JP2015110755A - Water vapor barrier resin compound, water vapor barrier film, coating material, and packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film having durability such as strength, breaking resistance, cold resistance, heat resistance, and retort resistance, transparency that gives visibility for contents, and barrier property to water vapor so as to maintain qualities in long-term storage, and a resin composition used for the film, and to provide a coating material for protecting a vapor deposition surface, which can give a film excellent in gas or water vapor barrier property, a gas or water vapor barrier film having a coating of the above coating material on a film, and a gas barrier film having resistance to a folding treatment.SOLUTION: A water vapor barrier resin is provided, which comprises a resin compound having a repeating unit of a specific structure; and a water vapor barrier film using the above resin is provided. The resin comprising the resin compound having a specific structure is used as a coating material for protecting a vapor deposition surface of a vapor deposition film.

Description

  The present invention includes a resin compound having a specific structure, a water vapor barrier resin compound, a water vapor barrier film, a coating material for protecting a vapor deposition surface of a vapor deposition film containing the resin composition, and coating the resin on the film. It relates to a barrier film.

Packaging materials typically used for packaging foods and beverages protect the contents from various distributions, storage such as refrigeration and processing such as heat sterilization, so that the strength, resistance to cracking, retort resistance, heat resistance In addition to functions such as sexuality, a wide variety of functions are required, such as excellent transparency so that the contents can be confirmed. On the other hand, when the bag is sealed by heat sealing, an unstretched polyolefin film having excellent heat processability is essential, but the unstretched polyolefin film has many functions that are insufficient as a packaging material. In particular, high barrier properties are required for the purpose of maintaining the quality of the contents and maintaining the content. Such a barrier packaging material is usually used as a composite flexible film in which different polymer materials and inorganic materials are laminated.

  When imparting a barrier function to a multilayer film, it is difficult to impart the barrier function to the unstretched polyolefin films used for the inner layer (sealant side) by coating or vapor deposition. Therefore, a barrier function is often imparted to various films (polyester resins such as polyethylene terephthalate (hereinafter abbreviated as PET), polyamide resins, stretched polyolefin resins) used on the outer layer side.

  When a barrier function is imparted to these outer layer side films by coating, as the barrier coating material, vinylidene chloride having a high retort resistance and gas or water vapor barrier property has been frequently used, but dioxins are generated at the time of disposal firing, etc. There is a problem. Further, when a polyvinyl alcohol resin or an ethylene-polyvinyl alcohol copolymer is used as a barrier coating material, there is a problem that the oxygen barrier property is high but the water vapor barrier property is poor. Further, a film provided with a vapor deposition layer of a metal oxide such as silica or alumina as a gas barrier layer is expensive and has a problem that the gas barrier performance varies due to cracks and pinholes due to poor flexibility.

  Patent Document 1 discloses a coating agent containing a polyester resin having a weight average molecular weight of more than 10,000 and not more than 40,000, a glass transition temperature of 50 to 100 ° C., and an acid value of 35 to 895 equivalent / ton, a polyisocyanate compound and a liquid medium. Yes, the equivalent ratio of the isocyanate end group amount of the polyisocyanate compound to the total molar amount of the acid value and hydroxyl value of the polyester resin is 0.8 to 2.0 times equivalent, (total of polyester resin and polyisocyanate compound) / A coating agent is described in which the liquid medium is 5/95 to 50/50 (mass ratio).

Of these, vinylidene chloride with high retort resistance and gas or water vapor barrier properties has been used extensively, but it has the above-mentioned problems, and a polyvinyl alcohol resin or an ethylene-polyvinyl alcohol copolymer is used as a barrier coating material. The oxygen barrier property is high, but there is a problem that the water vapor barrier property is remarkably lowered.
Further, a film provided with a vapor deposition layer of a metal oxide such as silica or alumina as a gas barrier layer is expensive and has a problem that the gas barrier performance varies due to cracks and pinholes due to poor flexibility.

  There are a stretched film and an unstretched film as the film for vapor deposition. Particularly, in the case of a metal vapor deposited film such as aluminum, both kinds of substrates are often used. However, since the thickness of the deposited layer is generally as thin as 10 to 50 nm, pinholes are likely to occur, and the gas barrier function may not be stable. In particular, when the base film is an unstretched film, the gas barrier is particularly unstable because the film is easily stretched compared to the stretched film and the base film itself has poor gas barrier properties. Therefore, it is difficult to use a film deposited on an unstretched film for packaging that requires stable gas barrier properties.

  On the other hand, a transparent vapor deposition film provided with a vapor deposition layer of a metal oxide such as silica or alumina as a gas barrier layer is hardly mass-produced with an unstretched film because the vapor deposition layer is more brittle than a metal. For this reason, vapor deposition on stretched films with high dimensional stability is the main component, but there is still a problem that barrier performance varies due to cracks and pinholes.

In order to solve the above problem that the gas barrier is unstable, it is widely performed to protect the vapor deposition layer with an overcoat layer. This is because transparent vapor deposition generally places a fragile metal oxide layer on the film, so that the barrier performance is not stable without an overcoat layer. For example, Patent Document 2 and Patent Document 3 disclose an overcoat technique for transparent vapor deposition, such as an inorganic oxide layer, a so-called transparent vapor deposition layer, a water-soluble polymer, (a) one or more metal alkoxides, (b 1) a gas barrier coating layer formed by applying a hydrolyzate of one or more metal alkoxides, or (c) an aqueous solution containing at least one tin chloride, or a gas barrier coating solution containing a water / alcohol mixed solution as a main component. A transparent gas barrier laminate having the following is described. The overcoat layer used in these technologies generally uses a water-soluble polymer, so it has poor coating drying properties and includes a sol-gel process that is difficult to control the reaction, making it difficult to manage and reuse the overcoat solution. However, the overcoat process has a complicated problem.

  Since a metal vapor deposition layer such as aluminum is a metal layer that has better followability to bending than transparent vapor deposition, there are few cases in which an overcoat layer is provided compared to transparent vapor deposition. However, since pinholes and the like are present at a certain ratio even in the metal vapor deposition layer, the barrier performance may be deteriorated based on these. In addition, since such a phenomenon occurs due to inferior heat resistance and dimensional stability of the film, in order to solve this problem, in Patent Document 4, the base material layer is composed of at least two layers, and the resin composition A made of polypropylene and The non-stretched aluminum vapor deposition which provided the aluminum vapor deposition layer on this base material layer which consists of the structure which laminated | stacked the resin composition B which is the mixture of the cyclic polyolefin polymer which consists of a copolymer of norbornene and ethylene, and polyolefin A film is illustrated. In this method, stability such as barrier properties is imparted by vapor deposition on a film substrate containing a cyclic polyolefin polymer having higher heat resistance and dimensional stability than polypropylene alone. However, since this method requires the use of a two-layer film as the substrate film, there is a problem that the production method is complicated and the cost is increased.

  Patent Document 5 describes a coating agent containing a polyester resin having a weight average molecular weight of more than 10,000 and not more than 40,000, a glass transition temperature of 50 to 100 ° C., and an acid value of 35 to 895 equivalent / ton, a polyisocyanate compound and a liquid medium. Yes, the equivalent ratio of the isocyanate end group amount of the polyisocyanate compound to the total molar amount of the acid value and hydroxyl value of the polyester resin is 0.8 to 2.0 times equivalent, (total of polyester resin and polyisocyanate compound) / A coating agent in which the liquid medium is 5/95 to 50/50 (mass ratio) is described, the mechanical strength as a vapor deposition protective layer is sufficient, does not block, and after chemical treatment or wet heat treatment In addition, it is possible to provide a coating agent that can protect the vapor deposition surface and hardly deteriorate the gas barrier property.

JP 2011-1636 A JP 2012-101505 A JP 2012-250470 A JP 2011-224921 A JP 2012-001636 A

In view of the above background art, the problems to be solved by the present invention are strength, resistance to cracking, durability such as cold resistance, heat resistance, retort resistance, transparency so that contents can be visually recognized, and quality maintenance in long-term storage. It is providing the film which has the barrier property with respect to water vapor | steam, and the resin composition used for this film.
The present invention also provides a coating material for vapor deposition surface protection that can provide a film having excellent gas or water vapor barrier properties, and a gas or water vapor barrier film obtained by coating the coating material on the film. Another object of the present invention is to provide a gas barrier film that is resistant to bending.

  General formula (1)

(In the formula, R ₁ represents an alicyclic alkylene group, and m represents an integer of 0 or 1, but when it represents 1, —X— represents any group selected from the following formulae.

Provided that R ₂ represents an alkylene group, an alkenylene group, an alkynylene group, an alicyclic alkylene group, a divalent aromatic group, an alkylene group involved in bonding, an alkenylene group, or a divalent aromatic group having an alkynylene group, and A group selected from divalent heterocyclic groups,
R ₃ is a group selected from an alkyl group, an alkenyl group, an alkynyl group, an alicyclic alkyl group, an aromatic group, an aromatic group having an alkylene group involved in bonding, and a heterocyclic group. )
The above problems have been solved by a resin compound having a repeating unit represented by the formula:
Moreover, the said subject was solved by using the resin compound which has the said specific structure as a coating material for the vapor deposition surface protection of a vapor deposition film.

According to the present invention, a water vapor barrier resin and a water vapor barrier having strength, resistance to cracking, durability such as cold resistance and heat resistance, transparency so that contents can be visually recognized, and a barrier property against water vapor for maintaining quality during long-term storage, and A protective film can be provided.
Moreover, the coating material for vapor deposition surface protection which can provide the film excellent in oxygen and water vapor | steam barrier property, the gas formed by coating this coating material on a film, or a water vapor | steam barrier film can be provided.

That is, this invention consists of the following.
1. General formula (1)

（式中、Ｒ_１は脂環式アルキレン基、ｍは０又は１の整数を表すが、１を表す場合には、―Ｘ―は、下記式から選ばれる何れかの基を表す。

(In the formula, R ₁ represents an alicyclic alkylene group, and m represents an integer of 0 or 1, but when it represents 1, —X— represents any group selected from the following formulae.

但し、Ｒ_２はアルキレン基、アルケニレン基、アルキニレン基、脂環式アルキレン基、２価の芳香族基、結合に関与するアルキレン基、アルケニレン基、若しくはアルキニレン基を有する２価の芳香族基、及び２価の複素環基から選ばれる基であり、
Ｒ_３は、アルキル基、アルケニル基、アルキニル基、脂環式アルキル基、芳香族基、結合に関与するアルキレン基を有する芳香族基、及び複素環基から選ばれる基である。）
で表される繰り返し単位を有する樹脂化合物。
２．前記脂環式アルキレン基が、トリシクロアルキレン基である１．に記載の樹脂化合物、
３．前記トリシクロアルキレン基が、トリシクロデシレン基である２．に記載の樹脂化合物、
４．１．〜３．の何れかに記載の樹脂化合物と硬化剤を反応させて得られる樹脂化合物、
５．前記硬化剤が、ポリイソシアネートである４．に記載の樹脂化合物、
６．前記ポリイソシアネートが、芳香族環を有するポリイソシアネートを含有するものである請求項５に記載の樹脂化合物、
７．芳香族環を有するポリイソシアネートが、メタキシレンジイソシアネート、又はメタキシレンジイソシアネートと２個以上の水酸基を有するアルコールとの反応生成物である６．に記載の樹脂化合物、
８．前記樹脂化合物がさらに板状無機化合物を含有する請求項１〜７に記載の樹脂化合物。
９・板状無機化合物が、層間が非イオン性であるか、或いは水に対して非膨潤性である８．に記載の樹脂化合物。
１０．板状無機化合物が、下記一般式（３）又は（４）で表されるホスホン酸誘導体又はリン酸誘導体で表面処理することにより得られる修飾板状無機化合物である８．に記載の樹脂化合物。

Provided that R ₂ represents an alkylene group, an alkenylene group, an alkynylene group, an alicyclic alkylene group, a divalent aromatic group, an alkylene group involved in bonding, an alkenylene group, or a divalent aromatic group having an alkynylene group, and A group selected from divalent heterocyclic groups,
R ₃ is a group selected from an alkyl group, an alkenyl group, an alkynyl group, an alicyclic alkyl group, an aromatic group, an aromatic group having an alkylene group involved in bonding, and a heterocyclic group. )
The resin compound which has a repeating unit represented by these.
2. 1. The alicyclic alkylene group is a tricycloalkylene group. A resin compound according to
3. 1. The tricycloalkylene group is a tricyclodecylene group. A resin compound according to
4.1. ~ 3. A resin compound obtained by reacting the resin compound according to any of the above and a curing agent,
5. 3. The curing agent is a polyisocyanate. A resin compound according to
6). The resin compound according to claim 5, wherein the polyisocyanate contains a polyisocyanate having an aromatic ring.
7). 5. Polyisocyanate having an aromatic ring is a reaction product of metaxylene diisocyanate or metaxylene diisocyanate and an alcohol having two or more hydroxyl groups. A resin compound according to
8). The resin compound according to claim 1, wherein the resin compound further contains a plate-like inorganic compound.
9. The plate-like inorganic compound is nonionic between layers or non-swellable with respect to water. The resin compound as described in.
10. 7. The plate-like inorganic compound is a modified plate-like inorganic compound obtained by surface treatment with a phosphonic acid derivative or a phosphoric acid derivative represented by the following general formula (3) or (4). The resin compound as described in.

（式（３）、（４）中、Ｒ_１及びＲ_２は、各々独立して、炭素数４〜３０の鎖状アルキル基若しくはアルケニル基、水酸基、アルコキシ基、芳香族基を有しても良い炭素数１〜３０の鎖状アルキル基若しくはアルケニル基、芳香族基、及び水酸基、アルコキシ基、芳香族基を有しても良い炭素数４〜３０の環状アルキル基若しくはアルケニル基から選ばれる基を表し、ｎは１又は２である。）
１１．１．〜１０．の何れかに記載の樹脂化合物を用いた水蒸気バリア材用樹脂化合物、
１２．１１．に記載の水蒸気バリア材用樹脂化合物を用いた水蒸気バリア性フィルム、
１３．１２．に記載の水蒸気バリア性フィルムを用いた包装材料、
１４．１．〜１０．の何れかに記載の樹脂化合物を含有する、蒸着フィルムの蒸着面保護用コーティング材、
１５．１４．に記載の蒸着フィルムの蒸着面保護用コーティング材を蒸着フィルムの蒸着面側にコーティングしてなるガス又は水蒸気バリア性フィルム、
１６．蒸着フィルムがアルミニウム蒸着フィルムである、１５．に記載のガス又は水蒸気バリア性フィルム、
１７．蒸着フィルムが透明蒸着フィルムである、１５．に記載のガス又は水蒸気バリア性フィルム、
１８．１５．〜１７．の何れかに記載のガス又は水蒸気バリア性フィルムを用いた包装材。

(In the formulas (3) and (4), R ₁ and R ₂ may each independently have a chain alkyl group or alkenyl group having 4 to 30 carbon atoms, a hydroxyl group, an alkoxy group, or an aromatic group. A group selected from a linear alkyl group or alkenyl group having 1 to 30 carbon atoms, an aromatic group, and a cyclic alkyl group or alkenyl group having 4 to 30 carbon atoms which may have a hydroxyl group, an alkoxy group or an aromatic group And n is 1 or 2.)
11.1. -10. A resin compound for a water vapor barrier material using the resin compound according to any one of
12.11. A water vapor barrier film using the water vapor barrier material resin compound according to claim 1,
13.12. Packaging material using the water vapor barrier film described in 1.
14.1. -10. A coating material for protecting a vapor deposition surface of a vapor deposition film, comprising the resin compound according to any one of
15.14. A gas or water vapor barrier film formed by coating the deposition surface protective coating material of the deposited film on the deposition surface side of the deposited film,
16. 15. The deposited film is an aluminum deposited film, Gas or water vapor barrier film according to
17. 15. The deposited film is a transparent deposited film, Gas or water vapor barrier film according to
18.15. -17. A packaging material using the gas or water vapor barrier film according to any one of the above.

  The water vapor barrier resin of the present invention is characterized by being a resin compound having a repeating unit represented by the general formula (1).

R ₁ in the general formula (1) is an alicyclic alkylene group, preferably a tricycloalkylene group, and particularly preferably the tricycloalkylene group is a tricyclodecylene group.

R ₂ represents an alkylene group, an alkenylene group, an alkynylene group, an alicyclic alkylene group, a divalent aromatic group, an alkylene group involved in bonding, an alkenylene group, or a divalent aromatic group having an alkynylene group, and 2 It is a group selected from a valent heterocyclic group.

Specific examples of the alkylene group include a butylene group and a hexylene group.
Specific examples of the alkenylene group include an ethenylene group.
Specific examples of the alkynylene group include an ethynylene group.
Specific examples of the alicyclic alkylene group include a cyclohexylene group and a tricyclodecylene group.
Specific examples of the divalent aromatic group include a phenylene group and a naphthylene group.
Specific examples of the divalent aromatic group having an alkylene group, alkenylene group, or alkynylene group involved in the bond include a xylylene group.
Specific examples of the divalent heterocyclic group include a pyridylene group.

R ₃ is a group selected from an alkyl group, an alkenyl group, an alkynyl group, an alicyclic alkyl group, an aromatic group, an aromatic group having an alkylene group involved in bonding, and a heterocyclic group.

Specific examples of the alkyl group include a butyl group and a pentyl group.
Specific examples of the alkenyl group include an ethenyl group.
Specific examples of the alkynyl group include an ethynyl group.
Specific examples of the alicyclic alkyl group, aromatic group, and aromatic group having an alkylene group involved in bonding include a cyclohexyl group, a tricyclodecyl group, a phenyl group, and a benzyl group.
Specific examples of the heterocyclic group include a pyridyl group and a thiophenyl group.

The resin compound of the present invention can be produced by combining known and commonly used production methods.
For example, the water vapor barrier resin having a repeating unit represented by the general formula (1) is a diol containing R ₁ alone, or a diol containing R ₁ , a dicarboxylic acid containing R ₂ and an aldehyde containing R ₃ , or It can be obtained by reacting dialkoxycarbonate in the presence of a polymerization catalyst.

  The polymerization catalyst is preferably an acid catalyst, and examples thereof include mineral acids such as sulfuric acid, Lewis acids such as tetraalkoxytitanium and solid acids such as cation exchange resins. The reaction temperature and reaction time can be appropriately selected. In the case of the reaction of diol alone or diol with dicarboxylic acid or dialkoxycarbonate, the reaction temperature is 150 to 250 ° C., and the reaction time is, for example, about 3 to 10 hours. You can give time. In the case of a reaction between a diol and an aldehyde, the reaction temperature is 70 to 120 ° C., and the reaction time is, for example, about 3 to 10 hours. In this case, the reaction solvent can be selected as appropriate, and a solvent azeotroped with water is particularly preferable, and examples thereof include cyclohexane and toluene.

Next, the water vapor barrier film of the present invention will be described.
The water vapor barrier film of the present invention can be produced by a known and usual method using the water vapor barrier resin.

  The water vapor barrier film of the present invention uses the above water vapor barrier resin to provide strength, resistance to cracking, durability such as cold resistance, transparency so that contents can be visually recognized, and water vapor for maintaining quality during long-term storage. It is characterized by having a barrier property against the above.

  Moreover, in order to improve the adhesiveness with respect to various film materials immediately after application | coating, you may add tackifiers, such as a xylene resin, a terpene resin, a phenol resin, a rosin resin, and a petroleum resin, as needed. When adding these, the range of 0.01-5 mass parts is preferable with respect to 100 mass parts of total amounts of the cured resin component.

(Plate-like inorganic compound)
The resin compound or coating material of the present invention may contain a plate-like inorganic compound. The plate-like inorganic compound used in the present invention has an effect of improving the laminate strength and barrier properties of the coating material.

  The plate-like inorganic compound used in the present invention has a feature that the laminate strength and the barrier property are improved by the plate-like shape. The charge between the layers of the plate-like inorganic compound does not directly affect the barrier property, but the dispersibility to the resin is greatly inferior with the ionic inorganic compound or the swellable inorganic compound with respect to water. The coating suitability becomes a problem because it becomes thickened and thixotropic. On the other hand, in the case of being uncharged (nonionic) or non-swelling with respect to water, even if the addition amount is increased, it is difficult to become thickened or thixotropic, so that the coating suitability can be ensured. Examples of the plate-like inorganic compound used in the present invention include hydrous silicates (phyllosilicate minerals, etc.), kaolinite-serpentine clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.) Light, chrysotile, etc.), pyrophyllite-talc group (pyrophyllite, talc, kerolai, etc.), smectite group clay mineral (montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, stevensite, etc.), vermiculite clay Minerals (vermiculite, etc.), mica or mica group clay minerals (mica, such as muscovite, phlogopite, margarite, tetrasilic mica, teniolite, etc.), chlorite group (cukeite, sudite, clinochlore, chamosite, nimite, etc.) Hydro Lucite, tabular barium sulfate, boehmite, and aluminum polyphosphate and the like. These minerals may be natural clay minerals or synthetic clay minerals. An inorganic layered compound is used individually or in combination of 2 or more types.

  Moreover, it is preferable that the plate-like inorganic compound used in the present invention is nonionic having no interlayer charge.

  Examples of the plate-like inorganic compound used in the present invention include kaolinite-serpentine clay minerals (such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite and chrysotile), and pyrophyllite. -The talc family (pyrophyllite, talc, kerolai, etc.) can be mentioned.

  Moreover, it is preferable that the plate-shaped inorganic compound used by this invention is non-swelling with respect to water.

  Examples of the plate-like inorganic compound used in the present invention include kaolinite-serpentine clay minerals (such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite and chrysotile), and pyrophyllite. -Talc (pyrophyllite, talc, kerolai, etc.), mica or mica clay mineral (mica, muscovite, phlogopite, etc.), margarite, tetrasilic mica, teniolite, etc. (Clinochlor, chamosite, nimite, etc.), hydrotalcite, plate-like barium sulfate and the like.

  The average particle diameter in the present invention means a particle diameter having the highest appearance frequency when the particle size distribution of a certain plate-like inorganic compound is measured with a light scattering measurement device. The average particle diameter of the plate-like inorganic compound used in the present invention is not particularly limited, but is preferably 0.1 μm or more, and more preferably 1 μm or more. If the average particle size is 0.1 μm or less, the length of the long side is short, so that there are problems that the detour path of the molecule does not become long and the barrier ability is difficult to improve and the adhesive force is difficult to improve. The side with a large average particle diameter is not particularly limited. When defects such as streaks occur on the coated surface by containing a large plate-like inorganic compound by the coating method, a material having an average particle diameter of 100 μm or less, more preferably 20 μm or less is preferably used.

  The aspect ratio of the plate-like inorganic compound used in the present invention is preferably high in order to improve the barrier ability due to the gas maze effect. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.

  The plate-like inorganic compound used in the present invention is a modified plate-like inorganic compound obtained by surface treatment with a phosphonic acid derivative or a phosphoric acid derivative represented by the following general formula (3) or (4). There may be.

(In the formulas (3) and (4), R ₁ and R ₂ may each independently have a chain alkyl group or alkenyl group having 4 to 30 carbon atoms, a hydroxyl group, an alkoxy group, or an aromatic group. A group selected from a linear alkyl group or alkenyl group having 1 to 30 carbon atoms, an aromatic group, and a cyclic alkyl group or alkenyl group having 4 to 30 carbon atoms which may have a hydroxyl group, an alkoxy group or an aromatic group And n is 1 or 2.)

The present invention is characterized in that the resin composition contains a modified plate-like inorganic compound surface-treated with the phosphonic acid derivative or the phosphoric acid derivative represented by the general formulas (3) and (4). The plate-like inorganic compound used in the present invention has an effect of increasing the water vapor barrier property of the multilayer film, but is surface-treated with the phosphonic acid derivative or the phosphoric acid derivative represented by the general formulas (3) and (4). The effect can be further enhanced by using a modified plate-like inorganic compound.
The above-mentioned thing can be mentioned as an example of the plate-shaped inorganic compound used for this invention.

  It is known that phosphonic acid is extremely reactive with the surface of inorganic compounds. In particular, there is a feature that a chemical bond can be formed by reacting not only with an OH group on the surface of an inorganic compound mainly composed of a metal oxide but also with an oxygen atom represented by MOM (M is a metal atom). Therefore, in addition to metal compounds, particularly metal oxides, metal hydroxides, natural minerals such as mica and clay, it is possible to organically modify the entire outer periphery of the surface of a single metal foil or the like whose surface is oxidized. In addition, these reaction rates are fast even at room temperature, and a monomolecular or bimolecular uniform organic thin film can be formed.

The R ₁ part of the general formula (3) may have a C 4-30 chain alkyl group or alkenyl group, a hydroxyl group, an alkoxy group, or an aromatic group, and a C 1-30 chain alkyl group. Alternatively, it can be dissolved in a general-purpose solvent by being a group selected from an alkenyl group, an aromatic group, a hydroxyl group, an alkoxy group, a cyclic alkyl group having 4 to 30 carbon atoms or an alkenyl group which may have an aromatic group. By being easy, the modification reaction to the plate-like inorganic compound in the solvent can be easily performed, and sufficient hydrophobicity can be imparted to the plate-like inorganic compound after the surface modification. At this time, when the carbon number is smaller than 4, sufficient hydrophobicity cannot be imparted to the plate-like inorganic compound, and when the carbon number of R ₁ is larger than 30, it can be dissolved in a general-purpose solvent. It becomes difficult. Specifically, in the case of a linear alkylphosphonic acid having 4 to 30 carbon atoms, hexylphosphonic acid, octylphosphonic acid, laurylphosphonic acid, octadecylphosphonic acid, tetracosylphosphonic acid, etc. In the case of hydroxyl group, hydroxyethyl phosphonic acid or the like in the case of a hydroxyl group, butoxyphosphonic acid or the like in the case of an alkoxy group, and phenylphosphonic acid or naphthylphosphonic acid in the case of an aromatic group. .

The phosphoric acid derivative used in the present invention is represented by the general formula (4).
It is known that phosphoric acid, like phosphonic acid, is extremely reactive with the surface of inorganic compounds. In particular, there is a feature that a chemical bond can be formed by reacting not only with an OH group on the surface of an inorganic compound mainly composed of a metal oxide but also with an oxygen atom represented by MOM (M is a metal atom). Therefore, in addition to metal compounds, particularly metal oxides, metal hydroxides, natural minerals such as mica and clay, it is possible to organically modify the entire outer periphery of the surface of a single metal foil or the like whose surface is oxidized. These reaction rates are fast even at room temperature, and a monomolecular or bimolecular uniform organic thin film can be formed.

R _{2 in} the general formula (4) is a chain alkyl group or alkenyl group having 4 to 30 carbon atoms, or a chain alkyl group or alkenyl group having 1 to 30 carbon atoms having a hydroxyl group, an alkoxy group, or an aromatic group. It may be an aromatic group, or may be a general purpose by being a C1-C30 cyclic alkyl group or alkenyl group that may have a hydroxyl group, an alkoxy group, or an aromatic group. By being easily dissolved in the solvent, the modification reaction to the plate-like inorganic compound in the solvent can be easily performed, and sufficient hydrophobicity can be imparted to the plate-like inorganic compound after the surface modification. At this time, when the carbon number is smaller than 4, sufficient hydrophobicity cannot be imparted to the plate-like inorganic compound, and when the carbon number of R ₁ is larger than 30, it can be dissolved in a general-purpose solvent. It becomes difficult. In this case, specifically, in the case of a chain alkyl phosphate ester having 4 to 30 carbon atoms, partial butyl phosphate, isodecyl phosphate, octadecyl phosphate, etc., and in the case of a chain alkenyl phosphate ester, oleyl phosphate In the case of a phosphate ester having a hydroxyl group, hydroxyethyl phosphate, etc., in the case of an alkoxy group, methoxybutyl phosphate, etc., in the case of a phosphate ester having an aromatic group, benzyl phosphate, phenyl phosphate Etc. can be illustrated.
In the present invention, a plate-like inorganic compound whose surface is modified with a phosphonic acid derivative or a phosphoric acid derivative is referred to as a modified plate-like inorganic compound.

(solvent)
The solvent used in the present invention dissolves a phosphonic acid derivative or a phosphoric acid derivative and gives a reaction field to the plate-like inorganic compound, thereby modifying the phosphonic acid derivative or the phosphoric acid derivative to the plate-like inorganic compound. It is to make it easy. Specifically, ester solvents such as ethyl acetate, propyl acetate and butyl acetate; ketone solvents such as acetone, 2-butanone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; fats such as n-hexane Examples include ethers such as group hydrocarbons, tetrahydrofuran, dimethyl ether, diethyl ether, dibutyl ether, anisole and the like. Among these, ethyl acetate and 2-butanone are particularly preferably used because they are frequently used in the current adhesive for dry lamination.

(Concentration of phosphonic acid derivative or phosphoric acid derivative)
The concentration at which the phosphonic acid derivative or phosphoric acid derivative is dissolved is not particularly limited, but in order to rapidly react the phosphonic acid derivative or phosphoric acid derivative with the plate-like inorganic compound, 0.001 to 0 is used. It is preferably between 1 mol / L, more preferably between 0.005 and 0.05 mol / L.

(Quantity ratio between plate-like inorganic compound and phosphonic acid derivative or phosphoric acid derivative)
The amount ratio between the plate-like inorganic compound and the phosphonic acid derivative or phosphoric acid derivative is such that the phosphonic acid derivative or the phosphoric acid derivative can cover the entire circumference of the plate-like inorganic compound with a single-layer or multi-layer thin film. If it is. Therefore, an appropriate quantitative ratio is determined by the dispersion size of the plate-like inorganic compound in the solvent. When the plate-like inorganic compound is non-swelled in the solvent and a plurality of inorganic compound layers are laminated, the amount ratio of the phosphonic acid derivative or the phosphoric acid derivative may be small, and generally 1% by mass or less of the plate-like inorganic compound. It becomes.

  On the other hand, when the plate-like inorganic compound is swellable and the inorganic compound layer is dispersed into a single layer, it may be about several mass%. In the production process, adding a large excess of the phosphonic acid derivative or phosphoric acid derivative in an amount larger than that necessary to modify the entire circumference of the plate-like inorganic compound in the process means that the unreacted phosphonic acid derivative or phosphorus Care must be taken because the acid derivative may easily take up water by associating with the water entering during use.

  As a method for dispersing the plate-like inorganic substance or the like in the coating material of the present invention, a known dispersion method can be used. For example, an ultrasonic homogenizer, a high-pressure homogenizer, a paint conditioner, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, a nano mill, an SC mill, a nanomizer, and the like can be mentioned, and even more preferably, a high shear force is generated. Examples of equipment that can be used include Henschel mixer, pressure kneader, Banbury mixer, planetary mixer, two-roll, three-roll. One of these may be used alone, or two or more devices may be used in combination.

  The film of the present invention can also block gases other than oxygen or water vapor. Examples of the target gas include oxygen, alcohol, inert gas, and volatile organic substances (fragrance).

(Target alcohol)
The alcohol targeted for blocking by the film of the present invention is a material generally classified as an alcohol having a structure in which a hydroxyl group is bonded to an alkyl chain in at least one place. There is no limit. Moreover, monohydric alcohol or polyhydric alcohol can be used. Examples of the monohydric alcohol include methanol, ethanol, 1-propanol, 2-propanol, butanol, pentanol, neopentyl glycol, hexanol, benzyl alcohol, allyl alcohol, and cyclohexanol.
Examples of the polyhydric alcohol include ethylene glycol, propanediol, butanediol, glycerin, and trimethylpropane. Furthermore, in addition to amino alcohols such as N, N-diethylethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine and N-ethylethanolamine, alcohol compounds containing ether groups such as diethylene glycol and triethylene glycol Etc. can also be used.

  Moreover, as the state of the alcohol compound, a material that is a gas to a liquid in a normal temperature region is preferable because of high effectiveness of the present invention.

(Target inert gas)
The inert gas that is intended to be blocked by the film of the present invention is inert to foods and is less likely to cause general chemical changes, and thus prevents contact of oxygen and water vapor around foods, etc. It is a gas useful for maintaining the flavor of food, maintaining its contents, and preventing oxidation. Specifically, in addition to nitrogen and carbon dioxide, helium, neon, argon, krypton, xenon, and radon rare gases can be exemplified. Of these, nitrogen, argon, and carbon dioxide are widely used as the inert gas.

(fragrance)
Volatile organic substances (fragrance) targeted for blocking by the film of the present invention are cocoa, soy sauce, sauce, miso, coffee, lemonene, methyl salicylate, menthol, cheese, fragrance, shampoo, rinse, detergent, and soft. Sanitary field containing scent components such as agents, soaps, pet food, insect repellents, fragrances, hair dyes, perfumes, pesticides and the like.

  Since the film of the present invention is capable of shutting off gas, the adsorbent such as activated carbon and zeolite, deodorant, water purifier cartridge, rice grains, instant noodles, mineral water, somen noodles, cotton, etc. It is also preferably used for applications where it is desired to prevent the entry of fragrances and where it is desired to prevent leakage of scents to the outside.

(Form of film coat)
The coating material of the present invention can be used for film coating on polymers, paper and the like. Since the coated film is excellent in gas or water vapor barrier properties, it can be used as a gas or water vapor barrier film.

  The film used by this invention does not have limitation in particular, The thermoplastic resin film according to the desired use can be selected suitably. For food packaging, for example, PET film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched polypropylene film, OPP: Polyolefin film such as biaxially stretched polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, and the like. These may be subjected to stretching treatment. As the stretching treatment method, it is common to perform simultaneous biaxial stretching or sequential biaxial stretching after the resin is melt-extruded by extrusion film forming method or the like to form a sheet. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.

Moreover, you may perform various surface treatments, such as a flame treatment and a corona discharge treatment, as needed so that the coat layer without defects, such as a film break and a repellency, may be formed in the film surface.
The water vapor barrier resin composition of the present invention can be used by coating on a substrate film or the like. The coating method is not particularly limited and may be performed by a known method. For example, in the case of a solvent type whose viscosity can be adjusted, it is often applied by a gravure roll coating method. Moreover, when it is a solventless type and has a high viscosity at room temperature and is not suitable for gravure roll coating, it can be coated with a roll coater while heating. When using a roll coater, it is preferable to apply in a state where the coating agent of the present invention is heated from room temperature to about 120 ° C. so that the viscosity of the coating agent is about 500 to 2500 mPa · s.

(Coating on evaporated film)
The coating material of the present invention can also be used to significantly improve the gas barrier property of the deposited film. At that time, various vapor deposition films are used as objects to which the coating material is applied. Films coated with this material are more excellent in gas barrier properties and water vapor barrier properties than ordinary vapor deposited films, and can be used as high gas barrier films and high water vapor barrier films.

(Vapor deposition layer type)
The kind of the vapor deposition layer of the vapor deposition film to which the coating material used in the present invention is applied is not particularly limited as long as it can provide gas barrier properties. A metal vapor deposition or metal oxide vapor deposition currently widely used for packaging is preferably exemplified. Various metals can be exemplified as the metal deposition, but aluminum which is particularly inexpensive and widely used is preferable.

  As the metal oxide, aluminum oxide (AlOx) and silicon oxide (SiOx) are preferably exemplified as materials having high versatility. In addition to this, a film in which various organic compounds and inorganic compounds are vapor-deposited, or a vapor-deposited material of a plurality of types may be used. There is no restriction | limiting in particular as a vapor deposition method, The vacuum evaporation method which is a physical vapor deposition method, and the CVD method which is a chemical vapor deposition method can be illustrated. The thickness of the vapor deposition layer is not particularly limited as long as the vapor barrier layer alone can exhibit a certain gas barrier function and a coating layer is provided on the vapor barrier layer to further increase the barrier film. However, if the vapor deposition layer is too thin, the contribution of the vapor deposition layer to the gas barrier is reduced, and even if the coating of the present invention is used, a sufficient gas barrier function cannot be expressed. Is 3 to 70 nm, more preferably 5 to 60 nm.

  In addition, these vapor deposition films can be used with or without being overcoated or undercoated in advance as a vapor deposition protection. However, in particular, a vapor-deposited film having no coating layer is preferably used because it can sufficiently exhibit the barrier improving function of the coating of the present invention.

(Vapor deposition film type)
The film using the coating material in the present invention is not particularly limited, and a thermoplastic resin film according to a desired application can be appropriately selected. For food packaging, for example, polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: linear low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched) Polyolefin film such as polypropylene film and OPP (biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, cycloolefin copolymer film, and the like. These films can be preferably used with or without stretching treatment. Films that have been subjected to a stretching treatment have the advantage that the coating operation is easier and easier to use than dimensional stability and rigidity. On the other hand, the unstretched film is inferior in the dimensional stability, rigidity, and heat resistance of the substrate, so the vapor deposition layer has many defects and the gas barrier is often not stable, so the barrier function can be achieved by using the coating material of the present invention. There is an advantage that can have a big effect on strengthening.

(Part that coats the deposited film)
In this invention, when coating a vapor deposition film, it is necessary to give to the vapor deposition surface side. This is because the coating material of the present invention provides an extremely excellent barrier improving function by efficiently filling defect portions such as pinholes and cracks in vapor deposition. When the coating material is installed on the film surface opposite to the vapor deposition surface, such a reinforcing effect cannot be imparted and the barrier improving effect is limited.

  In the present invention, in order to provide a higher barrier function, a barrier film containing a gas barrier layer such as polyvinyl alcohol, an ethylene / vinyl alcohol copolymer, or vinylidene chloride is used in combination to provide a higher barrier function. Also good.

(Coating method for evaporated film)
The coating method of the coating material of the present invention is not particularly limited as long as the deposition surface of the deposition film can be coated. Specific examples of the coating method include various coating methods such as roll coating and gravure coating. There is no particular limitation on the apparatus used for coating.

(Coating thickness on the deposited film)
When coating the vapor deposition film of the present invention, the film thickness for applying the coating material is not particularly limited. However, the coating material of the present invention enhances the gas barrier reinforcement effect by blocking the deposition defects. Therefore, the coating film thickness does not need to be thick as long as even a deposition defect can be blocked, and a barrier improving effect can be obtained if it is 0.1 μm or more. A preferable thickness range is preferably in the range of 0.2 to 5 μm, more preferably in the range of 0.3 to 3 μm, in view of the balance between the difficulty of causing coating defects and the drying property.

(Layer structure in which coating on vapor deposition film is used)
The following configurations are assumed as the layer configuration in which the coating on the vapor deposition film of the present invention is used. In any case, a good barrier function can be imparted by coating directly on the deposited layer. The method of use may be a single layer or a multilayer such as a laminate.
1) As a configuration using a metal vapor-deposited stretch film such as aluminum,
・ Coating / Ink / Vaporized stretched film / Laminate adhesive / Sealant film ・ Overcoat varnish / Ink / Coating / Vaporized stretched film / Laminate adhesive / Sealant film 2) When using transparent vapor deposited stretched film such as aluminum oxide
・ Transparent vapor-deposited stretched film / coating / ink / laminate adhesive / sealant film 3) As a configuration using a metal vapor-deposited unstretched film such as aluminum ・ Stretched film / ink / laminate adhesive / coating / metal vapor-deposited unstretched film Coating / Ink / Metal-deposited unstretched film / Overcoat varnish / Ink / Coating / Metal-deposited unstretched film 4) When using a transparent deposited unstretched film such as aluminum oxide ・ Stretched film / Ink / Laminating adhesive / Coating / Transparent Vaporized Unstretched Film ・ Coating / Ink / Transparent Vaporized Unstretched Film ・ Overcoat Varnish / Ink / Coating / Transparent Vaporized Unstretched Film Each layer configuration has two or less film layers and the ink layer was printed. A high gas barrier film can be provided. In particular, when a metal or a transparent vapor deposition unstretched film is used, a single-layer high barrier film can be provided.

  Next, the present invention will be specifically described with reference to examples and comparative examples. Unless otherwise indicated, “part” and “%” are based on mass.

(Example 1) Production of polycondensate of tricyclodecane dimethanol and cyclohexanecarbaldehyde In a reaction vessel equipped with a stirrer and Dean-Stark tube, 35 parts of tricyclodecane dimethanol, 20 parts of cyclohexanecarbaldehyde, 55 parts of cyclohexane, 3.5 parts of ion exchange resin (H type) was charged, and the inside was heated to reflux with stirring. It reacted for 7 hours, removing the water to produce | generate with a Die Stark tube. After cooling the interior to room temperature, the ion exchange resin was removed by filtration to obtain the desired polycondensate solution. The number average molecular weight of this polymer was 2,700, and the weight average molecular weight was 7,300. Moreover, cyclohexane was added so that it might become 40% of non volatile matters, and the resin solution (1) was obtained.

(Example 2) Production of polycondensate of tricyclodecane dimethanol and benzaldehyde In a reaction vessel equipped with a stirrer and a Dean-Stark tube, 39 parts of tricyclodecane dimethanol, 21 parts of benzaldehyde, 61 parts of cyclohexane, ion exchange resin 4 0.0 part was charged and the inside was heated to reflux with stirring. It reacted for 7 hours, removing the water to produce | generate with a Die Stark tube. After cooling the interior to room temperature, the ion exchange resin was removed by filtration to obtain the desired polycondensate solution (2) having a nonvolatile content of 33%. The number average molecular weight of this polymer was 1,400, and the weight average molecular weight was 3,500.

(Example 3) Production of polycondensate of cyclohexanedimethanol and cyclohexanecarbaldehyde In a reaction vessel equipped with a stirrer and a Dean-Stark tube, 35 parts of tricyclodecane dimethanol, 27 parts of cyclohexanecarbaldehyde, 62 parts of cyclohexane, ion exchange 3.5 parts of resin was charged and the inside was heated to reflux with stirring. It reacted for 7 hours, removing the water to produce | generate with a Die Stark tube. After cooling the interior to room temperature, the ion exchange resin was removed by filtration to obtain the desired polycondensate solution (3) having a nonvolatile content of 35%. The number average molecular weight of this polymer was 2,900, and the weight average molecular weight was 8,500.

(Example 4) Production of coating film Using a bar coater, the resin liquid obtained in Example 1 is a PET film (Toyo) having a thickness of 12 μm so that the coating amount is 2.0 g / m ² (solid content). This was applied to “E-5100” manufactured by Spinning Co., Ltd.) to obtain a coating film. This coating film was used for water vapor transmission rate measurement.

(Example 5) Production of coating liquid and coating film Using the solution (1) obtained in Example 1, m-xylylene diisocyanate (XDI) was blended as shown in Table 1, and the resin coating liquid was prepared. Obtained. Using a bar coater, the coating solution was applied to a PET film (“E-5100” manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm so that the coating amount was 2.0 g / m ² (solid content). A coating film was obtained by aging at a temperature of 40 ° C. for 3 days. This coating film was used for water vapor transmission rate measurement.

(Example 6) Production of coating liquid and coating film The same procedure as in Example 4 was conducted except that the resin liquid (2) produced in Example 2 was used.

(Example 7) Production of coating liquid and coating film The same procedure as in Example 4 was conducted except that the resin liquid (3) produced in Example 3 was used.

(Example 8) Production of polycondensate of tricyclodecane dimethanol In a reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, and a Liebig condenser, 151 parts of tricyclodecane dimethanol, paratoluenesulfonic acid monohydrate 14 .5 parts was charged and the inside was heated to 170 ° C. with stirring. While introducing nitrogen into the interior, the interior was depressurized to 300 mbar and reacted for 7 hours while removing the generated water. After returning the inside to normal pressure and cooling to 80 ° C., 500 parts of toluene was added and dissolved. After washing with a 1 mol / L aqueous sodium hydroxide solution and saturated brine, the solvent was removed with an evaporator. Furthermore, the target polycondensate (4) was obtained by re-dissolving in MEK and reprecipitating from isopropanol. The number average molecular weight of this polymer was 1,000, and the weight average molecular weight was 3,000.

(Example 9) Production of coating solution and coating film As shown in Table 1, the resin obtained in Example 3 was dissolved in THF so as to have a nonvolatile content of 30% to obtain a resin coating solution. Using a bar coater, the coating solution is applied to a 12 μm thick PET film (“E-5100” manufactured by Toyobo Co., Ltd.) so that the coating amount is 2.0 g / m ² (solid content). A film was obtained. This coating film was used for water vapor transmission rate measurement.

(Comparative Example 1) Production of polycondensate of tricyclodecane dimethanol and octylcarbaldehyde In a reaction vessel equipped with a stirrer and Dean-Stark tube, 55 parts of tricyclodecane dimethanol, 35 parts of octylcarbaldehyde, 90 parts of cyclohexane, Ion exchange resin 5.5 parts was charged and the inside was heated to reflux with stirring. It reacted for 7 hours, removing the water to produce | generate with a Die Stark tube. After the inside was cooled to room temperature, the ion exchange resin was removed by filtration to obtain a target polycondensate solution having a nonvolatile content of 37%. This polymer had a number average molecular weight of 2,000 and a weight average molecular weight of 5,200.

(Comparative Example 2) Production of coating liquid and coating film Using the resin liquid produced in Comparative Example 1, m-xylylene diisocyanate (XDI) was blended as shown in Table 1 to obtain a resin coating liquid. . Using a bar coater, the coating solution was applied to a PET film (“E-5100” manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm so that the coating amount was 2.0 g / m ² (solid content). A coating film was obtained by aging at a temperature of 40 ° C. for 3 days. This coating film was used for water vapor transmission rate measurement.

Comparative Example 3 Production Method of Polycondensate of 1,6-Hexanediol and Cyclohexanecarbaldehyde In a reaction vessel equipped with a stirrer and Dean-Stark tube, 40 parts of tricyclodecane dimethanol, 38 parts of octylcarbaldehyde, and cyclohexane 78 And 4.0 parts of ion exchange resin were charged, and the inside was heated to reflux with stirring. It reacted for 7 hours, removing the water to produce | generate with a Die Stark tube. After the inside was cooled to room temperature, the ion exchange resin was removed by filtration to obtain a desired polycondensate solution having a nonvolatile content of 40%. The number average molecular weight of this polymer was 2,300, and the weight average molecular weight was 5,500.

(Comparative Example 4) Production of coating liquid and coating film Using the resin liquid produced in Comparative Example 3, m-xylylene diisocyanate (XDI) was blended as shown in Table 1 to obtain a resin coating liquid. . Using a bar coater, the coating solution was applied to a PET film (“E-5100” manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm so that the coating amount was 2.0 g / m ² (solid content). A coating film was obtained by aging at a temperature of 40 ° C. for 3 days. This coating film was used for water vapor transmission rate measurement.

[Preparation of modified plate-like inorganic compound]
(Preparation Example 1)
A solution of 0.70 parts by mass of octylphosphonic acid (referred to as OPA manufactured by Aldrich) and 622 parts by mass of tetrahydrofuran was prepared, and 10 parts by mass of muscovite (Y1800 manufactured by Yamaguchi Mica Co., Ltd .: average major axis 10 μm) was added to the solution. In addition, the mixture was stirred at room temperature for 5 hours. Thereafter, the suspension was filtered, washed and dried to obtain OPA-Y1800.

[Preparation of resin coating solution containing plate-like inorganic compound]
(Example 10)
Using the resin solution prepared in Example 1, the plate-like inorganic compound prepared in Preparation Example 1 was blended as shown in Table 1 to prepare a coating solution. This was applied to a 12 μm PET film (“E-5100” manufactured by Toyobo Co., Ltd.) and dried at 80 ° C. for 30 seconds to obtain a coating film, which was used as a moisture permeability measurement sample.
(Example 11)
Using the resin solution prepared in Example 1, m-xylylene diisocyanate (XDI) and the plate-like inorganic compound prepared in Preparation Example 1 were blended as shown in Table 1 to prepare a coating solution. This was applied to a 12 μm PET film (“E-5100” manufactured by Toyobo Co., Ltd.) and dried at 80 ° C. for 30 seconds to obtain a coating film. Aging was performed for 3 days at 40 ° C. to obtain a moisture permeability measurement sample.
(Example 12)
Application and coating were performed in the same manner as in Example 10 except that the untreated plate-like inorganic compound was used instead of the plate-like inorganic compound, and the coating film was used as a moisture permeability measurement sample.

(Water vapor permeability test method)
The coating film PET obtained by the above method is arranged on the high humidity side, and the transmittance of the coating film obtained by the cup method “JIS K0208” including the base material of the coating film is transmitted using the following formula. The rate was calculated. Furthermore, the coating amount (g / m ² ) was measured, and the transmittance per 5 g / m ^{2 of} resin was calculated.

Ｐ ：水蒸気バリア性コーティングフィルムの水蒸気透過率（ＭＶＴＲ）
Ｐ１：塗膜単体の水蒸気透過率
Ｐ２：１２μｍのＰＥＴフィルムの水蒸気透過率（５０ｇ／ｍ^２・２４時間として計算）
結果を、表１に示す。

P: Water vapor transmission rate (MVTR) of water vapor barrier coating film
P1: Water vapor transmission rate of coating film alone P2: Water vapor transmission rate of PET film of 12 μm (calculated as 50 g / m ² · 24 hours)
The results are shown in Table 1.

* 1 Resin liquid produced in Example 1 is used as it is.

[Preparation of coating liquid using polycondensate combined with isocyanate curing agent]
The polycondensates (1) to (4) obtained in the examples were blended with XDI as a curing agent so as to have an OH / NCO ratio of 1.40, and THF was added so as to have a nonvolatile content of 30%, A uniform coating solution was prepared by stirring with a stirrer at room temperature.

[Adjustment of non-barrier adhesive]
Dick Dry LX-703VL (manufactured by DIC Graphics: polyester polyol), KR-90S (manufactured by DIC Graphics), and ethyl acetate are mixed at a ratio of 30/2/68. Thus, a non-barrier adhesive was obtained. This was used for the production of a multilayer film described later.

[Film production method]
The coating liquid was applied to the vapor deposition surface side of the vapor deposition film with a bar coater, and the diluted solvent was volatilized and dried by a blow dryer set at a temperature of 80 ° C. In any of the examples, a uniform coating film was obtained. This was further aged at 40 ° C. for 3 days to promote the reaction of the curing agent, and thus an evaporated film with an overcoat was obtained. These were subjected to various evaluations (oxygen permeability measurement, water vapor permeability measurement, bending test) described later. The evaluation results are shown in Table 2.

[Multilayer film production method]
A non-barrier adhesive was applied to a coating amount of 5.0 g / m ² (solid content) using a bar coater on the overcoat coated surface of the vapor-deposited film prepared by the above method, The diluted solvent was volatilized and dried with a drier set at a temperature of 70 ° C. Next, the adhesive surface of the film to which the adhesive was applied and the LLDPE film (“TUX-HC (60 μm)” manufactured by Tosero Co., Ltd.) were laminated to produce a multilayer film. The multilayer film was aged over 40 ° C./3 days to promote the reaction of the curing agent, and the water vapor barrier multilayer film of the present invention was obtained.

[Oxygen permeability test method]
Films obtained in various Examples and Comparative Examples were used in an atmosphere of 23 ° C. 0% and 90% RH according to JIS-K7126 (isobaric method) using an oxygen permeability measuring device OX-TRAN2 / 21MH manufactured by Mocon. Measured with Note that RH indicates humidity.

[Water vapor permeability test method]
Films obtained in various examples and comparative examples were measured under an atmosphere of 40 ° C. and 90% RH according to the conductivity method “ISO-15106-3” using an Illinois water vapor permeability measuring device 7002. .

[Bending test method]
The multi-layer film after aging was adjusted to a size of 20 cm × 20 cm, bent so as to become a valley with a width of 5 mm, and then bent again so as to become a valley with a width of 5 mm in a vertical direction, and a bending test was performed. In order to evaluate the gas barrier property against the bending treatment, the film after the bending test was subjected to various evaluations (measurement of oxygen transmission rate, measurement of water vapor transmission rate).
The evaluation results are shown in Tables 2-4.

Transparent PET: Barrier Rocks 1011HG (manufactured by Toray Film Processing Co., Ltd.)
Aluminum vapor deposition PET: VMPET 1510HG (manufactured by Toray Film Processing Co., Ltd.)
Unstretched vapor deposited film / Aluminum vapor deposited CPP: VMCPP2203

  It is clear that water vapor and oxygen barrier properties are improved by using a tricyclodecane-containing polycondensate as an overcoat agent for transparent vapor deposition films and aluminum vapor deposition films.

Since the resin compound of the present invention has a water vapor barrier property, it can be used as various packaging materials including food products.
Moreover, since the film using the coating material for vapor deposition surface protection of this invention has favorable oxygen and water vapor | steam barrier property, the said coating material is, for example, for solar cells other than the coating material for film laminates for the said packaging materials. Suitable for applications where water vapor barrier properties are desired, such as coating materials for protective films and coating materials for electronic devices such as coating materials for barrier substrates for display elements, coating materials for building materials, and coating materials for industrial materials. Can be used.
Furthermore, since it is excellent in bending resistance, it can be suitably used as a packaging material that requires a complicated packaging form and stability of the barrier function.

Claims (18)

General formula (1)

(In the formula, R ₁ represents an alicyclic alkylene group, and m represents an integer of 0 or 1, but when it represents 1, —X— represents any group selected from the following formulae.

Provided that R ₂ represents an alkylene group, an alkenylene group, an alkynylene group, an alicyclic alkylene group, a divalent aromatic group, an alkylene group involved in bonding, an alkenylene group, or a divalent aromatic group having an alkynylene group, and A group selected from divalent heterocyclic groups,
R ₃ is a group selected from an alkyl group, an alkenyl group, an alkynyl group, an alicyclic alkyl group, an aromatic group, an aromatic group having an alkylene group involved in bonding, and a heterocyclic group. )
The resin compound which has a repeating unit represented by these. The resin compound according to claim 1, wherein the alicyclic alkylene group is a tricycloalkylene group. The resin compound according to claim 2, wherein the tricycloalkylene group is a tricyclodecylene group. A resin compound obtained by reacting the resin compound according to claim 1 with a curing agent. The resin compound according to claim 4, wherein the curing agent is polyisocyanate. The resin compound according to claim 5, wherein the polyisocyanate contains a polyisocyanate having an aromatic ring. The resin compound according to claim 6, wherein the polyisocyanate having an aromatic ring is a reaction product of metaxylene diisocyanate or metaxylene diisocyanate and an alcohol having two or more hydroxyl groups. The resin compound according to claim 1, wherein the resin compound further contains a plate-like inorganic compound. The resin compound according to claim 8, wherein the plate-like inorganic compound is nonionic between layers or nonswellable with respect to water. The resin compound according to claim 8, wherein the plate-like inorganic compound is a modified plate-like inorganic compound obtained by surface treatment with a phosphonic acid derivative or a phosphoric acid derivative represented by the following general formula (3) or (4): .

(In the formulas (3) and (4), R ₁ and R ₂ may each independently have a chain alkyl group or alkenyl group having 4 to 30 carbon atoms, a hydroxyl group, an alkoxy group, or an aromatic group. A group selected from a linear alkyl group or alkenyl group having 1 to 30 carbon atoms, an aromatic group, and a cyclic alkyl group or alkenyl group having 4 to 30 carbon atoms which may have a hydroxyl group, an alkoxy group or an aromatic group And n is 1 or 2.) The resin compound for water vapor | steam barrier materials using the resin compound in any one of Claims 1-10. The water vapor | steam barrier film using the resin compound for water vapor | steam barrier materials of Claim 11. A packaging material using the water vapor barrier film according to claim 12. The coating material for the vapor deposition surface protection of a vapor deposition film containing the resin compound in any one of Claims 1-10. The gas or water vapor | steam barrier film formed by coating the coating material for the vapor deposition surface protection of the vapor deposition film of Claim 14 on the vapor deposition surface side of a vapor deposition film. The gas or water vapor | steam barrier film of Claim 15 whose vapor deposition film is an aluminum vapor deposition film. The gas or water vapor | steam barrier film of Claim 15 whose vapor deposition film is a transparent vapor deposition film. The packaging material using the gas or water vapor | steam barrier film in any one of Claims 15-17.