JP6808664B2 - Hydroxypolyurethane resin aqueous dispersion composition, gas barrier coating agent and gas barrier film using this - Google Patents

Description

The present invention relates to a novel aqueous dispersion composition of a hydroxypolyurethane resin that can be used as a binder resin for paints and coating agents. Specifically, when used as a material such as water-dispersed paint, the performance as a heat-resistant paint and gas barrier paint that can form a film comparable to the film formed with conventional solvent-based paints from the viewpoint of film functionality. The present invention relates to an aqueous dispersion composition of a hydroxypolyurethane resin. Furthermore, the present invention relates to a technique capable of providing a highly environmentally friendly product because carbon dioxide can be incorporated into the chemical structure of the constituent hydroxypolyurethane resin.

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, as a novel polyurethane-based resin, a hydroxypolyurethane resin having both a urethane bond and a hydroxyl group in its chemical structure has been developed, and its industrial application is expected (see Patent Document 1). While existing polyurethane resins can be obtained by using isocyanate compounds and polyols as raw materials, hydroxypolyurethane resins are largely produced by using epoxy compounds, carbon dioxide and amine compounds as raw materials and combining these raw materials. different. Since carbon dioxide used as a raw material is incorporated as a -CO-O- bond in the chemical structure of hydroxypolyurethane resin, it is a resin material that should be noted from the viewpoint of effective utilization of carbon dioxide, which is a greenhouse gas. is there.

The hydroxypolyurethane resin can be used as a resin having excellent mechanical strength like the existing polyurethane resin, but further, 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 fields of paints and coatings are promising as applications of hydroxypolyurethane resins. However, since the hydroxypolyurethane resins developed so far have a chemical structure having a hydroxyl group together with a urethane bond, their solubility in an organic solvent is low, and they differ depending on the base material and processing equipment used in each application. In many cases, it is difficult to deal with various solvent compositions, which is a problem in application. On the other hand, by using a hydroxypolyurethane resin as an aqueous dispersion, this problem can be solved, and at the same time, it has been studied and proposed to be applied as an aqueous paint which is being replaced with a solvent-based paint in recent years. (See Patent Document 4).

However, according to the study by the present inventors, this technique is obtained by carboxyl-forming the hydroxyl groups of the hydroxypolyurethane resin by the half-ester method in order to obtain an aqueous dispersion, and therefore, it is suitable for hydrolysis of the half-ester portion. As a result, there remains a problem in that the storage stability of the aqueous dispersion is poor, and the problem has not been completely solved. Further, the method of using the hydroxyl group of the hydroxypolyurethane resin for the reaction to reduce the amount of the hydroxyl group has an advantage of contributing to the improvement of water resistance, but has a drawback in the application utilizing the functionality of the hydroxyl group. Become.

As another method, a method has been devised in which an amine compound containing a carboxylic acid is used as a raw material to obtain a hydroxypolyurethane resin having a carboxyl group (see Patent Document 5). However, according to the study by the present inventors, in this method, since the carboxyl group and the amino group form an ionic bond in the synthetic reaction system, the reaction with the cyclic carbonate is difficult to proceed, and DMF (DMF) It requires a reaction in a high boiling point solvent such as dimethylformamide), and has a drawback that it is difficult to increase the molecular weight. Further, the high boiling point solvent used has a problem that it cannot be distilled off under reduced pressure after phase inversion emulsification, and is not a perfect method for producing an aqueous dispersion (emulsion).

As a method for solving these problems, the present inventors have already proposed a method of synthesizing a hydroxypolyurethane resin having a secondary transamination group and carboxylating the amino group in the main chain (Patent Document 6). reference). The aqueous dispersion obtained by this method has the advantages of excellent storage stability and a film having excellent gas barrier properties.

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 Japanese Unexamined Patent Publication No. 2016-194029

However, the aqueous dispersions of the hydroxypolyurethane resins developed so far as described above are all based on a method of incorporating an anionic group in the chemical structure of the hydroxypolyurethane resin, and are resins having an anionic group. The disadvantage of the aqueous dispersion is that the dispersion state becomes unstable under acidic conditions. In particular, when used as a paint, a higher performance film can be obtained by adding various fillers and cross-linking agents to the aqueous dispersion of the base hydroxypolyurethane resin. However, there is a drawback that it cannot be used in combination with an additive having acidity or a filler having excellent dispersibility under acidic conditions, and further development is desired in order to establish it as a practical technology.

Therefore, an object of the present invention is to overcome the problems of the prior art and to combine a cationized hydroxypolyurethane resin with an additive that disperses well under acidic conditions, specifically, a filler such as silica fine particles. To provide an aqueous dispersion composition capable of realizing the stability of the aqueous dispersion composition and the ability to form a film having good gas barrier properties when made possible and put into practical use by the above combination, and the aqueous dispersion. It is an object of the present invention to provide a product such as a film having excellent gas barrier properties by using a body composition.

The above object is achieved by the following invention, i.e., the present invention
[1] An aqueous dispersion composition for a gas barrier coating.
The component (A) contains a hydroxypolyurethane resin containing a cationic group having at least a cationic group and a hydroxyl group, the component (B) contains silica fine particles, and the component (C) contains a metal chelate compound. Therefore, the component (B) is contained in an amount of 1 to 120 parts by mass with respect to 100 parts by mass of the component (A), and the total content of the component (A) and the component (B) is It is 10 to 50% by mass, and the content of the component (C) is 1 to 10% by mass with respect to 100% by mass of the total solid content of the component (A), the component (B) and the component (C). Provided is an aqueous dispersion composition of a hydroxypolyurethane resin, which is characterized by a mass%.

Preferred embodiments of the above-mentioned aqueous dispersion composition of the hydroxypolyurethane resin include those having the following configurations.
[2] The following general formula (11) for adding water to emulsify the hydroxypolyurethane resin containing the cationic group of the component (A) in its structure, which is represented by the following general formula (1). The aqueous dispersion composition of a hydroxypolyurethane resin according to [1], which has a repeating unit having a chemical structure containing a cationic group represented by.

［上記一般式（１）中のＸは、ないか、或いは、モノマー単位由来の脂肪族炭化水素又は脂環式炭化水素又は芳香族炭化水素からなる化学構造を示し、該構造中に、酸素原子、窒素原子、硫黄原子及びエステル結合を含んでいてもよく、エーテル結合を介してＹ₁及び／又はＹ₂と結合する構造であってもよい。−Ｙ₁−は、下記式（２）〜（５）のいずれか１つの化学構造を示し、また、−Ｙ₂−は、下記式（２）、（６）〜（１０）のいずれか１つの化学構造を示し、式（４）、（５）、（７）〜（１０）中のＲは、水素原子かＣＨ₃を示す。−Ｚ−は、下記一般式（１１）で示されるカチオン性基を含む化学構造を示す。式中の＊は、結合手であることを示す記号である。］

[X in the above general formula (1) indicates a chemical structure composed of an aliphatic hydrocarbon or an alicyclic hydrocarbon or an aromatic hydrocarbon which is absent or derived from a monomer unit, and an oxygen atom is contained in the structure. , A nitrogen atom, a sulfur atom and an ester bond may be contained, and the structure may be bonded to Y ₁ and / or Y ₂ via an ether bond. −Y ₁ − represents the chemical structure of any one of the following formulas (2) to (5), and −Y ₂ − is any one of the following formulas (2), (6) to (10). Two chemical structures are shown, and R in the formulas (4), (5), (7) to (10) indicates a hydrogen atom or CH ₃ . -Z- indicates a chemical structure containing a cationic group represented by the following general formula (11). * In the formula is a symbol indicating that it is a bond. ]

［上記一般式（１１）中、Ｒ₄は脂肪族炭化水素であり、該構造中には酸素原子を含んでもよい。Ｒ₁、Ｒ₂、Ｒ₃は、それぞれ独立して、その構造中にエーテル結合を含んでもよい炭素数１〜１０のアルキレン基である。ｎは、０〜３の整数である。］
なお、上記で規定した粒子径は、測定した粒度分布から計算により得られたメジアン径（＝ｄ５０値）である。

[In the above general formula (11), R ₄ is an aliphatic hydrocarbon, and an oxygen atom may be contained in the structure. R ₁ , R ₂ , and R ₃ are alkylene groups having 1 to 10 carbon atoms, which may independently contain an ether bond in their structure. n is an integer from 0 to 3. ]
The particle size specified above is the median diameter (= d50 value) obtained by calculation from the measured particle size distribution.

[3] Further, the repeating unit constituting the hydroxypolyurethane resin of the component (A) has a structure different from that of the repeating unit having a chemical structure containing a cationic group represented by the general formula (1). The units are mixed, and the repeating unit of the other structure is replaced with a chemical structure in which -Z- in the general formula (1) contains a cationic group represented by the general formula (11). The chemical structure according to [2], which is a hydrocarbon having 1 to 100 carbon atoms or an aromatic hydrocarbon having 6 to 100 carbon atoms, which may contain oxygen atoms and nitrogen atoms in the structure. Hydrodisperse composition of hydroxypolyurethane resin.

[4] The hydroxypolyurethane resin of the component (A) has a weight average molecular weight in the range of 1000 to 100,000 and a concentration of cationic groups in its structure in the range of 500 g / mol to 2000 g / mol. The aqueous dispersion composition of the hydroxypolyurethane resin according to [2] or [3], wherein the hydroxyl value is in the range of 150 mgKOH / g to 300 mgKOH / g.

[5] The hydroxypolyurethane resin of the component (A) is a compound having at least two 5-membered cyclic carbonate structures having a 5-membered cyclic carbonate structure synthesized by using carbon dioxide as a raw material in at least a part thereof. It was obtained by a double addition reaction of a compound having at least two amino groups, and 1 to 20% by mass of the total mass was occupied by the carbon dioxide-derived -O-CO- bond [1]. The aqueous dispersion composition of the hydroxypolyurethane resin according to any one of [4].

[6] The hydroxypolyurethane resin according to any one of [1] to [5], wherein the silica fine particles of the component (B) are spherical or scaly fine particles having a particle diameter of 0.001 μm to 5 μm. Aqueous dispersion composition.

[7] The aqueous dispersion composition of a hydroxypolyurethane resin according to any one of [1] to [6], wherein the metal chelate compound of the component (C) is a titanium lactic acid chelate or a zirconyl chloride compound.

The present invention, as another embodiment
[8] Provided is a gas barrier coating agent comprising the aqueous dispersion composition of the hydroxypolyurethane resin according to any one of the above [1] to [7].

The present invention, as another embodiment
[9] A coating layer having a thickness of 0.1 to 100 μm is laminated on the base material and at least one of the base materials, and the coating layer is the hydroxypolyurethane according to any one of the above [1] to [7]. The oxygen permeability, which is formed by using the aqueous dispersion composition of the resin, is 50 mL / m ² · day · atm or less at 23 ° C. and 65% constant temperature and humidity. Provided is a gas barrier film.

According to the present invention, when a hydroxypolyurethane resin containing a cationic group and an additive such as silica fine particles that disperse well under acidic conditions are combined to form an aqueous dispersion composition, stability is formed. Provided is an aqueous dispersion composition of a hydroxypolyurethane resin for a gas barrier coating, which makes the coating layer have a good gas barrier property. The aqueous dispersion composition of the hydroxypolyurethane resin provided by the present invention has excellent stability and can be stored for a long period of time as compared with the aqueous dispersion composition of the hydroxypolyurethane resin provided in the prior art. Further, the gas barrier performance of the coating film (coating film layer) obtained from the aqueous dispersion composition of the present invention is more excellent than that of the coating film obtained by the conventional aqueous dispersion composition of hydroxypolyurethane resin. .. Further, the hydroxypolyurethane resin constituting the present invention is a resin that can be produced by using carbon dioxide as a raw material (forming material), and in addition to reducing the environmental load due to being an aqueous material, further Since it can contribute to the reduction of environmental load, it is also useful to be able to provide highly environmentally friendly products.

Next, the present invention will be described in detail with reference to preferred embodiments for carrying out the invention. The present invention relates to an aqueous dispersion composition for a gas barrier coating, and relates to a hydroxypolyurethane resin containing a cationic group having a cationic group and a hydroxyl group in the structure as a component (A) (hereinafter, “cationic hydroxypolyurethane resin”). ”), Silica fine particles as the component (B), and a metal chelate compound as the component (C). Then, the component (B) is contained in the range of 1 to 120 parts by mass with respect to 100 parts by mass of the component (A), and the total of the component (A) and the component (B) is totaled. The content is 10 to 50% by mass, and the content of the component (C) is 100% by mass based on the total solid content of the component (A), the component (B), and the component (C). It is characterized by being 1 to 10% by mass.

<Ingredient (A)>
The cationic hydroxypolyurethane resin of the component (A) constituting the present invention may have a cationic group and a hydroxyl group in its structure, but is more preferably one having the following constitution. That is, in the structure of the cationic hydroxypolyurethane resin, a cationic group represented by the following general formula (1) for phase inversion emulsification by adding water (hereinafter, simply " It is preferable that it has a repeating unit having a chemical structure containing "cationic group"). According to the studies by the present inventors, by using the cationic hydroxypolyurethane resin having the above-mentioned structural characteristics, the problem that the dispersed state becomes unstable under acidic conditions is more reliably solved. Even when various fillers and cross-linking agents are added to obtain a high-performance film, the hydroxypolyurethane resin and the hydroxypolyurethane resin aqueous dispersion composition in which the above additives are more stably dispersed in water can be obtained. can do. Hereinafter, a cationic hydroxypolyurethane resin having the above structure, which is useful as the component (A) constituting the present invention, will be described.

［上記一般式（１）中のＸは、ないか、或いは、モノマー単位由来の脂肪族炭化水素又は脂環式炭化水素又は芳香族炭化水素からなる化学構造を示し、該構造中に、酸素原子、窒素原子、硫黄原子及びエステル結合を含んでいてもよく、エーテル結合を介してＹ₁及び／又はＹ₂と結合する構造であってもよい。−Ｙ₁−は、下記式（２）〜（５）のいずれか１つの化学構造を示し、また、−Ｙ₂−は、下記式（２）、（６）〜（１０）のいずれか１つの化学構造を示し、式（４）、（５）、（７）〜（１０）中のＲは、水素原子かＣＨ₃を示す。−Ｚ−は、下記一般式（１１）で示されるカチオン性基を含む化学構造を示す。式中の＊は、結合手であることを示す記号である。］

[X in the above general formula (1) indicates a chemical structure composed of an aliphatic hydrocarbon or an alicyclic hydrocarbon or an aromatic hydrocarbon which is absent or derived from a monomer unit, and an oxygen atom is contained in the structure. , A nitrogen atom, a sulfur atom and an ester bond may be contained, and the structure may be bonded to Y ₁ and / or Y ₂ via an ether bond. −Y ₁ − represents the chemical structure of any one of the following formulas (2) to (5), and −Y ₂ − is any one of the following formulas (2), (6) to (10). Two chemical structures are shown, and R in the formulas (4), (5), (7) to (10) indicates a hydrogen atom or CH ₃ . -Z- indicates a chemical structure containing a cationic group represented by the following general formula (11). * In the formula is a symbol indicating that it is a bond. ]

［上記一般式（１１）中、Ｒ₄は脂肪族炭化水素であり、該構造中には酸素原子を含んでもよい。Ｒ₁、Ｒ₂、Ｒ₃は、それぞれ独立して、その構造中にエーテル結合を含んでもよい炭素数１〜１０のアルキレン基である。ｎは、０〜３の整数である。］

[In the above general formula (11), R ₄ is an aliphatic hydrocarbon, and an oxygen atom may be contained in the structure. R ₁ , R ₂ , and R ₃ are alkylene groups having 1 to 10 carbon atoms, which may independently contain an ether bond in their structure. n is an integer from 0 to 3. ]

The cationic hydroxypolyurethane resin useful as the component (A) constituting the present invention described above has a repeating unit represented by the general formula (1) in its structure. In this case, the entire resin may or may be composed of the repeating unit, and the repeating unit constituting the hydroxypolyurethane resin is the repeating unit represented by the above general formula (1). It may have a structure in which repeating units having different structures are mixed. For example, instead of a chemical structure having a different -Z- portion of the repeating unit represented by the general formula (1), specifically, a chemical structure containing a cationic group represented by the general formula (11). Examples thereof include those having a chemical structure in which the −Z− moiety is a hydrocarbon having 1 to 100 carbon atoms or an aromatic hydrocarbon having 6 to 100 carbon atoms, which may contain oxygen atoms and nitrogen atoms in its structure. Be done.

The structure of the repeating unit represented by the general formula (1) included in the structure of the cationic hydroxypolyurethane resin useful for the present invention may be such that all the repeating units in the resin have the same structure. A plurality of types corresponding to the structure represented by the general formula (1) may be mixed. Specifically, for example, the repeating unit contained in the structure of the hydroxypolyurethane resin may be such that both Y ₁ and Y ₂ in the general formula (1) have the chemical structure of the formula (2). For example, a hydroxypolyurethane resin in which Y ₁ in the general formula (1) is the formula (3) and Y ₂ is the chemical structure of the formula (6) may be mixed.

Next, a method for producing an aqueous dispersion containing a cationic hydroxypolyurethane resin preferably used as the component (A) constituting the present invention will be described. As a general method for producing a polymer emulsion, there are a forced emulsification type in which a surfactant is used as an emulsifier and a self-emulsification type in which a hydrophilic group is introduced into the polymer chain to form emulsified particles in the polymer chain itself. The aqueous dispersion useful as the component (A) constituting the present invention belongs to the above-mentioned self-emulsifying type. As shown in the structure of the general formula (11), self-emulsification is possible by introducing a quaternary ammonium structure which is a cationic group as a hydrophilic group necessary for emulsification into the structure of the resin. In addition, the dispersibility of the composition having a structure in which the component (B) is combined with silica fine particles that disperse well under acidic conditions and the metal chelate functioning as a cross-linking agent is contained as the component (C) is improved. It is a thing. Therefore, the -Z- portion of the repeating unit represented by the general formula (1) is different, specifically, the degree to which those having a chemical structure in which -Z- is a hydrocarbon or an aromatic hydrocarbon is mixed is mixed. It is preferable that the concentration of the cationic group of the entire resin is in the range of 500 g / mol to 2000 g / mol.

The hydroxypolyurethane resin having the structure represented by the general formula (1) can be produced by the following steps. From the double addition reaction of a compound having at least two 5-membered cyclic carbonates (hereinafter, may be simply abbreviated as cyclic carbonate or cyclic carbonate compound) in one molecule and a compound having at least two amino groups in one molecule. can get.

In the reaction between the cyclic carbonate forming the polymer chain of the hydroxypolyurethane resin and the amine, there are two types of cleavage of the cyclic carbonate, and it is known that the two types of structures shown in the following model reactions occur.

The cyclic carbonate used in the production of the hydroxypolyurethane resin is preferably one obtained by reacting an epoxy compound with carbon dioxide. 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.

By using the cyclic carbonate compound synthesized from carbon dioxide as a raw material as described above in the polyaddition reaction, the obtained polyurethane resin has an -O-CO- bond in which carbon dioxide is immobilized in its structure. It will be what you have. The content of carbon dioxide-derived -O-CO- bonds (immobilized amount of carbon dioxide) in the polyurethane resin should be as large as possible from the standpoint of effectively using carbon dioxide as a raw material. For example, the hydroxypolyurethane resin obtained by the above-mentioned synthetic method can contain carbon dioxide in the range of 1 to 20% by mass in its structure.

Examples of the catalyst used in the above 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. It is mentioned as preferable. 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 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 when producing a hydroxypolyurethane resin suitable as the component (A) constituting the aqueous dispersion composition of the present invention is not particularly limited, and two or more cyclics in one molecule. Anything having a carbonate structure can be used. For example, cyclic carbonates can be used for those having a benzene skeleton, an aromatic polycyclic skeleton, a condensed polycyclic aromatic skeleton, and any of an aliphatic system and an alicyclic system. 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 .

The following compounds are exemplified as those having a benzene skeleton, an aromatic polycyclic skeleton, and a condensed polycyclic aromatic skeleton.

Examples of the aliphatic or alicyclic cyclic carbonate include the following compounds.

In the synthesis of the hydroxypolyurethane resin suitable as the component (A) constituting the present invention, a five-membered cyclic carbonate structure as listed above, which is synthesized by using carbon dioxide as a raw material at least a part thereof, is used. It is preferable to use as an intermediate a precursor produced by a polyaddition reaction between a compound having at least two 5-membered cyclic carbonate structures and an amino compound having at least two amino groups. Preferred amino compounds used in this case include compounds represented by the following general formula (12), which have both at least two primary amino groups and at least one secondary amino group in the molecule. Be done. The amino compound represented by the following general formula (12) can be used in combination with a conventionally known polyfunctional amine.

［一般式（１２）中のＲ₁、Ｒ₂、Ｒ₃は、それぞれ独立して、その化学構造中にエーテル結合を含んでもよい炭素数１〜１０のアルキレン基である。ｎは０〜３の整数である。］

[R ₁ , R ₂ , and R ₃ in the general formula (12) are alkylene groups having 1 to 10 carbon atoms which may independently contain an ether bond in their chemical structure. n is an integer from 0 to 3. ]

Examples of the compound represented by the general formula (12) include diethylenetriamine, triethylenetetramine, iminobispropylamine, tetraethylenepentamine, N, N'-bis (3-aminopropyl) -1,3-propylene diamine. , N, N'-bis (3-aminopropyl) -1,4-butylenediamine and the like, and one or more of these compounds can be used.

As the polyfunctional amine compound that can be used in combination with the above amine compound, any conventionally known compound 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), aromatic polyamines such as metaphenylenediamine and diaminodiphenylmethane.

Synthesis of a hydroxypolyurethane resin in which the secondary amino group in the structure of the amino compound represented by the general formula (12) described above does not react with the cyclic carbonate and the secondary amino group is contained in the main chain. It has already been reported in "J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 5899-5905". Also in the present invention, since the reaction form is as described in the above document, a hydroxypolyurethane resin containing a secondary amino group will be used as an intermediate for the next reaction. Here, the reaction conditions of the cyclic carbonate compound and the amine compound containing the compound represented by the general formula (12) may be, for example, mixing the two and reacting them at a temperature of 40 to 200 ° C. for 4 to 24 hours. By doing so, a hydroxypolyurethane resin containing a secondary amino group as an intermediate can be obtained.

The above reaction 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 (THF), which has a boiling point that allows easy evaporation and distillation after phase inversion emulsification.

As described above, the hydroxypolyurethane resin suitable as the component (A) constituting the present invention can be produced without using a catalyst. It is also possible to carry out the reaction in the presence of the catalysts listed below for the purpose of promoting the reaction. 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 cationic group into the above-mentioned hydroxypolyurethane resin, which is suitable as the component (A) constituting the present invention, will be described. For example, a compound having both a cationic group and an epoxy group and a secondary amino group in the structure of a hydroxypolyurethane resin having a secondary amino group as an intermediate in the main chain obtained by the above method (hereinafter, A cationic group can be introduced into the hydroxypolyurethane resin by the reaction with (abbreviated as "cationizing agent").

More specifically, the cationic group can be introduced into the hydroxypolyurethane resin by reacting the secondary amino group of the intermediate hydroxypolyurethane resin with the epoxy group of the cationizing agent. The reaction between the secondary amino group and the epoxy group can be allowed to proceed even at room temperature, but in order to shorten the production time, the polymerization reaction of the hydroxypolyurethane resin containing the secondary amino group in the main chain is continued. Therefore, it is preferable to carry out the reaction at the same reaction temperature. For example, when tetrahydrofuran is used, it is preferable to carry out the polymerization reaction at a temperature of about 40 ° C. to 60 ° C., which is the synthesis temperature of the hydroxypolyurethane resin.

The cationizing agent that can be used in the above reaction is not particularly limited as long as it is a compound having both a cationic group and an epoxy group. For example, a condensate of dialkylamine and epichlorohydrin is methyl chloride. It can be obtained by grade 4 in.

Some of them are commercially available as commonly used cationizing agents, and it is easy to use them. For example, glycidyltrimethylammonium chloride represented by the following structural formula can be mentioned.

According to the studies by the present inventors, the type of cyclic carbonate compound, the type of amine compound, the ratio of amine containing secondary amine used, and the type of cationizing agent used in the above-mentioned polymerization reaction of the hydroxypolyurethane resin are appropriately selected. The amount of cationic groups in the obtained hydroxypolyurethane resin can be controlled by changing to.

Further, according to the study by the present inventors, the amount of the cationic group and the size of the emulsified particle tend to decrease as the amount of the cationic group increases. On the contrary, it was found that the emulsified particle size becomes large as the amount of cationic groups decreases, and the emulsified state becomes unstable from a certain size. For this reason, the particle size of the emulsified particles of the hydroxypolyurethane resin used in the present invention in a dispersed state is preferably in the range of 0.001 μm to 0.1 μm (1 nm to 100 nm) for d50. .. Although it depends on the application, it is more preferably adjusted so as to be in the range of 0.005 μm to 0.05 μm. The particle size of the hydroxypolyurethane resin specified in the present invention is a median diameter (= d50 value) obtained by calculation from the measured particle size distribution. As will be described later, in the examples, the particle size distribution of the polymer-dispersed particles in the aqueous dispersion was measured with a Microtrac UPA EX-150 (trade name, manufactured by Nikkiso Co., Ltd.), which is a dynamic light scattering nanotrack particle size analyzer. It is shown by the value of d50 obtained from the particle size distribution.

Further, since the stability of the emulsified particles is also affected by the molecular weight of the resin, it is preferable that the weight average molecular weight of the resin particles is in the range of 1000 to 100,000, and more preferably 2000 to 70000.

Further, if the amount of the cationic group introduced into the structure of the hydroxypolyurethane resin suitable as the component (A) constituting the present invention is too small, sufficient phase inversion emulsification cannot be performed, and if it is too large, the formed film is formed. Since the water resistance is adversely affected, the cationic group concentration is preferably in the range of 500 g / mol to 2000 g / mol. Further, it is more preferable that the content is in the range of 650 to 1300 g / mol. The "cationic group concentration" is a calculation of the molecular weight of one cationic group from the amount of the cationizing agent used in the reaction.

Further, the amount of hydroxyl groups in the structure of the hydroxypolyurethane resin suitable as the component (A) constituting the present invention is a hydroxyl group in consideration of both the realization of excellent gas barrier properties of the film and the realization of a good function as a film. The valence is preferably in the range of 150 mgKOH / g to 300 mgKOH / g.

As described above, the hydroxypolyurethane resin containing a cationic group which becomes an ionic group in water can be emulsified by phase inversion by gradually adding water to the solvent solution, and the present invention can be easily carried out. An O / W type emulsion, which is an aqueous dispersion of a hydroxypolyurethane resin suitable as the component (A) constituting the above, can be obtained. The amount of water added during phase inversion depends on factors such as the chemical structure of the hydroxypolyurethane resin, the type of solvent used in resin synthesis, resin concentration, and viscosity, but is generally before phase inversion. It is about 50 to 200 parts with respect to 100 parts of the resin. 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 low temperature of, for example, about 10 ° C. to 30 ° C. in order to reduce the solubility of water in the resin solution before the phase inversion. ..

Further, if the solvent used for producing the hydroxypolyurethane resin is volatilized by heating the O / W type emulsion produced by phase inversion emulsification under reduced pressure conditions, it is suitable as the component (A) constituting the present invention. It is possible to obtain an aqueous dispersion in which only the hydroxypolyurethane resin is dispersed in water. The heating conditions and depressurizing conditions for volatilizing the solvent described above differ depending on the boiling point of the solvent to be volatilized, but it is preferable that water does not evaporate first, and is generally in the range of 300 Torr to 50 Torr and 20 ° C to 70 ° C. Adjust with. The aqueous dispersion composition of the present invention comprises a hydroxypolyurethane resin as a component (A), silica fine particles as a component (B) described later, and a chelate compound as a component (C) dispersed in water. However, the solvent of the final composition does not necessarily have to be water alone, and it can be used even if the solvent before the phase inversion remains, and it may be adjusted according to the intended use.

The hydroxypolyurethane resin suitable as the component (A) constituting the present invention is, for example, a hydroxypolyurethane resin having the above-mentioned peculiar structure in water obtained by the above-mentioned method having 0.001 μm to 0.1 μm. It is preferable to use an aqueous dispersion dispersed by the particle size. By using the aqueous dispersion as the component (A), the present invention can be easily made by simply mixing a dispersion of silica fine particles as the component (B) described later and a solution of a chelate compound as the component (C). An aqueous dispersion composition of a hydroxypolyurethane resin can be obtained. When an aqueous dispersion of resin is used as the component (A), the content of the hydroxypolyurethane resin dispersed in water is not particularly limited depending on the application, but is the solid content in the aqueous dispersion, for example, 10 to 50. It is preferably about mass%.

The aqueous dispersion composition of the hydroxypolyurethane resin of the present invention requires the resin of the component (A) described above, and further, at least the silica fine particles as the component (B) and the metal chelate compound as the component (C). It contains 3 components as essential components. Hereinafter, these components will be described.

<Ingredient (B)>
The silica fine particles as the component (B) constituting the present invention are not particularly limited, but the average particle size thereof is preferably 0.001 μm to 5 μm, preferably 0.001 μm to 1 μm. Further, it may be surface-treated.

Silica is an inorganic material having the same chemical structure as glass and has a property of not allowing gas to permeate like an organic material. Therefore, it is possible to improve the gas barrier property by increasing the amount of silica fine particles added. However, according to the studies by the present inventors, if the amount added is too large, the strength of the formed coating film may decrease or the adhesion of the coating film to the substrate may decrease. Therefore, the amount of the component (B) added needs to be in the range of 1 to 120 parts by mass with respect to 100 parts by mass (solid content) of the component (A). The preferred range is 10 to 100 parts by mass. The shape of the silica fine particles is not particularly limited, and any spherical or scaly one can be used. According to the studies by the present inventors, it is preferable to use scaly silica fine particles having a high aspect ratio rather than spherical silica fine particles because a higher gas barrier property can be imparted with a small amount of addition. ..

<Component (C)>
The metal chelate compound which is the component (C) constituting the present invention functions as a component for improving the water resistance of the formed coating layer. The hydroxypolyurethane resin containing a cationic group of the component (A), which is an essential component constituting the aqueous dispersion composition of the present invention, has a drawback of being inferior in water resistance due to the hydrophilicity of the cationic group. The metal chelate compound of the component (C) used in combination functions as a component that compensates for this point and improves the water resistance of the formed film. Here, an isocyanate-based cross-linking agent can also be used for cross-linking the hydroxyl groups in the structure of the hydroxypolyurethane resin, and in this case as well, the water resistance of the formed film can be improved. However, according to the studies by the present inventors, by using the metal chelate compound, in addition to the function of improving the water resistance of the coating film, surprisingly, it becomes possible to form a coating film having a better gas barrier property. We found it useful in this respect as well. The present inventors have explained that the reason why the above effect was obtained is that the curing (crosslinking) reaction between the metal chelate compound of the component (C) and the hydroxyl group in the component (A) has a short distance between the crosslink points and Since high-density cross-linking can be performed, it is considered that the cross-linking has made it possible to improve the gas barrier property under a certain humidity even though the amount of hydroxyl groups in the structure of the hydroxypolyurethane resin is reduced. There is.

The metal chelate compound of the component (C) constituting the present invention is preferably water-soluble in terms of use, and is a counter ion of a cationic group in the structure of the hydroxypolyurethane resin of the component (A) to be used in combination. A compound chelated with a compound that does not react with is more preferable. Since the hydroxypolyurethane resin, which is the main component of the aqueous dispersion composition of the present invention, has a cationic group, a ligand having an anionic substance is preferable in terms of coating stability. Particularly preferable specific compounds include titanium lactic acid chelate (titanium lactic acid chelate) and zirconium chloride compound (aminocarboxylic acid chelate of zirconium chloride). The content of the component (C) in the aqueous dispersion composition of the present invention is 1 with respect to 100% by mass of the total solid content of the component (A), the component (B) and the component (C). It is required to be 10% by mass. More preferably, it is 3 to 8% by mass. The metal chelate compound of the component (C) crosslinks the hydroxyl groups used in combination, but if the amount added is less than 1% by mass, the water resistance of the coating film becomes inferior. On the other hand, if the amount added is too large, the amount of hydroxyl groups in the component (A) becomes too small, and the gas barrier property is lowered.

In addition, the aqueous dispersion composition of the present invention, which is obtained by adding a metal chelate compound as exemplified above as the component (C) constituting the present invention, suppresses the cross-linking reaction and further improves the storage stability. It is preferable to make the composition weakly acidic. On the other hand, unlike the conventional anion-type resin, the hydroxypolyurethane resin containing the cationic group of the component (A), which is essential in the present invention, is stable even under acidic conditions, so that hydrochloric acid, phosphoric acid, lactic acid, etc. The pH can be adjusted to acidic by adding the acid of.

<Other additives>
The aqueous dispersion composition of the present invention may be configured by adding various rheology adjusting agents according to the required properties at the time of processing (during use). Further, various additives may be added to the aqueous dispersion composition of the present invention, if necessary, and for example, an antioxidant, a light stabilizer, an ultraviolet absorber and the like can be appropriately added.

<Gas barrier film>
Provided is the gas barrier coating agent of the present invention capable of forming a coating film (coating layer) having more excellent gas barrier properties by containing the aqueous dispersion composition of the hydroxypolyurethane resin of the present invention having the above characteristics. Can be done.

The gas barrier film of the present invention is formed by laminating a coating layer having a thickness of 0.1 to 100 μm on a base material and at least one of the base materials, and the coating layer is water-dispersed of the hydroxypolyurethane resin of the present invention. It is formed by using a body composition, and its oxygen permeability is 50 mL / m ² · day · atm or less at 23 ° C. and 65% constant temperature and humidity. The gas barrier film of the present invention can be easily obtained by the following method using the gas barrier coating agent of the present invention described above.

As a method for obtaining a coating film (coating film layer) containing the aqueous dispersion composition of the present invention, the gas barrier coating agent of the present invention is applied to a film as a base material, for example, a gravure coater, a knife coater, or a reverse coater. , A bar coater, a spray coater, a slit coater, or the like to volatilize water and the remaining solvent. By doing so, it is possible to obtain the gas barrier film of the present invention comprising a base material and a hydroxypolyurethane coating layer formed by the aqueous dispersion composition of the present invention on at least one of the base materials. it can.

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, but 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)]
In a reaction vessel equipped with a stirrer and a recirculator with an open air port, 100 parts of bisphenol A diglycidyl ether (trade name: jER828, manufactured by Japan Epoxy Resin Co., Ltd.) having an epoxy equivalent of 192 and sodium iodide (Japanese) as a catalyst 20 parts (manufactured by Kojun Yakuhin Co., Ltd.) and 100 parts of N-methyl-2-pyrrolidone as a reaction solvent were charged. 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 subjected to infrared spectroscopic analysis by FT-IR (manufactured by Horiba Seisakusho Co., Ltd., trade name: FT-720, measured using the same apparatus in the following production examples), and found to be 910 cm ^-1. The absorption from the epoxy group of the raw material in the vicinity has disappeared, and the absorption from the carbonyl of the carbonate group, which is not present in the raw material, was confirmed around 1800 cm ^-1 . In addition, as a result of high performance liquid chromatography analysis by HPLC [manufactured by JASCO Corporation, LC-2000 (trade name), column: FinepakSIL C18-T5, mobile phase: acetonitrile + water], 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. Result of FT-IR analysis, absorption derived from the epoxy group of the raw material in the vicinity of ^-1 910 cm As with I-A is lost, the absorption of carbonyl derived carbonate group which is not present in the raw materials in the vicinity of 1800 cm ^-1 confirmed. The purity by HPLC analysis was 97%. The proportion of carbon dioxide-derived components in the chemical structure of IB was 28.4% (calculated value).

<Manufacture of an aqueous dispersion of a cationic group-containing hydroxypolyurethane resin used in Examples>
[Dispersion Production Example 1 for Examples]
(Synthesis of hydroxypolyurethane resin before phase inversion emulsification)
100 parts of the compound IA obtained in Production Example 1, 12.0 parts of diethylenetriamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and hexamethylenediamine (in a reaction vessel equipped with a stirrer and a refluxer having an open air port). 13.6 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) and 188 parts of tetrahydrofuran (hereinafter abbreviated as THF) as a reaction solvent were added, and the reaction was carried out for 24 hours while stirring at a temperature of 60 ° C. to form an intermediate structure. A hydroxypolyurethane resin having a secondary amino group was obtained. 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 of the resin measured using the obtained resin solution was 52.1 mgKOH / g as a conversion value of 100% of the resin content.

Next, 25.3 parts of Catiomaster G (trade name, glycidyltrimethylammonium chloride, manufactured by Yokkaichi Kogyo Co., Ltd., 70% solid content aqueous solution) was added to this resin solution as a cationizing agent, and the reaction was carried out at 60 ° C. to perform FT. After confirming by -IR that the peak of 910 cm ^-1 derived from the epoxy group of the cationizing agent disappeared, the cationization reaction was terminated to obtain a hydroxypolyurethane resin solution having a cationic group before phase inversion emulsification.

In order to confirm the physical properties of the obtained resin, the above resin solution was applied to a paper pattern with a bar coater so that the film thickness at the time of drying was 50 μm, and the solvent was dried in an oven at 70 ° C. , The paper pattern was peeled off to obtain a resin film made of resin. The appearance and mechanical strength (breaking strength and breaking elongation) of the obtained resin film were evaluated by the method described later. Further, for the resin, the molecular weight (measured by GPC), the concentration of the cationic group, and the hydroxyl value were measured by the method described later. At that time, since it is difficult to measure the hydroxyl value after cationization, the hydroxyl value of the amino group-containing hydroxypolyurethane before cationization was measured and calculated assuming that the cationization reaction was 100% performed. The results are shown in Table 1. The mass% of carbon dioxide to be packed in the resin skeleton of this cationic group-containing hydroxypolyurethane resin is 14.3% (calculated value).

(Manufacturing of aqueous dispersion)
Next, 100 parts of the resin solution obtained above was transferred to a reaction vessel equipped with a stirring blade and capable of heating and depressurizing, and 100 parts of ion-exchanged water was gradually added 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 hydroxypolyurethane resin was dispersed in water. The obtained aqueous dispersion was adjusted so that the solid content was 28%, and was an apparently uniform aqueous dispersion. The particle size distribution of the polymer dispersed particles in the aqueous dispersion was d50 = 0.025 μm (= 25 nm). The particle size distribution was measured using UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.). The same applies to other examples.

[Dispersion Production Example 2 for Examples]
(Synthesis of hydroxypolyurethane resin before phase inversion emulsification)
In a reaction vessel similar to that used in Dispersion Production Example 1, 100 parts of the compound IB obtained in Production Example 2, 21.9 parts of m-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc.), and diethylenetriamine were placed. 16.6 parts and 208 parts of THF as a reaction solvent were added, and the reaction was carried out for 24 hours while stirring at a temperature of 60 ° C. to obtain a hydroxypolyurethane resin having a secondary amino group in the structure as an intermediate. The result of the reaction progress confirmation by FT-IR performed on the resin solution after the reaction was the same as that in the case of Dispersion Production Example 1. The amine value of the resin measured using the obtained resin solution was 65.2 mgKOH / g as a conversion value of 100% resin content. Next, 34.9 parts of Catiomaster G was added as a cationizing agent, and the reaction was carried out at 60 ° C. to obtain a cationic group-containing hydroxypolyurethane resin solution before phase inversion emulsification. The obtained resin was analyzed in the same manner as in Dispersion Production Example 1, and the results are shown in Table 1. The mass% of carbon dioxide to be packed in the resin skeleton of this cationic group-containing hydroxypolyurethane resin is 17.4% (calculated value).

(Manufacturing of aqueous dispersion)
Then, in the same manner as in Dispersion Production Example 1, 406 parts of water was added to carry out phase inversion emulsification, and then THF was distilled off to obtain a hydroxypolyurethane aqueous dispersion. The particle size distribution of the polymer dispersed particles in the aqueous dispersion was d50 = 0.020 μm (= 20 nm).

[Dispersion Production Example 3 for Examples]
(Synthesis of hydroxypolyurethane resin before phase inversion emulsification)
In a reaction vessel similar to that used in Dispersion Production Example 1, 100 parts of Compound IA obtained in Production Example 1, 13.6 parts of hexamethylenediamine, iminobispropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) ) To 15.3 parts and THF as a reaction solvent to 193 parts, and the reaction was carried out for 24 hours while stirring at a temperature of 60 ° C. to obtain a hydroxypolyurethane resin having a secondary amino group in the structure as an intermediate. It was. The result of confirming the reaction progress of the resin solution after the reaction by FT-IR was the same as that of Dispersion Production Example 1. The amine value of the resin measured using the obtained resin solution was 50.8 mgKOH / g as a conversion value of 100% resin content. Next, 25.3 parts of Catiomaster G was added as a cationizing agent, and the reaction was carried out at 60 ° C. to obtain a cationic group-containing hydroxypolyurethane resin solution before phase inversion emulsification. The obtained resin was analyzed in the same manner as in Dispersion Production Example 1, and the results are shown in Table 1. The mass% of carbon dioxide to be packed in the resin skeleton of this cationic group-containing hydroxypolyurethane resin is 14.0% (calculated value).

(Manufacturing of aqueous dispersion)
Then, in the same manner as in Dispersion Production Example 1, 365 parts of water was added to carry out phase inversion emulsification, and then THF was distilled off to obtain a hydroxypolyurethane aqueous dispersion. The particle size distribution of the polymer dispersed particles in the aqueous dispersion was d50 = 0.022 μm (= 22 nm).

[Dispersion production example a for comparative example]
In a reaction vessel similar to that used in Dispersion Production Example 1, 100 parts of the compound IA obtained in Production Example 1, 13.6 parts of hexamethylenediamine, 12.0 parts of diethylenetriamine, and a reaction solvent As a result, 188 parts of THF was added, and the reaction was carried out for 24 hours while stirring at a temperature of 60 ° C. to obtain a hydroxypolyurethane resin having a secondary amino group in the structure as an intermediate. The result of confirming the reaction progress of the resin solution after the reaction by FT-IR was the same as that of Dispersion Production Example 1. The amine value of the resin measured using the obtained resin solution was 52.1 mgKOH / g as a conversion value of 100% of the resin content.

Next, 16.3 parts of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to this resin solution, and the reaction was carried out at room temperature. The peak of 1800 cm ^-1 derived from the acid anhydride carbonyl disappeared by FT-IR. Confirmed and terminated the reaction. To this reaction solution, 16.9 parts of triethylamine was added as a reaction catalyst to obtain a hydroxypolyurethane resin solution having a carboxyl group in the structure before phase inversion emulsification. Then, a resin film was prepared in the same manner as in Resin Synthesis Example 1, and the appearance and mechanical strength of the film, the molecular weight (GPC), the cationic group concentration, and the hydroxyl value of the resin were measured. The results are shown in Table 1. The mass% of carbon dioxide tightened in the resin skeleton of this cationic group-containing hydroxypolyurethane resin is 14.5% (calculated value).

Next, 347 parts of ion-exchanged water was added into the reaction vessel 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 hydroxypolyurethane resin was dispersed in water. The obtained aqueous dispersion was adjusted to have a solid content of 28%. The obtained aqueous dispersion was an apparently uniform aqueous dispersion. The particle size distribution of the polymer-dispersed particles in the aqueous dispersion was d50 = 0.020 μm (= 20 nm).

(Evaluation method)
Each resin obtained in each of Dispersion Production Examples 1 to 3 for Examples and Dispersion Production Example a for Comparative Example, and each film produced with each aqueous dispersion 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 hydroxypolyurethane resin obtained in each dispersion production example. Specifically, it is shown by 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 hydroxypolyurethane resin. For example, in the case of Dispersion Production Example 1, the amount of the carbon dioxide-derived component of the compound IA used is 20.5%, and the calculated value of the carbon dioxide concentration in the polyurethane is as follows. Become.
(100 parts x 20.5%) /143.3 Total amount = 14.3% by mass

[Molecular weight]
In the present invention, the molecular weight of the resin was measured by GPC (gel permeation chromatography) using DMF as a mobile phase. Specifically, it was measured by using GPC-8220 (trade name) manufactured by Tosoh Corporation and using Super AW2500 + AW3000 + AW4000 + AW5000 as a column. The measurement result was expressed as a polystyrene-equivalent value by weight average molecular weight.

[Hydroxy group value]
Based on the measured values obtained by measuring the hydroxyl value of the transamination-containing hydroxypolyurethane resin before cationization by a titration method based on JIS K-1557, the cationizing agent used was assumed to have undergone 100% cationization reaction. The hydroxyl value was taken as the weight and the calculated value calculated assuming that one hydroxyl group was generated by the reaction between the cationizing agent and the amino group.

[Cationic group concentration]
The molecular weight of one cationic group was calculated from the amount of the cationizing agent used in the reaction, and used as the concentration of the cationic group. The unit is g / mol.
For example, in the case of Dispersion Production Example 1, since the amount of the active ingredient of the cationizing agent used is 17.7 g and the molecular weight of the cationizing agent is 151.6, it is calculated as follows.
143.3 Total amount (g) ÷ (17.7 ÷ 151.6) = 1228 g / mol

[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 using a haze meter HZ-1 (trade name, manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K-7105. Here, all the 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 of 90% or more and haze of 0.5% or less ×: Not applicable to ○

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

<Manufacturing of aqueous dispersion composition and film>
[Example 1]
2N Hydrochloric acid was added to 100 parts of the aqueous dispersion having a solid content of 28% obtained in Dispersion Production Example 1 to prepare a hydroxypolyurethane aqueous dispersion adjusted to pH = 4 using litmus test paper, and this was used as the component (A). There was. In another container, as the component (B), 56 Sun Lovely HN-050 (trade name, manufactured by AGC SI Tech Co., Ltd., solid content 15%), which is a dispersion liquid of scaly silica fine particles having an average particle diameter of 0.5 μm. Partial measurement was performed, and the hydroxypolyurethane aqueous dispersion of the component (A) adjusted to pH 4 was gradually added with stirring to homogenize. Next, 3 parts of Organix TC-310 (trade name, manufactured by Matsumoto Fine Chemical Co., Ltd., solid content 44%), which is a Ti lactic acid chelate, was added as the component (C), and Gosenex K434 (Nippon Synthetic) was added as a thickener. Made by PVA Co., Ltd., dissolved in water in advance to adjust the concentration to 30%, the same applies to the following examples), 10 parts were added, and the mixture was stirred and homogenized with a homomixer to prepare an aqueous dispersion composition.

The aqueous dispersion composition obtained above was applied to a base material to prepare a gas barrier film as described below. Specifically, first, a PET film having a thickness of 25 μm, Lumirror S10 (trade name, manufactured by Toray Industries, Inc., measured oxygen transmittance: 61 mL, 20 μm / m ² , day, atm) was used as the base material, and the corona-treated surface thereof. It was applied onto the film so that the film thickness at the time of drying was 10 μm, and dried at 100 ° C. for 3 minutes. Then, it was aged in an oven at 50 ° C. for 48 hours to form a coating layer on the substrate to obtain a multi-layer film. Using the obtained multi-layer film, the appearance (appearance of the coating film), water resistance and gas barrier property of the formed film layer were evaluated. Each measurement method will be described later. The results are shown in Table 2. The blending ratio of each component is shown in Table 2 in terms of solid content, with component A (resin content) as 100 parts.

[Example 2]
As the component (A), 100 parts of the same aqueous dispersion having a solid content of 28% as used in Example 1 was adjusted to pH = 4, and as the component (B), an average particle size of 1.5 μm and a scaly shape were used. Using 53 parts of Sun Lovely HN-150 (trade name, manufactured by AGC SI Tech Co., Ltd., solid content 16%), which is a dispersion of silica fine particles, and using 3 parts of TC-310, which is a Ti lactic acid chelate, as the component (C) An aqueous dispersion composition was obtained by the same operation as in Example 1 using 10 parts of the above-mentioned Gosenex K434 (30%) as a thickener. Using the obtained aqueous dispersion composition, a multilayer film was obtained by the same substrate and operation as in Example 1. Then, the appearance (appearance of the coating film), water resistance and gas barrier property of the formed film layer were evaluated in the same manner as in Example 1, and the results are shown in Table 2. The same evaluation was performed on the multilayer films obtained in the other examples and comparative examples, and the results are summarized in Table 2.

[Example 3]
As the component (A), 100 parts of the same aqueous dispersion having a solid content of 28% as used in Example 1 was adjusted to pH = 4, and as the component (B), the average particle size was 0.04-0. Using 42 parts of Snowtex ST-AK-L (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 20%), which is a dispersion of 05 μm spherical silica fine particles, TC, which is a Ti lactic acid chelate, is used as the component (C). An aqueous dispersion composition was obtained by the same operation as in Example 1 using 3 parts of −310 and 10 parts of Gosenex K434 (30%) described above as a thickener. Using the obtained composition, a multilayer film was obtained by the same substrate and operation as in Example 1.

[Example 4]
As the component (A), 100 parts of the same aqueous dispersion used in Example 1 was adjusted to pH = 4, and as the component (B), an average particle size of 0.04-0.05 μm and spherical silica were used. 140 parts of Snowtex ST-AK-L (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 20%), which is a dispersion of fine particles, is used, and 10 parts of TC-310, which is a Ti lactic acid chelate, is used as the component (C). , 10 parts of the above-mentioned Gosenex K434 (30%) was used as a thickener, and an aqueous dispersion composition was obtained by the same operation as in Example 1. Using the obtained composition, a multilayer film was obtained by the same substrate and operation as in Example 1.

[Example 5]
As the component (A), 100 parts of the aqueous dispersion having a solid content of 28% obtained in Production Example 2 was adjusted to pH = 4 in the same manner as in Example 1, and as the component (B), Example 1 was used. Organix ZC-126 (trade name, manufactured by Matsumoto Fine Chemiquel Co., Ltd.), which is the same zirconyl chloride compound as used in Example 5, containing 75 parts of Sun Lovely HN-050 similar to that used in Example 5 as component (C). 5 parts of solid content (30%) was used, and 10 parts of Gosenex K434 (30%) described above was used as a thickener, and an aqueous dispersion composition was obtained by the same operation as in Example 1. Using the obtained composition, a multilayer film was obtained by the same substrate and operation as in Example 1.

[Example 6]
As the component (A), 100 parts of the aqueous dispersion having a solid content of 28% obtained in Production Example 3 was adjusted to pH = 4 in the same manner as in Example 1, and the silica fine particles of the component (B) were used. 30 parts of Sunlabry HN-150 similar to that used in Example 2 was used, and 5 parts of Olgatics ZC-126, which is the same zirconyl chloride compound used in Example 5, was used as the component (C) as a thickener. An aqueous dispersion composition was obtained by the same operation as in Example 1 using 10 parts of the above-mentioned Gosenex K434 (30%). Using the obtained composition, a multilayer film was obtained by the same substrate and operation as in Example 1.

[Comparative Example 1]
Dispersion used as component (A) in Example 1 The aqueous dispersion with a solid content of 28% obtained in Example 1 was used as it was, and the silica component of the components (B) and (C) used in Examples was used. And, without adding the metal chelate component, only 10 parts of the above-mentioned Gosenex K434 (30%) was used as a thickener to obtain an aqueous dispersion composition. Using the obtained composition, a multi-layer film of Comparative Example was obtained by the same substrate and operation as in Example 1.

[Comparative Example 2]
An aqueous dispersion composition was obtained by the same materials and operations as in Example 1 except that the amount of Organtics TC-310, which is a Ti lactic acid chelate used as the component (C), was reduced to 0.5 parts. Using the obtained composition, a multi-layer film of Comparative Example was obtained by the same substrate and operation as in Example 1.

[Comparative Example 3]
Instead of the Ti lactic acid chelate Organtis TC-310 used as the component (C) in Example 1, the water-dispersible polyisocyanate Duranate WB40-100 (trade name, manufactured by Asahi Kasei Co., Ltd., NCO% = 16.6) ) Was used in two parts, and an aqueous dispersion composition was obtained by the same materials and operations as in Example 1. Using the obtained composition, a multilayer film was obtained by the same substrate and operation as in Example 1.

[Comparative Example 4]
When 2N hydrochloric acid was added to 100 parts of the aqueous dispersion having a solid content of 28% obtained in Comparative Production Example a and an attempt was made to adjust the pH to 4 using a litmus test paper, the resin aggregated and precipitated. It was discontinued and the pH-adjusted aqueous dispersion was used as it was. In a separate container, 56 parts of Sunlabry HN-050, which is a dispersion of silica fine particles used as the component (B) in Example 1, was weighed, and pH-adjusted dispersion production example a. The obtained hydroxypolyurethane The aqueous dispersion was added slowly with stirring. However, as soon as the addition of silica was started, the silica was shock-aggregated and the whole became a gel, so the addition operation was stopped. I didn't make a film because I couldn't coat it.

(Evaluation)
The characteristics of each aqueous dispersion composition of Examples 1 to 6 and Comparative Examples 1 to 4 and the evaluation of each film produced using each aqueous dispersion composition were carried out by the following methods and criteria. Then, the results of Examples are shown in Table 2, and the results of Comparative Examples are summarized in Table 3.

[Storage stability]
Each aqueous dispersion composition of Examples and Comparative Examples was placed in a closed plastic container and stored in a constant temperature bath at 25 ° C. Then, the states after 1 day, 7 days, and 30 days were visually observed and evaluated according to the following criteria, respectively. The evaluation results are summarized in Tables 2 and 3.
〔Evaluation criteria〕
◯: No particle settling and no increase in viscosity Δ: Particles are settled, but easily redispersed by stirring. Viscosity increase does not occur ×: Viscosity increases or gels

[Appearance of coating film]
For each of the multi-layer films produced in Examples and Comparative Examples, the appearance of the formed coating film layer (coating film appearance) was visually observed and evaluated according to the following criteria. The evaluation results are summarized in Tables 2 and 3.
〔Evaluation criteria〕
◯: Transparent, uniform and glossy coating film surface Δ: The coating film surface is not glossy and turbid ×: There is unevenness due to the aggregate

[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 24 hours at room temperature was visually observed and evaluated according to the following criteria. The evaluation results are summarized in Tables 2 and 3.
〔Evaluation criteria〕
◯: No change is seen Δ: Part of the coating film is whitened ×: The coating film is swollen

[Adhesion]
For each of the multi-layer films produced in Examples and Comparative Examples, cellophane tape was pressure-bonded to a part of the coating film surface and slowly peeled off by hand, and the degree of peeling of the coating film was observed and evaluated according to the following criteria. The evaluation results are summarized in Tables 2 and 3.
〔Evaluation criteria〕
◯: No peeling of the coating film Δ: Part of the coating film was peeled off ×: The coating film was completely peeled off

[Gas barrier property]
For each of the double glazing films produced in Examples and Comparative Examples, the oxygen permeability was measured in accordance with JIS K-7126, and this was used as an evaluation value of gas barrier property. That is, it can be judged that the lower this value is, the better the gas barrier property is. Specifically, using an oxygen permeability measuring device OX-TRAN 2/21ML (trade name, manufactured by MOCON), oxygen permeability under constant temperature and humidity conditions at a temperature of 23 ° C. and a humidity of 65%. (Oxygen permeability) was measured. The measured value is a value as a double glazing film, and the unit is mL / m ² · day · atm. The thickness of the coating film layer (coating film) obtained by applying the paint of the example or comparative example in the film is actually measured using a precision thickness measuring instrument (manufactured by Ozaki Seisakusho Co., Ltd.) and is 10 μm. Is confirmed. The evaluation results are summarized in Tables 2 and 3.

As shown in Table 2, the aqueous dispersion composition of the examples of the present invention had a high degree of dispersion of silica and was excellent in storage stability. In particular, the silica fine particles Sun Lovely (trade name) used as the component (B) in Examples 1, 2, 5 and 6 are scaly and prone to aggregation and sedimentation. It was confirmed that the aqueous dispersion composition was also in a stable state. The present inventors coexist the reason why the excellent storage stability was realized with the hydroxyl group in the structure of the hydroxypolyurethane resin which is the component (A) constituting the aqueous dispersion composition of the example (B). It is considered that the affinity of the silica fine particles of the component) with the silanol group on the silica surface contributed.

Further, when the coating film layer (coating film) was formed using the aqueous dispersion composition of the example of the present invention, the appearance of the coating film at the time of drying was also good, and a transparent film was obtained. It also has water resistance by cross-linking a part of the hydroxyl groups with a metal chelate compound.

Further, the hydroxypolyurethane resin constituting the aqueous dispersion composition of the present invention is a resin having excellent gas barrier properties, and a coating layer (coating film) exhibiting excellent gas barrier properties can be formed. Table 3 shows. From the results of the aqueous dispersion composition of the comparative example shown, it was confirmed that higher gas barrier properties could be realized as compared with the comparative example of the prior art. More specifically, it was obtained by adding silica fine particles of the component (B) specified in the present invention and cross-linking with a metal chelate compound of the component (C) coexisting in an amount in the range specified in the present invention. The coating has a higher gas barrier property. That is, the cross-linking with the metal chelate compound of the component (C) does not inhibit the crystal structure of the resin because the distance between the cross-links is shortened, and is compared with the cross-linking with an organic cross-linking agent such as isocyanate used in Comparative Example 3. It was confirmed that it is particularly effective in improving the gas barrier property.

According to the present invention, it is possible to provide an aqueous dispersion composition of a hydroxypolyurethane resin capable of long-term storage required industrially and having excellent gas barrier properties. In order to obtain a stable aqueous dispersion state, a cationic group was introduced into the structure of the hydroxypolyurethane resin before phase inversion emulsification by adding water, but since the hydroxyl group is also present in the structure, the conventional method It has the same mechanical strength as the coating film made of hydroxypolyurethane resin, and can be expected to be applied to conventional applications. Further, the hydroxypolyurethane 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 (9)

An aqueous dispersion composition for a gas barrier coating,
As the component (A), a hydroxypolyurethane resin containing at least a cationic group and a hydroxyl group in the structure and having a cationic group concentration in the range of 500 g / mol to 2000 g / mol, and as the component (B). , Silica fine particles and a metal chelate compound as the component (C).
The component (B) is contained in an amount of 1 to 120 parts by mass with respect to 100 parts by mass of the component (A), and the total content of the component (A) and the component (B) is 10 to 10. 50% by mass,
The content of the component (C) is 1 to 10% by mass with respect to 100% by mass of the total solid content of the component (A), the component (B) and the component (C). Hydroxypolyurethane resin aqueous dispersion composition. The hydroxypolyurethane resin containing the cationic group of the component (A) is represented by the following general formula (11) for phase inversion emulsification by adding water, which is represented by the following general formula (1), in its structure. The aqueous dispersion composition of a hydroxypolyurethane resin according to claim 1, which has a repeating unit having a chemical structure containing a cationic group.

[X in the above general formula (1) indicates a chemical structure composed of an aliphatic hydrocarbon or an alicyclic hydrocarbon or an aromatic hydrocarbon which is absent or derived from a monomer unit, and an oxygen atom is contained in the structure. , A nitrogen atom, a sulfur atom and an ester bond may be contained, and the structure may be bonded to Y ₁ and / or Y ₂ via an ether bond. −Y ₁ − represents the chemical structure of any one of the following formulas (2) to (5), and −Y ₂ − is any one of the following formulas (2), (6) to (10). Two chemical structures are shown, and R in the formulas (4), (5), (7) to (10) represents a hydrogen atom or CH ₃ . -Z- indicates a chemical structure containing a cationic group represented by the following general formula (11). * In the formula is a symbol indicating that it is a bond. ]

[In the general formula (11), R ₄ is an aliphatic hydrocarbon, may contain an oxygen atom in the structure. R ₁ , R ₂ , and R ₃ are alkylene groups having 1 to 10 carbon atoms, which may independently contain an ether bond in their structure. n is an integer from 0 to 3. ] Further, the repeating unit constituting the hydroxypolyurethane resin of the component (A) is mixed with a repeating unit having a structure different from that of the repeating unit having a chemical structure containing a cationic group represented by the general formula (1). In the structure, the repeating unit of the other structure is such that -Z- in the general formula (1) is replaced with a chemical structure containing a cationic group represented by the general formula (11). The hydroxypolyurethane resin according to claim 2, which has a chemical structure which is a hydrocarbon having 1 to 100 carbon atoms or an aromatic hydrocarbon having 6 to 100 carbon atoms, which may contain an oxygen atom and a nitrogen atom. Aqueous dispersion composition. Wherein component (A) hydroxy polyurethane resin, the ranges of weight average molecular weight of 10,000 to 100,000, and any of claims 1-3 hydroxyl value of that is in the range of 150mgKOH / g~300mgKOH / g aqueous dispersion composition of the hydroxy polyurethane resin according to item 1. The hydroxypolyurethane resin of the component (A) has at least a compound having a five-membered cyclic carbonate structure synthesized by using carbon dioxide as a raw material, and at least a compound having at least two five-membered cyclic carbonate structures. It is obtained by a double addition reaction of a compound having two amino groups, and 1 to 20% by mass of the total mass is occupied by the carbon dioxide-derived —O—CO— bond according to claims 1 to 4. The aqueous dispersion composition of the hydroxypolyurethane resin according to any one item. The aqueous dispersion of the hydroxypolyurethane resin according to any one of claims 1 to 5, wherein the silica fine particles of the component (B) are spherical or scaly fine particles having a particle diameter of 0.001 μm to 5 μm. Composition. The aqueous dispersion composition of a hydroxypolyurethane resin according to any one of claims 1 to 6, wherein the metal chelate compound of the component (C) is a titanium lactic acid chelate or a zirconyl chloride compound. A gas barrier coating agent comprising the aqueous dispersion composition of the hydroxypolyurethane resin according to any one of claims 1 to 7. A coating layer having a thickness of 0.1 to 100 μm is laminated on a base material and at least one of the base materials, and the coating layer is the hydroxypolyurethane resin according to any one of claims 1 to 7. A gas barrier property formed by using an aqueous dispersion composition, wherein the oxygen permeability is 50 mL / m ² · day · atm or less at 23 ° C. and 65% constant temperature and humidity. the film.