共重合体等;
ビニル系樹脂、例えば、ポリ塩化ビニル、ポリ塩化ビニリデン、塩化ビニル・塩化ビニリデン共重合体、ポリアクリル酸メチル、ポリメタクリル酸メチル等;
ポリアミド樹脂、例えば、ナイロン6、ナイロン6-6、ナイロン6-10、ナイロン11、ナイロン12等;
ポリエステル樹脂、例えば、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート、ポリエチレンナフタレート、及びこれらの共重合ポリエステル等;
ポリカーボネート樹脂;
ポリフエニレンオキサイド樹脂;
生分解性樹脂、例えば、ポリ乳酸など;
などを基材樹脂(A)として使用することができる。勿論、成形性が損なわれない限り、これらの熱可塑性樹脂のブレンド物を、基材樹脂(A)として使用することもできる。
特に容器等の包装材料として用いる場合には、ポリエステル樹脂やオレフィン系樹脂が好適であり、比較的低い成形温度で成形でき、後述する酸素吸収成分の熱劣化を少なくし、高いガスバリア性を確保できるという点で、ポリエステル樹脂が最適である。
このような共重合ポリエステルにおいて、テレフタル酸以外の二塩基酸としては、
芳香族ジカルボン酸、例えば、イソフタル酸、フタル酸、ナフタレンジカルボン酸等;
脂環族ジカルボン酸、例えば、シクロヘキサンジカルボン酸等;
脂肪族ジカルボン酸、例えば、コハク酸、アジピン酸、セバチン酸、ドデカンジオン酸等;
等の1種又は2種以上の組み合わせを例示することができる。エチレングリコール以外のジオール成分としては、
プロピレングリコール、
1,4-ブタンジオール、
ジエチレングリコール、
1,6-ヘキシレングリコール、
シクロヘキサンジメタノール、
ビスフェノールAのエチレンオキサイド付加物
等の1種又は2種以上が挙げられる。
尚、以下に述べる酸素吸収成分(B)を構成する酸無水物等に由来する二塩基酸成分が、エステル交換等により、上記の共重合成分としてPET系ポリエステル中に導入されることもある。
本発明において、酸素を吸収する酸素吸収成分(B)としては、下記式
(1):
nは、前記環Xに結合した置換基Yの数を示し、0又は1の整
数であり、
Yはアルキル基である、
で表わされる酸無水物から誘導されるエステル、アミド、イミド又はジカルボン酸、及び該酸無水物に由来する構成単位を有する重合体からなる群より選択された少なくとも一種が使用される。
ビシクロ[2.2.1]ヘプト-2-エン、
トリシクロ[4.4.0.12.5]-3-ウンデセン、
テトラシクロ[4.4.0.12.5.17.10]-3-ドデセン、
ペンタシクロ[8.4.0.12.5.19.12.08.13]-3-ヘキサデセ
ン、
ペンタシクロ[6.6.1.13.6.02.7.09.14]-4-ヘキサデセン
等が挙げられるが、酸素吸収成分単位重量あたりの不飽和結合基数が大きい方が酸素吸収能力において有利であるとの観点から、シクロヘキセン環又は1つの不飽和結合を有するビシクロ環が好適であり、特に、シクロヘキセン環又はビシクロ[2.2.1]ヘプト-2-エンが好適である。
-ジカルボン酸無水物を挙げることができる。
また、上記の酸無水物が構成単位として組み込まれている重合体も酸素吸収成分(B)として使用される。
このようなエステルは、例えば下記式で表される。
R-O-OC-Z-CO-O-R
HOOC-Z-CO-O-R
或いは
HOOC-Z-CO-O-R-O-CO-Z-COOH
式中、Zは、酸無水物が有する不飽和脂肪族環であり、
Rは、反応に用いたアルコールに由来する有機基である。
用いるアミンとしては、特に制限されず、メチルアミン、エチルアミン、プロピルアミン等の脂肪族アミンや、フェニルアミン等の芳香族アミンの何れも使用することができる。アミドは、酸無水物基を形成している2個のカルボニル基の内の一方がアミド化されたものであってもよいし、両方がアミド化されたものであってもよい。さらに、アミンとしては、モノアミンに限定されず、ジアミン、トリアミン等の多価アミンも使用することができる。多価アミンを使用する場合には、1分子中のアミンの数に相当する数の不飽和脂環構造を導入することができる。
HOOC-Z-CONH-R
或いは
HOOC-Z-CONH-R-CONH-Z-COOH
式中、Zは、酸無水物が有する不飽和脂肪族環であり、
Rは、反応に用いたアミンに由来する有機基である、
で表されるアミドを熱処理することにより得られ、下記式;
Z-(CO)2-N-R
或いは
Z-(CO)2-N-R-N-(CO)2-Z
式中、Z及びRは、上記と同じである、
で表される。
HOOC-Z-COOH
式中、Z及びRは、上記と同じである、
で表される。
酸素吸収成分(B)として好適に使用し得る上記共重合ポリエステルの数平均分子量は、一般に、1000乃至1000000程度である。
上述した(A)及び(B)の成分を含有する本発明の酸素吸収性樹脂組成物は、必要に応じて、例えばポリスチレン等のスチレン系重合体に代表されるベンジル水素を有する化合物を併用し、酸素吸収性をより高めることができる。即ち、ベンジル水素は引き抜かれやすく、例えば溶融混練等に際して引き抜かれ、酸素と反応し難い安定なラジカルを生成し、これがラジカル供給源となって前述した酸素吸収成分(B)のラジカルを生成せしめ、酸素と接触したときの酸素吸収成分(B)の酸化を促進する。従って、このような酸化促進成分の併用により、より一層酸素吸収性能を高めることができる。
このような遷移金属触媒における遷移金属としては、鉄、コバルト、ニッケル、銅、銀、錫、チタン、ジルコニウム、バナジウム、クロム、マンガン等が代表的であり、特に前述した酸素吸収成分(B)の酸化を促進させ、酸素吸収性を高めるという観点から、コバルトが最適である。このような遷移金属の触媒は、一般に、これら遷移金属の低価数の無機塩、有機塩或いは錯塩の形で使用される。その具体的な形態は公知であり、例えば特開2004-161796号等に詳細に記載されている。
ナイロン6、
ナイロン6・6、
ナイロン6/6・6共重合体、
ポリメタキシリレンジアジパミド(MXD6)、
ナイロン6・10、
ナイロン11、
ナイロン12、
ナイロン13
等のポリアミド樹脂が代表的である。これらのポリアミドの中でも、末端アミノ基量が40eq/106g以上、特に50eq/106gを超えるポリメタキシリレンジアジパミドは、酸化劣化に対する耐性も高いので、好適である。
ポリアミド樹脂以外のガスバリア性樹脂としては、エチレン-ビニルアルコール共重合体が代表的である。例えば、エチレン含有量が20乃至60モル%、特に25乃至50モル%のエチレン-酢酸ビニル共重合体を、ケン化度が96%以上、特に99モル%以上となるようにケン化して得られる共重合体ケン化物が、好適に使用される。
上記のようなガスバリア性樹脂は、フィルムを形成し得るに足る分子量を有していればよい。
N-ヒドロキシフタルイミド、
N-ヒドロキシテトラクロロフタルイミド、
N-ヒドロキシテトラブロモフタルイミド、
N-ヒドロキシヘキサヒドロフタルイミド、
3-スルホニル-N-ヒドロキシフタルイミド、
3-メトキシカルボニル-N-ヒドロキシフタルイミド、
3-メチル-N-ヒドロキシフタルイミド、
3-ヒドロキシ-N-ヒドロキシフタルイミド、
4-ニトロ-N-ヒドロキシフタルイミド、
4-クロロ-N-ヒドロキシフタルイミド、
4-メトキシ-N-ヒドロキシフタルイミド、
4-ジメチルアミノ-N-ヒドロキシフタルイミド、
4-カルボキシ-N-ヒドロキシヘキサヒドロフタルイミド、
4-メチル-N-ヒドロキシヘキサヒドロフタルイミド、
を挙げることができる。N-ヒドロキシフタルイミド化合物の配合量は、本発明の樹脂組成物基準で、0.001~1重量%が好ましい。
上述した酸素吸収性樹脂組成物は、一般的には、前述した各成分を、非酸化性雰囲気中で押出機等を用いて混練することにより調製されるが、一部の成分を予め混合しておき、残りの成分を後から混合する等の手段も採用することができる。
例えば、基材樹脂(A)の熱可塑性樹脂の一部と、二軸押出機を用いて脱気しながら酸素吸収成分(B)及び適宜配合される他の配合剤とを溶融混練してマスターバッチペレットを調製しておき、使用直前に、残りの熱可塑性樹脂を混練して成形に供することもできる。この場合、マスターバッチの調製に用いられる熱可塑性樹脂と後から混練する熱可塑性樹脂とが異なる物性を有するものであってもよい。このような手段を採用することにより、用途に応じて物性を調整することができる。
また、酸素吸収に際して、異臭の原因となる低分子量分解物の副生を伴わないため、内容物の酸化劣化を防止し且つフレーバーを損なわないという点でも、包装材の分野に極めて好適である。従って、本発明の樹脂組成物は、例えばフィルム、シート、カップ、トレイ、ボトル、チューブ或いは蓋体等の形態で包装材として好適に使用される。また、粉末、フィルム、シート等の形態で密封包装容器内の酸素を吸収する目的で使用することもできる。
このような単層構造の包装容器では、上記樹脂組成物からなる層の優れた酸素吸収による酸素バリア性を活かして、その容器壁を薄肉化することができ、容器の軽量化や省資源化、低コスト化を実現できる。
尚、以下の層構成において、以下の略号を使用した。
OAR:本発明の酸素吸収性樹脂組成物を用いて形成された酸素吸収層
PET:ポリエチレンテレフタレート層
PE:低、中或いは高密度ポリエチレン、直鎖低密度ポリエチレンまた
は線状超低密度ポリエチレンからなる層
PP:ポリプロピレンからなる層
COC:環状オレフィン樹脂の層
GBAR:芳香族ポリアミド或いはエチレン・ビニルアルコール共重合
体からなるガスバリア層
PET/OAR
三層構造の例;
PE/OAR/PET
PET/OAR/PET
GBAR/OAR/PET
PE/OAR/COC
四層構造;
PE/PET/OAR/PET
PE/OAR/GBAR/PET
PET/OAR/GBAR/PET
PE/OAR/GBAR/COC
PE/OAR/GBAR/PE
五層構造;
PET/OAR/PET/OAR/PET
PE/PET/OAR/GBAR/PET
PET/OAR/GBAR/COC/PET
PET/OAR/PET/COC/PET
PE/OAR/GBAR/COC/PET
PE/GBAR/OAR/GBAR/PE
PP/GBAR/OAR/GBAR/PP
六層構造;
PET/OAR/PET/OAR/GBAR/PET
PE/PET/OAR/COC/GBAR/PET
PET/OAR/GBAR/PET/COC/PET
PE/GBAR/OAR/PE/GBAR/PE
PP/GBAR/OAR/PP/GBAR/PP
七層構造;
PET/OAR/COC/PET/GBAR/OAR/PET
上記の多層構造では、何れの側が容器の内面側或いは外面側に形成されていてもよい。
各層の間の接着性が不十分な場合には、適宜、不飽和カルボン酸で変性されたオレフィン系樹脂などの接着剤樹脂の層を間に介在させることも可能である。
このような多層構造の包装容器は、共押出や共射出等による多層化を利用して、前述した単層構造の場合と同様にして成形を行うことにより製造される。
また、透明性にも優れているため、透明性の要求される用途にも好適に使用できる。
以下に、実施例及び比較例で使用した材料及び試験方法を示す。
<基材樹脂(A)>
(A1):シクロヘキサンジメタノール含有ポリエチレンテレフタレート
樹脂(S2008:SKケミカル製)
(A2):ポリエチレン(G806:住友化学工業製)
(A3):エチレン-ビニルアルコール共重合体(L171B:クラレ
製)
(A4):ポリメタキシリレンジアジパミド(T620:東洋紡製)
(A5):ポリエチレンテレフタレート(BK6180:日本ユニペット
製)
(A6):ポリエチレンテレフタレート(RT543CTHP:日本ユニ
ペット製)
(BX):
4-メチル-Δ3-テトラヒドロ無水フタル酸を45重量%およびcis-3-メチル-Δ4-テトラヒドロ無水フタル酸を21重量%含有するメチルテトラヒドロ無水フタル酸混合物(HN-2200:日立化成製)を酸素吸収成分の原料とし、下記の合成例で用いた。
比較例1及び2においては、該メチルテトラヒドロ無水フタル酸混合物をそのまま酸素吸収成分(BX)として使用した。
この酸素吸収成分原料のTGA曲線は、図1で、BXで示されている。
(BY):
5-ノルボルネン‐2,3-ジカルボン酸無水物(東京化成工業製)を酸素吸収成分の原料とした。
比較例3においては、これをそのまま酸素吸収成分(BY)として使用した。
(BZ):
メチル‐5-ノルボルネン‐2,3-ジカルボン酸無水物(東京化成工業製)を酸素吸収成分の原料とした。
比較例4においては、これをそのまま酸素吸収成分(BZ)として使用した。
遷移金属触媒:ネオデカン酸コバルト(DICNATE5000:大日本イ
ンキ化学工業製)
有機ラジカル触媒:NHPI(N-ヒドロキシフタルイミド)(東京化成工
業製)
(合成例1)
攪拌装置、窒素導入管を備えた100mLの3ツ口フラスコに
酸素吸収成分原料;BX 10g、及び
アミン成分;ステアリルアミン(東京化成工業製) 14.5g
を仕込み、窒素雰囲気下120℃~180℃で、生成する水を取り除きながら約6時間反応させた。反応液を冷却した後クロロホルムに溶解し、1N塩酸水溶液で洗浄し、その後1N水酸化ナトリウム水溶液で洗浄した。有機層を硫酸ナトリウムで脱水した後、減圧下で加熱することにより酸素吸収成分(B1)を得た。
IRスペクトルより、メチルテトラヒドロ無水フタル酸由来の1780cm-1のピークの消失とイミドに由来する1708cm-1のピークの出現を確認した。
この酸素吸収成分のTGA曲線は、図1において、B1で示されている。
得られた酸素吸収成分の主たる構成成分の構造式は、以下の通りである。
アミン成分としてラウリルアミン(東京化成工業製)を13g用いた以外は合成例1と同様に合成を行い、酸素吸収成分(B2)を得た。
この酸素吸収成分のTGA曲線は、図1において、B2で示されている。
得られた酸素吸収成分の主たる構成成分の構造式は、以下の通りである。
アミン成分としてヘキサメチレンジアミン(東京化成工業製)を3.1g用いた以外は合成例1と同様に合成を行い、酸素吸収成分(B3)を得た。
この酸素吸収成分のTGA曲線は、図1において、B3で示されている。
得られた酸素吸収成分の主たる構成成分の構造式は、以下の通りである。
アミン成分としてメタキシリレンジアミン(東京化成工業製)を3.7g用いた以外は合成例1と同様に合成を行い、酸素吸収成分(B4)を得た。
この酸素吸収成分のTGA曲線は、図1において、B4で示されている。
得られた酸素吸収成分の主たる構成成分の構造式は、以下の通りである。
アミン成分としてパラキシリレンジアミン(東京化成工業製)を3.7g用いた以外は合成例1と同様に合成を行い、酸素吸収成分(B5)を得た。
この酸素吸収成分のTGA曲線は、図2において、B5で示されている。
得られた酸素吸収成分の主たる構成成分の構造式は、以下の通りである。
アミン成分として1,3-ビス(アミノメチル)シクロヘキサン(東京化成工業製)を3.85g用いた以外は合成例1と同様に合成を行い、酸素吸収成分(B6)を得た。
この酸素吸収成分のTGA曲線は、図2において、B6で示されている。
得られた酸素吸収成分の主たる構成成分の構造式は、以下の通りである。
攪拌装置、窒素導入管、滴下ロートを備えた300mLのセパラブルフラスコに酸素吸収成分原料BXを10g仕込み、窒素置換した。ここに、アミン成分として、蒸留水15mlに溶かしたメタキシレンジアミン3.7gを滴下ロートにて加え、生成した沈殿を40℃で12時間真空乾燥することで酸素吸収成分(B7)を得た。
得られた酸素吸収成分の主たる構成成分の構造式は、以下の通りである。
攪拌装置、窒素導入管を備えた300mLのセパラブルフラスコに
酸素吸収成分原料;BX 25.0g、
ビスヒドロキシエチルテレフタレート(BHET)(東京化成工業製)
30.0g、及び
エステル化触媒;チタニウムテトライソプロポキシド(キシダ化学製)
0.25mL
を仕込み、窒素雰囲気下120℃~180℃で、生成する水を取り除きながら約6時間反応させることで、テレフタル酸-エチレングリコール-酸素吸収成分原料BXを構成モノマーとする共重合ポリエステルからなる酸素吸収成分(B8)を得た。
酸素吸収成分原料BXを26.6g、BHETを20.0gとした以外は合成例8と同様に合成を行い、テレフタル酸-エチレングリコール-酸素吸収成分原料BXを構成モノマーとする共重合ポリエステルからなる酸素吸収成分(B9)を得た。
攪拌装置、窒素導入管、Dean-Stark型水分離器を備えた300mLのセパラブルフラスコに
無水フタル酸(東京化成工業製) 25g、
メタキシレンジアミン 10.7g、
トルエン(和光純薬製) 15ml、及び
N, N-ジメチルホルムアミド(DMF)(和光純薬社製)
15ml
を仕込み、窒素雰囲気中120℃で、生成する水を取り除きながら約4時間反応させた。反応液に2-プロパノールを100mL加え、得られたスラリーを吸引ろ過し、2-プロパノール25mLで洗浄した。その後40℃で12時間真空乾燥することで化合物(B10)を得た。
得られた化合物の構造式は、以下の通りである。
仕込みを
1,2,3,6-テトラヒドロ無水フタル酸(リカシッドTH:新日本
理化製) 25g、
メタキシレンジアミン 11.1g、
トルエン 15mL、
DMF 15mL
とした以外は、合成例10と同様に合成を行い、化合物(B11)を得た。
得られた化合物の構造式は、以下の通りである。
攪拌装置、窒素導入管、Dean-Stark型水分離器を備えた300mLのセパラブルフラスコに、
酸素吸収成分原料;BY 25g、
メタキシレンジアミン 10.36g、
キシレン(和光純薬社製) 20g、及び
N‐メチルピロリドン(和光純薬社製) 13.6g
を仕込み、窒素雰囲気中120~160℃で、生成する水を取り除きながら約4時間反応させた。反応液を200mLの2-プロパノールに加え、得られたスラリーを吸引ろ過し、2-プロパノール25mLで洗浄した。その後40℃で12時間真空乾燥することで酸素吸収成分(B12)を得た。
得られた酸素吸収成分の構造式は、以下の通りである。
攪拌装置、窒素導入管、Dean-Stark型水分離器を備えた300mLのセパラブルフラスコに、
酸素吸収成分原料;BY 25g、
ステアリルアミン 24.6g、
キシレン(和光純薬製) 20g、及び
N‐メチルピロリドン(和光純薬製) 13.6g
を仕込み、窒素雰囲気中120~160℃で、生成する水を取り除きながら約4時間反応させた。反応液を200mLの蒸留水に加え、得られたスラリーを吸引ろ過し、蒸留水25mLで洗浄した。その後40℃で12時間真空乾燥することで酸素吸収成分(B13)を得た。
得られた酸素吸収成分の構造式は、以下の通りである。
酸素吸収成分原料としてBZを25g、メタキシレンジアミンを9.55g用いた以外は合成例12と同様に合成を行い、酸素吸収成分(B14)を得た。
得られた酸素吸収成分の構造式は、以下の通りである。
酸素吸収成分原料としてBZを25g、ステアリルアミンを37.78g用いた以外は合成例13と同様に合成を行い、酸素吸収成分(B15)を得た。
得られた酸素吸収成分の構造式は、以下の通りである。
造粒設備付帯二軸押出機{TEM-35B:東芝機械(株)}を用い、基材樹脂Aに各種構成成分を混合混練しストランド状に押出し、樹脂組成ペレットを得た。
この際、バレル設定温度を基材樹脂に応じ以下のように設定した。
A1,A2 200℃
A3 220℃
A4 260℃
A5,A6 280℃
構成成分の導入は、固体ペレット状のものはポリエステル樹脂とのドライブレンドにより、液状のものは液体フィーダー(モーノポンプ:兵神装備製)により押出機中途の開口部から添加した。
種々の樹脂組成ペレットを凍結粉砕機で粉砕後定量し、内容量58mlの酸素不透過性容器{ハイレトフレックス:東洋製罐(株)製ポリプロピレン/スチール箔/ポリプロピレン製カップ状積層容器}に入れ、蓋材{ポリプロピレン(内層)/アルミ箔/ポリエステル(外層)}でヒートシールし、23、50℃条件下で保存した。7日間経過後のこの容器内酸素濃度をマイクロガスクロマトグラフ装置(アジレント・テクノロジー社製;M200)にて測定し、酸素吸収量(cc/g)を算出した。
熱重量分析装置(TGA7:Perkin―Elmer社製)を用い加熱速度10℃/minの条件で各酸素吸収成分を試験した。結果を図1及び図2に示す。
基材樹脂A1に、酸素吸収成分B1を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B2を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B3を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B4を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B1を樹脂組成物基準で10重量%、前記遷移金属触媒を樹脂組成物基準で金属換算量で0.035重量%(350ppm)添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B2を樹脂組成物基準で10重量%、前記遷移金属触媒を樹脂組成物基準で金属換算量で0.035重量%(350ppm)添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B3を樹脂組成物基準で10重量%、前記遷移金属触媒を樹脂組成物基準で金属換算量で0.035重量%(350ppm)添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B4を樹脂組成物基準で10重量%、前記遷移金属触媒を樹脂組成物基準で金属換算量で0.035重量%(350ppm)添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A2に、酸素吸収成分B1を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A2に、酸素吸収成分B4を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A3に、酸素吸収成分B1を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A3に、酸素吸収成分B4を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A4に、酸素吸収成分B1を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A4に、酸素吸収成分B4を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B5を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B6を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B7を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A5に、酸素吸収成分B1を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A5に、酸素吸収成分B4を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A6に、酸素吸収成分B1を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A6に、酸素吸収成分B4を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B1を樹脂組成物基準で5重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B4を樹脂組成物基準で5重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、いずれも樹脂組成物基準で酸素吸収成分B1を5重量%、有機ラジカル触媒としてのNHPIを0.5重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、いずれも樹脂組成物基準で酸素吸収成分B4を5重量%、有機ラジカル触媒としてのNHPIを0.5重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B8を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分B9を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、いずれも樹脂組成物基準で酸素吸収成分B12を10重量%、有機ラジカル触媒としてのNHPIを0.5重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、いずれも樹脂組成物基準で酸素吸収成分B13を10重量%、有機ラジカル触媒としてのNHPIを0.5重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、いずれも樹脂組成物基準で酸素吸収成分B14を10重量%、有機ラジカル触媒としてのNHPIを0.5重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、いずれも樹脂組成物基準で酸素吸収成分B15を10重量%、有機ラジカル触媒としてのNHPIを0.5重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A5に、いずれも樹脂組成物基準で酸素吸収成分B13を10重量%、前記遷移金属触媒を金属換算量で0.035重量%(350ppm)添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A5に、いずれも樹脂組成物基準で酸素吸収成分B15を10重量%、前記遷移金属触媒を金属換算量で0.035重量%(350ppm)添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分BXを樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、酸素吸収成分BXを樹脂組成物基準で10重量%、前記遷移金属触媒を樹脂組成物基準で金属換算量で0.035重量%(350ppm)添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、化合物B10を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、化合物B11を樹脂組成物基準で10重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、いずれも樹脂組成物基準で酸素吸収成分原料BYを10重量%、有機ラジカル触媒としてのNHPIを0.5重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
基材樹脂A1に、いずれも樹脂組成物基準で酸素吸収成分原料BZを10重量%、有機ラジカル触媒としてのNHPIを0.5重量%添加した樹脂組成物ペレットを上記方法で作製し、樹脂組成物の酸素吸収量(cc/g)を算出した。その結果を表1に示す。
Claims (9)
- 前記式(1)において、n=1である、請求項1に記載の酸素吸収性樹脂組成物。
- 前記式(1)において、環Xが、シクロヘキセン環である、請求項2に記載の酸素吸収性樹脂組成物。
- 前記式(1)において、環Xが、1つの不飽和結合を有するビシクロ環である、請求項1に記載の酸素吸収性樹脂組成物。
- 前記酸素吸収成分(B)が、前記式(1)の酸無水物とアミンとの反応により形成されるアミドを熱処理して得られるイミドである請求項1に記載の酸素吸収性樹脂組成物。
- 前記基材樹脂(A)がポリエステル樹脂である請求項1に記載の酸素吸収性樹脂組成物。
- 請求項1に記載の酸素吸収性樹脂組成物からなる少なくとも一つの層が器壁中に形成されていることを特徴とする包装容器。
- 前記酸素吸収性樹脂組成物からなる層が、容器内容物と接する位置に形成されている請求項7に記載の包装容器。
- 前記酸素吸収性樹脂組成物からなる層のみから容器壁が形成されている請求項7に記載の包装容器。
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KR20190052044A (ko) | 2016-09-28 | 2019-05-15 | 도요세이칸 그룹 홀딩스 가부시키가이샤 | 가스 배리어성이 우수한 성형체 |
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Also Published As
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JPWO2013099921A1 (ja) | 2015-05-07 |
US20140335297A1 (en) | 2014-11-13 |
KR20150103302A (ko) | 2015-09-09 |
CN104039892B (zh) | 2016-10-05 |
KR101844546B1 (ko) | 2018-04-02 |
EP2799497A4 (en) | 2015-11-18 |
KR20140098219A (ko) | 2014-08-07 |
KR101590126B1 (ko) | 2016-01-29 |
EP2799497B1 (en) | 2018-09-12 |
US10233306B2 (en) | 2019-03-19 |
CN104039892A (zh) | 2014-09-10 |
JP6079640B2 (ja) | 2017-02-15 |
EP2799497A1 (en) | 2014-11-05 |
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