WO2019203131A1 - 不飽和二重結合含有化合物、それを用いた酸素吸収剤、及び樹脂組成物 - Google Patents
不飽和二重結合含有化合物、それを用いた酸素吸収剤、及び樹脂組成物 Download PDFInfo
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- WO2019203131A1 WO2019203131A1 PCT/JP2019/015850 JP2019015850W WO2019203131A1 WO 2019203131 A1 WO2019203131 A1 WO 2019203131A1 JP 2019015850 W JP2019015850 W JP 2019015850W WO 2019203131 A1 WO2019203131 A1 WO 2019203131A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
- C07C43/1785—Unsaturated ethers containing hydroxy or O-metal groups having more than one ether bound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/44—Materials comprising a mixture of organic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/012—Additives improving oxygen scavenging properties
Definitions
- the present invention relates to a specific unsaturated double bond-containing compound, an oxygen absorbent using the compound, and a resin composition.
- Radical polymerizable resins such as unsaturated polyester resins used for paints and the like have an unsaturated bond in the polymer main chain, and are crosslinked and cured by a vinyl crosslinking agent.
- these radically polymerizable resins are used for coatings, there is a problem that they are usually hindered by oxygen in the air because they are cross-linked in an air atmosphere, the curing becomes slow, and the surface becomes sticky.
- Patent Documents 1 and 2 propose a technique of adding an oxygen absorbent to a resin. Further, as the oxygen absorbent, Patent Documents 3 and 4 describe allyl glycidyl ether and the like.
- the present invention has been made in view of the above-described conventional problems, and an unsaturated double bond-containing compound having an oxygen absorption capability capable of sufficiently proceeding a crosslinking reaction or a curing reaction when used in a paint or the like.
- the purpose is to provide. Moreover, it aims at providing the oxygen absorber containing this unsaturated double bond containing compound, and the resin composition containing this.
- the inventors of the present invention can stabilize the generated radical more than the conventional oxygen absorbent according to the unsaturated double bond-containing compound represented by the following general formula (I). As a result, it was found that the oxygen radical scavenging performance was higher, that is, the oxygen absorption performance, and the present invention was completed through further studies based on the findings.
- X and Y each independently represent a chalcogen atom
- R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms
- aryl Each of R 3 and R 4 is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group.
- J represents a linking group comprising an aliphatic hydrocarbon having 3 to 15 carbon atoms, and the linking group may have an arbitrary carbon atom substituted with an oxygen atom, a (meth) acryloyloxy group, a styryloxy group, and It may have as a substituent at least one selected from the group consisting of alkenyloxy groups having 2 to 5 carbon atoms.
- n is an arbitrary integer of 1 to 5. However, when a plurality of Y are present, they may be different atoms.
- [2] The unsaturated double bond-containing compound according to [1], wherein X and Y in the general formula (I) are oxygen atoms.
- R 5 represents a hydrogen atom or a methyl group
- R 6 represents any one of a hydroxyl group, a (meth) acryloyloxy group, a styryloxy group, and an alkenyloxy group having 2 to 5 carbon atoms. . ]
- [6] The unsaturated double bond-containing compound according to [5], wherein R 5 in the general formula (II) is a hydrogen atom.
- R 7 The unsaturated double bond-containing compound according to [5] or [6], wherein R 6 is a hydroxyl group in the general formula (II).
- An oxygen absorbent comprising the unsaturated double bond-containing compound according to any one of [1] to [7].
- the oxygen absorbent according to [8] which contains 0.001 to 10 mol% of a transition metal salt with respect to the vinyl group in the unsaturated double bond-containing compound.
- a resin composition comprising the oxygen absorbent according to [8] or [9] and a resin.
- an unsaturated double bond-containing compound having oxygen absorption ability that can sufficiently cause a crosslinking reaction and a curing reaction to proceed when used in paints and the like.
- the oxygen absorber containing this unsaturated double bond containing compound and the resin composition containing this can be provided.
- the unsaturated double bond-containing compound of the present invention is a compound represented by the following general formula (I).
- X and Y each independently represent a chalcogen atom
- R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms
- aryl Each of R 3 and R 4 is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group.
- J represents a linking group comprising an aliphatic hydrocarbon having 3 to 15 carbon atoms, and the linking group may have an arbitrary carbon atom substituted with an oxygen atom, a (meth) acryloyloxy group, a styryloxy group, and It may have as a substituent at least one selected from the group consisting of alkenyloxy groups having 2 to 5 carbon atoms.
- n is an arbitrary integer of 1 to 5. However, when a plurality of Y are present, they may be different atoms.
- X and Y each independently represent a chalcogen atom.
- X and Y are each preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom, from the viewpoint of ease of production of the unsaturated double bond-containing compound and from the viewpoint of improving oxygen absorption performance.
- R 1 and R 2 each independently represents any of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, and an aralkyl group.
- alkyl group having 1 to 6 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include isopentyl group, neopentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
- alkenyl group having 2 to 6 carbon atoms examples include vinyl, allyl, 1-propenyl, 2-propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, cis-3-hexenyl. Group, a cyclohexenyl group, and the like.
- aryl group examples include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
- aralkyl group examples include a benzyl group, a 2-phenylethyl group, a 2-naphthylethyl group, and a diphenylmethyl group.
- R 1 and R 2 are each independently preferably any one of an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. Is more preferable, and a methyl group is still more preferable.
- R 3 and R 4 in the general formula (I) each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group.
- alkyl group having 1 to 6 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include isopentyl group, neopentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
- alkenyl group having 2 to 6 carbon atoms examples include vinyl, allyl, 1-propenyl, 2-propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, cis-3-hexenyl. Group, a cyclohexenyl group, and the like.
- aryl group examples include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
- aralkyl group examples include a benzyl group, a 2-phenylethyl group, a 2-naphthylethyl group, and a diphenylmethyl group.
- R 3 and R 4 are preferably each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, or an aryl group, A methyl group is more preferable, and a hydrogen atom is still more preferable.
- R 3 is preferably a hydrogen atom
- R 4 is preferably a hydrogen atom or a methyl group, both of which are hydrogen atoms. Is more preferable.
- J represents a linking group composed of an aliphatic hydrocarbon having 3 to 15 carbon atoms, and the linking group may have any carbon atom substituted with an oxygen atom, and (meth) acryloyloxy
- the substituent may have at least one selected from the group consisting of a group, a styryloxy group, and an alkenyloxy group having 2 to 5 carbon atoms.
- the linking group an aliphatic hydrocarbon group having 3 to 10 carbon atoms is preferable, and an aliphatic hydrocarbon group having 3 to 5 carbon atoms is more preferable, from the viewpoint of easy handling of the unsaturated double bond-containing compound. .
- the linking group may have as a substituent at least one selected from the group consisting of a (meth) acryloyloxy group, a styryloxy group, and an alkenyloxy group having 2 to 5 carbon atoms.
- the styryloxy group include a 4-vinylphenoxy group.
- the alkenyloxy group having 2 to 5 carbon atoms may be a vinyloxy group having 2 to 5 carbon atoms.
- the substituent that the linking group has is preferably a (meth) acryloyloxy group from the viewpoint of improving the oxygen absorption performance of the unsaturated double bond-containing compound.
- linking group examples include, for example, a linking group having any structure represented by the following general formula (J-1). From the viewpoint of availability of raw materials, the following general formula (J -2) is preferred, and from the viewpoint of improving the oxygen absorption performance of the unsaturated double bond-containing compound, a linking group represented by the following general formula (J-3) is more preferred.
- “*” represents a bonding point with X to Y.
- R 5 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
- R 7 represents any of a (meth) acryloyloxy group, a styryloxy group, and an alkenyloxy group having 2 to 5 carbon atoms, preferably a (meth) acryloyloxy group.
- the alkenyloxy group having 2 to 5 carbon atoms may be a vinyloxy group having 2 to 5 carbon atoms.
- n is an arbitrary integer of 1 to 5, preferably 1 to 4, more preferably 1 or 2, from the viewpoint of availability of raw materials.
- the unsaturated double bond-containing compound represented by the general formula (I) include, for example, the following compounds. From the viewpoint of oxygen absorption performance, the unsaturated compound represented by the following general formula (II) A compound containing a double bond is preferred.
- R 5 represents a hydrogen atom or a methyl group
- R 6 represents any one of a hydroxyl group, a (meth) acryloyloxy group, a styryloxy group, and an alkenyloxy group having 2 to 5 carbon atoms. . ]
- R 5 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
- R 6 represents any one of a hydroxyl group, a (meth) acryloyloxy group, a styryloxy group, and an alkenyloxy group having 2 to 5 carbon atoms, preferably a hydroxyl group or a (meth) acryloyloxy group.
- the alkenyloxy group having 2 to 5 carbon atoms may be a vinyloxy group having 2 to 5 carbon atoms.
- the method for producing the unsaturated double bond-containing compound of the present invention is not particularly limited, and can be produced by applying known methods alone or in combination.
- an unsaturated double bond-containing compound represented by the following formula (A-1) is produced, 1- (3-methyl-2-butenoxy) which is a corresponding epoxy compound in the presence of an acid catalyst such as sulfuric acid. It can be produced by allowing water to act on -2,3-epoxypropane to open the ring.
- stirring is preferably performed at a temperature of about 25 to 70 ° C. for about 30 minutes to 10 hours.
- the oxygen absorbent of the present invention contains an unsaturated double bond-containing compound represented by the general formula (I). As described above, since the unsaturated double bond-containing compound of the present invention is excellent in oxygen absorption performance, when an oxygen absorbent containing the compound is used in paints, the crosslinking reaction and the curing reaction can be sufficiently advanced.
- the oxygen absorbent of the present invention has sufficient oxygen absorption performance because it contains the unsaturated double bond-containing compound of the present invention, but may further contain a transition metal salt in order to further improve the oxygen absorption performance.
- the transition metal constituting the transition metal salt include transition metal elements of the fourth period such as titanium, vanadium, chromium, manganese, iron, cobalt, nickel and copper, and fifth period of the ruthenium, rhodium and the like.
- a transition metal element is mentioned.
- the transition metal element in the fourth period is preferable, manganese, iron, cobalt, nickel, and copper are more preferable, and cobalt is more preferable.
- the counter ion of the transition metal in the transition metal salt is preferably an anion species derived from an organic acid from the viewpoint of compatibility.
- the organic acid has a cyclic structure or substituent, whether saturated or unsaturated, linear or branched.
- An organic acid having 2 to 30 carbon atoms which may be present is preferable, for example, acetic acid, stearic acid, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, oleic acid, capric acid, And naphthenic acid.
- transition metal salt used in the present invention any combination of the transition metal and the counter ion can be used. From the viewpoint of balance between production cost and oxygen absorption performance, cobalt 2-ethylhexanoate, Cobalt neodecanoate and cobalt stearate are preferred.
- the oxygen absorbent contains a transition metal salt
- the content thereof is preferably 0.001 to 10 mol%, more preferably 0.005 to 5 mol%, based on the vinyl group in the unsaturated double bond-containing compound. 0.01 to 1 mol% is more preferable, and 0.1 to 1 mol% is still more preferable.
- the content of the transition metal salt is within the above range, sufficient oxygen absorption performance can be imparted to the oxygen absorbent.
- the oxygen absorbent of the present invention may contain various additives in addition to the unsaturated double bond-containing compound represented by the general formula (I) and the transition metal salt as long as the effects of the present invention are not impaired. Specifically, fillers, UV absorbers, pigments, thickeners, low shrinkage agents, anti-aging agents, plasticizers, aggregates, flame retardants, stabilizers, fiber reinforcements, dyes, antioxidants, leveling An agent, an anti-sagging agent, and the like may be included.
- the oxygen absorbent of the present invention exhibits excellent oxygen absorption performance even at room temperature.
- the oxygen absorption amount at 20 ° C. when the oxygen absorbent of the present invention contains a transition metal salt is preferably 4 mL / g or more, more preferably 5 mL / g or more as a value after 1 day. More preferably, it is 6 mL / g or more.
- the oxygen absorption amount at 60 ° C. when the oxygen absorbent of the present invention contains a transition metal salt is preferably 15 mL / g or more, more preferably 20 mL / g or more, as a value after 1 day. Preferably it is 25 mL / g or more.
- the oxygen absorption amount at 20 ° C. when the oxygen absorbent of the present invention does not contain a transition metal salt is preferably 0.2 mL / g or more, more preferably 0.4 mL / g, as a value after 5 days. Or more, more preferably 0.6 mL / g or more.
- the oxygen absorption amount at 60 ° C. when the oxygen absorbent of the present invention does not contain a transition metal salt is preferably 10 mL / g or more, more preferably 20 mL / g or more, as a value after 5 days. More preferably, it is 25 mL / g or more.
- oxygen absorption amount can be measured by the method as described in an Example.
- the oxygen absorbent of the present invention can be obtained by mixing the unsaturated double bond-containing compound represented by the general formula (I) with a transition metal salt and various additives as necessary. Specifically, the unsaturated double bond-containing compound represented by the general formula (I) and the transition metal salt can be obtained by stirring and mixing.
- the resin composition of the present invention contains the oxygen absorbent of the present invention and a resin. Since the unsaturated double bond-containing compound represented by the general formula (I) itself has a polymerizable group or a reactive group, even if it is added to the resin, it inhibits the crosslinking reaction or polymerization reaction of the resin. Hateful. Therefore, the resin composition of the present invention is excellent in that the yield of the crosslinking reaction or polymerization reaction of the resin is difficult to decrease even in the presence of oxygen.
- resin used for the resin composition of this invention is resin used for a coating material, an adhesive agent, a coating agent, etc., there will be no restriction
- the resin may be a radically polymerizable resin or an active energy ray curable resin such as a UV curable resin.
- the resin is preferably an active energy ray curable resin because the effects of the present invention are more remarkably exhibited, although depending on the application.
- the resin include, for example, a resin curable by radical polymerization reaction such as unsaturated polyester resin, vinyl ester resin, (meth) acrylic resin having a polymerizable group, and urethane (meth) acrylate resin;
- a resin curable by radical polymerization reaction such as unsaturated polyester resin, vinyl ester resin, (meth) acrylic resin having a polymerizable group, and urethane (meth) acrylate resin
- examples include polyvinyl alcohol, ethylene-vinyl acetate copolymer, partially or completely saponified ethylene-vinyl acetate copolymer, epoxy resin, polyester resin, polyolefin resin, cyclic polyolefin resin, and other resins that require oxygen barrier properties.
- a fluororesin, a polyamide resin such as polyamide 66, a polycarbonate resin, a polyurethane resin, or the like may be used as necessary.
- the unsaturated polyester resin examples include polyhydric alcohol compounds such as propylene glycol-phthalic anhydride-maleic anhydride copolymer, ethylene glycol-phthalic anhydride-maleic anhydride copolymer, and ⁇ , ⁇ -unsaturated polymers.
- polyhydric alcohol compounds such as propylene glycol-phthalic anhydride-maleic anhydride copolymer, ethylene glycol-phthalic anhydride-maleic anhydride copolymer, and ⁇ , ⁇ -unsaturated polymers.
- examples thereof include a copolymer with a basic acid compound and another polybasic acid compound, and a copolymer obtained by adding a radical polymerizable monomer such as styrene to the copolymer.
- polyhydric alcohol compound examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, hydrogenated bisphenol A, and hydrogenated bisphenol F.
- Examples of the ⁇ , ⁇ -unsaturated polybasic acid compound include maleic anhydride, maleic acid, fumaric acid, itaconic acid, and citraconic acid.
- Examples of the other polybasic acid compound include anhydrous anhydride. Examples include phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, het acid, adipic acid, and sebacic acid. These may be used alone or in combination of two or more.
- copolymers may further contain a glycidyl compound of an unsaturated alcohol such as allyl glycidyl ether as one of the copolymer components.
- a glycidyl compound of an unsaturated alcohol such as allyl glycidyl ether
- vinyl ester resin examples include those obtained by adding (meth) acrylic acid to the end of a bisphenol A type epoxy resin, and those obtained by adding (meth) acrylic acid to an epoxy resin.
- Examples of the urethane (meth) acrylate resin include those obtained by adding (meth) acrylic acid to an isocyanate group residual polymer synthesized from a polyhydric alcohol compound and an excess polyvalent isocyanate compound.
- the polyhydric alcohol compound can be the same as the polyhydric alcohol compound in the description of the unsaturated polyester resin.
- Examples of the polyhydric isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene. Diisocyanate etc. are mentioned.
- the content of the unsaturated double bond-containing compound represented by the general formula (I) in the resin composition of the present invention is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin.
- the amount is preferably 0.2 to 30 parts by mass, and more preferably 0.5 to 10 parts by mass.
- the resin composition of the present invention includes pigments, dyes, fillers, ultraviolet absorbers, thickeners, low shrinkage agents, anti-aging agents, plasticizers, aggregates, flame retardants, stabilizers, fiber reinforcements, and antioxidants.
- An agent, a leveling agent, an anti-sagging agent, and the like may be included as appropriate.
- the resin composition of the present invention may contain, for example, styrene, (meth) acrylic acid ester, etc. as a diluent, and the effect of the present invention is more effective when (meth) acrylic acid ester is included from the viewpoint of polymerizability. This is particularly preferable because it is remarkably played.
- the pigment include titanium oxide, bengara, aniline black, carbon black, cyanine blue, and chrome yellow.
- the filler include talc, mica, kaolin, calcium carbonate, and clay.
- the resin composition of the present invention can be obtained by mixing the resin and the oxygen absorbent of the present invention. Specifically, it can be obtained by mixing the oxygen absorbent of the present invention, a resin, and optional components as necessary by stirring or the like.
- the resin composition of the invention can be preferably used for applications such as paints, adhesives, and coating agents.
- the sample bottle was left in a constant temperature bath at 20 ° C., and the remaining oxygen amount in the sample bottle after 1 day, 5 days and 15 days was measured using a residual oxygen meter (manufactured by Iijima Electronics Co., Ltd .; Pack Master RO- 103).
- the amount of residual oxygen in a sample bottle prepared in the same manner except that no oxygen absorbent was added and left standing under the same conditions was measured in the same manner, and the difference in the amount of residual oxygen was determined as the amount of oxygen absorbed by the oxygen absorbent ( 20 ° C.) [mL / g]. The same test was performed three times and the average value was adopted.
- a reactor equipped with a stirrer, a thermometer, and a dropping funnel was charged with 50.6 g of 1M sulfuric acid aqueous solution under a nitrogen stream. While maintaining the internal temperature at 20 ° C. or lower, 30.1 g (0.212 mol) of 1- (3-methyl-2-butenoxy) -2,3-epoxypropane was added dropwise with stirring. The temperature was raised to. The mixture was stirred at an internal temperature of 40 ° C. for 1 hour. The reaction solution was neutralized with a 10 wt% aqueous sodium hydroxide solution and extracted with toluene.
- Example 2 In a glass sample bottle, 5.00 g (31.2 mmol) of 1- (3-methyl-2-butenoxy) -2,3-hydroxypropane and cobalt (II) stearate (manufactured by Wako Pure Chemical Industries, Ltd .; purity 90 %) 23 mg (0.034 mmol; 0.11 mol% with respect to vinyl group in 1- (3-methyl-2-butenoxy) -2,3-hydroxypropane) was added and stirred well to obtain an oxygen absorber. . The evaluation results are shown in Table 1.
- Example 3 In Example 2, an oxygen absorbent was obtained in the same manner except that cobalt stearate (II) was not added. The evaluation results are shown in Table 1.
- Example 2 [Comparative Example 1] In Example 2, 5.00 g of 1- (3-methyl-2-butenoxy) -2,3-hydroxypropane represented by the following formula (E-1) (manufactured by Tokyo Chemical Industry Co., Ltd .; purity 99%; 37. Example 2 except that the amount of cobalt (II) stearate was changed from 23 mg to 29 mg (0.046 mmol; 0.12 mol% with respect to the vinyl group of compound (E-1)). The oxygen absorber was prepared by the same method. The evaluation results are shown in Table 1.
- Example 2 In Example 3, except that 1- (3-methyl-2-butenoxy) -2,3-hydroxypropane was changed to the compound (E-1) represented by the above formula (Tokyo Chemical Industry Co., Ltd .; purity 99%). Was prepared in the same manner as in Example 3 to obtain an oxygen absorbent. The evaluation results are shown in Table 1.
- the unsaturated double bond-containing compound of the present invention has an excellent oxygen absorbing ability even at room temperature. Surprisingly, it can be seen that oxygen can be absorbed without using a transition metal salt, and the crosslinking reaction and curing reaction of the resin composition can be sufficiently developed.
- the oxygen absorbent of the present invention is, for example, a resin crosslinking reaction or a curing reaction including a curing process involving a radical polymerization reaction such as an unsaturated polyester resin, a vinyl ester resin, a (meth) acrylic resin, and a urethane (meth) acrylate resin. It can be suitably used as an oxygen absorbent that suppresses adverse effects due to oxygen in water.
- the oxygen barrier performance is improved in a resin that requires oxygen barrier properties such as polyvinyl alcohol, ethylene-vinyl acetate copolymer part or completely saponified product. Can do.
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Abstract
Description
[1]下記一般式(I)で表される不飽和二重結合含有化合物。
[一般式(I)中、X及びYはそれぞれ独立してカルコゲン原子を表し、R1、R2はそれぞれ独立して炭素数1~6のアルキル基、炭素数2~6のアルケニル基、アリール基、及びアラルキル基のいずれかを表し、R3、R4はそれぞれ独立して水素原子、炭素数1~6のアルキル基、炭素数2~6のアルケニル基、アリール基、及びアラルキル基のいずれかを表す。Jは炭素数3~15の脂肪族炭化水素からなる連結基を表し、前記連結基は任意の炭素原子が酸素原子に置換されていてもよく、(メタ)アクリロイルオキシ基、スチリルオキシ基、及び炭素数2~5のアルケニルオキシ基からなる群より選ばれる少なくとも1つを置換基として有していてもよい。nは1~5の任意の整数である。ただし、Yが複数存在する場合は、それぞれ異なる原子であってもよい。]
[2]前記一般式(I)においてX及びYが酸素原子である、[1]に記載の不飽和二重結合含有化合物。
[3]前記一般式(I)においてR3が水素原子である、[1]又は[2]に記載の不飽和二重結合含有化合物。
[4]前記一般式(I)においてR4が水素原子又はメチル基である、[1]~[3]のいずれかに記載の不飽和二重結合含有化合物。
[5]下記一般式(II)で表される、[1]~[4]のいずれかに記載の不飽和二重結合含有化合物。
[一般式(II)中、R5は水素原子又はメチル基を表し、R6は水酸基、(メタ)アクリロイルオキシ基、スチリルオキシ基、及び炭素数2~5のアルケニルオキシ基のいずれかを表す。]
[6]前記一般式(II)においてR5が水素原子である、[5]に記載の不飽和二重結合含有化合物。
[7]前記一般式(II)においてR6が水酸基である、[5]又は[6]に記載の不飽和二重結合含有化合物。
[8][1]~[7]のいずれかに記載の不飽和二重結合含有化合物を含む酸素吸収剤。
[9]前記不飽和二重結合含有化合物中のビニル基に対して遷移金属塩を0.001~10mol%含む、[8]に記載の酸素吸収剤。
[10][8]又は[9]に記載の酸素吸収剤及び樹脂を含む樹脂組成物。
[11]前記樹脂が活性エネルギー線硬化性樹脂である、[10]に記載の樹脂組成物。
本発明の不飽和二重結合含有化合物は、下記一般式(I)で表される化合物である。
[一般式(I)中、X及びYはそれぞれ独立してカルコゲン原子を表し、R1、R2はそれぞれ独立して炭素数1~6のアルキル基、炭素数2~6のアルケニル基、アリール基、及びアラルキル基のいずれかを表し、R3、R4はそれぞれ独立して水素原子、炭素数1~6のアルキル基、炭素数2~6のアルケニル基、アリール基、及びアラルキル基のいずれかを表す。Jは炭素数3~15の脂肪族炭化水素からなる連結基を表し、前記連結基は任意の炭素原子が酸素原子に置換されていてもよく、(メタ)アクリロイルオキシ基、スチリルオキシ基、及び炭素数2~5のアルケニルオキシ基からなる群より選ばれる少なくとも1つを置換基として有していてもよい。nは1~5の任意の整数である。ただし、Yが複数存在する場合は、それぞれ異なる原子であってもよい。]
前記連結基としては、不飽和二重結合含有化合物の取扱いの容易性の観点から、炭素数3~10の脂肪族炭化水素基が好ましく、炭素数3~5の脂肪族炭化水素基がより好ましい。
前記連結基が有する置換基としては、不飽和二重結合含有化合物の酸素吸収性能を向上させる観点から、(メタ)アクリロイルオキシ基が好ましい。
本発明の酸素吸収剤は、前記一般式(I)で表される不飽和二重結合含有化合物を含むものである。前述のとおり本発明の不飽和二重結合含有化合物は酸素吸収性能に優れるため、これを含む酸素吸収剤を塗料等に用いた場合は、架橋反応や硬化反応を十分に進行させることができる。
本発明の酸素吸収剤は、本発明の不飽和二重結合含有化合物を含むため十分な酸素吸収性能を有するが、酸素吸収性能を更に向上させるために遷移金属塩を更に含んでもよい。
前記遷移金属塩を構成する遷移金属としては、例えば、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル及び銅等の第4周期の遷移金属元素や、ルテニウム、及びロジウム等の第5周期の遷移金属元素が挙げられる。これらの中でも、酸素吸収剤の酸素吸収性能を向上させる観点から、第4周期の遷移金属元素が好ましく、マンガン、鉄、コバルト、ニッケル及び銅がより好ましく、コバルトが更に好ましい。
本発明の酸素吸収剤中の一般式(I)で表される不飽和二重結合含有化合物の含有量に特に制限はないが、効果的に酸素を吸収する観点から、50質量%以上が好ましく、60質量%以上がより好ましく、70質量%以上が更に好ましく、80質量%以上がより更に好ましく、85質量%以上がより更に好ましく、90質量%以上がより更に好ましい。また、酸素吸収剤の製造コストの観点から、実質的に100質量%が好ましく、99.9質量%以下がより好ましく、99.8質量%以下が更に好ましい。
本発明の酸素吸収剤は、一般式(I)で表される不飽和二重結合含有化合物及び遷移金属塩の他に、本発明の効果を損なわない範囲で各種添加剤を含んでもよい。具体的には、充填剤、紫外線吸収剤、顔料、増粘剤、低収縮化剤、老化防止剤、可塑剤、骨材、難燃剤、安定剤、繊維強化材、染料、酸化防止剤、レベリング剤、及びたれ止め剤等を含んでもよい。
本発明の酸素吸収剤は常温においても優れた酸素吸収性能を示す。具体的に、本発明の酸素吸収剤が遷移金属塩を含む場合の20℃における酸素吸収量は、1日後の値として、好ましくは4mL/g以上であり、より好ましくは5mL/g以上であり、更に好ましくは6mL/g以上である。
なお、酸素吸収剤の酸素吸収量の上限に制限はなく、酸素吸収量は実施例に記載の方法により測定することができる。
本発明の酸素吸収剤は、一般式(I)で表される不飽和二重結合含有化合物と、必要に応じて遷移金属塩や各種添加剤とを混合することにより得ることができる。具体的には、一般式(I)で表される不飽和二重結合含有化合物と、遷移金属塩とを撹拌、混合するなどして得ることができる。
本発明の樹脂組成物は、本発明の酸素吸収剤及び樹脂を含むものである。一般式(I)で表される不飽和二重結合含有化合物は、それ自体が重合性基や反応性基を有するため、樹脂に配合しても該樹脂の架橋反応や重合反応等を阻害しにくい。したがって、本発明の樹脂組成物は、酸素存在下でも樹脂の架橋反応や重合反応等の収率が低下しにくい点で優れている。
本発明の樹脂組成物に用いる樹脂は、塗料、接着剤、及びコーティング剤等に用いられる樹脂であれば特に制限はない。当該樹脂はラジカル重合性樹脂であってもよく、また、UV硬化性樹脂等の活性エネルギー線硬化性樹脂であってもよい。用途等にもよるが本発明の効果がより顕著に奏されることなどから、当該樹脂は活性エネルギー線硬化性樹脂であることが好ましい。
樹脂の具体例としては、例えば、不飽和ポリエステル樹脂、ビニルエステル樹脂、重合性基を有する(メタ)アクリル樹脂、及びウレタン(メタ)アクリレート樹脂等のラジカル重合反応により硬化可能な樹脂;
ポリビニルアルコール、エチレン-酢酸ビニル共重合体、エチレン-酢酸ビニル共重合体の部分又は完全鹸化物、エポキシ樹脂、ポリエステル樹脂、ポリオレフィン樹脂、環状ポリオレフィン樹脂等の酸素バリア性が求められる樹脂等が挙げられる。
また、前記樹脂以外にも必要に応じて、フッ素樹脂、ポリアミド66等のポリアミド樹脂、ポリカーボネート樹脂、ポリウレタン樹脂等を用いてもよい。
本発明の樹脂組成物中における一般式(I)で表される不飽和二重結合含有化合物の含有量は、樹脂100質量部に対して、好ましくは0.1~50質量部であり、より好ましくは0.2~30質量部であり、更に好ましくは0.5~10質量部である。
本発明の樹脂組成物は、顔料、染料、充填剤、紫外線吸収剤、増粘剤、低収縮化剤、老化防止剤、可塑剤、骨材、難燃剤、安定剤、繊維強化材、酸化防止剤、レベリング剤、及びたれ止め剤等を適宜含んでもよい。また、本発明の樹脂組成物は、希釈剤として、例えばスチレン、(メタ)アクリル酸エステル等を含んでもよく、重合性の観点から(メタ)アクリル酸エステルを含む場合に本発明の効果がより顕著に奏されるため特に好ましい。
顔料としては、例えば、酸化チタン、ベンガラ、アニリンブラック、カーボンブラック、シアニンブルー、及びクロムイエロー等が挙げられる。充填剤としては、例えば、タルク、マイカ、カオリン、炭酸カルシウム、及びクレー等が挙げられる。
本発明の樹脂組成物は、樹脂と本発明の酸素吸収剤とを混合することにより得ることができる。具体的には、本発明の酸素吸収剤、樹脂、及び必要に応じて任意成分を撹拌等によって混合することにより得ることができる。
発明の樹脂組成物は、例えば、塗料、接着剤、及びコーティング剤等の用途に好ましく用いることができる。
実施例又は比較例で得た酸素吸収剤から100mgを精秤し、内容量20mLのサンプル瓶に入れた。その後、係るサンプル瓶内の湿度調整のため、0.5mLのイオン交換水が入った小瓶を該サンプル瓶に入れ、該サンプル瓶の開口部をポリテトラフルオロエチレン樹脂でシールされたゴムキャップ及びアルミシールで塞いだ。係るサンプル瓶を20℃の恒温槽に静置し、1日間、5日間及び15日間経過後の該サンプル瓶内の残存酸素量を、残存酸素計(飯島電子工業株式会社製;パックマスターRO-103)を使用して測定した。酸素吸収剤を入れなかったこと以外は同様に調製し、同条件で静置したサンプル瓶内の残存酸素量を同様に測定し、これらの残存酸素量の差を酸素吸収剤の酸素吸収量(20℃)[mL/g]とした。同じ試験を3度行い、その平均値を採用した。
酸素吸収量(20℃)の測定において、恒温槽の温度を20℃から60℃に変更したこと以外は同様にして、酸素吸収剤の酸素吸収量(60℃)[mL/g](3度の試験の平均値)を測定した。
1-(3-メチル-2-ブテノキシ)-2,3-ヒドロキシプロパンの合成
ガラス製サンプル瓶中に、1-(3-メチル-2-ブテノキシ)-2,3-ヒドロキシプロパン5.00g(31.2mmol)とステアリン酸コバルト(II)(和光純薬工業社製;純度90%)23mg(0.034mmol;1-(3-メチル-2-ブテノキシ)-2,3-ヒドロキシプロパン中のビニル基に対して0.11mol%)を加えよく撹拌し、酸素吸収剤を得た。評価結果を表1に示す。
実施例2において、ステアリン酸コバルト(II)を加えなかったこと以外は同様にして酸素吸収剤を得た。評価結果を表1に示す。
実施例2において、1-(3-メチル-2-ブテノキシ)-2,3-ヒドロキシプロパンを下記式に示す化合物(E-1)5.00g(東京化成工業社製;純度99%;37.8mmol)に変更し、ステアリン酸コバルト(II)の量を23mgから29mg(0.046mmol;化合物(E-1)のビニル基に対して0.12mol%)に変更したこと以外は実施例2と同様の手法で調製し、酸素吸収剤を得た。評価結果を表1に示す。
実施例3において、1-(3-メチル-2-ブテノキシ)-2、3-ヒドロキシプロパンを上記式に示す化合物(E-1)(東京化成工業社製;純度99%)に変更したこと以外は実施例3と同様の手法で調製し、酸素吸収剤を得た。評価結果を表1に示す。
Claims (11)
- 下記一般式(I)で表される不飽和二重結合含有化合物。
[一般式(I)中、X及びYはそれぞれ独立してカルコゲン原子を表し、R1、R2はそれぞれ独立して炭素数1~6のアルキル基、炭素数2~6のアルケニル基、アリール基、及びアラルキル基のいずれかを表し、R3、R4はそれぞれ独立して水素原子、炭素数1~6のアルキル基、炭素数2~6のアルケニル基、アリール基、及びアラルキル基のいずれかを表す。Jは炭素数3~15の脂肪族炭化水素からなる連結基を表し、前記連結基は任意の炭素原子が酸素原子に置換されていてもよく、(メタ)アクリロイルオキシ基、スチリルオキシ基、及び炭素数2~5のアルケニルオキシ基からなる群より選ばれる少なくとも1つを置換基として有していてもよい。nは1~5の任意の整数である。ただし、Yが複数存在する場合は、それぞれ異なる原子であってもよい。] - 前記一般式(I)においてX及びYが酸素原子である、請求項1に記載の不飽和二重結合含有化合物。
- 前記一般式(I)においてR3が水素原子である、請求項1又は2に記載の不飽和二重結合含有化合物。
- 前記一般式(I)においてR4が水素原子又はメチル基である、請求項1~3のいずれかに記載の不飽和二重結合含有化合物。
- 前記一般式(II)においてR5が水素原子である、請求項5に記載の不飽和二重結合含有化合物。
- 前記一般式(II)においてR6が水酸基である、請求項5又は6に記載の不飽和二重結合含有化合物。
- 請求項1~7のいずれかに記載の不飽和二重結合含有化合物を含む酸素吸収剤。
- 前記不飽和二重結合含有化合物中のビニル基に対して遷移金属塩を0.001~10mol%含む、請求項8に記載の酸素吸収剤。
- 請求項8又は9に記載の酸素吸収剤及び樹脂を含む樹脂組成物。
- 前記樹脂が活性エネルギー線硬化性樹脂である、請求項10に記載の樹脂組成物。
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EP3782975A1 (en) | 2021-02-24 |
US11396486B2 (en) | 2022-07-26 |
JPWO2019203131A1 (ja) | 2021-05-13 |
US20210163391A1 (en) | 2021-06-03 |
EP3782975A4 (en) | 2022-03-23 |
KR20210004990A (ko) | 2021-01-13 |
TW201943684A (zh) | 2019-11-16 |
JP7265536B2 (ja) | 2023-04-26 |
EP3782975B1 (en) | 2023-07-05 |
CN112041293A (zh) | 2020-12-04 |
TWI802679B (zh) | 2023-05-21 |
CN112041293B (zh) | 2023-10-20 |
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