WO2022102755A1 - Oxygen-absorbing unsaturated polyester resin, oxygen-absorbing composition including same, oxygen-absorbing adhesive, oxygen-absorbing laminate using oxygen-absorbing composition, and oxygen-absorbing film - Google Patents

Oxygen-absorbing unsaturated polyester resin, oxygen-absorbing composition including same, oxygen-absorbing adhesive, oxygen-absorbing laminate using oxygen-absorbing composition, and oxygen-absorbing film Download PDF

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Publication number
WO2022102755A1
WO2022102755A1 PCT/JP2021/041782 JP2021041782W WO2022102755A1 WO 2022102755 A1 WO2022102755 A1 WO 2022102755A1 JP 2021041782 W JP2021041782 W JP 2021041782W WO 2022102755 A1 WO2022102755 A1 WO 2022102755A1
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Prior art keywords
oxygen
absorbing
oxygen absorption
oxygen absorbing
mass
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PCT/JP2021/041782
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French (fr)
Japanese (ja)
Inventor
奈月 太田
彩乃 山村
由起菜 井形
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共同印刷株式会社
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Priority claimed from JP2020189805A external-priority patent/JP2022078855A/en
Priority claimed from JP2021118299A external-priority patent/JP2023013856A/en
Priority claimed from JP2021124329A external-priority patent/JP2023019543A/en
Application filed by 共同印刷株式会社 filed Critical 共同印刷株式会社
Publication of WO2022102755A1 publication Critical patent/WO2022102755A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts

Definitions

  • the present invention relates to an unsaturated polyester resin for oxygen absorption, an oxygen absorbing composition containing the resin, an oxygen absorbing adhesive, an oxygen absorbing laminate using the oxygen absorbing composition, and an oxygen absorbing film.
  • packaging materials having oxygen absorption performance have been widely used for the purpose of suppressing quality deterioration of contents such as foods.
  • Patent Document 1 has an oxygen-absorbing coating layer containing an oxygen-absorbing resin component having a carbon-carbon unsaturated bond and a reactive functional group and a cross-linking agent, and has an oxygen barrier layer and an oxygen-absorbing coating.
  • An oxygen-absorbing coating layer containing an oxygen-absorbing resin component having a carbon-carbon unsaturated bond and a reactive functional group and a cross-linking agent and has an oxygen barrier layer and an oxygen-absorbing coating.
  • a laminated body for oxygen absorption in which a film layer and a heat seal layer are laminated in this order is described.
  • Patent Document 2 describes an oxygen-absorbing polyester-based composition using tetrahydrophthalic acid or a derivative thereof, or tetrahydrophthalic anhydride or a derivative thereof as a raw material as an oxygen-absorbing resin composition having excellent adhesiveness and oxygen absorption. Resin compositions containing resins have been proposed.
  • the raw materials such as tetrahydrophthalic acid and tetrahydrohydroan phthalic acid have extremely high reactivity with oxygen. Therefore, it exhibits excellent oxygen absorption performance.
  • Patent Document 3 proposes an oxygen scavenger made of a polymer containing a cyclohexene ring, a container using the oxygen scavenger, and the like as an oxygen-absorbing substance having a new structure.
  • the oxygen scavenger containing a cyclohexene ring described in Patent Document 3 has a cyclic allyl structure in which the ring is less likely to be fragmented or split after oxidation, and thus suppresses the generation of oxidative by-products that adversely affect odor or taste. It is said that it can be done.
  • the present invention has been made in view of the above background, and has an oxygen-absorbing resin having a structure not described in References 1 to 3, and an oxygen-absorbing composition containing the resin. , An oxygen absorbing adhesive, an oxygen absorbing laminate using an oxygen absorbing composition, and an oxygen absorbing film.
  • the present inventors have diligently studied oxygen-absorbing substances, and by condensing an unsaturated dicarboxylic acid that exhibits oxygen absorption performance due to an ethylenically unsaturated bond with an alicyclic diol, oxygen absorption is achieved. They have found that unsaturated polyesters showing good results can be obtained, and have completed the present invention. That is, the present invention is as follows.
  • ⁇ Aspect 1 An unsaturated polyester resin for oxygen absorption containing a structural unit obtained by condensing an unsaturated dicarboxylic acid and an alicyclic diol.
  • ⁇ Aspect 2 The unsaturated polyester resin for oxygen absorption according to aspect 1, further comprising a structural unit obtained by condensing a saturated carboxylic acid and an alicyclic diol.
  • ⁇ Aspect 3 An oxygen absorbing film containing the oxygen absorbing unsaturated polyester resin according to the first or second aspect.
  • ⁇ Aspect 4 An oxygen absorbing composition comprising the unsaturated polyester resin for oxygen absorption according to the first or second aspect.
  • ⁇ Aspect 5 The oxygen absorbing composition according to aspect 4, which comprises a catalyst.
  • ⁇ Aspect 6 The oxygen absorbing composition according to aspect 4 or 5, which comprises a curing agent.
  • ⁇ Aspect 7 The oxygen absorbing composition according to aspect 6, wherein the amount of the curing agent blended is 50 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the unsaturated polyester resin for oxygen absorption.
  • ⁇ Aspect 8 The oxygen absorbing composition according to any one of aspects 4 to 7, which comprises an antioxidant.
  • ⁇ Aspect 9 >> The oxygen absorption according to aspect 8, wherein the antioxidant is at least one of pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and triphenylphosphine. Composition for.
  • ⁇ Aspect 10 The oxygen absorbing composition according to any one of aspects 4 to 9, comprising saturated polyester.
  • ⁇ Aspect 11 An oxygen absorbing film containing the oxygen absorbing composition according to any one of aspects 4 to 10.
  • ⁇ Aspect 12 An oxygen absorbing adhesive comprising the oxygen absorbing composition according to any one of aspects 4 to 10.
  • ⁇ Aspect 13 An oxygen absorbing adhesive film containing the oxygen absorbing adhesive according to aspect 12.
  • ⁇ Aspect 14 An oxygen absorption laminate comprising an oxygen absorption composition layer comprising the oxygen absorption composition according to any one of aspects 4 to 10.
  • ⁇ Aspect 15 An oxygen absorbing laminate comprising an oxygen absorbing adhesive layer comprising the oxygen absorbing adhesive according to aspect 12.
  • ⁇ Aspect 16 The oxygen absorption laminate according to aspect 14, wherein the oxygen barrier layer, the oxygen absorption composition layer, and the heat seal layer are laminated in this order.
  • ⁇ Aspect 17 The oxygen absorption laminate according to aspect 15, wherein the oxygen barrier layer, the oxygen absorption adhesive layer, and the heat seal layer are laminated in this order.
  • ⁇ Aspect 18 A packaging material comprising any one selected from the group consisting of the oxygen absorbing film according to the third or eleventh aspect, the oxygen absorbing adhesive film according to the thirteenth aspect, and the oxygen absorbing laminated body according to the fourteenth to seventeenth aspects.
  • the unsaturated polyester resin for oxygen absorption of the present invention has an ethylenically carbon-carbon unsaturated bond having oxygen absorption performance and also has an alicyclic structure derived from an alicyclic diol. Therefore, the oxygen absorption performance of the unsaturated bond can be assisted by the alicyclic structure, and a higher oxygen absorption performance can be realized.
  • the unsaturated polyester resin for oxygen absorption of the present invention contains a structural unit in which an unsaturated dicarboxylic acid and an alicyclic diol are condensed.
  • the unsaturated polyester resin for oxygen absorption of the present invention uses an unsaturated dicarboxylic acid having an ethylenically carbon-carbon unsaturated bond that exhibits oxygen absorption performance as a raw material, it is an ethylenic carbon derived from the unsaturated dicarboxylic acid. -It will have a carbon unsaturated bond. Therefore, the unsaturated polyester resin for oxygen absorption of the present invention has oxygen absorption performance.
  • the unsaturated polyester resin for oxygen absorption of the present invention uses an alicyclic diol as a diol for producing an ester bond, it has an alicyclic structure derived from the alicyclic diol. Since the alicyclic structure can assist the oxygen absorption performance of the unsaturated bond, the unsaturated polyester resin for oxygen absorption of the present invention can realize a higher oxygen absorption performance.
  • alicyclic diols can be used to achieve higher oxygen absorption performance is that the space between molecules is created by steric damage due to the alicyclic structure derived from alicyclic diols. It is considered that oxygen can easily enter the inside of the resin through the space, and as a result, the contact opportunity between oxygen and the carbon-carbon unsaturated bond is improved.
  • the unsaturated dicarboxylic acid constituting the unsaturated polyester resin for oxygen absorption of the present invention is a carboxylic acid having at least one ethylenically unsaturated bond, which is a carbon-carbon unsaturated bond, and having two carboxyl groups. be.
  • the carbon-carbon unsaturated bond may be present in the main chain of the unsaturated dicarboxylic acid, in the side chain, or in both. Further, a carbon-carbon unsaturated bond may exist between adjacent carbons forming a ring to form an unsaturated alicyclic structure.
  • the two carboxyl groups may be dehydrated and condensed to form an acid anhydride.
  • the unsaturated dicarboxylic acid may have a structure having an aliphatic ring.
  • Examples of the unsaturated dicarboxylic acid include unsaturated aliphatic dicarboxylic acids.
  • unsaturated aliphatic dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, anhydrides of these acids, unhydrogenated dimer acid, cyclohexene dicarboxylic acid, and the like. Examples thereof include a terpene-maleic acid adduct.
  • unsaturated dicarboxylic acid not only one type of unsaturated dicarboxylic acid but also two or more types may be used.
  • unsaturated dicarboxylic acid may be either cis or trans, or a mixture thereof.
  • the unsaturated dicarboxylic acid is preferably fumaric acid or maleic acid from the viewpoint of easy availability.
  • the content of the unsaturated dicarboxylic acid is not particularly limited, but is, for example, 20 mol% or more, 40 mol% or more, among the carboxylic acid components which are constituents of the unsaturated polyester resin for oxygen absorption of the present invention. It may be 50 mol% or more, 70 mol% or more, 80 mol% or more, or 98 mol% or more.
  • the alicyclic diol constituting the unsaturated polyester resin for oxygen absorption of the present invention has an alicyclic structure having at least one non-aromatic carbon ring and two different hydroxyl groups. It is an alicyclic compound having a structure bonded to carbon.
  • the unsaturated polyester resin for oxygen absorption of the present invention can realize higher oxygen absorption performance by containing a structural unit in which an unsaturated dicarboxylic acid and an alicyclic diol are condensed.
  • the alicyclic structure derived from the alicyclic diol assists the oxygen absorption performance due to the unsaturated bond derived from the unsaturated dicarboxylic acid in the unsaturated polyester resin for oxygen absorption of the present invention. It is considered that a space is created between molecules due to steric hindrance due to the alicyclic structure, and oxygen easily enters the inside of the resin through the space, and as a result, the contact opportunity between oxygen and the carbon-carbon unsaturated bond is improved.
  • the alicyclic diol may have an alicyclic structure having at least one non-aromatic carbon ring, and the alicyclic structure may be a saturated hydrocarbon even if it is a saturated hydrocarbon. It may be an unsaturated cyclic hydrocarbon containing one double bond in the ring. When a carbon-carbon double bond is formed in the ring, the double bond can react with oxygen to exhibit oxygen absorption performance.
  • the alicyclic diol may be a monocyclic ring or a condensed ring.
  • a fused ring at least one non-aromatic carbon ring may be provided, and the aromatic ring may be fused.
  • the alicyclic diol is not particularly limited, but for example, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3. -Cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 5-norbornene-2,3-dimethylol and the like can be mentioned.
  • the alicyclic diol not only one type but also two or more types may be used.
  • the alicyclic diol may be either cis or trans, or a mixture thereof.
  • an alicyclic diol having a structure having a large steric hindrance makes it easier for oxygen to enter. Therefore, for example, an alicyclic diol having a fused ring such as tricyclodecanedimethanol or pentacyclopentadecanedimethanol According to the above, it is possible to enjoy a higher effect.
  • the content of the alicyclic diol is not particularly limited, but is, for example, 20 mol% or more, 40 mol% or more, 50 in the diol component which is a constituent component of the unsaturated polyester resin for oxygen absorption of the present invention. It may be mol% or more, 70 mol% or more, 80 mol% or more, or 98 mol% or more.
  • the content of the structural unit in which the unsaturated dicarboxylic acid and the alicyclic diol are condensed is not particularly limited, but the unsaturated polyester for oxygen absorption of the present invention is not particularly limited. For example, it may be 20 mol% or more, 40 mol% or more, 50 mol% or more, 70 mol% or more, 80 mol% or more, or 98 mol% or more with respect to the entire constituent unit of the resin.
  • the unsaturated polyester resin for oxygen absorption of the present invention may contain other structural units in addition to the structural unit obtained by condensing the unsaturated dicarboxylic acid and the alicyclic diol.
  • the other structural units are not particularly limited, and are, for example, a structural unit in which the above-mentioned unsaturated dicarboxylic acid and a diol other than the above-mentioned alicyclic diol are condensed, and a dicarboxylic acid other than the above-mentioned unsaturated dicarboxylic acid. It may be a structural unit in which an acid and the above-mentioned alicyclic diol are condensed, or a structural unit in which a dicarboxylic acid other than the above-mentioned unsaturated dicarboxylic acid and a diol other than the above-mentioned alicyclic diol are condensed. Further, it may be a structural unit derived from a copolymerization component other than the dicarboxylic acid and the diol.
  • the alicyclic structure derived from the alicyclic diol plays an important role in realizing higher oxygen absorption performance. Therefore, if the other structural unit is a unit containing an alicyclic structure derived from an alicyclic diol, it can contribute to the realization of a higher level of oxygen absorption performance.
  • the dicarboxylic acid other than the unsaturated dicarboxylic acid described above is not particularly limited, and may be a known dicarboxylic acid conventionally used for producing polyester.
  • it may be a dicarboxylic acid having no unsaturated bond, and may be oxalic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, tridecanoic acid, methylmalonic acid, ethylmalonic acid. , Dimethylmalonic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, tetramethylsuccinic acid and the like.
  • the two carboxyl groups may be dehydrated and condensed to form an acid anhydride.
  • the diol other than the alicyclic diol described above is not particularly limited, and may be a known diol conventionally used for producing polyester.
  • aliphatic diols, aromatic diols and the like can be mentioned.
  • aliphatic diol examples include ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, and 2-ethyl-2-butyl-1. , 3-Propanediol, polyethylene glycol, polytetramethylene ether glycol and the like.
  • aromatic diol examples include xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis (4'-hydroxyphenyl) propane, and 2,2-bis (4'- ⁇ -hydroxyethoxyphenyl) propane. , Bis (4-hydroxyphenyl) sulfone, bis (4- ⁇ -hydroxyethoxyphenyl) sulfonic acid and the like.
  • the aromatic diol may be an ethylene oxide adduct, a propylene oxide adduct, or the like to which an alkylene oxide is further added.
  • the copolymerization component other than the dicarboxylic acid and the diol is not particularly limited, and it is a raw material monomer copolymerizable with the dicarboxylic acid or the diol when producing the unsaturated polyester resin for oxygen absorption of the present invention. All you need is.
  • hydroxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, p- ⁇ -hydroxyethoxybenzoic acid, alkoxycarboxylic acids, stearyl alcohol, heneikosanol, octacosanol, benzyl alcohol, stearic acid, behenic acid, benzoic acid, etc.
  • Monofunctional components such as t-butylbenzoic acid, benzoylbenzoic acid, tricarbaryl acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol , Polyfunctional components having trifunctionality or higher such as sugar ester, and the like can be mentioned.
  • the method for producing an unsaturated polyester resin for oxygen absorption of the present invention is not particularly limited, and can be applied to a known method for producing a polyester resin.
  • a slurry is prepared from a dicarboxylic acid component containing an unsaturated dicarboxylic acid and a diol component containing an alicyclic diol, and if necessary, a catalyst, an auxiliary agent, a solvent and the like are added, and then the esterification reaction is allowed to proceed. .. Since the esterification reaction proceeds without a catalyst, it may be carried out without a catalyst.
  • the supply amounts of the dicarboxylic acid component and the diol component are not particularly limited, but usually, the diol component is excessively reacted and the excess diol component is distilled off from the system as the esterification reaction progresses. preferable.
  • the molar ratio of the diol component to the dicarboxylic acid component may be, for example, in the range of 1.0 to 2.0, the lower limit may be 1.05 or more, or 1.1 or more, and the upper limit may be 1. It may be 7 or less, or 1.6 or less.
  • the oxygen absorbing film containing the oxygen absorbing unsaturated polyester resin of the present invention is a film containing the above-mentioned oxygen absorbing unsaturated polyester resin of the present invention as a raw material.
  • the oxygen absorbing film containing the oxygen absorbing unsaturated polyester resin is prepared by blending the oxygen absorbing unsaturated polyester resin of the present invention with other components such as additives for imparting functionality and the like, if necessary. May be.
  • the blending amount of the unsaturated polyester resin for oxygen absorption of the present invention in the oxygen absorbing film is 50% by mass or more, 60% by mass or more, 70% by mass or more, and 80% by mass with respect to the entire constituent material of the oxygen absorbing film. As mentioned above, it may be 90% by mass or more, or 95% by mass or more.
  • the oxygen absorbing film containing the oxygen absorbing unsaturated polyester resin is a film containing, for example, the unsaturated polyester resin for oxygen absorbing of the present invention and other components such as additives blended as necessary. It may be an unstretched film obtained by melt-extruding it into a shape and quenching it with a cooling drum.
  • it may be a uniaxial or biaxially stretched film obtained by preheating the unstretched film and performing uniaxial stretching, sequential biaxial stretching, or simultaneous biaxial stretching.
  • the oxygen absorbing composition of the present invention is a composition containing the above-mentioned unsaturated polyester resin for oxygen absorption of the present invention.
  • the oxygen absorbing composition of the present invention has oxygen absorbing performance by containing the unsaturated polyester resin for oxygen absorption of the present invention.
  • the blending amount of the unsaturated polyester of the present invention is 60% by mass or more, more preferably 60% by mass, based on the total 100% by mass of the polyester components constituting the oxygen absorbing composition. If it is 80% by mass or more, a high level of oxygen absorption capacity can be exhibited.
  • the oxygen absorbing composition of the present invention may contain any component, solvent, or the like in addition to the above-mentioned unsaturated polyester resin for oxygen absorption of the present invention.
  • the oxygen absorbing composition of the present invention may contain a catalyst as an arbitrary component in addition to the above-mentioned unsaturated polyester resin for oxygen absorption of the present invention.
  • the presence of the catalyst can enhance the oxygen absorption performance of the unsaturated polyester resin for oxygen absorption.
  • the catalyst is not particularly limited, and examples thereof include a metal salt composed of a transition metal or a Group 12 element and an organic acid.
  • the transition metal include iron, cobalt and the like
  • examples of the Group 12 element include zinc.
  • the organic acid include stearic acid, citric acid, fumaric acid, gluconic acid, lauric acid, ethylenediamine-N, N, N', N'-tetraacetic acid, 2,4-pentandionic acid and the like.
  • examples of the catalyst blended in the oxygen absorbing composition of the present invention include zinc stearate, cobalt stearate, iron stearate, and the like, and any of these may include oxygen in the oxygen absorbing composition of the present invention. Absorption performance can be improved.
  • the blending amount thereof is, for example, 10 to 500 ppm in terms of the mass of the transition metal or Group 12 element with respect to the total solid content mass of the oxygen absorbing composition. It may be there.
  • the amount of the catalyst compounded is 20 ppm or more, 40 ppm or more, 60 ppm or more, 80 ppm or more, 100 ppm or more, 150 ppm or more, or 200 ppm or more in terms of the mass of the transition metal or Group 12 element with respect to the total solid content mass of the oxygen absorbing composition. It may be 450 ppm or less, 400 ppm or less, 350 ppm or less, 300 ppm or less, 250 ppm or less, or 200 ppm or less.
  • the oxygen absorbing composition of the present invention may contain a curing agent as an arbitrary component in addition to the above-mentioned unsaturated polyester resin for oxygen absorption of the present invention.
  • the unsaturated polyester can be three-dimensionally crosslinked, and an insoluble and infusible cured product can be formed.
  • the curing speed can be adjusted and can be controlled according to the application.
  • the curing agent is blended in an amount in a specific range with respect to the unsaturated polyester resin for oxygen absorption, it is a raw material for the polyester resin when a packaging material is formed from the composition for oxygen absorption. It is possible to suppress the elution of low molecular weight components such as dicarboxylic acid and / or diol from the packaging material.
  • the curing agent is not particularly limited, and a known curing agent used in the field of polyester-based resin can be used.
  • a known curing agent used in the field of polyester-based resin can be used.
  • isocyanate-based curing agents, peroxides and the like can be mentioned.
  • isocyanate-based curing agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenedi isocyanate, p-phenylenedi isocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4'-diphenylmethane diisocyanate, 2 , 2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenylenediisocyanate, 3,3'-dichloro-4,4'-biphenylene Diisocyanate, 1,5-naphthalenediocyanate, 1,5-tetrahydronaphthalenediocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhex
  • the isocyanate-based curing agent may be a polyisocyanate compound having an increased molecular weight.
  • examples of the polyisocyanate compound include adduct, isocyanurate, and burette.
  • the isocyanate-based curing agent may be used alone or in combination of two or more.
  • peroxide examples include ketone peroxides, peroxydicarbonates, hydroperoxides, diacyl peroxides, peroxyketals, dialkyl peroxides, peroxyesters and the like.
  • the oxygen absorbing composition of the present invention contains a curing agent
  • the blending amount thereof can be appropriately set according to the molding cycle and the intended use.
  • it may be 0.1 to 1000 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin constituting the oxygen absorbing composition.
  • the oxygen absorbing composition of the present invention contains a plurality of types of polyester resins (for example, unsaturated polyester resin and saturated polyester resin), it is 0.1 to 0.1 to 100 parts by mass of the total solid content. It may be 1000 parts by mass.
  • the blending amount of the curing agent is 0.2% by mass or more, 0.5% by mass or more, 1% by mass or more, and 3% by mass with respect to 100% by mass of the unsaturated polyester resin constituting the oxygen absorbing composition. 5% by mass or more, 7% by mass or more, 10% by mass or more, 50% by mass or more, 75% by mass or more, 100% by mass or more, 200% by mass or more, 300% by mass or more, 400% by mass or more, or 500% by mass. % Or more, 900% by mass or less, 800% by mass or less, 700% by mass or less, 600% by mass or less, 500% by mass or less, 300% by mass or less, 100% by mass or less, 90% by mass or less, 80% by mass. Below, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 8% by mass or less, or 6% by mass or less. good.
  • the oxygen absorbing composition of the present invention may contain saturated polyester as an arbitrary component in addition to the above-mentioned unsaturated polyester resin for oxygen absorption of the present invention.
  • saturated polyester can impart adhesiveness to the obtained composition and further improve the laminating strength.
  • the oxygen absorbing composition of the present invention contains a saturated polyester in addition to the oxygen absorbing unsaturated polyester resin of the present invention, the oxygen absorbing composition of the present invention can be used as at least an adhesive. Can be made to work.
  • the oxygen absorbing composition of the present invention functions as an adhesive, it is possible to form a laminated body having oxygen absorbing performance by sandwiching it between the two layers as an adhesive layer.
  • a process such as applying a heat-sealing agent or laminating a sheet-sealing film, which has been conventionally required for forming a laminate having a heat-sealing layer, or heat-sealing.
  • a step of forming an adhesive layer in advance is not required for attaching the sex film, and deterioration of oxygen absorption performance due to the step can be avoided.
  • the saturated polyester is not particularly limited, and can be appropriately selected from polyesters having no reactive unsaturated bond and used.
  • it may be an aliphatic polyester, an aromatic polyester, or an alicyclic polyester, and two or more of these may be applied at the same time.
  • the oxygen absorbing composition of the present invention contains saturated polyester
  • the blending amount thereof can be appropriately set according to the use of the composition. For example, it may be 1 to 99% by mass with respect to a total of 100% by mass of the unsaturated polyester and the saturated polyester constituting the oxygen absorbing composition.
  • the blending amount of the saturated polyester is 5% by mass or more, 10% by mass or more, 15% by mass or more, and 20% by mass or more with respect to 100% by mass of the total of the unsaturated polyester and the saturated polyester constituting the oxygen absorbing composition. , 30% by mass or more, 40% by mass or more, 60% by mass or more, or 80% by mass or more, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less. , 40% by mass or less, 35% by mass or less, or 30% by mass or less.
  • the oxygen absorbing composition of the present invention may contain a solvent as an arbitrary component.
  • the solvent can dissolve the unsaturated polyester resin for oxygen absorption of the present invention and any component, and can improve handling and the like.
  • the solvent used in the oxygen absorbing composition of the present invention is not particularly limited, and a known solvent used as a solvent for the polyester-based composition can be applied.
  • the blending amount of the solvent is not particularly limited, and can be appropriately selected depending on the use of the composition, the molding cycle, and the like.
  • the oxygen absorbing composition of the present invention may contain an antioxidant as an arbitrary component.
  • the presence of the antioxidant suppresses the deterioration of the oxygen absorption performance of the oxygen absorbing composition of the present invention over time.
  • the antioxidant is not particularly limited, and a known antioxidant can be used.
  • a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, and the like can be mentioned.
  • hindered phenolic antioxidant examples include 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate and 1,1,3-tri (4-hydroxy-).
  • phosphorus-based antioxidants include triphenylphosphite, triphenylphosphine, 3,9-bis (p-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [ 5.5] Undecane, 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] Undecane, tri (monononylphenyl) phosphite , Triphenoxyphosphine, Isodecylphosphite, Isodecylphenylphosphite, Diphenyl2-ethylhexylphosphite, Dinonylphenylbis (nonylphenyl) ester phosphoric acid, 1,1,3-Tris (2-methyl-4) -Ditridecylphosphite-5-t-butylphenyl
  • thioether-based antioxidant examples include 4,4'-thiobis [2-t-butyl-5-methylphenol] bis [3- (dodecylthio) propionate] and thiobis [2- (1,1-) as thioether-based agents.
  • Dimethylethyl) -5-methyl-4,1-phenylene] bis [3- (tetradecylthio) -propionate], pentaerythritol tetrakis (3-n-dodecylthiopropionate), bis (tridecyl) thiodipropionate The island is mentioned.
  • the antioxidant may be blended alone or in combination of two or more.
  • pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] or triphenylphosphine is preferable.
  • the amount of the antioxidant is 5 ppm or more, 10 ppm or more, 20 ppm or more, 30 ppm or more, 40 ppm or more, 50 ppm or more, 60 ppm by mass or more, 70 ppm or more, 80 ppm or more with respect to 100 parts by mass of the unsaturated polyester resin for oxygen absorption. , 90 ppm or more, or 100 ppm or more, and may be 1000 ppm or less, 900 ppm or less, 800 ppm or less, 700 ppm or less, 600 ppm or less, 500 ppm or less, 400 ppm or less, or 300 ppm or less.
  • the method for producing the oxygen absorbing composition of the present invention is not particularly limited, and a method known as a method for producing a polyester-based composition can be applied.
  • the oxygen absorbing film containing the oxygen absorbing composition of the present invention is a film containing the above-mentioned oxygen absorbing composition of the present invention as a raw material.
  • the blending amount of the oxygen absorbing composition of the present invention in the oxygen absorbing film is 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, based on the total constituent materials of the oxygen absorbing film. It may be 90% by mass or more, or 95% by mass or more.
  • the obtained solution is applied onto an object such as a release paper to remove the solvent. It may be an unstretched film obtained by curing the film.
  • it may be an unstretched film obtained by melting the oxygen absorbing composition of the present invention and extruding it into a film shape, and then preheating the unstretched film to uniaxially stretch, sequentially biaxially stretch, or. It may be a uniaxial or biaxially stretched film obtained by carrying out simultaneous biaxial stretching.
  • the oxygen absorbing adhesive of the present invention is an adhesive containing the above-mentioned oxygen absorbing composition of the present invention. Since the oxygen absorbing adhesive of the present invention contains the oxygen absorbing composition of the present invention, it has oxygen absorbing performance. At the same time, it has adhesiveness.
  • a laminated body having oxygen absorbing performance For example, conventionally, a laminated body having a heat seal layer can be formed.
  • a step required for forming such as applying a heat-sealing agent or laminating a sheet-sealing film, or a step of pre-forming an adhesive layer for attaching a heat-sealing film, etc. Is no longer necessary, and deterioration of oxygen absorption performance due to the process can be avoided.
  • the oxygen absorbing adhesive of the present invention contains, in addition to the above-mentioned oxygen absorbing composition of the present invention, an arbitrary component for imparting adhesiveness, an arbitrary component for imparting functionality, a solvent, or the like. can do.
  • an arbitrary component for imparting adhesiveness an arbitrary component for imparting functionality, a solvent, or the like.
  • the oxygen absorbing composition of the present invention described above contains saturated polyester and the oxygen absorbing composition itself has adhesiveness and functions as an adhesive, it is intended to impart adhesiveness. Any component may or may not be added.
  • the oxygen absorbing adhesive film containing the oxygen absorbing adhesive of the present invention is a film containing the above-mentioned oxygen absorbing adhesive of the present invention as a raw material.
  • the blending amount of the oxygen absorbing adhesive of the present invention in the oxygen absorbing adhesive film is 50% by mass or more, 60% by mass or more, 70% by mass or more, and 80 with respect to the entire constituent materials of the oxygen absorbing adhesive film. It may be mass% or more, 90 mass% or more, or 95 mass% or more.
  • the oxygen absorbing adhesive film for example, after dissolving the oxygen absorbing adhesive of the present invention in a solvent, the obtained solution is applied onto an object such as a release paper, and the solvent is removed to cure the film. It may be an unstretched film obtained by the above.
  • the oxygen absorption laminate of the present invention is a laminate including an oxygen absorption composition layer comprising the oxygen absorption composition of the present invention described above.
  • the oxygen absorbing laminate of the present invention is not particularly limited as long as it includes the oxygen absorbing composition layer made of the oxygen absorbing composition of the present invention.
  • the other layer include an oxygen barrier layer for imparting a function to the laminated body, a heat seal layer, and the like, and an adhesive layer for adhering each layer.
  • the oxygen absorption laminate of the present invention has, for example, a structure in which an oxygen barrier layer, an oxygen absorption composition layer composed of the oxygen absorption composition of the present invention, and a heat seal layer are laminated in this order. May be.
  • the heat seal layer is heat welded.
  • Various packages can be formed by making them. The surface in contact with the contents filled in the package is a heat seal layer, and the surface in contact with oxygen contained in the atmosphere or the like outside the package is an oxygen barrier layer.
  • the oxygen absorption laminate has an oxygen barrier layer, an oxygen absorption composition layer, and a heat seal layer laminated in this order, oxygen permeation from the outside can be prevented while preventing oxygen permeation from the outside. It can absorb oxygen inside the package. As a result, oxygen existing inside the package can be eliminated at a higher level, and oxidative deterioration of the contents can be avoided.
  • the oxygen absorbing composition layer constituting the oxygen absorbing laminated body of the present invention is a layer containing an oxygen absorbing adhesive having adhesiveness, it is necessary to form an oxygen absorbing composition layer.
  • sandwiching the composition between the two layers to be bonded to form an oxygen absorbing adhesive layer it is possible to bond the two layers and realize a laminated body that exhibits oxygen absorption performance by itself.
  • the oxygen barrier layer exhibits a function of blocking oxygen and is a layer for imparting oxygen barrier properties to the oxygen absorbing laminate.
  • the oxygen barrier layer is not particularly limited, and can be produced from a material known in the field of packaging materials.
  • a layer made of ethylene-vinyl alcohol copolymer (EVOH), nylon (NY), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN), etc. or a PET film on which silica, alumina, aluminum, etc. are vapor-deposited.
  • EVOH ethylene-vinyl alcohol copolymer
  • nylon NY
  • PVDC polyvinylidene chloride
  • PAN polyacrylonitrile
  • the thickness of the oxygen barrier layer and the like are not particularly limited, and can be appropriately set according to the use of the laminate.
  • the heat seal layer is a layer to be heat-welded when forming a structure such as a package. Therefore, the heat seal layer is arranged so as to be the innermost layer of the laminated body.
  • the material constituting the heat seal layer is not particularly limited as long as it can be heat-bonded and can impart sufficient seal strength to the molded structure.
  • Known materials can be applied, such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene (PP), ethylene- Examples thereof include propylene copolymer (EP), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ionomer resin, ethylene-vinyl acetate copolymer (EVA) and the like.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene
  • EP propylene copolymer
  • EAA ethylene-acrylic acid copolymer
  • EAA ethylene-methacrylic acid copolymer
  • EVA ionomer resin
  • the resin or the like constituting the heat seal layer may be a blend of not only one type but also two or more types, and if necessary, an additive or the like for imparting functionality or the like is blended. May be good.
  • the method for producing the oxygen absorbing laminate of the present invention is not particularly limited, and a known method can be applied.
  • a dry lamination method, a hot melt lamination method, an extrusion lamination method, a sandwich lamination method and the like can be mentioned.
  • An oxygen absorbing film containing the unsaturated polyester resin for oxygen absorption of the present invention an oxygen absorbing film containing the oxygen absorbing composition of the present invention, an oxygen absorbing adhesive film containing the oxygen absorbing adhesive of the present invention, and an oxygen absorbing adhesive film of the present invention.
  • the oxygen absorbing laminate of the present invention can be suitably used as a packaging material.
  • An oxygen absorbing film containing the unsaturated polyester resin for oxygen absorption of the present invention an oxygen absorbing film containing the oxygen absorbing composition of the present invention, an oxygen absorbing adhesive film containing the oxygen absorbing adhesive of the present invention, and an oxygen absorbing adhesive film of the present invention.
  • the packaging material provided with any one selected from the group consisting of the oxygen absorbing laminate of the present invention can exhibit oxygen absorbing performance, for example, a pharmaceutical product, a pharmaceutical department, which wants to block contact between the contents and oxygen. It can be suitably used as a packaging material for external products, cosmetics, detergents, foods, paints and the like.
  • each of the unsaturated polyester resins obtained in Production Examples 1 to 5 contains a structural unit in which an unsaturated dicarboxylic acid and a diol are condensed, and a structural unit in which a saturated carboxylic acid and a diol are condensed.
  • Methyl ethyl ketone, toluene, ethyl acetate, methanol, ethanol, and isopropyl alcohol were prepared as solvents, and those dissolved in any of these at room temperature were marked with ⁇ , and those not dissolved in any of them were marked with x.
  • the results are shown in Table 1.
  • the unsaturated polyester C obtained in Production Example 3 using maleic anhydride, which is a cis form, as the unsaturated dicarboxylic acid is the same as the unsaturated polyester D obtained in Production Example 4 using fumaric acid, which is a solvent form. Unlike, it was dissolved in a solvent. It is probable that the unsaturated polyester containing the structural unit derived from fumaric acid, which is a trans form, had no solubility in the solvent because the molecular chain became too dense.
  • the unsaturated polyester E obtained in Production Example 5 using 3or4-methyl-1,2,3,6-tetrahydrophthalic anhydride as the unsaturated dicarboxylic acid has a ring as a constituent unit derived from the dicarboxylic acid. From this, it is considered that the molecular chains did not become dense and therefore showed solubility in the solvent.
  • the unsaturated polyesters A and B obtained in Production Examples 1 and 2 using fumaric acid as a trans form as the unsaturated dicarboxylic acid have an alicyclic type even if they have a structural unit derived from the dicarboxylic acid. Since it has a structural unit derived from tricyclodecanedimethanol, which is a diol, it is considered that the molecular chain did not become dense, and therefore it showed solubility in a solvent.
  • Antioxidant ⁇ Triphenylphosphine (JP-360 Johoku Chemical Industry Co., Ltd.) Irganox 1010 (Pentaerythritol Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], BASF)
  • Example and Comparative Example 80 ppm of the catalyst shown in Tables 2 to 5 was added in terms of the mass of cobalt, iron, or zinc with respect to the total solid content mass of the composition, followed by ethyl acetate. was added to prepare a composition which is an ethyl acetate solution having a solid content of 33% by mass.
  • a laminate was prepared by coating the film so as to have a thickness of 5 g / m 2 and laminating it with an LLDPE film (SE620N, Tamapoli Co., Ltd.) having a thickness of 30 ⁇ m.
  • composition of the ethyl acetate solution obtained in Examples 27 to 29 was applied to an alumina-deposited PET film having a thickness of 12 ⁇ m (Barrierlocks (registered trademark) 1011SBR2, Toray Film Processing Co., Ltd.) in an amount of 5 g / m.
  • a laminated body was prepared by coating the film so as to have a thickness of 2 and laminating it with a CPP film having a thickness of 20 ⁇ m (Pyrene (registered trademark) film-CT P1128, Toyobo Co., Ltd.).
  • the obtained laminate was cut into 10 cm ⁇ 10 cm (100 cm 2 ), sealed with air in a 43 mL airtight container, and stored at 23 ° C. for 7 days.
  • the oxygen concentration in the container after 7 days was measured using a non-destructive oxygen concentration meter (Fibox3, PreSens), and the oxygen absorption amount per area of the laminate was obtained from the obtained oxygen concentration and the oxygen concentration in the atmosphere. (ML / m 2 ) was calculated.
  • Tables 2 and 3 The results are shown in Tables 2 and 3.
  • the eluate in the bag was measured with an ultraviolet / visible / near-infrared spectrophotometer (model: UH4150, Hitachi High-Tech Science Corporation) and had an absorbance at 220 nm. It was confirmed. The results are shown in Table 3. If the absorbance is less than 0.15, it can be said that the elution is small.
  • the unsaturated polyester A obtained in Production Example 1 and the unsaturated polyester B obtained in Production Example 2, which contain a structural unit derived from an alicyclic diol, were compared with Comparative Examples 2 and 3. It showed high oxygen absorption performance. It is considered that this is because a space is created between molecules due to steric hindrance due to the structure derived from the alicyclic diol, and oxygen easily enters through the space.
  • Example 3 to 6 which are compositions in which saturated polyester is blended with unsaturated polyester, are the same as Example 1 in which the polyester component is composed only of unsaturated polyester. In comparison, it can be seen that the adhesive strength is improved.

Abstract

Provided are an oxygen-absorbing resin that has a novel structure and can absorb oxygen, an oxygen-absorbing composition that includes the resin, an oxygen-absorbing adhesive, an oxygen-absorbing laminate that uses the oxygen-absorbing composition, and an oxygen-absorbing film. The present invention involves condensing an alicyclic diol and an unsaturated dicarboxylic acid that has oxygen absorption ability due to an ethylenically unsaturated bond to obtain an unsaturated polyester that demonstrates favorable oxygen absorption.

Description

酸素吸収用不飽和ポリエステル樹脂、当該樹脂を含む酸素吸収用組成物、酸素吸収用接着剤、酸素吸収用組成物を用いた酸素吸収用積層体、及び酸素吸収用フィルムAn unsaturated polyester resin for oxygen absorption, an oxygen absorption composition containing the resin, an oxygen absorption adhesive, an oxygen absorption laminate using the oxygen absorption composition, and an oxygen absorption film.
　本発明は、酸素吸収用不飽和ポリエステル樹脂、当該樹脂を含む酸素吸収用組成物、酸素吸収用接着剤、酸素吸収用組成物を用いた酸素吸収用積層体、及び酸素吸収用フィルムに関する。 The present invention relates to an unsaturated polyester resin for oxygen absorption, an oxygen absorbing composition containing the resin, an oxygen absorbing adhesive, an oxygen absorbing laminate using the oxygen absorbing composition, and an oxygen absorbing film.
　従来、食品等の内容物の品質劣化を抑制する目的で、酸素吸収性能を有する包材が広く使用されている。 Conventionally, packaging materials having oxygen absorption performance have been widely used for the purpose of suppressing quality deterioration of contents such as foods.
　特許文献１には、炭素－炭素不飽和結合及び反応性官能基を有する酸素吸収性樹脂成分と、架橋剤とが含まれる酸素吸収性塗膜層を有し、酸素バリア層、酸素吸収性塗膜層、及びヒートシール層が、この順に積層された酸素吸収用積層体が記載されている。 Patent Document 1 has an oxygen-absorbing coating layer containing an oxygen-absorbing resin component having a carbon-carbon unsaturated bond and a reactive functional group and a cross-linking agent, and has an oxygen barrier layer and an oxygen-absorbing coating. A laminated body for oxygen absorption in which a film layer and a heat seal layer are laminated in this order is described.
　また、特許文献２には、接着性及び酸素吸収性に優れた酸素吸収性樹脂組成物として、テトラヒドロフタル酸若しくはその誘導体、又はテトラヒドロ無水フタル酸若しくはその誘導体を原料として用いた酸素吸収性ポリエステル系樹脂を含む樹脂組成物が提案されている。 Further, Patent Document 2 describes an oxygen-absorbing polyester-based composition using tetrahydrophthalic acid or a derivative thereof, or tetrahydrophthalic anhydride or a derivative thereof as a raw material as an oxygen-absorbing resin composition having excellent adhesiveness and oxygen absorption. Resin compositions containing resins have been proposed.
　特許文献２に記載された酸素吸収性組成物からなる酸素吸収用接着剤層を有する酸素吸収性フィルムは、原料となるテトラヒドロフタル酸やテトラヒドロ無水フタル酸等が、酸素との非常に高い反応性を有するため、優れた酸素吸収性能を発現する。 In the oxygen-absorbing film having an oxygen-absorbing adhesive layer made of the oxygen-absorbing composition described in Patent Document 2, the raw materials such as tetrahydrophthalic acid and tetrahydrohydroan phthalic acid have extremely high reactivity with oxygen. Therefore, it exhibits excellent oxygen absorption performance.
　また、不飽和脂環構造と酸素との反応においては、樹脂の自動酸化反応による副生成物である、低分子量の分解成分の発生を抑制することができる。このため、食品包装等の分野において問題となる、匂い等の発生を抑制できるとともに、酸素吸収前後にわたって強いラミネート強度を維持することができるとされている。 Further, in the reaction between the unsaturated alicyclic structure and oxygen, it is possible to suppress the generation of low molecular weight decomposition components, which are by-products of the autoxidation reaction of the resin. Therefore, it is said that it is possible to suppress the generation of odors and the like, which is a problem in the field of food packaging, and to maintain strong laminating strength before and after oxygen absorption.
　特許文献３には、新たな構造を有する酸素吸収性物質として、シクロヘキセン環を含むポリマーによる酸素スカベンジャー、及び当該酸素スカベンジャーを用いた容器等が提案されている。 Patent Document 3 proposes an oxygen scavenger made of a polymer containing a cyclohexene ring, a container using the oxygen scavenger, and the like as an oxygen-absorbing substance having a new structure.
　特許文献３に記載されたシクロヘキセン環を含む酸素スカベンジャーは、酸化後に環が断片化あるいは分裂する傾向が小さい環状アリル構造を有することから、匂い又は味に悪影響を与える酸化副生物の発生を抑制することができるとされている。 The oxygen scavenger containing a cyclohexene ring described in Patent Document 3 has a cyclic allyl structure in which the ring is less likely to be fragmented or split after oxidation, and thus suppresses the generation of oxidative by-products that adversely affect odor or taste. It is said that it can be done.
特開２００３－２６８３１０号公報Japanese Unexamined Patent Publication No. 2003-268310 特開２０１４－１３６４２１号公報Japanese Unexamined Patent Publication No. 2014-136421 特表２００３－５２１５５２号公報Special Table 2003-521552A
　酸素吸収性を有する物質については、今後も様々なニーズに対応する必要があり、更なる種類の樹脂等が要請されている。 Regarding substances with oxygen absorption, it is necessary to continue to meet various needs in the future, and further types of resins and the like are required.
　本発明は、上記の背景に鑑みてなされたものであり、引用文献１～３には記載されていない構造を有する、酸素吸収性を有する酸素吸収用樹脂、当該樹脂を含む酸素吸収用組成物、酸素吸収用接着剤、酸素吸収用組成物を用いた酸素吸収用積層体、及び酸素吸収用フィルムを提供することを目的とする。 The present invention has been made in view of the above background, and has an oxygen-absorbing resin having a structure not described in References 1 to 3, and an oxygen-absorbing composition containing the resin. , An oxygen absorbing adhesive, an oxygen absorbing laminate using an oxygen absorbing composition, and an oxygen absorbing film.
　本発明者らは、酸素吸収性を有する物質について鋭意研究し、エチレン性不飽和結合による酸素吸収性能を発現する不飽和ジカルボン酸と、脂環式ジオールとを縮合させることで、酸素吸収性を良好に示す不飽和ポリエステルが得られることを見出し、本発明を完成させるに至った。すなわち、本発明は、以下のとおりである。 The present inventors have diligently studied oxygen-absorbing substances, and by condensing an unsaturated dicarboxylic acid that exhibits oxygen absorption performance due to an ethylenically unsaturated bond with an alicyclic diol, oxygen absorption is achieved. They have found that unsaturated polyesters showing good results can be obtained, and have completed the present invention. That is, the present invention is as follows.
　《態様１》
　不飽和ジカルボン酸と脂環式ジオールとが縮合した構成単位を含む、酸素吸収用不飽和ポリエステル樹脂。
　《態様２》
　更に、飽和カルボン酸と脂環式ジオールとが縮合した構成単位を含む、態様１に記載の酸素吸収用不飽和ポリエステル樹脂。
　《態様３》
　態様１又は２に記載の酸素吸収用不飽和ポリエステル樹脂を含む酸素吸収用フィルム。
　《態様４》
　態様１又は２に記載の酸素吸収用不飽和ポリエステル樹脂を含む、酸素吸収用組成物。
　《態様５》
　触媒を含む、態様４に記載の酸素吸収用組成物。
　《態様６》
　硬化剤を含む、態様４又は５に記載の酸素吸収用組成物。
　《態様７》
　前記硬化剤の配合量が、前記酸素吸収用不飽和ポリエステル樹脂１００質量部に対して、５０質量部以上１０００質量部以下である、態様６に記載の酸素吸収用組成物。
　《態様８》
　酸化防止剤を含む、態様４～７のいずれか一態様に記載の酸素吸収用組成物。
　《態様９》
　前記酸化防止剤は、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、及びトリフェニルホスファイトの少なくともいずれかである、態様８に記載の酸素吸収用組成物。
　《態様１０》
　飽和ポリエステルを含む、態様４～９のいずれか一態様に記載の酸素吸収用組成物。
　《態様１１》
　態様４～１０のいずれか一態様に記載の酸素吸収用組成物を含む酸素吸収用フィルム。
　《態様１２》
　態様４～１０のいずれか一態様に記載の酸素吸収用組成物からなる酸素吸収用接着剤。
　《態様１３》
　態様１２に記載の酸素吸収用接着剤を含む酸素吸収用接着剤フィルム。
　《態様１４》
　態様４～１０のいずれか一態様に記載の酸素吸収用組成物からなる酸素吸収用組成物層を備える、酸素吸収用積層体。
　《態様１５》
　態様１２に記載の酸素吸収用接着剤からなる酸素吸収用接着剤層を備える、酸素吸収用積層体。
　《態様１６》
　酸素バリア層と、前記酸素吸収用組成物層と、ヒートシール層とが、この順で積層された、態様１４に記載の酸素吸収用積層体。
　《態様１７》
　酸素バリア層と、前記酸素吸収用接着剤層と、ヒートシール層とが、この順で積層された、態様１５に記載の酸素吸収用積層体。
　《態様１８》
　態様３又は１１に記載の酸素吸収用フィルム、態様１３に記載の酸素吸収用接着剤フィルム、及び態様１４～１７に記載の酸素吸収用積層体からなる群より選ばれるいずれかを備える包装材。 << Aspect 1 >>
An unsaturated polyester resin for oxygen absorption containing a structural unit obtained by condensing an unsaturated dicarboxylic acid and an alicyclic diol.
<< Aspect 2 >>
The unsaturated polyester resin for oxygen absorption according to aspect 1, further comprising a structural unit obtained by condensing a saturated carboxylic acid and an alicyclic diol.
<< Aspect 3 >>
An oxygen absorbing film containing the oxygen absorbing unsaturated polyester resin according to the first or second aspect.
<< Aspect 4 >>
An oxygen absorbing composition comprising the unsaturated polyester resin for oxygen absorption according to the first or second aspect.
<< Aspect 5 >>
The oxygen absorbing composition according to aspect 4, which comprises a catalyst.
<< Aspect 6 >>
The oxygen absorbing composition according to aspect 4 or 5, which comprises a curing agent.
<< Aspect 7 >>
The oxygen absorbing composition according to aspect 6, wherein the amount of the curing agent blended is 50 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the unsaturated polyester resin for oxygen absorption.
<< Aspect 8 >>
The oxygen absorbing composition according to any one of aspects 4 to 7, which comprises an antioxidant.
<< Aspect 9 >>
The oxygen absorption according to aspect 8, wherein the antioxidant is at least one of pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and triphenylphosphine. Composition for.
<< Aspect 10 >>
The oxygen absorbing composition according to any one of aspects 4 to 9, comprising saturated polyester.
<< Aspect 11 >>
An oxygen absorbing film containing the oxygen absorbing composition according to any one of aspects 4 to 10.
<< Aspect 12 >>
An oxygen absorbing adhesive comprising the oxygen absorbing composition according to any one of aspects 4 to 10.
<< Aspect 13 >>
An oxygen absorbing adhesive film containing the oxygen absorbing adhesive according to aspect 12.
<< Aspect 14 >>
An oxygen absorption laminate comprising an oxygen absorption composition layer comprising the oxygen absorption composition according to any one of aspects 4 to 10.
<< Aspect 15 >>
An oxygen absorbing laminate comprising an oxygen absorbing adhesive layer comprising the oxygen absorbing adhesive according to aspect 12.
<< Aspect 16 >>
The oxygen absorption laminate according to aspect 14, wherein the oxygen barrier layer, the oxygen absorption composition layer, and the heat seal layer are laminated in this order.
<< Aspect 17 >>
The oxygen absorption laminate according to aspect 15, wherein the oxygen barrier layer, the oxygen absorption adhesive layer, and the heat seal layer are laminated in this order.
<< Aspect 18 >>
A packaging material comprising any one selected from the group consisting of the oxygen absorbing film according to the third or eleventh aspect, the oxygen absorbing adhesive film according to the thirteenth aspect, and the oxygen absorbing laminated body according to the fourteenth to seventeenth aspects.
　本発明の酸素吸収用不飽和ポリエステル樹脂は、酸素吸収性能を有するエチレン性の炭素－炭素不飽和結合を有するとともに、脂環式ジオールに由来する脂環式構造を有する。このため、不飽和結合の酸素吸収性能を、脂環式構造により補助することができ、より高度な酸素吸収性能を実現することができる。 The unsaturated polyester resin for oxygen absorption of the present invention has an ethylenically carbon-carbon unsaturated bond having oxygen absorption performance and also has an alicyclic structure derived from an alicyclic diol. Therefore, the oxygen absorption performance of the unsaturated bond can be assisted by the alicyclic structure, and a higher oxygen absorption performance can be realized.
　《酸素吸収用不飽和ポリエステル樹脂》
　本発明の酸素吸収用不飽和ポリエステル樹脂は、不飽和ジカルボン酸と脂環式ジオールとが縮合した構成単位を含む。 << Unsaturated polyester resin for oxygen absorption >>
The unsaturated polyester resin for oxygen absorption of the present invention contains a structural unit in which an unsaturated dicarboxylic acid and an alicyclic diol are condensed.
　エチレン性不飽和結合である炭素－炭素不飽和結合を有する物質は、不飽和結合と酸素とが反応することで、酸素吸収性能を発現することが知られている。本発明の酸素吸収用不飽和ポリエステル樹脂は、酸素吸収性能を発現するエチレン性の炭素－炭素不飽和結合を有する不飽和ジカルボン酸を原料として用いるため、不飽和ジカルボン酸に由来するエチレン性の炭素－炭素不飽和結合を有することとなる。このため、本発明の酸素吸収用不飽和ポリエステル樹脂は、酸素吸収性能を有する。 It is known that a substance having a carbon-carbon unsaturated bond, which is an ethylenically unsaturated bond, exhibits oxygen absorption performance by reacting the unsaturated bond with oxygen. Since the unsaturated polyester resin for oxygen absorption of the present invention uses an unsaturated dicarboxylic acid having an ethylenically carbon-carbon unsaturated bond that exhibits oxygen absorption performance as a raw material, it is an ethylenic carbon derived from the unsaturated dicarboxylic acid. -It will have a carbon unsaturated bond. Therefore, the unsaturated polyester resin for oxygen absorption of the present invention has oxygen absorption performance.
　更に、本発明の酸素吸収用不飽和ポリエステル樹脂は、エステル結合を作製するためのジオールとして、脂環式ジオールを用いるため、脂環式ジオールに由来する脂環式構造を有することとなる。脂環式構造は、不飽和結合の酸素吸収性能を補助することができるため、本発明の酸素吸収用不飽和ポリエステル樹脂は、より高度な酸素吸収性能を実現することができる。 Further, since the unsaturated polyester resin for oxygen absorption of the present invention uses an alicyclic diol as a diol for producing an ester bond, it has an alicyclic structure derived from the alicyclic diol. Since the alicyclic structure can assist the oxygen absorption performance of the unsaturated bond, the unsaturated polyester resin for oxygen absorption of the present invention can realize a higher oxygen absorption performance.
　理論に拘束されるものではないが、脂環式ジオールを用いることで、より高度な酸素吸収性能を実現できる理由は、脂環式ジオール由来の脂環式構造による立体障害により分子間に空間ができ、当該空間を通して樹脂の内部まで酸素が入り込み易くなり、その結果、酸素と炭素－炭素不飽和結合との接触機会が向上するためと考えられる。 Although not bound by theory, the reason why alicyclic diols can be used to achieve higher oxygen absorption performance is that the space between molecules is created by steric damage due to the alicyclic structure derived from alicyclic diols. It is considered that oxygen can easily enter the inside of the resin through the space, and as a result, the contact opportunity between oxygen and the carbon-carbon unsaturated bond is improved.
　＜不飽和ジカルボン酸＞
　本発明の酸素吸収用不飽和ポリエステル樹脂を構成する不飽和ジカルボン酸は、少なくとも１個のエチレン性不飽和結合である炭素－炭素不飽和結合を有するとともに、２個のカルボキシル基をするカルボン酸である。 <Unsaturated dicarboxylic acid>
The unsaturated dicarboxylic acid constituting the unsaturated polyester resin for oxygen absorption of the present invention is a carboxylic acid having at least one ethylenically unsaturated bond, which is a carbon-carbon unsaturated bond, and having two carboxyl groups. be.
　炭素－炭素不飽和結合は、不飽和ジカルボン酸の主鎖に存在していても、側鎖に存在していても、また、両者に存在していてもよい。また、炭素－炭素不飽和結合は、環を形成している隣接する炭素の間に存在し、不飽和脂環構造を形成してもよい。 The carbon-carbon unsaturated bond may be present in the main chain of the unsaturated dicarboxylic acid, in the side chain, or in both. Further, a carbon-carbon unsaturated bond may exist between adjacent carbons forming a ring to form an unsaturated alicyclic structure.
　また、２個のカルボキシル基は、脱水縮合して酸無水物を形成していてもよい。 Further, the two carboxyl groups may be dehydrated and condensed to form an acid anhydride.
　更に、不飽和ジカルボン酸は、脂肪族環を有する構造を有していてもよい。 Further, the unsaturated dicarboxylic acid may have a structure having an aliphatic ring.
　不飽和ジカルボン酸としては、例えば、不飽和脂肪族ジカルボン酸が挙げられる。不飽和脂肪族ジカルボン酸としては、例えば、フマル酸、マレイン酸、イタコン酸、メサコン酸、シトラコン酸、グルタコン酸、テトラヒドロフタル酸、これらの酸の無水物、未水添ダイマー酸、シクロヘキセンジカルボン酸、テルペン－マレイン酸付加体等が挙げられる。 Examples of the unsaturated dicarboxylic acid include unsaturated aliphatic dicarboxylic acids. Examples of unsaturated aliphatic dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, anhydrides of these acids, unhydrogenated dimer acid, cyclohexene dicarboxylic acid, and the like. Examples thereof include a terpene-maleic acid adduct.
　なお、不飽和ジカルボン酸は、１種のみならず、２種以上を用いてもよい。不飽和ジカルボン酸が異性体を有する場合には、シス、トランスのいずれであってもよく、これらの混合物であってもよい。 It should be noted that not only one type of unsaturated dicarboxylic acid but also two or more types may be used. When the unsaturated dicarboxylic acid has an isomer, it may be either cis or trans, or a mixture thereof.
　本発明においては、入手の容易性等の観点から、不飽和ジカルボン酸は、フマル酸、又はマレイン酸であることが好ましい。 In the present invention, the unsaturated dicarboxylic acid is preferably fumaric acid or maleic acid from the viewpoint of easy availability.
　不飽和ジカルボン酸の含有量は、特に限定されるものではないが、本発明の酸素吸収用不飽和ポリエステル樹脂の構成成分となるカルボン酸成分中、例えば、２０モル％以上、４０モル％以上、５０モル％以上、７０モル％以上、８０モル％以上、又は９８モル％以上であってもよい。 The content of the unsaturated dicarboxylic acid is not particularly limited, but is, for example, 20 mol% or more, 40 mol% or more, among the carboxylic acid components which are constituents of the unsaturated polyester resin for oxygen absorption of the present invention. It may be 50 mol% or more, 70 mol% or more, 80 mol% or more, or 98 mol% or more.
　＜脂環式ジオール＞
　本発明の酸素吸収用不飽和ポリエステル樹脂を構成する脂環式ジオールは、少なくとも１個の芳香族性を有しない炭素環を有する脂環式構造を有するとともに、２個の水酸基が２個の異なる炭素に結合している構造を有する脂環式化合物である。 <Alicyclic diol>
The alicyclic diol constituting the unsaturated polyester resin for oxygen absorption of the present invention has an alicyclic structure having at least one non-aromatic carbon ring and two different hydroxyl groups. It is an alicyclic compound having a structure bonded to carbon.
　本発明の酸素吸収用不飽和ポリエステル樹脂は、不飽和ジカルボン酸と脂環式ジオールとが縮合した構成単位を含むことにより、より高度な酸素吸収性能を実現することができる。 The unsaturated polyester resin for oxygen absorption of the present invention can realize higher oxygen absorption performance by containing a structural unit in which an unsaturated dicarboxylic acid and an alicyclic diol are condensed.
　脂環式ジオールに由来する脂環式構造は、本発明の酸素吸収用不飽和ポリエステル樹脂において、不飽和ジカルボン酸由来の不飽和結合による酸素吸収性能を補助する。脂環式構造による立体障害により分子間に空間ができ、当該空間を通して樹脂の内部まで酸素が入り込み易くなり、その結果、酸素と炭素－炭素不飽和結合との接触機会を向上させると考えられる。 The alicyclic structure derived from the alicyclic diol assists the oxygen absorption performance due to the unsaturated bond derived from the unsaturated dicarboxylic acid in the unsaturated polyester resin for oxygen absorption of the present invention. It is considered that a space is created between molecules due to steric hindrance due to the alicyclic structure, and oxygen easily enters the inside of the resin through the space, and as a result, the contact opportunity between oxygen and the carbon-carbon unsaturated bond is improved.
　脂環式ジオールは、少なくとも１個の芳香族性を有しない炭素環を有する脂環式構造を有していればよく、脂環式構造は、飽和炭化水素であっても、炭素－炭素二重結合を環内に１個含む不飽和環状炭化水素であってもよい。環内に炭素－炭素二重結合を有する場合には、当該二重結合は、酸素と反応して酸素吸収性能を発揮することが可能となる。 The alicyclic diol may have an alicyclic structure having at least one non-aromatic carbon ring, and the alicyclic structure may be a saturated hydrocarbon even if it is a saturated hydrocarbon. It may be an unsaturated cyclic hydrocarbon containing one double bond in the ring. When a carbon-carbon double bond is formed in the ring, the double bond can react with oxygen to exhibit oxygen absorption performance.
　また、脂環式ジオールは、単環であっても縮合環であってもよい。縮合環の場合には、少なくとも１個の芳香族性を有しない炭素環を備えていればよく、芳香族性を有する環が縮合していてもよい。 Further, the alicyclic diol may be a monocyclic ring or a condensed ring. In the case of a fused ring, at least one non-aromatic carbon ring may be provided, and the aromatic ring may be fused.
　脂環式ジオールとしては、特に限定されるものではないが、例えば、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、１，２－シクロヘキサンジメタノール、１，３－シクロヘキサンジメタノール、１，４－シクロヘキサンジメタノール、１，４－シクロヘキサンジエタノール、トリシクロデカンジメタノール、ペンタシクロペンタデカンジメタノール、５－ノルボルネン－２，３－ジメチロール等が挙げられる。 The alicyclic diol is not particularly limited, but for example, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3. -Cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 5-norbornene-2,3-dimethylol and the like can be mentioned.
　なお、脂環式ジオールは、１種のみならず、２種以上を用いてもよい。脂環式ジオールが異性体を有する場合には、シス、トランスのいずれであってもよく、これらの混合物であってもよい。 As the alicyclic diol, not only one type but also two or more types may be used. When the alicyclic diol has an isomer, it may be either cis or trans, or a mixture thereof.
　本発明においては、立体障害の大きい構造を有する脂環式ジオールが、より酸素を入り込み易くすることから、例えば、トリシクロデカンジメタノール、ペンタシクロペンタデカンジメタノール等の縮合環を有する脂環式ジオールによれば、より高い効果を享受することが可能となる。 In the present invention, an alicyclic diol having a structure having a large steric hindrance makes it easier for oxygen to enter. Therefore, for example, an alicyclic diol having a fused ring such as tricyclodecanedimethanol or pentacyclopentadecanedimethanol According to the above, it is possible to enjoy a higher effect.
　脂環式ジオールの含有量は、特に限定されるものではないが、本発明の酸素吸収用不飽和ポリエステル樹脂の構成成分となるジオール成分中、例えば、２０モル％以上、４０モル％以上、５０モル％以上、７０モル％以上、８０モル％以上、又は９８モル％以上であってもよい。 The content of the alicyclic diol is not particularly limited, but is, for example, 20 mol% or more, 40 mol% or more, 50 in the diol component which is a constituent component of the unsaturated polyester resin for oxygen absorption of the present invention. It may be mol% or more, 70 mol% or more, 80 mol% or more, or 98 mol% or more.
　＜不飽和ジカルボン酸と脂環式ジオールとが縮合した構成単位＞
　本発明の酸素吸収用不飽和ポリエステル樹脂において、不飽和ジカルボン酸と脂環式ジオールとが縮合した構成単位の含有量は、特に限定されるものではないが、本発明の酸素吸収用不飽和ポリエステル樹脂が有する構成単位全体に対して、例えば、２０モル％以上、４０モル％以上、５０モル％以上、７０モル％以上、８０モル％以上、又は９８モル％以上であってもよい。 <Constituent unit in which unsaturated dicarboxylic acid and alicyclic diol are condensed>
In the unsaturated polyester resin for oxygen absorption of the present invention, the content of the structural unit in which the unsaturated dicarboxylic acid and the alicyclic diol are condensed is not particularly limited, but the unsaturated polyester for oxygen absorption of the present invention is not particularly limited. For example, it may be 20 mol% or more, 40 mol% or more, 50 mol% or more, 70 mol% or more, 80 mol% or more, or 98 mol% or more with respect to the entire constituent unit of the resin.
　＜その他の構成単位＞
　本発明の酸素吸収用不飽和ポリエステル樹脂は、不飽和ジカルボン酸と脂環式ジオールとが縮合した構成単位以外に、その他の構成単位を含んでいてもよい。 <Other building blocks>
The unsaturated polyester resin for oxygen absorption of the present invention may contain other structural units in addition to the structural unit obtained by condensing the unsaturated dicarboxylic acid and the alicyclic diol.
　その他の構成単位としては、特に限定されるものではなく、例えば、上記した不飽和ジカルボン酸と、上記した脂環式ジオール以外のジオールとが縮合した構成単位、上記した不飽和ジカルボン酸以外のジカルボン酸と、上記した脂環式ジオールとが縮合した構成単位、あるいは、上記した不飽和ジカルボン酸以外のジカルボン酸と、上記した脂環式ジオール以外のジオールとが縮合した構成単位であってよい。また、ジカルボン酸及びジオール以外の共重合成分に由来する構成単位であってもよい。 The other structural units are not particularly limited, and are, for example, a structural unit in which the above-mentioned unsaturated dicarboxylic acid and a diol other than the above-mentioned alicyclic diol are condensed, and a dicarboxylic acid other than the above-mentioned unsaturated dicarboxylic acid. It may be a structural unit in which an acid and the above-mentioned alicyclic diol are condensed, or a structural unit in which a dicarboxylic acid other than the above-mentioned unsaturated dicarboxylic acid and a diol other than the above-mentioned alicyclic diol are condensed. Further, it may be a structural unit derived from a copolymerization component other than the dicarboxylic acid and the diol.
　中では、飽和カルボン酸と脂環式ジオールとが縮合した構成単位を含むことが好ましい。本発明の酸素吸収用不飽和ポリエステル樹脂において、脂環式ジオールに由来する脂環式構造は、より高度な酸素吸収性能を実現するために重要な役割を果たす。したがって、その他の構成単位が、脂環式ジオールに由来する脂環構造を含む単位であれば、より高いレベルの酸素吸収性能の実現に寄与することができる。 Among them, it is preferable to contain a structural unit in which a saturated carboxylic acid and an alicyclic diol are condensed. In the unsaturated polyester resin for oxygen absorption of the present invention, the alicyclic structure derived from the alicyclic diol plays an important role in realizing higher oxygen absorption performance. Therefore, if the other structural unit is a unit containing an alicyclic structure derived from an alicyclic diol, it can contribute to the realization of a higher level of oxygen absorption performance.
　上記した不飽和ジカルボン酸以外のジカルボン酸としては、特に限定されるものではなく、従来、ポリエステルを製造する際に用いられている公知のジカルボン酸であってよい。 The dicarboxylic acid other than the unsaturated dicarboxylic acid described above is not particularly limited, and may be a known dicarboxylic acid conventionally used for producing polyester.
　例えば、不飽和結合を有さないジカルボン酸であってよく、シュウ酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、トリデカンニ酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、メチルコハク酸、２，２－ジメチルコハク酸、２，３－ジメチルコハク酸、テトラメチルコハク酸等が挙げられる。 For example, it may be a dicarboxylic acid having no unsaturated bond, and may be oxalic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, tridecanoic acid, methylmalonic acid, ethylmalonic acid. , Dimethylmalonic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, tetramethylsuccinic acid and the like.
　また、２個のカルボキシル基は、脱水縮合して酸無水物を形成していてもよい。 Further, the two carboxyl groups may be dehydrated and condensed to form an acid anhydride.
　上記した脂環式ジオール以外のジオールとしては、特に限定されるものではなく、従来、ポリエステルを製造する際に用いられている公知のジオールであってよい。例えば、脂肪族ジオール、芳香族ジオール等が挙げられる。 The diol other than the alicyclic diol described above is not particularly limited, and may be a known diol conventionally used for producing polyester. For example, aliphatic diols, aromatic diols and the like can be mentioned.
　脂肪族ジオールとしては、例えば、エチレングリコール、ジエチレングリコール、トリメチレングリコール、テトラメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール、オクタメチレングリコール、デカメチレングリコール、ネオペンチルグリコール、２－エチル－２－ブチル－１，３－プロパンジオール、ポリエチレングリコール、ポリテトラメチレンエーテルグリコール等が挙げられる。 Examples of the aliphatic diol include ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, and 2-ethyl-2-butyl-1. , 3-Propanediol, polyethylene glycol, polytetramethylene ether glycol and the like.
　芳香族ジオールとしては、例えば、キシリレングリコール、４，４’－ジヒドロキシビフェニル、２，２－ビス（４’－ヒドロキシフェニル）プロパン、２，２－ビス（４’－β－ヒドロキシエトキシフェニル）プロパン、ビス（４－ヒドロキシフェニル）スルホン、ビス（４－β－ヒドロキシエトキシフェニル）スルホン酸等が挙げられる。芳香族ジオールは、更にアルキレンオキシドが付加された、エチレンオキシド付加物又はプロピレンオキシド付加物等となっていてもよい。 Examples of the aromatic diol include xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis (4'-hydroxyphenyl) propane, and 2,2-bis (4'-β-hydroxyethoxyphenyl) propane. , Bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid and the like. The aromatic diol may be an ethylene oxide adduct, a propylene oxide adduct, or the like to which an alkylene oxide is further added.
　また、ジカルボン酸及びジオール以外の共重合成分としても、特に限定されるものではなく、本発明の酸素吸収用不飽和ポリエステル樹脂を製造する際に、ジカルボン酸又はジオールと共重合可能な原料モノマーであればよい。 Further, the copolymerization component other than the dicarboxylic acid and the diol is not particularly limited, and it is a raw material monomer copolymerizable with the dicarboxylic acid or the diol when producing the unsaturated polyester resin for oxygen absorption of the present invention. All you need is.
　例えば、グリコール酸、ｐ－ヒドロキシ安息香酸、ｐ－β－ヒドロキシエトキシ安息香酸等のヒドロキシカルボン酸やアルコキシカルボン酸、及び、ステアリルアルコール、ヘネイコサノール、オクタコサノール、ベンジルアルコール、ステアリン酸、ベヘン酸、安息香酸、ｔ－ブチル安息香酸、ベンゾイル安息香酸等の単官能成分、トリカルバリル酸、トリメリット酸、トリメシン酸、ピロメリット酸、ナフタレンテトラカルボン酸、没食子酸、トリメチロールエタン、トリメチロールプロパン、グリセロール、ペンタエリスリトール、シュガーエステル等の三官能以上の多官能成分等が挙げられる。 For example, hydroxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, p-β-hydroxyethoxybenzoic acid, alkoxycarboxylic acids, stearyl alcohol, heneikosanol, octacosanol, benzyl alcohol, stearic acid, behenic acid, benzoic acid, etc. Monofunctional components such as t-butylbenzoic acid, benzoylbenzoic acid, tricarbaryl acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol , Polyfunctional components having trifunctionality or higher such as sugar ester, and the like can be mentioned.
　＜酸素吸収用不飽和ポリエステル樹脂の製造方法＞
　本発明の酸素吸収用不飽和ポリエステル樹脂の製造方法は、特に限定されるものではなく、公知のポリエステル樹脂の製造方法と適用することができる。 <Manufacturing method of unsaturated polyester resin for oxygen absorption>
The method for producing an unsaturated polyester resin for oxygen absorption of the present invention is not particularly limited, and can be applied to a known method for producing a polyester resin.
　例えば、不飽和ジカルボン酸を含むジカルボン酸成分と、脂環式ジオールを含むジオール成分とからスラリーを調製し、必要に応じて触媒、助剤、溶媒等を添加した後、エステル化反応を進行させる。なお、エステル化反応は無触媒でも進行するため、無触媒にて実施してもよい。 For example, a slurry is prepared from a dicarboxylic acid component containing an unsaturated dicarboxylic acid and a diol component containing an alicyclic diol, and if necessary, a catalyst, an auxiliary agent, a solvent and the like are added, and then the esterification reaction is allowed to proceed. .. Since the esterification reaction proceeds without a catalyst, it may be carried out without a catalyst.
　ジカルボン酸成分とジオール成分の供給量は、特に限定されるものではないが、通常、ジオール成分を過剰にして反応させ、余剰のジオール成分はエステル化反応の進行と共に系外に留去することが好ましい。 The supply amounts of the dicarboxylic acid component and the diol component are not particularly limited, but usually, the diol component is excessively reacted and the excess diol component is distilled off from the system as the esterification reaction progresses. preferable.
　ジカルボン酸成分に対するジオール成分のモル比は、例えば、１．０～２．０の範囲であってよく、下限は、１．０５以上、又は１．１以上であってよく、上限は、１．７以下、又は１．６以下であってよい。 The molar ratio of the diol component to the dicarboxylic acid component may be, for example, in the range of 1.0 to 2.0, the lower limit may be 1.05 or more, or 1.1 or more, and the upper limit may be 1. It may be 7 or less, or 1.6 or less.
　《酸素吸収用不飽和ポリエステル樹脂を含む酸素吸収用フィルム》
　本発明の酸素吸収用不飽和ポリエステル樹脂を含む酸素吸収用フィルムは、上記の本発明の酸素吸収用不飽和ポリエステル樹脂を原料として含むフィルムである。酸素吸収用不飽和ポリエステル樹脂を含む酸素吸収用フィルムは、本発明の酸素吸収用不飽和ポリエステル樹脂に、必要に応じて、機能性等を付与するための添加剤等の他の成分が配合されていてもよい。 << Oxygen absorption film containing unsaturated polyester resin for oxygen absorption >>
The oxygen absorbing film containing the oxygen absorbing unsaturated polyester resin of the present invention is a film containing the above-mentioned oxygen absorbing unsaturated polyester resin of the present invention as a raw material. The oxygen absorbing film containing the oxygen absorbing unsaturated polyester resin is prepared by blending the oxygen absorbing unsaturated polyester resin of the present invention with other components such as additives for imparting functionality and the like, if necessary. May be.
　酸素吸収用フィルムにおける本発明の酸素吸収用不飽和ポリエステル樹脂の配合量は、酸素吸収用フィルムの構成材料全体に対して、５０質量％以上、６０質量％以上、７０質量％以上、８０質量％以上、９０質量％以上、又は９５質量％以上であってよい。 The blending amount of the unsaturated polyester resin for oxygen absorption of the present invention in the oxygen absorbing film is 50% by mass or more, 60% by mass or more, 70% by mass or more, and 80% by mass with respect to the entire constituent material of the oxygen absorbing film. As mentioned above, it may be 90% by mass or more, or 95% by mass or more.
　酸素吸収用不飽和ポリエステル樹脂を含む酸素吸収用フィルムは、例えば、本発明の酸素吸収用不飽和ポリエステル樹脂、及び必要に応じて配合された添加剤等の他の成分を含む組成物を、フィルム状に溶融押出し、冷却ドラムにより急冷することで得られる、未延伸フィルムであってもよい。 The oxygen absorbing film containing the oxygen absorbing unsaturated polyester resin is a film containing, for example, the unsaturated polyester resin for oxygen absorbing of the present invention and other components such as additives blended as necessary. It may be an unstretched film obtained by melt-extruding it into a shape and quenching it with a cooling drum.
　あるいは、次いで、未延伸フィルムを予熱して、一軸延伸、逐次二軸延伸、又は同時二軸延伸を実施することで得られる、一軸又は二軸延伸フィルムであってもよい。 Alternatively, it may be a uniaxial or biaxially stretched film obtained by preheating the unstretched film and performing uniaxial stretching, sequential biaxial stretching, or simultaneous biaxial stretching.
　《酸素吸収用組成物》
　本発明の酸素吸収用組成物は、上記した本発明の酸素吸収用不飽和ポリエステル樹脂を含む組成物である。本発明の酸素吸収用組成物は、本発明の酸素吸収用不飽和ポリエステル樹脂を含むことで、酸素吸収性能を有する。 << Composition for oxygen absorption >>
The oxygen absorbing composition of the present invention is a composition containing the above-mentioned unsaturated polyester resin for oxygen absorption of the present invention. The oxygen absorbing composition of the present invention has oxygen absorbing performance by containing the unsaturated polyester resin for oxygen absorption of the present invention.
　なお、本発明の酸素吸収用組成物は、酸素吸収用組成物を構成するポリエステル成分の合計１００質量％に対して、本発明の不飽和ポリエステルの配合量が、６０質量％以上、より好ましくは８０質量％以上であれば、高いレベルの酸素吸収能を発揮させることができる。 In the oxygen absorbing composition of the present invention, the blending amount of the unsaturated polyester of the present invention is 60% by mass or more, more preferably 60% by mass, based on the total 100% by mass of the polyester components constituting the oxygen absorbing composition. If it is 80% by mass or more, a high level of oxygen absorption capacity can be exhibited.
　＜酸素吸収用組成物の構成成分＞
　本発明の酸素吸収用組成物は、上記した本発明の酸素吸収用不飽和ポリエステル樹脂以外に、任意の成分や溶媒等が配合されていてもよい。 <Components of Oxygen Absorption Composition>
The oxygen absorbing composition of the present invention may contain any component, solvent, or the like in addition to the above-mentioned unsaturated polyester resin for oxygen absorption of the present invention.
　（触媒）
　本発明の酸素吸収用組成物は、上記した本発明の酸素吸収用不飽和ポリエステル樹脂以外に、任意の成分として、触媒を含んでいてもよい。触媒を存在させることで、酸素吸収用不飽和ポリエステル樹脂の酸素吸収性能を高めることができる。 (catalyst)
The oxygen absorbing composition of the present invention may contain a catalyst as an arbitrary component in addition to the above-mentioned unsaturated polyester resin for oxygen absorption of the present invention. The presence of the catalyst can enhance the oxygen absorption performance of the unsaturated polyester resin for oxygen absorption.
　触媒としては、特に限定されるものではなく、例えば、遷移金属又は第１２族元素と、有機酸とからなる金属塩が挙げられる。遷移金属としては、例えば、鉄、コバルト等が挙げられ、第１２族元素としては、例えば亜鉛が挙げられる。また、有機酸としては、例えばステアリン酸、クエン酸、フマル酸、グルコン酸、ラウリン酸、エチレンジアミン－Ｎ，Ｎ，Ｎ’，Ｎ’－四酢酸、２，４－ペンタンジオン酸等が挙げられる。 The catalyst is not particularly limited, and examples thereof include a metal salt composed of a transition metal or a Group 12 element and an organic acid. Examples of the transition metal include iron, cobalt and the like, and examples of the Group 12 element include zinc. Examples of the organic acid include stearic acid, citric acid, fumaric acid, gluconic acid, lauric acid, ethylenediamine-N, N, N', N'-tetraacetic acid, 2,4-pentandionic acid and the like.
　したがって、本発明の酸素吸収用組成物に配合される触媒としては、例えば、ステアリン酸亜鉛、ステアリン酸コバルト、ステアリン酸鉄等が挙げられ、いずれによっても、本発明の酸素吸収用組成物の酸素吸収性能を高めることができる。 Therefore, examples of the catalyst blended in the oxygen absorbing composition of the present invention include zinc stearate, cobalt stearate, iron stearate, and the like, and any of these may include oxygen in the oxygen absorbing composition of the present invention. Absorption performance can be improved.
　本発明の酸素吸収用組成物が触媒を含む場合には、その配合量は、酸素吸収用組成物の全固形分質量に対する遷移金属又は第１２族元素の質量換算で、例えば、１０～５００ｐｐｍであってよい。 When the oxygen absorbing composition of the present invention contains a catalyst, the blending amount thereof is, for example, 10 to 500 ppm in terms of the mass of the transition metal or Group 12 element with respect to the total solid content mass of the oxygen absorbing composition. It may be there.
　触媒の配合量は、酸素吸収用組成物の全固形分質量に対する遷移金属又は第１２族元素の質量換算で、２０ｐｐｍ以上、４０ｐｐｍ以上、６０ｐｐｍ以上、８０ｐｐｍ以上、１００ｐｐｍ以上、１５０ｐｐｍ以上、又は２００ｐｐｍ以上であってよく、４５０ｐｐｍ以下、４００ｐｐｍ以下、３５０ｐｐｍ以下、３００ｐｐｍ以下、２５０ｐｐｍ以下、又は２００ｐｐｍ以下であってよい。 The amount of the catalyst compounded is 20 ppm or more, 40 ppm or more, 60 ppm or more, 80 ppm or more, 100 ppm or more, 150 ppm or more, or 200 ppm or more in terms of the mass of the transition metal or Group 12 element with respect to the total solid content mass of the oxygen absorbing composition. It may be 450 ppm or less, 400 ppm or less, 350 ppm or less, 300 ppm or less, 250 ppm or less, or 200 ppm or less.
　（硬化剤）
　本発明の酸素吸収用組成物は、上記した本発明の酸素吸収用不飽和ポリエステル樹脂以外に、任意の成分として、硬化剤を含んでいてもよい。硬化剤を存在させることで、不飽和ポリエステルを三次元架橋させることができ、不溶不融の硬化物を形成することができる。また、硬化スピードを調整することができ、用途に応じてコントロールすることが可能となる。更には、硬化剤が酸素吸収用不飽和ポリエステル樹脂に対して特定の範囲の量で配合されていることで、酸素吸収用組成物から包装材を形成したときに、ポリエステル系樹脂の原料であるジカルボン酸及び／又はジオール等の低分子量成分が包装材から溶出することを抑制することができる。 (Hardener)
The oxygen absorbing composition of the present invention may contain a curing agent as an arbitrary component in addition to the above-mentioned unsaturated polyester resin for oxygen absorption of the present invention. By the presence of the curing agent, the unsaturated polyester can be three-dimensionally crosslinked, and an insoluble and infusible cured product can be formed. In addition, the curing speed can be adjusted and can be controlled according to the application. Furthermore, since the curing agent is blended in an amount in a specific range with respect to the unsaturated polyester resin for oxygen absorption, it is a raw material for the polyester resin when a packaging material is formed from the composition for oxygen absorption. It is possible to suppress the elution of low molecular weight components such as dicarboxylic acid and / or diol from the packaging material.
　硬化剤としては、特に限定されるものではなく、ポリエステル系樹脂の分野において用いられている、公知の硬化剤を用いることができる。例えば、イソシアネート系硬化剤や過酸化物等を挙げることができる。 The curing agent is not particularly limited, and a known curing agent used in the field of polyester-based resin can be used. For example, isocyanate-based curing agents, peroxides and the like can be mentioned.
　イソシアネート系硬化剤としては、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート、４，４'－ジフェニルメタンジイソシアネート、２，４'－ジフェニルメタンジイソシアネート、２，２'－ジフェニルメタンジイソシアネート、３，３'－ジメチル－４，４'－ビフェニレンジイソシアネート、３，３'－ジメトキシ－４，４'－ビフェニレンジイソシアネート、３，３'－ジクロロ－４，４'－ビフェニレンジイソシアネート、１，５－ナフタレンジイソシアネート、１，５－テトラヒドロナフタレンジイソシアネート、テトラメチレンジイソシアネート、１，６－ヘキサメチレンジイソシアネート、ドデカメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、１，３－シクロヘキシレンジイソシアネート、１，４－シクロヘキシレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、水素添加キシリレンジイソシアネート、リジンジイソシアネート、イソホロンジイソシアネート、４，４'－ジシクロヘキシルメタンジイソシアネート、又は、３，３'－ジメチル－４，４'－ジシクロヘキシルメタンジイソシアネート等が挙げられる。 Examples of the isocyanate-based curing agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenedi isocyanate, p-phenylenedi isocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4'-diphenylmethane diisocyanate, 2 , 2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenylenediisocyanate, 3,3'-dichloro-4,4'-biphenylene Diisocyanate, 1,5-naphthalenediocyanate, 1,5-tetrahydronaphthalenediocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4- Cycloheximethylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, or 3,3'-dimethyl-4,4'-dicyclohexyl Examples thereof include methane diisocyanate.
　なお、イソシアネート系硬化剤は、分子量が増大されたポリイソシアネート化合物であってもよい。ポリイソシアネート化合物としては、例えば、アダクトやイソシアヌレート、ビュレット体等が挙げられる。また、イソシアネート系硬化剤は、１種単独で用いても、２種以上を組み合わせて用いてもよい。 The isocyanate-based curing agent may be a polyisocyanate compound having an increased molecular weight. Examples of the polyisocyanate compound include adduct, isocyanurate, and burette. Further, the isocyanate-based curing agent may be used alone or in combination of two or more.
　過酸化物としては、例えば、ケトンパーオキサイド類、パーオキシジカーボネート類、ハイドロパーオキサイド類、ジアシルパーオキサイド類、パーオキシケタール類、ジアルキルパーオキサイド類、パーオキシエステル類等が挙げられる。 Examples of the peroxide include ketone peroxides, peroxydicarbonates, hydroperoxides, diacyl peroxides, peroxyketals, dialkyl peroxides, peroxyesters and the like.
　本発明の酸素吸収用組成物が硬化剤を含む場合には、その配合量は、成形サイクルや用途に応じて、適宜設定することができる。例えば、酸素吸収用組成物を構成する不飽和ポリエステル樹脂１００質量部に対して０．１～１０００質量部であってよい。なお、本発明の酸素吸収用組成物が、複数種のポリエステル樹脂（例えば不飽和ポリエステル樹脂と飽和ポリエステル樹脂）を含む場合には、その合計固形分質量１００質量部に対して、０．１～１０００質量部であってよい。 When the oxygen absorbing composition of the present invention contains a curing agent, the blending amount thereof can be appropriately set according to the molding cycle and the intended use. For example, it may be 0.1 to 1000 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin constituting the oxygen absorbing composition. When the oxygen absorbing composition of the present invention contains a plurality of types of polyester resins (for example, unsaturated polyester resin and saturated polyester resin), it is 0.1 to 0.1 to 100 parts by mass of the total solid content. It may be 1000 parts by mass.
　また、硬化剤の配合量は、酸素吸収用組成物を構成する不飽和ポリエステル樹脂１００質量％に対して、０．２質量％以上、０．５質量％以上、１質量％以上、３質量％以上、５質量％以上、７質量％以上、１０質量％以上、５０質量％以上、７５質量％以上、１００質量％以上、２００質量％以上、３００質量％以上、４００質量％以上、又は５００質量％以上であってよく、９００質量％以下、８００質量％以下、７００質量％以下、６００質量％以下、５００質量％以下、３００質量％以下、１００質量％以下、９０質量％以下、８０質量％以下、７０質量％以下、６０質量％以下、５０質量％以下、４０質量％以下、３０質量％以下、２０質量％以下、１０質量％以下、８質量％以下、又は６質量％以下であってよい。 The blending amount of the curing agent is 0.2% by mass or more, 0.5% by mass or more, 1% by mass or more, and 3% by mass with respect to 100% by mass of the unsaturated polyester resin constituting the oxygen absorbing composition. 5% by mass or more, 7% by mass or more, 10% by mass or more, 50% by mass or more, 75% by mass or more, 100% by mass or more, 200% by mass or more, 300% by mass or more, 400% by mass or more, or 500% by mass. % Or more, 900% by mass or less, 800% by mass or less, 700% by mass or less, 600% by mass or less, 500% by mass or less, 300% by mass or less, 100% by mass or less, 90% by mass or less, 80% by mass. Below, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 8% by mass or less, or 6% by mass or less. good.
　（飽和ポリエステル）
　本発明の酸素吸収用組成物は、上記した本発明の酸素吸収用不飽和ポリエステル樹脂以外に、任意の成分として、飽和ポリエステルを含んでいてもよい。飽和ポリエステルを存在させることで、得られる組成物に接着性を付与し、ラミネート強度をより向上させることができる。 (Saturated polyester)
The oxygen absorbing composition of the present invention may contain saturated polyester as an arbitrary component in addition to the above-mentioned unsaturated polyester resin for oxygen absorption of the present invention. The presence of the saturated polyester can impart adhesiveness to the obtained composition and further improve the laminating strength.
　すなわち、本発明の酸素吸収用組成物が、本発明の酸素吸収用不飽和ポリエステル樹脂以外に、飽和ポリエステルを含んでいる態様であれば、本発明の酸素吸収用組成物は、少なくとも接着剤として機能させることができる。本発明の酸素吸収用組成物が、接着剤として機能する場合には、接着層として２層の間に挟み込むことで、酸素吸収性能を有する積層体を形成することができる。 That is, if the oxygen absorbing composition of the present invention contains a saturated polyester in addition to the oxygen absorbing unsaturated polyester resin of the present invention, the oxygen absorbing composition of the present invention can be used as at least an adhesive. Can be made to work. When the oxygen absorbing composition of the present invention functions as an adhesive, it is possible to form a laminated body having oxygen absorbing performance by sandwiching it between the two layers as an adhesive layer.
　その結果、例えば、従来、ヒートシール層を有する積層体を形成するために必要とされていた、ヒートシール剤を塗工したり、シートシール性フィルムをラミネートしたりする等の工程、又はヒートシール性フィルムを貼り付けるために接着層を予め形成する工程等が必要なくなり、当該工程に起因する酸素吸収性能の低下を回避することができる。 As a result, for example, a process such as applying a heat-sealing agent or laminating a sheet-sealing film, which has been conventionally required for forming a laminate having a heat-sealing layer, or heat-sealing. A step of forming an adhesive layer in advance is not required for attaching the sex film, and deterioration of oxygen absorption performance due to the step can be avoided.
　飽和ポリエステルとしては、特に限定されるものではなく、反応性の不飽和結合を有さないポリエステルから適宜選択して用いることができる。例えば、脂肪族ポリエステルであっても、芳香族ポリエステルであっても、脂環式ポリエステルであってもよく、これらの２種以上を、同時に適用してもよい。 The saturated polyester is not particularly limited, and can be appropriately selected from polyesters having no reactive unsaturated bond and used. For example, it may be an aliphatic polyester, an aromatic polyester, or an alicyclic polyester, and two or more of these may be applied at the same time.
　本発明の酸素吸収用組成物が飽和ポリエステルを含む場合には、その配合量は、組成物の用途に応じて適宜設定することができる。例えば、酸素吸収用組成物を構成する不飽和ポリエステルと飽和ポリエステルとの合計１００質量％に対して、１～９９質量％であってよい。 When the oxygen absorbing composition of the present invention contains saturated polyester, the blending amount thereof can be appropriately set according to the use of the composition. For example, it may be 1 to 99% by mass with respect to a total of 100% by mass of the unsaturated polyester and the saturated polyester constituting the oxygen absorbing composition.
　飽和ポリエステルの配合量は、酸素吸収用組成物を構成する不飽和ポリエステルと飽和ポリエステルとの合計１００質量％に対して、５質量％以上、１０質量％以上、１５質量％以上、２０質量％以上、３０質量％以上、４０質量％以上、６０質量％以上、又は８０質量％以上であってよく、９０質量％以下、８０質量％以下、７０質量％以下、６０質量％以下、５０質量％以下、４０質量％以下、３５質量％以下、又は３０質量％以下であってよい。 The blending amount of the saturated polyester is 5% by mass or more, 10% by mass or more, 15% by mass or more, and 20% by mass or more with respect to 100% by mass of the total of the unsaturated polyester and the saturated polyester constituting the oxygen absorbing composition. , 30% by mass or more, 40% by mass or more, 60% by mass or more, or 80% by mass or more, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less. , 40% by mass or less, 35% by mass or less, or 30% by mass or less.
　（溶媒）
　本発明の酸素吸収用組成物は、任意の成分として、溶媒を含んでいてもよい。溶媒は、本発明の酸素吸収用不飽和ポリエステル樹脂及び任意の成分を溶解して、取り扱い等を向上させることができる。 (solvent)
The oxygen absorbing composition of the present invention may contain a solvent as an arbitrary component. The solvent can dissolve the unsaturated polyester resin for oxygen absorption of the present invention and any component, and can improve handling and the like.
　本発明の酸素吸収用組成物に用いられる溶媒は、特に限定されるものではなく、ポリエステル系組成物の溶媒として用いられている公知の溶媒を適用することができる。 The solvent used in the oxygen absorbing composition of the present invention is not particularly limited, and a known solvent used as a solvent for the polyester-based composition can be applied.
　溶媒の配合量についても特に限定されるものではなく、組成物の用途や成形サイクル等に応じて、適宜選択することができる。 The blending amount of the solvent is not particularly limited, and can be appropriately selected depending on the use of the composition, the molding cycle, and the like.
　＜酸化防止剤＞
　本発明の酸素吸収用組成物は、任意の成分として、酸化防止剤を含んでいても良い。酸化防止剤が存在することで、本発明の酸素吸収用組成物は、経時による酸素吸収性能の低下が抑制される。 <Antioxidant>
The oxygen absorbing composition of the present invention may contain an antioxidant as an arbitrary component. The presence of the antioxidant suppresses the deterioration of the oxygen absorption performance of the oxygen absorbing composition of the present invention over time.
　酸化防止剤としては、特に限定されるものではなく、公知の酸化防止剤を用いることができる。例えば、ヒンダードフェノール系酸化防止剤、リン系酸化防止剤、チオエーテル系酸化防止剤等を挙げることができる。 The antioxidant is not particularly limited, and a known antioxidant can be used. For example, a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, and the like can be mentioned.
　ヒンダードフェノール系酸化防止剤としては、例えば、１，３，５－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）イソシアヌレート、１，１，３－トリ（４－ヒドロキシ－２－メチル－５－ｔ－ブチルフェニル）ブタン、１，１－ビス（３－ｔ－ブチル－６－メチル－４－ヒドロキシフェニル）ブタン、３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシ－ベンゼンプロパノイック酸、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、３－（１，１－ジメチルエチル）－４－ヒドロキシ－５－メチル－ベンゼンプロパノイック酸、３，９－ビス［１，１－ジメチル－２－［（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニロキシ］エチル］－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、１，３，５－トリメチル－２，４，６－トリス（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシベンジル）ベンゼン等が挙げられる。 Examples of the hindered phenolic antioxidant include 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate and 1,1,3-tri (4-hydroxy-). 2-Methyl-5-t-butylphenyl) butane, 1,1-bis (3-t-butyl-6-methyl-4-hydroxyphenyl) butane, 3,5-bis (1,1-dimethylethyl)- 4-Hydroxy-benzenepropanoic acid, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3- (1,1-dimethylethyl) -4-hydroxy- 5-Methyl-benzenepropanoic acid, 3,9-bis [1,1-dimethyl-2-[(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2, 4,8,10-Tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3', 5'-di-t-butyl-4'-hydroxybenzyl) Benzene and the like can be mentioned.
　リン系酸化防止剤としては、例えば、トリフェニルホスファイト、トリフェニルホスフィン、３，９－ビス（ｐ－ノニルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジフォスファスピロ［５．５］ウンデカン、３，９－ビス（オクタデシロキシ）－２，４，８，１０－テトラオキサ－３，９－ジフォスファスピロ［５．５］ウンデカン、トリ（モノノニルフェニル）フォスファイト、トリフェノキシフォスフィン、イソデシルフォスファイト、イソデシルフェニルフォスファイト、ジフェニル２－エチルヘキシルフォスファイト、ジノニルフェニルビス（ノニルフェニル）エステルフォスフォラス酸、１，１，３－トリス（２－メチル－４－ジトリデシルフォスファイト－５－ｔ－ブチルフェニル）ブタン、トリス（２，４－ジ－ｔ－ブチルフェニル）フォスファイト、ペンタエリスリトールビス（２，４－ジ－ｔ－ブチルフェニルフォスファイト）、２，２’－メチレンビス（４，６－ジ－ｔ－ブチルフェニル）２－エチルヘキシルフォスファイト、ビス（２，６－ジ－ｔ－ブチル－４－メチルフェニル）ペンタエリスリトールジフォスファイト等が挙げられる。 Examples of phosphorus-based antioxidants include triphenylphosphite, triphenylphosphine, 3,9-bis (p-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [ 5.5] Undecane, 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] Undecane, tri (monononylphenyl) phosphite , Triphenoxyphosphine, Isodecylphosphite, Isodecylphenylphosphite, Diphenyl2-ethylhexylphosphite, Dinonylphenylbis (nonylphenyl) ester phosphoric acid, 1,1,3-Tris (2-methyl-4) -Ditridecylphosphite-5-t-butylphenyl) butane, tris (2,4-di-t-butylphenyl) phosphite, pentaerythritol bis (2,4-di-t-butylphenylphosphite), 2 , 2'-Methylenebis (4,6-di-t-butylphenyl) 2-ethylhexylphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and the like.
　チオエーテル系酸化防止剤としては、例えば、チオエーテル系として４，４’－チオビス［２－ｔ－ブチル－５－メチルフェノール］ビス［３－（ドデシルチオ）プロピオネート］、チオビス［２－（１，１－ジメチルエチル）－５－メチル－４，１－フェニレン］ビス［３－（テトラデシルチオ）－プロピオネート］、ペンタエリスリトールテトラキス（３－ｎ－ドデシルチオプロピオネート）、ビス（トリデシル）チオジプロピオネート島が挙げられる。 Examples of the thioether-based antioxidant include 4,4'-thiobis [2-t-butyl-5-methylphenol] bis [3- (dodecylthio) propionate] and thiobis [2- (1,1-) as thioether-based agents. Dimethylethyl) -5-methyl-4,1-phenylene] bis [3- (tetradecylthio) -propionate], pentaerythritol tetrakis (3-n-dodecylthiopropionate), bis (tridecyl) thiodipropionate The island is mentioned.
　酸化防止剤は、１種単独で配合しても、２種以上を併用してもよい。 The antioxidant may be blended alone or in combination of two or more.
　中では、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、又はトリフェニルホスファイトが好ましい。 Among them, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] or triphenylphosphine is preferable.
　（配合量）
　酸化防止剤の配合量は、酸素吸収用不飽和ポリエステル樹脂１００質量部に対して、５ｐｐｍ以上、１０ｐｐｍ以上、２０ｐｐｍ以上、３０ｐｐｍ以上、４０ｐｐｍ以上、５０ｐｐｍ以上、６０ｐｐｍ質量部以上、７０ｐｐｍ以上、８０ｐｐｍ以上、９０ｐｐｍ以上、又は１００ｐｐｍ以上であってよく、１０００ｐｐｍ以下、９００ｐｐｍ以下、８００ｐｐｍ以下、７００ｐｐｍ以下、６００ｐｐｍ以下、５００ｐｐｍ以下、４００ｐｐｍ以下、又は３００ｐｐｍ以下であってよい。 (Mixing amount)
The amount of the antioxidant is 5 ppm or more, 10 ppm or more, 20 ppm or more, 30 ppm or more, 40 ppm or more, 50 ppm or more, 60 ppm by mass or more, 70 ppm or more, 80 ppm or more with respect to 100 parts by mass of the unsaturated polyester resin for oxygen absorption. , 90 ppm or more, or 100 ppm or more, and may be 1000 ppm or less, 900 ppm or less, 800 ppm or less, 700 ppm or less, 600 ppm or less, 500 ppm or less, 400 ppm or less, or 300 ppm or less.
　＜酸素吸収用組成物の製造方法＞
　本発明の酸素吸収用組成物の製造方法は、特に限定されるものではなく、ポリエステル系組成物の製造方法として公知の方法を適用することができる。 <Manufacturing method of oxygen absorption composition>
The method for producing the oxygen absorbing composition of the present invention is not particularly limited, and a method known as a method for producing a polyester-based composition can be applied.
　《酸素吸収用組成物を含む酸素吸収用フィルム》
　本発明の酸素吸収用組成物を含む酸素吸収用フィルムは、上記の本発明の酸素吸収用組成物を原料として含むフィルムである。 << Oxygen absorption film containing oxygen absorption composition >>
The oxygen absorbing film containing the oxygen absorbing composition of the present invention is a film containing the above-mentioned oxygen absorbing composition of the present invention as a raw material.
　酸素吸収用フィルムにおける本発明の酸素吸収用組成物の配合量は、酸素吸収用フィルムの構成材料全体に対して、５０質量％以上、６０質量％以上、７０質量％以上、８０質量％以上、９０質量％以上、又は９５質量％以上であってよい。 The blending amount of the oxygen absorbing composition of the present invention in the oxygen absorbing film is 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, based on the total constituent materials of the oxygen absorbing film. It may be 90% by mass or more, or 95% by mass or more.
　酸素吸収用組成物を含む酸素吸収用フィルムは、例えば、本発明の酸素吸収用組成物を溶媒に溶解した後に、得られた溶液を離型紙等の対象物の上に塗布し、溶媒を除去して硬化等させて得られる、未延伸フィルムであってもよい。 In the oxygen absorbing film containing the oxygen absorbing composition, for example, after dissolving the oxygen absorbing composition of the present invention in a solvent, the obtained solution is applied onto an object such as a release paper to remove the solvent. It may be an unstretched film obtained by curing the film.
　あるいは、本発明の酸素吸収用組成物を溶融し、フィルム形状に押し出して得られる未延伸フィルムであってもよいし、次いで、未延伸フィルムを予熱して、一軸延伸、逐次二軸延伸、又は同時二軸延伸を実施して得られる、一軸又は二軸延伸フィルムであってもよい。 Alternatively, it may be an unstretched film obtained by melting the oxygen absorbing composition of the present invention and extruding it into a film shape, and then preheating the unstretched film to uniaxially stretch, sequentially biaxially stretch, or. It may be a uniaxial or biaxially stretched film obtained by carrying out simultaneous biaxial stretching.
　《酸素吸収用接着剤》
　本発明の酸素吸収用接着剤は、上記した本発明の酸素吸収用組成物を含む接着剤である。本発明の酸素吸収用接着剤は、本発明の酸素吸収用組成物を含むため、酸素吸収性能を有する。同時に、接着性を有する。 << Adhesive for oxygen absorption >>
The oxygen absorbing adhesive of the present invention is an adhesive containing the above-mentioned oxygen absorbing composition of the present invention. Since the oxygen absorbing adhesive of the present invention contains the oxygen absorbing composition of the present invention, it has oxygen absorbing performance. At the same time, it has adhesiveness.
　このため、本発明の酸素吸収用接着剤を接着層として２層の間に挟み込むことで、酸素吸収性能を有する積層体を形成することができ、例えば、従来、ヒートシール層を有する積層体を形成するために必要とされていた、ヒートシール剤を塗工したり、シートシール性フィルムをラミネートしたりする等の工程、又はヒートシール性フィルムを貼り付けるために接着層を予め形成する工程等が必要なくなり、当該工程に起因する酸素吸収性能の低下を回避することができる。 Therefore, by sandwiching the oxygen absorbing adhesive of the present invention as an adhesive layer between two layers, it is possible to form a laminated body having oxygen absorbing performance. For example, conventionally, a laminated body having a heat seal layer can be formed. A step required for forming, such as applying a heat-sealing agent or laminating a sheet-sealing film, or a step of pre-forming an adhesive layer for attaching a heat-sealing film, etc. Is no longer necessary, and deterioration of oxygen absorption performance due to the process can be avoided.
　＜酸素吸収用接着剤の構成成分＞
　本発明の酸素吸収用接着剤は、上記した本発明の酸素吸収用組成物以外に、接着性を付与するための任意の成分、機能性を付与するための任意の成分、又は溶媒等を配合することができる。なお、上記した本発明の酸素吸収用組成物が飽和ポリエステルを含む態様であり、酸素吸収用組成物自体が接着性を有し、接着剤として機能する場合には、接着性を付与するための任意の成分は、添加してもしなくてもよい。 <Components of Oxygen Absorption Adhesive>
The oxygen absorbing adhesive of the present invention contains, in addition to the above-mentioned oxygen absorbing composition of the present invention, an arbitrary component for imparting adhesiveness, an arbitrary component for imparting functionality, a solvent, or the like. can do. When the oxygen absorbing composition of the present invention described above contains saturated polyester and the oxygen absorbing composition itself has adhesiveness and functions as an adhesive, it is intended to impart adhesiveness. Any component may or may not be added.
　《酸素吸収用接着剤フィルム》
　本発明の酸素吸収用接着剤を含む酸素吸収用接着剤フィルムは、上記の本発明の酸素吸収用接着剤を原料として含むフィルムである。 << Adhesive film for oxygen absorption >>
The oxygen absorbing adhesive film containing the oxygen absorbing adhesive of the present invention is a film containing the above-mentioned oxygen absorbing adhesive of the present invention as a raw material.
　酸素吸収用接着剤フィルムにおける本発明の酸素吸収用接着剤の配合量は、酸素吸収用接着剤フィルムの構成材料全体に対して、５０質量％以上、６０質量％以上、７０質量％以上、８０質量％以上、９０質量％以上、又は９５質量％以上であってよい。 The blending amount of the oxygen absorbing adhesive of the present invention in the oxygen absorbing adhesive film is 50% by mass or more, 60% by mass or more, 70% by mass or more, and 80 with respect to the entire constituent materials of the oxygen absorbing adhesive film. It may be mass% or more, 90 mass% or more, or 95 mass% or more.
　酸素吸収用接着剤フィルムは、例えば、本発明の酸素吸収用接着剤を溶媒に溶解した後に、得られた溶液を離型紙等の対象物の上に塗布し、溶媒を除去して硬化等させて得られる、未延伸フィルムであってもよい。 For the oxygen absorbing adhesive film, for example, after dissolving the oxygen absorbing adhesive of the present invention in a solvent, the obtained solution is applied onto an object such as a release paper, and the solvent is removed to cure the film. It may be an unstretched film obtained by the above.
　《酸素吸収用積層体》
　本発明の酸素吸収用積層体は、上記した本発明の酸素吸収用組成物からなる酸素吸収用組成物層を備える積層体である。 << Laminate for oxygen absorption >>
The oxygen absorption laminate of the present invention is a laminate including an oxygen absorption composition layer comprising the oxygen absorption composition of the present invention described above.
　本発明の酸素吸収用積層体は、本発明の酸素吸収用組成物からなる酸素吸収用組成物層を備えていれば、その他の層は特に限定されるものではない。その他の層としては、例えば、積層体に機能を付与するための酸素バリア層、ヒートシール層等、あるいは、各層を接着するための接着層等が挙げられる。 The oxygen absorbing laminate of the present invention is not particularly limited as long as it includes the oxygen absorbing composition layer made of the oxygen absorbing composition of the present invention. Examples of the other layer include an oxygen barrier layer for imparting a function to the laminated body, a heat seal layer, and the like, and an adhesive layer for adhering each layer.
　本発明の酸素吸収用積層体は、例えば、酸素バリア層と、本発明の酸素吸収用組成物からなる酸素吸収用組成物層と、ヒートシール層とが、この順で積層された構成であってもよい。 The oxygen absorption laminate of the present invention has, for example, a structure in which an oxygen barrier layer, an oxygen absorption composition layer composed of the oxygen absorption composition of the present invention, and a heat seal layer are laminated in this order. May be.
　本発明の酸素吸収用積層体が、酸素バリア層と、酸素吸収用組成物層と、ヒートシール層とが、この順で積層された構成となっている場合には、ヒートシール層を熱溶着させることで各種の包装体を形成することができる。包装体に充填された内容物が接する面は、ヒートシール層となり、包装体の外部である大気等に含まれる酸素が接触する面は、酸素バリア層となる。 When the oxygen absorption laminate of the present invention has an oxygen barrier layer, an oxygen absorption composition layer, and a heat seal layer laminated in this order, the heat seal layer is heat welded. Various packages can be formed by making them. The surface in contact with the contents filled in the package is a heat seal layer, and the surface in contact with oxygen contained in the atmosphere or the like outside the package is an oxygen barrier layer.
　したがって、酸素吸収用積層体が、酸素バリア層と、酸素吸収用組成物層と、ヒートシール層とが、この順で積層された構成となっていれば、外部からの酸素透過を防ぎつつ、包装体内部の酸素を吸収することができる。その結果、より高度なレベルで、包装体内部に存在する酸素を排除することができ、内容物の酸化劣化を回避することができる。 Therefore, if the oxygen absorption laminate has an oxygen barrier layer, an oxygen absorption composition layer, and a heat seal layer laminated in this order, oxygen permeation from the outside can be prevented while preventing oxygen permeation from the outside. It can absorb oxygen inside the package. As a result, oxygen existing inside the package can be eliminated at a higher level, and oxidative deterioration of the contents can be avoided.
　また、本発明の酸素吸収用積層体を構成する酸素吸収用組成物層が、接着性を有する酸素吸収用接着剤を含む層である場合には、酸素吸収用組成物層を形成するための組成物を、接着したい２層の間に挟み込んで酸素吸収用接着剤層とすることで、当該２層を接着するとともに、自身により酸素吸収性能を発揮する積層体を実現できる。 Further, when the oxygen absorbing composition layer constituting the oxygen absorbing laminated body of the present invention is a layer containing an oxygen absorbing adhesive having adhesiveness, it is necessary to form an oxygen absorbing composition layer. By sandwiching the composition between the two layers to be bonded to form an oxygen absorbing adhesive layer, it is possible to bond the two layers and realize a laminated body that exhibits oxygen absorption performance by itself.
　したがって、酸素吸収性能を備える層を形成するために、接着層を設ける工程を別に必要とせず、酸素吸収用積層体を形成することができる。そして、別に設ける必要のあった工程に起因する、酸素吸収性能の低下を回避することができる。 Therefore, in order to form a layer having oxygen absorption performance, it is possible to form an oxygen absorption laminate without requiring a separate step of providing an adhesive layer. Then, it is possible to avoid a decrease in oxygen absorption performance due to a process that needs to be provided separately.
　＜その他の層＞
　（酸素バリア層）
　酸素バリア層は、酸素を遮断する機能を発現し、酸素吸収用積層体に酸素バリア性を付与するための層となる。 <Other layers>
(Oxygen barrier layer)
The oxygen barrier layer exhibits a function of blocking oxygen and is a layer for imparting oxygen barrier properties to the oxygen absorbing laminate.
　酸素バリア層としては、特に限定されるものではなく、包装材料の分野にて公知の材料から作製することができる。例えば、エチレン－ビニルアルコール共重合体（ＥＶＯＨ）、ナイロン（ＮＹ）、ポリ塩化ビニリデン（ＰＶＤＣ）、又はポリアクリロニトリル（ＰＡＮ）等からなる層や、シリカ、アルミナ、又はアルミ等が蒸着されたＰＥＴフィルムやナイロンフィルム、更には、アルミ箔や、ＰＥＴとアルミ箔との積層体、ナイロンとアルミ箔との積層体等が挙げられる。 The oxygen barrier layer is not particularly limited, and can be produced from a material known in the field of packaging materials. For example, a layer made of ethylene-vinyl alcohol copolymer (EVOH), nylon (NY), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN), etc., or a PET film on which silica, alumina, aluminum, etc. are vapor-deposited. , Nylon film, aluminum foil, a laminate of PET and aluminum foil, a laminate of nylon and aluminum foil, and the like.
　本発明の酸素吸収用積層体においては、酸素バリア層の厚み等については特に限定されるものではなく、積層体の用途に応じて、適宜設定することができる。 In the oxygen absorbing laminate of the present invention, the thickness of the oxygen barrier layer and the like are not particularly limited, and can be appropriately set according to the use of the laminate.
　（ヒートシール層）
　ヒートシール層は、例えば包装体等の構造体を形成する際に、熱溶着される層となる。このため、ヒートシール層は、積層体の最内層となるように配置される。 (Heat seal layer)
The heat seal layer is a layer to be heat-welded when forming a structure such as a package. Therefore, the heat seal layer is arranged so as to be the innermost layer of the laminated body.
　ヒートシール層を構成する材料としては、熱接着が可能であり、成形された構造体に十分なシール強度を付与できるものであれば、特に限定されるものではない。公知の材料を適用することができ、例えば、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、ポリプロピレン（ＰＰ）、エチレン－プロピレン共重合体（ＥＰ）、エチレン－アクリル酸共重合体（ＥＡＡ）、エチレン－メタクリル酸共重合体（ＥＭＡＡ）、アイオノマー樹脂、エチレン－酢酸ビニル共重合体（ＥＶＡ）等が挙げられる。 The material constituting the heat seal layer is not particularly limited as long as it can be heat-bonded and can impart sufficient seal strength to the molded structure. Known materials can be applied, such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene (PP), ethylene- Examples thereof include propylene copolymer (EP), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA), ionomer resin, ethylene-vinyl acetate copolymer (EVA) and the like.
　なお、ヒートシール層を構成する樹脂等は、１種のみならず、２種以上がブレンドされていてもよく、必要に応じて、機能性等を付与するための添加剤等が配合されていてもよい。 The resin or the like constituting the heat seal layer may be a blend of not only one type but also two or more types, and if necessary, an additive or the like for imparting functionality or the like is blended. May be good.
　＜酸素吸収用積層体の製造方法＞
　本発明の酸素吸収用積層体の製造方法は、特に限定されるものではなく、公知の方法を適用することができる。例えば、ドライラミネーション法、ホットメルトラミネーション法、エクストルージョンラミネーション法、及びサンドイッチラミネーション方法等が挙げられる。 <Manufacturing method of laminate for oxygen absorption>
The method for producing the oxygen absorbing laminate of the present invention is not particularly limited, and a known method can be applied. For example, a dry lamination method, a hot melt lamination method, an extrusion lamination method, a sandwich lamination method and the like can be mentioned.
　《用途》
　本発明の酸素吸収用不飽和ポリエステル樹脂を含む酸素吸収用フィルム、本発明の酸素吸収用組成物を含む酸素吸収用フィルム、本発明の酸素吸収用接着剤を含む酸素吸収用接着剤フィルム、及び本発明の酸素吸収用積層体は、包装材として好適に用いることができる。 《Use》
An oxygen absorbing film containing the unsaturated polyester resin for oxygen absorption of the present invention, an oxygen absorbing film containing the oxygen absorbing composition of the present invention, an oxygen absorbing adhesive film containing the oxygen absorbing adhesive of the present invention, and an oxygen absorbing adhesive film of the present invention. The oxygen absorbing laminate of the present invention can be suitably used as a packaging material.
　本発明の酸素吸収用不飽和ポリエステル樹脂を含む酸素吸収用フィルム、本発明の酸素吸収用組成物を含む酸素吸収用フィルム、本発明の酸素吸収用接着剤を含む酸素吸収用接着剤フィルム、及び本発明の酸素吸収用積層体から成る群より選ばれるいずれかを備える包装材は、酸素吸収性能を発揮することができるため、例えば、内容物と酸素との接触を遮断したい、医薬品、医薬部外品、化粧品、洗剤、食品、塗料等の包装材として、好適に用いることができる。 An oxygen absorbing film containing the unsaturated polyester resin for oxygen absorption of the present invention, an oxygen absorbing film containing the oxygen absorbing composition of the present invention, an oxygen absorbing adhesive film containing the oxygen absorbing adhesive of the present invention, and an oxygen absorbing adhesive film of the present invention. Since the packaging material provided with any one selected from the group consisting of the oxygen absorbing laminate of the present invention can exhibit oxygen absorbing performance, for example, a pharmaceutical product, a pharmaceutical department, which wants to block contact between the contents and oxygen. It can be suitably used as a packaging material for external products, cosmetics, detergents, foods, paints and the like.
　以下、実施例及び比較例等により、本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
　《製造例１～５》
　＜不飽和ポリエステル樹脂の製造＞
　表１に示される不飽和ジカルボン酸と飽和ジカルボン酸とを、製造例１～２においては４：６のモル比となるように、製造例３～５においては９：１のモル比となるように準備し、表１に示されるジオールと反応させることで、不飽和ポリエステル樹脂を合成した。 << Manufacturing Examples 1 to 5 >>
<Manufacturing of unsaturated polyester resin>
The unsaturated dicarboxylic acid and the saturated dicarboxylic acid shown in Table 1 have a molar ratio of 4: 6 in Production Examples 1 and 2, and a molar ratio of 9: 1 in Production Examples 3 to 5. An unsaturated polyester resin was synthesized by reacting with the diols shown in Table 1.
　すなわち、製造例１～２では、不飽和ジカルボン酸と脂環式ジオールとが縮合した構成単位を含む不飽和ポリエステル樹脂を合成し、製造例３～５では、不飽和ジカルボン酸と脂肪族ジオールとが縮合した構成単位を含む不飽和ポリエステル樹脂を合成した。 That is, in Production Examples 1 and 2, an unsaturated polyester resin containing a structural unit obtained by condensing an unsaturated dicarboxylic acid and an alicyclic diol was synthesized, and in Production Examples 3 to 5, an unsaturated dicarboxylic acid and an aliphatic diol were used. An unsaturated polyester resin containing a condensed constituent unit was synthesized.
　そして、製造例１～５で得られたいずれの不飽和ポリエステル樹脂においても、不飽和ジカルボン酸とジオールとが縮合した構成単位と、飽和カルボン酸とジオールとが縮合した構成単位とを含む。 Then, each of the unsaturated polyester resins obtained in Production Examples 1 to 5 contains a structural unit in which an unsaturated dicarboxylic acid and a diol are condensed, and a structural unit in which a saturated carboxylic acid and a diol are condensed.
　＜溶剤への溶解性評価＞
　製造例１～５で得られた不飽和ポリエステルについて、常温における溶剤への溶解性について評価した。 <Evaluation of solubility in solvent>
The unsaturated polyesters obtained in Production Examples 1 to 5 were evaluated for their solubility in a solvent at room temperature.
　溶剤として、メチルエチルケトン、トルエン、酢酸エチル、メタノール、エタノール、及びイソプロピルアルコールを準備し、常温にて、これらのいずれかに溶解したものを○、いずれにも溶解しなかったものを×とした。結果を表１に示す。 Methyl ethyl ketone, toluene, ethyl acetate, methanol, ethanol, and isopropyl alcohol were prepared as solvents, and those dissolved in any of these at room temperature were marked with ◯, and those not dissolved in any of them were marked with x. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　＜考察＞
　不飽和ジカルボン酸として、ｃｉｓ体である無水マレイン酸を使用した製造例３で得られた不飽和ポリエステルＣは、ｔｒａｎｓ体であるフマル酸を使用した製造例４で得られた不飽和ポリエステルＤと異なり、溶剤に溶解した。これは、ｔｒａｎｓ体であるフマル酸由来の構成単位を含む不飽和ポリエステルは、分子鎖が密になりすぎるため、溶媒への溶解性がなかったものと考えられる。 <Discussion>
The unsaturated polyester C obtained in Production Example 3 using maleic anhydride, which is a cis form, as the unsaturated dicarboxylic acid is the same as the unsaturated polyester D obtained in Production Example 4 using fumaric acid, which is a solvent form. Unlike, it was dissolved in a solvent. It is probable that the unsaturated polyester containing the structural unit derived from fumaric acid, which is a trans form, had no solubility in the solvent because the molecular chain became too dense.
　また、不飽和ジカルボン酸として、３ｏｒ４－メチル－１，２，３，６－テトラヒドロ無水フタル酸を使用した製造例５で得られた不飽和ポリエステルＥは、ジカルボン酸由来の構成単位が環を有することから、分子鎖が密にならず、このため溶媒への溶解性を示したと考えられる。 Further, the unsaturated polyester E obtained in Production Example 5 using 3or4-methyl-1,2,3,6-tetrahydrophthalic anhydride as the unsaturated dicarboxylic acid has a ring as a constituent unit derived from the dicarboxylic acid. From this, it is considered that the molecular chains did not become dense and therefore showed solubility in the solvent.
　更に、不飽和ジカルボン酸として、ｔｒａｎｓ体であるフマル酸を使用した製造例１及び２で得られた不飽和ポリエステルＡ及びＢは、ジカルボン酸由来の構成単位を有していても、脂環式ジオールであるトリシクロデカンジメタノール由来の構成単位を有することから、分子鎖が密にならず、このため溶媒への溶解性を示したと考えられる。 Further, the unsaturated polyesters A and B obtained in Production Examples 1 and 2 using fumaric acid as a trans form as the unsaturated dicarboxylic acid have an alicyclic type even if they have a structural unit derived from the dicarboxylic acid. Since it has a structural unit derived from tricyclodecanedimethanol, which is a diol, it is considered that the molecular chain did not become dense, and therefore it showed solubility in a solvent.
　《実施例１～２９、比較例１～３》
　＜組成物の作製＞
　それぞれ製造例１、２、３、及び５で得られた、不飽和ポリエステルＡ、Ｂ、Ｃ、及びＥを用いて、これらを含む組成物を作製した。なお、不飽和ポリエステルＡ及びＢは、不飽和ジカルボン酸と脂環式ジオールとが縮合した構成単位を含み、他方で不飽和ポリエステルＣ及びＤは、不飽和ジカルボン酸と直鎖状脂肪族ジオールとが縮合した構成単位を含む。 << Examples 1 to 29, Comparative Examples 1 to 3 >>
<Preparation of composition>
Using unsaturated polyesters A, B, C, and E obtained in Production Examples 1, 2, 3, and 5, respectively, a composition containing these was prepared. The unsaturated polyesters A and B contain a structural unit obtained by condensing an unsaturated dicarboxylic acid and an alicyclic diol, while the unsaturated polyesters C and D contain an unsaturated dicarboxylic acid and a linear aliphatic diol. Contains building blocks condensed with.
　（組成物の成分）
　組成物に配合した各種成分を以下に示す。 (Ingredients of composition)
The various components blended in the composition are shown below.
　１．不飽和ポリエステル
　　　・製造例１で得られた不飽和ポリエステルＡ
　　　・製造例２で得られた不飽和ポリエステルＢ
　　　・製造例３で得られた不飽和ポリエステルＣ
　　　・製造例５で得られた不飽和ポリエステルＥ 1. 1. Unsaturated polyester-Unsaturated polyester A obtained in Production Example 1
-Unsaturated polyester B obtained in Production Example 2
-Unsaturated polyester C obtained in Production Example 3
-Unsaturated polyester E obtained in Production Example 5
　２．飽和ポリエステル
　　　・ポリエステル系ポリオール（タケラック（登録商標）Ａ－５２５Ｓ、三井化学株式会社） 2. 2. Saturated polyester / polyester-based polyol (Takelac (registered trademark) A-525S, Mitsui Chemicals, Inc.)
　３．硬化剤
　　　・イソシアネート化合物（タケネート（登録商標）Ａ－５０、三井化学株式会社） 3. 3. Curing agent-Isocyanate compound (Takenate (registered trademark) A-50, Mitsui Chemicals, Inc.)
　４．触媒
　　　・ステアリン酸コバルト（II）
　　　・ステアリン酸亜鉛（II）
　　　・ステアリン酸鉄（III）
　　　・オクチル酸亜鉛 4. Catalyst ・ Cobalt stearate (II)
・ Zinc stearate (II)
・ Iron stearate (III)
・ Zinc octylate
　５．酸化防止剤
　　　・トリフェニルホスファイト（ＪＰ－３６０　城北化学工業株式会社）
　　　・イルガノックス１０１０（ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、ＢＡＳＦ社） 5. Antioxidant ・ Triphenylphosphine (JP-360 Johoku Chemical Industry Co., Ltd.)
Irganox 1010 (Pentaerythritol Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], BASF)
　（操作）
　各実施例、及び比較例において、表２～５に示される、不飽和ポリエステル、及び飽和ポリエステルを、それぞれの表に示される固形分質量比となるように準備した。続いて、不飽和ポリエステルと飽和ポリエステルの合計固形分質量１００質量部に対して、表２～５に示される配合量となるようにそれぞれ硬化剤を混合した。 (operation)
In each Example and Comparative Example, the unsaturated polyester and the saturated polyester shown in Tables 2 to 5 were prepared so as to have the solid content mass ratio shown in each table. Subsequently, a curing agent was mixed with 100 parts by mass of the total solid content of the unsaturated polyester and the saturated polyester so as to have the blending amounts shown in Tables 2 to 5.
　更に、各実施例、及び比較例において、それぞれ表２～５に示される触媒を、組成物の全固形分質量に対する、コバルト、鉄、又は亜鉛の質量換算で８０ｐｐｍ添加し、続いて、酢酸エチルを添加して、固形分３３質量％となる酢酸エチル溶液である組成物を調製した。 Further, in each Example and Comparative Example, 80 ppm of the catalyst shown in Tables 2 to 5 was added in terms of the mass of cobalt, iron, or zinc with respect to the total solid content mass of the composition, followed by ethyl acetate. Was added to prepare a composition which is an ethyl acetate solution having a solid content of 33% by mass.
　更に、実施例２８及び２９において、表５に示される酸化防止剤を２００ｐｐｍ配合し、組成物を調製した。 Further, in Examples 28 and 29, 200 ppm of the antioxidant shown in Table 5 was blended to prepare a composition.
　＜積層体の作製＞
　実施例１～２６、及び比較例１～３で得られた酢酸エチル溶液である組成物を、厚み１２μｍのシリカ蒸着ＰＥＴフィルム（テックバリア（登録商標）Ｌ、三菱ケミカル株式会社）に、塗布量が５ｇ／ｍ２となるように塗工し、厚み３０μｍのＬＬＤＰＥフィルム（ＳＥ６２０Ｎ、タマポリ株式会社）と貼り合わせることで、積層体を作製した。また、実施例２７～２９で得られた酢酸エチル溶液である組成物を、厚み１２μｍのアルミナ蒸着ＰＥＴフィルム（バリアロックス（登録商標）１０１１ＳＢＲ２、東レフィルム加工株式会社）に、塗布量が５ｇ／ｍ２となるように塗工し、厚み２０μｍのＣＰＰフィルム（パイレン（登録商標）フィルム－ＣＴ　Ｐ１１２８、東洋紡株式会社）と貼り合わせることで、積層体を作製した。 <Manufacturing of laminated body>
Amount of the composition which is the ethyl acetate solution obtained in Examples 1 to 26 and Comparative Examples 1 to 3 applied to a silica-deposited PET film (Tech Barrier (registered trademark) L, Mitsubishi Chemical Co., Ltd.) having a thickness of 12 μm. A laminate was prepared by coating the film so as to have a thickness of 5 g / m 2 and laminating it with an LLDPE film (SE620N, Tamapoli Co., Ltd.) having a thickness of 30 μm. Further, the composition of the ethyl acetate solution obtained in Examples 27 to 29 was applied to an alumina-deposited PET film having a thickness of 12 μm (Barrierlocks (registered trademark) 1011SBR2, Toray Film Processing Co., Ltd.) in an amount of 5 g / m. A laminated body was prepared by coating the film so as to have a thickness of 2 and laminating it with a CPP film having a thickness of 20 μm (Pyrene (registered trademark) film-CT P1128, Toyobo Co., Ltd.).
　＜酸素吸収量の測定＞
　得られた積層体を１０ｃｍ×１０ｃｍ（１００ｃｍ２）にカットし、４３ｍＬの密閉容器に空気とともに封入し、２３℃で７日間保管した。７日後の容器内の酸素濃度を、非破壊酸素濃度計（Ｆｉｂｏｘ３、ＰｒｅＳｅｎｓ社）を用いて測定し、得られた酸素濃度と大気中の酸素濃度とから、積層体の面積当りの酸素吸収量（ｍＬ／ｍ２）を算出した。結果を表２及び表３に示す。 <Measurement of oxygen absorption>
The obtained laminate was cut into 10 cm × 10 cm (100 cm 2 ), sealed with air in a 43 mL airtight container, and stored at 23 ° C. for 7 days. The oxygen concentration in the container after 7 days was measured using a non-destructive oxygen concentration meter (Fibox3, PreSens), and the oxygen absorption amount per area of the laminate was obtained from the obtained oxygen concentration and the oxygen concentration in the atmosphere. (ML / m 2 ) was calculated. The results are shown in Tables 2 and 3.
　＜溶出テスト＞
　得られた積層体１０ｃｍ×１０ｃｍ×２枚を、ＬＬＤＰＥ面又はＣＰＰ面を向かい合わせて３辺を幅１０ｍｍでシールして、三方シール袋を作製した。続いて、三方シール袋に水２１．３ｇ入れて、幅１０ｍｍでトップシールし、四方シール袋とした。 <Elution test>
The obtained laminated body 10 cm × 10 cm × 2 sheets was sealed with the LLDPE surface or the CPP surface facing each other with a width of 10 mm on three sides to prepare a three-way seal bag. Subsequently, 21.3 g of water was put in a three-way seal bag and top-sealed with a width of 10 mm to form a four-way seal bag.
　作製した四方シール袋を７０℃で２４時間保管した後、袋内の溶出液について、紫外・可視・近赤外分光光度計（型式：ＵＨ４１５０、株式会社日立ハイテクサイエンス）で測定し、２２０ｎｍの吸光度を確認した。結果を表３に示す。吸光度０．１５未満であれば溶出が少ないと言える。 After storing the prepared four-sided seal bag at 70 ° C for 24 hours, the eluate in the bag was measured with an ultraviolet / visible / near-infrared spectrophotometer (model: UH4150, Hitachi High-Tech Science Corporation) and had an absorbance at 220 nm. It was confirmed. The results are shown in Table 3. If the absorbance is less than 0.15, it can be said that the elution is small.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　＜考察＞
　比較例１より、不飽和ポリエステル樹脂を含まない接着剤は、酸素吸収性能を有していないことが判る。 <Discussion>
From Comparative Example 1, it can be seen that the adhesive containing no unsaturated polyester resin does not have oxygen absorption performance.
　また、比較例２及び３より、脂環式ジオール由来の構成単位を含まない、製造例３で得られた不飽和ポリエステルＣ、及び製造例５で得られた不飽和ポリエステルＥは、酸素吸収性能が低いことが判る。 Further, from Comparative Examples 2 and 3, the unsaturated polyester C obtained in Production Example 3 and the unsaturated polyester E obtained in Production Example 5, which do not contain a structural unit derived from an alicyclic diol, have oxygen absorption performance. It turns out that is low.
　一方で、脂環式ジオール由来の構成単位を含む、製造例１で得られた不飽和ポリエステルＡ、及び製造例２で得られた不飽和ポリエステルＢは、比較例２及び３と比較して、高い酸素吸収性能を示した。これは、脂環式ジオール由来の構造による立体障害により分子間に空間ができ、当該空間を通して酸素が入り込みやすいためだと考えられる。 On the other hand, the unsaturated polyester A obtained in Production Example 1 and the unsaturated polyester B obtained in Production Example 2, which contain a structural unit derived from an alicyclic diol, were compared with Comparative Examples 2 and 3. It showed high oxygen absorption performance. It is considered that this is because a space is created between molecules due to steric hindrance due to the structure derived from the alicyclic diol, and oxygen easily enters through the space.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　＜考察＞
　実施例１８～２７と実施例１４との比較より、不飽和ポリエステル１００質量部に対して硬化剤を５０質量部以上添加すると、溶出液の吸光度が０．１５未満となることが判る。これは、残留していたポリエステル樹脂原料であるジカルボン酸モノマーのカルボキシル基と、硬化剤のイソシアネート基とが反応してアミド結合となること、残留していたポリエステル樹脂原料であるジオールモノマーの水酸基と、硬化剤のイソシアネート基とが反応してウレタン結合となること等によって、ポリエステル樹脂組成物からの低分子成分の溶出が低減したためと考えられる。 <Discussion>
From the comparison between Examples 18 to 27 and Example 14, it can be seen that when 50 parts by mass or more of the curing agent is added to 100 parts by mass of the unsaturated polyester, the absorbance of the eluate becomes less than 0.15. This is because the carboxyl group of the dicarboxylic acid monomer, which is the remaining polyester resin raw material, reacts with the isocyanate group of the curing agent to form an amide bond, and the hydroxyl group of the diol monomer, which is the remaining polyester resin raw material. It is considered that the elution of low molecular weight components from the polyester resin composition was reduced by reacting with the isocyanate group of the curing agent to form a urethane bond.
　＜剥離強度の測定＞
　実施例１、３～６、１４、１８～２０、及び比較例１で作製した組成物の接着性を評価するため、組成物を用いて作製した積層体について、シリカ蒸着ＰＥＴフィルム層とＬＬＤＰＥフィルム層との間の剥離強度の測定を行った。 <Measurement of peel strength>
In order to evaluate the adhesiveness of the compositions prepared in Examples 1, 3 to 6, 14, 18 to 20, and Comparative Example 1, the silica-deposited PET film layer and the LLDPE film were used for the laminate prepared using the composition. The peel strength between the layers was measured.
　測定にあたっては、ＪＩＳ　Ｋ　６８５４－３に従って、Ｔ型剥離試験を実施した。各積層体から、幅１５ｍｍ、長さ２００ｍｍ（非接着部５０ｍｍを含む）の試験片を切り出し、ストログラフＶＧＳ０５－Ｅ（東洋精機（株）製）を用いて、２３℃５０％ＲＨの雰囲気下にて、剥離速度３００ｍｍ／ｍｉｎにて剥離強度を測定した。結果を表３に示す。なお、剥離ができたものを「剥離」、測定中に試料が破壊したものを、「破壊」と表示する。 In the measurement, a T-type peeling test was carried out according to JIS K 6854-3. A test piece having a width of 15 mm and a length of 200 mm (including a non-adhesive portion of 50 mm) was cut out from each laminate, and was used in a strograph VGS05-E (manufactured by Toyo Seiki Co., Ltd.) under an atmosphere of 23 ° C. and 50% RH. The peel strength was measured at a peeling speed of 300 mm / min. The results are shown in Table 3. In addition, the one that can be peeled off is referred to as "peeling", and the one that the sample is destroyed during the measurement is indicated as "destruction".
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　＜考察＞
　実施例１と実施例３～６との比較より、不飽和ポリエステルに飽和ポリエステルが配合された組成物である実施例３～６は、ポリエステル成分が不飽和ポリエステルのみで構成される実施例１と比較して、接着強度が向上していることが判る。 <Discussion>
From the comparison between Examples 1 and Examples 3 to 6, Examples 3 to 6, which are compositions in which saturated polyester is blended with unsaturated polyester, are the same as Example 1 in which the polyester component is composed only of unsaturated polyester. In comparison, it can be seen that the adhesive strength is improved.
　実施例１４と実施例１８～２０との比較より、ポリエステル成分が不飽和ポリエステルのみで構成される場合であっても、硬化剤の配合量を増加させることで、接着強度が向上していることが判る。 From the comparison between Examples 14 and 18 to 20, even when the polyester component is composed only of unsaturated polyester, the adhesive strength is improved by increasing the blending amount of the curing agent. I understand.
　＜保管期間（日）と酸素吸収量の測定＞
　酸化防止剤を配合した実施例２８及び２９のサンプルについて、それぞれ表５に示す保管期間（日）に対する酸素吸収量を、実施例１等の場合と同様にして測定した。結果を表５に示す。 <Measurement of storage period (days) and oxygen absorption>
For the samples of Examples 28 and 29 containing the antioxidant, the amount of oxygen absorbed for the storage period (days) shown in Table 5 was measured in the same manner as in Example 1 and the like. The results are shown in Table 5.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　＜考察＞
　実施例２８及び２９と実施例２７との比較より、酸化防止剤を配合した実施例２８及び２９は、酸化防止剤を配合していない実施例２７と比較して、経時による酸素吸収性能の低下が抑制できていることが分かる。 <Discussion>
From the comparison between Examples 28 and 29 and Example 27, the oxygen absorption performance of Examples 28 and 29 containing the antioxidant was deteriorated with time as compared with Example 27 not containing the antioxidant. Can be seen to be suppressed.

Claims (18)

  1. 　不飽和ジカルボン酸と脂環式ジオールとが縮合した構成単位を含む、酸素吸収用不飽和ポリエステル樹脂。 An unsaturated polyester resin for oxygen absorption that contains a structural unit in which an unsaturated dicarboxylic acid and an alicyclic diol are condensed.
  2. 　更に、飽和カルボン酸と脂環式ジオールとが縮合した構成単位を含む、請求項１に記載の酸素吸収用不飽和ポリエステル樹脂。 The unsaturated polyester resin for oxygen absorption according to claim 1, further comprising a structural unit obtained by condensing a saturated carboxylic acid and an alicyclic diol.
  3. 　請求項１又は２に記載の酸素吸収用不飽和ポリエステル樹脂を含む酸素吸収用フィルム。 An oxygen absorption film containing the unsaturated polyester resin for oxygen absorption according to claim 1 or 2.
  4. 　請求項１又は２に記載の酸素吸収用不飽和ポリエステル樹脂を含む、酸素吸収用組成物。 An oxygen absorbing composition comprising the unsaturated polyester resin for oxygen absorption according to claim 1 or 2.
  5. 　触媒を含む、請求項４に記載の酸素吸収用組成物。 The oxygen absorbing composition according to claim 4, which comprises a catalyst.
  6. 　硬化剤を含む、請求項４又は５に記載の酸素吸収用組成物。 The oxygen absorbing composition according to claim 4 or 5, which comprises a curing agent.
  7. 　前記硬化剤の配合量が、前記酸素吸収用不飽和ポリエステル樹脂１００質量部に対して、５０質量部以上１０００質量部以下である、請求項６に記載の酸素吸収用組成物。  The oxygen absorbing composition according to claim 6, wherein the blending amount of the curing agent is 50 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the unsaturated polyester resin for oxygen absorption. The
  8. 　酸化防止剤を含む、請求項４～７のいずれか一項に記載の酸素吸収用組成物。 The oxygen absorbing composition according to any one of claims 4 to 7, which contains an antioxidant.
  9. 　前記酸化防止剤は、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、及びトリフェニルホスファイトの少なくともいずれかである、請求項８に記載の酸素吸収用組成物。 The oxygen according to claim 8, wherein the antioxidant is at least one of pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and triphenylphosphine. Composition for absorption.
  10. 　飽和ポリエステルを含む、請求項４～９のいずれか１項に記載の酸素吸収用組成物。 The oxygen absorbing composition according to any one of claims 4 to 9, which comprises saturated polyester.
  11. 　請求項４～１０のいずれか１項に記載の酸素吸収用組成物を含む酸素吸収用フィルム。 An oxygen absorbing film containing the oxygen absorbing composition according to any one of claims 4 to 10.
  12. 　請求項４～１０のいずれか１項に記載の酸素吸収用組成物からなる酸素吸収用接着剤。 An oxygen absorbing adhesive comprising the oxygen absorbing composition according to any one of claims 4 to 10.
  13. 　請求項１２に記載の酸素吸収用接着剤を含む酸素吸収用接着剤フィルム。 An oxygen absorbing adhesive film containing the oxygen absorbing adhesive according to claim 12.
  14. 　請求項４～１０のいずれか１項に記載の酸素吸収用組成物からなる酸素吸収用組成物層を備える、酸素吸収用積層体。 An oxygen absorption laminate comprising an oxygen absorption composition layer comprising the oxygen absorption composition according to any one of claims 4 to 10.
  15. 　請求項１２に記載の酸素吸収用接着剤からなる酸素吸収用接着剤層を備える、酸素吸収用積層体。 An oxygen absorbing laminate comprising the oxygen absorbing adhesive layer comprising the oxygen absorbing adhesive according to claim 12.
  16. 　酸素バリア層と、前記酸素吸収用組成物層と、ヒートシール層とが、この順で積層された、請求項１４に記載の酸素吸収用積層体。 The oxygen absorption laminate according to claim 14, wherein the oxygen barrier layer, the oxygen absorption composition layer, and the heat seal layer are laminated in this order.
  17. 　酸素バリア層と、前記酸素吸収用接着剤層と、ヒートシール層とが、この順で積層された、請求項１１５に記載の酸素吸収用積層体。 The oxygen absorption laminate according to claim 115, wherein the oxygen barrier layer, the oxygen absorption adhesive layer, and the heat seal layer are laminated in this order.
  18. 　請求項３又は１１に記載の酸素吸収用フィルム、請求項１３に記載の酸素吸収用接着剤フィルム、及び請求項１４～１７に記載の酸素吸収用積層体からなる群より選ばれるいずれかを備える包装材 It comprises any one selected from the group consisting of the oxygen absorption film according to claim 3 or 11, the oxygen absorption adhesive film according to claim 13, and the oxygen absorption laminate according to claims 14 to 17. Packaging material
PCT/JP2021/041782 2020-11-13 2021-11-12 Oxygen-absorbing unsaturated polyester resin, oxygen-absorbing composition including same, oxygen-absorbing adhesive, oxygen-absorbing laminate using oxygen-absorbing composition, and oxygen-absorbing film WO2022102755A1 (en)

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JP2020189805A JP2022078855A (en) 2020-11-13 2020-11-13 Unsaturated polyester resin for oxygen absorption, composition for oxygen absorption and adhesive for oxygen absorption containing the resin, and laminate for oxygen absorption and film for oxygen absorption using composition for oxygen absorption
JP2021118299A JP2023013856A (en) 2021-07-16 2021-07-16 Polyester resin composition, adhesive, film, laminate, and packaging material
JP2021-118299 2021-07-16
JP2021124329A JP2023019543A (en) 2021-07-29 2021-07-29 Oxygen-absorbing unsaturated polyester resin composition, oxygen-absorbing adhesive, oxygen-absorbing film, oxygen-absorbing laminate, and packaging material
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5655417A (en) * 1979-10-12 1981-05-16 Mitsubishi Petrochem Co Ltd Unsaturated polyester resin composition for coating basic inorganic decorative sheet
JPH05247194A (en) * 1992-03-04 1993-09-24 Showa Highpolymer Co Ltd Production of high molecular weight unsaturated polyester
JP2010260886A (en) * 2009-04-30 2010-11-18 Mitsubishi Rayon Co Ltd Method for producing cross-linked polyester resin
WO2015046359A1 (en) * 2013-09-27 2015-04-02 Dic株式会社 Moisture barrier resin composition, adhesive, and coating agent
JP2015067836A (en) * 2013-09-27 2015-04-13 エボニック インダストリーズ アクチエンゲゼルシャフトＥｖｏｎｉｋ Ｉｎｄｕｓｔｒｉｅｓ ＡＧ Liquid additive for improving adhesion and production method thereof
JP2020121453A (en) * 2019-01-30 2020-08-13 スタープラスチック工業株式会社 Laminated film, package, and method for producing laminated film

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5655417A (en) * 1979-10-12 1981-05-16 Mitsubishi Petrochem Co Ltd Unsaturated polyester resin composition for coating basic inorganic decorative sheet
JPH05247194A (en) * 1992-03-04 1993-09-24 Showa Highpolymer Co Ltd Production of high molecular weight unsaturated polyester
JP2010260886A (en) * 2009-04-30 2010-11-18 Mitsubishi Rayon Co Ltd Method for producing cross-linked polyester resin
WO2015046359A1 (en) * 2013-09-27 2015-04-02 Dic株式会社 Moisture barrier resin composition, adhesive, and coating agent
JP2015067836A (en) * 2013-09-27 2015-04-13 エボニック インダストリーズ アクチエンゲゼルシャフトＥｖｏｎｉｋ Ｉｎｄｕｓｔｒｉｅｓ ＡＧ Liquid additive for improving adhesion and production method thereof
JP2020121453A (en) * 2019-01-30 2020-08-13 スタープラスチック工業株式会社 Laminated film, package, and method for producing laminated film

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