JP2012087285A - Deoxidation coating agent, coating film containing deoxidation agent and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deoxidation coating agent which contains an organic deoxidation agent, a polyolefin resin having a specific composition and an aqueous medium, is excellent in coatability, and provides a coating film excellent in deoxidation function and in storage stability.SOLUTION: The deoxidation coating agent contains: an organic deoxidation agent; a polyolefin resin containing an olefin-based hydrocarbon unit and a unit having a quaternized amino group; and an aqueous medium. The content of the unit having the quaternized amino group is ≥0.1 and <10 mol% to 100 mol% of all structure units constituting the polyolefin resin. The unit having the quaternized amino group has a carbonyl group derived from an unsaturated carboxylic acid unit or an unsaturated carboxylic acid anhydride unit.

Description

  The present invention relates to an oxygen scavenger containing an organic oxygen scavenger, a specific polyolefin resin and an aqueous medium, an oxygen scavenger-containing coating film containing an organic oxygen scavenger and a specific polyolefin resin, The present invention relates to a laminate in which the oxygen scavenger-containing coating film is laminated.

  It is indispensable to provide a deoxidizing function to packaging materials for food, medical / pharmaceuticals, and electrical / electronic parts. There are roughly two types of materials for providing oxygen scavenging functions: metal oxygen scavengers and organic oxygen scavengers, but metal oxygen scavengers react with metal detectors used for foreign object detection surveys. There is a problem.

There is no such problem with organic oxygen scavengers, and in particular, ascorbic acid is widely used as a main component of oxygen scavenging materials because of its nature of reducing oxygen.
There are various forms of using an organic oxygen scavenger as a component of the oxygen scavenging material, but in general, a method of using it by kneading it into a resin material (Patent Document 1) or an ascorbic acid segment in a polymer chain (Patent Document 2), a method of using a porous material impregnated with a solution containing an organic oxygen absorber (Patent Document 3), and impregnating a water absorbent resin with a solution containing an organic oxygen absorber (Patent Document 4), and a method (Patent Document 5) in which a solution containing ascorbic acid is placed on a support to coat the surface has also been proposed.

  However, the method (Patent Document 1) used by kneading into a resin material has an advantage that an oxygen scavenging layer can be laminated on a desired packaging substrate, but the organic oxygen scavenger is thermally decomposed during kneading. There is a concern to do. Further, since the adhesion of the deoxidized layer is poor, there is a problem that an adhesive layer needs to be interposed between the substrate and the base material.

  Moreover, although the method (patent document 2) which introduce | transduces an ascorbic acid segment into a polymer chain solves said problem, the complexity of introducing the ascorbic acid segment into a polymer chain is needed. In addition, there was a problem in terms of adhesion when the obtained polymer was directly laminated on a desired packaging substrate.

  The method of using a porous material impregnated with a solution containing an organic oxygen scavenger (Patent Document 3) has a problem that the use is limited because the base material is limited to the porous material. . Moreover, since the decomposition reaction of the organic oxygen scavenger accompanying the oxygen removal reaction proceeds promptly after production, there is a problem that the storage stability is poor.

  A method of using a solution containing an organic oxygen scavenger impregnated in a water-absorbent resin (Patent Document 4) is a method in which a necessary material is filled and sealed in a packaging material and used as an oxygen absorbent package. Since the water-absorbent resin, which is one of the constituent materials, is a gel in which a water-soluble resin is partially crosslinked to make it water-insoluble, it has poor adhesion to the substrate and is difficult to be laminated on the desired substrate. .

  And the method (patent document 5) which puts the solution containing ascorbic acid on a support body, and coat | covers the surface (patent document 5) places an ink-form thru | or cream-form oxygen absorber on the base material which has a hygroscopic property, and water | moisture content. This is a technique of covering with a covering material while maintaining the state of inclusion. Therefore, the base material is limited to those having hygroscopicity, and there is a problem that the surface must be further coated, and the decomposition reaction of the organic oxygen scavenger accompanying the deoxygenation reaction proceeds promptly after production. There was a problem of poor storage stability.

JP 2004-136479 A Japanese Patent Laid-Open No. 9-328521 JP-A-62-14939 JP-A-3-86238 JP-A-10-353

  The present invention solves the above-mentioned problems, and can be easily applied on a desired substrate, and the obtained coating film is deoxygenated on the substrate with good adhesion. It is intended to provide a coating agent, and to provide a deoxidant-containing coating film that is laminated with good adhesion on a desired substrate and has excellent storage stability. An object of the present invention is to provide a laminate in which a coating film containing an organic oxygen scavenger with good adhesion is laminated on a material.

  As a result of studies conducted by the present inventors to solve the above-described problems, an organic oxygen scavenger, a polyolefin resin having a specific composition and an oxygen scavenger coating containing an aqueous medium are excellent in coatability and obtained. The coating film was found to be excellent in a deoxygenation function and storage stability, and reached the present invention.

That is, the gist of the present invention is as follows.
[1] An oxygen scavenger comprising an organic oxygen scavenger, a polyolefin resin containing an olefinic hydrocarbon unit and a unit having a quaternized amino group, and an aqueous medium.
[2] The content of the unit having a quaternized amino group is 0.1 mol% or more and less than 10 mol% with respect to 100 mol% of all the structural units constituting the polyolefin resin. The deoxidizing paint according to [1].
[3] The desorption according to [1] or [2], wherein the unit having a quaternized amino group has a carbonyl group derived from an unsaturated carboxylic acid unit or an unsaturated carboxylic anhydride unit. Oxygen paint.
[4] A unit having a quaternized amino group includes an N-substituted imide unit derived from an unsaturated carboxylic anhydride unit, and a substituent represented by the following formula (1) as the N-substituent. The deoxidizing paint according to any one of [1] to [3], wherein
_{^{- (CH 2) n N +}} R 1 R 2 R 3 · X - (1)
Wherein R ¹ and R ² are alkyl groups having 1 to 5 carbon atoms or hydroxyalkyl groups having 1 to 5 carbon atoms, R ³ is a residue of a quaternizing agent introduced by quaternization reaction, X ⁻ Is an anionic counter ion, and n is an integer of 1 to 5.)
[5] The organic oxygen scavenger contains at least one of ascorbic acid, catechol, erythorbic acid, pyrogallol, hydroquinone, reducing sugar, and tannic acid, any of [1] to [4] Deoxygenating coating agent according to crab.
[6] The oxygen scavenger according to any one of [1] to [5], wherein the pH is 2 to 6.
[7] The deoxygenation coating agent according to any one of [1] to [6], which does not substantially contain a nonvolatile aqueous dispersion aid.
[8] An oxygen scavenger-containing coating film comprising an organic oxygen scavenger and a polyolefin resin containing an olefinic hydrocarbon unit and a unit having a quaternized amino group.
[9] The content of the unit having a quaternized amino group is 0.1 mol% or more and less than 10 mol% with respect to 100 mol% of all the structural units constituting the polyolefin resin. The oxygen scavenger-containing coating film according to [8].
[10] The desorption according to [8] or [9], wherein the unit having a quaternized amino group has a carbonyl group derived from an unsaturated carboxylic acid unit or an unsaturated carboxylic anhydride unit. Oxygen agent-containing coating film.
[11] A unit having a quaternized amino group is an N-substituted imide unit derived from an unsaturated carboxylic anhydride unit, and a substituent represented by the following formula (1) as the N-substituent: The oxygen-absorbing agent-containing coating film according to any one of [8] to [10],
_{^{- (CH 2) n N +}} R 1 R 2 R 3 · X - (1)
Wherein R ¹ and R ² are alkyl groups having 1 to 5 carbon atoms or hydroxyalkyl groups having 1 to 5 carbon atoms, R ³ is a residue of a quaternizing agent introduced by quaternization reaction, X ⁻ Is an anionic counter ion, and n is an integer of 1 to 5.)
[12] An oxygen scavenger-containing coating film obtained by applying the oxygen scavenger coating composition according to any one of [1] to [7].
[13] A laminate comprising the base material and the oxygen scavenger-containing coating film according to any one of [8] to [12] laminated thereon.
[14] A laminate comprising a sealant layer laminated on the oxygen scavenger-containing coating film of the laminate according to [13].
[15] The laminate according to [13] or [14], wherein the substrate has a barrier property.

  Since the oxygen scavenger of the present invention contains an organic oxygen scavenger, a polyolefin resin having a specific composition, and an aqueous medium, it can be applied to various substrates and is uniform on various substrates. A good coating can be formed, and the workability is excellent. And since it is a water system, it is excellent also in environmental conservation.

  The deoxidant-containing coating film of the present invention has a deoxygenation function and is excellent in storage stability. For this reason, the laminated body of this invention can use a various material as a base material, is excellent in a deoxidation function, and can be preserve | saved for a long time in air | atmosphere. And by making a bag etc. of the laminated body of this invention, it becomes possible to use suitably as packaging materials, such as a foodstuff, a medical / medicine, an electrical / electronic component.

Hereinafter, the present invention will be described in detail.
The oxygen scavenger of the present invention (hereinafter sometimes abbreviated as “coating agent”) includes an organic oxygen scavenger, a polyolefin resin having a specific composition (hereinafter sometimes referred to as polyolefin resin A), and an aqueous medium. . Specifically, the oxygen scavenger of the present invention is an aqueous ink in which a polyolefin resin having a quaternized amino group is dispersed in an aqueous medium, and an organic oxygen scavenger is dissolved in the aqueous medium. It is.

  The oxygen scavenger-containing coating film of the present invention (hereinafter sometimes abbreviated as “coating film”) contains an organic oxygen scavenger and polyolefin resin A. The oxygen scavenger-containing coating film of the present invention is preferably obtained by coating the oxygen scavenger coating composition of the present invention. That is, it is preferable that the deoxygenation coating agent of the present invention is applied, the aqueous medium is removed by drying after coating.

  Examples of the organic oxygen scavenger contained in the oxygen scavenger and oxygen scavenger-containing coating of the present invention include ascorbic acid, catechol, erythorbic acid, pyrogallol, hydroquinone, reducing sugars, and tannic acid. These may be used alone or in combination. Of these, ascorbic acid, catechol, pyrogallol, and tannic acid are preferable, and ascorbic acid is particularly preferable from the viewpoint of cost and effect.

  In addition, organic acid salts such as sodium ascorbate are known as general organic oxygen scavengers, but in the present invention, a stable oxygen scavenger cannot be obtained. Is preferably not used.

  The polyolefin resin A contained in the oxygen scavenger and oxygen scavenger-containing coating of the present invention contains, as constituent components, an olefinic hydrocarbon unit and a unit having a quaternized amino group.

  As the olefinic hydrocarbon unit in the present invention, those having 2 to 6 carbon atoms are preferable, ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene. Alkenes such as 1-hexene and dienes such as butadiene and isoprene, and may have a plurality of these units. Among these, ethylene, propylene, 1-butene, and isobutene are preferable, and ethylene and propylene are more preferable from the viewpoint of ease of production of the resin, ease of aqueous dispersion, and adhesion to various materials.

  The content of the olefinic hydrocarbon unit in the polyolefin resin A in the present invention is preferably 65 to 99.9 mol%, more preferably 70 to 99.9 mol%, and 80 to 99.8 mol%. More preferably, 85-99.7 mol% is especially preferable. When the content of the olefinic hydrocarbon unit is less than 65 mol%, the water resistance and solvent resistance of the coating film obtained from the coating tends to decrease. When the content exceeds 99.9 mol%, the polyolefin resin A It tends to be difficult to disperse in water.

  On the other hand, the unit having a quaternized amino group is a component that forms the polyolefin resin A, and means a unit having one or more quaternized amino groups in the unit.

  And the polyolefin resin A is equipped with the capability to disperse | distribute in an aqueous medium with the unit which has this quaternized amino group. That is, since the amino group is quaternized, the polyolefin resin A already has an amino cation. Therefore, even in the absence of a neutralizing agent for neutralizing the amino group, an aqueous medium in an acidic region can be used. A stable dispersion can be obtained. The electrostatic repulsion between the amino cations can prevent aggregation between the polyolefin resin particles in the aqueous medium. As a result, the deoxidizing coating composition of the present invention becomes a cationic aqueous coating composition that is stable in the acidic region in which the polyolefin resin is uniformly dispersed. Here, the aqueous coating material in which the polyolefin resin is uniformly dispersed is a portion where the solid content concentration is locally different from other portions such as precipitation, phase separation or skinning in the aqueous medium. It means that there is no state.

  Aggregation between resin particles can be suppressed by utilizing the electrostatic repulsion between amino cations as described above. In the present invention, as long as the polyolefin resin to be used has a certain amount of units having a quaternized amino group in the structural unit, aggregation of the resin can basically be suppressed. However, since the resin agglomeration largely depends on the resin structure, the resin agglomeration can be more effectively suppressed by devising the resin structure. In this regard, according to studies by the present inventors, it is more effective to increase the number of quaternized amino groups than to increase the number of quaternized amino groups contained in the unit having a quaternized amino group. It was found that there is a tendency to suppress the aggregation of the resin. In this case, it was also found that the latter is more effective even if the total number of amino cations in the resin is the same. Although these reasons are not clear, it is effective to spread the quaternized amino group in the resin to suppress the aggregation of the resin, and the structure of the unit having the quaternized amino group itself is: It is considered that the ratio contributing to the aggregation suppressing effect is low. Therefore, in order to more effectively suppress the aggregation of the resin, it may be sufficient to adjust only the content of the unit having a quaternized amino group, and the quaternized amino group contained in the unit is sufficient. There is basically no need to consider the structure such as the number.

  The content of the unit having a quaternized amino group is preferably 0.1 mol% or more and less than 10 mol% with respect to 100 mol% of all the structural units constituting the polyolefin resin A. Preferably they are 0.1 mol% or more and less than 4 mol%. Furthermore, it is preferably 0.2 mol% or more and less than 3 mol%, particularly preferably 0.3 mol% or more and less than 2 mol%, most preferably 0.3 mol% or more and less than 1 mol%. is there. When the content of the unit having a quaternized amino group is less than 0.1 mol%, it is difficult to disperse the polyolefin resin in water, which is not preferable. On the other hand, if it is 10 mol% or more, the storage stability after aqueous dispersion tends to decrease, and the adhesion, water resistance, and solvent resistance of the resin tend to decrease, which is not preferable. The content of units having a quaternized amino group can generally be measured by NMR analysis.

  The unit having a quaternized amino group preferably has a carbonyl group derived from an unsaturated carboxylic acid unit or an unsaturated carboxylic anhydride unit. As a method for producing the polyolefin resin A in the present invention, after producing a polyolefin resin having a tertiary amino group as a precursor by reacting an amino compound with a unit having a carboxyl group or a carboxylic anhydride group, Examples include a method of quaternizing a part or all of the tertiary amino group with a quaternizing agent described later. This is because the quaternized amino group can be easily introduced without cost. Therefore, in the polyolefin resin A, if the quaternized amino group is introduced as described above in forming the unit having a quaternized amino group, the production cost of the polyolefin resin A is reduced as a result. Can be suppressed. Generally, when an amino compound is reacted with a unit having a carboxyl group or a carboxylic acid anhydride group, the carbonyl group remains as soon as the amino group is introduced. Therefore, the presence of a carbonyl group derived from an unsaturated carboxylic acid unit or an unsaturated carboxylic acid anhydride unit in a unit having a quaternized amino group reduces the cost for producing the polyolefin resin A. This is recognized as the proof of what was planned, and can be said to be a preferred embodiment.

  As the amino compound, a diamine having a primary amine and a tertiary amine in the molecule is preferably employed, and a tertiary amino group can be effectively introduced. Furthermore, a quaternized amino group can be introduced by quaternizing part or all of the tertiary amino group with a quaternizing agent described later.

Furthermore, in the present invention, from the viewpoint of the dispersion stability of the coating material and the improvement of the adhesiveness and heat resistance of the resin, the unit having the quaternized amino group is N- derived from an unsaturated carboxylic anhydride unit. It preferably has a substituted imide unit and a substituent represented by the following formula (1) as its N-substituent.
_{^{- (CH 2) n N +}} R 1 R 2 R 3 · X - (1)
Wherein R ¹ and R ² are alkyl groups having 1 to 5 carbon atoms or hydroxyalkyl groups having 1 to 5 carbon atoms, R ³ is a residue of a quaternizing agent introduced by quaternization reaction, X ⁻ Is an anionic counter ion, and n is an integer of 1 to 5.)

  Examples of the substituent represented by the formula (1) include N, N-dimethylaminoethyl group, N, N-dimethylaminopropyl group, N, N-dimethylaminobutyl group, N, N-diethylaminoethyl group, N, Examples thereof include quaternized N-diethylaminopropyl group, N, N-diethylaminobutyl group and the like with a quaternizing agent. Of these, N, N-dimethylaminopropyl group quaternized with a quaternizing agent is preferable.

  Examples of the unsaturated carboxylic acid anhydride constituting the N-substituted imide unit derived from the unsaturated carboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, and the like, and are easily copolymerized with the olefinic hydrocarbon unit. Maleic anhydride is preferred.

  Specific examples of the N-substituted imide unit derived from the unsaturated carboxylic anhydride unit include N, N-dimethylaminoethylmaleimide, N, N-dimethylaminopropylmaleimide, N, N-dimethylaminobutylmaleimide, N, N -Diethylaminoethylmaleimide, N, N-diethylaminopropylmaleimide, N, N-diethylaminobutylmaleimide and the like are quaternized. Two or more of these may be copolymerized.

  And when content of the N-substituted imide unit derived from the unsaturated carboxylic anhydride unit in polyolefin resin A increases, the heat resistance improvement effect tends to increase, and when the content decreases, the heat resistance improvement effect. Tend to be lower. Although the detailed mechanism by which the heat resistance changes depending on the content of the N-substituted imide unit derived from the unsaturated carboxylic acid anhydride unit is unknown, the polyolefin resin A becomes rigid by having an imide ring structure in its main chain, It is assumed that heat resistance is imparted. Therefore, heat resistance is improved also in the coating film of the present invention.

  When the content of the N-substituted imide unit derived from the unsaturated carboxylic acid anhydride unit is less than 0.1 mol%, the heat resistance improvement effect tends to be insufficient, and the coating film or laminate of the present invention In rare cases, the environment and conditions in which the body can be used are limited. Further, it tends to be difficult to disperse the polyolefin resin A in water, which is not preferable. On the other hand, when the content of the N-substituted imide unit derived from the unsaturated carboxylic acid anhydride unit is 10 mol% or more, the storage stability after the aqueous dispersion is lowered, the resin adhesion, water resistance, The solvent property tends to decrease, which is not preferable.

In the present invention, the unit having an amino group other than the N-substituted imide unit derived from the unsaturated carboxylic anhydride unit and the substituent represented by the formula (1) as the N-substituent In addition, an N-substituted amide unit derived from an unsaturated carboxylic acid unit and a substituent represented by the formula (1) as the N-substituent, an alkyl ester unit derived from an unsaturated carboxylic acid unit, What has the substituent represented by Formula (1) as the alkyl group is mentioned.
Examples of the unsaturated carboxylic acid constituting the N-substituted amide unit derived from the unsaturated carboxylic acid unit include acrylic acid and methacrylic acid. Specific examples of N-substituted amide units derived from unsaturated carboxylic acid units include N, N-dimethylaminopropylacrylamide, N, N-diethylaminoethylacrylamide, N, N-dimethylaminopropylmethacrylamide, N, N-diethylamino. Examples include quaternized propylmethacrylamide and the like.
Examples of the unsaturated carboxylic acid constituting the alkyl ester unit derived from the unsaturated carboxylic acid unit include acrylic acid and methacrylic acid. Specific examples of the alkyl ester unit derived from the unsaturated carboxylic acid unit include N, N-dimethylaminopropyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl methacrylate, and the like. Quaternized.
Two or more of these may be copolymerized.

  The polyolefin resin A in the present invention contains an olefinic hydrocarbon unit and a unit having a quaternized amino group, and may contain other monomer units as necessary.

  Other monomer units include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate; dimethyl maleate, diethyl maleate , Maleic esters such as dibutyl maleate; vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate and vinyl alcohol obtained by saponifying vinyl esters with basic compounds, etc .; acrylic acid, methacrylic acid, maleic acid, anhydrous Examples thereof include unsaturated carboxylic acids such as maleic acid, itaconic acid and itaconic anhydride.

  Especially, it is preferable that the polyolefin resin A in this invention has a (meth) acrylic acid ester unit. By having this unit, the coating film of the present invention using the polyolefin resin A is further improved in adhesion to the substrate.

  The content of other monomer units is preferably 25 mol% or less, more preferably from 0.1 to 20 mol%, still more preferably from 1 to 15 mol%. When the content exceeds 25 mol%, the strength of the coating film of the present invention using the polyolefin resin A tends to be lowered, which is not preferable.

  As molecular weight of polyolefin resin A in this invention, it is preferable that it is 5000-500000 in a mass mean molecular weight, 10000-200000 is more preferable, 15000-100000 is further more preferable, 20000-80000 is especially preferable. When the weight average molecular weight is less than 5,000, the adhesiveness and solvent resistance of the coating film of the present invention using the polyolefin resin A tend to decrease. When the weight average molecular weight exceeds 500,000, the polyolefin resin A is water-based. There is a tendency that aqueous dispersion in a medium becomes difficult.

  However, since a polyolefin resin is generally poorly soluble in a solvent, it may be difficult to measure the molecular weight. In such a case, the melt flow rate value indicating the fluidity of the molten resin is used as a measure of the molecular weight.

  The melt flow rate value of polyolefin resin A in the present invention (according to JIS K7210: 1999) is preferably 0.1 to 2000 g / 10 minutes, more preferably 0.5 to 1000 g / 10 minutes, It is more preferably 1 to 500 g / 10 minutes, and particularly preferably 2 to 200 g / 10 minutes. When the melt flow rate value exceeds 2000 g / 10 min, the adhesiveness and solvent resistance of the coating film of the present invention using the polyolefin resin A tend to decrease, and when it is less than 0.1 g / 10 min Tends to make it difficult to disperse the polyolefin resin in the present invention in an aqueous medium.

  The polyolefin resin A in the present invention has excellent processing characteristics, softness characteristics, etc., but the most characteristic property is that it is excellent in water dispersibility, and is stable in the acidic region by the aqueous dispersion method described later. It can be made into a cationic aqueous dispersion. In addition, since the polyolefin resin A in the present invention has excellent water dispersibility, it is not necessary to chlorinate for the purpose of improving solubility and water dispersibility, and it is preferable not to halogenate from the viewpoint of environmental conservation. .

  The method for producing the polyolefin resin A in the present invention is not particularly limited. In the present invention, the unit having a quaternized amino group includes an N-substituted imide unit derived from an unsaturated carboxylic anhydride unit, and a substituent represented by the above formula (1) as the N-substituent. It is preferable to have. Taking this as an example, after producing a polyolefin resin having a tertiary amino group as a precursor, a part or all of the tertiary amino group is quaternized with a quaternizing agent.

As a method for producing a polyolefin resin having a tertiary amino group as a precursor, (A) an unsaturated carboxylic acid anhydride and a primary amine compound having a substituent represented by the following formula (2) are imidized. A method in which an N-substituted imide derived from an unsaturated carboxylic anhydride unit is prepared in advance and copolymerized with an olefinic hydrocarbon and, if necessary, other monomers; (B) prepared in advance A method of grafting an N-substituted imide derived from an unsaturated carboxylic acid anhydride unit onto a polyolefin resin or olefin copolymer, (C) a copolymer comprising an olefinic hydrocarbon unit and an unsaturated carboxylic acid anhydride unit as constituent components Examples thereof include a method of imidizing a polymer and a primary amine compound having a substituent represented by the formula (2).
_{^{- (CH 2) n NR 1}} R 2 (2)
^(Wherein, R 1, ^{R 2} is a hydroxyalkyl group of 1 to 5 alkyl group or a C 1 to 5 carbon atoms, n is an integer of 1-5.)

  In particular, in the method (C), a copolymer having raw material olefinic hydrocarbon units and unsaturated carboxylic anhydride units as constituents is obtained as an olefin-carboxylic anhydride copolymer at a low price from the market. It is possible to imidize an amino compound without using a special apparatus, and it is possible to easily obtain a polyolefin resin having a tertiary amino group as a precursor, which is preferable. .

  Olefin hydrocarbon units and unsaturated carboxylic acid anhydrides constituting a copolymer having an olefinic hydrocarbon unit and an unsaturated carboxylic anhydride unit as constituent components (hereinafter abbreviated as an acid anhydride-containing copolymer). The kind and content of the substance unit may be those satisfying the structure of the polyolefin resin A obtained after the imidization reaction and the subsequent quaternization reaction. The acid anhydride-containing copolymer may have a monomer unit other than the olefinic hydrocarbon unit and the unsaturated carboxylic acid anhydride unit.

  Examples of the unsaturated carboxylic acid anhydride unit constituting the acid anhydride-containing copolymer include maleic anhydride and itaconic anhydride, and are maleic anhydride because they are easily copolymerized with olefinic hydrocarbon units. Is preferred.

  The content of the unsaturated carboxylic anhydride unit in the acid anhydride-containing copolymer is preferably 0.1 mol% or more and less than 10 mol%, and more preferably 0.1 mol% or more and less than 7 mol%. Preferably, it is 0.1 mol% or more and less than 4 mol%, more preferably 0.2 mol% or more and less than 3 mol%, and particularly preferably 0.3 mol% or more, 2 mol% or more. It is less than mol%, most preferably 0.3 mol% or more and less than 1 mol%. When the content of the unsaturated carboxylic acid anhydride is less than 0.1 mol%, the effect of improving the heat resistance of the resulting polyolefin resin A becomes insufficient, and it is difficult to disperse the polyolefin resin A in water. Become. On the other hand, when the content of the unsaturated carboxylic acid anhydride is 10 mol% or more, the storage stability after aqueous dispersion decreases, or the adhesion, water resistance, and solvent resistance of the resulting polyolefin resin A decrease. Tend to.

  In addition, as monomer units (other monomer units) other than the olefinic hydrocarbon units and unsaturated carboxylic anhydride units constituting the acid anhydride-containing copolymer, methyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as ethyl, propyl (meth) acrylate and butyl (meth) acrylate; maleic acid esters such as dimethyl maleate, diethyl maleate and dibutyl maleate; vinyl formate, vinyl acetate, vinyl propionate And vinyl alcohols obtained by saponifying vinyl esters with basic compounds, etc .; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid. Especially, it is preferable that the anhydride containing copolymer in this invention has a (meth) acrylic acid ester unit. By having this unit, the adhesiveness and adhesiveness to the base material of the coating film obtained when it is set as the aqueous dispersion of this invention improve more.

  The state of copolymerization of the acid anhydride-containing copolymer is not particularly limited, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization (graft modification).

  Specific examples of the acid anhydride-containing copolymer include ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, ethylene-maleic anhydride graft copolymer, ethylene- (meth) acrylate methyl- Maleic anhydride terpolymer, ethylene- (meth) acrylic acid ethyl-maleic anhydride terpolymer, ethylene- (meth) acrylic acid propyl-maleic anhydride terpolymer, ethylene- (meth) Ethylene- (meth) acrylic ester-maleic anhydride terpolymers such as butyl acrylate-maleic anhydride terpolymer, propylene-maleic anhydride graft copolymer, propylene-butene-maleic anhydride graft Examples thereof include a copolymer and a propylene-butene-ethylene-maleic anhydride graft copolymer.

  Among these, since the adhesiveness to the base material of the coating film using polyolefin resin A obtained is further improved, ethylene- (meth) methyl acrylate-maleic anhydride terpolymer, ethylene- (meta ) Ethyl acrylate-maleic anhydride terpolymer, ethylene- (meth) acrylic acid propyl-maleic anhydride terpolymer, ethylene- (meth) acrylate butyl-maleic anhydride terpolymer, etc. An ethylene- (meth) acrylic ester-maleic anhydride terpolymer is preferred.

  These acid anhydride-containing copolymers are available from Arkema “Bondyne”, “Rotada”, “Olevac”, Nippon Polyethylene “Lex Pearl ET”, “Adtex”, NOF “MODIPA”, Sanyo Chemical It can be widely obtained from the market as “Umex” manufactured by the company, “Admer” manufactured by Mitsui Chemicals, and “Auroren” manufactured by Nippon Paper Chemicals.

In the method (C) as described above, a tertiary amino group serving as a precursor is obtained by imidizing the acid anhydride-containing copolymer and an amino compound represented by the following formula (3). The polyolefin resin which has is obtained.
^{_{H 2 N- (CH 2) n}} NR 1 R 2 (3)
(Wherein R ¹ and R ² are alkyl groups having 1 to 5 carbon atoms or hydroxyalkyl groups having 1 to 5 carbon atoms, and n is an integer of 1 to 5)
^Wherein, R 1, ^{R 2} is a hydroxyalkyl group of 1 to 5 alkyl group or a C 1 to 5 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. When the number of carbon atoms is 6 or more, the boiling point of the amino compound is increased, and unreacted substances are likely to remain in the polyolefin resin having a tertiary amino group as a precursor to be obtained, resulting in a decrease in water resistance. When either or both of R ¹ and R ² are hydrogen, both amino groups in the amino compound molecule react with the carboxylic acid anhydride during the imidation reaction, resulting in olefins. The copolymer forms a crosslinked structure, making aqueous dispersion difficult.
Moreover, in formula, n is an integer of 1-5, Comprising: The integer of 2-4 is preferable and the integer of 2-3 is preferable. When n is 0, there is a risk of explosion during handling. When n is 6 or more, the boiling point of the amino compound is high, and it is not contained in the polyolefin resin having a tertiary amino group as a precursor. The reaction product tends to remain and water resistance decreases.

  As described above, the amino compound represented by the formula (3) (hereinafter abbreviated as “amino compound”) is a diamine having a primary amine and a tertiary amine in the molecule. It is possible to generate an N-substituted unsaturated carboxylic imide having a dialkylaminoalkyl group as a substituent by imide bonding of a primary amine in the molecule with a carboxylic acid anhydride of an acid anhydride-containing copolymer. Become.

  Examples of the amino compound represented by the formula (3) include N, N-dialkylaminoalkylamine, among which N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-dimethylaminobutylamine. N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminobutylamine and the like are preferable.

  In addition, when an acid anhydride-containing copolymer as described above and an amino compound are subjected to an imidization reaction, a known apparatus and method can be used. Examples thereof include a method of heating and stirring the acid anhydride-containing copolymer and the amino compound in a reaction vessel, and a method of heating and stirring continuously with an extruder.

  The polyolefin resin A can be obtained by quaternizing part or all of the tertiary amino group of the polyolefin resin having a tertiary amino group to be a precursor obtained by the above-described method with a quaternizing agent.

  Examples of the quaternizing agent that can be used in the present invention include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, ethyl bromide, benzyl bromide, methyl iodide, and ethyl iodide. , Alkyl halides such as benzyl iodide; epoxies such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether; methanesulfonic acid Examples thereof include alkyl such as methyl and methyl paratoluene sulfonate, and methyl aryl sulfonate. Among these, dialkyl sulfates and alkyl halides are preferable because of excellent quaternization reactivity, and dialkyl sulfates are more preferable. These may be used alone or in combination of two or more.

  The addition amount of the quaternizing agent is 0.5 to 5 times equivalent to the number of moles of the substituent represented by the formula (2) contained in the polyolefin resin having a tertiary amino group as a precursor. Moles are preferred, 0.6 to 2 times equivalent moles are more preferred, 0.8 to 1.5 times equivalent moles are more preferred, and 0.9 to 1.0 times equivalent moles are particularly preferred. When the content of the quaternizing agent is less than 0.5 equivalent mole, it is difficult to disperse the obtained polyolefin resin A in water, and when it exceeds 5 equivalent mole, the effect of addition does not change.

  As a quaternization method using a quaternizing agent, a known method can be used. For example, a polyolefin resin having a tertiary amino group as a precursor and a quaternizing agent are mixed in a reaction vessel. Examples thereof include a method of heating and stirring, and a method of continuously heating and stirring with an extruder. The reaction temperature required for quaternization is usually in the range of 30 to 200 ° C., and the required reaction time is usually 1 minute or longer. Under such reaction conditions, by mixing a polyolefin resin having a tertiary amino group as a precursor and a quaternizing agent, some or all of the substituents represented by the formula (2) are mixed. Can be quaternized to obtain a polyolefin resin A having a substituent represented by the formula (1).

  The oxygen scavenger of the present invention contains the polyolefin resin A having the above specific composition and the organic oxygen scavenger, but the total concentration (solid content concentration) of the polyolefin resin A and the organic oxygen scavenger is 1-40 mass% is preferable, 3-20 mass% is especially preferable, and 5-15 mass% is more preferable. When the solid content concentration is less than 1% by mass, it is difficult to form a coating film having a sufficient thickness when applied to the substrate. On the other hand, when the solid content concentration exceeds 40% by mass, the aqueous polyolefin resin in the present invention The dispersibility of the resin may decrease.

  Further, the mass ratio of the organic oxygen absorber and the polyolefin resin A contained in the oxygen scavenger and oxygen scavenger-containing coating of the present invention is not particularly limited. Considering the adhesion to the substrate and the deoxidizing effect of the deoxidizing coating agent, the mass ratio of the polyolefin resin A to the organic deoxidizing agent (polyolefin resin A / organic deoxidizing agent) is 1/99 to 99/1. In particular, it is preferably 1/99 to 70/30, more preferably 5/95 to 60/40.

  The oxygen scavenger of the present invention is an oxygen scavenger containing an organic oxygen absorber as described above and the polyolefin resin of the present invention in an aqueous medium. In addition, the aqueous medium in the deoxidation coating agent of this invention means water or the liquid mixture of water and an organic solvent.

  In the present invention, since the polyolefin resin A contains the quaternized substituent represented by the formula (1) and already has an amino cation, neutralization for neutralizing the amino group in particular. Even if an agent is not added, a stable dispersion can be obtained in an aqueous medium in an acidic region. The electrostatic repulsion between the amino cations can prevent aggregation between the polyolefin resin particles in the aqueous medium. As a result, the deoxidizing coating composition of the present invention becomes a cationic aqueous coating composition that is stable in the acidic region in which the polyolefin resin is uniformly dispersed.

  Conventionally, as a method for uniformly dispersing a polyolefin resin in an aqueous medium, a polyolefin resin having a carboxyl group at a terminal and a basic compound (specifically, ammonia, triethylamine, N, N-dimethylethanolamine, etc. There is also a method of neutralizing a polyolefin resin with a basic compound by containing an organic amine compound). At this time, carboxyl anions are generated by neutralization, and electrostatic repulsion between the generated carboxyl anions can prevent aggregation between polyolefin resin particles in an aqueous medium, and can impart dispersion stability. .

  When such a polyolefin resin having a carboxyl group is used, in order to maintain the dispersion stability of the polyolefin resin, it is necessary to maintain an aqueous dispersion in which the polyolefin resin is dispersed in an aqueous medium in the basic region. If an organic oxygen scavenger such as ascorbic acid is added to the aqueous dispersion in the basic region, the stability of the aqueous dispersion is reduced and the polyolefin resin is agglomerated or the organic oxygen scavenger is significantly decomposed. The problem of being promoted arises. Therefore, it is preferable that the oxygen scavenger containing an organic oxygen scavenger is maintained in a neutral to acidic region.

  Therefore, in the coating composition of the present invention, by using the polyolefin resin A having a quaternized amino group as described above, a stable cation can be obtained in an acidic region in which the polyolefin resin A is uniformly dispersed in an aqueous medium. Therefore, the organic oxygen scavenger can be contained stably, in other words, without significantly promoting decomposition.

  The deoxidizing paint of the present invention preferably has a pH of 2-6. If the pH of the coating exceeds 6, the storage stability of the coating may be poor. On the other hand, when the pH is less than 2, decomposition of the organic oxygen scavenger may be remarkably accelerated.

  To make the pH of the oxygen scavenger within this range, it is possible to disperse the polyolefin resin A in an aqueous medium, but it can also be adjusted by the content of the organic oxygen scavenger. It is. Moreover, pH adjustment is also possible by adding an acidic compound as needed. The acidic compound that can be added for the purpose of adjusting the pH preferably has an acid dissociation constant (pKa) of 8 or less. Specific examples include organic acids such as formic acid, acetic acid, propionic acid, butyric acid, and valeric acid; Examples include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid. Among these, organic acids having relatively low corrosivity are preferable, and formic acid and acetic acid are more preferable.

  It is preferable that the acidic compound is not contained in the oxygen scavenger-containing coating film of the present invention. When an acidic compound is contained in the oxygen-absorbing agent-containing coating film of the present invention, the adhesion to the substrate tends to be lowered or the water resistance tends to be lowered. For this reason, it is preferable that an acidic compound is volatile, specifically, it is preferable that a boiling point is 20-250 degreeC, 30-200 degreeC is more preferable, 50-150 degreeC is further more preferable, 50-120 ° C is particularly preferred.

  In the deoxidizing paint of the present invention, the polyolefin resin A is dispersed in an aqueous medium, and the number average particle diameter of the polyolefin resin A in the deoxygenating paint is 1000 nm or less. Among them, 500 nm or less is preferable, 200 nm or less is more preferable, 100 nm or less is more preferable, 90 nm or less is particularly preferable, and 80 nm or less is most preferable. When the number average particle diameter exceeds 1000 nm, the storage stability of the coating tends to decrease, or the film-forming property upon coating tends to be non-uniform. In addition, it is possible to make the number average particle diameter of polyolefin resin A into 1000 nm or less by obtaining the deoxidation coating agent of this invention with the manufacturing method as mentioned later.

  Furthermore, the volume average particle diameter of the polyolefin resin A in the coating is preferably 1000 nm or less, preferably 500 nm or less, more preferably 200 nm or less, further preferably 100 nm or less, and particularly preferably 90 nm or less. When the volume average particle diameter of the polyolefin resin A exceeds 1000 nm, the storage stability of the coating tends to decrease, or the film-forming property upon coating tends to be non-uniform.

  The particle size distribution degree (volume average particle size / number average particle size) of the polyolefin resin A in the coating agent is preferably 1 to 3, from the viewpoint of storage stability and coating property of the coating agent. 5 is more preferable, and 1-2 is more preferable. When the degree of distribution of the particle diameter exceeds 3, the storage stability of the coating may be lowered.

  Here, the number average particle diameter and the volume average particle diameter of the polyolefin resin A are measured by a dynamic light scattering method which is generally used for measuring the particle diameter of the fine particles.

  It is preferable that the deoxygenating coating material of the present invention substantially does not contain a nonvolatile aqueous dispersion aid. When the non-volatile aqueous dispersion aid is contained, it remains in the coating film obtained by applying the coating agent, and the coating film is plasticized or hydrophilized. For this reason, the adhesiveness to the base material of a coating film, water resistance, solvent resistance, etc. fall. In addition, there is a concern that the non-volatile auxiliary agent bleeds out to the surface of the coating film to reduce the deoxygenation function.

  Here, “substantially free of non-volatile aqueous dispersion aid” means that the non-volatile aqueous dispersion aid is not actively added to the deoxidized coating agent, and is 100 parts by mass of polyolefin resin A. It means that the content of the non-volatile aqueous dispersion aid is less than 0.1 parts by mass, and preferably this content is zero. Nonvolatile means that it does not have a boiling point at normal pressure or has a high boiling point (for example, 300 ° C. or higher) at normal pressure.

  "Nonvolatile aqueous dispersion aid" refers to a nonvolatile drug or compound added for the purpose of promoting aqueous dispersion or stabilizing aqueous dispersion in aqueous dispersion of polyolefin resin A. Specific examples include emulsifiers, compounds having a protective colloid effect, modified waxes, acid-modified compounds having a high acid value, and water-soluble polymers. Examples of the emulsifier include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide. Compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters Examples of the cationic emulsifier include quaternary ammonium salts such as alkyltrimethylammonium salt and dialkyldimethylammonium salt, and alkylamine salts. Examples of the amphoteric emulsifier include laurylbetaine, lauryldimethylamine oxide, and the like. It is done.

  Compounds having protective colloid action, modified waxes, high amino modified compounds, acid modified compounds with high acid value, water-soluble polymers include polyvinyl alcohol (PVA), amino modified PVA, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch , Polyvinyl pyrrolidone, polyacrylic acid and salts thereof, amino group-containing polyethylene wax, amino group-containing polypropylene wax, amino group-containing polyethylene-propylene wax, etc. Examples thereof include water-soluble acrylic copolymers having amino groups, gelatin, gum arabic, and casein, which are generally used as fine particle dispersion stabilizers.

  In the present invention, the aqueous medium refers to water or a mixed liquid of water and an organic solvent. When the aqueous medium contains an organic solvent, the coating property to the substrate can be improved.

  The content of the organic solvent in the oxygen scavenging agent of the present invention is the ratio of the polyolefin resin A and the organic oxygen scavenger, the total concentration of the polyolefin resin A and the organic oxygen scavenger (solid content concentration), pH, organic Although various adjustments are made depending on the type and use of the solvent, it is preferably 1 to 97% by mass, more preferably 5 to 95% by mass in the coating agent, and 10 to 90% by mass. Is more preferable, and it is especially preferable that it is 20-80 mass%. When the organic solvent content exceeds 97% by mass, the storage stability of the coating may be lowered. When it is less than 1% by mass, the effect of improving the coating property tends to be poor.

  In addition, when the aqueous dispersion of polyolefin resin A, which will be described later, is added, an organic solvent is added so that even if the content of quaternized amino groups is small, a nonvolatile aqueous dispersion aid is substantially added. Even if not, the dispersion of the polyolefin resin in the aqueous medium in the present invention can be promoted, and the particle diameter of the polyolefin resin in the present invention can be reduced.

  In the aqueous dispersion of the polyolefin resin in the present invention, the content of the organic solvent in the aqueous medium is preferably 50% by mass or less, more preferably 1 to 40% by mass, and more preferably 2 to 35% by mass. More preferably, 3-30 mass% is especially preferable. When the content of the organic solvent exceeds 50% by mass, the effect of promoting aqueous dispersion tends to be unchanged or reduced.

  The organic solvent preferably has a solubility in water at 20 ° C. of 50 g / L or more, more preferably 100 g / L or more, and 600 g in order to improve the storage stability of the deoxygenating coating. / L or more is more preferable, and it is particularly preferable that it dissolves at an arbitrary ratio with water at 20 ° C.

  Moreover, it is preferable that the boiling point of an organic solvent is 30-250 degreeC, and it is more preferable that it is 50-200 degreeC. When the boiling point of the organic solvent is less than 30 ° C., the proportion of volatilization during preparation or storage of the deoxidized coating agent or during coating increases, and the effect of addition may not be sufficiently enhanced. Moreover, also in the aqueous dispersion of polyolefin resin A described later, the volatilization ratio increases, and the dispersion efficiency may not be sufficiently increased. When the boiling point exceeds 250 ° C., it tends to remain in the coating film obtained from the coating agent, and the adhesiveness to the substrate, water resistance and solvent resistance tend to decrease.

  Specific examples of the organic solvent having a solubility in water at 20 ° C. of 50 g / L or more and a boiling point of 30 to 250 ° C. include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol. , Tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and the like; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone and isophorone, ethers such as tetrahydrofuran and dioxane; ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate , Isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, dimethyl carbonate, etc., ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene Glycol glycol derivatives such as methyl ether acetate; more, 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, and the like. In addition, you may use these organic solvents in mixture of 2 or more types.

  Among the above, from the viewpoint of price and handling, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether are preferable. Ethanol, n-propanol, isopropanol and tetrahydrofuran are particularly preferred.

  In addition, to the deoxidizing paint of the present invention, addition of a resin other than the polyolefin resin in the present invention, a leveling agent, an antifoaming agent, an antioxidant, an ultraviolet absorber, a coloring agent, etc., as long as the characteristics are not impaired. Things may be added.

  Especially, the hardness of the coating film obtained can be raised by adding a crosslinking agent. As a crosslinking agent, a crosslinking agent having a self-crosslinking property; a compound having a plurality of functional groups that react with an amino group, an acrylate ester or a carboxyl group in a molecule; a metal complex having a multivalent coordination site, or the like is used. Specifically, hydrazide compounds, isocyanate compounds, melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents, organic peroxides, and the like are preferable. Two or more of these crosslinking agents may be used in combination.

Next, a method for producing the deoxidizing paint of the present invention will be described.
From the viewpoint of dispersion stability of polyolefin resin A, an aqueous dispersion of polyolefin resin A is used as a method for obtaining an oxygen scavenger containing an organic oxygen scavenger as described above, a polyolefin resin having a specific composition, and an aqueous medium. It is most preferable to prepare in advance and obtain it by mixing with an organic oxygen scavenger. If it does in this way, the outstanding dispersion | distribution and storage stability which polyolefin resin aqueous dispersion has will be maintained, and the function maintenance of an organic oxygen absorber will become easy by mixing with an organic oxygen absorber when needed. Hereinafter, this method will be described in detail.

First, the manufacturing method of the aqueous dispersion of polyolefin resin A is demonstrated.
As an aqueous dispersion method for obtaining an aqueous dispersion of polyolefin resin A, a method of heating and stirring together with an aqueous medium in a sealable container is preferable. Any container may be used as long as it is equipped with a tank into which a liquid can be charged and can appropriately stir the mixture of the aqueous medium and the resin powder or granular material charged into the tank. As such an apparatus, a solid / liquid stirring apparatus or an emulsifier can be used, and it is preferable that the apparatus is pressure resistant. The stirring method and the rotation speed of the stirring are not particularly limited, but sufficient aqueous formation can be achieved even with low-speed stirring at which the resin is in a floating state in an aqueous medium, and high-speed stirring (for example, 1000 rpm or more) is not essential. For this reason, the aqueous dispersion can be produced with a simple apparatus.

  A polyolefin resin A and an aqueous medium (water and an organic solvent) are charged into the container as described above, and then the temperature in the tank is 80 to 250 ° C, preferably 90 to 200 ° C, more preferably 100 to 190 ° C. While maintaining the temperature, the polyolefin resin A can be sufficiently dispersed by preferably stirring for 5 to 180 minutes. Thereafter, the aqueous dispersion can be obtained by cooling to 40 ° C. or lower, preferably with stirring. When the temperature in the tank is less than 80 ° C., the dispersion effect of the polyolefin resin A is low, and even if the temperature exceeds 250 ° C., the effect of aqueous dispersion is not further improved.

  According to this method, an aqueous dispersion in which the polyolefin resin A is well dispersed can be obtained without substantially adding a non-volatile aqueous additive.

  The aqueous dispersion obtained by the above-described method is very well dispersed, and there is little or no undispersed resin remaining. However, a filtration step may be provided when the aqueous dispersion is dispensed in order to remove foreign substances in the container and a small amount of undispersed resin. Although the filtration method is not limited, For example, the method of carrying out pressure filtration (for example, air pressure 0.5MPa) with a 300 mesh stainless steel filter (wire diameter 0.035mm, plain weave) is mentioned. By providing such a filtration step, even if an undispersed resin is present, it can be removed, so that the use of an aqueous dispersion is not a problem in subsequent steps.

  As described above, an aqueous dispersion in which the polyolefin resin A is uniformly dispersed in an aqueous medium is prepared.

  The number average particle size of the polyolefin resin A in the aqueous dispersion is preferably 1000 nm or less, more preferably 500 nm or less, more preferably 200 nm or less, still more preferably 100 nm or less, and particularly preferably 90 nm or less. Preferably, 80 nm or less is most preferable. When the number average particle diameter exceeds 1000 nm, the storage stability of the aqueous dispersion tends to decrease, or the film-forming property when applied tends to be non-uniform.

  Furthermore, the volume average particle diameter of the polyolefin resin A in the aqueous dispersion is preferably 1000 nm or less, preferably 500 nm or less, more preferably 200 nm or less, still more preferably 100 nm or less, and particularly preferably 90 nm or less. When the volume average particle diameter of the polyolefin resin A exceeds 1000 nm, the storage stability of the aqueous dispersion tends to decrease, or the film-forming property upon application tends to be non-uniform.

  Further, a part of the organic solvent contained in the aqueous dispersion of polyolefin resin A can be removed from the aqueous dispersion by a solvent removal operation called stripping. By such stripping, the content of the organic solvent can be reduced to 0.1% by mass or less as necessary. Even if the content of the organic solvent is 0.1% by mass or less, there is no influence on the performance of the aqueous dispersion. Examples of the stripping method include a method in which the aqueous dispersion is heated with stirring at normal pressure or reduced pressure to distill off the organic solvent.

  As the solid content concentration of the polyolefin resin A contained in the aqueous dispersion, the aqueous dispersion is used in order to maintain good mixing stability and coating properties when used as a deoxygenating coating, and thickness when applied. 2-60 mass% is preferable, 5-50 mass% is more preferable, 10-45 mass% is further more preferable.

  By mixing the aqueous dispersion of polyolefin resin A obtained as described above and an organic oxygen scavenger, the oxygen scavenger of the present invention can be obtained. In mixing, a known apparatus can be used. In addition, in order to maintain the dispersion stability of the deoxidized coating material of the present invention, it is preferable to adjust the pH so that the pH of the aqueous dispersion becomes 2-6.

  In addition, as a method for adjusting the total concentration (solid content concentration) of the polyolefin resin A and the organic oxygen scavenger in the oxygen scavenger of the present invention, for example, a method of distilling off the aqueous medium in the paint, A method of diluting with water or the above-mentioned organic solvent can be mentioned, and the total concentration can be easily adjusted.

Next, the coating film and laminate of the present invention will be described.
The deoxygenation coating agent of the present invention is excellent in film forming property (coating film forming property), and can form a coating film easily by coating and drying. Furthermore, since it has excellent adhesion to a wide variety of substrates such as resin materials, paper, synthetic paper, fabrics, metal materials, and glass materials, these materials can be used as the substrate.
The laminate of the present invention is obtained by laminating the oxygen scavenger-containing coating film of the present invention on a substrate. The oxygen scavenger-containing coating on the substrate is preferably obtained by applying the oxygen scavenger of the present invention.

  The thickness of the oxygen scavenger-containing coating in the laminate of the present invention can be appropriately selected depending on the form and required performance, but is preferably 0.05 to 1000 μm, more preferably 0.1 to 100 μm. Preferably, 0.2-50 micrometers is especially preferable.

  Examples of paper that can be used for the substrate include Japanese paper, craft paper, liner paper, art paper, coated paper, carton paper, glassine paper, semi-glassine paper, and the like.

  The structure of the synthetic paper that can be used for the substrate is not particularly limited, and may be a single layer structure or a multilayer structure. As a multilayer structure, for example, a two-layer structure of a base material layer and a surface layer, a three-layer structure in which a surface layer exists on the front and back surfaces of the base material layer, and another resin film layer exists between the base material layer and the surface layer. A multilayer structure can be exemplified. Each layer may contain an inorganic or organic filler. A microporous synthetic paper having a large number of fine voids can also be used.

  Resin materials that can be used for the substrate include polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polylactic acid (PLA), polyolefin resins such as polyethylene (PE) and polypropylene (PP), and polystyrene. Resin, nylon 6, polyamide resin such as poly-m-xylylene adipamide (MXD6 nylon), polycarbonate resin, polyacrylonitrile resin, polyimide resin, and multilayers of these resins (for example, nylon 6 / MXD6 nylon / Nylon 6, nylon 6 / ethylene-vinyl alcohol copolymer / nylon 6), mixtures and the like.

  Base materials made of these resin materials include those formed into a plate shape by injection molding, etc., those melted and stretched into a sheet shape, those obtained by further stretching a sheet into a film shape, resin materials or raw materials thereof. Examples include a solution obtained by coating and drying the solution. These resins may contain known additives and stabilizers such as antistatic agents, plasticizers, lubricants, antioxidants and the like. Moreover, in order to improve the adhesiveness when laminating with other materials, the surface of the base material made of a resin material may be subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment and the like. Furthermore, silica, alumina or the like may be deposited.

  Examples of the fabric that can be used for the substrate include fibers made of the above-described synthetic resins, and woven and knitted fabrics and nonwoven fabrics using natural fibers such as cotton, silk, and hemp.

  Examples of metal materials that can be used for the substrate include metal foils such as aluminum foil and copper foil, and metal plates such as aluminum plates and copper plates. Examples of glass materials include glass plates and fabrics made of glass fibers. Is mentioned.

  As a method of providing the oxygen scavenger-containing coating film of the present invention on a substrate, a method of removing an aqueous medium or the like from the oxygen scavenger after applying the oxygen scavenger coating of the present invention on the substrate, on a release paper And a method of transferring a coating film obtained by applying the deoxidizing coating agent of the present invention to remove an aqueous medium or the like onto a substrate. Among these, the former method is simple and preferable.

  Since the deoxidizing coating composition of the present invention is excellent in film forming property, when coating, known film forming methods such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain A flow coating method, a spray coating method, a dip coating method, a brush coating method, or the like can be employed, and it can be uniformly applied to various substrate surfaces. After coating, if necessary, the temperature is set near room temperature, followed by drying or heat treatment for drying and baking to remove the aqueous medium and the like. As a result, it is possible to obtain a laminate in which a uniform coating film is well adhered (adhered) to the substrate surface.

  When performing heat treatment for drying or drying and baking, a normal hot air circulation type oven, an infrared heater, or the like may be used. Further, the heating temperature and the heating time are appropriately selected depending on the properties and types of the coating agent and the base material. However, in consideration of economy, the heating temperature is preferably 30 to 250 ° C., 60 to 200 ° C. is more preferable, 80 to 180 ° C. is particularly preferable, and the heating time is preferably 1 second to 20 minutes, more preferably 5 seconds to 15 minutes, and particularly preferably 5 seconds to 10 minutes. As described above, when a cross-linking agent is added to the deoxidized coating composition of the present invention, it is desirable to appropriately select the heating temperature and time depending on the type of the cross-linking agent in order to sufficiently advance the cross-linking reaction.

  Since the oxygen scavenger-containing coating film of the present invention contains the polyolefin resin A, it has heat sealability. Therefore, as a laminate of the present invention, when a resin film, a sheet, synthetic paper, or a metal foil is used as a base material, an oxygen scavenger-containing coating film is overlapped and heat-treated to form a package. You can also Examples of such a package include a three-side seal bag, a four-side seal bag, a gusset packaging bag, and a pillow packaging bag.

  Furthermore, the laminate of the present invention preferably has a sealant layer laminated on the oxygen scavenger-containing coating film. The sealant layer does not exhibit adhesiveness at room temperature and has heat sealability. By providing the sealant layer, the heat sealability can be further improved, which is suitable for the above-described package.

  The method for providing the sealant layer is not particularly limited, but a sealant resin described later is formed into a sheet or film, placed on the coating surface of the laminate of the present invention, and bonded by heat (thermal lamination, dry lamination), Examples thereof include a method of extruding and bonding a melted sealant resin to the coating surface of the laminate of the present invention (extrusion laminating method).

  Since the oxygen-absorbing agent-containing coating film of the present invention contains the polyolefin resin A, since it has excellent laminating suitability, any laminating method can be used, but the extrusion laminating method, which is the most economical method, This is an optimum method capable of exhibiting the performance of the deoxidizing paint of the present invention.

  The thickness of the sealant layer is preferably in the range of 10 to 50 μm, and more preferably in the range of 20 to 40 μm. If the sealant layer exceeds 50 μm, the deoxygenation reaction may take time. On the other hand, if the thickness of the sealant layer is less than 10 μm, the effect of providing the sealant layer is poor.

  As the resin forming the sealant layer, a known sealant resin can be used. Specifically, polyethylene such as low density polyethylene (LDPE) and high density polyethylene (HDPE), acid-modified polyethylene, polypropylene, acid-modified polypropylene, copolymerized polypropylene, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic Examples thereof include polyolefin resins such as acid ester copolymers, ethylene- (meth) acrylic acid copolymers, and ionomers. Among them, polyethylene resins excellent in low-temperature heat sealability are preferable, and polyethylene is particularly preferable because of its low cost.

  Further, in a laminate having a sealant layer, a polypropylene resin chuck may be provided on the sealant layer to form a packaging bag with a chuck.

  Furthermore, in the laminate of the present invention, it is preferable that the substrate has a barrier property. When the base material has barrier properties, for example, in the case of a package, it is possible to prevent oxygen from being mixed from the outside.

  Examples of the base material having a barrier property include a base formed from a soft metal foil such as an aluminum foil, or a resin material having a barrier property such as vinylidene chloride resin, modified PVA, ethylene vinyl alcohol copolymer, MXD nylon, and the like. Examples thereof include a base material obtained by laminating a barrier layer on a base material formed of a material or a material having no barrier property.

  Examples of the barrier layer include a soft metal foil such as an aluminum foil, a vapor deposition layer such as aluminum vapor deposition, silica vapor deposition, alumina vapor deposition, and silica alumina binary vapor deposition, and a layer made of the above-described resin material having a barrier property. .

The barrier property of the substrate having a barrier property may be appropriately selected depending on the use such as the contents to be packaged and the storage period, but the oxygen permeability is 100 ml / m ² · day · MPa (20 ° C., 90% RH) or less. is preferably, more preferably less ^{20ml / m 2 · day · MPa} , 10ml / m 2 · day · MPa more preferably ^{less, 1ml / m 2 · day ·} MPa or less are particularly preferred. The water vapor permeability is preferably 100 g / m ² · day (40 ° C., 90% RH) or less, more preferably 20 g / m ² · day or less, still more preferably 10 g / m ² · day or less, and 1 g / m. ² · day or less is particularly preferable.

  As the base material having a barrier property, a base material obtained by laminating a barrier layer on a base material formed from a material having no barrier property is preferable. From the viewpoint of the barrier property, an aluminum foil or aluminum is preferable as the barrier layer. Further, a vapor deposition layer such as silica and alumina is preferable, and an aluminum foil is more preferable because it is inexpensive. Although the thickness of aluminum foil is not specifically limited, The range of 3-50 micrometers is preferable from an economical surface.

  As a base material on which a vapor deposition layer such as aluminum, silica, and alumina is laminated, it is easy to use a commercially available vapor deposition film. As such a vapor deposition film, for example, “IB series” manufactured by Dai Nippon Printing Co., Ltd. "GL, GX series" manufactured by Toppan Printing Co., Ltd., "Barrier Rocks", "VM-PET", "YM-CPP", "VM-OPP" manufactured by Toray Film Co., Ltd., "Tech Barrier" manufactured by Mitsubishi Plastics "Metaline" manufactured by Tosero Co., Ltd., "MOS", "Tetrait", and "Bright" manufactured by Oike Kogyo Co., Ltd. can be used. A protective coat layer may be provided on the vapor deposition layer.

  In addition, as the base material having a barrier property, there are those in which a coating material containing a barrier resin is coated on the base material and those in which the resin is laminated on the base material by a co-extrusion method. Is preferable because it is simple.

  Commercially available barrier films include Kuraray's "Clarista" and "Eval", Kureha Chemical Industry's "Besera", Mitsubishi Plastics' "Super Neal", Kojin's "Co-Barrier", and Unitika "Savix", "Embron M", "Embron E", "Emblem DC", "Embret DC", "NV", manufactured by Tosero "K-OP", "A-OP", manufactured by Daicel "Senesi" and so on.

  As a method of laminating the coating film of the present invention on a substrate having a barrier property, after applying the deoxidizing coating agent of the present invention on the substrate having the barrier property described above, it is dried to obtain an aqueous medium or the like. A method of removing, a method of transferring a coating film obtained by applying the deoxidizing coating agent of the present invention on a release paper and then drying to remove an aqueous medium etc. onto a substrate having a barrier property The former method is simple and preferable.

  Further, as a method of obtaining a laminate of the present invention having a sealant layer using a substrate having a barrier property, for example, the deoxidizing coating agent of the present invention is applied onto a substrate having a barrier property, A method of laminating the sealant layer by removing the aqueous medium by drying to form a coating film and then melt-extruding (extrusion laminating) the resin in-line is simple and particularly preferred.

  In addition, in the laminate of the present invention, as long as the effects as described above are not impaired, a layer capable of imparting other functions, specifically, a moisture absorption layer, a printing layer, an antistatic layer, an ultraviolet absorption layer, An adhesive layer, an adhesive layer, and the like may be laminated.

  The deoxidant-containing coating film of the present invention exhibits a deoxygenation function when moisture comes close to it. For this reason, as long as moisture is not in close proximity, it can be stored in the atmosphere for a long time without having to maintain a special environment, and there is no problem in use after long-term storage.

  Even in a laminate in which a sealant layer is laminated on a coating film, a deoxygenation reaction proceeds, so that a bag can be made and a liquid can be sealed.

  When the laminate of the present invention is used to develop a deoxygenation function, gas or liquid moisture is preferably used as moisture to be brought close to, and liquid is most preferred because of the wide range of use. Its liquidity is preferably acidic or basic rather than neutral.

  When bringing the liquid close, moisture may be brought into direct contact with the coating film or sealant layer of the laminate, or moisture may be adsorbed on a water-absorbing material and the material may be brought into contact with the coating film or sealant layer. . When using the laminated body of this invention as a packaging material, the water | moisture content derived from the content can also be used as a method of making a water | moisture content contact a laminated body directly. That is, when the laminate is used as a packaging material and an article holding a liquid or moisture is enclosed in the packaging material, a deoxidation function starts to appear.

  Moreover, when water | moisture content is adsorb | sucked to the material which has water absorption, any material derived from a plant, an animal origin, petroleum origin, and a mineral can be used as a material which has water absorption. Any shape can be used as long as it can contact the deoxidation layer, such as a sheet shape, a thread shape, a cotton shape, a gel shape, and a clay shape. Specifically, paper, a nonwoven fabric, a woven / knitted fabric, an activated carbon sheet, etc. are mentioned.

  The activated carbon sheet is a sheet of activated carbon (a substance mainly composed of porous carbon). The manufacturing method of activated carbon and an activated carbon sheet is not specifically limited, A commercial item can also be used. For example, “activated carbon fiber sheet” manufactured by Unitika Ltd., “AFT activated carbon sheet” manufactured by Ajinomoto Fine Techno Co., “kura sheet” manufactured by Kuraray Chemical Co., Ltd. and the like can be exemplified.

The present invention will be specifically described below with reference to examples. Various characteristic values in the examples were measured or evaluated by the following methods.
1. Characteristics of acid anhydride-containing copolymer and polyolefin resin (1) Structure
^It calculated | required from < ¹ > H-NMR analysis (ECA500, 500MHz by JEOL Ltd.). Tetrachloroethane (d ₂ ) was used as a solvent and measurement was performed at 120 ° C.
(2) Mass average molecular weight measurement A GPC apparatus (model HLC-8020GPC, column is TSK-GEL) manufactured by Tosoh Corporation was used. The eluent was orthodichlorobenzene, and the mass average molecular weight was measured at 40 ° C. It calculated | required from TSK standard polystyrene conversion. In addition, when it cannot measure without melt | dissolving in trichlorobenzene, the following melt flow rate value was made into the parameter | index of molecular weight.
(3) Melt flow rate value (MFR)
Measured by the method described in JIS K7210: 1999 (polyethylene resin is 190 ° C., 2160 g load).

2. Characteristics of aqueous dispersion of polyolefin resin (1) Appearance The color tone of the aqueous dispersion was evaluated by visual observation.
(2) Average particle diameter of polyolefin resin in aqueous dispersion Using Nikkiso Co., Ltd., Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340, dynamic light scattering method), the aqueous dispersion after 300 mesh filtration The number average particle diameter (nm) and volume average particle diameter (nm) of the polyolefin resin were determined. The refractive index of the resin used for particle diameter calculation was 1.50, and the refractive index of the medium was 1.33.
(3) Solid content concentration An appropriate amount of the aqueous dispersion after 300 mesh filtration was weighed, and this was heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight, and the solid content concentration (mass%) was determined. .
(4) pH
The pH at a temperature of 20 ° C. was measured using a pH meter (Horiba, Ltd., F-52).

3. Characteristics of coating material (1) Appearance The color tone of the coating material was evaluated by visual observation.
(2) Average particle diameter of polyolefin resin in coating material Polyolefin resin in coating material after 300 mesh filtration using Nikkiso Co., Ltd., Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340, dynamic light scattering method) The number average particle diameter (nm) and the volume average particle diameter (nm) were determined. The refractive index of the resin used for particle diameter calculation was 1.50, and the refractive index of the medium was 1.33.
(3) Solid Content Concentration An appropriate amount of the coating material after 300 mesh filtration was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight, and the solid content concentration (mass%) was determined.
(4) pH
The pH at a temperature of 20 ° C. was measured using a pH meter (Horiba, Ltd., F-52).

4). Characteristics of Coating Film and Laminate (1) Deoxygenation capacity The oxygen concentration change in the sample bag was evaluated.
<Laminated bodies of Examples 1 to 11 and Comparative Examples 1, 2, and 5>
Two 5 cm square samples were cut from the obtained laminate, and the filter paper or activated carbon sheet (collectively referred to as “sandwich material”) shown below was sandwiched between the two laminates so that the coating film surfaces were in contact with each other. The thing was made into the deoxidation material. Enclose the oxygen scavenging material in a bag made of a three-layer film of polyester, aluminum, and polyethylene laminated in this order ("Rami Zip" manufactured by AS ONE), remove the air in the bag, and heat seal the insertion slot The bag was sealed. Thereafter, 5 ml of air was injected by a syringe through a septum to prepare a sample bag.
<Laminated bodies of Examples 12 and 13 and Comparative Example 6>
Two samples of 10 cm square were cut out from the obtained laminate, and the activated carbon sheet shown below was sandwiched between the two laminates so that the sealant layers of the two laminates were in contact with each other. The four sides were sealed by heat sealing with a seal width of 20 mm. Thereafter, 5 ml of air was injected by a syringe through a septum to prepare a sample bag.
The sample bag prepared above was stored in the storage environment (A or B) shown below, and then the oxygen concentration in the sample bag was measured using an oxygen concentration meter (Check Point O ₂ / CO ₂ manufactured by PBI Dansentor). In addition, the oxygen concentration in the air measured with this apparatus was 21.0%.
Sandwich material (5cm square):
a: Filter paper containing 10% by mass aqueous sodium hydroxide (ADVANTEC, No. 1)
b: Water-containing activated carbon sheet (manufactured by Unitika, activated carbon fiber sheet FMS-C039)
Sample bag storage environment:
A: 25 ° C., 15 days B: 50 ° C., 10 days

(2) Adhesiveness As a base material, linear low density polyethylene (PE) film (manufactured by Tosero Co., Ltd., thickness 50 μm), stretched polypropylene (OPP) film (manufactured by Tosero Corp., thickness 50 μm), stretched polyethylene terephthalate (PET) film (Unitika, thickness 25 μm), stretched polyamide (Ny6) film (Unitika, thickness 25 μm) was used. After applying the deoxidizing paint obtained on each substrate with a wire bar, it was dried at 120 ° C. for 1 minute to obtain a laminate having a coating film having a thickness of 1 μm.
After leaving the obtained laminate at room temperature for 1 day, cellophane tape (TF-12 manufactured by Nichiban Co., Ltd.) was attached to the coating surface, and the degree of peeling when the tape was peeled off at a stretch was visually evaluated according to the following criteria. .
○: No peeling at all.
Δ: A part was peeled off.
X: Most peeled off.

(3) Laminate strength A test piece having a width of 15 mm was taken from the laminate, and a base material (aluminum foil) was removed from the end of the test piece by T-type peeling using a tensile tester (precision universal material testing machine 2020, manufactured by Intesco). ) And the sealant layer were peeled to measure the strength. The measurement was performed in an atmosphere of 20 ° C. and 65% RH at a pulling rate of 200 mm / min.

The following resins were used as the acid anhydride-containing copolymer.
HX8290: “Bondaine HX8290” manufactured by Arkema
UM1001: "Yumex 1001" manufactured by Sanyo Chemical
EA-MAH:
Ethylene, ethyl acrylate, and maleic anhydride were prepared by high-pressure radical polymerization based on the methods described in British Patent No. 2091745, US Pat. No. 4,617,366, and US Pat. No. 4,644,044.
The characteristic values of the acid anhydride-containing copolymer are summarized in Table 1.

(Production of polyolefin resin P-1)
A 1-liter separable flask equipped with a thermometer, a stirrer, a liquid injector, and a Dimroth is charged with 250 g of acid anhydride-containing copolymer “HX8290” and 500 g of toluene, and the stirrer is rotated at 100 prm. Then, the flask was put into an oil bath at 170 ° C. After a few minutes, it was confirmed that toluene was boiled, but the generated steam was refluxed into the flask through the Dimroth. After confirming that the resin was completely dissolved after several minutes, dimethylaminopropylamine [(H ₂ N— (CH ₂ ) ₃ N (CH ₃ ) ₂ ], hereinafter abbreviated as DMAPA) as an amino compound] Was added in an amount equivalent to 0.6 times the number of moles of the carboxylic anhydride unit of “HX8290”. The resin temperature in the flask after the addition was 115 ° C., and this state was maintained and an imidization reaction was performed. After 30 minutes, the mounting direction of the Dimroth was changed, and the pressure was further gradually reduced, and toluene and unreacted amino compound in the flask were removed by distillation. After confirming that no vapor of toluene and unreacted amino compound was generated from the inside of the flask, the pressure was further released for 10 minutes while maintaining the reduced pressure of 4 kPa (abs), the stirrer was stopped, the flask was taken out of the oil bath, The inner polyolefin resin P-1 was obtained.

(Production of polyolefin resin P-2)
Except having changed the acid anhydride containing copolymer into "UM1001", operation similar to polyolefin resin P-1 was performed, and polyolefin resin P-2 was obtained. The resin temperature during the imidation reaction was in the range of 113 to 118 ° C.

  The characteristic values of the obtained polyolefin resins P-1 and P-2 are shown in Table 2.

(Production of polyolefin resin Q-1)
In a 0.5 liter separable flask equipped with a thermometer, stirrer, liquid injector, and Dimroth, 150 g of polyolefin resin P-1 and 100 g of toluene were charged, and the stirrer was rotated at 100 prm. It put into the oil bath of 150 degreeC. After a few minutes, boiling of toluene was confirmed, but the generated steam was refluxed into the flask through the Dimroth. After a few minutes, it was confirmed that the polyolefin resin P-1 was completely dissolved. Next, diethyl sulfate (hereinafter abbreviated as DES) as a quaternizing agent was added in an amount of 1 equivalent to the number of moles of the substituent represented by the formula (2) contained in the polyolefin resin P-1. The temperature in the flask after the addition was 109 ° C., and this state was maintained to perform the quaternization reaction. After 30 minutes, the mounting direction of the Dimroth was changed, and the pressure was gradually reduced. Toluene and unreacted DES in the flask were removed by distillation. After confirming that no steam was generated from the inside of the flask, the pressure was released when the reduced pressure of 4 kPa (abs) was maintained for 10 minutes, the stirrer was stopped, the flask was taken out from the oil bath, and the inside of the flask was quaternized. Polyolefin resin Q-1 was obtained.

(Production of polyolefin resin Q-2)
The polyolefin resin P-1 used for the quaternization reaction was changed to the polyolefin resin P-2, and the same quaternization reaction as that of the polyolefin resin Q-1 was performed to obtain a polyolefin resin Q-2.

(Preparation of aqueous polyolefin resin dispersion E-1)
In a sealable 1 liter pressure-resistant glass container equipped with a stirrer and a heater, 140 g (20% by mass) of the obtained polyolefin resin Q-1 and n-propanol (hereinafter abbreviated as NPA) as an organic solvent in an aqueous medium Of distilled water was added so that the total amount of raw materials would be 700 g. Next, the container was sealed, and stirring and mixing were performed at a rotational speed of the stirring blade of 400 rpm. By stirring, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, the heater was turned on, the temperature inside the container was set to 130 ° C., and the mixture was further stirred for 120 minutes. Thereafter, the heater was turned off and cooled while stirring. Stirring was stopped when the internal temperature became 40 ° C. or lower, and the content in the glass container was filtered with a 300-mesh stainless steel filter to obtain a cationic aqueous dispersion E-1.

(Preparation of aqueous polyolefin resin dispersion E-2)
The polyolefin resin Q-1 was changed to the polyolefin resin Q-2, and the same operation as that of the aqueous dispersion E-1 was performed to obtain a cationic aqueous dispersion E-2.

(Preparation of aqueous polyolefin resin dispersion E-3)
In a sealed 1 liter pressure-resistant glass container equipped with a stirrer and a heater, 140 g (20% by mass) of an acid anhydride-containing copolymer “HX-8290” as a resin and triethylamine as an anhydrous maleic resin as a neutralizer Distilled water was charged so that the amount of the acid unit was 2.0 times equivalent mole, 140 g (20% by mass) of NPA as the organic solvent, and the total amount of the raw material was 700 g, the vessel was sealed, The mixture was stirred and mixed at a rotation speed of 400 rpm. By stirring, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, the heater was turned on, the temperature inside the container was set to 130 ° C., and the mixture was further stirred for 120 minutes. Thereafter, the heater was turned off and cooled while stirring. Stirring was stopped when the internal temperature became 40 ° C. or lower, and the content in the glass container was filtered with a 300-mesh stainless steel filter to obtain an anionic aqueous dispersion E-3.

(Preparation of aqueous polyolefin resin dispersion E-4)
An anionic aqueous dispersion E-4 was obtained in the same manner as in E-3 except that the acid anhydride-containing copolymer “EA-MAH” was used as the resin.

  The characteristic values of the obtained aqueous dispersions E-1 to E-4 are shown in Table 3.

Example 1
Ascorbic acid was used as an organic oxygen scavenger and added to the aqueous polyolefin resin dispersion E-1 so that ascorbic acid was 90 parts by mass with respect to 10 parts by mass of the polyolefin resin solid content. Furthermore, after adding NPA and distilled water so that the total content of NPA is 50% by mass of the coating material and the total solid content is 10% by mass, mixing and stirring the deoxygenating coating material Obtained.
And as a base material, after using the PET film (the unitika company make, thickness 100micrometer) and applying the deoxidation coating agent obtained by the corona treatment surface with a wire bar, it was dried at 120 degreeC for 1 minute, and thickness A laminate having a 4.5 μm thick coating film was obtained.
In addition, at the time of measuring the deoxygenation ability of the obtained laminate, the sandwich material a was used, and the sample bag storage environment was A.

Example 2
Except having used E-2 as a polyolefin resin aqueous dispersion, it carried out similarly to Example 1 and obtained the deoxidation coating agent. Further, a laminate was obtained in the same manner as in Example 1.
In addition, at the time of measuring the deoxygenation ability of the obtained laminate, the sandwich material a was used, and the sample bag storage environment was A.

Examples 3-5
The organic oxygen scavenger ascorbic acid was changed to tannic acid (Example 3), pyrocatechol (Example 4), and pyrogallol (Example 5). Got. Further, a laminate was obtained in the same manner as in Example 1.
In addition, at the time of measuring the deoxygenation ability of the obtained laminate, the sandwich material a was used, and the sample bag storage environment was A.

Example 6
A deoxygenation coating agent was obtained in the same manner as in Example 1 except that the amount of ascorbic acid added was changed so that ascorbic acid was 50 parts by mass with respect to 50 parts by mass of the solid content of the polyolefin resin. Further, a laminate was obtained in the same manner as in Example 1.
In addition, at the time of measuring the deoxygenation ability of the obtained laminate, the sandwich material a was used, and the sample bag storage environment was A.

Example 7
In the measurement of the deoxygenation capacity of the laminate obtained in Example 1, the sandwich material b was used, and the sample bag storage environment was A.

Example 8
In the measurement of the deoxygenation ability of the laminate obtained in Example 6, the sandwich material b was used, and the sample bag storage environment was A.

Examples 9, 10
A laminate was obtained in the same manner as in Example 1 except that the deoxygenation coating agent obtained in Example 6 was used and the thickness of the coating film was changed to 1.5 μm and 8.0 μm.
In the measurement of the deoxygenation capacity of the obtained laminate, the sandwich material b was used and the sample bag storage environment was A.

Example 11
The laminate obtained in Example 6 was stored in the atmosphere at a temperature of 25 ° C. and a humidity of 60% for 10 days, and then the oxygen scavenging ability of the laminate was measured.
In the measurement of the deoxygenation capacity of the obtained laminate, the sandwich material b was used, and the sample bag storage environment was B.

Example 12
A biaxially stretched polyester resin film ("Embret PET-12" manufactured by Unitika Ltd.) with a thickness of 12 μm is used as the base material, and a two-component curable polyurethane system is applied to the corona-treated surface of the polyester resin film using a gravure coater. A base material having a barrier layer in which an adhesive (made by Toyo Morton Co., Ltd.) is coated and dried so that the coating amount after drying is 5 g / m ^2, and an aluminum foil having a thickness of 7 μm is bonded as a barrier layer. Got.
Next, after applying the oxygen scavenger obtained in Example 6 on the aluminum foil surface of the barrier layer with a wire bar, the coating was dried at 120 ° C. for 1 minute to form a coating film having a thickness of 1.5 μm. It was.
Next, using a laminator equipped with an extruder, LDPE (L211 manufactured by Sumitomo Chemical Co., Ltd.) was melt-extruded as a sealant resin on the coating film to obtain a laminate in which a sealant layer having a thickness of 30 μm was formed.
In the measurement of the deoxygenation capacity of the obtained laminate, the sandwich material b was used, and the sample bag storage environment was B.

Example 13
An oxygen scavenger was obtained in the same manner as in Example 6 except that the organic oxygen scavenger ascorbic acid was changed to tannic acid. And the laminated body was obtained like Example 12 and the deoxygenation ability was measured.
In the measurement of the deoxygenation capacity of the obtained laminate, the sandwich material b was used, and the sample bag storage environment was B.

Comparative Example 1
Addition of isopropanol (hereinafter abbreviated as IPA) and distilled water to polyolefin resin aqueous dispersion E-1 so that the total content of IPA is 50% by mass of the coating material and the total solid content is 10% by mass Then, a mixture and agitation were used as the coating agent. And the laminated body was obtained like Example 1 and the deoxygenation ability was measured.
In the measurement of the deoxygenation capacity of the obtained laminate, the sandwich material a was used and the sample bag storage environment was A.

Comparative Example 2
Ascorbic acid and NPA in an aqueous solution adjusted to pH 3.2 by adding formic acid to distilled water, the solid content concentration is 10% by mass, and the total content of NPA is 50% by mass of the coating agent After the addition, a deoxygenation coating agent was obtained by mixing and stirring. Using the obtained deoxidizing paint, a laminate was obtained in the same manner as in Example 1, and the deoxidizing ability was measured.
In the measurement of the deoxygenation capacity of the obtained laminate, the sandwich material a was used and the sample bag storage environment was A.

Comparative Examples 3 and 4
Deoxygenating paint as in Example 1 except that polyolefin resin aqueous dispersions E-3 and E-4 were used and ascorbic acid was adjusted to 50 parts by mass with respect to 50 parts by mass of polyolefin resin solids. Although it tried to obtain, it aggregated and the coating agent was not able to be obtained.

Comparative Example 5
Ascorbic acid is used as an organic oxygen scavenger, and in an 8% by mass aqueous solution of PVA (“VC-10” manufactured by Nippon Vinegar Poval Co., Ltd., polymerization degree: 1,000) with respect to 50 parts by mass of PVA resin solid content Ascorbic acid was added to 50 parts by mass. Furthermore, after adding distilled water so that total solid content might be 10 mass%, the deoxidation coating agent was obtained by mixing and stirring.
A laminate was obtained in the same manner as in Example 1 except that the obtained deoxygenating coating was used, and the deoxygenating ability was measured.
In the measurement of the deoxygenation capacity of the obtained laminate, the sandwich material a was used and the sample bag storage environment was A.

Comparative Example 6
A laminate was obtained in the same manner as in Example 12 except that the deoxidizing paint prepared in Comparative Example 5 was used, and the deoxygenating ability was measured.
In the measurement of the deoxygenation capacity of the obtained laminate, the sandwich material b was used, and the sample bag storage environment was B.

  Table 4 shows the coating materials and coating films obtained in Examples 1 to 13 and Comparative Examples 1 to 6, and characteristic values and evaluations of the laminates.

As is clear from Examples 1 to 13, the coating film and laminate obtained from the deoxygenating coating material of the present invention were excellent in adhesion to various substrates and excellent in deoxidizing ability.
As is clear from Example 6, the adhesiveness to the substrate was improved by reducing the proportion of the organic oxygen absorber contained in the oxygen absorber coating. As is clear from Examples 9 and 10, the deoxygenation ability improved as the coating film thickness increased. Furthermore, as is clear from Examples 7 and 8, by contacting the hydrated activated carbon sheet with the deoxygenated coating film, it was possible to deoxidize well even if the liquidity of the water contacted with the coating film was not basic. Further, as is clear from Examples 12 and 13, even a laminate having a sealant layer on the coating film had a good oxygen scavenging ability and an excellent laminate strength. As apparent from Example 11, the coating film and laminate of the present invention were excellent in storage stability.
On the other hand, since the coating material of Comparative Example 1 did not contain an oxygen scavenger, the obtained laminate did not exhibit oxygen scavenging ability. Since the coating agent of Comparative Example 2 did not contain polyolefin resin A, it had poor adhesion. In Comparative Examples 3 and 4, an anionic aqueous dispersion comprising a polyolefin resin, a basic compound, and an aqueous medium was used as the aqueous polyolefin resin dispersion. Couldn't get. In Comparative Example 5, since PVA was used as the resin, the adhesiveness with the substrate was poor. In Comparative Example 6, since PVA was used as the resin, the laminate strength was poor.

Claims (15)

  An oxygen scavenger, comprising an organic oxygen scavenger, a polyolefin resin containing an olefinic hydrocarbon unit and a unit having a quaternized amino group, and an aqueous medium.   The content of units having a quaternized amino group is 0.1 mol% or more and less than 10 mol% with respect to 100 mol% of all structural units constituting the polyolefin resin. The deoxidizing paint according to 1.   The deoxygenating coating composition according to claim 1 or 2, wherein the unit having a quaternized amino group has a carbonyl group derived from an unsaturated carboxylic acid unit or an unsaturated carboxylic anhydride unit. The unit having a quaternized amino group has an N-substituted imide unit derived from an unsaturated carboxylic anhydride unit and a substituent represented by the following formula (1) as the N-substituent. The deoxidizing paint according to any one of claims 1 to 3.
_{^{- (CH 2) n N +}} R 1 R 2 R 3 · X - (1)
Wherein R ¹ and R ² are alkyl groups having 1 to 5 carbon atoms or hydroxyalkyl groups having 1 to 5 carbon atoms, R ³ is a residue of a quaternizing agent introduced by quaternization reaction, X ⁻ Is an anionic counter ion, and n is an integer of 1 to 5.)   The organic oxygen scavenger contains at least one of ascorbic acid, catechol, erythorbic acid, pyrogallol, hydroquinone, reducing sugar, and tannic acid. Oxygen paint.   pH is 2-6, The deoxidation coating agent in any one of Claims 1-5 characterized by the above-mentioned.   The deoxidizing paint according to any one of claims 1 to 6, which is substantially free of a non-volatile aqueous dispersion aid.   An oxygen scavenger-containing coating film comprising an organic oxygen scavenger and a polyolefin resin containing an olefinic hydrocarbon unit and a unit having a quaternized amino group.   The content of units having a quaternized amino group is 0.1 mol% or more and less than 10 mol% with respect to 100 mol% of all structural units constituting the polyolefin resin. 8. A coating film containing oxygen scavenger according to 8.   10. The oxygen scavenger-containing coating film according to claim 8, wherein the unit having a quaternized amino group has a carbonyl group derived from an unsaturated carboxylic acid unit or an unsaturated carboxylic anhydride unit. . The unit having a quaternized amino group has an N-substituted imide unit derived from an unsaturated carboxylic anhydride unit and a substituent represented by the following formula (1) as the N-substituent. The oxygen-absorbing agent-containing coating film according to any one of claims 8 to 10.
_{^{- (CH 2) n N +}} R 1 R 2 R 3 · X - (1)
Wherein R ¹ and R ² are alkyl groups having 1 to 5 carbon atoms or hydroxyalkyl groups having 1 to 5 carbon atoms, R ³ is a residue of a quaternizing agent introduced by quaternization reaction, X ⁻ Is an anionic counter ion, and n is an integer of 1 to 5.)   An oxygen scavenger-containing coating film obtained by applying the oxygen scavenger according to claim 1.   A laminate comprising the base material and the oxygen scavenger-containing coating film according to any one of claims 8 to 12 laminated thereon.   A laminate having a sealant layer laminated on the oxygen scavenger-containing coating film of the laminate according to claim 13. The laminate according to claim 13 or 14, wherein the substrate has a barrier property.