JP6813338B2 - Polyhydroxyurethane resin aqueous dispersion composition containing clay mineral, gas barrier coating agent and gas barrier resin film using the aqueous dispersion composition. - Google Patents

Description

The present invention relates to a technique for an aqueous dispersion composition that has achieved a good composite of a polyhydroxyurethane resin and a clay mineral, which can be widely used as a binder resin for paints and coating agents. The present invention relates to a technique capable of providing a highly environmentally friendly product because it can be used as a water-dispersed paint material and carbon dioxide can be incorporated into the chemical structure of the constituent polyhydroxyurethane resin. .. In particular, from the viewpoint of the functionality of the film to be formed, it is possible to realize the formation of a film showing better gas barrier properties by showing coating film suitability comparable to that of a coating film formed with a conventional solvent-based paint. , A technique for providing an aqueous dispersion composition which is a composite material of a polyhydroxyurethane resin and a clay mineral.

Polyurethane resin is a resin having excellent strength, flexibility, abrasion resistance, and oil resistance, and is widely used as a resin for paints and adhesives. In recent years, a polyhydroxyurethane resin having both a urethane bond and a hydroxyl group in its chemical structure has been developed as a novel polyurethane-based resin, and its industrial application is expected (see Patent Document 1). While existing polyurethane resins are obtained by using isocyanate compounds and polyols as raw materials, polyhydroxyurethane resins are produced by using epoxy compounds, carbon dioxide and amine compounds as raw materials and combining these raw materials. Since carbon dioxide used as a raw material is incorporated as a -CO-O- bond in the chemical structure of the polyhydroxyurethane resin, it should be noted from the viewpoint of effective utilization of carbon dioxide, which is a greenhouse gas. Is.

The polyhydroxyurethane resin can be a resin having excellent mechanical strength like the existing polyurethane resin, but further, an application utilizing the functionality derived from the hydroxyl group, which is not in the structure of the existing polyurethane resin, is being studied. For example, application as a heat-resistant paint utilizing the cross-linking reaction of hydroxyl groups (see Patent Document 2) and application to a gas barrier film utilizing the gas barrier property derived from hydroxyl groups are being studied (see Patent Document 3).

As in these conventional techniques, the paint field and the coating field are promising as application applications of the polyhydroxyurethane resin. However, since the polyhydroxyurethane resins developed so far have a chemical structure having a hydroxyl group together with a urethane bond, they have low solubility in an organic solvent and dissolve depending on the base material and processing equipment used in each application. In many cases, the properties are different, and it is difficult to deal with various solvent compositions, which is a problem in application. On the other hand, by using polyhydroxyurethane resin as an aqueous dispersion, this problem can be solved, and at the same time, application to water-based paints, which are being replaced with solvent-based paints in recent years, has been studied and proposed. (See Patent Document 4). Further, as another method, a method of obtaining a polyhydroxyurethane resin having a carboxyl group by using an amine compound containing a carboxylic acid as a raw material has been proposed (see Patent Document 5).

Further, as described above, the film made of the polyhydroxyurethane resin has a function as a gas barrier film. Here, as a method for improving the gas barrier property of the polyhydroxyurethane resin, a method of compounding with a clay mineral has been proposed (Patent Document 6). Generally, in order to disperse the clay mineral in the resin, a hydrophobization treatment such as substituting the metal cation ion between the layers with an organic onium salt is required, and the clay mineral is hydrophobic even by the method in the prior art described above. After the conversion process, it is compounded.

U.S. Pat. No. 30,72613 Japanese Unexamined Patent Publication No. 2011-102005 Japanese Unexamined Patent Publication No. 2012-172144 JP-A-2007-297544 Japanese Unexamined Patent Publication No. 6-25409 JP 2015-007197

However, according to the studies by the present inventors, the above-mentioned water-based technology has problems to be solved as described below. Since the technique described in Patent Document 4 is obtained by carboxyl-forming the hydroxyl groups of the polyhydroxyurethane resin by the half ester method in order to obtain an aqueous dispersion, water is caused by hydrolysis of the half ester portion. The problem remained in that the storage stability of the dispersion was poor, and the problem was not completely solved. Further, the point that the hydroxyl group of the polyhydroxyurethane resin in the above technology is used for the reaction and reduced has an advantage that it contributes to the improvement of water resistance, but this is a drawback in the application utilizing the functionality of the hydroxyl group. There is a problem such as becoming.

Further, the technique described in Patent Document 5 has a problem that the carboxyl group and the amino group form an ionic bond in the synthetic reaction system and the reaction with the cyclic carbonate is difficult to proceed, and DMF (dimethylformamide) It is necessary to react in a high boiling point solvent such as, and there is also a problem that it is difficult to increase the molecular weight. Further, the high boiling point solvent used in the technique described in Patent Document 5 has a problem that it cannot be distilled off under reduced pressure after phase inversion emulsification, and it is difficult to say that it is a perfect method for producing an aqueous dispersion (emulsion). It was.

Further, the above-mentioned method of compounding with a clay mineral for improving the gas barrier property of the polyhydroxyurethane resin has a problem that a complicated step is required for the hydrophobization treatment of the clay mineral. Further, according to the study by the present inventors, a part of the organic onium salt may inhibit the crystallization of the resin and may be a factor of lowering the gas barrier property. Therefore, it is considered preferable to exhibit the gas barrier property if it can be compounded with the resin in an aqueous solvent in which the unmodified clay mineral can be dispersed. However, according to the study by the present inventors, the clay mineral can be used in an unmodified state in the compounding in water, but when a resin having an anionic group is used for the dispersion of the aqueous resin, the anionic group is used. And the anionic ions on the surface of the clay mineral layer have a repulsive action, and the dispersed state becomes unstable. On the other hand, for example, Japanese Patent Application Laid-Open No. 2005-139436 proposes to add a cationic component as a third component when an aqueous dispersion of a polyurethane resin having a carboxyl group is obtained. There is. However, such addition of the third component is not an effective method because it inhibits the crystallization of the resin as in the case of the organic onium salt.

Therefore, an object of the present invention is that it can be used as a film-forming resin for water-based paints and coating agents, overcomes the problems of the prior art when a polyhydroxyurethane resin is used, and has a good composite with clay minerals. An aqueous dispersion composition containing a polyhydroxyurethane resin and a clay mineral, which can further improve the gas barrier property of the formed film, can be put into practical use, and has good stability. It is to provide things. Another object of the present invention is to provide a gas barrier water-based coating agent and a resin film having excellent gas barrier properties by using the aqueous dispersion composition.

The above object is achieved by the following invention, that is, the present invention contains an anionic polyhydroxyurethane resin having a carboxyl group and a hydroxyl group as a component (A) and a layered clay mineral as a component (B). In the aqueous dispersion composition which is a composite material, the total content of the component (A) and the component (B) is 10 to 50% by mass, and 100 parts by mass of the component (A) is added. On the other hand, the chemical structure of the anionic polyhydroxyurethane resin containing the component (B) in the range of 1 to 100 parts by mass and having the carboxyl group and the hydroxyl group of the component (A) is described by the following general formula (1). A clay mineral-containing polyhydroxyurethane resin aqueous dispersion composition having a repeating unit represented by) as a basic structure and having a chemical structural site having a carboxyl group represented by the following general formula (6). provide.

［一般式（１）中、−Ｘ−は、直接結合か、炭素数１〜３０の脂肪族炭化水素基、炭素数４〜４０の脂環式炭化水素基又は炭素数６〜４０の芳香族炭化水素基であり、これらの基の構造中には、エーテル結合、アミノ結合、スルホニル結合及びエステル結合のいずれか、或いは、置換基として、水酸基、ハロゲン原子及び繰り返し単位１〜３０の炭素数２〜６からなるポリアルキレングリコール鎖のいずれかを含んでもよい。Ｙ−は、炭素数１〜１５の脂肪族炭化水素基、炭素数４〜１５の脂環式炭化水素基又は炭素数６〜１５の芳香族炭化水素基であり、これらの基の構造中には、エーテル結合又はスルホニル結合、或いは、置換基として水酸基及びハロゲン原子のいずれかを含んでもよい。−Ｚ₁−、−Ｚ₂−は、それぞれ独立に、下記式（２）、式（３）、一般式（４）及び一般式（５）からなる群から選ばれる少なくともいずれかの構造を示し、繰り返し単位内及び繰り返し単位間のいずれにおいても、これらの式（２）〜（５）から選ばれる２種以上の構造が混在してもよい。また、これらの式（２）〜（５）のいずれの式を選択した場合も、右側の結合手は酸素原子と結合し、且つ、左側の結合手はＸと結合し、Ｘが直接結合の場合は、他方のＺの左側の結合手と結合する。］

［一般式（４）又は（５）中、Ｒは、水素原子又はメチル基を示す。］

[In the general formula (1), -X- is a direct bond, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 40 carbon atoms, or an aromatic group having 6 to 40 carbon atoms. It is a hydrocarbon group, and in the structure of these groups, any one of ether bond, amino bond, sulfonyl bond and ester bond, or as a substituent, a hydroxyl group, a halogen atom and 2 carbon atoms of repeating units 1 to 30 It may contain any of the polyalkylene glycol chains consisting of ~ 6. Y− is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group having 4 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms, and is contained in the structure of these groups. May contain either an ether bond or a sulfonyl bond, or a hydroxyl group or a halogen atom as a substituent. −Z ₁ − and −Z ₂ − independently represent at least one structure selected from the group consisting of the following equations (2), (3), general equations (4) and (5). , Two or more types of structures selected from these formulas (2) to (5) may be mixed in both within the repeating unit and between the repeating units. In addition, when any of these equations (2) to (5) is selected, the bond on the right side is bonded to the oxygen atom, the bond on the left side is bonded to X, and X is directly bonded. In the case, it joins with the other join hand on the left side of Z. ]

[In the general formula (4) or (5), R represents a hydrogen atom or a methyl group. ]

［一般式（６）中、−Ｗ−は、炭素数１〜３０の脂肪族炭化水素基、炭素数４〜４０の脂環式炭化水素基又は炭素数６〜４０の芳香族炭化水素基であり、これらの基の構造中には、エーテル結合、アミノ結合、スルホニル結合及びエステル結合のいずれか、或いは、置換基として、水酸基、ハロゲン原子及び繰り返し単位１〜３０の炭素数２〜６からなるポリアルキレングリコール鎖のいずれかを含んでもよい。Ｙ−は、一般式（１）の結合手のあるウレタン構造と結合する部分であって、前記一般式（１）中のＹ−として選択できるものを選択し得る。−Ｖ−は、炭素数１〜１０の炭化水素基又は炭素数６〜１０の芳香族炭化水素基であり、これらの基の構造中には、酸素原子又は窒素原子を含んでもよい。］

[In the general formula (6), -W- is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 40 carbon atoms, or an aromatic hydrocarbon group having 6 to 40 carbon atoms. In the structure of these groups, any of ether bond, amino bond, sulfonyl bond and ester bond, or as a substituent, it is composed of a hydroxyl group, a halogen atom and 2 to 6 carbon atoms of repeating units 1 to 30. It may contain any of the polyalkylene glycol chains. Y-is a portion to be bonded to the urethane structure having a bond of the general formula (1), and can be selected as Y- in the general formula (1). -V- is a hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the structure of these groups may contain an oxygen atom or a nitrogen atom. ]

Preferred forms of the clay mineral-containing polyhydroxyurethane resin aqueous dispersion composition of the present invention include those having the following configurations. The weight average molecular weight of the anionic polyhydroxyurethane resin of the component (A) is in the range of 1000 to 100,000, and the acid value thereof is in the range of 15 mgKOH / g to 50 mgKOH / g, and the hydroxyl value thereof. Is in the range of 150 mgKOH / g to 250 mgKOH / g; the basic structural portion represented by the general formula (1) of the anionic polyhydroxyurethane resin which is the component (A) is made of carbon dioxide as a raw material at least in a part thereof. It is composed of a polyaddition reaction product of a compound having at least two 5-membered cyclic carbonate structures and a compound having at least two primary amino groups, and is composed of an anionic polyhydroxy of the component (A). The carbon dioxide-derived -O-CO- bond accounts for 1 to 30% by mass of the total mass of the urethane resin; the layered clay mineral of the component (B) is montmorillonite, saponite, hectrite, vermiculite, etc. Being at least one selected from the group consisting of kaolinite and mica;

Further, as another embodiment of the present invention, there is provided a gas barrier water-based coating agent containing the above-mentioned clay mineral-containing polyhydroxyurethane resin aqueous dispersion composition as an essential component.

Further, as another embodiment, the present invention has a base material and a coating layer provided on at least one of the base materials and formed of a composite material containing a polyhydroxyurethane resin and a clay mineral. The composite material is a polyhydroxyurethane resin aqueous dispersion composition containing any of the above clay minerals, the thickness of the coating layer is 0.1 to 100 μm, and oxygen permeation of the coating layer. A gas barrier resin film having a ratio of 10 mL / m ² · day · atm or less under a humidity of 23 ° C. and 65%.

According to the present invention, an aqueous dispersion composition in which a polyhydroxyurethane resin and a clay mineral are well compounded and dispersed in water, which can be used as a film-forming resin for an aqueous paint or coating agent, is prepared. Provided. The aqueous dispersion composition provided by the present invention is superior in stability to the aqueous dispersion of the resin provided in the prior art, can be stored for a long period of time, and is made of a polyhydroxyurethane resin. Since the number of hydroxyl groups can be controlled to a certain amount, the performance of the coating film (coating layer) obtained from the polyhydroxyurethane resin is also the coating obtained from the conventional solvent-type polyhydroxyurethane resin in terms of adhesion and water resistance, for example. It can achieve the same performance as a film.

In addition, the aqueous dispersion composition of the present invention is obtained by dispersing clay minerals known to improve gas barrier properties in water in a good state, so that a film having better gas barrier properties can be easily produced. can do. Further, since the aqueous dispersion composition of the present invention can be used as a film-forming resin for water-based paints, by using this, in the environment of an organic solvent at the time of use, which is a problem with solvent-based paints. It is possible to provide a water-based paint or the like which can satisfy the performance of the coating film (coating layer) and reduce the environmental load. The polyhydroxyurethane resin constituting the aqueous dispersion composition of the present invention is a resin that can be produced by using carbon dioxide as a raw material (forming material), and because it is an aqueous material, it can reduce the environmental load. In addition, it is also useful in this respect because it can contribute to further reduction of the environmental load.

Next, the present invention will be described in detail with reference to preferred embodiments for carrying out the invention. The aqueous dispersion composition of the present invention obtained by combining a polyhydroxyurethane resin and a clay mineral to achieve a state in which they are well dispersed is a carboxyl group of the component (A) having the following specific structure. It contains an anionic polyhydroxyurethane resin having a hydroxyl group and a layered clay mineral of the component (B), and the total content of the component (A) and the component (B) is 10 to 50 mass by mass. %, The component (B) is contained in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the component (A).

An anionic polyhydroxyurethane resin having a carboxyl group and a hydroxyl group, which is a component (A) that characterizes the present invention (hereinafter, may be simply referred to as a component (A) or a polyhydroxyurethane resin) is a chemical thereof. The structure is characterized by having a repeating unit represented by the following general formula (1) as a basic structure and having a chemical structural site having a carboxyl group represented by the following general formula (6).

［一般式（１）中、−Ｘ−は、直接結合か、炭素数１〜３０の脂肪族炭化水素基、炭素数４〜４０の脂環式炭化水素基又は炭素数６〜４０の芳香族炭化水素基であり、これらの基の構造中には、エーテル結合、アミノ結合、スルホニル結合及びエステル結合のいずれか、或いは、置換基として、水酸基、ハロゲン原子及び繰り返し単位１〜３０の炭素数２〜６からなるポリアルキレングリコール鎖のいずれかを含んでもよい。Ｙ−は、炭素数１〜１５の脂肪族炭化水素基、炭素数４〜１５の脂環式炭化水素基又は炭素数６〜１５の芳香族炭化水素基であり、これらの基の構造中には、エーテル結合又はスルホニル結合、或いは、置換基として水酸基及びハロゲン原子のいずれかを含んでもよい。−Ｚ₁−、−Ｚ₂−は、それぞれ独立に、下記式（２）、式（３）、一般式（４）及び一般式（５）からなる群から選ばれる少なくともいずれかの構造を示し、繰り返し単位内及び繰り返し単位間のいずれにおいても、これらの式（２）〜（５）から選ばれる２種以上の構造が混在してもよい。また、これらの式（２）〜（５）のいずれの式を選択した場合も、右側の結合手は酸素原子と結合し、且つ、左側の結合手はＸと結合し、Ｘが直接結合の場合は、他方のＺの左側の結合手と結合する。］

[In the general formula (1), -X- is a direct bond, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 40 carbon atoms, or an aromatic group having 6 to 40 carbon atoms. It is a hydrocarbon group, and in the structure of these groups, any one of ether bond, amino bond, sulfonyl bond and ester bond, or as a substituent, a hydroxyl group, a halogen atom and 2 carbon atoms of repeating units 1 to 30 It may contain any of the polyalkylene glycol chains consisting of ~ 6. Y− is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group having 4 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms, and is contained in the structure of these groups. May contain either an ether bond or a sulfonyl bond, or a hydroxyl group or a halogen atom as a substituent. −Z ₁ − and −Z ₂ − independently represent at least one structure selected from the group consisting of the following equations (2), (3), general equations (4) and (5). , Two or more types of structures selected from these formulas (2) to (5) may be mixed in both within the repeating unit and between the repeating units. In addition, when any of these equations (2) to (5) is selected, the bond on the right side is bonded to the oxygen atom, the bond on the left side is bonded to X, and X is directly bonded. In the case, it joins with the other join hand on the left side of Z. ]

［一般式（４）又は（５）中、Ｒは、水素原子又はメチル基を示す。］

[In the general formula (4) or (5), R represents a hydrogen atom or a methyl group. ]

［一般式（６）中、−Ｗ−は、炭素数１〜３０の脂肪族炭化水素基、炭素数４〜４０の脂環式炭化水素基又は炭素数６〜４０の芳香族炭化水素基であり、これらの基の構造中には、エーテル結合、アミノ結合、スルホニル結合及びエステル結合のいずれか、或いは、置換基として、水酸基、ハロゲン原子及び繰り返し単位１〜３０の炭素数２〜６からなるポリアルキレングリコール鎖のいずれかを含んでもよい。Ｙ−は、一般式（１）の結合手のあるウレタン構造と結合する部分であって、前記一般式（１）中のＹ−として選択できるものを選択し得る。−Ｖ−は、炭素数１〜１０の炭化水素基又は炭素数６〜１０の芳香族炭化水素基であり、これらの基の構造中には、酸素原子又は窒素原子を含んでもよい。］

[In the general formula (6), -W- is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 40 carbon atoms, or an aromatic hydrocarbon group having 6 to 40 carbon atoms. In the structure of these groups, any of ether bond, amino bond, sulfonyl bond and ester bond, or as a substituent, it is composed of a hydroxyl group, a halogen atom and 2 to 6 carbon atoms of repeating units 1 to 30. It may contain any of the polyalkylene glycol chains. Y-is a portion to be bonded to the urethane structure having a bond of the general formula (1), and can be selected as Y- in the general formula (1). -V- is a hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the structure of these groups may contain an oxygen atom or a nitrogen atom. ]

The polyhydroxyurethane resin constituting the present invention has a repeating unit in its basic structure, and the structure represented by the above general formula (1) may have the same repeating unit. The structure is not limited to this, and a plurality of different structures may be mixed as long as the structure is within the range specified above. For example, both Z ₁ and Z _{2 in} the general formula (1) may be composed only of those having the chemical structure of the formula (2). For example, Z ₁ is the chemistry of the general formula (4). A mixture of structures, Z ₂ having a chemical structure of the general formula (5), and Z ₁ and Z ₂ having a chemical structure of the formula (3) may be mixed. Similarly, the structure represented by the general formula (6) having in the basic structure may have the same structure for all the repeating units in the resin, but may be a mixture of different structures. .. Further, Y in the general formula (1) and Y in the general formula (6), which constitute the basic structure, may have the same structure, but can be −Y specified in the present invention. The structures may be different from each other as long as they are within the range of. Further, Y may be different for each repeating unit. That is, a plurality of Ys having different structures may be mixed in the basic structure of the polyhydroxyurethane resin that characterizes the present invention.

Here, as a general method for producing a polymer emulsion, there are a forced emulsification method using a surfactant as an emulsifier and a self-emulsification method in which a hydrophilic group is introduced into the polymer chain to form emulsified particles on the polymer chain itself. .. The aqueous dispersion of the present invention belongs to the above-mentioned self-emulsifying type. That is, as shown in the structure of the general formula (6), the polyhydroxyurethane resin constituting the present invention has a carboxyl group which is an anionic group as a hydrophilic group necessary for emulsification in the structure of the resin. By introducing, self-emulsification is possible.

The polyhydroxyurethane resin having the repeating unit represented by the general formula (1) as the basic structure can produce a portion of the basic structure by the following steps. Specifically, a compound having at least two 5-membered cyclic cyclic carbonates in one molecule (hereinafter, may be simply referred to as a cyclic carbonate compound) and a compound having at least two primary amino groups in one molecule (hereinafter, may be simply referred to as a cyclic carbonate compound). Hereinafter, it may be simply referred to as an amine compound).

It is known that in the reaction between cyclic carbonate and amine, which forms a polymer chain of polyhydroxyurethane resin, there are two types of cleavage of the cyclic carbonate, and two types of structures shown in the following model reactions occur. There is.

Therefore, the structures of −Z ₁ − and −Z ₂ − of the general formula (1) representing the polyhydroxyurethane obtained by the heavy addition reaction become the structure of either the above formula (2) or the formula (3). , Its existence is random.

As the cyclic carbonate compound used in the production of the polyhydroxyurethane resin constituting the present invention, it is preferable that the cyclic carbonate structure is obtained by the reaction of the epoxy compound and carbon dioxide as described below. Specifically, for example, the epoxy compound as a raw material is reacted in the presence of a catalyst at a temperature of 0 ° C. to 160 ° C. in a carbon dioxide atmosphere pressurized to about atmospheric pressure to 1 MPa for 4 to 24 hours. As a result, a cyclic carbonate compound in which carbon dioxide is immobilized on the ester moiety can be obtained.

The polyhydroxyurethane resin obtained by using the cyclic carbonate compound synthesized from carbon dioxide as a raw material as described above in the polyaddition reaction has carbon dioxide immobilized in its structure-O-CO-. It will have a bond. The content of carbon dioxide-derived -O-CO- bonds (immobilized amount of carbon dioxide) in the polyhydroxyurethane resin should be as high as possible from the standpoint of effectively using carbon dioxide as a raw material. The polyhydroxyurethane resin obtained by the above-mentioned synthesis method can contain carbon dioxide in the range of 1 to 30% by mass in its structure.

Examples of the catalyst used for the reaction between the epoxy compound and carbon dioxide include salts such as lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, and sodium iodide, and quaternary ammonium salts. Is mentioned as a suitable one. The amount used is 1 to 50 parts by mass, preferably 1 to 20 parts by mass per 100 parts by mass of the epoxy compound. In addition, triphenylphosphine or the like may be used in combination in order to improve the solubility of these catalyst salts.

The reaction between the epoxy compound and carbon dioxide described above can also be carried out in the presence of an organic solvent. As the organic solvent, any one that dissolves the above-mentioned catalyst can be used. Specifically, for example, amide-based solvents such as N, N-dimethylformamide, dimethylsulfoxide, dimethylacetamide, and N-methyl-2-pyrrolidone, alcohol-based solvents such as methanol, ethanol, propanol, ethylene glycol, and propylene glycol, Preferable examples thereof include ether solvents such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran.

The structure of the cyclic carbonate compound that can be used for producing the polyhydroxyurethane resin constituting the present invention is not particularly limited, and any cyclic carbonate compound having two or more cyclic carbonate structures in one molecule can be used. For example, a compound having a benzene skeleton, an aromatic polycyclic skeleton, a condensed polycyclic aromatic skeleton, or an aliphatic or alicyclic cyclic carbonate compound can be used. The compounds that can be used are illustrated below with structural formulas. In addition, R in the structural formulas listed below is either a hydrogen atom or CH ₃ .

Examples of the cyclic carbonate compound having a benzene skeleton, an aromatic polycyclic skeleton, and a condensed polycyclic aromatic skeleton are as follows.

The following compounds are exemplified as aliphatic or alicyclic cyclic carbonates.

The polyhydroxyurethane resin constituting the aqueous dispersion composition of the present invention is a compound having two or more five-membered cyclic carbonate structures, as listed above, which are partially synthesized using carbon dioxide as a raw material. And, it is preferable that it is produced by a polyaddition reaction with a compound having two or more primary amino groups.

As the compound having a primary amino group, conventionally known compounds can be used. Preferred are, for example, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane (also known as hexamethylenediamine), 1,8-diaminooctane, 1,10-diamino. Chain aliphatic polyamines such as decane and 1,12-diaminododecane, cyclic aliphatic polyamines such as isophoronediamine, norbornandiamine, 1,6-cyclohexanediamine, piperazine and 2,5-diaminopyridine, xylylene diamine (also known as: Examples thereof include aliphatic polyamines having an aromatic ring such as metaxylene diamine), and aromatic polyamines such as metaphenylenediamine and diaminodiphenylmethane.

The polyhydroxyurethane resin constituting the aqueous dispersion composition of the present invention has a repeating unit of the general formula (1) that can be produced as described above as a basic structure, and has the following general formula (6) in the structure. It is characterized in that a chemical structural site having the indicated carboxyl group is introduced.

［一般式（６）中、−Ｗ−は、炭素数１〜３０の脂肪族炭化水素基、炭素数４〜４０の脂環式炭化水素基又は炭素数６〜４０の芳香族炭化水素基であり、これらの基の構造中には、エーテル結合、アミノ結合、スルホニル結合及びエステル結合のいずれか、或いは、置換基として、水酸基、ハロゲン原子及び繰り返し単位１〜３０の炭素数２〜６からなるポリアルキレングリコール鎖のいずれかを含んでもよい。Ｙ−は、一般式（１）の結合手のあるウレタン構造と結合する部分であって、前記一般式（１）中のＹ−として選択できるものを選択し得る。−Ｖ−は、炭素数１〜１０の炭化水素基又は炭素数６〜１０の芳香族炭化水素基であり、これらの基の構造中には、酸素原子又は窒素原子を含んでもよい。］

[In the general formula (6), -W- is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 40 carbon atoms, or an aromatic hydrocarbon group having 6 to 40 carbon atoms. In the structure of these groups, any of ether bond, amino bond, sulfonyl bond and ester bond, or as a substituent, it is composed of a hydroxyl group, a halogen atom and 2 to 6 carbon atoms of repeating units 1 to 30. It may contain any of the polyalkylene glycol chains. Y-is a portion to be bonded to the urethane structure having a bond of the general formula (1), and can be selected as Y- in the general formula (1). -V- is a hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the structure of these groups may contain an oxygen atom or a nitrogen atom. ]

Introducing the chemical structural site having a carboxyl group represented by the general formula (6) into the basic structure can be carried out by, for example, the following production method. By introducing this chemical structural site into water, , An aqueous dispersion in which the polyhydroxyurethane resin is well dispersed can be easily obtained. Specifically, first, in a hydrophilic solvent, a compound having two epoxy groups and a compound having two five-membered cyclic carbonate structures are added to the compound having two primary amino groups. The reaction is carried out to obtain a polyhydroxyurethane resin containing a secondary amino group in its structure, and the secondary amino group is further reacted with a cyclic acid anhydride to form a carboxyl group as an ionic group in its structure. Obtain a polyhydroxyurethane resin having. As a result, the polyhydroxyurethane resin can be satisfactorily dispersed by neutralizing the carboxyl group in the polyhydroxyurethane resin obtained above and then adding water for phase inversion emulsification. The details of the above manufacturing method will be described below.

As a more preferable form of the above production method, the compound having a primary amino group and the compound having an epoxy group have an equivalent ratio of an amino group to an epoxy group of primary amino group / epoxy group = 4/1. The reaction was carried out under the condition that the amount of the primary amino group was excessive, so that the primary amino group remained unreacted, and then, for example, the cyclic obtained by using carbon dioxide as a raw material, as described above. By subjecting the carbonate compound to a polyaddition reaction with the remaining primary amino group, a polyhydroxyurethane resin having a structure in which the chemical structure site of the general formula (6) is introduced into the above-mentioned basic structure can be stably obtained. Can be done. Then, by performing the above-mentioned phase inversion emulsification after that, an aqueous dispersion of a polyhydroxyurethane resin that is finely dispersed in water can be stably obtained.

The mechanism by which the polyhydroxyurethane resin having the structure specified in the present invention can be stably obtained by configuring as described above will be described below. A compound having two primary amino groups and a compound having two epoxy groups have an active hydrogen equivalent ratio of 1.0 (1/2 in the molar ratio of primary amino group / epoxy group). When the reaction is carried out, a three-dimensional reaction occurs and a cured resin product is obtained. However, since the cured resin product having a three-dimensional chemical structure does not dissolve in a solvent, the aqueous dispersion intended by the present invention cannot be produced. On the other hand, for example, when the reaction is carried out under the condition of an excess amount of the primary amino group such that the equivalent ratio of the primary amino group to the epoxy group is primary amino group / epoxy group = 4/1 or more, 1 is added to both ends. A compound having a secondary amino group and having a secondary amino group inside the structure is obtained as an intermediate. Then, by using the intermediate, the structure of the general formula (6) can be stabilized as the chemical structural part of the polyhydroxyurethane resin having the repeating unit represented by the general formula (1) as the basic structure. Can be introduced.

The reaction formula in the case of primary amino group / epoxy group = 4/1 is shown below. By carrying out the reaction under such an excess amount condition of amino groups, a mixture of the compound (a) as an intermediate having the following structure and the compound having a primary amino group remaining unreacted can be obtained. Can be done.

The compound (a) in the mixture obtained as described above has a primary amino group at both ends, and has two primary amino groups in one molecule used in the above reaction. Similar to the compound, it can undergo a transamination reaction with the cyclic carbonate compound described above.

The compound (a) has a primary amino group at both ends, but also has a secondary amino group in its structure. In this case, it has already been reported that the secondary amino group in the structure does not react with the cyclic carbonate. For example, the synthesis of polyhydroxyurethane containing a secondary amino group in the main chain by a double addition reaction of a compound containing a primary amino group and a secondary amino group and a cyclic carbonate compound is performed by "J. Polym. Sci., Part. A: Polym. Chem. 2005, 43, 5899-5905 ”. Also in the production method used in the present invention, the reaction form is as described in the above-mentioned document. Therefore, as described above, it has a primary amino group at both ends and a secondary amino group inside. A polyhydroxyurethane resin containing a secondary amino group in its basic structure can be obtained by passing through a compound having the same structure as that of the compound (a). In the present invention, the secondary amino group that will remain in the hydroxyurethane due to the chemical structural site of the general formula (6) introduced into the basic structure is reacted with the cyclic acid anhydride in the next step. Introduce a carboxyl group. As a result, the repeating unit represented by the general formula (1) described above, which can form the aqueous dispersion composition of the present invention, is used as the basic structure, and the structure has a carboxyl group represented by the general formula (6). A polyhydroxyurethane resin having a chemical structural part can be obtained. That is, in the next step, the polyhydroxyurethane resin can be finely dispersed in water by adding water and emulsifying the phase inversion.

As described above, the polyhydroxyurethane resin constituting the aqueous dispersion composition of the present invention can be basically formed by the following three-step steps.
(1) First, a compound having at least two epoxy groups is reacted with a compound having at least two primary amino groups under an excess amount condition of the primary amino groups so that the primary amino groups remain. A step of producing a compound (a) having a primary amino group at both ends and a secondary amino group inside, which is an intermediate.
(2) A compound having at least two 5-membered cyclic carbonate structures is polymerized with respect to the compound (a) which is the product of the step (1) with the primary amino group remaining, and the secondary is secondary. A polymerization step for obtaining a polyhydroxyurethane resin having an amino group.
(3) A step of introducing an ionic group by adding a cyclic acid anhydride to the polyhydroxyurethane resin having a secondary amino group obtained in the step (2).

Here, it is also possible to omit the step (1) and to react the cyclic carbonate compound with the epoxy compound and the compound having an amino group at once to obtain a polyhydroxyurethane having a secondary amino group. .. However, according to the studies of the present inventors, in this case, when the amount of the epoxy compound used is increased, that is, when more secondary amino groups are introduced into the main chain, the epoxy compound is produced. The probability of reacting with the secondary amino group in the compound (a) is high, and gelation due to three-dimensionalization is more likely to occur as compared with the case of going through the step (1), which is not suitable as an industrial production method. It is hard to say that it is suitable.

As the compound having at least two primary amino groups that can be used in the above step (1), conventionally known compounds can be used. Specifically, the same amine compound that can be used for synthesizing the polyhydroxyurethane resin having the repeating unit of the general formula (1) as the basic structure described above can be used. Therefore, the description thereof will be omitted.

The compound having an epoxy group that can be used in the step (1) is also not particularly limited except that it is at least bifunctional. For example, the epoxy compound used as a raw material for obtaining the above-mentioned cyclic carbonate compound is suitable. Specifically, in the cyclic carbonate compound exemplified above, a compound in which all of the terminal five-membered cyclic cyclic carbonate groups are epoxy groups is used as a raw material, and the compounds having these epoxy groups are used. Both can be used.

The conditions required for the double addition reaction of the two types of compounds performed in the steps (1) and (2), that is, the double addition reaction of the cyclic carbonate compound and the amine compound, and the heavy addition reaction of the epoxy compound and the amine compound are , Both are the same. For example, both may be mixed and reacted at a temperature of 40 to 200 ° C. for 4 to 24 hours.

All of the above reactions can be carried out without a solvent, but in the present invention, it is preferable to carry out the reaction in a hydrophilic solvent in consideration of the reaction of the next step and the emulsification step. Examples of preferable hydrophilic solvents that can be used in this case include, for example, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, methanol, ethanol, propanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, and the like. Examples thereof include ethylene glycol dimethyl ether, propylene glycol methyl ether, diethylene glycol monomethyl ether, and diethylene glycol dimethyl ether. Among the solvents listed above, a particularly preferable solvent is tetrahydrofuran having a boiling point at which evaporation and distillation is easy after phase inversion emulsification.

As described above, the polyhydroxyurethane resin that characterizes the present invention can be produced without using a catalyst, but in order to promote the reaction, in the presence of a catalyst as described below. It is also possible to do it with. For example, basic catalysts such as triethylamine, tributylamine, diazabicycloundecene (DBU), triethylenediamine (DABCO), pyridine and hydroxypyridine, Lewis acid catalysts such as tetrabutyltin and dibutyltin dilaurylate can be used. The preferable amount of these catalysts to be used is in the range of 0.01 to 10 parts by mass with respect to the total amount (100 parts by mass) of the carbonate compound and the amine compound used in the reaction.

Next, the reaction of introducing a carboxyl group into the polyhydroxyurethane resin, which is the step of introducing an ionic group in the above step (3), will be described. In the step (3), a carboxyl group is introduced into the polyhydroxyurethane resin by reacting the secondary amino group of the polyhydroxyurethane obtained in the above step (2) with a cyclic acid anhydride.

The cyclic acid anhydride that can be used in the above reaction is not particularly limited. Any compound in which the carboxyl groups of a compound having a plurality of carboxyl groups are dehydrated and condensed in the molecule can be preferably used. Specifically, for example, succinic anhydride, itaconic acid anhydride, maleic acid anhydride, caronic acid anhydride, citraconic acid anhydride, glutaric acid anhydride, diglycolic acid anhydride, 1, 2, 3, 4 An aliphatic acid anhydride such as butanetetracarboxylic acid anhydride and its derivatives, phthalic acid, trimellitic acid anhydride, 1,2-naphthalic acid anhydride, pyromellitic acid anhydride and other aromatic acid anhydrides. , 1,1-Cyclohexanediacetate anhydride, 1-cyclohexene-1,2-dicarboxylic acid anhydride, 1,1-cyclopentanediacetate anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, etc. Any alicyclic acid anhydride or the like can be used. Among these, particularly preferable compounds include succinic anhydride and maleic anhydride because compounds having a low molecular weight exhibit emulsion stability even when used in a small amount.

According to the study by the present inventors, the compound (a) is shown first depending on the amount of the epoxy compound used in the above step (1) and the ratio of the cyclic carbonate compound used in the above step (2). , The amount of secondary amino groups in the intermediate polyhydroxyurethane resin can be controlled, thereby the carboxyl groups in the polyhydroxyurethane resin obtained after the reaction with the cyclic acid anhydride in step (3). You can also control the amount.

Further, according to the study by the present inventors, the amount of carboxyl groups introduced into the polyhydroxyurethane resin is substantially proportional to the size of the emulsified particles formed in the step of adding water to the resin for phase inversion emulsification. Yes, the larger the amount of carboxyl groups, the smaller the emulsified particle size. On the contrary, when the number of carboxyl groups decreases, the diameter of the emulsified particles increases, and the emulsified state becomes unstable from a certain size. The emulsified particles of the polyhydroxyurethane resin dispersed in water constituting the present invention obtained as described above are, for example, finely dispersed with a particle size in the range of 0.001 μm to 10 μm. Although it depends on the application, it is more preferable that the content is adjusted to be in the range of 0.001 μm to 2 μm.

Further, if the amount of the carboxyl group introduced into the polyhydroxyurethane resin, which is required when forming the aqueous dispersion composition of the present invention, is too small, phase inversion emulsification cannot be performed, and if it is too large, the water resistance of the coating film is high. It is preferable to adjust the blending ratio so that the acid value is 15 mgKOH / g to 50 mgKOH / g. Further, since the stability of the emulsified particles is also affected by the molecular weight of the resin, the weight average molecular weight of the resin is preferably in the range of 1000 to 100,000.

By using the aqueous dispersion composition of the present invention, which is easily obtained as described above and in which the polyhydroxyurethane resin is well dispersed in water, a coating layer or a film can be formed. One of the objects of the present invention is to make these coating layers and films have higher gas barrier properties. The gas barrier property is exhibited by the presence of hydroxyl groups in the structure of the resin, and the degree of gas barrier property of the formed film depends on the amount of hydroxyl groups in the structure of the film-forming resin used. When the number of hydroxyl groups is small, the gas barrier property is inferior, and when the number of hydroxyl groups is too large, there is no particular problem with the barrier property, but the resin becomes hard and the adhesion deteriorates. Therefore, according to the study by the present inventors, this is the case. A preferable range of the amount of hydroxyl groups in the structure of the resin required to achieve the above object is a hydroxyl value in the range of 150 mgKOH / g to 250 mgKOH / g.

The carboxyl group present in the structure of the resin constituting the aqueous dispersion of the present invention may remain as it is when water is added and phase-inverted emulsified to form an aqueous dispersion, but in water. It is preferable to neutralize a part, preferably all of the carboxyl groups, as a neutralizing salt in order to promote the ionization in the above. It is possible to leave the carboxyl group unneutralized for use in cross-linking and modification reactions, but if it is only used as an ionic group for emulsification, the neutralizer should be the equivalent amount of the carboxyl group. It is preferable that all of them are neutralized salts by using an excess amount of about 1 to 10%.

In the above, examples of the basic compound used for neutralization include ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine and dimethyl. Organic amines such as ethanolamine, diethylethanolamine, morpholine, N-methylmorpholin, 2-amino-2-ethyl-1-propanol, trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, triethanolamine, etc. Examples thereof include alkali metals such as lithium, potassium and sodium, and inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium hydroxide and ammonia, which can be used in combination. Among these basic compounds, a particularly preferable compound is one that is volatile at the time of forming a coating film, and for example, triethylamine is preferably used. When a neutralized salt is prepared by using triethylamine or the like, the basic compound volatilizes when the coating film is formed, so that the water resistance of the coating film (coating layer) is improved.

The polyhydroxyurethane resin obtained by the method described above has a repeating unit represented by the general formula (1) as a basic structure and a chemical structural portion having a carboxyl group represented by the general formula (6). Including. In this way, since it contains a carboxyl group or a salt thereof which becomes an ionic group in water, phase inversion (phase inversion emulsification) can be carried out by gradually adding water to the solvent solution, and an oil-in-water type can be used. A (O / W type) emulsion is obtained.

The amount of water used for phase inversion depends on factors such as the chemical structure of the polyhydroxyurethane resin, the type of solvent used in the synthesis of the resin, the resin concentration, and the viscosity, but is approximately 50 to 200. It is about a mass part. The apparatus used for phase inversion may be the same as the apparatus used for the synthesis reaction, but a continuous emulsifier or disperser may also be used. Usually, the phase inversion step does not need to be particularly heated, and it is efficient and preferable to carry out the phase inversion step at a temperature of about 10 ° C. to 30 ° C. in order to reduce the solubility of water in the resin solution before the phase inversion.

Further, by heating the O / W type emulsion obtained above under reduced pressure conditions, the solvent used for producing the polyhydroxyurethane resin is volatilized, so that only the resin component is dispersed in water. A dispersion can be obtained. The heating conditions and depressurizing conditions at this time differ depending on the boiling point of the solvent to be volatilized, but it is preferable that water does not evaporate first, and it is generally preferable to adjust the temperature in the range of 300 Torr to 50 Torr and 20 ° C. to 70 ° C. The aqueous dispersion composition of the present invention is obtained by dispersing a polyhydroxyurethane resin in water, but the final solvent does not necessarily have to be water alone, and the solvent before phase inversion remains. It can be used even if it is used, and it can be adjusted according to the application.

The aqueous dispersion composition of the present invention has, for example, as the component (B) with respect to the aqueous dispersion of the anionic polyhydroxyurethane resin having the carboxyl group and the hydroxyl group of the component (A) obtained as described above. By dispersing the layered clay mineral, both can be complexed to easily obtain the aqueous dispersion composition of the present invention. At this time, it is also a preferable form to use a clay mineral that has been swollen and dispersed in water in advance.

A clay mineral is a substance having a layered structure, which is composed of a large number of sheets laminated with a silicate mineral having a layered structure or the like. In the present invention, this layered clay mineral is used. Specific examples thereof include montmorillonite, saponite, hectorite, vermiculite, kaolinite and mica, and particularly preferable ones are montmorillonite, saponite and mica (mica). These clay minerals can be used both naturally and synthetically.

Clay minerals having the above characteristics are usually swollen by water, and the distance between layers is widened. In the aqueous dispersion composition of the present invention, the resin penetrates between the layers of the swollen clay minerals, so that the dispersed state is stabilized and a film in which the clay minerals are uniformly dispersed can be formed at the time of film formation. Cationic substances such as sodium ions are usually inserted between the layers of clay minerals, and a polymer having an anionic carboxyl group introduced, such as the polyhydroxyurethane resin used in the present invention, invades the layers. Is unlikely to occur. However, it has been found that when the anionic polyhydroxyurethane resin of the component (A) used in the present invention is applied, uniform dispersion is achieved. The present inventors consider the reason as follows. That is, the resin used in the present invention has a secondary amide group at a site close to the carboxyl group in the structure, and the cationic property of the secondary amide group contributes to the resin to be clay. We believe that it was possible to easily penetrate between the layers of minerals.

It is widely known that a resin film in which clay minerals are uniformly dispersed has a high gas barrier property, and the same effect is exhibited in a film formed by using the aqueous dispersion composition of the present invention. .. The amount of the clay mineral used to constitute the aqueous dispersion composition of the present invention is 1 to 100 parts (B), which is a layered clay mineral, with respect to 100 parts by mass of the component (A), which is an anionic polyhydroxyurethane resin. Must be parts by mass. If the amount of the layered clay mineral as the component (B) is larger than the above range, the coating film (coating film) becomes hard and easily cracked or the transparency is deteriorated, while the amount of the component (B) is the above. If it is less than the range, the effect of improving the gas barrier property is weakened. As a preferable range, the component (B) is 3 to 50 parts by mass with respect to 100 parts by mass of the component (A).

The concentration of the aqueous dispersion composition of the present invention is such that the total content of (A) anionic polyhydroxyurethane resin component and (B) layered clay mineral component is 10 to 50 mass as the concentration in the aqueous dispersion. Must be%. It is preferably 20 to 40% by mass. The concentration can be adjusted to the optimum level according to various processing methods for obtaining a coating film.

In the production of the aqueous dispersion composition of the present invention, the method for dispersing the layered clay mineral of the component (B) in the aqueous dispersion of the anionic polyhydroxyurethane resin of the component (A) is not particularly limited. For example, even in the method of adding the clay mineral of the component (B) as it is and dispersing it in the aqueous dispersion of the resin easily obtained as described above, the clay mineral dispersed in water in advance is added. It may be a method of addition, and any of them can be applied. The dispersion of water-swellable clay minerals is more efficient with water alone than with an aqueous dispersion of resin, so the latter is preferable in terms of production efficiency.

When the layered clay mineral of the component (B) is dispersed in water or in the aqueous dispersion of the anionic polyhydroxyurethane resin of the component (A), it can be carried out only by ordinary stirring, but especially at a high concentration. It may take a long time to disperse. Therefore, in order to shorten the production process, it is preferable to heat to 70 ° C. or higher and stir. Further, since the dispersion liquid exhibits high thixotropy, it is more effective to use a disperser such as a stirrer or an ultrasonic disperser.

The aqueous dispersion composition of the present invention can be used by adding various rheology adjusters according to the required properties at the time of processing (during use). In addition, various additives may be added to the aqueous dispersion composition of the present invention as needed, and for example, an antioxidant, a light stabilizer, an ultraviolet absorber and the like can be added.

Further, the aqueous dispersion composition of the present invention can be used to prepare a crosslinked coating film by blending and using a curing agent that can be dissolved and dispersed in water. The curing agent that can be used at this time is not particularly limited. Examples thereof include water-dispersible components capable of reacting with hydroxyl groups, polyisocyanates, blocked isocyanates, epoxy compounds, metal chelate compounds such as aluminum and titanium, melamine resins, and aldehyde compounds. Further, a cross-linking agent capable of reacting with a carboxyl group can also be used, and in addition to the above compound, a water-dispersible carbodiimide or the like can also be used.

As a method for obtaining a coating film (coating) using the aqueous dispersion composition of the present invention, an aqueous dispersion composition of the present invention is applied to a film as a base material, for example, a gravure coater, a knife coater, a reverse coater, and the like. It may be applied by a bar coater, a spray coater, a slit coater or the like to volatilize water and the remaining solvent. By doing so, the present invention comprises a base material and at least one of the base materials having a film layer having a polyhydroxyurethane resin and a clay mineral formed by the aqueous dispersion composition of the present invention. Resin film can be obtained.

The film material used as the base material in the above is not particularly limited, and any polymer material conventionally used as a packaging material can be used. Examples thereof include polyolefin resins such as polyethylene, polypropylene and polystyrene, polyester resins such as polyethylene terephthalate and polylactic acid, polyamide resins such as nylon 6 and nylon 66, and copolymers of polyimides and these resins. .. Further, if necessary, these polymer materials may appropriately contain additives such as known antistatic agents, ultraviolet absorbers, plasticizers, lubricants, and colorants.

Next, the present invention will be described in more detail with reference to specific production examples, examples and comparative examples. The present invention is not limited to these examples. In the following examples, "part" and "%" are based on mass unless otherwise specified.

[Production Example 1: Synthesis of Cyclic Carbonate-Containing Compound (IA)]
100 parts of bisphenol A diglycidyl ether (trade name: jER828, manufactured by Japan Epoxy Resin Co., Ltd.) with an epoxy equivalent of 192, 20 parts of sodium iodide (manufactured by Wako Pure Chemical Industries, Ltd.), and 100 parts of N-methyl-2-pyrrolidone. , Placed in a reaction vessel equipped with a stirrer and a recirculator with an air opening. Then, carbon dioxide was continuously blown with stirring, and the reaction was carried out at 100 ° C. for 10 hours. Then, 1400 parts of isopropanol was added to the solution after completion of the reaction, and the reaction product was precipitated as a white precipitate and separated by filtration. The obtained precipitate was recrystallized from toluene to obtain 52 parts of a white powder (yield 42%).

The powder obtained above was analyzed by FT-720 (trade name, manufactured by Horiba Seisakusho Co., Ltd., measured by the same device in the following production example), which is a Fourier transform infrared spectrophotometer (FT-IR). However, the absorption derived from the epoxy group of the raw material near 910 cm ^-1 disappeared, and the absorption derived from the carbonyl group of the carbonate group which is not present in the raw material was confirmed around 1800 cm ^-1 . In addition, as a result of analysis by LC-2000 (trade name, manufactured by JASCO Corporation, column FinepakSIL C18-T5; mobile phase acetonitrile + water), which is high performance liquid chromatography (HPLC), the peak of the raw material disappeared and the high polarity side. A new peak appeared in, and its purity was 98%. As a result of DSC measurement (differential scanning calorimetry), the melting point was 178 ° C. and the melting point range was ± 5 ° C.

From the above, it was confirmed that this powder is a compound having a structure represented by the following formula in which a cyclic carbonate group is introduced by a reaction between an epoxy group and carbon dioxide. This was abbreviated as IA. The proportion of carbon dioxide-derived components in the chemical structure of IA was 20.5% (calculated value).

[Production Example 2: Synthesis of Cyclic Carbonate-Containing Compound (IB)]
The following formula (IB) was used in the same manner as in Production Example 1 described above, except that hydroquinone diglycidyl ether having an epoxy equivalent of 115 (trade name: Denacol EX203, manufactured by Nagase ChemteX Corporation) was used as the epoxy compound. A cyclic carbonate compound having the structure represented was synthesized (yield 55%). The obtained IB was a white crystal and had a melting point of 141 ° C. As a result of FT-IR analysis, the absorption from the epoxy group of the raw material around 910 cm ^-1 disappeared as in IA, and the absorption from the carbonyl group of the carbonate group which is not present in the raw material around 1800 cm ^-1. Was confirmed. The purity by HPLC analysis was 97%. The proportion of carbon dioxide-derived components in the chemical structure of IB was 28.0% (calculated value).

<Manufacturing of carboxyl group-containing polyhydroxyurethane resin before dispersion in water>
[Example 1 of resin synthesis for examples]
10 parts of bisphenol A diglycidyl ether (trade name: jER828, manufactured by Japan Epoxy Resin Co., Ltd.) and hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) in a reaction vessel equipped with a stirrer and a refluxer with an air opening. 30.1 parts and 99 parts of tetrahydrofuran (THF) as a reaction solvent were added, and the reaction was carried out for 12 hours with stirring at a temperature of 60 ° C. Next, 100 parts of the cyclic carbonate-containing compound IA obtained in Production Example 1 was added, and the reaction was carried out for 24 hours while stirring at a temperature of 60 ° C. When the resin solution after the reaction was analyzed by FT-IR, 1800 cm ^-1 absorption due carbonyl group of cyclic carbonates that have been observed in the vicinity has completely disappeared, the new urethane bonds in the vicinity of 1760 cm ^-1 Absorption derived from the carbonyl group was confirmed. The amine value measured using the obtained resin solution was 20.1 mgKOH / g as a conversion value of 100% resin content.

Next, 124 parts of THF was added to this resin solution to dilute it, then 5.2 parts of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and the reaction was carried out at room temperature, and the reaction was carried out at room temperature. After confirming that the peak of 1800 cm ^-1 had disappeared, the reaction was terminated to obtain a solution of a carboxyl group-containing polyhydroxyurethane resin having the structure specified in the present invention before addition of water for phase inversion emulsification.

In order to confirm the physical properties of the obtained resin, the resin solution obtained above is applied to a release paper with a bar coater so that the film thickness at the time of drying becomes 50 μm, and the solvent is dried in an oven at 80 ° C. After that, the release paper was peeled off to obtain a resin film made of the resin obtained in Resin Synthesis Example 1. The appearance, mechanical strength, oxygen permeability (gas barrier property), acid value of the resin, hydroxyl value of the resin, and molecular weight (GPC) of this resin film were measured. Each measurement method will be described later. The results are shown in Table 1.

[Resin Synthesis Example 2 for Examples]
Using the same reaction vessel as that used in Resin Synthesis Example 1, 22.4 parts of bisphenol A diglycidyl ether, 33.9 parts of hexamethylenediamine, and 114 parts of tetrahydrofuran (THF) were added to make Resin Synthesis Example 1. It was reacted in the same manner as. Next, 100 parts of the previously obtained IA was added, and the reaction was carried out in the same manner as in Resin Synthesis Example 1. The result of confirming the reaction progress of the resin solution after the reaction by FT-IR was the same as that of Resin Synthesis Example 1. The amine value of the obtained resin was 39.2 mgKOH / g as a conversion value of 100% of the resin content. Next, 143 parts of THF was added to dilute the mixture, and 11.4 parts of maleic anhydride was added and reacted to introduce a carboxyl group, and water was added to the resin solution before phase inversion emulsification, as in Resin Synthesis Example 1. Got Then, in order to confirm the physical properties of the obtained resin, a resin film was produced in the same manner as in Resin Synthesis Example 1, and the appearance of the film, mechanical strength, oxygen permeability, acid value of the resin, hydroxyl value of the resin, And the molecular weight (GPC) was measured. The results are shown in Table 1.

[Resin Synthesis Example 3 for Examples]
Using the same reaction vessel as that used in Resin Synthesis Example 1, 22.4 parts of bisphenol A diglycidyl ether, 39.7 parts of m-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company), and 118 parts of tetrahydrofuran (THF) were added. In addition, the reaction was carried out in the same manner as in Resin Synthesis Example 1. Next, 100 parts of the previously obtained IA was added, and the reaction was carried out in the same manner as in Resin Synthesis Example 1. The result of confirming the reaction progress of the resin solution after the reaction by FT-IR was the same as that of Resin Synthesis Example 1. The amine value of the obtained resin was 38.1 mgKOH / g as a conversion value of 100% of the resin content. Next, 148 parts of tetrahydrofuran is added to dilute, and 11.4 parts of maleic anhydride is added and reacted to introduce a carboxyl group, and water is added to the resin solution before phase inversion emulsification, as in Resin Synthesis Example 1. Got Then, in order to confirm the physical properties of the obtained resin, a resin film was produced in the same manner as in Resin Synthesis Example 1, and the appearance of the film, mechanical strength, oxygen permeability, acid value of the resin, hydroxyl value of the resin, And the molecular weight (GPC) was measured. The results are shown in Table 1.

[Example 4 of resin synthesis for examples]
Using the same reaction vessel as that used in Resin Synthesis Example 1, hydroquinone diglycidyl ether (trade name: Denacol EX203, manufactured by Nagase Chemitex Co., Ltd.) 8.2 parts, metaxylylenediamine 48.8 parts, tetrahydrofuran ( 111 parts of THF) was added, and the reaction was carried out in the same manner as in Resin Synthesis Example 1. Next, 100 parts of the previously obtained IB was added, and the reaction was carried out in the same manner as in Resin Synthesis Example 1. The result of confirming the reaction progress of the resin solution after the reaction by FT-IR was the same as that of Resin Synthesis Example 1. The amine value of the obtained resin was 26.5 mgKOH / g as a conversion value of 100% of the resin content. Next, 139 parts of THF was added for dilution, and 7 parts of maleic anhydride was added and reacted in the same manner as in Resin Synthesis Example 1 to introduce a carboxyl group, and water was added to obtain a resin solution before phase inversion emulsification. .. Then, in order to confirm the physical properties of the obtained resin, a resin film was produced in the same manner as in Resin Synthesis Example 1, and the appearance of the film, mechanical strength, oxygen permeability, acid value of the resin, hydroxyl value of the resin, And the molecular weight (GPC) was measured. The results are shown in Table 1.

[Plastic synthesis example a for comparative example]
In a reaction vessel similar to that used in Resin Synthesis Example 1, 100 parts of the cyclic carbonate-containing compound IA obtained in Production Example 1, 27.1 parts of hexamethylenediamine, and 198 parts of tetrahydrofuran (THF) were added. The reaction was carried out for 24 hours with stirring at a temperature of 60 ° C. to obtain a resin solution for comparative example. The obtained resin solution is a normal polyhydroxyurethane resin containing no carboxyl group. Next, 117 parts of THF was added to the reaction solution for dilution, and then 9.2 parts of maleic anhydride and 11.8 parts of triethylamine as a catalyst were added to carry out a reaction at 60 ° C. for 2 hours to react maleic anhydride. A resin solution before phase inversion emulsification was obtained. Unlike the polyhydroxyurethane resin specified in the present invention, this resin is a polyhydroxyurethane resin obtained by a conventional formulation in which a carboxyl group is introduced by half-esterifying a hydroxyl group. In order to confirm the physical properties of the obtained resin, a resin film was prepared in the same manner as in Resin Synthesis Example 1, and the appearance, mechanical strength, oxygen permeability, acid value of the resin, hydroxyl value of the resin, and molecular weight ( GPC) was measured. The results are shown in Table 1.

[Resin synthesis example b for comparative example]
In a reaction vessel similar to that used in Resin Synthesis Example 1, 100 parts of the cyclic carbonate-containing compound IB obtained in Production Example 2, 31.8 parts of metaxylene diamine, and 96.8 parts of tetrahydrofuran (THF) were placed. The reaction was carried out for 24 hours with stirring at a temperature of 60 ° C. to obtain a resin solution for comparative example. The obtained resin solution is a normal polyhydroxyurethane resin containing no carboxyl group. Next, 121 parts of THF was added to the reaction solution to dilute it, then 9.2 parts of maleic anhydride and 9.4 parts of triethylamine as a catalyst were added, and the reaction was carried out at 60 ° C. for 2 hours to react maleic anhydride. , A resin solution before phase inversion emulsification was obtained. This resin is a polyhydroxyurethane resin obtained by a conventional formulation in which a carboxyl group is introduced by half-esterifying a hydroxyl group, unlike the polyhydroxyurethane resin of the examples specified in the present invention. In order to confirm the physical properties of the obtained resin, a resin film was prepared in the same manner as in Resin Synthesis Example 1, and the appearance, mechanical strength, oxygen permeability, acid value of the resin, hydroxyl value of the resin, and molecular weight ( GPC) was measured. The results are shown in Table 1.

(Evaluation)
The resins obtained in Resin Synthesis Examples 1 to 4 for Examples and Resin Synthesis Examples a and b for Comparative Examples described above, and the films prepared from each resin were evaluated by the following methods and criteria. .. The carbon dioxide content of each resin was calculated as follows. The evaluation results are summarized in Table 1.

[Carbon dioxide content]
The carbon dioxide content was determined by calculating the mass% of the carbon dioxide-derived segment of the raw material in the chemical structure of the polyhydroxyurethane resin used in each synthesis example. Specifically, it is shown as a calculated value calculated from the theoretical amount of carbon dioxide contained in the monomer used in synthesizing the compounds I-A and IB used in the synthesis reaction of the polyurethane resin. For example, in the case of the resin synthesis example 1 for the examples, the amount of the carbon dioxide-derived component of the compound IA used is 20.5%, and from this, in the polyurethane of the resin synthesis example 1 for the examples. The carbon dioxide concentration of (100 parts × 20.5%) /145.3 total amount = 14% by mass.

[Molecular weight]
In Table 1, the weight average molecular weight as a polystyrene-equivalent value measured by GPC measurement using DMF as a mobile phase is shown. The GPC measurement was performed using a GPC-8220 (trade name) manufactured by Tosoh Corporation with a column Super AW2500 + AW3000 + AW4000 + AW5000.

[Film appearance]
The total light transmittance and haze of each of the produced resin films were measured and evaluated according to the following criteria. The total light transmittance and haze were both measured by a haze meter HZ-1 (trade name, manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K-7105. The total amount of light measured by the haze meter is the total light transmittance, and the ratio of the diffused transmitted light to the total light transmittance is the haze.
<Evaluation criteria>
◯: Total light transmittance 90% or more Haze 5% or less ×: Not applicable to ○

[Acid value, hydroxyl value]
In each case, each resin was measured by a titration method based on JIS K-1557, and the content of each functional group per 1 g of the resin was expressed by mg equivalent of KOH. The unit is mgKOH / g.

[Mechanical strength]
As the mechanical strength of each of the produced resin films, the breaking point strength and the breaking point elongation were measured. The measurement was carried out at room temperature (25 ° C.) by a measurement method using Autograph AGS-J (trade name, manufactured by Shimadzu Corporation) in accordance with JIS K-6251.

[Gas barrier property (oxygen permeability)]
For each of the produced resin films, the oxygen permeability was measured in accordance with JIS K-7126, and this was used as the evaluation value of the gas barrier property. That is, it can be judged that the lower this value is, the better the gas barrier property is. Specifically, OX-TRAN 2/21 ML (trade name, manufactured by MOCON, the same applies hereinafter) was used as an oxygen permeability measuring device, and the temperature was 23 ° C. and the humidity was 65% under constant temperature and humidity conditions. The oxygen permeability was measured. Since the film used had a film thickness of 50 μm after drying, the values converted to a film thickness of 20 μm are shown in Table 1.

<Preparation of clay minerals>
[Production Example 3: Preparation of clay mineral dispersion A]
Using a high-speed stirrer homodisper, 95 parts of water and 5 parts of Kunipia F (trade name, manufactured by Kunimine Industries Co., Ltd.), which is a montmorillonite as a clay mineral, are premixed, and then an ultrasonic disperser (manufactured by Sonic Technology Co., Ltd.) is used. It was used to swell and disperse between clay mineral layers. It was confirmed that the clay mineral was uniformly dispersed, and this was designated as the clay mineral dispersion liquid A.

[Production Example 4: Preparation of clay mineral dispersion B]
Using a homodisper, 95 parts of water and 5 parts of Somasif ME-100 (trade name, manufactured by Corp Chemical Co., Ltd.), which is a synthetic mica as a clay mineral, are premixed, and then ultrasonically dispersed in the same manner as in Production Example 3. A dispersion of clay minerals was obtained using a machine. This was designated as clay mineral dispersion liquid B.

[Example 1]
(Manufacturing of aqueous dispersion of polyhydroxyurethane resin)
In a reaction vessel capable of stirring and distillation under reduced pressure, 100 parts of the resin solution (THF solution) obtained in Resin Synthesis Example 1 for Examples and 1.4 parts of triethylamine were charged. Then, 100 parts of ion-exchanged water was gradually added while stirring at room temperature to carry out phase inversion emulsification. Next, the reaction vessel was heated to 50 ° C. and depressurized, and THF was distilled off to obtain an aqueous dispersion in which the polyhydroxyurethane resin was dispersed in water of this example. The obtained aqueous dispersion was adjusted so that the solid content was 30%, and was an apparently uniform aqueous dispersion. The particle size distribution of the polymer-dispersed particles in the aqueous dispersion (measured by UPA-EX150 (trade name) manufactured by Nikkiso Co., Ltd., the same apparatus is used below) was d50 = 0.02 μm.

(Manufacture of Polyhydroxyurethane Resin Water Dispersion Composition Containing Clay Minerals)
10 parts (solid content 30%) of the aqueous dispersion of the polyhydroxyurethane resin obtained above and 10 parts (solid content 5%) of the clay mineral dispersion A prepared in Production Example 3 were mixed and used as a homodisper. With uniform stirring, an aqueous dispersion composition of a composite material in which a polyhydroxyurethane resin and a clay mineral were dispersed in water of this example was obtained. The stability of the obtained aqueous dispersion composition was stored in a constant temperature bath at 50 ° C. and evaluated by the method described later, and showed good stability.

Using the clay mineral-containing polyhydroxyurethane resin aqueous dispersion composition obtained above, a multilayer film was obtained as described below. Specifically, on the corona-treated surface of Pyrene P1111 (trade name, manufactured by Toyobo Co., Ltd., measured oxygen permeability: 1500 mL, 20 μm / m ² , day, atm), which is a non-stretched polypropylene film (CPP film) having a thickness of 40 μm. The clay mineral-containing polyhydroxyurethane resin aqueous dispersion composition obtained in the above was applied so that the film thickness at the time of drying was 5 μm, and dried at 100 ° C. to obtain a coating film (coating film) on the substrate. ) Was formed to obtain a multilayer film. The storage stability of the aqueous dispersion composition used was evaluated, and the appearance of the coating film, the light transmittance, the surface gloss, and the gas barrier property were evaluated using the film obtained above. Each measurement method will be described later. The results are shown in Table 2.

[Example 2]
10 parts of the aqueous dispersion of the polyhydroxyurethane resin obtained by the same formulation and method as in Example 1 and 20 parts (solid content 5%) of the clay mineral dispersion A prepared in Production Example 3 were mixed and homogenized. By uniformly stirring with a disper, an aqueous dispersion composition in which the polyhydroxyurethane resin and the clay mineral of this example were dispersed was obtained. Then, using the obtained aqueous dispersion composition, a multilayer film was prepared under the same substrate and conditions as those used in Example 1. The aqueous dispersion composition and film of this example obtained above were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[Example 3]
10 parts of the aqueous dispersion of the polyhydroxyurethane resin obtained by the same formulation and method as in Example 1 and 30 parts (solid content 5%) of the clay mineral dispersion A prepared in Production Example 3 were mixed and homogenized. By uniformly stirring with a disper, an aqueous dispersion composition in which the polyhydroxyurethane resin and the clay mineral of this example were dispersed was obtained. Then, using the obtained aqueous dispersion composition, a multilayer film was prepared under the same substrate and conditions as those used in Example 1. The aqueous dispersion composition and film of this example obtained above were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[Example 4]
10 parts of the aqueous dispersion of the polyhydroxyurethane resin obtained by the same formulation and method as in Example 1 and 60 parts (solid content 5%) of the clay mineral dispersion A prepared in Production Example 3 were mixed and homogenized. By uniformly stirring with a disper, an aqueous dispersion composition in which the polyhydroxyurethane resin and the clay mineral of this example were dispersed was obtained. Then, using the obtained aqueous dispersion composition, a multilayer film was prepared under the same substrate and conditions as those used in Example 1. The aqueous dispersion composition and film of this example obtained above were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[Example 5]
Instead of the resin solution obtained in Resin Synthesis Example 1 used in "Production of Polyhydroxyurethane Aqueous Dispersion" of Example 1, 100 parts of the resin solution obtained in Resin Synthesis Example 2 for Examples was used to obtain triethylamine. Phase inversion emulsification was carried out in the same manner as in Example 1 except that the amount was 2.8 parts, to obtain an aqueous dispersion in which the polyhydroxyurethane resin of this example was dispersed. The obtained aqueous dispersion was adjusted to have a solid content of 30% by adding water, and was an aqueous dispersion having a uniform appearance. Next, 10 parts (30% solid content) of the aqueous dispersion of the polyhydroxyurethane resin obtained above and 30 parts (5% solid content) of the clay mineral dispersion A prepared in Production Example 3 were mixed and homodisperse. To obtain an aqueous dispersion composition in which the polyhydroxyurethane resin and the clay mineral of this example were dispersed, the mixture was uniformly stirred with. Then, using the obtained aqueous dispersion composition, a multilayer film was prepared under the same substrate and conditions as those used in Example 1. The aqueous dispersion composition and film of this example obtained above were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[Example 6]
Instead of the resin solution obtained in Resin Synthesis Example 1 used in "Production of Polyhydroxyurethane Aqueous Dispersion" of Example 1, 100 parts of the resin solution obtained in Resin Synthesis Example 3 for Examples was used to obtain triethylamine. Phase inversion emulsification was carried out in the same manner as in Example 1 except that the amount was 2.7 parts, to obtain an aqueous dispersion in which the polyhydroxyurethane resin of this example was dispersed. The obtained aqueous dispersion was adjusted to have a solid content of 30% by adding water, and was an aqueous dispersion having a uniform appearance. Next, 10 parts (solid content 30%) of the aqueous dispersion of the polyhydroxyurethane resin obtained above and 30 parts (solid content 5%) of the clay mineral dispersion B prepared in Production Example 4 were mixed and homodisper. To obtain the polyhydroxyurethane aqueous dispersion composition in which the polyhydroxyurethane resin and the clay mineral of this example were dispersed, the mixture was uniformly stirred with. Then, using the obtained aqueous dispersion composition, a multilayer film was prepared under the same substrate and conditions as those used in Example 1. The aqueous dispersion composition and film of this example obtained above were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[Example 7]
Instead of the resin solution obtained in Resin Synthesis Example 1 used in "Production of Polyhydroxyurethane Aqueous Dispersion" of Example 1, 100 parts of the resin solution obtained in Resin Synthesis Example 4 for Examples was used to obtain triethylamine. Phase inversion emulsification was carried out in the same manner as in Example 1 except that the amount was 2.6 parts, to obtain an aqueous dispersion in which the polyhydroxyurethane resin of this example was dispersed. The obtained aqueous dispersion was adjusted to have a solid content of 30% by adding water, and was an aqueous dispersion having a uniform appearance. Next, 10 parts (30% solid content) of the aqueous dispersion of the polyhydroxyurethane resin obtained above and 30 parts of the clay mineral dispersion B prepared in Production Example 4 were mixed and uniformly stirred with a homodisper. , An aqueous dispersion composition in which the polyhydroxyurethane resin and the clay mineral of this example were dispersed was obtained. Then, using the obtained aqueous dispersion composition, a multilayer film was prepared under the same substrate and conditions as those used in Example 1. The aqueous dispersion composition and film of this example obtained above were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[Comparative Example 1]
Instead of the resin solution obtained in Resin Synthesis Example 1 used in "Production of Polyhydroxyurethane Aqueous Dispersion" of Example 1, the resin solution obtained in Resin Synthesis Example a for Comparative Example was used and already used during the reaction. An aqueous dispersion of a polyhydroxyurethane resin adjusted to a solid content of 30% was obtained in the same manner as in Example 1 except that the triethylamine used was not used. The particle size distribution of the polymer dispersed particles in the aqueous dispersion was d50 = 0.020 μm. Next, 10 parts (solid content 30%) of the obtained aqueous dispersion of the polyhydroxyurethane resin and 30 parts (solid content 5%) of the clay mineral dispersion A prepared in Production Example 3 were mixed and used as a homodisper. By uniformly stirring, an aqueous dispersion composition in which the polyhydroxyurethane resin and the clay mineral of the comparative example were dispersed was obtained. Then, using the obtained aqueous dispersion composition, a multilayer film was prepared under the same substrate and conditions as those used in Example 1. The same evaluation as in Example 1 was carried out using the aqueous dispersion and film of Comparative Example obtained above, and the results are shown in Table 3.

[Comparative Example 2]
Instead of the resin solution obtained in Resin Synthesis Example 1 used in "Production of Polyhydroxyurethane Aqueous Dispersion" of Example 1, the resin solution obtained in Resin Synthesis Example b for Comparative Example was used and already used during the reaction. An aqueous dispersion of a polyhydroxyurethane resin adjusted to a solid content of 30% was obtained in the same manner as in Example 1 except that the triethylamine used was not used. The particle size distribution of the polymer dispersed particles in the aqueous dispersion was d50 = 0.020 μm. Next, 10 parts (solid content 30%) of the obtained aqueous dispersion of the polyhydroxyurethane resin and 30 parts (solid content 5%) of the clay mineral dispersion A prepared in Production Example 3 were mixed and used as a homodisper. By uniformly stirring, an aqueous dispersion composition in which the polyhydroxyurethane resin and the clay mineral of the comparative example were dispersed was obtained. Then, using the obtained aqueous dispersion composition, a multilayer film was prepared under the same substrate and conditions as those used in Example 1. The same evaluation as in Example 1 was carried out using the aqueous dispersion and film of Comparative Example obtained above, and the results are shown in Table 3.

(Evaluation)
The characteristics of each of the aqueous dispersion compositions of Examples 1 to 7 and Comparative Examples 1 and 2 obtained above, and the evaluation of the film produced using each of the aqueous dispersion compositions as described above are as follows. The method and standard of the above were used. The results are summarized in Tables 2 and 3.

[Stability]
Each of the aqueous dispersion compositions of Examples and Comparative Examples was placed in a closed plastic container and stored in a constant temperature bath at 50 ° C. Then, the states after 1 month, 3 months, and 6 months were observed, respectively, and evaluated according to the following criteria, and the results are shown in Tables 2 and 3, respectively.
<Evaluation criteria>
◯: There is no sedimentation of polymer particles and clay minerals, and no change in appearance is observed.
Δ: Polymer particles and clay minerals are settled, but are easily redispersed by stirring.
X: The emulsified particles are destroyed and the resin component is settled, and cannot be redispersed even with stirring.

[Appearance of coating film]
The appearance of the coated surface (coating layer) of each of the multi-layer films produced in Examples and Comparative Examples was visually observed and evaluated according to the following criteria. The results are shown in Tables 2 and 3.
<Evaluation criteria>
◯: A transparent to translucent uniform film is formed, and there are no agglomerates that can be visually confirmed.
X: There are agglomerates that are not uniform due to streaks caused by agglomerates or that are visible.

[Total light transmittance: haze]
It was measured by a method conforming to JIS-K 7136 using a digital haze meter HGM-2DP (trade name, manufactured by Suga Test Instruments Co., Ltd.).

[water resistant]
For each of the multilayer films produced in Examples and Comparative Examples, the films were immersed in water, and the surface condition of the coating film after 1 hour at room temperature was visually observed and evaluated according to the following criteria. The results are shown in Tables 2 and 3.
<Evaluation criteria>
◯: No change is seen.
Δ: A part of the coating film is whitened.
X: The coating film is swollen.

[Gas barrier property]
For each film having a coating film (coating layer) on the surface prepared by using each of the aqueous dispersion compositions of Examples and Comparative Examples, the oxygen permeability was measured in accordance with JIS K-7126, and this was measured as a gas barrier. It was used as the evaluation value of sex. That is, it can be judged that the lower this value is, the better the gas barrier property is. Specifically, the oxygen permeability (oxygen permeability) was measured using an oxygen permeability measuring device under a constant temperature and humidity condition of a temperature of 23 ° C. and a humidity of 65%. The oxygen transmittance of the films prepared in Resin Synthesis Examples 1 to 5 for Examples shown in Table 1 above is a value converted into a film thickness of 20 μm, whereas it is shown in Tables 2 and 3. The measured values of the gas barrier properties of the resin films of Examples 1 to 7 and Comparative Examples 1 and 2 are the oxygen permeability as a film structure having a coating film (coating layer / coating layer) on the surface. The thickness of the coat layer obtained by applying each aqueous dispersion composition in the examples or comparative examples of the film shall be 5 μm as measured using a precision thickness measuring instrument (manufactured by Ozaki Seisakusho Co., Ltd.). Is confirmed. The results are shown in Tables 2 and 3. For reference, the aqueous dispersion (solid content 30%) of the polyhydroxyurethane resin used for preparing each aqueous dispersion composition before being composited with the clay mineral was used, and the coat layer was obtained in the same manner as above. A film having a coating film (coating layer) formed on the surface was prepared so that the thickness of the film was 5 μm, and the gas barrier property was measured. The results are shown at the bottom of Table 2.

As is clear from Table 2, it is possible to obtain an aqueous dispersion composition in which clay minerals and polyhydroxyurethane resin are uniformly dispersed by the technique of the present invention. In particular, the dispersibility stability of clay minerals is excellent as compared with the case of using the aqueous dispersion of the hydroxyurethane resin of the comparative example produced by the conventional formulation, which is because the polyhydroxyurethane resin used in the present invention has excellent dispersibility. , It is considered that it is derived from the fact that a carboxyl group is introduced into the structure via an amide bond. That is, the polymer chain of the polyhydroxyurethane resin produced by the conventional method hydrolyzed only with an anionic carboxyl group is less likely to penetrate between the layers of the clay mineral, and the poly having the structure specified in the present invention. It is considered that the hydroxyurethane resin was able to produce a uniform dispersion without inhibiting the invasion of the polymer chain between the layers of the clay mineral due to the presence of this amide bond. As a result, as shown in Table 2, none of the coating films (coating layers) formed using the aqueous dispersion composition of the example had agglomerates, although they used clay minerals. It was confirmed that the transparency was excellent.

In addition, the amide bond is superior in hydrolysis resistance as compared with the ester bond when a carboxyl group is introduced into a conventional hydroxyurethane resin, so that the stability of the polymer-dispersed particles is also good. Further, by forming a film using the aqueous dispersion composition in which the clay mineral and the polyhydroxyurethane resin are uniformly dispersed according to the present invention, a composite film of the clay mineral-polyhydroxyurethane resin can be easily obtained. It was also confirmed that a high gas barrier property can be realized even if the film thickness is thin, because the clay minerals are well dispersed.

According to the present invention, it is possible to provide an aqueous dispersion composition of a polyhydroxyurethane resin-clay mineral that can be stored for a long period of time, which is industrially required. Further, the aqueous dispersion composition can be easily formed into a polyhydroxyurethane-clay mineral composite film, and this film can be used as a gas barrier layer. Further, the formed film is expected to be used in a wide range of fields because it has an appearance without agglomerates and a gloss while using clay minerals. Furthermore, the polyhydroxyurethane resin that characterizes the present invention is a technique that is expected from the aspect of protecting the global environment because carbon dioxide can be used as a raw material thereof.

Claims (6)

An aqueous dispersion composition which is a composite material containing an anionic polyhydroxyurethane resin having a carboxyl group and a hydroxyl group as a component (A) and a layered clay mineral as a component (B).
The total content of the component (A) and the component (B) is 10 to 50% by mass.
The component (B) is contained in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the component (A).
The chemical structure of the anionic polyhydroxyurethane resin having a carboxyl group and a hydroxyl group of the component (A) has a repeating unit represented by the following general formula (1) as a basic structure and is represented by the following general formula (6). A clay mineral-containing polyhydroxyurethane resin aqueous dispersion composition having a chemical structural moiety having a carboxyl group.

[In the general formula (1), -X- is a direct bond, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 40 carbon atoms, or an aromatic group having 6 to 40 carbon atoms. It is a hydrocarbon group, and in the structure of these groups, any one of ether bond, amino bond, sulfonyl bond and ester bond, or as a substituent, a hydroxyl group, a halogen atom and 2 carbon atoms of repeating units 1 to 30 It may contain any of the polyalkylene glycol chains consisting of ~ 6. Y− is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group having 4 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms, and is contained in the structure of these groups. May contain either an ether bond or a sulfonyl bond, or a hydroxyl group or a halogen atom as a substituent. −Z ₁ − and −Z ₂ − independently represent at least one structure selected from the group consisting of the following equations (2), (3), general equations (4) and (5). , Two or more types of structures selected from these formulas (2) to (5) may be mixed in both within the repeating unit and between the repeating units. In addition, when any of these equations (2) to (5) is selected, the bond on the right side is bonded to the oxygen atom, the bond on the left side is bonded to X, and X is directly bonded. In the case, it joins with the other join hand on the left side of Z. ]

[In the general formula (4) or (5), R represents a hydrogen atom or a methyl group. ]

[In the general formula (6), -W- is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 40 carbon atoms, or an aromatic hydrocarbon group having 6 to 40 carbon atoms. In the structure of these groups, any of ether bond, amino bond, sulfonyl bond and ester bond, or as a substituent, it is composed of a hydroxyl group, a halogen atom and 2 to 6 carbon atoms of repeating units 1 to 30. It may contain any of the polyalkylene glycol chains. Y-is a portion to be bonded to the urethane structure having a bond of the general formula (1), and can be selected as Y- in the general formula (1). -V- is a hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the structure of these groups may contain an oxygen atom or a nitrogen atom. ] The anionic polyhydroxyurethane resin of the component (A) has a weight average molecular weight in the range of 1000 to 100,000 and an acid value in the range of 15 mgKOH / g to 50 mgKOH / g, and a hydroxyl value thereof. The clay mineral-containing polyhydroxyurethane resin aqueous dispersion composition according to claim 1, wherein the amount is in the range of 150 mgKOH / g to 250 mgKOH / g. A five-membered cyclic carbonate structure in which the basic structural portion represented by the general formula (1) of the anionic polyhydroxyurethane resin as the component (A) is synthesized by using carbon dioxide as a raw material at least a part thereof. It is composed of a polyaddition reaction product of a compound having at least two and a compound having at least two primary amino groups, and comprises 1 to 30% by mass of the total mass of the anionic polyhydroxyurethane resin of the component (A). The clay mineral-containing polyhydroxyurethane resin aqueous dispersion composition according to claim 1 or 2, wherein the carbon dioxide-derived —O—CO— bond occupies. The clay according to any one of claims 1 to 3, wherein the layered clay mineral of the component (B) is at least one selected from the group consisting of montmorillonite, saponite, hectorite, vermiculite, kaolinite and mica. A mineral-containing polyhydroxyurethane resin aqueous dispersion composition. A gas-barrier water-based coating agent comprising the clay mineral-containing polyhydroxyurethane resin aqueous dispersion composition according to any one of claims 1 to 4 as an essential component. It comprises a base material and a coating layer provided on at least one of the base materials and formed of a composite material containing a polyhydroxyurethane resin and a clay mineral.
The composite material is the clay mineral-containing polyhydroxyurethane resin aqueous dispersion composition according to any one of claims 1 to 4.
A gas barrier characterized in that the thickness of the coating layer is 0.1 to 100 μm, and the oxygen permeability of the coating layer is 10 mL / m ² · day · atm or less at 23 ° C. and 65% humidity. Sex resin film.