WO2012157656A1 - 酸素吸収剤 - Google Patents
酸素吸収剤 Download PDFInfo
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- WO2012157656A1 WO2012157656A1 PCT/JP2012/062450 JP2012062450W WO2012157656A1 WO 2012157656 A1 WO2012157656 A1 WO 2012157656A1 JP 2012062450 W JP2012062450 W JP 2012062450W WO 2012157656 A1 WO2012157656 A1 WO 2012157656A1
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- 0 CC(N(C(*)C(O)=O)C(C)=O)=O Chemical compound CC(N(C(*)C(O)=O)C(C)=O)=O 0.000 description 2
- RRNVQYGRDQOETQ-UHFFFAOYSA-N CC(C(NCc1cc(CNC(C(C)N)=O)ccc1)=O)N Chemical compound CC(C(NCc1cc(CNC(C(C)N)=O)ccc1)=O)N RRNVQYGRDQOETQ-UHFFFAOYSA-N 0.000 description 1
- FILJCZSJDUMYGZ-UHFFFAOYSA-N CC(C)(C)C(C(NCc1cc(CNC(C(C(C)(C)C)N)=O)ccc1)=O)N Chemical compound CC(C)(C)C(C(NCc1cc(CNC(C(C(C)(C)C)N)=O)ccc1)=O)N FILJCZSJDUMYGZ-UHFFFAOYSA-N 0.000 description 1
- UBGMWBDNUOVITG-UHFFFAOYSA-N CC(C)C(C(NCc1cc(CNC(C(C(C)C)N)=O)ccc1)=O)N Chemical compound CC(C)C(C(NCc1cc(CNC(C(C(C)C)N)=O)ccc1)=O)N UBGMWBDNUOVITG-UHFFFAOYSA-N 0.000 description 1
- YXINVBDRPAFINC-UHFFFAOYSA-N CC(C)CC(C(NCc1cccc(CNC(C(CC(C)C)N)=O)c1)=O)N Chemical compound CC(C)CC(C(NCc1cccc(CNC(C(CC(C)C)N)=O)c1)=O)N YXINVBDRPAFINC-UHFFFAOYSA-N 0.000 description 1
- GQQSVIZHZNOAKJ-UHFFFAOYSA-N CCC(C(NCc1cccc(CNC(C(CC)N)=O)c1)=O)N Chemical compound CCC(C(NCc1cccc(CNC(C(CC)N)=O)c1)=O)N GQQSVIZHZNOAKJ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
- B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
- B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
- A23L3/3418—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
- A23L3/3427—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
- A23L3/3436—Oxygen absorbent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2805—Sorbents inside a permeable or porous casing, e.g. inside a container, bag or membrane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/202—Polymeric adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/104—Oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
Definitions
- the present invention relates to an oxygen absorbent that removes oxygen in a package in which food or the like is packaged, and more particularly to an oxygen absorbent comprising a specific compound.
- an oxygen absorbent for removing oxygen in a package in which food or the like is packaged for example, those containing iron powder as a main component, those containing ascorbic acid or a salt thereof as a main component, and ethylenically unsaturated compounds such as polybutadiene Containing a transition metal catalyst such as cobalt, a metaxylylene bisphthalimide compound or a metaxylylene bis (1-oxo-2-isoindoline) compound and a transition metal catalyst such as cobalt, hexamethylene bisbenzyl Those containing an amide compound or a metaxylylene bisformamide compound and a transition metal catalyst such as cobalt are known (see, for example, Patent Documents 1 to 5).
- the iron-based oxygen absorbent has an advantage that it is inexpensive and easy to handle because oxygen is absorbed by an oxidation reaction of iron.
- iron-based oxygen absorbers require moisture to absorb oxygen, require high humidity in the system, and have limited storage targets.
- a metal detector for inspection of foreign matter cannot be used, or it cannot be put into a package before inspection of foreign matter.
- iron powder since iron powder is used, there is also a problem that the package containing the oxygen absorbent cannot be heated as it is in a microwave oven.
- the resin is colored and becomes opaque, so that there is a limitation in use that it cannot be used in the field of packaging that requires transparency.
- ascorbic acid-based oxygen absorbers absorb oxygen as the ascorbic acid decomposes.
- Ascorbic acid is widely used as an antioxidant for food additives, and ascorbic acid-based oxygen absorbers have the advantage of higher hygiene and safety than iron-based oxygen absorbers.
- Ascorbic acid-based oxygen absorbers have a problem that the oxygen absorption rate is slower than iron-based oxygen absorbers. If the oxygen absorption rate is slow, if the stored product in the package is very sensitive to oxygen, the stored product will be oxidized or decomposed by oxygen before the oxygen absorber absorbs oxygen. There is a problem.
- ascorbic acid-based oxygen absorbents containing transition metals for the purpose of improving the oxygen absorption rate are known.
- ethylenically unsaturated compounds such as polybutadiene, metaxylylene bisphthalimide compounds or metaxylylene bis (1-oxo-2-isoindoline) compounds, and hexamethylene bisbenzylamide compounds or metaxylylene bismethylamide compounds are The compounds themselves oxidize to absorb oxygen, but in order for these compounds to absorb oxygen, a transition metal is indispensable as an oxidation reaction accelerator.
- JP 54-35189 A JP-A-54-98348 JP-A-9-291120 Special table 2010-527389 Special table 2008-530345
- ascorbic acid-based oxygen absorbers have a mechanism in which oxygen is absorbed with the decomposition reaction of ascorbic acid, so that a decomposition product may be generated and an unpleasant odor may be generated in the package.
- some transition metals have an adverse effect on the human body and the environment, and oxygen absorbers that do not use transition metals are desired from the viewpoint of safety.
- ethylenically unsaturated compounds such as polybutadiene have a problem that, when blended with a resin, the resin is colored, the transparency is lowered, and the moldability is lowered due to a decrease in melt viscosity.
- An object of the present invention is to provide an oxygen absorbent that exhibits sufficient oxygen absorption performance without containing a metal.
- the present invention provides an oxygen absorbent as described in (1) below.
- R A1 represents a substituent
- R A2 represents an electron-donating group.
- m A represents an integer of 1 to 4
- n A represents an integer of 0 to 3.
- m A + n A is an integer of 1 to 4.
- Q A is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group.
- a (m A + n A ) -valent group containing one group is represented. However, Q A does not contain a carboxyl group.
- R B1 represents a substituent.
- m B represents an integer of 1 to 4
- n B represents an integer of 0 to 3.
- m B + n B is an integer of 1 to 4.
- Q B is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group. It represents a (m B + n B ) -valent group containing one group. However, Q B does not contain an amino group. ] [Wherein R C1 represents a substituent. n C represents an integer of 1 or 2. Q C is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group.
- R D1 represents a substituent
- R D2 represents an electron-donating group.
- m D represents an integer of 1 to 4
- n D represents an integer of 0 to 3.
- m D + n D is an integer of 1 to 4.
- Q D is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group.
- a (m D + n D ) -valent group containing one group is represented.
- R E1 represents a substituent.
- R E2 represents a hydrogen atom or a substituent.
- L E represents an imino group, an ether group, or sulfide group.
- m E represents an integer of 1 to 4
- n E represents an integer of 0 to 3, provided that m E + n E is 1 to 4.
- Q E represents a hydrogen atom or a (m E + n E ) -valent group.
- Ra F1 represents a substituent.
- Rb F1 represents a hydrogen atom or a substituent.
- Q F1 represents a hydrogen atom or a substituent.
- L F1 represents an imino group, an ether group, or a sulfide group.
- n F represents an integer of 1 to 2.
- Ra F2 represents a substituent.
- Q F2 represents a hydrogen atom or a substituent.
- L F2 represents an imino group, an ether group, a sulfide group, or a substituted or unsubstituted alkylene group.
- Ra F3 represents a substituent.
- Q F31 and Q F32 each represent a hydrogen atom or a substituent.
- L F3 represents an imino group, an ether group, or a sulfide group.
- the present invention includes the following preferred embodiments (2) to (32).
- the oxygen absorbent according to (1) comprising at least one amide compound represented by the general formula (AI).
- R A1 in the general formula (AI) is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms
- R A2 is an amino group
- the oxygen absorbent according to (2) which is a hydroxyl group or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
- Q A in the general formula (AI) is a metaxylylene group.
- R A1 in the general formula (AI) is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and R A2 is an amino group.
- the oxygen absorbent according to (1) comprising at least one amide compound represented by the general formula (BI).
- Q B in the general formula (BI) is a group containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group having 6 to 12 carbon atoms, (9) or (10) The oxygen absorbent according to 1.
- the oxygen absorbent according to (1) comprising at least one imide compound represented by the general formula (CI).
- Q C in general formula (C-I) is an ethylene group, an oxygen-absorbing agent according to (13) or (14).
- (16) (13) A resin composition comprising 1 to 30% by mass of the oxygen absorbent according to any one of (15).
- the oxygen absorbent according to (1) comprising at least one ester compound represented by the general formula (DI).
- R D1 in the general formula (DI) is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
- Absorbent (19) The oxygen absorbent according to (17) or (18), wherein R D2 in the general formula (DI) is an amino group.
- Q D in the general formula (DI) is a group containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group having 2 to 6 carbon atoms, (17) to (20) The oxygen absorbent according to any one of the above.
- the oxygen absorbent according to (1) comprising at least one compound represented by the general formula (EI).
- L E is an imino group, an oxygen-absorbing agent according to (21).
- Q E is a metaxylylene group.
- R E1 is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
- the oxygen absorbent according to (1) comprising at least one compound represented by any one of the general formulas (FI) to (F-III).
- (29) (27) or (28), wherein Ra F1 , Ra F2 and Ra F3 are each a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
- Oxygen absorber comprising at least one compound represented by any one of the general formulas (FI) to (F-III).
- the oxygen absorbent of the present invention can exhibit sufficient oxygen absorption performance without containing a metal.
- the oxygen absorbent of the present invention can exhibit sufficient oxygen absorption performance without containing a metal.
- 3 is a GC chart of amide compound A-1 obtained in Example A-1.
- 3 is a GC chart of amide compound B-1 obtained in Example B-1.
- 3 is a GC chart of imide compound C-1 obtained in Example C-1.
- 3 is a GC chart of the ester compound D-1 obtained in Example D-1.
- 2 is a GC chart of Compound E-1 obtained in Example E-1.
- 2 is a GC chart of Compound F-1 obtained in Example F-1.
- the oxygen absorbent of the present invention comprises at least one amide compound represented by the general formula (AI); at least one amide compound represented by the general formula (BI); At least one imide compound represented by CI); at least one ester compound represented by formula (DI); at least one compound represented by formula (EI); Or at least one compound represented by any one of the above general formulas (FI) to (F-III).
- an oxygen absorbent comprising at least one amide compound represented by the general formula (AI) (hereinafter sometimes referred to as “oxygen absorbent (A)”), the general formula (BI) An oxygen absorbent comprising at least one amide compound represented by the formula (hereinafter also referred to as “oxygen absorbent (B)”), at least one imide represented by the general formula (CI)
- An oxygen absorbent comprising a compound hereinafter also referred to as “oxygen absorbent (C)”
- an oxygen absorbent comprising at least one ester compound represented by the general formula (DI) hereinafter referred to as “ Oxygen absorber (D) ”
- an oxygen absorber comprising at least one compound represented by the general formula (EI) hereinafter also referred to as“ oxygen absorber (E) ”)
- the oxygen absorbent (A) is composed of at least one amide compound represented by the following general formula (AI).
- AI general formula
- R A1 represents a substituent
- R A2 represents an electron-donating group
- m A represents an integer of 1 to 4
- n A represents an integer of 0 to 3.
- m A + n A is an integer of 1 to 4.
- Q A is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group.
- a (m A + n A ) -valent group containing one group is represented. However, Q A does not contain a carboxyl group. ]
- R A1 represents a substituent.
- substituents include a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (1 to 15, preferably 1 to 6 carbon atoms).
- Straight chain, branched or cyclic alkyl group for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group), alkenyl group (Straight chain, branched or cyclic alkenyl groups having 2 to 10, preferably 2 to 6 carbon atoms, eg vinyl group, allyl group), alkynyl groups (2 to 10, preferably 2 to 6 An alkynyl group having a carbon atom, such as an ethynyl group, a propargyl group, an aryl group (an aryl group having 6 to 16, preferably 6 to 10 carbon atoms, such as a Nyl group, naphthyl group), heterocyclic group (5- to 6-membered aromatic or non-aromatic heterocyclic compound obtained by removing one hydrogen atom
- a rucarbonyl group for example, an acetyl group, a pivaloyl group, a benzoyl group), an amino group (amino group, an alkylamino group having 1 to 10, preferably 1 to 6 carbon atoms, 6 to 12, preferably 6 Anilino group having ⁇ 8 carbon atoms, or a heterocyclic amino group having 1-12, preferably 2-6 carbon atoms (eg amino, methylamino, anilino), mercapto, alkylthio A group (an alkylthio group having 1 to 10, preferably 1 to 6 carbon atoms, such as a methylthio group, an ethylthio group), an arylthio group (an arylthio having 6 to 12, preferably 6 to 8 carbon atoms) Groups such as phenylthio groups), heterocyclic thio groups (heterocyclic thio groups having 2 to 10, preferably 1 to 6 carbon atoms, such as 2-benzothiazo
- R A2 represents an electron donating group, for example, an amino group (amino group, an alkylamino group having 1 to 10, preferably 1 to 6 carbon atoms, 6 to 12, preferably 6 to 8 carbon atoms).
- An anilino group having a carbon atom, or a heterocyclic amino group having 1 to 12, preferably 2 to 6, carbon atoms such as an amino group, a methylamino group, an anilino group, a hydroxyl group, an alkoxy group (1 to 10 Linear, branched or cyclic alkoxy groups having 1 to 6 carbon atoms, for example methoxy, ethoxy groups, alkyl groups (1 to 15 and preferably having 1 to 6 carbon atoms) Linear, branched or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, 2-ethylhexyl, cyclopropyl,
- those having a hydrogen atom may be further substituted with the above groups, for example, an alkyl group substituted with a hydroxyl group (for example, a hydroxyethyl group), an alkyl group substituted with an alkoxy group (Eg, methoxyethyl group), an alkyl group substituted with an aryl group (eg, benzyl group), an aryl group substituted with an alkyl group (eg, p-tolyl group), an aryloxy group substituted with an alkyl group ( Examples thereof include, but are not limited to, 2-methylphenoxy group.
- the carbon number mentioned above shall not include the carbon number of the further substituent.
- a benzyl group is regarded as a C 1 alkyl group substituted with a phenyl group, and is not regarded as a C 7 alkyl group substituted with a phenyl group.
- the following description of the number of carbon atoms shall be similarly understood unless otherwise specified.
- R A1 is preferably a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms and a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
- a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted phenyl group are more preferable.
- preferable R A1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, 1-methylpropyl group, 2-methylpropyl group, hydroxymethyl group, 1 Examples include, but are not limited to, -hydroxyethyl group, mercaptomethyl group, methylsulfanylethyl group, phenyl group, naphthyl group, benzyl group, 4-hydroxybenzyl group and the like.
- R A2 is preferably an amino group, a hydroxyl group, and an alkyl group from the viewpoint of oxygen absorption, more preferably an amino group, a hydroxyl group, and a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and the amino group is further preferable.
- Q A is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group.
- Represents a group containing one group, from an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group and a heterocyclic group represents at least one group was removed from the parent compound which contains (m a + n a) hydrogen atoms (m a + n a) valent group selected from the group consisting of.
- the aromatic hydrocarbon group, saturated or unsaturated alicyclic hydrocarbon group, linear or branched saturated or unsaturated aliphatic hydrocarbon group and heterocyclic group may be substituted or unsubstituted.
- Q A may contain a hetero atom, and may contain an ether group, a sulfide group, a carbonyl group, a hydroxy group, an amino group, a sulfoxide group, a sulfone group, and the like. However, Q A does not contain a carboxyl group.
- Examples of the parent compound containing an aromatic hydrocarbon group include benzene, naphthalene, anthracene, phenanthrene, pyrene, biphenyl, diphenyl ether, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl alkane (for example, diphenylmethane, diphenylethane, diphenylpropane). ), Diphenylmethanone, anthraquinone and the like.
- Examples of the group containing an aromatic hydrocarbon group include phenyl, benzyl, orthophenylene, metaphenylene, paraphenylene, orthoxylylene, metaxylylene, paraxylylene, naphthyl, naphthylene, anthracenyl.
- Examples of the parent compound containing a saturated or unsaturated alicyclic hydrocarbon group include 3 to 6 such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, dicyclohexylalkane (for example, dicyclohexylmethane, dicyclohexylethane, dicyclohexylpropane).
- the compound containing a member ring is mentioned.
- crosslinking structures, such as norbornane and adamantane are also mentioned.
- Examples of the group containing a saturated or unsaturated alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylene group, a cyclohexylenemethylene group, a methylcyclohexyl group, and an alkylenedicyclohexylene.
- Groups for example, methylenedicyclohexylene group, ethylenedicyclohexylene group, propylenedicyclohexylene group), decahydronaphthalenyl group, decahydronaphthalenylene group, norbornyl group, adamantanyl group and the like.
- a linear or branched saturated or unsaturated aliphatic hydrocarbon group for example, a linear or branched alkane having 1 to 12 carbon atoms (for example, methane, ethane, propane, n-butane, n-hexane, n-octane, n-nonane, n-decane, n-dodecane, 2-methylpentane, 2,2,4-trimethylhexane, 2,4,4-trimethylhexane), ether group Containing alkanes (eg, dipropyl ether, 1,4-butanediol dipropyl ether, polyethylene oxide, polypropylene oxide), alkanes containing amino groups (eg, diethylamine, dihexylamine, triethylamine, polyethyleneamine), sulfide groups Containing alkanes (eg methylpropyl sulfide) etc.
- alkanes
- Examples of the group containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group include a linear or branched alkyl group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group), linear or branched alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-octylene group, n-nonylene group, n-decylene group, n-dodecylene group, 2-methyl-1,5-pentylene group, 2,2,4-trimethylhexylene Group, 2,4,4-trimethylhexylene group), an alkylene group having an ether group (for example, oxydipropylene group,
- Examples of the parent compound containing a heterocyclic group include 5- to 6-membered heterocyclic compounds such as pyrrolidine, piperidine, pyridine, pyrimidine, and triazine, and condensed heterocyclic compounds such as quinoline and isoquinoline.
- Examples of the group containing a heterocyclic group include a pyrrolidinyl group, piperidinyl group, pyridinyl group, pyridinylene group, pyrimidinyl group, pyrimidinylene group, triazinyl group, triazinylene group, quinolinyl group, quinolinylene group, and isoquinolinyl group.
- n A represents an integer of 0 to 3.
- m A + n A represents the valence of Q A and represents an integer of 1 to 4.
- m A is 2 to 4, and n A is 0.
- a method for producing the amide compound represented by the general formula (AI) will be described.
- the method for producing the amide compound represented by the general formula (AI) is not particularly limited, but the compound represented by the following general formula (A-1) and the amine represented by the following general formula (A-2) A method of producing by dehydration condensation reaction with a compound is preferred.
- R A1 and R A2 has the same meaning as R A1 and R A2 in the general formula (A-I), and preferred ranges are also the same.
- m A + n A and Q A are as defined m A + n A and Q A in the general formula (A-I), and preferred ranges are also the same.
- Examples of the compound represented by the general formula (A-1) include alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, tert-leucine, isoleucine, serine, threonine, cysteine, methionine, 2-phenylglycine, ⁇ -amino acids having tertiary hydrogen at the ⁇ -carbon such as phenylalanine, tyrosine, histidine, tryptophan, proline; ⁇ -hydroxy acids such as 2-hydroxybutyric acid, malic acid, tartaric acid; 2-methylbutyric acid, methylmalonic acid, methylsuccinic acid Examples thereof include, but are not limited to, carboxylic acids having an alkyl group at the ⁇ -position.
- the compound represented by the general formula (A-1) has an asymmetric carbon, it may be any of D-form, L-form, and racemate, or allo-form.
- ⁇ -amino acids having tertiary hydrogen at the ⁇ carbon are particularly preferable from the viewpoints of availability of raw materials and improvement of oxygen absorption.
- alanine is most preferred from the viewpoint of ease of supply and inexpensive price.
- an amino compound containing an aromatic hydrocarbon group an amino compound containing a saturated or unsaturated alicyclic hydrocarbon group, linear or branched
- An amino compound containing a saturated saturated or unsaturated aliphatic hydrocarbon group or an amino compound containing a heterocyclic group is preferred.
- the amino compound containing an aromatic hydrocarbon group include orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, and paraphenylenediamine.
- amino compound containing a saturated or unsaturated alicyclic hydrocarbon group examples include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, , 4-diaminocyclohexane and the like.
- amino compounds containing linear or branched saturated or unsaturated aliphatic hydrocarbon groups include ethylenediamine trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, and octamethylenediamine.
- Examples of the amino compound containing a heterocyclic group include diaminopyridine and diaminotriazine. Among these, from the viewpoint of oxygen absorption, metaxylylenediamine is preferable.
- the reaction conditions in the dehydration condensation reaction between the compound represented by the general formula (A-1) and the amine compound represented by the general formula (A-2) are not particularly limited and can be appropriately determined.
- the reaction temperature is usually 170 to 250 ° C., preferably 200 to 220 ° C.
- a phosphorus atom-containing compound such as sodium hypophosphite, potassium hypophosphite or lithium hypophosphite may be used as a catalyst.
- the oxygen absorbent (A) is composed of at least one amide compound represented by the general formula (AI). That is, the oxygen absorbent (A) may be a mixture of two or more amide compounds represented by the general formula (AI).
- AI amide compound represented by the general formula (A-2)
- the compound represented by the general formula (A-1) and the amine compound represented by the general formula (A-2) As a result of the dehydration condensation reaction, a dimer obtained by reacting one molecule of the compound represented by the general formula (A-1) with one molecule of the amine compound represented by the general formula (A-2)
- An amide compound and a trimeric amide compound in which two molecules of the compound represented by the general formula (A-1) and one molecule of the amine compound represented by the general formula (A-2) are reacted are formed. Can do.
- the oxygen absorbent (A) may be a mixture thereof.
- the amide compound constituting the oxygen absorbent (A) is excellent in oxygen absorbability.
- the amount of oxygen absorbed per gram of the amide compound constituting the oxygen absorbent (A) is preferably 3 cc / g or more, more preferably 10 cc / g or more.
- the upper limit value of the oxygen absorption amount is not particularly limited and is preferably as high as possible. However, 20 cc / g or less is suitable as an oxygen absorbent.
- the measuring method of oxygen absorption amount is performed by the method as described in an Example.
- the mechanism by which the amide compound constituting the oxygen absorbent (A) exhibits good oxygen absorption performance has not yet been clarified, it is estimated as follows.
- tertiary hydrogen bonded to the carbon atom adjacent to the amide bond dissociates as a proton to form a radical. That is, since the carbonyl group that is an electron withdrawing group and the electron donating group R A2 are bonded to the carbon atom to which the tertiary hydrogen is bonded, when the tertiary hydrogen is dissociated as a proton, It is considered that a very stable radical is generated by a phenomenon called a captative effect in which unpaired electrons existing on a carbon atom are energetically stabilized. When oxygen and water are present here, it is considered that oxygen reacts with this radical to show oxygen absorption performance. It has also been found that the higher the humidity and temperature, the higher the reactivity.
- the oxygen absorbent (A) As a more preferable usage form of the oxygen absorbent (A), a form in which the amide compound represented by the general formula (AI) is supported on a carrier from the viewpoint of easy handling and improvement of the oxygen absorption rate.
- a carrier used for loading include diatomaceous earth, activated carbon, zeolite, alumina, silica, titania, zirconia, and ceria.
- the oxygen absorbent (A) is used in a small bag.
- a sachet or the like filled with the oxygen absorbent (A) By disposing a sachet or the like filled with the oxygen absorbent (A) in the package, the oxygen concentration in the package can be lowered, and the stored product in the package can be stored in a good state.
- an oxygen absorbent (A) can also be mix
- Packaging materials and packaging containers obtained by molding and processing a resin composition in which an oxygen absorbent (A) is blended with a resin raw material can maintain the oxygen concentration in the packaging body low, and the stored material in the packaging body is excellent. Can be saved in state.
- the oxygen absorbent content in the resin composition is preferably 1 to 30% by mass from the viewpoint of oxygen absorption performance, resin moldability and appearance. More preferably, it is 3 to 20% by mass, and still more preferably 5 to 10% by mass.
- the oxygen absorbent (B) is composed of at least one amide compound represented by the following general formula (BI).
- R B1 represents a substituent.
- m B represents an integer of 1 to 4
- n B represents an integer of 0 to 3.
- m B + n B is an integer of 1 to 4.
- Q B is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group. It represents a (m B + n B ) -valent group containing one group. However, Q B does not contain an amino group.
- R B1 represents a substituent, and examples of the substituent include the same as those exemplified as the substituent for R A1 . Suitable examples of R B1 are the same as those of R A1 .
- Q B is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group.
- the aromatic hydrocarbon group, saturated or unsaturated alicyclic hydrocarbon group, linear or branched saturated or unsaturated aliphatic hydrocarbon group and heterocyclic group may be substituted or unsubstituted.
- Q B may contain a hetero atom, and may contain an ether group, a sulfide group, a carbonyl group, a hydroxy group, a sulfoxide group, a sulfone group, and the like. However, Q B does not contain an amino group.
- Examples of the parent compound containing an aromatic hydrocarbon group include benzene, naphthalene, anthracene, phenanthrene, pyrene, biphenyl, diphenyl ether, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl alkane (for example, diphenylmethane, diphenylethane, diphenylpropane). ), Diphenylmethanone, anthraquinone and the like.
- Examples of the group containing an aromatic hydrocarbon group include a phenyl group, a hydroxyphenyl group, a benzyl group, an orthophenylene group, a metaphenylene group, a paraphenylene group, a hydroxyorthophenylene group, a hydroxymetaphenylene group, and a hydroxyparaphenylene group.
- Examples of the parent compound containing a saturated or unsaturated alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, dicyclohexylalkane (eg, dicyclohexylmethane, dicyclohexylethane, dicyclohexylpropane), cyclopropene, cyclobutene , Cyclopentene, cyclohexene, cyclohexadiene, and other compounds containing a 3- to 6-membered ring.
- the compound containing condensed rings such as decahydronaphthalene
- crosslinking structures such as norbornane, norbornene, norbornadiene, adamantane
- examples of the group containing a saturated or unsaturated alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a hydroxycyclohexyl group, a cyclohexylene group, a methylcyclohexyl group, and an alkylenedicyclohexylene group.
- methylene dicyclohexylene group ethylene dicyclohexylene group, propylene dicyclohexylene group
- cyclopropenyl group cyclobutenyl group
- cyclopentenyl group cyclohexenyl group, cyclohexenylene group, cyclohexadienyl group, decahydronaphtha
- Examples include a rhenyl group, a decahydronaphthalenylene group, a norbornyl group, a norbornenyl group, a norbornadienyl group, an adamantanyl group, and the like.
- a linear or branched saturated or unsaturated aliphatic hydrocarbon group for example, a linear or branched alkane having 1 to 24 carbon atoms (for example, methane, ethane, propane, 2-methylpropane, n-butane, 2-methylbutane, n-hexane, n-octane, n-nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane), carbon number 2 ⁇ 24 linear or branched alkenes (eg, ethylene, propylene, n-butene, n-heptene, n-hexene, n-hexadiene, n-octene, n-octadiene, n-decene, n-decadiene, n -Dodecene,
- Examples of the group containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group include a linear or branched alkyl group having 1 to 24 carbon atoms (for example, a methyl group, an ethyl group, n-propyl group, 2-methylpropyl group, 2-hydroxypropyl group, n-butyl group, 2-methylbutyl group, 2-hydroxybutyl group, n-hexyl group, n-octyl group, n-decyl group, n- Dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group), linear or branched alkylene group having 1 to 24 carbon atoms (for example, methylene group, ethylene group, n-propylene group, 2- Methylpropylene group, 2-hydroxypropylene group, 2-propanonyl group, n-butylene group, 2-methyl
- Examples of the parent compound containing a heterocyclic group include 5- to 6-membered heterocyclic compounds such as tetrahydrofuran, furan, thiophene, and tetrahydropyran.
- Examples of the group containing a heterocyclic group include a tetrahydrofuranyl group, a furanyl group, a thiophenyl group, and a tetrahydropyranyl group.
- n B represents an integer of 0 to 3.
- m B + n B represents the valence of Q B and represents an integer of 1 to 4.
- m B is 2 to 4, and n B is 0.
- a method for producing the amide compound represented by the general formula (BI) will be described.
- the method for producing the amide compound represented by the general formula (BI) is not particularly limited, but the ⁇ -amino acid represented by the following general formula (B-1) and the following general formula (B-2) are represented.
- a method of producing by a dehydration condensation reaction with a carboxylic acid compound is preferred.
- R B1 has the same meaning as R B1 in the general formula ( BI ), and the preferred range is also the same.
- m B + n B and Q B have the same meanings as m B + n B and Q B in the general formula (B-I), and preferred ranges are also the same.
- Examples of the ⁇ -amino acid having tertiary hydrogen at the ⁇ carbon represented by the general formula (B-1) include alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, tert-leucine, isoleucine, serine, threonine. , Cysteine, methionine, 2-phenylglycine, phenylalanine, tyrosine, histidine, tryptophan, proline and the like, but are not limited thereto. Moreover, these can be used individually or in combination of 2 or more types.
- the ⁇ -amino acid represented by the general formula (B-1) may be any of D-form, L-form and racemate, and may be an allo-form. Among these, alanine is most preferable from the viewpoints of availability of raw materials and improvement of oxygen absorption.
- Examples of the carboxylic acid compound represented by the general formula (B-2) include a carboxylic acid compound containing an aromatic hydrocarbon group, a carboxylic acid compound containing a saturated or unsaturated alicyclic hydrocarbon group, and a straight chain.
- a carboxylic acid compound containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group or a carboxylic acid compound containing a heterocyclic group is preferred.
- the carboxylic acid compound containing an aromatic hydrocarbon group include benzoic acid, terephthalic acid, isophthalic acid, orthophthalic acid, and the like.
- Examples of the carboxylic acid compound containing a saturated or unsaturated alicyclic hydrocarbon group include cyclohexane carboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,4-cyclohexene dicarboxylic acid, and the like.
- Examples of the carboxylic acid compound containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group include malonic acid, methylmalonic acid, hydroxymalonic acid, succinic acid, methylsuccinic acid, malic acid, tartaric acid, Examples include crotonic acid, maleic acid, glutaric acid, adipic acid, sorbic acid, hexadienedioic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
- Examples of the carboxylic acid compound containing a heterocyclic group include tetrahydrofuran-2-carboxylic acid and 2-furancarboxylic acid.
- adipic acid is preferable from the viewpoint of availability of raw materials and oxygen absorption.
- the reaction conditions in the dehydration condensation reaction between the ⁇ -amino acid represented by the general formula (B-1) and the carboxylic acid compound represented by the general formula (B-2) are not particularly limited and can be appropriately determined.
- the reaction temperature is usually 160 to 250 ° C., preferably 180 to 220 ° C.
- a phosphorus atom-containing compound such as sodium hypophosphite, potassium hypophosphite or lithium hypophosphite may be used as a catalyst.
- the oxygen absorbent (B) is composed of at least one amide compound represented by the general formula (BI). That is, the oxygen absorbent (B) may be a mixture of two or more amide compounds represented by the general formula (BI).
- the carboxylic acid compound represented by the general formula (B-2) is a dicarboxylic acid
- the ⁇ -amino acid represented by the general formula (B-1) and the general formula (B-2) As a result of the dehydration condensation reaction with the carboxylic acid compound, one molecule of the ⁇ -amino acid represented by the general formula (B-1) and one molecule of the carboxylic acid compound represented by the general formula (B-2)
- a dimeric amide compound obtained by reacting with each other, two molecules of an ⁇ -amino acid represented by the general formula (B-1) and one molecule of a carboxylic acid compound represented by the general formula (B-2) Can react to form a trimer amide compound. A mixture of these may be sufficient as an oxygen absorber (B).
- the amide compound constituting the oxygen absorbent (B) is excellent in oxygen absorbability.
- the amount of oxygen absorbed per 1 g of the amide compound constituting the oxygen absorbent (B) is preferably 3 cc / g or more, more preferably 5 cc / g or more.
- the upper limit value of the oxygen absorption amount is not particularly limited and is preferably as high as possible. However, 20 cc / g or less is suitable as an oxygen absorbent.
- the measuring method of oxygen absorption amount is performed by the method as described in an Example.
- the mechanism by which the amide compound constituting the oxygen absorbent (B) exhibits good oxygen absorption performance has not yet been clarified, it is estimated as follows.
- tertiary hydrogen bonded to the carbon atom adjacent to the amide bond dissociates as a proton to form a radical. That is, when a tertiary hydrogen is dissociated as a proton because a carboxyl group that is an electron withdrawing group and an amino group that is an electron donating group are bonded to the carbon atom to which the tertiary hydrogen is bonded. It is considered that a very stable radical is generated by a phenomenon called a captative effect in which unpaired electrons existing on the carbon atom are energetically stabilized. When oxygen and water are present here, it is considered that oxygen reacts with this radical to show oxygen absorption performance. It has also been found that the higher the humidity and temperature, the higher the reactivity.
- the oxygen absorbent (B) As a more preferable usage form of the oxygen absorbent (B), a form in which the amide compound represented by the general formula (BI) is supported on a carrier from the viewpoint of easy handling and improvement of the oxygen absorption rate.
- the carrier used for loading include diatomaceous earth, activated carbon, zeolite, alumina, silica, titania, zirconia, and ceria.
- the oxygen absorbent (B) is used in a small bag. By disposing a sachet or the like filled with the oxygen absorbent (B) in the package, the oxygen concentration in the package can be lowered, and the stored product in the package can be stored in a good state.
- an oxygen absorbent (B) can also be mix
- Packaging materials and packaging containers obtained by molding and processing a resin composition in which an oxygen absorbent (B) is blended with a resin raw material can keep the oxygen concentration in the package low, and the stored material in the package is good. Can be saved in state.
- the content of the oxygen absorbent in the resin composition is preferably 1 to 30% by mass from the viewpoints of oxygen absorption performance and resin moldability and appearance. More preferably, it is 3 to 20% by mass, and still more preferably 5 to 10% by mass.
- the oxygen absorbent (C) is composed of at least one imide compound represented by the following general formula (CI).
- CI general formula
- R C1 represents a substituent.
- n C represents an integer of 1 or 2.
- Q C is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group. Represents a 2n C- valent group containing one group.
- R C1 represents a substituent, and examples of the substituent include the same as those exemplified as the substituent for R A1 . Suitable examples of R C1 are the same as those of R A1 .
- Q C is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group.
- the aromatic hydrocarbon group, saturated or unsaturated alicyclic hydrocarbon group, linear or branched saturated or unsaturated aliphatic hydrocarbon group and heterocyclic group may be substituted or unsubstituted.
- Q C may contain a hetero atom, an ether group, a sulfide group, a carbonyl group, hydroxy group, a carboxyl group, a sulfoxide group, may contain a sulfone group.
- Examples of the parent compound containing an aromatic hydrocarbon group include benzene, naphthalene, anthracene, phenanthrene, pyrene, biphenyl, diphenyl ether, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl alkane (for example, diphenylmethane, diphenylethane, diphenylpropane). ), Diphenylmethanone, anthraquinone and the like.
- Examples of the group containing an aromatic hydrocarbon group include an orthophenylene group, a 4-carboxyorthophenylene group, a benzene-1,2,4,5-tetrayl group, a 2,3-naphthylene group, and a naphthalene-2,3.
- 6,7-tetrayl group 1,8-naphthylene group, naphthalene-1,4,5,8-tetrayl group, 2,3-anthracenylene group, 2,2'-biphenylylene group, biphenyl-2,3,3 ', 4'-tetrayl group, biphenyl-3,3', 4,4'-tetrayl group, diphenyl ether-2,3,3 ', 4'-tetrayl group, diphenyl ether-3,3', 4,4'- Tetrayl group, diphenylsulfone-3,3 ′, 4,4′-tetrayl group, diphenylmethanone-3,3 ′, 4,4′-tetrayl group, 2,3-anthraquinonylene group, etc. It is.
- Examples of the parent compound containing a saturated or unsaturated alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, dicyclohexylalkane (for example, dicyclohexylmethane, dicyclohexylethane, dicyclohexylpropane), cyclohexene and the like. And compounds containing a 6-membered ring.
- compounds containing condensed rings such as decahydronaphthalene, norbornane, norbornene, norbornadiene, bicyclo [2,2,2] oct-5-ene, bicyclo [2,2,2] oct-7-ene, adamantane
- compounds containing a crosslinked structure such as Examples of the group containing a saturated or unsaturated alicyclic hydrocarbon group include a cyclopropylene group, a cyclobutane-1,2,3,4-tetrayl group, a 1,2-cyclopentylene group, and a cyclopentane-1 , 2,3,4-tetrayl group, 1,2-cyclohexylene group, 4-methyl-1,2-cyclohexylene group, 4-carboxy-1,2-cyclohexylene group, cyclohexane-1,2,4 5-tetrayl group, 4-cyclohexene-1,2-diyl group, 3-methyl-4-cyclo
- Examples of the base compound containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group include, for example, a linear or branched alkane having 2 to 24 carbon atoms (for example, ethane, propane, n- Butane, n-hexane, n-octane, n-nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane, n-docosane, n-tetracosane), carbon number 2 To 24 linear or branched alkenes (eg, ethylene, propylene, n-butene, n-heptene, n-hexene, n-octene, n-decene, n-dodecene, n-tetradecene, n-
- Examples of the group containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group include a linear or branched alkylene group having 2 to 24 carbon atoms (for example, ethylene group, butane-1 , 2-diyl group, hexane-1,2-diyl group, octane-1,2-diyl group, decane-1,2-diyl group, dodecane-1,2-diyl group, tetradecane-1,2-diyl group Hexadecane-1,2-diyl group, octadecane-1,2-diyl group, eicosane-1,2-diyl group), linear or branched alkenylene group having 2 to 24 carbon atoms (for example, ethenylene group, 2-propylene-1,2-diyl group, 2-butene-2,3-diyl group, 4-pentene-1,2-diyl group, 4-methyl-4
- Examples of the parent compound containing a heterocyclic group include 5- to 6-membered heterocyclic compounds such as tetrahydrofuran, tetrahydrothiophene, tetrahydropyran, tetrahydrothiopyran, dithiin and the like.
- Examples of the group containing a heterocyclic group include a 5,6-dihydro-1,4-dithiin-2,3-diyl group.
- n C represents an integer of 1 or 2, and is preferably 1.
- a method for producing the imide compound represented by the general formula (CI) will be described.
- the method for producing the imide compound represented by the general formula (CI) is not particularly limited, but the ⁇ -amino acid represented by the following general formula (C-1) and the following general formula (C-2) are represented.
- a method of producing by a dehydration condensation reaction with a carboxylic anhydride compound is preferred.
- R C1 has the same meaning as R C1 in the general formula (CI), and the preferred range is also the same.
- n C and Q C are the same as n C and Q C in the general formula (C-I), and preferred ranges are also the same.
- Examples of the ⁇ -amino acid having tertiary hydrogen at the ⁇ carbon represented by the general formula (C-1) include alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, tert-leucine, isoleucine, serine, threonine. , Cysteine, methionine, 2-phenylglycine, phenylalanine, tyrosine, histidine, tryptophan, proline and the like, but are not limited thereto. Moreover, these can be used individually or in combination of 2 or more types.
- the ⁇ -amino acid represented by the general formula (C-1) may be any of D-form, L-form, and racemate, or allo-form. Among these, alanine is most preferable from the viewpoints of availability of raw materials and improvement of oxygen absorption.
- Examples of the carboxylic anhydride compound represented by the general formula (C-2) include an carboxylic anhydride compound containing an aromatic hydrocarbon group and a carboxylic anhydride compound containing a saturated or unsaturated alicyclic hydrocarbon group.
- a carboxylic anhydride compound containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group and a carboxylic anhydride compound containing a heterocyclic group are preferred.
- Examples of the carboxylic anhydride compound containing an aromatic hydrocarbon group include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.
- Examples of the carboxylic anhydride compound containing a saturated or unsaturated alicyclic hydrocarbon group include 1,2-cyclohexanedicarboxylic anhydride, 4-carboxy-1,2-cyclohexanedicarboxylic anhydride, 4-cyclohexene. -1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride and the like.
- Examples of the carboxylic acid compound containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group include succinic anhydride, maleic anhydride, itaconic anhydride, and allyl succinic anhydride.
- Examples of the carboxylic acid compound containing a heterocyclic group include 5,6-dihydro-1,4-dithiin-2,3-dicarboxylic acid anhydride.
- succinic anhydride is preferable from the viewpoint of availability of raw materials and oxygen absorption.
- the reaction conditions in the dehydration condensation reaction between the ⁇ -amino acid represented by the general formula (C-1) and the carboxylic anhydride compound represented by the general formula (C-2) are not particularly limited and may be appropriately determined. it can.
- the reaction temperature is usually 160 to 250 ° C., preferably 180 to 220 ° C.
- a phosphorus atom-containing compound such as sodium hypophosphite, potassium hypophosphite or lithium hypophosphite may be used as a catalyst.
- the oxygen absorbent (C) is composed of at least one imide compound represented by the general formula (CI). That is, the oxygen absorbent (C) may be a mixture of two or more imide compounds represented by the above general formula (CI).
- the carboxylic anhydride compound represented by the general formula (C-2) is a tetracarboxylic anhydride
- the ⁇ -amino acid represented by the general formula (C-1) and the general formula (C-2) As a result of the dehydration condensation reaction with the carboxylic anhydride compound represented by (1), one molecule of ⁇ -amino acid represented by the general formula (C-1) and one molecule of the general formula (C-2)
- a trimer imide compound reacted with the carboxylic anhydride compound formed can be formed.
- the imide compound constituting the oxygen absorbent (C) is excellent in oxygen absorbability.
- the amount of oxygen absorbed per gram of the imide compound constituting the oxygen absorbent (C) is preferably 3 cc / g or more, more preferably 5 cc / g or more.
- the upper limit value of the oxygen absorption amount is not particularly limited and is preferably as high as possible. However, 20 cc / g or less is suitable as an oxygen absorbent.
- the measuring method of oxygen absorption amount is performed by the method as described in an Example.
- the mechanism by which the imide compound constituting the oxygen absorbent (C) exhibits good oxygen absorption performance has not yet been clarified, it is estimated as follows.
- the tertiary hydrogen bonded to the carbon atom to which R C1 is bonded dissociates as a proton to form a radical. That is, when a tertiary hydrogen is dissociated as a proton because a carboxyl group that is an electron withdrawing group and an amino group that is an electron donating group are bonded to the carbon atom to which the tertiary hydrogen is bonded.
- the oxygen absorbent (C) As a more preferable usage form of the oxygen absorbent (C), a form in which the imide compound represented by the general formula (CI) is supported on the carrier from the viewpoint of easy handling and improvement of the oxygen absorption rate.
- the carrier used for loading include diatomaceous earth, activated carbon, zeolite, alumina, silica, titania, zirconia, and ceria.
- the oxygen absorbent (C) is used in a small bag.
- the oxygen concentration in the package can be lowered, and the stored product in the package can be stored in a good state.
- an oxygen absorbent (C) can also be mix
- Packaging materials and packaging containers obtained by molding and processing a resin composition in which an oxygen absorbent (C) is blended with a resin raw material can maintain the oxygen concentration in the package low, and the stored material in the package is excellent. Can be saved in state.
- the oxygen absorbent (C) is blended in the resin raw material
- the content of the oxygen absorbent in the resin composition is preferably 1 to 30% by mass from the viewpoints of oxygen absorption performance and resin moldability and appearance. More preferably, it is 3 to 20% by mass, and still more preferably 5 to 10% by mass.
- the oxygen absorbent (D) is composed of at least one ester compound represented by the following general formula (DI).
- DI general formula
- R D1 represents a substituent
- R D2 represents an electron-donating group
- m D represents an integer of 1 to 4
- n D represents an integer of 0 to 3.
- m D + n D is an integer of 1 to 4.
- Q D is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group.
- a (m D + n D ) -valent group containing one group is represented. ]
- R D1 represents a substituent, and examples of the substituent include the same as those exemplified as the substituent for R A1 . Suitable examples of R D1 are the same as those of R A1 .
- R D2 represents an electron donating group, and examples of the electron donating group include those exemplified as the electron donating group for R A2 . Suitable examples of R D2 are the same as those of R A2 .
- Q D is at least selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group.
- Represents a group containing one group, from an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group and a heterocyclic group represents at least one group was removed from the parent compound which contains (m D + n D) hydrogen atoms (m D + n D) valent group selected from the group consisting of.
- the aromatic hydrocarbon group, saturated or unsaturated alicyclic hydrocarbon group, linear or branched saturated or unsaturated aliphatic hydrocarbon group and heterocyclic group may be substituted or unsubstituted.
- Q D may contain a hetero atom, and may contain an ether group, a sulfide group, a carbonyl group, an amino group, a sulfoxide group, a sulfone group, and the like.
- Examples of the parent compound containing an aromatic hydrocarbon group include benzene, naphthalene, anthracene, phenanthrene, pyrene, biphenyl, diphenyl ether, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl alkane (for example, diphenylmethane, diphenylethane, diphenylpropane). ), Diphenylmethanone, anthraquinone and the like.
- Examples of the group containing an aromatic hydrocarbon group include a phenyl group, a methylphenyl group, a benzyl group, an orthophenylene group, a metaphenylene group, a paraphenylene group, a benzenetriyl group, a naphthyl group, a naphthylmethyl group, and a naphthylene group.
- Examples of the parent compound containing a saturated or unsaturated alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, dicyclohexylalkane (eg, dicyclohexylmethane, dicyclohexylethane, dicyclohexylpropane), cyclopropene, cyclobutene , Cyclopentene, cyclohexene, and the like.
- the compound containing condensed rings such as decahydronaphthalene
- crosslinking structures such as norbornane, norbornene, norbornadiene, adamantane, are also mentioned.
- Examples of the group containing a saturated or unsaturated alicyclic hydrocarbon group include a cyclopropyl group, a cyclopropylene group, a cyclobutyl group, a cyclobutylene group, a cyclopentyl group, a cyclopentylene group, a cyclohexyl group, a cyclohexylene group, A cyclohexanetriyl group, a decahydronaphthalenyl group, a decahydronaphthalenylene group, a norbornyl group, a norbornylene group, a norbornenyl group, a norbornenylene group, an adamantanyl group, an adamantanilene group and the like can be mentioned.
- a linear or branched saturated or unsaturated aliphatic hydrocarbon group for example, a linear or branched alkane having 1 to 24 carbon atoms (for example, methane, ethane, propane, 2-methylpropane, n-butane, 2-methylbutane, n-hexane, n-octane, n-nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane, n -Docosane, n-tetracosane), linear or branched alkene having 2 to 24 carbon atoms (eg, ethylene, propylene, n-butene, n-hexene, n-octene, n-decene, n-dodecene, n -T
- Examples of the group containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group include a linear or branched alkyl group having 1 to 24 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, 2-methylpropyl group, n-butyl group, 2-methylbutyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n -Octadecyl group, n-eicosanyl group, n-docosanyl group, n-tetracosanyl group), linear or branched alkylene group having 1 to 24 carbon atoms (for example, methylene group, ethylene group, propylene group, 2-methyl) Propylene group, n-butylene group, 2-methylbutylene
- Examples of the parent compound containing a heterocyclic group include 5- to 6-membered heterocyclic compounds such as pyrrolidine, tetrahydrofuran, tetrahydrothiophene, pyrrole, furan, thiophene, piperidine, tetrahydropyran, pyridine, indole, quinoline, chromene, etc. These condensed heterocyclic compounds are mentioned.
- Examples of the group containing a heterocyclic group include a pyrrolidinyl group, a tetrahydrofuranyl group, a piperidinyl group, a pyridinyl group, an indolyl group, and a quinolinyl group.
- n D represents an integer of 0 to 3.
- m D + n D represents the valence of Q D and represents an integer of 1 to 4.
- m D is 2 to 4, and n D is 0.
- ester compound represented by the general formula (DI) Preferred specific examples of the ester compound represented by the general formula (DI) are shown below, but the present invention is not limited thereto.
- the method for producing the ester compound represented by the general formula (DI) is not particularly limited, but the compound represented by the following general formula (D-1) and the alcohol represented by the following general formula (D-2) A method of producing by dehydration condensation reaction with a compound is preferred.
- R D1 and R D2 are the same meaning as R D1 and R D2 in the general formula (D-I), and preferred ranges are also the same.
- R D3 represents a hydrogen atom and a substituted or unsubstituted alkyl group, preferably a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and a hydrogen atom and a substituted or unsubstituted carbon group having 1 to 2 carbon atoms.
- An alkyl group is more preferable, and a hydrogen atom is still more preferable.
- m D + n D and Q D are as defined m D + n D and Q D in the general formula (D-I), and preferred ranges are also the same.
- Examples of the compound represented by the general formula (D-1) include alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, tert-leucine, isoleucine, serine, threonine, cysteine, methionine, 2-phenylglycine, ⁇ -amino acids having tertiary hydrogen at the ⁇ carbon such as phenylalanine, tyrosine, histidine, tryptophan, proline; alanine methyl, methyl 2-aminobutyrate, valine methyl, norvaline methyl, leucine methyl, norleucine methyl, tert-leucine methyl, Isoleucine methyl, serine methyl, threonine methyl, cysteine methyl, methionine methyl, 2-phenylglycine methyl, phenylalanine methyl, tyrosine methyl, histidine methyl, tryptophan methyl,
- ⁇ -amino acid alkyl ester having tertiary hydrogen at ⁇ -carbon ⁇ -hydroxy acid such as 2-hydroxybutyric acid, malic acid, tartaric acid; ⁇ -hydroxy acid alkyl ester such as ethyl 2-hydroxybutyrate, dimethyl malate, dimethyl tartrate
- carboxylic acid having an alkyl group at the ⁇ -carbon such as 2-methylbutyric acid, methylmalonic acid, methylsuccinic acid, etc .; Although ester etc. can be illustrated, it is not limited to these. Moreover, these can be used individually or in combination of 2 or more types.
- the compound represented by the general formula (D-1) may be any of D-form, L-form, racemate, and allo-form.
- ⁇ -amino acids having tertiary hydrogen at the ⁇ carbon are particularly preferable from the viewpoints of availability of raw materials and improvement of oxygen absorption.
- alanine is most preferred from the viewpoint of ease of supply and inexpensive price.
- Examples of the alcohol compound represented by the general formula (D-2) include an alcohol compound containing an aromatic hydrocarbon group, an alcohol compound containing a saturated or unsaturated alicyclic hydrocarbon group, linear or branched. An alcohol compound containing a saturated saturated or unsaturated aliphatic hydrocarbon group or an alcohol compound containing a heterocyclic group is preferred. Examples of the alcohol compound containing an aromatic hydrocarbon group include phenol, benzyl alcohol, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, and the like.
- Examples of the alcohol compound containing a saturated or unsaturated alicyclic hydrocarbon group include cyclohexanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and the like.
- Examples of the alcohol compound containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol and the like.
- Examples of the alcohol compound containing a heterocyclic group include 2-hydroxypyridine and 2-hydroxyquinoline. Among these, ethylene glycol is preferable from the viewpoint of availability of raw materials and oxygen absorption.
- the reaction conditions in the dehydration condensation reaction between the compound represented by the general formula (D-1) and the alcohol compound represented by the general formula (D-2) are not particularly limited and can be appropriately determined.
- the reaction temperature is usually 100 to 250 ° C, preferably 120 to 220 ° C.
- an inorganic acid such as hydrochloric acid or sulfuric acid may be used as a catalyst.
- the oxygen absorbent (D) is composed of at least one ester compound represented by the general formula (DI). That is, the oxygen absorbent (D) may be a mixture of two or more ester compounds represented by the general formula (DI).
- the alcohol compound represented by the general formula (D-2) is a diol compound
- the compound represented by the general formula (D-1) and the alcohol compound represented by the general formula (D-2) As a result of the dehydration-condensation reaction, a dimer obtained by reacting one molecule of the compound represented by the general formula (D-1) with one molecule of the alcohol compound represented by the general formula (D-2)
- the oxygen absorbent (D) may be a mixture thereof.
- the ester compound constituting the oxygen absorbent (D) is excellent in oxygen absorption.
- the amount of oxygen absorbed per 1 g of the ester compound constituting the oxygen absorbent (D) is preferably 3 cc / g or more, more preferably 5 cc / g or more.
- the upper limit value of the oxygen absorption amount is not particularly limited and is preferably as high as possible. However, 20 cc / g or less is suitable as an oxygen absorbent.
- the measuring method of oxygen absorption amount is performed by the method as described in an Example.
- the ester compound constituting the oxygen absorbent (D) exhibits good oxygen absorption performance.
- the tertiary hydrogen bonded to the carbon atom to which R D1 is bonded dissociates as a proton to form a radical. That is, since a carbonyl group that is an electron-withdrawing group and R D2 that is an electron-donating group such as an amino group are bonded to the carbon atom to which the tertiary hydrogen is bonded, the tertiary hydrogen is used as a proton.
- the oxygen absorbent (D) As a more preferable form of use of the oxygen absorbent (D), a form in which the ester compound represented by the general formula (DI) is supported on a carrier from the viewpoint of easy handling and improvement of the oxygen absorption rate.
- a carrier used for loading include diatomaceous earth, activated carbon, zeolite, alumina, silica, titania, zirconia, and ceria.
- the oxygen absorbent (D) is used in a small bag.
- a sachet or the like filled with the oxygen absorbent (D) By disposing a sachet or the like filled with the oxygen absorbent (D) in the package, the oxygen concentration in the package can be lowered, and the stored product in the package can be stored in a good state.
- an oxygen absorbent (D) can also be mix
- Packaging materials and packaging containers obtained by molding and processing a resin composition in which an oxygen absorbent (D) is blended with a resin raw material can keep the oxygen concentration in the package low, and the stored material in the package is good. Can be saved in state.
- the oxygen absorbent content in the resin composition is preferably 1 to 30% by mass from the viewpoints of oxygen absorption performance and resin moldability and appearance. More preferably, it is 3 to 20% by mass, and still more preferably 5 to 10% by mass.
- the oxygen absorbent (E) is composed of at least one compound represented by the following general formula (EI).
- R E1 represents a substituent.
- R E2 represents a hydrogen atom or a substituent.
- L E represents an imino group, an ether group, or sulfide group.
- m E represents an integer of 1 to 4
- n E represents an integer of 0 to 3, provided that m E + n E is 1 to 4.
- Q E represents a hydrogen atom or a (m E + n E ) -valent group.
- R E1 represents a substituent, and examples of the substituent include the same as those exemplified as the substituent for R A1 .
- a suitable example of R E1 is the same as that of R A1 .
- R E2 represents a hydrogen atom or a substituent, and examples of the substituent include the same functional groups as the substituent represented by R E1 .
- R E2 is preferably a hydrogen atom and a substituted or unsubstituted alkyl group, more preferably a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and a hydrogen atom and a substituted or unsubstituted carbon group having 1 to 4 carbon atoms. More preferred are 2 alkyl groups.
- R E2 examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and the like, but are not limited thereto. Among these, a methyl group and an ethyl group are more preferable.
- L E is an imino group (-NH-), an ether group (-O-), a or sulfide groups (-S-), an imino group is preferred from the viewpoint of oxygen-absorbing.
- Q E represents a hydrogen atom or a (m E + n E ) -valent group
- examples of the (m E + n E ) -valent group include an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, and Represents a group containing at least one group selected from the group consisting of linear or branched saturated or unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbons Obtained by removing (m E + n E ) hydrogen atoms from a parent compound containing a group and at least one group selected from the group consisting of a linear or branched saturated or unsaturated aliphatic hydrocarbon group Residue.
- the aromatic hydrocarbon group, the saturated or unsaturated alicyclic hydrocarbon group, and the linear or branched saturated or unsaturated aliphatic hydrocarbon group may be substituted or unsubstituted.
- Q E may contain a hetero atom, and may contain an ether group, a sulfide group, a carbonyl group, a hydroxy group, an amino group, a sulfoxide group, a sulfone group, and the like.
- Q E represents a hydrogen atom
- Examples of the base compound containing an aromatic hydrocarbon group include benzene, naphthalene, anthracene, phenanthrene, pyrene, biphenyl, diphenyl ether, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl alkane (for example, diphenylmethane, diphenylethane, diphenylpropane). ), Diphenylmethanone, anthraquinone and the like.
- Examples of the group containing an aromatic hydrocarbon group include a phenyl group, benzyl group, tolyl group, orthophenylene group, metaphenylene group, paraphenylene group, tolylene group, orthoxylylene group, metaxylylene group, paraxylylene group, and naphthyl.
- Examples of the parent compound containing a saturated or unsaturated alicyclic hydrocarbon group include 3 to 6 such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, dicyclohexylalkane (for example, dicyclohexylmethane, dicyclohexylethane, dicyclohexylpropane).
- the compound containing a member ring is mentioned.
- crosslinking structures, such as norbornane and adamantane are also mentioned.
- Examples of the group containing a saturated or unsaturated alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylene group, a cyclohexylenedimethylene group, and an alkylenedicyclohexylene group (for example, Methylenedicyclohexylene group, ethylenedicyclohexylene group, propylenedicyclohexylene group), decahydronaphthalenyl group, decahydronaphthalenylene group, norbornyl group, adamantanyl group and the like.
- the base compound containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group for example, a linear or branched alkane having 1 to 24 carbon atoms (for example, methane, ethane, propane, n-butane, n-hexane, n-octane, n-nonane, n-decane, n-dodecane, n-octadecane, 2,2,4-trimethylhexane, 2,4,4-trimethylhexane) and the like.
- a linear or branched alkane having 1 to 24 carbon atoms for example, methane, ethane, propane, n-butane, n-hexane, n-octane, n-nonane, n-decane, n-dodecane, n-octadecane, 2,2,4-trimethylhexane, 2,4,4-tri
- Examples of the group containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group include a linear or branched alkyl group having 1 to 24 carbon atoms (for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-octadecyl group), linear or branched alkylene group having 1 to 12 carbon atoms (for example, methylene Group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-octylene group, n-nonylene group, n-decylene group, n-dodecylene group, 2,2,4-trimethylhexylene group 2,4,4-trimethylhexylene group) and the like.
- n E represents an integer of 1 to 4
- n E represents an integer of 0 to 3, provided that m E + n E is 1 to 4.
- m E is preferably 1 to 2, more preferably 2.
- n E is preferably 0.
- m E + n E is preferably 1 to 2, more preferably 2.
- a method for producing the compound represented by the general formula (EI) will be described.
- the production method of the compound represented by the general formula (EI) is not particularly limited, but the compound represented by the following general formula (E-1) and / or its hydrochloride and the following general formula (E-2) The method of manufacturing by reaction with the compound represented by these is preferable.
- R E1, R E2 and L E are as defined R E1, R E2 and L E in the general formula (E-I), and preferred ranges are also the same.
- m E , n E and Q E is, m E in the general formula (E-I), have the same meanings as n E and Q E, the preferable range is also the same .
- Examples of the compound represented by the general formula (E-1) include ⁇ -amino acids (for example, alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, tert-leucine, isoleucine, serine, threonine, cysteine, methionine).
- ⁇ -amino acids for example, alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, tert-leucine, isoleucine, serine, threonine, cysteine, methionine.
- the compound represented by the general formula (E-1) has an asymmetric carbon, it may be any of D-form, L-form, racemate, and allo-form.
- an ⁇ -amino acid alkyl ester having a tertiary hydrogen at the ⁇ carbon is particularly preferable from the viewpoint of ease of synthesis and improvement of oxygen absorption.
- alanine methyl is most preferred from the viewpoint of oxygen absorption.
- Examples of the compound represented by the general formula (E-2) include isocyanic acid (Q E is a hydrogen atom), a compound containing an aromatic hydrocarbon group, and a saturated or unsaturated alicyclic hydrocarbon group.
- Q E is a hydrogen atom
- a compound or a compound containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group is preferred.
- Examples of the compound containing an aromatic hydrocarbon group include phenyl isocyanate, tolyl isocyanate, benzyl isocyanate, 1-naphthyl isocyanate, 2-biphenyl isocyanate, 1,4-phenylene diisocyanate, tolylene-2, Examples include 6-diisocyanate, metaxylylene diisocyanate, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 4,4′-diphenylmethane diisocyanate, and the like.
- Examples of the compound containing a saturated or unsaturated alicyclic hydrocarbon group include cyclohexyl isocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, and the like.
- Examples of the compound containing a linear or branched saturated or unsaturated aliphatic hydrocarbon group include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, dodecyl isocyanate, and isocyanate.
- Examples include octadecyl acid, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
- metaxylylene diisocyanate is preferable from the viewpoint of oxygen absorption.
- the reaction conditions for the reaction of the compound represented by the general formula (E-1) and / or its hydrochloride with the general formula (E-2) are not particularly limited and can be determined as appropriate.
- the reaction temperature is usually 30 to 150 ° C., preferably 40 to 100 ° C.
- a tertiary amine catalyst such as triethylamine, tripropylamine, triethylenediamine, diazabicycloundecene or the like may be used.
- the oxygen absorbent (E) comprises at least one compound represented by the general formula (EI). That is, the oxygen absorbent (E) may be a mixture of two or more compounds represented by the general formula (EI).
- the dimer compound reacted with the compound, and two molecules of the compound represented by the general formula (E-1) and one molecule of the compound represented by the general formula (E-2) reacted.
- Trimeric compounds can be formed.
- the oxygen absorbent (E) may be a mixture thereof.
- the compound constituting the oxygen absorbent (E) is excellent in oxygen absorption.
- the amount of oxygen absorbed per gram of the compound constituting the oxygen absorbent (E) is preferably 3 cc / g or more, more preferably 5 cc / g or more.
- the upper limit value of the oxygen absorption amount is not particularly limited and is preferably as high as possible. However, 20 cc / g or less is suitable as an oxygen absorbent.
- the measuring method of oxygen absorption amount is performed by the method as described in an Example.
- Compound constituting the oxygen absorbing agent (E) is a tertiary hydrogen bonded to the carbon atom located between the carbonyl group and L E to form a radical by dissociation as a proton. That is, since on the carbon atom to which tertiary hydrogen bonded and the L E is a carbonyl group and an electron-donating group is an electron withdrawing groups attached, when the tertiary hydrogen is dissociated as a proton It is considered that a very stable radical is generated by a phenomenon called a captative effect in which unpaired electrons existing on the carbon atom are energetically stabilized. When oxygen and water are present here, it is considered that oxygen reacts with this radical to show oxygen absorption performance. It has also been found that the higher the humidity and temperature, the higher the reactivity.
- the oxygen absorbent (E) As a more preferable usage form of the oxygen absorbent (E), a form in which the compound represented by the general formula (EI) is supported on a carrier is preferable from the viewpoint of easy handling and improvement of the oxygen absorption rate.
- the carrier used for loading include diatomaceous earth, activated carbon, zeolite, alumina, silica, titania, zirconia, and ceria.
- Oxygen absorbent (E) is preferably used in a small bag. By arranging a sachet or the like filled with the oxygen absorbent (E) in the package, the oxygen concentration in the package can be lowered, and the stored product in the package can be stored in a good state.
- an oxygen absorbent (E) can also be mix
- Packaging materials and packaging containers obtained by molding and processing a resin composition in which an oxygen absorbent (E) is blended with a resin raw material can maintain the oxygen concentration in the package low, and the stored material in the package is excellent. Can be saved in state.
- the oxygen absorbent (E) is blended in the resin raw material
- the content of the oxygen absorbent in the resin composition is preferably 1 to 30% by mass from the viewpoints of oxygen absorption performance and resin moldability and appearance. More preferably, it is 3 to 20% by mass, and still more preferably 5 to 10% by mass.
- the oxygen absorbent (F) is composed of at least one compound represented by any one of the following general formulas (FI) to (F-III).
- Ra F1 represents a substituent.
- Rb F1 represents a hydrogen atom or a substituent.
- Q F1 represents a hydrogen atom or a substituent.
- L F1 represents an imino group, an ether group, or a sulfide group.
- n F represents an integer of 1 to 2.
- Ra F2 represents a substituent.
- Q F2 represents a hydrogen atom or a substituent.
- L F2 represents an imino group, an ether group, a sulfide group, or a substituted or unsubstituted alkylene group.
- Ra F3 represents a substituent.
- Q F31 and Q F32 each represent a hydrogen atom or a substituent.
- L F3 represents an imino group, an ether group, or a sulfide group.
- Ra F1 in the general formula (FI), Ra F2 in the general formula (F-II), and Ra F3 in the general formula (F-III) each represent a substituent, and the substituent includes a substituent for R A1
- Suitable examples of Ra F1 , Ra F2 and Ra F3 are the same as those of R A1 .
- Rb F1 represents a hydrogen atom or a substituent, and examples of the substituent include the same functional groups as the substituents represented by Ra F1 , Ra F2 or Ra F3 .
- Rb F1 is preferably a hydrogen atom and a substituted or unsubstituted alkyl group, more preferably a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and a hydrogen atom and a substituted or unsubstituted carbon group having 1 to 4 carbon atoms. More preferred are 2 alkyl groups.
- Rb F1 examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group, but are not limited thereto. Among these, a methyl group and an ethyl group are more preferable.
- Q F1 in the general formula (FI), Q F2 in the general formula (F-II), and Q F31 and Q F32 in the general formula (F-III) each represent a hydrogen atom or a substituent. Is exemplified by the same functional group as the substituent represented by Ra F1 , Ra F2 or Ra F3 .
- Q F31 and Q F32 may be the same as or different from each other.
- Q F1 , Q F2 , Q F31 and Q F32 are each preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aryl group.
- An unsubstituted alkyl group having 1 to 12 carbon atoms and a substituted or unsubstituted alkenyl group having 1 to 4 carbon atoms are more preferable.
- preferred Q F1 , preferred examples of Q F2 , preferred examples of Q F31 and preferred examples of Q F32 include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n Examples include, but are not limited to, -butyl group, t-butyl group, 2-ethylhexyl group, decyl group, stearyl group, allyl group, phenyl group, benzyl group and the like. Among these, an allyl group is more preferable from the viewpoint of oxygen absorption.
- L F1 in formula (FI) represents an imino group (—NH—), an ether group (—O—), or a sulfide group (—S—).
- L F1 is preferably an imino group from the viewpoint of oxygen absorption performance.
- L F2 in formula (F-II) represents an imino group (—NH—), an ether group (—O—), a sulfide group (—S—) or a substituted or unsubstituted alkylene group.
- the alkylene group preferably has 1 to 4 carbon atoms.
- L F2 is preferably an imino group, an ether group, a sulfide group, and a methylene group from the viewpoint of oxygen absorption performance, and more preferably an imino group.
- L F3 in the general formula (F-III) represents an imino group (—NH—), an ether group (—O—), or a sulfide group (—S—).
- L F3 is preferably an imino group from the viewpoint of oxygen absorption performance.
- n F represents an integer of 1 to 2.
- the plurality of Ra F1 may be the same or different from each other, and the plurality of L F1 may be the same or different from each other.
- a method for producing the compound represented by any one of formulas (FI) to (F-III) will be described.
- the method for producing the compound represented by any one of the general formulas (FI) to (F-III) is not particularly limited, but the compound represented by the following general formula (Fi) and / or its hydrochloride And a compound produced by an epoxy ring-opening reaction between the compound represented by formula (F-ii) and
- Ra Fi represents a substituent.
- Rb Fi represents a hydrogen atom or a substituent.
- L Fi represents an imino group, an ether group, a sulfide group, or a substituted or unsubstituted alkylene group. However, when L Fi is a substituted or unsubstituted alkylene group, Rb Fi is a hydrogen atom.
- Q Fii represents a hydrogen atom or a substituent.
- Ra Fi in the general formula ( Fi ) corresponds to Ra F1 in the general formula (FI), Ra F2 in the general formula (F-II), or Ra F3 in the general formula (F-III) after the reaction. It is a part to do. Therefore, Ra Fi is synonymous with Ra F1 , Ra F2 and Ra F3 .
- Rb Fi in the general formula ( Fi ) is a portion corresponding to Rb F1 in the general formula (FI) after the reaction. Therefore, Rb Fi is synonymous with Rb F1 .
- L Fi is a substituted or unsubstituted alkylene group
- Rb Fi is a hydrogen atom.
- L Fi in the general formula ( Fi ) corresponds to L F1 in the general formula (FI), L F2 in the general formula (F-II), or L F3 in the general formula (F-III) after the reaction. It is a part to do. Therefore, L Fi represents an imino group (—NH—), an ether group (—O—), a sulfide group (—S—) or a substituted or unsubstituted alkylene group, and an imino group is preferred.
- Q Fii of the general formula (F-ii) is, after the reaction, Q F1 of the general formula (FI), Q F2 of the general formula (F-II), Q F31 or Q of the general formula (FI) This is the part corresponding to F32 . Therefore, Q Fii is synonymous with Q F1 , Q F2 , Q F31, and Q F32 .
- Examples of the compound represented by the general formula (Fi) include ⁇ -amino acids (for example, alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, tert-leucine, isoleucine, serine, threonine, cysteine, methionine).
- ⁇ -amino acids for example, alanine, 2-aminobutyric acid, valine, norvaline, leucine, norleucine, tert-leucine, isoleucine, serine, threonine, cysteine, methionine.
- the compound represented by the general formula (Fi) has an asymmetric carbon, it may be D-form, L-form, racemate, or allo-form.
- an ⁇ -amino acid alkyl ester having a tertiary hydrogen at the ⁇ carbon is particularly preferable from the viewpoint of ease of synthesis and improvement of oxygen absorption.
- alanine methyl is most preferred from the viewpoint of oxygen absorption.
- Examples of the compound represented by the general formula (F-ii) include glycidose, methyl glycidyl ether, ethyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, Examples include stearyl glycidyl ether, phenyl glycidyl ether, and benzyl glycidyl ether, but are not limited thereto. Moreover, these can be used individually or in combination of 2 or more types. Among these, allyl glycidyl ether is preferable from the viewpoints of availability of raw materials and oxygen absorption improvement.
- Reaction conditions in the epoxy ring-opening reaction between the compound represented by the general formula (Fi) and / or its hydrochloride and the compound represented by the general formula (F-ii) are not particularly limited and are appropriately determined. be able to.
- the reaction temperature is usually 30 to 150 ° C., preferably 40 to 100 ° C.
- the oxygen absorbent (F) comprises at least one compound represented by any one of the general formulas (FI) to (F-III). That is, the oxygen absorbent (F) may be a compound represented by any one of the general formulas (FI) to (F-III), or a mixture of these compounds (that is, two or more kinds of general Mixtures of compounds of formula (FI), mixtures of two or more compounds of general formula (F-II), mixtures of two or more compounds of general formula (F-III), one or more general formulas ( A mixture of a compound of FI) and one or more compounds of general formula (F-II), one or more compounds of general formula (FI) and one or more of general formulas (F-III) Mixtures with compounds, mixtures of one or more compounds of general formula (F-II) with one or more compounds of general formula (F-III), and one or more compounds of general formula (FI) A mixture of one or more compounds of general formula (F-II) and one or more compounds of general formula (F-III)) Good.
- one molecule of the general formula (Fi) A dimer compound obtained by reacting one compound of the general formula (F-ii) with one molecule, and two molecules of the general formula (Fi) and one molecule of the general formula (F-ii) Trimeric compounds can be formed that have reacted with the compound.
- the oxygen absorbent (F) is preferably composed of at least one compound represented by the general formula (FI) from the viewpoint of ease of synthesis.
- the compound constituting the oxygen absorbent (F) is excellent in oxygen absorption.
- the amount of oxygen absorbed per gram of the compound constituting the oxygen absorbent (F) is preferably 5 cc / g or more, more preferably 10 cc / g or more.
- the upper limit value of the oxygen absorption amount is not particularly limited and is preferably as high as possible, but is preferably 30 cc / g or less as an oxygen absorbent.
- the measuring method of oxygen absorption amount is performed by the method as described in an Example.
- the compound constituting the oxygen absorbent (F) exhibits good oxygen absorption performance.
- the tertiary hydrogen bonded to the carbon atom located between the carbonyl group and L F1 (L F2 or L F3 ) dissociates as a proton to form a radical.
- a more preferred form of use of the oxygen absorbent (F) is a compound represented by any one of the above general formulas (FI) to (F-III) from the viewpoint of easy handling and improvement of the oxygen absorption rate.
- a form in which is supported on a carrier is preferable.
- the carrier used for loading include diatomaceous earth, activated carbon, zeolite, alumina, silica, titania, zirconia, and ceria.
- the oxygen absorbent (F) is used in a small bag.
- the oxygen concentration in the package can be lowered, and the stored product in the package can be stored in a good state.
- an oxygen absorbent (F) can also be mix
- Packaging materials and packaging containers obtained by molding and processing a resin composition in which an oxygen absorbent (F) is blended with a resin raw material can maintain the oxygen concentration in the package low, and the stored material in the package is excellent. Can be saved in state.
- the oxygen absorbent content in the resin composition is preferably 1 to 30% by mass from the viewpoints of oxygen absorption performance, resin moldability and appearance. More preferably, it is 3 to 20% by mass, and still more preferably 5 to 10% by mass.
- Examples A-1 to A-13, Comparative Examples A-1 to A-3, Examples D-1 to D-13, and Comparative Examples D-1 to D-2 10 mg of the synthesized compound was added to methanol. It melt
- Examples B-1 to B-11, Comparative Examples B-1 to B-3, Examples C-1 to C-12, and Comparative Examples C-1 to C-3 10 mg of the synthesized compound was added to 10 ml of methanol. After dissolution, 100 ⁇ l of 10N HCl was added to esterify the carboxylic acid end, and then subjected to measurement.
- Example> cotton containing 2 g of the synthesized amide compound was used as a sample.
- Comparative Example A-3 a sample obtained by wrapping 2 g of a synthesized phthalimide compound powder in a medicine wrapping paper was used.
- Comparative Examples D-1 and D-2 a sample in which 2 g of the synthesized compound was wrapped in medicine wrapping paper was used as a sample.
- Examples E-1 to E-9, Comparative Examples E-1 to E-2, Examples F-1 to F-10, and Comparative Examples F-1 to F-3 a solution containing the synthesized compound as a sample Cotton containing 4 g was used.
- Comparative Examples C-4 to C-6, Examples D-14 to D-19 and Comparative Examples D-3 to D-4 as a sample, a film having a thickness of about 100 ⁇ m prepared by blending the synthesized compounds A test piece cut into 400 cm 2 was used.
- Example A-1 98.00 g of DL-alanine (manufactured by Musashino Chemical Laboratories) 98.00 g (1. 1 mol) and metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) 74.91 g (0.55 mol) were charged, the system was sufficiently purged with nitrogen, and then heated with stirring under a small amount of nitrogen stream to produce The temperature was raised to 220 ° C. while removing condensed water to be removed from the system. The mixture was kept at 220 ° C. until the generation of condensed water stopped, and then cooled to room temperature to obtain amide compound A-1.
- a GC chart of the synthesized amide compound A-1 is shown in FIG. From FIG. 1, the obtained amide compound A-1 is 2-amino-N- (3-aminomethylbenzyl) -propionamide (a dimeric amide of one DL-alanine molecule and one metaxylylenediamine molecule). Compound) and N, N′-metaxylylenebis (2-aminopropionamide) (trimeric amide compound of two DL-alanine molecules and one metaxylylenediamine molecule) could be identified. . In the following Examples A-2 to A-13 and Comparative Examples A-1 to A-3, the synthesized amide compounds or phthalimide compounds were identified by the same method.
- Example A-2 Amide compound A-2 was obtained in the same manner as in Example A-1, except that DL-alanine was changed to DL-2-aminobutyric acid (manufactured by Nippon Finechem Co., Ltd., purified product).
- Example A-3 Amide compound A-3 was obtained in the same manner as in Example A-1, except that DL-alanine was changed to DL-valine (manufactured by Sinogel Amino Acid Co., Ltd).
- Example A-4 Amide compound A-4 was obtained in the same manner as in Example A-1, except that DL-alanine was changed to DL-leucine (manufactured by Ningbo Haishu Bio-technology).
- Example A-5 Amide compound A-5 was obtained in the same manner as in Example A-1, except that DL-alanine was changed to DL-tert-leucine (a refined product manufactured by Nippon Finechem Co., Ltd.).
- Example A-6 Amide compound A-6 was obtained in the same manner as in Example A-1, except that DL-alanine was changed to DL-phenylalanine (manufactured by Sinogel Amino Acid Co., Ltd).
- Example A-7 Amide compound A-7 was obtained in the same manner as in Example A-1, except that DL-alanine was changed to DL-2-hydroxybutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example A-8 Amide compound A-8 was obtained in the same manner as in Example A-1, except that DL-alanine was changed to DL-2-methylbutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example A-9 Amide compound A-9 was obtained in the same manner as in Example A-1, except that metaxylylenediamine was changed to 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example A-10 Amide compound A-10 was obtained in the same manner as in Example A-1, except that metaxylylenediamine was changed to 1,3-bis (aminomethyl) cyclohexane (Mitsubishi Gas Chemical Co., Ltd.).
- Example A-11 Amide compound A-11 was obtained in the same manner as in Example A-1, except that metaxylylenediamine was changed to hexamethylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.) and the final reaction temperature was 200 ° C. .
- Example A-12 Amide compound A-12 was prepared in the same manner as in Example A-1, except that metaxylylenediamine was changed to 1,4-butanediol bis (3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.). Obtained.
- Example A-13 Amide compound A-13 was obtained in the same manner as in Example A-1, except that metaxylylenediamine was changed to benzylamine (manufactured by Wako Pure Chemical Industries, Ltd.).
- Comparative Example A-1 Amide compound A-14 was obtained in the same manner as in Example A-1, except that DL-alanine was changed to glycine having a secondary hydrogen at the ⁇ -position (manufactured by Kanto Chemical Co., Inc.).
- Comparative Example A-2 The same as Example A-1 except that DL-alanine was changed to 2-aminoisobutyric acid (2-amino-2-methylpropanoic acid, manufactured by Nippon Finechem Co., Ltd.) which does not have hydrogen at the ⁇ -position. By the method, amide compound A-15 was obtained.
- Comparative Example A-3 118.50 g (0) of phthalic anhydride (manufactured by Kanto Chemical Co., Inc.) precisely weighed in a reaction vessel having an internal volume of 300 ml equipped with a stirrer, a partial condenser, a full condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube .80 mol) was charged, and the system was sufficiently purged with nitrogen, and then heated to 140 ° C. with stirring under a small nitrogen stream.
- phthalic anhydride manufactured by Kanto Chemical Co., Inc.
- Example A-14 An eggplant flask having an internal volume of 1000 ml was charged with 90 g of the amide compound A-1 obtained in Example A-1 and 500 g of methanol and stirred to dissolve the amide compound A-1, and then diatomaceous earth (Tokyo Diatomite Industry ( Co., Ltd., trade name: Microcell E) was added. While this was heated to 40 ° C. in an oil bath, methanol was removed using a rotary evaporator to obtain an amide compound carrier.
- diatomaceous earth Tokyo Diatomite Industry ( Co., Ltd., trade name: Microcell E) was added. While this was heated to 40 ° C. in an oil bath, methanol was removed using a rotary evaporator to obtain an amide compound carrier.
- amide compound carrier 10% by mass of an amide compound carrier was added to a linear low density polyethylene (LLDPE, manufactured by Nippon Polyethylene Co., Ltd., trade name: Novatec LL UF240) and dry blended.
- LLDPE linear low density polyethylene
- the obtained blend was formed into a film by a twin screw extruder having two screws with a diameter of 30 mm at an extrusion temperature of 180 ° C., a screw rotation speed of 40 rpm, a feed screw rotation speed of 18 rpm, and a take-off speed of 2.6 m / min.
- An amide compound blend film A-1 having a thickness of 200 mm and a thickness of 95 to 105 ⁇ m was produced.
- Example A-15 An amide compound blend film A-2 was produced in the same manner as in Example A-14, except that amide compound A-1 was changed to amide compound A-2 obtained in Example A-2.
- Example A-16 An amide compound blend film A-3 was produced in the same manner as in Example A-14 except that the amide compound A-1 was changed to the amide compound A-3 obtained in Example A-3.
- Example A-17 An amide compound blend film A-4 was produced in the same manner as in Example A-14, except that the amide compound A-1 was changed to the amide compound A-4 obtained in Example A-4.
- Example A-18 An amide compound blend film A-5 was produced in the same manner as in Example A-14, except that amide compound A-1 was changed to amide compound A-5 obtained in Example A-5.
- Example A-19 An amide compound blend film A-6 was produced in the same manner as in Example A-14, except that amide compound A-1 was changed to amide compound A-6 obtained in Example A-6.
- Comparative Example A-4 An amide compound blend film A-7 was produced in the same manner as in Example A-14 except that the amide compound A-1 was changed to the amide compound A-14 obtained in Comparative Example A-1.
- Comparative Example A-5 An amide compound blend film A-8 was produced in the same manner as in Example A-14, except that the amide compound A-1 was changed to the amide compound A-15 obtained in Comparative Example A-2.
- Comparative Example A-6 The phthalimide compound blend was prepared in the same manner as in Example A-14 except that the amide compound A-1 was changed to the phthalimide compound obtained in Comparative Example A-3 and the phthalimide compound was added to LLDPE without being supported on diatomaceous earth. Film A-9 was produced.
- the oxygen absorbent (A) can be blended with the resin raw material, and any film made of the resin composition containing the oxygen absorbent (A) absorbs oxygen without using a transition metal. Performance can be expressed (Examples A-14 to A-19).
- Example B-1 DL-alanine (manufactured by Musashino Chemical Laboratory Co., Ltd.) 106.91 g (1.) in a 300 ml internal volume reaction vessel equipped with a stirrer, partial condenser, total condenser, thermometer, and nitrogen introduction tube. 2 mol) and 58.46 g (0.40 mol) of adipic acid (manufactured by Asahi Kasei Chemicals Corporation), the system was sufficiently purged with nitrogen, and then heated with stirring under a small nitrogen stream to produce condensed water. The temperature was raised to 200 ° C. while removing from the system. The mixture was kept at 200 ° C. until the generation of condensed water stopped, and then cooled to room temperature to obtain amide compound B-1.
- adipic acid manufactured by Asahi Kasei Chemicals Corporation
- a GC chart of the synthesized amide compound B-1 is shown in FIG. 2.
- the obtained amide compound B-1 is N- (5-carboxypentanoyl) DL-alanine (a dimeric amide compound of one DL-alanine molecule and one adipic acid molecule) and N, N It could be identified as a mixture of '-adipoylbis (DL-alanine) (trimeric amide compound of two DL-alanine molecules and one adipic acid molecule).
- the synthesized amide compounds were identified by the same method.
- Example B-2 An amide compound B-2 was obtained in the same manner as in Example B-1, except that DL-alanine was changed to DL-2-aminobutyric acid (manufactured by Nippon Finechem Co., Ltd., purified product).
- Example B-3 An amide compound B-3 was obtained in the same manner as in Example B-1, except that DL-alanine was changed to DL-valine (Sinogel Amino Acid Co., Ltd.).
- Example B-4 Amide compound B-4 was obtained in the same manner as in Example B-1, except that DL-alanine was changed to DL-leucine (manufactured by Ningbo Haishu Bio-technology).
- Example B-5 Amide compound B-5 was obtained in the same manner as in Example B-1, except that DL-alanine was changed to DL-tert-leucine (a refined product manufactured by Nippon Finechem Co., Ltd.).
- Example B-6 Amide compound B-6 was obtained in the same manner as in Example B-1, except that DL-alanine was changed to DL-phenylalanine (manufactured by Sinogel Amino Acid Co., Ltd).
- Example B-7 Amide compound B-7 was obtained in the same manner as in Example B-1, except that adipic acid was changed to sebacic acid (manufactured by Ito Oil Co., Ltd.) and the final reaction temperature was 215 ° C.
- Example B-8 Amide compound B-8 was obtained in the same manner as in Example B-1, except that adipic acid was changed to dodecanedioic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and the final reaction temperature was 220 ° C.
- Example B-9 An amide compound B-9 was obtained in the same manner as in Example B-1, except that adipic acid was changed to sorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example B-10 Amide compound B-10 was obtained in the same manner as in Example B-1, except that adipic acid was changed to benzoic acid (manufactured by Kanto Chemical Co., Inc.).
- Example B-11 Amide compound B-11 was obtained in the same manner as in Example B-1, except that adipic acid was changed to cyclohexanecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Comparative Example B-1 The amide compound B- was prepared in the same manner as in Example B-1, except that DL-alanine was changed to glycine having secondary hydrogen at the ⁇ -position (manufactured by Kanto Chemical Co., Inc.) and the final reaction temperature was 165 ° C. 12 was obtained.
- Comparative Example B-2 The same as Example B-1, except that DL-alanine was changed to 2-aminoisobutyric acid (2-amino-2-methylpropanoic acid, manufactured by Nippon Finechem Co., Ltd.) which does not have hydrogen at the ⁇ -position. By the method, amide compound B-13 was obtained.
- Comparative Example B-3 65.76 g (0. 45 mol), and the inside of the system was sufficiently purged with nitrogen, and then heated to 160 ° C. with stirring under a small nitrogen stream.
- 96.44 g (0.90 mol) of benzylamine manufactured by Kanto Chemical Co., Inc. was added dropwise to the molten adipic acid, and the temperature was raised to 200 ° C. while removing the condensed water produced outside the system. After maintaining at 200 ° C. until the generation of condensed water ceased, the mixture was cooled to room temperature to obtain amide compound B-14.
- the amide compound obtained using glycine or 2-aminoisobutyric acid which is an ⁇ -amino acid having no tertiary hydrogen at the ⁇ -position, showed almost no oxygen absorption performance (Comparative Examples B-1 and B-2). Further, although the hexamethylene bisbenzylamide compound is used as an oxygen scavenger in combination with a transition metal catalyst such as cobalt, the system in which no transition metal is added showed little oxygen absorption performance (Comparative Example B-3). . In contrast, the amide compound represented by the general formula (BI) obtained by using an ⁇ -amino acid having tertiary hydrogen at the ⁇ -position can exhibit oxygen absorption performance without using a transition metal. (Examples B-1 to B-11).
- Example B-12 An eggplant flask having an internal volume of 1000 ml was charged with 60 g of the amide compound B-1 obtained in Example B-1 and 500 g of methanol and stirred to dissolve the amide compound B-1, and then diatomaceous earth (Tokyo Diatomite Industry ( Co., Ltd., trade name: Microcell E) was added. While this was heated to 40 ° C. in an oil bath, methanol was removed using a rotary evaporator to obtain an amide compound carrier.
- diatomaceous earth Tokyo Diatomite Industry ( Co., Ltd., trade name: Microcell E) was added. While this was heated to 40 ° C. in an oil bath, methanol was removed using a rotary evaporator to obtain an amide compound carrier.
- amide compound support 10% by mass of an amide compound support was added to a linear low density polyethylene (LLDPE, manufactured by Nippon Polyethylene Co., Ltd., trade name: Novatec LL UF240) and dry blended.
- LLDPE linear low density polyethylene
- the obtained blend was formed into a film by a twin screw extruder having two screws with a diameter of 30 mm at an extrusion temperature of 180 ° C., a screw rotation speed of 40 rpm, a feed screw rotation speed of 18 rpm, and a take-off speed of 2.6 m / min.
- An amide compound blend film B-1 having a thickness of 200 mm and a thickness of 95 to 105 ⁇ m was produced.
- Example B-13 An amide compound blend film B-2 was produced in the same manner as in Example B-12, except that the amide compound B-1 was changed to the amide compound B-2 obtained in Example B-2.
- Example B-14 An amide compound blend film B-3 was produced in the same manner as in Example B-12, except that the amide compound B-1 was changed to the amide compound B-3 obtained in Example B-3.
- Example B-15 An amide compound blend film B-4 was produced in the same manner as in Example B-12, except that the amide compound B-1 was changed to the amide compound B-4 obtained in Example B-4.
- Example B-16 An amide compound blend film B-5 was produced in the same manner as in Example B-12, except that the amide compound B-1 was changed to the amide compound B-5 obtained in Example B-5.
- Example B-17 An amide compound blend film B-6 was produced in the same manner as in Example B-12, except that the amide compound B-1 was changed to the amide compound B-6 obtained in Example B-6.
- Comparative Example B-4 An amide compound blend film B-7 was produced in the same manner as in Example B-12, except that the amide compound B-1 was changed to the amide compound B-12 obtained in Comparative Example B-1.
- Comparative Example B-5 An amide compound blend film B-8 was produced in the same manner as in Example B-12, except that the amide compound B-1 was changed to the amide compound B-13 obtained in Comparative Example B-2.
- Comparative Example B-6 Same as Example B-14 except that amide compound B-1 was changed to amide compound B-14 obtained in Comparative Example B-3 and amide compound B-14 was added to LLDPE without being supported on diatomaceous earth.
- An amide compound blend film B-9 was prepared by the method described above.
- the oxygen absorbent (B) can be blended with the resin raw material, and any film made of the resin composition containing the oxygen absorbent (B) absorbs oxygen without using a transition metal. Performance can be expressed (Examples B-12 to B-17).
- Example C-1 DL-alanine (manufactured by Musashino Chemical Laboratory Co., Ltd.) 80.18 g (0. 90 mol) and 90.06 g (0.90 mol) of succinic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) are charged, and the inside of the system is sufficiently purged with nitrogen. The temperature was raised to 200 ° C. while removing condensed water out of the system. The mixture was heated and held at 200 ° C. until the generation of condensed water stopped, and then cooled to room temperature to obtain an imide compound C-1.
- succinic anhydride manufactured by Tokyo Kasei Kogyo Co., Ltd.
- a GC chart of the synthesized imide compound C-1 is shown in FIG. From FIG. 3, it was identified that the obtained imide compound C-1 was 2-succinimide propionic acid (a dimeric imide compound of one molecule of DL-alanine and one molecule of succinic anhydride).
- the synthesized imide compounds were identified by the same method.
- Example C-2 An imide compound C-2 was obtained in the same manner as in Example C-1, except that DL-alanine was changed to DL-2-aminobutyric acid (manufactured by Nippon Finechem Co., Ltd., purified product).
- Example C-3 Imide compound C-3 was obtained in the same manner as in Example C-1, except that DL-alanine was changed to DL-valine (manufactured by Sinogel Amino Acid Co., Ltd).
- Example C-4 An imide compound C-4 was obtained in the same manner as in Example C-1, except that DL-alanine was changed to DL-leucine (manufactured by Ningbo Haishu Bio-technology).
- Example C-5 Imide compound C-5 was obtained in the same manner as in Example C-1, except that DL-alanine was changed to DL-tert-leucine (a refined product manufactured by Nippon Finechem Co., Ltd.).
- Example C-6 An imide compound C-6 was obtained in the same manner as in Example C-1, except that DL-alanine was changed to DL-phenylalanine (manufactured by Sinogel Amino Acid Co., Ltd.).
- Example C-7 An imide compound C-7 was obtained in the same manner as in Example C-1, except that the succinic anhydride was changed to maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example C-8 An imide compound C-8 was obtained in the same manner as in Example C-1, except that succinic anhydride was changed to phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example C-9 An imide compound C-9 was obtained in the same manner as in Example C-1, except that succinic anhydride was changed to trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Co., Inc.).
- Example C-10 An imide compound C-10 was obtained in the same manner as in Example C-1, except that the succinic anhydride was changed to cis-1,2-cyclohexanedicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example C-11 An imide compound C-11 was obtained in the same manner as in Example C-1, except that the succinic anhydride was changed to 4-carboxy-1,2-cyclohexanedicarboxylic anhydride (Mitsubishi Gas Chemical Co., Ltd.). .
- Example C-12 An imide compound C-12 was obtained in the same manner as in Example C-1, except that the succinic anhydride was changed to 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Comparative Example C-1 The imide compound C- was prepared in the same manner as in Example C-1, except that DL-alanine was changed to glycine having secondary hydrogen at the ⁇ -position (manufactured by Kanto Chemical Co., Inc.) and the final reaction temperature was 165 ° C. 13 was obtained.
- Comparative Example C-2 The same as Example C-1, except that DL-alanine was changed to 2-aminoisobutyric acid (2-amino-2-methylpropanoic acid, manufactured by Nippon Finechem Co., Ltd.) which does not have hydrogen at the ⁇ -position.
- the imide compound C-14 was obtained by this method.
- Comparative Example C-3 118.50 g (0) of phthalic anhydride (manufactured by Kanto Chemical Co., Inc.) precisely weighed in a reaction vessel having an internal volume of 300 ml equipped with a stirrer, a partial condenser, a full condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube .80 mol) was charged, and the system was sufficiently purged with nitrogen, and then heated to 140 ° C. with stirring under a small nitrogen stream. To the molten phthalic anhydride, 54.48 g (0.40 mol) of metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) was added dropwise, and the temperature was raised to 200 ° C. while removing the generated condensed water out of the system. The mixture was heated and maintained at 260 ° C. until generation of condensed water stopped, and then cooled to room temperature to obtain an imide compound C-15.
- phthalic anhydride manufactured by
- the imide compound obtained using glycine or 2-aminoisobutyric acid which is an ⁇ -amino acid having no tertiary hydrogen at the ⁇ -position, showed almost no oxygen absorption performance (Comparative Example C- 1 and C-2).
- the metaxylylene bisphthalimide compound is used as an oxygen scavenger in combination with a transition metal catalyst such as cobalt, the system in which no transition metal is added showed almost no oxygen absorption performance (Comparative Example C-3).
- the imide compound represented by the general formula (CI) obtained by using an ⁇ -amino acid having tertiary hydrogen at the ⁇ -position can exhibit oxygen absorption performance without using a transition metal. (Examples C-1 to C-12).
- Example C-13 An eggplant flask having an internal volume of 1000 ml was charged with 60 g of the imide compound C-1 obtained in Example C-1 and 500 g of methanol and stirred to dissolve the imide compound C-1, and then diatomaceous earth (Tokyo Diatomaceous Earth Industry ( Co., Ltd., trade name: Microcell E) was added. While this was heated to 40 ° C. in an oil bath, methanol was removed using a rotary evaporator to obtain an imide compound-carrying product.
- diatomaceous earth Tokyo Diatomaceous Earth Industry ( Co., Ltd., trade name: Microcell E) was added. While this was heated to 40 ° C. in an oil bath, methanol was removed using a rotary evaporator to obtain an imide compound-carrying product.
- LLDPE linear low density polyethylene
- Novatec LL UF240 linear low density polyethylene
- the obtained blend was formed into a film by a twin screw extruder having two screws with a diameter of 30 mm at an extrusion temperature of 180 ° C., a screw rotation speed of 40 rpm, a feed screw rotation speed of 18 rpm, and a take-off speed of 2.6 m / min.
- An imide compound blend film C-1 having a thickness of 200 mm and a thickness of 95 to 105 ⁇ m was produced.
- Example C-14 An imide compound blend film C-2 was produced in the same manner as in Example C-13, except that the imide compound C-1 was changed to the imide compound C-2 obtained in Example C-2.
- Example C-15 An imide compound blend film C-3 was produced in the same manner as in Example C-13, except that the imide compound C-1 was changed to the imide compound C-3 obtained in Example C-3.
- Example C-16 An imide compound blend film C-4 was produced in the same manner as in Example C-13, except that the imide compound C-1 was changed to the imide compound C-4 obtained in Example C-4.
- Example C-17 An imide compound blend film C-5 was produced in the same manner as in Example C-13, except that the imide compound C-1 was changed to the imide compound C-5 obtained in Example C-5.
- Example C-18 An imide compound blend film C-6 was produced in the same manner as in Example C-13, except that the imide compound C-1 was changed to the imide compound C-6 obtained in Example C-6.
- Comparative Example C-4 An imide compound blend film C-7 was produced in the same manner as in Example C-13, except that the imide compound C-1 was changed to the imide compound C-13 obtained in Comparative Example C-1.
- Comparative Example C-5 An imide compound blend film C-8 was produced in the same manner as in Example C-13, except that the imide compound C-1 was changed to the imide compound C-14 obtained in Comparative Example C-2.
- Comparative Example C-6 Similar to Example C-13, except that the imide compound C-1 was changed to the imide compound C-15 obtained in Comparative Example C-3, and the imide compound C-15 was added to LLDPE without being supported on diatomaceous earth.
- the imide compound blend film C-9 was produced by the method described above.
- the oxygen absorbent (C) can be blended with the resin raw material, and any film made of the resin composition containing the oxygen absorbent (C) absorbs oxygen without using a transition metal. Performance can be expressed (Examples C-13 to C-18).
- Example D-1 89.09 g of DL-alanine (manufactured by Musashino Chemical Laboratory Co., Ltd.) precisely weighed in a reaction vessel having an internal volume of 300 ml equipped with a stirrer, a partial condenser, a total condenser, a thermometer, and a nitrogen introduction tube. 00 mol), 31.03 g (0.50 mol) of ethylene glycol (Kanto Chemical Co., Ltd.) and 90.00 g (0.86 to 0.91 mol) of hydrochloric acid (35-37%, Kanto Chemical Co., Ltd.) After sufficiently replacing the inside of the system with nitrogen, the system was heated with stirring under a small nitrogen stream, and the temperature was raised to 150 ° C. while removing water contained in the charged raw materials and the condensed water to be produced out of the system. The mixture was heated and held at 150 ° C. until generation of condensed water stopped, and then cooled to room temperature to obtain ester compound D-1.
- a GC chart of the synthesized ester compound D-1 is shown in FIG. From FIG. 4, the obtained ester compound D-1 was ethylene glycol mono (2-aminopropanoyl) ether (a dimer ester compound of one DL-alanine molecule and one ethylene glycol molecule) and ethylene glycol bis ( 2-aminopropanoyl) ether (trimeric ester compound of two DL-alanine molecules and one ethylene glycol molecule) could be identified.
- the synthesized ester compounds were identified by the same method.
- Example D-2 The ester compound D-2 was obtained in the same manner as in Example D-1, except that DL-alanine was changed to DL-2-aminobutyric acid (manufactured by Nippon Finechem Co., Ltd., purified product).
- Example D-3 An ester compound D-3 was obtained in the same manner as in Example D-1, except that DL-alanine was changed to DL-valine (manufactured by Sinogel Amino Acid Co., Ltd).
- Example D-4 The ester compound D-4 was obtained in the same manner as in Example D-1, except that DL-alanine was changed to DL-leucine (manufactured by Ningbo Haishu Bio-technology).
- Example D-5 An ester compound D-5 was obtained in the same manner as in Example D-1, except that DL-alanine was changed to DL-tert-leucine (a refined product manufactured by Nippon Finechem Co., Ltd.).
- Example D-6 An ester compound D-6 was obtained in the same manner as in Example D-1, except that DL-alanine was changed to DL-phenylalanine (manufactured by Sinogel Amino Acid Co., Ltd).
- Example D-7 The ester compound D-7 was obtained in the same manner as in Example D-1, except that DL-alanine was changed to L-alanine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and hydrochloric acid was not added. .
- Example D-8 An ester compound D-8 was obtained in the same manner as in Example D-1, except that DL-alanine was changed to DL-2-hydroxybutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example D-9 An ester compound D-9 was obtained in the same manner as in Example D-1, except that DL-alanine was changed to DL-2-methylbutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example D-10 An ester compound D-10 was obtained in the same manner as in Example D-1, except that ethylene glycol was changed to 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example D-11 Implemented except that DL-alanine was changed to L-alanine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.), ethylene glycol was changed to benzyl alcohol (manufactured by Kanto Chemical Co., Ltd.), and hydrochloric acid was not added.
- the ester compound D-11 was obtained in the same manner as in Example D-1.
- Example D-12 An ester compound D-12 was obtained in the same manner as in Example D-1, except that ethylene glycol was changed to 1,4-benzenediol (manufactured by Tokyo Chemical Industry Co., Ltd.).
- Example D-13 An ester compound D-13 was obtained in the same manner as in Example D-1, except that ethylene glycol was changed to 1,4-cyclohexanediol (produced by Tokyo Chemical Industry Co., Ltd., cis / trans mixture).
- Comparative Example D-1 An ester compound D-14 was obtained in the same manner as in Example D-1, except that DL-alanine was changed to glycine having a secondary hydrogen at the ⁇ -position (manufactured by Kanto Chemical Co., Inc.).
- Comparative Example D-2 The same as Example D-1, except that DL-alanine was changed to 2-aminoisobutyric acid (2-amino-2-methylpropanoic acid, manufactured by Nippon Finechem Co., Ltd.) which has no hydrogen at the ⁇ -position.
- the ester compound D-15 was obtained by this method.
- the ester compound obtained using glycine or 2-aminoisobutyric acid which is an ⁇ -amino acid having no tertiary hydrogen at the ⁇ -position, showed almost no oxygen absorption performance (Comparative Examples D-1 and D-2).
- the ester compound represented by the general formula (DI) obtained by using an ⁇ -amino acid having tertiary hydrogen at the ⁇ -position can exhibit oxygen absorption performance without using a transition metal. (Examples D-1 to D-13).
- Example D-14 An eggplant flask having an internal volume of 1000 ml was charged with 60 g of the ester compound D-1 obtained in Example D-1 and 500 g of methanol, and stirred to dissolve the ester compound D-1, and then diatomaceous earth (Tokyo Diatomaceous Earth Industry ( Co., Ltd., trade name: Microcell E) was added. While heating this to 40 ° C. in an oil bath, methanol was removed using a rotary evaporator to obtain an ester compound-carrying product.
- diatomaceous earth Tokyo Diatomaceous Earth Industry ( Co., Ltd., trade name: Microcell E) was added. While heating this to 40 ° C. in an oil bath, methanol was removed using a rotary evaporator to obtain an ester compound-carrying product.
- an ester compound support 10% by mass of an ester compound support was added to a linear low density polyethylene (LLDPE, manufactured by Nippon Polyethylene Co., Ltd., trade name: Novatec LL UF240) and dry blended.
- LLDPE linear low density polyethylene
- the obtained blend was formed into a film by a twin screw extruder having two screws with a diameter of 30 mm at an extrusion temperature of 180 ° C., a screw rotation speed of 40 rpm, a feed screw rotation speed of 18 rpm, and a take-off speed of 2.6 m / min.
- An ester compound blend film D-1 having a thickness of 200 mm and a thickness of 95 to 105 ⁇ m was produced.
- Example D-15 An ester compound blend film D-2 was produced in the same manner as in Example D-14, except that the ester compound D-1 was changed to the ester compound D-2 obtained in Example D-2.
- Example D-16 An ester compound blend film D-3 was produced in the same manner as in Example D-14 except that the ester compound D-1 was changed to the ester compound D-3 obtained in Example D-3.
- Example D-17 An ester compound blend film D-4 was produced in the same manner as in Example D-14, except that the ester compound D-1 was changed to the ester compound D-4 obtained in Example D-4.
- Example D-18 An ester compound blend film D-5 was produced in the same manner as in Example D-14, except that the ester compound D-1 was changed to the ester compound D-5 obtained in Example D-5.
- Example D-19 An ester compound blend film D-6 was produced in the same manner as in Example D-14, except that the ester compound D-1 was changed to the ester compound D-6 obtained in Example D-6.
- Comparative Example D-3 An ester compound blend film D-7 was produced in the same manner as in Example D-14 except that the ester compound D-1 was changed to the ester compound D-14 obtained in Comparative Example D-1.
- Comparative Example D-4 An ester compound blend film D-8 was produced in the same manner as in Example D-14 except that the ester compound D-1 was changed to the ester compound D-15 obtained in Comparative Example D-2.
- the oxygen absorbent (D) can be blended with the resin raw material, and any film made of the resin composition containing the oxygen absorbent (D) absorbs oxygen without using a transition metal. Performance can be expressed (Examples D-14 to D-19).
- Example E-1 41.87 g (0.30 mol) of L-alanine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a 300 ml internal reaction vessel equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet tube and nitrogen exhaust tube. , N, N-dimethylformamide (manufactured by Kanto Chemical Co., Inc.) 70.10 g (equivalent to the total weight of the raw material) was charged, and the system was sufficiently purged with nitrogen. The temperature was raised to ° C.
- a GC chart of the synthesized compound E-1 is shown in FIG. From FIG. 5, the obtained compound E-1 is N- (6-isocyanatohexylcarbamoyl) -L-alanine methyl (a dimer compound of one L-alanine methyl molecule and one metaxylylene diisocyanate molecule). ) And N, N′-metaxylylenebis (carbamoyl-L-alanine methyl) (a trimeric compound of two L-alanine methyl molecules and one metaxylylene diisocyanate molecule). It was. In the following Examples E-2 to E-9 and Comparative Examples E-1 to E-2, the synthesized compounds were identified by the same technique.
- Example E-2 The compound E-2 was synthesized in the same manner as in Example E-1, except that L-alanine methyl hydrochloride was changed to DL-2-aminobutyric acid methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.). Obtained.
- Example E-3 Synthesis was carried out in the same manner as in Example E-1, except that L-alanine methyl hydrochloride was changed to L-valine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound E-3.
- Example E-4 Synthesis was carried out in the same manner as in Example E-1, except that L-alanine methyl hydrochloride was changed to L-leucine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound E-4.
- Example E-5 Synthesis was performed in the same manner as in Example E-1, except that L-alanine methyl hydrochloride was changed to L-tert-leucine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound E-5. It was.
- Example E-6 Synthesis was carried out in the same manner as in Example E-1, except that L-alanine methyl hydrochloride was changed to L-phenylalanine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound E-6.
- Example E-7 Synthesis was performed in the same manner as in Example E-1, except that metaxylylene diisocyanate was changed to 4,4′-dicyclohexylmethane diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.). Obtained.
- Example E-8 Synthesis was performed in the same manner as in Example E-1, except that metaxylylene diisocyanate was changed to hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound E-8.
- Example E-9 Synthesis was performed in the same manner as in Example E-1 except that metaxylylene diisocyanate was changed to butyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound E-9.
- Example E-1 The compound E was synthesized in the same manner as in Example E-1, except that L-alanine methyl hydrochloride was changed to glycine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) having secondary hydrogen at the ⁇ -position. -10 was obtained.
- Comparative Example E-2 Synthesis was performed in the same manner as in Example E-1, except that L-alanine methyl hydrochloride was changed to ⁇ -aminoisobutyric acid methyl hydrochloride having no hydrogen at the ⁇ -position (manufactured by Sigma-Aldich Co.). E-11 was obtained.
- Example F-1 41.87 g (0) of L-alanine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) precisely weighed in a reaction vessel having an internal volume of 300 ml equipped with a stirrer, thermometer, dropping funnel, nitrogen introduction tube, and nitrogen exhaust tube. .30 mol), N, N-dimethylformamide (manufactured by Kanto Chemical Co., Inc.) 76.11 g (equivalent to the total weight of the raw materials), the system was thoroughly purged with nitrogen, and stirred under a small amount of nitrogen stream The temperature was raised to 60 ° C.
- a GC chart of the synthesized compound F-1 is shown in FIG. From FIG. 6, the obtained compound F-1 is N- (2-hydroxy-3-allyloxypropyl) L-alanine methyl (a dimer compound of one molecule of L-alanine methyl and one molecule of allyl glycidyl ether). ) And N- [N- (2-hydroxy-3-allyloxypropyl) L-alanyl] L-alanine methyl (trimeric compound of two L-alanine methyl molecules and one allyl glycidyl ether molecule) I was able to identify it. In the following Examples F-2 to F-10 and Comparative Examples F-1 to F-3, the synthesized compounds were identified by the same technique.
- Example F-2 The compound F-2 was synthesized in the same manner as in Example F-1, except that L-alanine methyl hydrochloride was changed to DL-2-aminobutyric acid methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.). Obtained.
- Example F-3 Synthesis was performed in the same manner as in Example F-1, except that L-alanine methyl hydrochloride was changed to L-valine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound F-3.
- Example F-4 Synthesis was carried out in the same manner as in Example F-1, except that L-alanine methyl hydrochloride was changed to L-leucine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound F-4.
- Example F-5 Synthesis was performed in the same manner as in Example F-1 except that L-alanine methyl hydrochloride was changed to L-tert-leucine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound F-5. It was.
- Example F-6 Synthesis was carried out in the same manner as in Example F-1, except that L-alanine methyl hydrochloride was changed to L-phenylalanine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound F-6.
- Example F-7 Synthesis was performed in the same manner as in Example F-1 except that allyl glycidyl ether was changed to butyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound F-7.
- Example F-8 Synthesis was performed in the same manner as in Example F-1 except that allyl glycidyl ether was changed to 2-ethylhexyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound F-8.
- Example F-9 Synthesis was performed in the same manner as in Example F-1 except that allyl glycidyl ether was changed to benzyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain compound F-9.
- Example F-10 Except for changing L-alanine methyl hydrochloride to DL-alanine, N, N-dimethylformamide to water, and allyl glycidyl ether to phenol pentaethylene oxide glycidyl ether (manufactured by Nagase ChemteX Corporation, Denacol EX145) Synthesis was performed in the same manner as in Example F-1 to obtain compound F-10.
- Comparative Example F-1 Compound F-11 was obtained in the same manner as in Example F-1, except that L-alanine methyl hydrochloride was not charged.
- Comparative Example F-2 The compound F was synthesized in the same manner as in Example F-1, except that L-alanine methyl hydrochloride was changed to glycine methyl hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) having secondary hydrogen at the ⁇ -position. -12 was obtained.
- Comparative Example F-3 The compound F-13 was synthesized in the same manner as in Example F-1, except that DL-alanine was changed to ⁇ -aminoisobutyric acid methyl hydrochloride having no hydrogen at the ⁇ -position (manufactured by Sigma-Aldich Co.). Got.
- an ⁇ -amino acid having a tertiary hydrogen at the ⁇ -position or a compound obtained using an ⁇ -amino acid alkyl ester having a tertiary hydrogen at the ⁇ -position exhibits oxygen absorption performance without using a transition metal.
- the oxygen absorbent of the present invention can exhibit sufficient oxygen absorption performance without containing a metal.
- the oxygen absorbent of the present invention can exhibit sufficient oxygen absorption performance without containing a metal.
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Abstract
Description
しかし、鉄系の酸素吸収剤は、酸素を吸収するのに水分を必要とし、系内が高湿度であることが要求され、保存対象が限られている。また、鉄粉を使用しているため、異物検査のための金属探知機を使用することができない、又は異物検査前に包装体内に投入できないという問題がある。また、鉄粉を使用しているために、この酸素吸収剤を同封した包装体をそのまま電子レンジで加熱することができないという問題もある。さらに、樹脂中に分散させると樹脂が着色して不透明となるため、透明性が要求される包装の分野には使用できないという用途上の制約がある。
アスコルビン酸系の酸素吸収剤は、鉄系の酸素吸収剤に比べて、酸素の吸収速度が遅いという問題がある。酸素吸収速度が遅いと、包装体内の保存物が酸素に対して非常に敏感なものである場合は、酸素吸収剤が酸素を吸収する前に保存物が酸素により酸化され、あるいは分解されてしまうという問題がある。このような問題を解決するために、酸素吸収速度を向上させる目的で遷移金属を配合したアスコルビン酸系の酸素吸収剤が知られている。
(1)
下記一般式(A-I)で表される少なくとも1種のアミド化合物;下記一般式(B-I)で表される少なくとも1種のアミド化合物;下記一般式(C-I)で表される少なくとも1種のイミド化合物;下記一般式(D-I)で表される少なくとも1種のエステル化合物;下記一般式(E-I)で表される少なくとも1種の化合物;又は下記一般式(F-I)~(F-III)のいずれかで表される少なくとも1種の化合物、よりなる酸素吸収剤。
(2)
前記一般式(A-I)で表される少なくとも1種のアミド化合物よりなる、(1)に記載の酸素吸収剤。
(3)
前記一般式(A-I)におけるRA1が、置換もしくは無置換の炭素数1~6のアルキル基又は置換もしくは無置換の炭素数6~10のアリール基であり、RA2が、アミノ基、水酸基、又は置換もしくは無置換の炭素数1~6のアルキル基である、(2)に記載の酸素吸収剤。
(4)
前記一般式(A-I)におけるQAがメタキシリレン基である、(2)又は(3)に記載の酸素吸収剤。
(5)
前記一般式(A-I)におけるRA1が、置換もしくは無置換の炭素数1~6のアルキル基又は置換もしくは無置換の炭素数6~10のアリール基であり、RA2がアミノ基である、(3)又は(4)に記載の酸素吸収剤。
(6)
前記一般式(A-I)におけるRA1が、置換もしくは無置換の炭素数1~6のアルキル基であり、RA2が水酸基である、(3)又は(4)に記載の酸素吸収剤。
(7)
前記一般式(A-I)におけるRA1及びRA2が、それぞれ独立に置換もしくは無置換の炭素数1~6のアルキル基である、(3)又は(4)に記載の酸素吸収剤。
(8)
(2)~(7)のいずれかに記載の酸素吸収剤を1~30質量%含む樹脂組成物。
前記一般式(B-I)で表される少なくとも1種のアミド化合物よりなる、(1)に記載の酸素吸収剤。
(10)
前記一般式(B-I)におけるRB1が、置換もしくは無置換の炭素数1~6のアルキル基又は置換もしくは無置換の炭素数6~10のアリール基である、(9)に記載の酸素吸収剤。
(11)
前記一般式(B-I)におけるQBが、炭素数6~12の直鎖状もしくは分岐状の飽和もしくは不飽和の脂肪族炭化水素基を含有する基である、(9)又は(10)に記載の酸素吸収剤。
(12)
(9)~(11)のいずれかに記載の酸素吸収剤を1~30質量%含む樹脂組成物。
前記一般式(C-I)で表される少なくとも1種のイミド化合物よりなる、(1)に記載の酸素吸収剤。
(14)
前記一般式(C-I)におけるRC1が、置換もしくは無置換の炭素数1~6のアルキル基又は置換もしくは無置換の炭素数6~10のアリール基である、(13)に記載の酸素吸収剤。
(15)
前記一般式(C-I)におけるQCがエチレン基である、(13)又は(14)に記載の酸素吸収剤。
(16)
(13)~(15)のいずれかに記載の酸素吸収剤を1~30質量%含む樹脂組成物。
前記一般式(D-I)で表される少なくとも1種のエステル化合物よりなる、(1)に記載の酸素吸収剤。
(18)
前記一般式(D-I)におけるRD1が、置換もしくは無置換の炭素数1~6のアルキル基又は置換もしくは無置換の炭素数6~10のアリール基である、(17)に記載の酸素吸収剤。
(19)
前記一般式(D-I)におけるRD2が、アミノ基である(17)又は(18)に記載の酸素吸収剤。
(20)
前記一般式(D-I)におけるQDが、炭素数2~6の直鎖状もしくは分岐状の飽和もしくは不飽和の脂肪族炭化水素基を含有する基である、(17)~(20)のいずれかに記載の酸素吸収剤。
(21)
(17)~(20)のいずれかに記載の酸素吸収剤を1~30質量%含む樹脂組成物。
前記一般式(E-I)で表される少なくとも1種の化合物よりなる、(1)に記載の酸素吸収剤。
(22)
LEがイミノ基である、(21)に記載の酸素吸収剤。
(23)
QEがメタキシリレン基である、(21)又は(22)に記載の酸素吸収剤。
(24)
RE1が置換もしくは無置換の炭素数1~6のアルキル基又は置換もしくは無置換の炭素数6~10のアリール基である、(21)~(23)のいずれかに記載の酸素吸収剤。
(25)
RE2が水素原子又は置換もしくは無置換の炭素数1~4のアルキル基である、請求項(21)~(24)のいずれかに記載の酸素吸収剤。
(26)
(21)~(25)のいずれかに記載の酸素吸収剤を1~30質量%含む樹脂組成物。
前記一般式(F-I)~(F-III)のいずれかで表される少なくとも1種の化合物よりなる、(1)に記載の酸素吸収剤。
(28)
LF1、LF2及びLF3が、それぞれイミノ基である、(27)に記載の酸素吸収剤。
(29)
RaF1、RaF2及びRaF3が、それぞれ置換もしくは無置換の炭素数1~6のアルキル基又は置換もしくは無置換の炭素数6~10のアリール基である、(27)又は(28)に記載の酸素吸収剤。
(30)
RbF1が水素原子又は置換もしくは無置換の炭素数1~4のアルキル基である、(27)~(29)のいずれかに記載の酸素吸収剤。
(31)
QF1、QF2、QF31及びQF32が、それぞれ水素原子、置換もしくは無置換の炭素数1~24のアルキル基、置換もしくは無置換の炭素数1~6のアルケニル基、又は置換もしくは無置換の炭素数6~10のアリール基である、(27)~(30)のいずれかに記載の酸素吸収剤。
(32)
(27)~(31)のいずれかに記載の酸素吸収剤を1~30質量%含む樹脂組成物。
以下に、一般式(A-I)で表される少なくとも1種のアミド化合物よりなる酸素吸収剤(以後、「酸素吸収剤(A)」と呼ぶこともある)、一般式(B-I)で表される少なくとも1種のアミド合物よりなる酸素吸収剤(以後、「酸素吸収剤(B)」と呼ぶこともある)、一般式(C-I)で表される少なくとも1種のイミド化合物よりなる酸素吸収剤(以後、「酸素吸収剤(C)」と呼ぶこともある)、一般式(D-I)で表される少なくとも1種のエステル化合物よりなる酸素吸収剤(以後、「酸素吸収剤(D)」と呼ぶこともある)、一般式(E-I)で表される少なくとも1種の化合物よりなる酸素吸収剤(以後、「酸素吸収剤(E)」と呼ぶこともある)、一般式(F-I)~(F-III)のいずれかで表される少なくとも1種の化合物よりなる酸素吸収剤(以後、「酸素吸収剤(F)」と呼ぶこともある)、の各々について詳細に説明する。
酸素吸収剤(A)は、下記一般式(A-I)で表される少なくとも1種のアミド化合物よりなる。
なお、官能基が更に置換されている場合、上述した炭素数には、更なる置換基の炭素数は含まれないものとする。例えば、ベンジル基は、フェニル基で置換された炭素数1のアルキル基と見なし、フェニル基で置換された炭素数7のアルキル基とは見なさない。以降の炭素数に記載についても、特に断りが無い限り、同様に解するものとする。
好ましいRA1の具体例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、t-ブチル基、1-メチルプロピル基、2-メチルプロピル基、ヒドロキシメチル基、1-ヒドロキシエチル基、メルカプトメチル基、メチルスルファニルエチル基、フェニル基、ナフチル基、ベンジル基、4-ヒドロキシベンジル基等を例示できるが、これらに限定されるものではない。これらの中でも、メチル基、エチル基、イソプロピル基、t-ブチル基、2-メチルプロピル基、及びベンジル基がより好ましい。
RA2としては、酸素吸収性の観点から、アミノ基、水酸基、及びアルキル基が好ましく、アミノ基、水酸基、及び置換もしくは無置換の炭素数1~6のアルキル基がより好ましく、アミノ基が更に好ましい。
前記一般式(A-I)で表されるアミド化合物の製造方法は特に限定されないが、下記一般式(A-1)で表される化合物と下記一般式(A-2)で表されるアミン化合物との脱水縮合反応により製造する方法が好ましい。
前記一般式(A-1)で表される化合物が不斉炭素を有する場合、D体、L体、ラセミ体のいずれであってもよく、アロ体であってもよい。
これらの中でも、原料の入手性や酸素吸収性向上等の観点から、α炭素に3級水素を有するα-アミノ酸が特に好ましい。また、α-アミノ酸の中でも、供給しやすさ、安価な価格といった点から、アラニンが最も好ましい。
芳香族炭化水素基を含有するアミノ化合物としては、例えばオルトキシリレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン、パラフェニレンジアミン等が挙げられる。飽和もしくは不飽和の脂環式炭化水素基を含有するアミノ化合物としては、例えば1,3-ビス(アミノメチル)シクロヘキサン、1,4-ビス(アミノメチル)シクロヘキサン、1,3-ジアミノシクロヘキサン、1,4-ジアミノシクロヘキサン等が挙げられる。直鎖状もしくは分岐状の飽和もしくは不飽和の脂肪族炭化水素基を含有するアミノ化合物としては、例えばエチレンジアミントリメチレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、2-メチル-1,5-ペンタンジアミン、2,2,4-トリメチルヘキサメチレンジアミン、2,4,4-トリメチルヘキサメチレンジアミン等が挙げられる。複素環基を含有するアミノ化合物としては、例えばジアミノピリジン、ジアミノトリアジン等が挙げられる。これらの中でも、酸素吸収性の観点から、メタキシリレンジアミンが好ましい。
酸素吸収剤(A)を樹脂原料に配合する場合、酸素吸収性能、並びに樹脂の成形性及び外観の観点から、樹脂組成物中の酸素吸収剤の含有量は、好ましくは1~30質量%、より好ましくは3~20質量%、更に好ましくは5~10質量%である。
酸素吸収剤(B)は、下記一般式(B-I)で表される少なくとも1種のアミド化合物よりなる。
前記一般式(B-I)で表されるアミド化合物の製造方法は特に限定されないが、下記一般式(B-1)で表されるα-アミノ酸と下記一般式(B-2)で表されるカルボン酸化合物との脱水縮合反応により製造する方法が好ましい。
前記一般式(B-1)で表されるα-アミノ酸は、D体、L体、ラセミ体のいずれであってもよく、アロ体であってもよい。
これらの中でも、原料の入手性や酸素吸収性向上等の観点から、アラニンが最も好ましい。
芳香族炭化水素基を含有するカルボン酸化合物としては、例えば、安息香酸、テレフタル酸、イソフタル酸、オルトフタル酸、等が挙げられる。飽和もしくは不飽和の脂環式炭化水素基を含有するカルボン酸化合物としては、例えば、シクロヘキサンカルボン酸、1,4-シクロヘキサンジカルボン酸、1,4-シクロヘキセンジカルボン酸等が挙げられる。直鎖状もしくは分岐状の飽和もしくは不飽和の脂肪族炭化水素基を含有するカルボン酸化合物としては、例えば、マロン酸、メチルマロン酸、ヒドロキシマロン酸、コハク酸、メチルコハク酸、リンゴ酸、酒石酸、クロトン酸、マレイン酸、グルタル酸、アジピン酸、ソルビン酸、ヘキサジエン二酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸等が挙げられる。複素環基を含有するカルボン酸化合物としては、例えばテトラヒドロフラン-2-カルボン酸、2-フランカルボン酸等が挙げられる。これらの中でも、原料の入手性や酸素吸収性の観点から、アジピン酸が好ましい。
酸素吸収剤(B)を樹脂原料に配合する場合、酸素吸収性能、並びに樹脂の成形性及び外観の観点から、樹脂組成物中の酸素吸収剤の含有量は、好ましくは1~30質量%、より好ましくは3~20質量%、更に好ましくは5~10質量%である。
酸素吸収剤(C)は、下記一般式(C-I)で表される少なくとも1種のイミド化合物よりなる。
前記一般式(C-I)で表されるイミド化合物の製造方法は特に限定されないが、下記一般式(C-1)で表されるα-アミノ酸と下記一般式(C-2)で表される無水カルボン酸化合物との脱水縮合反応により製造する方法が好ましい。
前記一般式(C-1)で表されるα-アミノ酸は、D体、L体、ラセミ体のいずれであってもよく、アロ体であってもよい。
これらの中でも、原料の入手性や酸素吸収性向上等の観点から、アラニンが最も好ましい。
芳香族炭化水素基を含有する無水カルボン酸化合物としては、例えば、無水フタル酸、無水トリメリット酸、無水ピロメリット酸等が挙げられる。飽和もしくは不飽和の脂環式炭化水素基を含有する無水カルボン酸化合物としては、例えば、1,2-シクロヘキサンジカルボン酸無水物、4-カルボキシ-1,2-シクロヘキサンジカルボン酸無水物、4-シクロヘキセン-1,2-ジカルボン酸無水物、5-ノルボルネン-2,3-ジカルボン酸無水物等が挙げられる。直鎖状もしくは分岐状の飽和もしくは不飽和の脂肪族炭化水素基を含有するカルボン酸化合物としては、例えば、無水コハク酸、無水マレイン酸、無水イタコン酸、無水アリルコハク酸等が挙げられる。複素環基を含有するカルボン酸化合物としては、例えば、5,6-ジヒドロ-1,4-ジチイン-2,3-ジカルボン酸無水物等が挙げられる。これらの中でも、原料の入手性や酸素吸収性の観点から、無水コハク酸が好ましい。
酸素吸収剤(C)を樹脂原料に配合する場合、酸素吸収性能、並びに樹脂の成形性及び外観の観点から、樹脂組成物中の酸素吸収剤の含有量は、好ましくは1~30質量%、より好ましくは3~20質量%、更に好ましくは5~10質量%である。
酸素吸収剤(D)は、下記一般式(D-I)で表される少なくとも1種のエステル化合物よりなる。
前記一般式(D-I)で表されるエステル化合物の製造方法は特に限定されないが、下記一般式(D-1)で表される化合物と下記一般式(D-2)で表されるアルコール化合物との脱水縮合反応により製造する方法が好ましい。
前記一般式(D-1)で表される化合物が不斉炭素を有する場合、D体、L体、ラセミ体のいずれであってもよく、アロ体であってもよい。
これらの中でも、原料の入手性や酸素吸収性向上等の観点から、α炭素に3級水素を有するα-アミノ酸が特に好ましい。また、α-アミノ酸の中でも、供給しやすさ、安価な価格といった点から、アラニンが最も好ましい。
芳香族炭化水素基を含有するアルコール化合物としては、例えば、フェノール、ベンジルアルコール、1,2-ベンゼンジオール、1,3-ベンゼンジオール、1,4-ベンゼンジオール等が挙げられる。飽和もしくは不飽和の脂環式炭化水素基を含有するアルコール化合物としては、例えば、シクロヘキサノール、1,2-シクロヘキサンジオール、1,3-シクロヘキサンジオール、1,4-シクロヘキサンジオール等が挙げられる。直鎖状もしくは分岐状の飽和もしくは不飽和の脂肪族炭化水素基を含有するアルコール化合物としては、例えば、エチレングリコール、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール等が挙げられる。複素環基を含有するアルコール化合物としては、例えば、2-ヒドロキシピリジン、2-ヒドロキシキノリン等が挙げられる。これらの中でも、原料の入手性や酸素吸収性の観点から、エチレングリコールが好ましい。
酸素吸収剤(D)を樹脂原料に配合する場合、酸素吸収性能、並びに樹脂の成形性及び外観の観点から、樹脂組成物中の酸素吸収剤の含有量は、好ましくは1~30質量%、より好ましくは3~20質量%、更に好ましくは5~10質量%である。
酸素吸収剤(E)は、下記一般式(E-I)で表される少なくとも1種の化合物よりなる。
RE2としては、水素原子及び置換もしくは無置換のアルキル基が好ましく、水素原子及び置換もしくは無置換の炭素数1~4のアルキル基がより好ましく、水素原子及び置換もしくは無置換の炭素数1~2のアルキル基がさらに好ましい。
好ましいRE2の具体例としては、水素原子、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、t-ブチル基等を例示できるが、これらに限定されるものではない。これらの中でも、メチル基、エチル基がより好ましい。
前記一般式(E-I)で表される化合物の製造方法は特に限定されないが、下記一般式(E-1)で表される化合物及び/またはその塩酸塩と下記一般式(E-2)で表される化合物との反応により製造する方法が好ましい。
前記一般式(E-1)で表される化合物が不斉炭素を有する場合、D体、L体、ラセミ体のいずれであってもよく、アロ体であってもよい。
これらの中でも、合成の容易性や酸素吸収性向上等の観点から、α炭素に3級水素を有するα-アミノ酸アルキルエステルが特に好ましい。また、α-アミノ酸アルキルエステルの中でも、酸素吸収性の観点から、アラニンメチルが最も好ましい。
芳香族炭化水素基を含有する化合物としては、例えばイソシアン酸フェニル、イソシアン酸トリル、イソシアン酸ベンジル、イソシアン酸1-ナフチル、イソシアン酸2-ビフェニル、1,4-フェニレンジイソシアナート、トリレン-2,6-ジイソシアナート、メタキシリレンジイソシアナート、3,3’-ジメチル-4,4’-ジイソシアナトビフェニル、4、4’-ジフェニルメタンジイソシアナート等が挙げられる。飽和もしくは不飽和の脂環式炭化水素基を含有する化合物としては、例えばイソシアン酸シクロヘキシル、1,3-ビス(イソシアナトメチル)シクロヘキサン、4,4‘-ジシクロヘキシルメタンジイソシアナート等が挙げられる。直鎖状もしくは分岐状の飽和もしくは不飽和の脂肪族炭化水素基を含有する化合物としては、例えばイソシアン酸メチル、イソシアン酸エチル、イソシアン酸プロピル、イソシアン酸ブチル、イソシアン酸ヘキシル、イソシアン酸ドデシル、イソシアン酸オクタデシル、ヘキサメチレンジイソシアナート、トリメチルヘキサメチレンジイソシアナート等が挙げられる。これらの中でも、酸素吸収性の観点から、メタキシリレンジイソシアナートが好ましい。
酸素吸収剤(E)を樹脂原料に配合する場合、酸素吸収性能、並びに樹脂の成形性及び外観の観点から、樹脂組成物中の酸素吸収剤の含有量は、好ましくは1~30質量%、より好ましくは3~20質量%、更に好ましくは5~10質量%である。
酸素吸収剤(F)は、下記一般式(F-I)~(F-III)のいずれかで表される少なくとも1種の化合物よりなる。
RbF1としては、水素原子及び置換もしくは無置換のアルキル基が好ましく、水素原子及び置換もしくは無置換の炭素数1~4のアルキル基がより好ましく、水素原子及び置換もしくは無置換の炭素数1~2のアルキル基がさらに好ましい。
好ましいRbF1の具体例としては、水素原子、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、t-ブチル基等を例示できるが、これらに限定されるものではない。これらの中でも、メチル基、エチル基がより好ましい。
QF1、QF2、QF31及びQF32としては、それぞれ、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、及び置換もしくは無置換のアリール基が好ましく、水素原子、置換もしくは無置換の炭素数1~24のアルキル基、置換もしくは無置換の炭素数1~6のアルケニル基、及び置換もしくは無置換の炭素数6~10のアリール基がより好ましく、水素原子、置換もしくは無置換の炭素数1~12のアルキル基、置換もしくは無置換の炭素数1~4のアルケニル基がさらに好ましい。
好ましいQF1の具体例、好ましいQF2の具体例、好ましいQF31の具体例及び好ましいQF32の具体例としては、それぞれ、水素原子、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、t-ブチル基、2-エチルヘキシル基、デシル基、ステアリル基、アリル基、フェニル基、ベンジル基等を例示できるが、これらに限定されるものではない。これらの中でも、酸素吸収性の観点から、アリル基がより好ましい。
一般式(F-II)のLF2はイミノ基(-NH-)、エーテル基(-O-)、スルフィド基(-S-)又は置換もしくは無置換のアルキレン基を表す。前記アルキレン基の炭素数は1~4が好ましい。LF2としては、酸素吸収性能の観点から、イミノ基、エーテル基及びスルフィド基及びメチレン基が好ましく、この中でもイミノ基がより好ましい。
一般式(F-III)のLF3はイミノ基(-NH-)、エーテル基(-O-)、又はスルフィド基(-S-)を表す。LF3としては、酸素吸収性能の観点から、イミノ基が好ましい。
前記一般式(F-I)~(F-III)のいずれかで表される化合物の製造方法は特に限定されないが、下記一般式(F-i)で表される化合物及び/またはその塩酸塩と下記一般式(F-ii)で表される化合物とのエポキシ開環反応により製造する方法が好ましい。
前記一般式(F-i)のRbFiは、反応後において一般式(F-I)のRbF1に相当する部分である。したがって、RbFiはRbF1と同義である。ただし、LFiが置換もしくは無置換のアルキレン基である場合は、RbFiは水素原子である。
前記一般式(F-i)のLFiは、反応後において一般式(F-I)のLF1、一般式(F-II)のLF2又は一般式(F-III)のLF3に相当する部分である。したがって、LFiはイミノ基(-NH-)、エーテル基(-O-)、スルフィド基(-S-)又は置換もしくは無置換のアルキレン基を表し、イミノ基が好ましい。
前記一般式(F-ii)のQFiiは、反応後において一般式(F-I)のQF1、一般式(F-II)のQF2又は一般式(F-I)のQF31若しくはQF32に相当する部分である。したがって、QFiiはQF1、QF2、QF31及びQF32と同義である。
前記一般式(F-i)で表される化合物が不斉炭素を有する場合、D体、L体、ラセミ体のいずれであってもよく、アロ体であってもよい。
これらの中でも、合成の容易性や酸素吸収性向上等の観点から、α炭素に3級水素を有するα-アミノ酸アルキルエステルが特に好ましい。また、α-アミノ酸アルキルエステルの中でも、酸素吸収性の観点から、アラニンメチルが最も好ましい。
これらの中でも、原料の入手性や酸素吸収性向上等の観点から、アリルグリシジルエーテルが好ましい。
例えば、前記一般式(F-i)で表される化合物と前記一般式(F-ii)で表される化合物とのエポシキ開環合反応の結果として、1分子の一般式(F-i)の化合物と1分子の一般式(F-ii)の化合物とが反応した二量体の化合物、及び2分子の一般式(F-i)の化合物と1分子の一般式(F-ii)の化合物とが反応した三量体の化合物が生成し得る。
酸素吸収剤(F)は、合成の容易性の観点から、一般式(F-I)で表される少なくとも1種の化合物よりなることが好ましい。
酸素吸収剤(F)を樹脂原料に配合する場合、酸素吸収性能、並びに樹脂の成形性及び外観の観点から、樹脂組成物中の酸素吸収剤の含有量は、好ましくは1~30質量%、より好ましくは3~20質量%、更に好ましくは5~10質量%である。
ガスクロマトグラフ及び質量分析計(Agilent社製、型式:6890N、5975、カラム:CP-Sil 8CB for amines 30m×0.25mmφ×0.25μm)を用いて、実施例及び比較例で合成した化合物の成分分析を実施した。測定条件は、キャリアガスとしてHeを1ml/minで供給し、インジェクション温度は300℃、オーブン温度は50℃から10℃/minで300℃まで昇温した。
なお、実施例A-1~A-13、比較例A-1~A-3、実施例D-1~D-13及び比較例D-1~D-2については、合成した化合物10mgをメタノール10mlに溶解し、測定に供した。実施例B-1~B-11、比較例B-1~B-3、実施例C-1~C―12及び比較例C-1~C-3については、合成した化合物10mgをメタノール10mlに溶解し、10NHClを100μl加えてカルボン酸末端をエステル化した後、測定に供した。
以下に示すサンプルを、アルミ箔積層フィルムからなる25cm×18cmの3方シール袋に、水10mlを含ませた綿と共に仕込み、袋内空気量が400mlとなるようにして密封した。袋内の湿度は100%RH(相対湿度)とした。40℃下で28日保存後に、袋内の酸素濃度を酸素濃度計(東レエンジニアリング(株)製、商品名:LC-700F)で測定し、この酸素濃度から酸素吸収量(cc/g)を計算した。数値が高いほど酸素吸収性能に優れ好ましい。
<サンプル>
実施例A-1~A-13及び比較例A-1~A-2では、サンプルとして、合成したアミド化合物2gを含ませた綿を用いた。
比較例A-3では、サンプルとして、合成したフタルイミド化合物の粉体2gを薬包紙に包んだものを用いた。
実施例B-1~B-11、比較例B-1~B-3、実施例C-1~C―12、比較例C-1~C-3、実施例D-1~D-13及び比較例D-1~D-2では、サンプルとして、合成した化合物2gを薬包紙に包んだものを用いた。
実施例E-1~E-9、比較例E-1~E-2、実施例F-1~F-10及び比較例F-1~F-3では、サンプルとして、合成した化合物を含む溶液4gを含ませた綿を用いた。
実施例A-14~A-19、比較例A-4~A-6、実施例B-12~B-17、比較例B-4~比較例B-6、実施例C-13~C―18、比較例C-4~C-6、実施例D-14~D-19及び比較例D-3~D-4では、サンプルとして、合成した化合物をブレンドして作製した厚み約100μmのフィルムを400cm2に切り出した試験片を用いた。
撹拌機、分縮器、全縮器、温度計、窒素導入管を備えた内容積300mlの反応容器に、精秤したDL-アラニン((株)武蔵野化学研究所製)98.00g(1.1mol)及びメタキシリレンジアミン(三菱ガス化学(株)製)74.91g(0.55mol)を仕込み、系内を十分に窒素置換した後、少量の窒素気流下で撹拌しながら加熱し、生成する縮合水を系外へ除きながら220℃まで昇温した。縮合水の生成が止まるまで220℃で加熱保持した後、室温まで冷却してアミド化合物A-1を得た。
以下の実施例A-2~A-13及び比較例A-1~A-3においても、同様の手法により、合成したアミド化合物又はフタルイミド化合物について同定した。
DL-アラニンをDL-2-アミノ酪酸((株)日本ファインケム製、精製品)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-2を得た。
DL-アラニンをDL-バリン(Sinogel Amino Acid Co.,Ltd製)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-3を得た。
DL-アラニンをDL-ロイシン(Ningbo Haishuo Bio-technology製)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-4を得た。
DL-アラニンをDL-tert-ロイシン((株)日本ファインケム製精製品)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-5を得た。
DL-アラニンをDL-フェニルアラニン(Sinogel Amino Acid Co.,Ltd製)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-6を得た。
DL-アラニンをDL-2-ヒドロキシ酪酸(東京化成工業(株)製)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-7を得た。
DL-アラニンをDL-2-メチル酪酸(東京化成工業(株)製)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-8を得た。
メタキシリレンジアミンを4,4’-ジアミノジフェニルエーテル(東京化成工業(株)製)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-9を得た。
メタキシリレンジアミンを1,3-ビス(アミノメチル)シクロヘキサン(三菱ガス化学(株)製)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-10を得た。
メタキシリレンジアミンをヘキサメチレンジアミン(和光純薬(株)製)に変更し、最終反応温度を200℃としたこと以外は実施例A-1と同様の方法でアミド化合物A-11を得た。
メタキシリレンジアミンを1,4-ブタンジオールビス(3-アミノプロピル)エーテル(東京化成工業(株)製)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-12を得た。
メタキシリレンジアミンをベンジルアミン(和光純薬(株)製)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-13を得た。
DL-アラニンをα位に2級水素を持つグリシン(関東化学(株)製)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-14を得た。
DL-アラニンをα位に水素を持たない2-アミノイソ酪酸(2-アミノ-2-メチルプロパン酸、(株)日本ファインケム製、精製品)に変更したこと以外は実施例A-1と同様の方法でアミド化合物A-15を得た。
撹拌機、分縮器、全縮器、温度計、滴下ロート、窒素導入管を備えた内容積300mlの反応容器に、精秤した無水フタル酸(関東化学(株)製)118.50g(0.80mol)を仕込み、系内を十分に窒素置換した後、少量の窒素気流下で撹拌しながら140℃まで昇温した。溶融した無水フタル酸にメタキシリレンジアミン(三菱ガス化学(株)製)54.48g(0.40mol)を滴下し、生成する縮合水を系外へ除きながら260℃まで昇温した。縮合水の生成が止まるまで260℃で加熱保持した後、室温まで冷却してフタルイミド化合物を得た。
内容積1000mlのナスフラスコに、実施例A-1で得られたアミド化合物A-1を90g、メタノールを500g仕込み、撹拌してアミド化合物A-1を溶解させた後、珪藻土(東京珪藻土工業(株)製、商品名:マイクロセルE)を30g添加した。これをオイルバスで40℃に加熱しながら、ロータリーエバポレーターを用いてメタノールを除去し、アミド化合物担持物を得た。
アミド化合物A-1を実施例A-2で得られたアミド化合物A-2に変更したこと以外は実施例A-14と同様の方法でアミド化合物ブレンドフィルムA-2を作製した。
アミド化合物A-1を実施例A-3で得られたアミド化合物A-3に変更したこと以外は実施例A-14と同様の方法でアミド化合物ブレンドフィルムA-3を作製した。
アミド化合物A-1を実施例A-4で得られたアミド化合物A-4に変更したこと以外は実施例A-14と同様の方法でアミド化合物ブレンドフィルムA-4を作製した。
アミド化合物A-1を実施例A-5で得られたアミド化合物A-5に変更したこと以外は実施例A-14と同様の方法でアミド化合物ブレンドフィルムA-5を作製した。
アミド化合物A-1を実施例A-6で得られたアミド化合物A-6に変更したこと以外は実施例A-14と同様の方法でアミド化合物ブレンドフィルムA-6を作製した。
アミド化合物A-1を比較例A-1で得られたアミド化合物A-14に変更したこと以外は実施例A-14と同様の方法でアミド化合物ブレンドフィルムA-7を作製した。
アミド化合物A-1を比較例A-2で得られたアミド化合物A-15に変更したこと以外は実施例A-14と同様の方法でアミド化合物ブレンドフィルムA-8を作製した。
アミド化合物A-1を比較例A-3で得られたフタルイミド化合物に変更し、フタルイミド化合物を珪藻土に担持せずにLLDPEに添加したこと以外は実施例A-14と同様の方法でフタルイミド化合物ブレンドフィルムA-9を作製した。
撹拌機、分縮器、全縮器、温度計、窒素導入管を備えた内容積300mlの反応容器に、精秤したDL-アラニン((株)武蔵野化学研究所製)106.91g(1.2mol)及びアジピン酸(旭化成ケミカルズ(株)製)58.46g(0.40mol)を仕込み、系内を十分に窒素置換した後、少量の窒素気流下で撹拌しながら加熱し、生成する縮合水を系外へ除きながら200℃まで昇温した。縮合水の生成が止まるまで200℃で加熱保持した後、室温まで冷却してアミド化合物B-1を得た。
以下の実施例B-2~B-11及び比較例B-1~B-3においても、同様の手法により、合成したアミド化合物について同定した。
DL-アラニンをDL-2-アミノ酪酸((株)日本ファインケム製、精製品)に変更したこと以外は実施例B-1と同様の方法でアミド化合物B-2を得た。
DL-アラニンをDL-バリン(Sinogel Amino Acid Co.,Ltd製)に変更したこと以外は実施例B-1と同様の方法でアミド化合物B-3を得た。
DL-アラニンをDL-ロイシン(Ningbo Haishuo Bio-technology製)に変更したこと以外は実施例B-1と同様の方法でアミド化合物B-4を得た。
DL-アラニンをDL-tert-ロイシン((株)日本ファインケム製精製品)に変更したこと以外は実施例B-1と同様の方法でアミド化合物B-5を得た。
DL-アラニンをDL-フェニルアラニン(Sinogel Amino Acid Co.,Ltd製)に変更したこと以外は実施例B-1と同様の方法でアミド化合物B-6を得た。
アジピン酸をセバシン酸(伊藤製油(株)製)に変更し、最終反応温度を215℃としたこと以外は実施例B-1と同様の方法でアミド化合物B-7を得た。
アジピン酸をドデカン二酸(東京化成工業(株)製)に変更し、最終反応温度を220℃としたこと以外は実施例B-1と同様の方法でアミド化合物B-8を得た。
アジピン酸をソルビン酸(東京化成工業(株)製)に変更したこと以外は実施例B-1と同様の方法でアミド化合物B-9を得た。
アジピン酸を安息香酸(関東化学(株)製)に変更したこと以外は実施例B-1と同様の方法でアミド化合物B-10を得た。
アジピン酸をシクロヘキサンカルボン酸(東京化成工業(株)製)に変更したこと以外は実施例B-1と同様の方法でアミド化合物B-11を得た。
DL-アラニンをα位に2級水素を持つグリシン(関東化学(株)製)に変更し、最終反応温度を165℃としたこと以外は実施例B-1と同様の方法でアミド化合物B-12を得た。
DL-アラニンをα位に水素を持たない2-アミノイソ酪酸(2-アミノ-2-メチルプロパン酸、(株)日本ファインケム製、精製品)に変更したこと以外は実施例B-1と同様の方法でアミド化合物B-13を得た。
撹拌機、分縮器、全縮器、温度計、滴下ロート、窒素導入管を備えた内容積300mlの反応容器に、精秤したアジピン酸(旭化成ケミカルズ(株)製)65.76g(0.45mol)を仕込み、系内を十分に窒素置換した後、少量の窒素気流下で撹拌しながら160℃まで昇温した。溶融したアジピン酸にベンジルアミン(関東化学(株)製)96.44g(0.90mol)を滴下し、生成する縮合水を系外へ除きながら200℃まで昇温した。縮合水の生成が止まるまで200℃で加熱保持した後、室温まで冷却してアミド化合物B-14を得た。
内容積1000mlのナスフラスコに、実施例B-1で得られたアミド化合物B-1を60g、メタノールを500g仕込み、撹拌してアミド化合物B-1を溶解させた後、珪藻土(東京珪藻土工業(株)製、商品名:マイクロセルE)を30g添加した。これをオイルバスで40℃に加熱しながら、ロータリーエバポレーターを用いてメタノールを除去し、アミド化合物担持物を得た。
アミド化合物B-1を実施例B-2で得られたアミド化合物B-2に変更したこと以外は実施例B-12と同様の方法でアミド化合物ブレンドフィルムB-2を作製した。
アミド化合物B-1を実施例B-3で得られたアミド化合物B-3に変更したこと以外は実施例B-12と同様の方法でアミド化合物ブレンドフィルムB-3を作製した。
アミド化合物B-1を実施例B-4で得られたアミド化合物B-4に変更したこと以外は実施例B-12と同様の方法でアミド化合物ブレンドフィルムB-4を作製した。
アミド化合物B-1を実施例B-5で得られたアミド化合物B-5に変更したこと以外は実施例B-12と同様の方法でアミド化合物ブレンドフィルムB-5を作製した。
アミド化合物B-1を実施例B-6で得られたアミド化合物B-6に変更したこと以外は実施例B-12と同様の方法でアミド化合物ブレンドフィルムB-6を作製した。
アミド化合物B-1を比較例B-1で得られたアミド化合物B-12に変更したこと以外は実施例B-12と同様の方法でアミド化合物ブレンドフィルムB-7を作製した。
アミド化合物B-1を比較例B-2で得られたアミド化合物B-13に変更したこと以外は実施例B-12と同様の方法でアミド化合物ブレンドフィルムB-8を作製した。
アミド化合物B-1を比較例B-3で得られたアミド化合物B-14に変更し、アミド化合物B-14を珪藻土に担持せずにLLDPEに添加したこと以外は実施例B-14と同様の方法でアミド化合物ブレンドフィルムB-9を作製した。
撹拌機、分縮器、全縮器、温度計、窒素導入管を備えた内容積300mlの反応容器に、精秤したDL-アラニン((株)武蔵野化学研究所製)80.18g(0.90mol)及び無水コハク酸(東京化成工業(株)製)90.06g(0.90mol)を仕込み、系内を十分に窒素置換した後、少量の窒素気流下で撹拌しながら加熱し、生成する縮合水を系外へ除きながら200℃まで昇温した。縮合水の生成が止まるまで200℃で加熱保持した後、室温まで冷却してイミド化合物C-1を得た。
以下の実施例C-2~C-12及び比較例C-1~C-3においても、同様の手法により、合成したイミド化合物について同定した。
DL-アラニンをDL-2-アミノ酪酸((株)日本ファインケム製、精製品)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-2を得た。
DL-アラニンをDL-バリン(Sinogel Amino Acid Co.,Ltd製)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-3を得た。
DL-アラニンをDL-ロイシン(Ningbo Haishuo Bio-technology製)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-4を得た。
DL-アラニンをDL-tert-ロイシン((株)日本ファインケム製精製品)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-5を得た。
DL-アラニンをDL-フェニルアラニン(Sinogel Amino Acid Co.,Ltd製)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-6を得た。
無水コハク酸を無水マレイン酸(東京化成工業(株)製)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-7を得た。
無水コハク酸を無水フタル酸(東京化成工業(株)製)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-8を得た。
無水コハク酸を無水トリメリット酸(三菱ガス化学(株)製)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-9を得た。
無水コハク酸をcis-1,2-シクロヘキサンジカルボン酸無水物(東京化成工業(株)製)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-10を得た。
無水コハク酸を4-カルボキシ-1,2-シクロヘキサンジカルボン酸無水物(三菱ガス化学(株)製)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-11を得た。
無水コハク酸を5-ノルボルネン-2,3-ジカルボン酸無水物(東京化成工業(株)製)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-12を得た。
DL-アラニンをα位に2級水素を持つグリシン(関東化学(株)製)に変更し、最終反応温度を165℃としたこと以外は実施例C-1と同様の方法でイミド化合物C-13を得た。
DL-アラニンをα位に水素を持たない2-アミノイソ酪酸(2-アミノ-2-メチルプロパン酸、(株)日本ファインケム製、精製品)に変更したこと以外は実施例C-1と同様の方法でイミド化合物C-14を得た。
撹拌機、分縮器、全縮器、温度計、滴下ロート、窒素導入管を備えた内容積300mlの反応容器に、精秤した無水フタル酸(関東化学(株)製)118.50g(0.80mol)を仕込み、系内を十分に窒素置換した後、少量の窒素気流下で撹拌しながら140℃まで昇温した。溶融した無水フタル酸にメタキシリレンジアミン(三菱ガス化学(株)製)54.48g(0.40mol)を滴下し、生成する縮合水を系外へ除きながら200℃まで昇温した。縮合水の生成が止まるまで260℃で加熱保持した後、室温まで冷却してイミド化合物C-15を得た。
内容積1000mlのナスフラスコに、実施例C-1で得られたイミド化合物C-1を60g、メタノールを500g仕込み、撹拌してイミド化合物C-1を溶解させた後、珪藻土(東京珪藻土工業(株)製、商品名:マイクロセルE)を30g添加した。これをオイルバスで40℃に加熱しながら、ロータリーエバポレーターを用いてメタノールを除去し、イミド化合物担持物を得た。
イミド化合物C-1を実施例C-2で得られたイミド化合物C-2に変更したこと以外は実施例C-13と同様の方法でイミド化合物ブレンドフィルムC-2を作製した。
イミド化合物C-1を実施例C-3で得られたイミド化合物C-3に変更したこと以外は実施例C-13と同様の方法でイミド化合物ブレンドフィルムC-3を作製した。
イミド化合物C-1を実施例C-4で得られたイミド化合物C-4に変更したこと以外は実施例C-13と同様の方法でイミド化合物ブレンドフィルムC-4を作製した。
イミド化合物C-1を実施例C-5で得られたイミド化合物C-5に変更したこと以外は実施例C-13と同様の方法でイミド化合物ブレンドフィルムC-5を作製した。
イミド化合物C-1を実施例C-6で得られたイミド化合物C-6に変更したこと以外は実施例C-13と同様の方法でイミド化合物ブレンドフィルムC-6を作製した。
イミド化合物C-1を比較例C-1で得られたイミド化合物C-13に変更したこと以外は実施例C-13と同様の方法でイミド化合物ブレンドフィルムC-7を作製した。
イミド化合物C-1を比較例C-2で得られたイミド化合物C-14に変更したこと以外は実施例C-13と同様の方法でイミド化合物ブレンドフィルムC-8を作製した。
イミド化合物C-1を比較例C-3で得られたイミド化合物C-15に変更し、イミド化合物C-15を珪藻土に担持せずにLLDPEに添加したこと以外は実施例C-13と同様の方法でイミド化合物ブレンドフィルムC-9を作製した。
撹拌機、分縮器、全縮器、温度計、窒素導入管を備えた内容積300mlの反応容器に、精秤したDL-アラニン((株)武蔵野化学研究所製)89.09g(1.00mol)、エチレングリコール(関東化学(株)製)31.03g(0.50mol)及び塩酸(関東化学(株)製、35~37%)90.00g(0.86~0.91mol)を仕込み、系内を十分に窒素置換した後、少量の窒素気流下で撹拌しながら加熱し、仕込んだ原料中に含まれる水及び生成する縮合水を系外へ除きながら150℃まで昇温した。縮合水の生成が止まるまで150℃で加熱保持した後、室温まで冷却してエステル化合物D-1を得た。
以下の実施例D-2~D-13及び比較例D-1~D-2においても、同様の手法により、合成したエステル化合物について同定した。
DL-アラニンをDL-2-アミノ酪酸((株)日本ファインケム製、精製品)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-2を得た。
DL-アラニンをDL-バリン(Sinogel Amino Acid Co.,Ltd製)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-3を得た。
DL-アラニンをDL-ロイシン(Ningbo Haishuo Bio-technology製)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-4を得た。
DL-アラニンをDL-tert-ロイシン((株)日本ファインケム製精製品)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-5を得た。
DL-アラニンをDL-フェニルアラニン(Sinogel Amino Acid Co.,Ltd製)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-6を得た。
DL-アラニンをL-アラニンメチル塩酸塩(東京化成工業(株)製)に変更し、塩酸を無添加としたこと以外は実施例D-1と同様の方法でエステル化合物D-7を得た。
DL-アラニンをDL-2-ヒドロキシ酪酸(東京化成工業(株)製)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-8を得た。
DL-アラニンをDL-2-メチル酪酸(東京化成工業(株)製)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-9を得た。
エチレングリコールを1,6-ヘキサンジオール(東京化成工業(株)製)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-10を得た。
DL-アラニンをL-アラニンメチル塩酸塩(東京化成工業(株)製)に変更し、エチレングリコールをベンジルアルコール(関東化学(株)製)に変更し、塩酸を無添加としたこと以外は実施例D-1と同様の方法でエステル化合物D-11を得た。
エチレングリコールを1,4-ベンゼンジオール(東京化成工業(株)製)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-12を得た。
エチレングリコールを1,4-シクロヘキサンジオール(東京化成工業(株)製、cis/trans混合)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-13を得た。
DL-アラニンをα位に2級水素を持つグリシン(関東化学(株)製)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-14を得た。
DL-アラニンをα位に水素を持たない2-アミノイソ酪酸(2-アミノ-2-メチルプロパン酸、(株)日本ファインケム製、精製品)に変更したこと以外は実施例D-1と同様の方法でエステル化合物D-15を得た。
内容積1000mlのナスフラスコに、実施例D-1で得られたエステル化合物D-1を60g、メタノールを500g仕込み、撹拌してエステル化合物D-1を溶解させた後、珪藻土(東京珪藻土工業(株)製、商品名:マイクロセルE)を30g添加した。これをオイルバスで40℃に加熱しながら、ロータリーエバポレーターを用いてメタノールを除去し、エステル化合物担持物を得た。
エステル化合物D-1を実施例D-2で得られたエステル化合物D-2に変更したこと以外は実施例D-14と同様の方法でエステル化合物ブレンドフィルムD-2を作製した。
エステル化合物D-1を実施例D-3で得られたエステル化合物D-3に変更したこと以外は実施例D-14と同様の方法でエステル化合物ブレンドフィルムD-3を作製した。
エステル化合物D-1を実施例D-4で得られたエステル化合物D-4に変更したこと以外は実施例D-14と同様の方法でエステル化合物ブレンドフィルムD-4を作製した。
エステル化合物D-1を実施例D-5で得られたエステル化合物D-5に変更したこと以外は実施例D-14と同様の方法でエステル化合物ブレンドフィルムD-5を作製した。
エステル化合物D-1を実施例D-6で得られたエステル化合物D-6に変更したこと以外は実施例D-14と同様の方法でエステル化合物ブレンドフィルムD-6を作製した。
エステル化合物D-1を比較例D-1で得られたエステル化合物D-14に変更したこと以外は実施例D-14と同様の方法でエステル化合物ブレンドフィルムD-7を作製した。
エステル化合物D-1を比較例D-2で得られたエステル化合物D-15に変更したこと以外は実施例D-14と同様の方法でエステル化合物ブレンドフィルムD-8を作製した。
撹拌機、温度計、滴下ロート、窒素導入管、窒素排気管を備えた内容積300mlの反応容器に、L-アラニンメチル塩酸塩(東京化成工業(株)製)41.87g(0.30mol)、N,N-ジメチルホルムアミド(関東化学(株)製)70.10g(原料の総重量と等量)を仕込み、系内を十分に窒素置換した後、少量の窒素気流下で撹拌しながら60℃まで昇温した。L-アラニンメチル塩酸塩が溶解したら、メタキシリレンジイソシアナート(東京化成工業(株)製)28.23g(0.15mol)を滴下し、60℃で1時間加熱保持した後、室温まで冷却して化合物E-1を得た。
以下の実施例E-2~E-9及び比較例E-1~E-2においても、同様の手法により、合成した化合物について同定した。
L-アラニンメチル塩酸塩をDL-2-アミノ酪酸メチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例E-1と同様の方法で合成を行い、化合物E-2を得た。
L-アラニンメチル塩酸塩をL-バリンメチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例E-1と同様の方法で合成を行い、化合物E-3を得た。
L-アラニンメチル塩酸塩をL-ロイシンメチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例E-1と同様の方法で合成を行い、化合物E-4を得た。
L-アラニンメチル塩酸塩をL-tert-ロイシンメチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例E-1と同様の方法で合成を行い、化合物E-5を得た。
L-アラニンメチル塩酸塩をL-フェニルアラニンメチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例E-1と同様の方法で合成を行い、化合物E-6を得た。
メタキシリレンジイソシアナートを4,4‘-ジシクロヘキシルメタンジイソシアナート(東京化成工業(株)製)に変更したこと以外は実施例E-1と同様の方法で合成を行い、化合物E-7を得た。
メタキシリレンジイソシアナートをヘキサメチレンジイソシアナート(東京化成工業(株)製)に変更したこと以外は実施例E-1と同様の方法で合成を行い、化合物E-8を得た。
メタキシリレンジイソシアナートをイソシアン酸ブチル(東京化成工業(株)製)に変更したこと以外は実施例E-1と同様の方法で合成を行い、化合物E-9を得た。
L-アラニンメチル塩酸塩をα位に2級水素を持つグリシンメチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例E-1と同様の方法で合成を行い、化合物E-10を得た。
L-アラニンメチル塩酸塩をα位に水素を持たないα-アミノイソ酪酸メチル塩酸塩(Sigma-Aldich Co.製)に変更したこと以外は実施例E-1と同様の方法で合成を行い、化合物E-11を得た。
撹拌機、温度計、滴下ロート、窒素導入管、窒素排気管を備えた内容積300mlの反応容器に、精秤したL-アラニンメチル塩酸塩(東京化成工業(株)製)41.87g(0.30mol)、N,N-ジメチルホルムアミド(関東化学(株)製)76.11g(原料の総重量と等量)を仕込み、系内を十分に窒素置換した後、少量の窒素気流下で撹拌しながら60℃まで昇温した。L-アラニンメチル塩酸塩が溶解したら、アリルグリシジルエーテル(東京化成工業(株)製)34.24g(0.30mol)を滴下し、60℃で1時間加熱保持した後、室温まで冷却して化合物F-1を得た。
以下の実施例F-2~F-10及び比較例F-1~F-3においても、同様の手法により、合成した化合物について同定した。
L-アラニンメチル塩酸塩をDL-2-アミノ酪酸メチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例F-1と同様の方法で合成を行い、化合物F-2を得た。
L-アラニンメチル塩酸塩をL-バリンメチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例F-1と同様の方法で合成を行い、化合物F-3を得た。
L-アラニンメチル塩酸塩をL-ロイシンメチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例F-1と同様の方法で合成を行い、化合物F-4を得た。
L-アラニンメチル塩酸塩をL-tert-ロイシンメチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例F-1と同様の方法で合成を行い、化合物F-5を得た。
L-アラニンメチル塩酸塩をL-フェニルアラニンメチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例F-1と同様の方法で合成を行い、化合物F-6を得た。
アリルグリシジルエーテルをブチルグリシジルエーテル(東京化成工業(株)製)に変更したこと以外は実施例F-1と同様の方法で合成を行い、化合物F-7を得た。
アリルグリシジルエーテルを2-エチルヘキシルグリシジルエーテル(東京化成工業(株)製)に変更したこと以外は実施例F-1と同様の方法で合成を行い、化合物F-8を得た。
アリルグリシジルエーテルをベンジルグリシジルエーテル(東京化成工業(株)製)に変更したこと以外は実施例F-1と同様の方法で合成を行い、化合物F-9を得た。
L-アラニンメチル塩酸塩をDL-アラニンに、N,N-ジメチルホルムアミドを水に、アリルグリシジルエーテルをフェノールペンタエチレンオキシドグリシジルエーテル(ナガセケムテックス(株)製、デナコールEX145)に変更したこと以外は実施例F-1と同様の方法で合成を行い、化合物F-10を得た。
L-アラニンメチル塩酸塩を仕込まなかったこと以外は実施例F-1と同様の操作を行い、化合物F-11を得た。
L-アラニンメチル塩酸塩をα位に2級水素を持つグリシンメチル塩酸塩(東京化成工業(株)製)に変更したこと以外は実施例F-1と同様の方法で合成を行い、化合物F-12を得た。
DL-アラニンをα位に水素を持たないα-アミノイソ酪酸メチル塩酸塩(Sigma-Aldich Co.製)に変更したこと以外は実施例F-1と同様の方法で合成を行い、化合物F-13を得た。
Claims (14)
- 下記一般式(A-I)で表される少なくとも1種のアミド化合物;下記一般式(B-I)で表される少なくとも1種のアミド化合物;下記一般式(C-I)で表される少なくとも1種のイミド化合物;下記一般式(D-I)で表される少なくとも1種のエステル化合物;下記一般式(E-I)で表される少なくとも1種の化合物;又は下記一般式(F-I)~(F-III)のいずれかで表される少なくとも1種の化合物、よりなる酸素吸収剤。
- 前記一般式(A-I)で表される少なくとも1種のアミド化合物よりなる、請求項1に記載の酸素吸収剤。
- 前記一般式(A-I)におけるRA1が、置換もしくは無置換の炭素数1~6のアルキル基又は置換もしくは無置換の炭素数6~10のアリール基であり、RA2が、アミノ基、水酸基、又は置換もしくは無置換の炭素数1~6のアルキル基である、請求項2に記載の酸素吸収剤。
- 前記一般式(B-I)で表される少なくとも1種のアミド化合物よりなる、請求項1に記載の酸素吸収剤。
- 前記一般式(B-I)におけるRB1が、置換もしくは無置換の炭素数1~6のアルキル基又は置換もしくは無置換の炭素数6~10のアリール基である、請求項4に記載の酸素吸収剤。
- 前記一般式(C-I)で表される少なくとも1種のイミド化合物よりなる、請求項1に記載の酸素吸収剤。
- 前記一般式(C-I)におけるRC1が、置換もしくは無置換の炭素数1~6のアルキル基又は置換もしくは無置換の炭素数6~10のアリール基である、請求項6に記載の酸素吸収剤。
- 前記一般式(D-I)で表される少なくとも1種のエステル化合物よりなる、請求項1に記載の酸素吸収剤。
- 前記一般式(D-I)におけるRD1が、置換もしくは無置換の炭素数1~6のアルキル基又は置換もしくは無置換の炭素数6~10のアリール基である、請求項8に記載の酸素吸収剤。
- 前記一般式(E-I)で表される少なくとも1種の化合物よりなる、請求項1に記載の酸素吸収剤。
- LEがイミノ基である、請求項10に記載の酸素吸収剤。
- 前記一般式(F-I)~(F-III)のいずれかで表される少なくとも1種の化合物よりなる、請求項1に記載の酸素吸収剤。
- LF1、LF2及びLF3が、それぞれイミノ基である、請求項12に記載の酸素吸収剤。
- 請求項1~13のいずれかに記載の酸素吸収剤を1~30質量%含む樹脂組成物。
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---|---|---|---|
EP12786081.5A EP2711077A4 (en) | 2011-05-18 | 2012-05-16 | OXYGEN ABSORBER |
JP2013515173A JP6020447B2 (ja) | 2011-05-18 | 2012-05-16 | 酸素吸収剤 |
CN201280024129.5A CN103561862A (zh) | 2011-05-18 | 2012-05-16 | 吸氧剂 |
US14/118,041 US20140117280A1 (en) | 2011-05-18 | 2012-05-16 | Oxygen absorber |
Applications Claiming Priority (12)
Application Number | Priority Date | Filing Date | Title |
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JP2011-111144 | 2011-05-18 | ||
JP2011111144 | 2011-05-18 | ||
JP2011-114563 | 2011-05-23 | ||
JP2011114563 | 2011-05-23 | ||
JP2011134574 | 2011-06-16 | ||
JP2011-134574 | 2011-06-16 | ||
JP2011137350 | 2011-06-21 | ||
JP2011137355 | 2011-06-21 | ||
JP2011-137369 | 2011-06-21 | ||
JP2011137369 | 2011-06-21 | ||
JP2011-137355 | 2011-06-21 | ||
JP2011-137350 | 2011-06-21 |
Publications (1)
Publication Number | Publication Date |
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WO2012157656A1 true WO2012157656A1 (ja) | 2012-11-22 |
Family
ID=47176973
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2012/062450 WO2012157656A1 (ja) | 2011-05-18 | 2012-05-16 | 酸素吸収剤 |
Country Status (6)
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US (1) | US20140117280A1 (ja) |
EP (1) | EP2711077A4 (ja) |
JP (1) | JP6020447B2 (ja) |
CN (1) | CN103561862A (ja) |
TW (1) | TW201309622A (ja) |
WO (1) | WO2012157656A1 (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140335297A1 (en) * | 2011-12-26 | 2014-11-13 | Toyo Seikan Group Holdings, Ltd. | Oxygen-absorbing resin composition |
JP2015093867A (ja) * | 2013-11-14 | 2015-05-18 | 雪印メグミルク株式会社 | 新規な静菌または抗菌剤 |
US9700599B2 (en) | 2012-11-13 | 2017-07-11 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
US9795678B2 (en) | 2014-05-14 | 2017-10-24 | Adocia | Fast-acting insulin composition comprising a substituted anionic compound and a polyanionic compound |
US10525133B2 (en) | 2014-05-14 | 2020-01-07 | Adocia | Aqueous composition comprising at least one protein and one solubilizing agent, preparation thereof and uses thereof |
WO2020071563A1 (ja) * | 2018-10-05 | 2020-04-09 | 株式会社日本触媒 | アルキレングリコール誘導体、洗剤用添加剤、及び洗剤組成物 |
US10792335B2 (en) | 2015-11-16 | 2020-10-06 | Adocia | Rapid-acting insulin composition comprising a substituted citrate |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3027051A4 (en) * | 2013-09-02 | 2017-04-12 | JP Patents L.L.C. | Oxygen uptake compositions and preservation of oxygen perishable goods |
US11104763B2 (en) * | 2017-04-06 | 2021-08-31 | Alliance For Sustainable Energy, Llc | Renewable polymers and resins and methods of making the same |
CN107632318A (zh) * | 2017-08-09 | 2018-01-26 | 中国原子能科学研究院 | 一种用于核素迁移研究的气氛控制*** |
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JPS5435189A (en) | 1977-08-24 | 1979-03-15 | Mitsubishi Gas Chem Co Inc | Oxygen absorber |
JPS5498348A (en) | 1978-01-19 | 1979-08-03 | Toppan Printing Co Ltd | Freshness preserving agent |
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- 2012-05-16 WO PCT/JP2012/062450 patent/WO2012157656A1/ja active Application Filing
- 2012-05-16 CN CN201280024129.5A patent/CN103561862A/zh active Pending
- 2012-05-16 JP JP2013515173A patent/JP6020447B2/ja active Active
- 2012-05-16 EP EP12786081.5A patent/EP2711077A4/en not_active Withdrawn
- 2012-05-16 US US14/118,041 patent/US20140117280A1/en not_active Abandoned
- 2012-05-17 TW TW101117621A patent/TW201309622A/zh unknown
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JPS5498348A (en) | 1978-01-19 | 1979-08-03 | Toppan Printing Co Ltd | Freshness preserving agent |
JPH09291120A (ja) | 1996-04-26 | 1997-11-11 | Ube Ind Ltd | ポリブタジエン粒子、その製造方法及び酸素吸収剤 |
JP2000084407A (ja) * | 1998-09-10 | 2000-03-28 | Otsuka Pharmaceut Factory Inc | 脱酸素剤 |
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JP2010527389A (ja) | 2007-05-10 | 2010-08-12 | コンスター インターナショナル, インコーポレイテッド | 脱酸素分子、脱酸素分子を含む物品およびこれらの使用方法 |
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Cited By (14)
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US20140335297A1 (en) * | 2011-12-26 | 2014-11-13 | Toyo Seikan Group Holdings, Ltd. | Oxygen-absorbing resin composition |
US10233306B2 (en) * | 2011-12-26 | 2019-03-19 | Toyo Seikan Group Holdings, Ltd. | Oxygen-absorbing resin composition |
US10646551B2 (en) | 2012-11-13 | 2020-05-12 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
US9700599B2 (en) | 2012-11-13 | 2017-07-11 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
US11324808B2 (en) | 2012-11-13 | 2022-05-10 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
US10583175B2 (en) | 2012-11-13 | 2020-03-10 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
US10881716B2 (en) | 2012-11-13 | 2021-01-05 | Adocia | Rapid-acting insulin formulation comprising a substituted anionic compound |
JP2015093867A (ja) * | 2013-11-14 | 2015-05-18 | 雪印メグミルク株式会社 | 新規な静菌または抗菌剤 |
US9795678B2 (en) | 2014-05-14 | 2017-10-24 | Adocia | Fast-acting insulin composition comprising a substituted anionic compound and a polyanionic compound |
US10525133B2 (en) | 2014-05-14 | 2020-01-07 | Adocia | Aqueous composition comprising at least one protein and one solubilizing agent, preparation thereof and uses thereof |
US10792335B2 (en) | 2015-11-16 | 2020-10-06 | Adocia | Rapid-acting insulin composition comprising a substituted citrate |
WO2020071563A1 (ja) * | 2018-10-05 | 2020-04-09 | 株式会社日本触媒 | アルキレングリコール誘導体、洗剤用添加剤、及び洗剤組成物 |
JPWO2020071563A1 (ja) * | 2018-10-05 | 2021-09-02 | 株式会社日本触媒 | アルキレングリコール誘導体、洗剤用添加剤、及び洗剤組成物 |
JP7185702B2 (ja) | 2018-10-05 | 2022-12-07 | 株式会社日本触媒 | アルキレングリコール誘導体、洗剤用添加剤、及び洗剤組成物 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2012157656A1 (ja) | 2014-07-31 |
CN103561862A (zh) | 2014-02-05 |
TW201309622A (zh) | 2013-03-01 |
US20140117280A1 (en) | 2014-05-01 |
JP6020447B2 (ja) | 2016-11-02 |
EP2711077A4 (en) | 2016-07-06 |
EP2711077A1 (en) | 2014-03-26 |
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