阅读说明：本技术 聚合物、使用了该聚合物的氧吸收剂、及固化性组合物 (Polymer, oxygen absorber using the same, and curable composition ) 是由 野口大树 福本隆司 西岛悠辉 于 2020-02-20 设计创作，主要内容包括：一种聚合物,其由下述通式(I)表示。(通式(I)中,X～(1)、X～(2)及X～(3)表示氧族元素原子。R～(1)及R～(2)各自独立地表示选自由氢原子、碳数1～18的烷基、碳数2～18的烯基及芳烷基组成的组中的任一者,R～(3)及R～(4)各自独立地表示选自由碳数1～6的烷基、碳数2～6的烯基、芳基及芳烷基组成的组中的任一者,R～(5)及R～(6)各自独立地表示选自由氢原子、碳数1～6的烷基、碳数2～6的烯基、芳基及芳烷基组成的组中的任一者,R～(7)表示氢原子或甲基,R～(8)表示选自由氢原子、碳数1～6的烷基、碳数2～6的烯基、芳基及芳烷基组成的组中的任一者。n为任意的整数。R～(3)、R～(4)、R～(5)及R～(6)未各自连结而形成环结构。)(A polymer represented by the following general formula (I). (in the general formula (I), X 1 、X 2 And X 3 Represents an oxygen group element atom. R 1 And R 2 Each independently represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms and an aralkyl group, R 3 And R 4 Each independently represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl groupR is any one of the group consisting of alkyl and aralkyl, R 5 And R 6 Each independently represents any one selected from the group consisting of a hydrogen atom, 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, and R 7 Represents a hydrogen atom or a methyl group, R 8 Represents any one selected from the group consisting of a hydrogen atom, 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. n is an arbitrary integer. R 3 、R 4 、R 5 And R 6 Not individually connected to form a ring structure. ))

1. A polymer represented by the following general formula (I),

in the general formula (I), X¹、X²And X³Represents an oxygen group element atom; r¹And R²Each independently represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms and an aralkyl group, R³And R⁴Each independently represents any one selected from the group consisting 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, R⁵And R⁶Each independently represents any one selected from the group consisting of a hydrogen atom, 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, and R⁷Represents a hydrogen atom or a methyl group, R⁸Represents any one selected from the group consisting of a hydrogen atom, 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; n is an arbitrary integer; r³、R⁴、R⁵And R⁶Not individually connected to form a ring structure.

2. The polymer according to claim 1, wherein, in the general formula (I), X¹And X²Is an oxygen atom.

3. The polymer according to claim 1 or 2, wherein, in the general formula (I), R is³And R⁴Is an alkyl group having 1 to 6 carbon atoms.

4. The polymer according to any one of claims 1 to 3, wherein, in the general formula (I), R is⁵、R⁶And R⁷Is a hydrogen atom.

5. The polymer according to any one of claims 1 to 4, wherein, in the general formula (I), R is⁸Is a hydrogen atom.

6. A polymer represented by the following general formula (II),

in the general formula (II), R¹¹、R¹²、R¹³And R¹⁴Each independently represents any one selected from the group consisting 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, R¹⁵Represents a hydrogen atom or a methyl group, R¹⁶Represents any one selected from the group consisting of a hydrogen atom, 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; n is an arbitrary integer.

7. The polymer according to claim 6, wherein, in the general formula (II), R¹⁶Is a hydrogen atom.

8. The polymer according to any one of claims 1 to 7, which has a polystyrene-reduced weight average molecular weight Mw of 300 to 50000 and a molecular weight distribution Mw/Mn of 1.05 to 10.0.

9. An oxygen absorber comprising the polymer of any one of claims 1 to 8.

10. The oxygen absorber of claim 9 comprising 0.001 to 10 mole% of a transition metal salt relative to the vinyl groups of the polymer.

11. A curable composition comprising the oxygen absorber according to claim 9 or 10 and a polymerizable monomer and/or a polymerizable resin.

12. The curable composition according to claim 11, wherein the polymerizable monomer and/or the polymerizable resin is a radical polymerizable monomer and/or a radical polymerizable resin.

13. A method for producing a polymer composition containing the following general formula (V) obtained by reacting a compound represented by the following general formula (III), a compound represented by the following general formula (IV), and a base,

in the general formula (III), R²¹And R²²Each independently represents one selected from the group consisting 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,

in the general formula (IV), R²³Represents a hydrogen atom or a methyl group,

in the general formula (V), R²¹、R²²And R²³Synonymous with the above, R²⁴Represents any one selected from the group consisting of a hydrogen atom, 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; n is an arbitrary integer.

14. The method for producing a polymer composition containing a compound represented by the general formula (V) according to claim 13, wherein the ratio of the compound represented by the general formula (III) to the compound represented by the general formula (IV) is 1/2 to 2/1.

Technical Field

The present invention relates to a specific polymer, an oxygen absorber using the polymer, and a curable composition.

Background

The radical polymerizable monomer and the radical polymerizable resin used in the coating material, the adhesive, the coating agent, and the like have an unsaturated bond and are cured by the vinyl crosslinking agent. When these radical polymerizable monomers and radical polymerizable resins are used in applications such as coating materials, adhesives, and coating agents, curing is usually performed in an air atmosphere, and therefore, curing is easily inhibited by oxygen in the air, and there are problems such as slow curing and surface tackiness. As a means for preventing these problems, it has been proposed to add a complex other than a radical polymerizable resin and use a polymerization method different from radical polymerization. Patent documents 1 and 2 propose techniques of adding an oxygen absorber as a complex to a radical polymerizable resin. Further, as an oxygen absorbent as a complex, allyl glycidyl ether and the like are described in patent documents 3 and 4. Patent document 5 describes a technique of curing a radical polymerizable resin by cationic polymerization using a photoacid generator. Patent document 6 describes a technique of adding a thiol compound to an olefin. However, the method of adding a conventional compound to a substrate and using the compound cannot provide a sufficient effect of preventing the inhibition of curing. In addition, when cationic polymerization is used as the polymerization method, there is a problem that the rate of the polymerization reaction is reduced by moisture in the air. Further, when a thiol compound is used as in patent document 6, there is a problem that a specific odor is generated.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 63-130610

Patent document 2: japanese laid-open patent publication No. 5-78459

Patent document 3: japanese laid-open patent publication No. 61-101518

Patent document 4: specification of U.S. Pat. No. 3644568

Patent document 5: japanese patent laid-open No. 2008-308420

Patent document 6: japanese patent laid-open publication No. 2004-277660

Disclosure of Invention

Problems to be solved by the invention

As described above, the problem of inhibition of curing by oxygen in the radical polymerizable monomer and the radical polymerizable resin has not been solved yet.

In addition, styrene and the like have been used as reactive diluents in many cases in coating applications, but the action of converting to a less volatile (meth) acrylate ester has been increasing from the viewpoint of environmental protection. However, when a (meth) acrylate is used, there is a problem that curing is more easily inhibited by oxygen than when a conventional reactive diluent is used.

Therefore, in curing in an environment such as under air which is likely to suffer from curing inhibition by oxygen, a method of suppressing curing inhibition is desired.

The present invention has been made in view of the above conventional problems, and an object of the present invention is to provide a polymer which can sufficiently progress a curing reaction and suppress inhibition of curing by oxygen even when used in a coating material, an adhesive, a coating agent, or the like. Further, an object of the present invention is to provide an oxygen absorber containing the polymer, and a curable composition containing the same.

Means for solving the problems

As a result of intensive studies, the present inventors have found that a polymer represented by the following general formula (I) or general formula (II) can stabilize generated radicals more than a conventional oxygen absorbent and exhibit higher oxygen radical trapping performance, that is, higher absorption performance, and have further repeated studies based on this finding, thereby completing the present invention.

Namely, the present invention provides the following [1] to [14 ].

[1] A polymer represented by the following general formula (I).

[ chemical formula 1]

(in the general formula (I), X¹、X²And X³Represents an oxygen group element atom (Japanese: カルコゲン atom). R¹And R²Each independently represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms and an aralkyl group, R³And R⁴Each independently represents any one selected from the group consisting 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, R⁵And R⁶Each independently represents any one selected from the group consisting of a hydrogen atom, 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, and R⁷Represents a hydrogen atom or a methyl group, R⁸Represents any one selected from the group consisting of a hydrogen atom, 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. n is an arbitrary integer. R³、R⁴、R⁵And R⁶Not individually connected to form a ring structure. )

[2]According to [1]Wherein, in the above general formula (I), X¹And X²Is an oxygen atom.

[3]According to [1]Or [ 2]]Wherein, in the above general formula (I), R³And R⁴Is an alkyl group having 1 to 6 carbon atoms.

[4]According to [1]～[3]The polymer according to any one of the above general formulae (I),R⁵、R⁶and R⁷Is a hydrogen atom.

[5]According to [1]～[4]The polymer according to any one of the above general formulae (I), wherein R is⁸Is a hydrogen atom.

[6] A polymer represented by the following general formula (II).

[ chemical formula 2]

(in the general formula (II), R¹¹、R¹²、R¹³And R¹⁴Each independently represents any one selected from the group consisting 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, R¹⁵Represents a hydrogen atom or a methyl group, R¹⁶Represents any one selected from the group consisting of a hydrogen atom, 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. n is an arbitrary integer. )

[7]According to [6]Wherein, in the above general formula (II), R¹⁶Is a hydrogen atom.

[8] The polymer according to any one of [1] to [7], which has a polystyrene-equivalent weight average molecular weight (Mw) of 300 to 50000 and a molecular weight distribution (Mw/Mn) of 1.05 to 10.0.

[9] An oxygen absorber comprising the polymer according to any one of [1] to [8 ].

[10] The oxygen absorber according to [9], which comprises 0.001 to 10 mol% of the transition metal salt based on the vinyl group of the polymer.

[11] A curable composition comprising the oxygen absorber according to [9] or [10], and a polymerizable monomer and/or a polymerizable resin.

[12] The curable composition according to [11], wherein the polymerizable monomer and/or the polymerizable resin is a radically polymerizable monomer and/or a radically polymerizable resin.

[13] A method for producing a polymer composition containing the following general formula (V), the polymer composition being obtained by reacting a compound represented by the following general formula (III), a compound represented by the following general formula (IV), and a base.

[ chemical formula 3]

(in the general formula (III), R²¹And R²²Each independently represents one selected from the group consisting 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. )

[ chemical formula 4]

(in the general formula (IV), R²³Represents a hydrogen atom or a methyl group. )

[ chemical formula 5]

(in the general formula (V), R²¹、R²²And R²³Synonymous with the above, R²⁴Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon atom²6 alkenyl group, aryl group and aralkyl group. n is an arbitrary integer. )

[14] The process for producing a polymer composition containing the general formula (V) according to [13], wherein the ratio of the compound represented by the general formula (III) to the compound represented by the general formula (IV) is 1/2 to 2/1.

Effects of the invention

According to the present invention, it is possible to provide a polymer having an oxygen absorbing property which can sufficiently progress a curing reaction even in a low temperature environment such as room temperature and can suppress inhibition of curing by oxygen when used for a coating material, an adhesive, a coating agent, or the like. Further, an oxygen absorber containing the polymer and a curable composition containing the same can be provided.

Detailed Description

The polymer represented by the general formula (I) or (II) of the present invention is capable of suppressing inhibition of curing by oxygen by allowing it to coexist with a polymerizable monomer such as a curable (meth) acrylate or a polymerizable resin such as an unsaturated polyester resin, and as a result, an excellent cured product can be provided. The mechanism of action has not been determined, but is presumably due to: in the polymerization reaction, the hydrogen atom bonded to the carbon constituting the double bond of the polymer represented by the general formula (I) or the general formula (II) of the present invention, which is activated by heat or active energy ray, preferentially reacts with oxygen which inhibits the polymerization reaction or a peroxide radical generated from oxygen by the polymerization reaction, thereby consuming oxygen or the peroxide radical. Further, according to the production method of the present invention, the polymer represented by the general formula (I) or the general formula (II) can be produced from the available raw materials by a simple method, and the obtained polymer composition can be used without purification, so that the cost required in the process can be reduced to reduce the price, and the method is suitable for use in coating applications and the like where low price is required.

Further, the polymer represented by the general formula (I) or the general formula (II) of the present invention is a polymer compound, and therefore easily remains in a cured product and is difficult to elute.

[ Polymer represented by the general formula (I) ]

The polymer of the present invention is a polymer represented by the following general formula (I).

[ chemical formula 6]

In the general formula (I), X¹、X²And X³Each independently represents an oxygen group element atom. From the viewpoint of ease of producing a polymer and the viewpoint of improving oxygen absorption performance, X¹、X²And X³Preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom.

General formula (I)R in (1)¹、R²Each independently represents any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms and an aralkyl group.

Examples of the alkyl group having 1 to 18 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, isobornyl, adamantyl, and the like.

Examples of the alkenyl group having 2 to 18 carbon atoms include: vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, octadecenyl, iso-3-hexenyl, cyclohexenyl, norbornenyl, isobornenyl and the like.

Examples of the aralkyl group include: benzyl, 2-phenylethyl, 2-naphthylethyl, diphenylmethyl and the like.

Among these, R¹、R²Preferably a hydrogen atom.

R in the general formula (I)³、R⁴Each independently represents 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.

Examples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

Examples of the alkenyl group having 2 to 6 carbon atoms include: vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, iso-3-hexenyl, cyclohexenyl and the like.

Examples of the aryl group include: phenyl, tolyl, xylyl, naphthyl, and the like.

Examples of the aralkyl group include: benzyl, 2-phenylethyl, 2-naphthylethyl, diphenylmethyl and the like.

Among these, R³And R⁴Each independently preferably represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.

R in the general formula (I)⁵And R⁶Each independently represents any of a hydrogen atom, 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.

Examples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

Examples of the alkenyl group having 2 to 6 carbon atoms include: vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, iso-3-hexenyl, cyclohexenyl and the like.

Examples of the aryl group include: phenyl, tolyl, xylyl, naphthyl, and the like.

Examples of the aralkyl group include: benzyl, 2-phenylethyl, 2-naphthylethyl, diphenylmethyl and the like.

Among these, R⁵And R⁶Each independently is preferably any of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, and an aryl group, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom. Wherein R is a group of groups having a structure in which the oxygen absorption property of the polymer is improved⁵Preferably a hydrogen atom, R⁶Preferably a hydrogen atom or a methyl group, more preferably both hydrogen atoms.

R in the general formula (I)³、R⁴、R⁵And R⁶Not connected to each other to form a condensed ring structure.

R in the general formula (I)⁷Represents a hydrogen atom or a methyl group. R⁷Preferably a hydrogen atom.

R in the general formula (I)⁸Represents any of a hydrogen atom, 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.

Examples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

Examples of the alkenyl group having 2 to 6 carbon atoms include: vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, iso-3-hexenyl, cyclohexenyl and the like.

Examples of the aryl group include: phenyl, tolyl, xylyl, naphthyl, and the like.

Examples of the aralkyl group include: benzyl, 2-phenylethyl, 2-naphthylethyl, diphenylmethyl and the like.

Among these, R⁸Preferably a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms, more preferably a hydrogen atom.

In the general formula (I), n is an arbitrary integer. From the viewpoint of oxygen absorption performance, n is preferably 2 to 150, and more preferably 2 to 50.

Specific examples of the polymer represented by the general formula (I) include the following polymers, and the like, and from the viewpoint of oxygen absorption performance, the polymer represented by the following general formula (II) is preferable.

[ chemical formula 7]

[ chemical formula 8]

(in the general formula (II), R¹¹、R¹²、R¹³And R¹⁴Each independently represents any one selected from the group consisting 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, R¹⁵Represents a hydrogen atom or a methyl group, R¹⁶Represents any one selected from the group consisting of a hydrogen atom, 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. n is an arbitrary integer. )

In the general formula (II), R¹¹、R¹²、R¹³And R¹⁴Each independently represents any one selected from the group consisting 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, and preferably R in the general formula (I)³And R⁴The same is true.

In the general formula (II), R¹⁵Represents a hydrogen atom or a methyl group, preferably a hydrogen atom. R¹⁶Represents any one selected from the group consisting of a hydrogen atom, 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, and is preferably a hydrogen atom.

In the general formula (II), n is an arbitrary integer. From the viewpoint of oxygen absorption performance, n is preferably 2 to 150, and more preferably 2 to 50.

The weight average molecular weight (Mw) of the polymer represented by the general formula (I) or (II) is preferably 300 to 50000 in terms of standard polystyrene. The weight average molecular weight (Mw) of the polymer represented by the general formula (I) in terms of standard polystyrene is more preferably 300 to 1000, and still more preferably 330 to 500. The weight average molecular weight (Mw) of the polymer represented by the general formula (II) in terms of standard polystyrene is more preferably 1000 to 25000, and still more preferably 3000 to 10000.

All of the "weight average molecular weight (Mw)", the "number average molecular weight (Mn)" and the "molecular weight distribution (Mw/Mn)" described later in the present specification are the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) in terms of standard polystyrene, which are determined by Gel Permeation Chromatography (GPC) measurement, and more specifically are values measured by the method described in examples.

The molecular weight distribution (Mw/Mn) of the polymers represented by the general formula (I) and the general formula (II) in terms of standard polystyrene is preferably 1.05 to 10.00, more preferably 1.05 to 5.00, and still more preferably 1.10 to 3.00.

[ oxygen absorber ]

The oxygen absorber of the present invention comprises a polymer represented by the above general formula (I) or general formula (II). As described above, the polymer of the present invention has excellent oxygen absorption performance, and therefore, when the oxygen absorber containing the polymer is used for a coating material, an adhesive, a coating agent, or the like, the curing reaction can be sufficiently performed.

The oxygen absorber of the present invention contains the polymer of the present invention and thus has sufficient oxygen absorption performance, but may further contain a transition metal salt to further improve the oxygen absorption performance.

Examples of the transition metal constituting the transition metal salt include: iron, nickel, copper, manganese, cobalt, rhodium, titanium, chromium, vanadium, ruthenium, and the like. Among these, from the viewpoint of improving the oxygen absorbing performance of the oxygen absorbent, iron, nickel, copper, manganese, and cobalt are preferable, and cobalt is more preferable.

The counter ion of the transition metal in the transition metal salt is preferably an anionic species derived from an organic acid from the viewpoint of compatibility, and examples of the organic acid include: acetic acid, stearic acid, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, oleic acid, decanoic acid, naphthenic acid, and the like.

The transition metal salt used in the present invention may be any transition metal salt in which the transition metal and the counter ion are combined, but from the viewpoint of balancing the production cost and the oxygen absorbing performance, cobalt 2-ethylhexanoate, cobalt neodecanoate, and cobalt stearate are preferable.

When 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%, even more preferably 0.01 to 1 mol%, and even more preferably 0.1 to 1 mol% with respect to the vinyl group in the polymer.

When the content of the transition metal salt is within the above range, sufficient oxygen absorption performance can be imparted to the oxygen absorbent.

The content of the polymer represented by the general formula (I) or the general formula (II) in the oxygen absorbent of the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 85% by mass or more, and further preferably 90% by mass or more, from the viewpoint of efficiently absorbing oxygen. From the viewpoint of the production cost of the oxygen absorbent, the content is preferably substantially 100 mass%, more preferably 99.9 mass% or less, and still more preferably 99.8 mass% or less.

The oxygen absorber of the present invention may contain various additives in addition to the polymer represented by the general formula (I) or the general formula (II) and the transition metal salt within a range not impairing the effects of the present invention. Specifically, a filler, an ultraviolet absorber, a pigment, a thickener, a low shrinkage agent, an age resistor, a plasticizer, an aggregate, a flame retardant, a stabilizer, a fiber reinforcement, a dye, an antioxidant, a leveling 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 normal temperature. Specifically, the oxygen absorption amount at 20 ℃ of the oxygen absorbent of the present invention when the transition metal salt is not contained is preferably 1.5mL/g or more, more preferably 2mL/g or more, and further preferably 3.5mL/g or more, as a value 15 days after the start of use as the oxygen absorbent.

The oxygen absorption amount at 60 ℃ in the oxygen absorbent of the present invention when the transition metal salt is not contained is preferably 45mL/g or more, more preferably 48mL/g or more, and further preferably 50mL/g or more, as a value 5 days after the start of use as the oxygen absorbent.

The upper limit of the oxygen absorption amount of the oxygen absorbent is not limited, and the oxygen absorption amount can be measured by the method described in examples.

The oxygen absorber of the present invention can be obtained by mixing the polymer represented by the general formula (I) or the general formula (II) with a transition metal salt and/or various additives as needed. Specifically, the polymer represented by the general formula (I) or the general formula (II) can be obtained by stirring, mixing, or the like, the polymer and the transition metal salt.

[ curable composition ]

The curable composition of the present invention comprises: the oxygen absorber of the present invention is used together with a polymerizable monomer and/or a polymerizable resin. The polymer represented by the general formula (I) or the general formula (II) has a polymerizable group or a reactive group itself, and even when incorporated into a polymerizable monomer and/or a resin, it is difficult to inhibit a crosslinking reaction, a polymerization reaction, or the like. Therefore, the curable composition of the present invention is excellent in that it hardly affects the crosslinking reaction and the polymerization reaction of the polymerizable monomer and the polymerizable resin even in the presence of oxygen.

The polymerizable monomer used in the curable composition of the present invention is not particularly limited if it is a polymerizable monomer that can be used in a coating material, an adhesive, a coating agent, and the like. The polymerizable monomer may be a thermosetting radical polymerizable monomer, or may be a polymerizable monomer used for an active energy ray curable resin such as a UV curable resin. The resin is preferably a thermosetting radical polymerizable monomer, depending on the application, from the viewpoint of more remarkably exhibiting the effects of the present invention.

Examples of the radical polymerizable monomer used in the present invention and the polymerizable monomer used in the active energy ray-curable resin include monofunctional compounds and polyfunctional compounds.

Examples of monofunctional compounds include: vinyl compounds such as styrene, vinyl ethers, vinyl esters and N-vinylpyrrolidone, (meth) acryl compounds such as (meth) acrylic acid and (meth) acrylic esters, and allyl compounds such as allyl alcohol and allyl ester.

Examples of the polyfunctional compound include: a poly (meth) acrylate having 1 or more (preferably 2 or more) (meth) acryloyloxy groups in the molecule, an unsaturated polyester resin, etc., and among these, a poly (meth) acrylate having 1 or more (preferably 2 or more) (meth) acryloyloxy groups in the molecule is preferable, and a urethane (meth) acrylate and an epoxy (meth) acrylate are particularly preferable from the viewpoints of the curing speed of the obtained curable composition, the coating performance after curing, etc. In the curable composition of the present invention, the polyfunctional compound may include only 1 species, or may include 2 or more species.

Examples of the urethane (meth) acrylate include: urethane (meth) acrylates obtained by adding hydroxyl group-containing (meth) acrylates to polymers having residual isocyanate groups, which are synthesized from polyols and excessive amounts of polyisocyanates, and the like.

Examples of the polyhydric alcohol include: ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, neopentyl glycol, hydrogenated bisphenol a, hydrogenated bisphenol F, and the like.

Examples of the polyisocyanate include: trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 2-butylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, 2, 4-or 2,4, 4-trimethylhexamethylene diisocyanate, lysine diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and the like. Among these, hexamethylene diisocyanate having excellent curability is preferable.

The urethane (meth) acrylate is preferably a urethane (meth) acrylate obtained by reacting hexamethylene diisocyanate, which is a polyvalent isocyanate, with pentaerythritol tri (meth) acrylate, which is a hydroxyl group-containing (meth) acrylate.

Examples of the epoxy (meth) acrylate include: epoxy (meth) acrylates obtained by adding (meth) acrylic acid to epoxy resins such as epoxy (meth) acrylates obtained by adding (meth) acrylic acid to bisphenol a type epoxy resins.

The polymerizable resin used in the curable composition of the present invention is not particularly limited as long as it is a resin that can be used for a coating material, an adhesive, a coating agent, and the like. The resin may be a radical polymerizable resin, or may be an active energy ray curable resin such as a UV curable resin. Although it depends on the application, the resin is preferably a radical polymerizable resin in order to more remarkably exhibit the effect of the present invention. Further, the oxygen absorbent of the present invention is excellent in oxygen absorption performance, and therefore can be preferably used for the purpose of absorbing oxygen contained in a resin in an oxygen barrier resin which requires low oxygen permeability.

Specific examples of the resin include: radical polymerizable resins such as unsaturated polyester resins, vinyl ester resins, (meth) acrylic resins having polymerizable groups, and urethane (meth) acrylate resins; and resins requiring oxygen barrier properties such as polyvinyl alcohol, ethylene-vinyl acetate copolymers, partially or completely saponified ethylene-vinyl acetate copolymers, epoxy resins, polyester resins, polyolefin resins, and cyclic polyolefin resins.

In addition to the above-mentioned resins, a fluororesin, a polyamide resin such as polyamide 66, a polycarbonate resin, a polyurethane resin, or the like may be used as necessary.

Examples of the unsaturated polyester resin include: copolymers of a polyol compound such as a propylene glycol-phthalic anhydride-maleic anhydride copolymer or an ethylene glycol-phthalic anhydride-maleic anhydride copolymer with an α, β -unsaturated polybasic acid compound and other polybasic acid compounds, and unsaturated polyester resins obtained by adding a radical polymerizable monomer such as styrene to the copolymers.

Examples of the polyol compound include: ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, neopentyl glycol, hydrogenated bisphenol A, hydrogenated bisphenol F, and the like.

Examples of the α, β -unsaturated polybasic acid compound include: maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, and examples of the other polybasic acid compounds include: phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, chlorendic acid (Japanese: ヘット acid), adipic acid, sebacic acid, and the like. These may be used alone, or 2 or more of them may be used in combination.

These copolymers may further contain, as one of the copolymerization components, a glycidyl compound of an unsaturated alcohol such as allyl glycidyl ether.

Examples of the vinyl ester resin include: vinyl ester resins obtained by adding (meth) acrylic acid to epoxy resins, such as vinyl ester resins obtained by adding (meth) acrylic acid to the ends of bisphenol a epoxy resins.

Examples of the urethane (meth) acrylate resin include: urethane (meth) acrylate obtained by adding (meth) acrylic acid to a polymer having residual isocyanate groups, which is synthesized from a polyol compound and an excess amount of a polyisocyanate compound. The polyol compound may be the same as the polyol compound in the description of the unsaturated polyester resin, and examples of the polyisocyanate compound include: toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and the like.

The content of the polymer represented by the general formula (I) or the general formula (II) in the curable composition of the present invention is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 40 parts by mass, and still more preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the resin.

The curable composition of the present invention may suitably contain a pigment, a dye, a filler, an ultraviolet absorber, a thickener, a low shrinkage agent, an antiaging agent, a plasticizer, an aggregate, a flame retardant, a stabilizer, a fiber-reinforcing material, an antioxidant, a leveling agent, an anti-sagging agent, and the like. The curable composition of the present invention may contain styrene, (meth) acrylate or the like as a diluent, and from the viewpoint of polymerizability, the curable composition of the present invention is particularly preferable because the effect of the present invention is more remarkably exhibited when the curable composition contains (meth) acrylate.

Examples of pigments include: titanium oxide, red lead, aniline black, carbon black, cyanine blue, chrome yellow, and the like. Examples of the filler include: talc, mica, kaolin, calcium carbonate, clay, and the like.

The curable composition of the present invention can be obtained by mixing a polymerizable monomer and/or a polymerizable resin with the oxygen absorber of the present invention. Specifically, the oxygen absorbent of the present invention can be obtained by mixing the oxygen absorbent, the resin, and optional components as needed by stirring or the like.

The curable composition of the present invention can be preferably used for applications such as paints, adhesives, inks, sealants, resist materials, and coating agents. In particular, it is preferably used in applications in which curing is performed in an environment such as under air, in which curing is easily inhibited by oxygen, or in a state in which oxygen is dissolved in the curable composition.

[ Process for producing Polymer composition comprising general formula (V) ]

The process for producing the polymer composition comprising the general formula (V) of the present invention is: a method for producing a polymer composition containing the following general formula (V), which is obtained by reacting a compound represented by the following general formula (III) or a compound represented by the following general formula (IV) with a base.

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

In the general formula (III), R²¹And R²²Each independently represents one selected from the group consisting 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. Preferred embodiment is the same as R in the above general formula (I)³And R⁴The same is true.

In the general formula (IV), R²³Represents a hydrogen atom or a methyl group.

In the general formula (V), R²¹、R²²And R²³Synonymous with the above, R²⁴Represents any one selected from the group consisting of a hydrogen atom, 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, and preferably R in the general formula (I)¹⁶The same is true. n is an arbitrary integer, and is preferably the same as n in the general formula (I).

In the production method of the present invention, a polymer can be easily obtained by reacting the compound represented by the above general formula (III) with the compound represented by the general formula (IV) in the presence of a base. Examples of the base that can be used include: inorganic bases such as alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, and alkaline earth metal hydroxides, and organic bases such as triethylamine, diisopropylamine, pyrimidine, diazabicycloundecene, pyridine, triphenylphosphine, and metal alkoxides. These may be used alone, or 2 or more kinds may be used in combination, and from the viewpoint of solubility in the reaction substrate and activity, sodium hydroxide or potassium hydroxide is preferable.

In the production method of the present invention, the ratio of the compound represented by the above general formula (III) (hereinafter, also referred to as compound (III)) to the compound represented by the general formula (IV) (hereinafter, also referred to as compound (IV)) is not particularly limited, but from the viewpoint of producing a polymer, compound (III)/compound (IV) is preferably 2/1 to 1/2. If the amount is more than 2/1, the reaction is stopped and the amount of the polymer produced is remarkably reduced, and if the amount is less than 1/2, side reactions proceed and the yield is remarkably reduced.

As a specific example of the production method of the present invention, for example, in the case of producing a polymer represented by the following formula (A-1), the polymer can be produced by reacting a compound capable of forming a polymerizable moiety, such as epichlorohydrin, with 3-methyl-2-buten-1-ol, which is a corresponding alcohol, in the presence of a base, such as potassium hydroxide. The reaction conditions are preferably about 60 to 150 ℃ and about 0.5 to 20 hours of stirring, from the viewpoint of sufficient reaction. In the purification, the reaction solution after polymerization may be used as it is, or a known method such as a silica gel column, an activated carbon column, or a distillation operation may be combined to obtain a desired purity.

[ chemical formula 12]

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The measurement of physical property values in examples, reference examples and comparative examples was performed by the following methods.

[¹H-NMR measurement conditions]

To 20mg of the oxygen absorber obtained in examples, reference examples, and comparative examples, 4g of deuterated chloroform was added to prepare a uniform solution, and the solution was subjected to the following measurement conditions¹H-NMR measurement.

The device comprises the following steps: ULTRASHIELD400PLUS, manufactured by Bruker "

Reference substance: tetramethylsilane

Measuring temperature: 25 deg.C

Cumulative number of times: 16 times (twice)

[ measurement by Gel Permeation Chromatography (GPC) ]

To 200mg of the oxygen absorbent obtained in examples or comparative examples, 2g of Tetrahydrofuran (THF) was added to prepare a uniform solution, and this solution was subjected to gel permeation chromatography under the following measurement conditions to determine the number of weight average molecular weights (Mw) and the number average molecular weights (Mn) in terms of standard polystyrene and calculate the molecular weight distribution (Mw/Mn).

The device comprises the following steps: HLC-8220GPC, manufactured by Tosoh corporation "

Column: connecting in series "TSKgel SuperHM-N (inner diameter 6mm, effective length 15 cm)" prepared from 3 Tosoh

Eluent: THF was circulated at a flow rate of 0.6 mL/min.

Sample injection amount: 10 μ L

A detector: RI (Ri)

Detector temperature: 40 deg.C

[ method for measuring oxygen absorption (20 ℃ C.) ]

100mg of the oxygen absorber obtained in examples or comparative examples was weighed out accurately and placed in a sample bottle having an internal volume of 20 mL. Thereafter, in order to adjust the humidity in the sample bottle, a vial containing 0.5mL of ion-exchanged water was placed in the sample bottle, and the opening of the sample bottle was closed with a rubber cap and an aluminum cap which were sealed with polytetrafluoroethylene resin.

The sample bottle was left to stand at 20 ℃ in a constant temperature bath, and the residual oxygen amount in the sample bottle was measured using a residual oxygen meter ("PACK MASTER RO-103" manufactured by Kashima electronic industries Co., Ltd.) after 1 day, 5 days, and 15 days from the start of use as an oxygen absorbent.

As a control, the residual oxygen amount was measured under the same conditions except that the oxygen absorbents obtained in examples and comparative examples were not placed, the difference (oxygen absorption amount) between the measured values obtained in examples and comparative examples and the measured values obtained in the control was obtained, and the oxygen absorption amount per 1g of the oxygen absorbent was calculated as the oxygen absorption amount (20 ℃ C.) [ mL/g ] of the oxygen absorbent. The same test was performed 3 times, and the average value was used.

[ method for measuring oxygen absorption (60 ℃ C.) ]

The oxygen absorption amount (60 ℃) of the oxygen absorbent [ mL/g ] (average of 3 tests) was measured in the same manner except that the temperature of the thermostatic bath in the measurement of the oxygen absorption amount (20 ℃) was changed from 20 ℃ to 60 ℃.

[ example 1]

Synthesis of alpha- (3-methyl-2-butenyloxy) -omega-hydroxypoly [ oxy (3-methyl-2-butenyloxymethylethyl-1, 2-diyl) ] (A-1)

[ chemical formula 13]

Into a reactor equipped with a stirrer, a thermometer and a dropping funnel, 1654g (19.2 mol, manufactured by Kuraray Co., Ltd.) of 3-methyl-2-buten-1-ol and 50% sodium hydroxide were charged under a nitrogen stream1842g (23.0 mol, manufactured by Kanto electrochemical Co., Ltd.) and 28g (0.084 mol, manufactured by Tokyo chemical Co., Ltd.) of dodecylbenzyldimethylammonium chloride were added. While keeping the internal temperature at 60 ℃ or lower, 1776g of epichlorohydrin (Fuji film and Wako pure chemical industries, Ltd., 19.2mol) was added dropwise with stirring, and after completion of the addition, the temperature was raised to 90 ℃. Stirred at an internal temperature of 90 ℃ for 9 hours and thereafter cooled to 25 ℃. The reaction solution was washed with 5000g of a 7.5% aqueous sodium bicarbonate solution, and then the upper layer was washed with 5000mL of ion-exchanged water. From the resulting organic layer, water and unreacted 3-methyl-2-buten-1-ol were distilled off by distillation to give α - (3-methyl-2-butenyloxy) - ω -hydroxypoly [ oxy (3-methyl-2-butenyloxymethylethane-1, 2-diyl) represented by the above general formula (A-1)]1996g (73% yield). Which is shown below¹H-NMR measurement results and GPC measurement results.

¹H-NMR(270MHz，CDCl₃，TMS)δ：5.37-5.32(m，5H)，4.02-3.99(brd，10H)，3.68-3.56(m，4H)，3.55-3.40(m，10H)，2.54(d，J＝3.8Hz，1H)，1.74(brs，15H)，1.66(brs，H)

GPC measurement: weight average molecular weight (Mw) 360, number average molecular weight (Mn) 300, molecular weight distribution (Mw/Mn) 1.2 (polystyrene equivalent)

[ reference example 1]

Synthesis of 1- (3-methyl-2-butenyloxy) -2, 3-epoxypropane (A-2)

[ chemical formula 14]

In a reactor equipped with a stirrer, a thermometer and a dropping funnel, 324g of 3-methyl-2-buten-1-ol (3.77 mol, manufactured by Kuraray corporation), 2300mL of cyclohexane, 226g of sodium hydroxide (5.65 mol, manufactured by fuji film and Wako pure chemical industries, Ltd.), 15.2g of trioctylmethylammonium chloride (37.3 mmol, manufactured by tokyo chemical industries, Ltd.), and 226mL of purified water were charged under a nitrogen stream. While keeping the internal temperature at 25 ℃ or lower, 698g of epichlorohydrin (Fuji film and Wako pure chemical industries, Ltd.) was added dropwise over 90 minutes with stirring7.54mol), after the end of the dropwise addition, the temperature was raised to 40 ℃ over 30 minutes. Stirred at an internal temperature of 40 ℃ for 3 hours and thereafter cooled to 25 ℃. The upper layer of the reaction mixture was washed 5 times with 670mL of saturated brine, and the organic layer was dried over sodium sulfate. The sodium sulfate was filtered, and the filtrate was concentrated to give 536g of a concentrate. This concentrate was purified by distillation to obtain 242g (1.67 mol; yield 44%) of 1- (3-methyl-2-butenyloxy) -2, 3-epoxypropane represented by the above formula (A-2). Which is shown below¹H-NMR measurement results.

¹H-NMR(400MHz，CDCl₃，TMS)δ：5.35(tquin，J＝6.8，1.2Hz，1H)，4.03(ddd，J＝19.6，12.0，7.2Hz，2H)，3.68(dd，J＝11.6，3.2Hz，1H)，3.99(dd，J＝11.2，5.6Hz，1H)，3.17-3.13(m，1H)，2.79(dd，J＝4.8，4.0Hz，1H)，2.60(dd，J＝5.2，2.8Hz，1H)，1.75(s，3H)，1.68(s，3H)。

[ example 2]

Synthesis of alpha-methoxy-omega-hydroxypoly [ oxy (3-methyl-2-butenyloxymethylethyl-1, 2-diyl) ] (A-3)

[ chemical formula 15]

In a reactor equipped with a stirrer, a thermometer and a dropping funnel, 20g (0.14 mol, manufactured by Kuraray Co., Ltd.) of 3-methyl-2-buten-1-ol and 76mg (1.4 mmol, manufactured by Fuji film and Wako pure chemical industries, Ltd.) of sodium methoxide were charged under a nitrogen flow. The internal temperature was raised to 110 ℃ and stirred for 9 hours, after which it was cooled to 25 ℃. After adding 1mL of acetic acid to the reaction mixture, the low-boiling components were removed by evaporation to obtain α -methoxy- ω -hydroxypoly [ oxy (3-methyl-2-butenyloxymethylethyl-1, 2-diyl) represented by the above general formula (A-3)]18.8g (yield 94%). Which is shown below¹H-NMR measurement results and GPC measurement results.

¹H-NMR(270MHz，CDCl₃，TMS)δ：5.34(t，J＝13.0Hz，47H)，4.05-3.90(brd，94H)，3.77-3.35(m，235H)，2.61(brs，1H)，1.74(brs，282H)，1.67(brs，282H)

GPC measurement: the weight average molecular weight (Mw) was 7600, the number average molecular weight (Mn) was 4800, and the molecular weight distribution (Mw/Mn) was 1.58 (polystyrene equivalent)

[ example 3]

In a glass sample bottle, 5.00g of the compound (A-1) was added and sufficiently stirred to obtain an oxygen absorber. The evaluation results are shown in table 1.

[ example 4]

An oxygen absorbent was obtained in the same manner as in example 3, except that the compound (A-1) in example 3 was changed to the compound (A-3). The evaluation results are shown in table 1.

Comparative example 1

An oxygen absorbent was obtained in the same manner as in example 3, except that 5.00g (manufactured by Tokyo chemical Co., Ltd.; purity: 99%; 29.0mmol) of the compound (E-1) represented by the following formula was used instead of the compound (A-1) in example 1. The evaluation results are shown in table 1.

[ chemical formula 16]

[ Table 1]

As shown in table 1, it is understood that the polymer of the present invention has excellent oxygen absorption energy even at normal temperature. Further, surprisingly, it was found that oxygen can be absorbed without using a transition metal salt, and the curing reaction of the curable composition can be sufficiently expressed.