JP4663672B2 - Resin composition and method for producing laminate - Google Patents

Description

  The present invention relates to a resin composition having excellent gas barrier properties and water resistance such as boil resistance and retort resistance, and a method for producing a laminate including a layer made of the resin composition.

  Conventionally, films made of thermoplastic resins such as polypropylene, polyester, and polyamide have excellent mechanical properties, heat resistance, transparency, etc., and foods such as confectionery bags, bonito packs, retort pouches, carbon dioxide beverage containers, etc. It is widely used as a packaging material in many fields such as fields, cosmetics, agricultural chemicals, and medical.

  The functions required for these packaging materials are diverse as described above. Among these functions required for these packaging materials, the barrier property as a content protection property, particularly the gas barrier property, improves the food storage stability. It is regarded as important as an important property that affects it. In other words, food alteration factors include oxygen, light, heat, moisture, etc. Among them, oxygen is particularly important as a causative substance.

  However, the gas barrier property is a weak point of general plastic materials. When the above-mentioned various films are used as packaging materials for food packaging, the barrier property against oxygen and other gases is insufficient, so that the oxidation deterioration And various problems such as deterioration of contents by aerobic microorganisms and flavor loss due to permeation of aroma components. Furthermore, in recent years, the necessity for gas barrier properties in packaging materials has increased more than ever due to the diversification of distribution forms, packaging techniques, additive regulations, changes in preferences, and the like.

  For this reason, in order to improve the gas barrier properties, various attempts have been made in recent years to develop gas barrier materials that are excellent in gas barrier properties, and laminates obtained by laminating the gas barrier layers made of the gas barrier materials on the various films described above are described above. It is attracting attention as a packaging material in various fields.

  In such a laminate, the gas barrier material is an indispensable material for effectively blocking oxygen and at the same time controlling the quality of food such as gas filling and vacuum packaging. By having a barrier function such as organic solvent vapor and aroma, it can be used for rust prevention, deodorization and sublimation prevention.

  Therefore, the inventors of the present application previously made a film laminate formed by laminating a film made of a resin composition containing a high hydrogen bonding resin and an inorganic layered compound on a base film as a laminate excellent in gas barrier properties. Proposed (JP-A-6-93133, JP-A-7-304128). This film laminated body is excellent in gas barrier property, and can be used suitably for the various uses mentioned above.

  However, although the above-mentioned film laminate has improved gas barrier properties as compared with conventional ones, it is still difficult to say that sufficient water resistance can be obtained under severe conditions such as boil resistance and retort resistance.

However, in addition to distribution forms, diversification of packaging technology, changes in additives, changes in taste, etc., demand for pack foods, boiled foods or retort foods is increasing in search of portability, convenience, and preservation. In recent food circumstances or various uses in various fields as described above, it can be said that packaging materials that are excellent in water resistance such as boil resistance and retort resistance as well as gas barrier properties are indispensable.

  The present invention has been made in view of the above-mentioned conventional problems, and its purpose is to produce a laminate having excellent water resistance such as boil resistance and retort resistance, and also having a high level of gas barrier properties. Another object is to provide a method for producing a resin composition used as a barrier material of the laminate.

  As a result of intensive studies aimed at achieving the above object, the present inventors have prepared at least a high hydrogen bonding resin, an inorganic layered compound, and a metal organic compound capable of undergoing a crosslinking reaction with the high hydrogen bonding resin. The laminate comprising a layer made of the resin composition is excellent in water resistance such as boil resistance and retort resistance, and also has a high level of gas barrier properties, and at least high hydrogen bonding properties The resin composition can be suitably produced from a mixed solution prepared by containing a resin, an inorganic layered compound, a metal organic compound capable of crosslinking with the high hydrogen bonding resin, and a liquid and having a pH of 5 or less. As a result, the present invention has been completed.

  That is, the method for producing a resin composition according to the present invention includes at least a high hydrogen bonding resin, an inorganic layered compound, and a metal organic that can undergo a crosslinking reaction with the high hydrogen bonding resin in order to solve the above-described problems. It includes a step of preparing a mixed solution containing a compound and a liquid at a pH of 5 or less, and a step of removing the liquid from the mixed solution.

  Also, the method for producing a laminate according to the present invention is a method for producing a laminate comprising a substrate and a layer made of a resin composition formed on the substrate, and at least a high hydrogen bond A step of preparing a mixed solution containing a functional resin, an inorganic layered compound, a metal organic compound capable of crosslinking reaction with the high hydrogen bonding resin, and a liquid at a pH of 5 or less, on at least one surface of the substrate It includes a step of applying a mixed solution and a step of forming a layer made of a resin composition by removing the liquid from the mixed solution applied onto the substrate.

  According to the above configuration, the inorganic layered compounds are opposed to each other due to the shape of the layer, and are oriented so as to be substantially parallel to the surface direction of the layer made of the resin composition. An effect is produced and a high level of gas barrier property can be imparted to the layer made of the resin composition.

  Moreover, according to said structure, by using the said metal organic compound as a crosslinking agent of the said high hydrogen bond resin, it is a layer which consists of the said resin composition, and water resistance of high level, such as boil resistance and retort resistance, is provided. Sex can be imparted. Furthermore, the stability of this liquid mixture can be improved by preparing the liquid mixture containing the said metal organic compound for manufacturing the said resin composition at pH 5 or less. Therefore, according to the above configuration, it is suitable as a laminate having excellent water resistance such as boil resistance and retort resistance and also having a high level of gas barrier properties, and a barrier material that gives the laminate the above physical properties. The resin composition used for can be suitably produced.

  As described above, the method for producing a resin composition according to claim 1 of the present invention includes at least a high hydrogen bonding resin, an inorganic layered compound, and a metal organic compound capable of undergoing a crosslinking reaction with the high hydrogen bonding resin. And a liquid containing the liquid are prepared at a pH of 5 or less, and a liquid is removed from the liquid mixture.

  As described above, the method for producing a resin composition according to claim 2 of the present invention is the method for producing a resin composition according to claim 1, wherein the mixed solution is prepared at a pH of 3 or less. .

  As described above, the method for producing a resin composition according to claim 3 of the present invention is the method for producing a resin composition according to claim 1 or 2, wherein the metal organic compound is a titanium organic compound or a zirconium organic compound. It is at least one compound selected from a compound, an aluminum organic compound, and a silicon organic compound.

  As mentioned above, the manufacturing method of the resin composition of Claim 4 which concerns on this invention WHEREIN: In the manufacturing method of the resin composition of any one of Claims 1-3, the said high hydrogen bond resin is the above-mentioned. It is at least one compound selected from polyvinyl alcohol, polysaccharides, and ethylene-vinyl alcohol copolymers.

  The method for producing a resin composition according to claim 5 according to the present invention, as described above, in the method for producing a resin composition according to any one of claims 1 to 4, in the high hydrogen bond resin. The ratio of the crosslinkable functional group is in the range of 20 mol% to 60 mol%.

  The method for producing a resin composition according to claim 6 according to the present invention, as described above, in the method for producing a resin composition according to any one of claims 1 to 5, in the high hydrogen bond resin. The ratio of the number of moles of the crosslinkable group of the metal organic compound to the number of moles of the crosslinkable functional group is in the range of 0.001 to 10.

  As mentioned above, the manufacturing method of the resin composition of Claim 7 which concerns on this invention is the aspect ratio of the said inorganic layered compound in the manufacturing method of the resin composition of any one of Claims 1-6. Is in the range of 50 to 5,000.

  As described above, the method for producing a resin composition according to claim 8 of the present invention is the method for producing a resin composition according to any one of claims 1 to 7, wherein the inorganic layered compound is used as a solvent. A compound that swells or cleaves.

  The method for producing a resin composition according to claim 9 according to the present invention is the weight of the inorganic layered compound with respect to the high hydrogen bonding resin in the method for producing a resin composition according to claims 1 to 8, as described above. The ratio is in the range of 1/20 to 10/1.

  According to said structure, the resin composition used suitably as a barrier material which provides water resistance, such as boil resistance and retort resistance, and a gas barrier property in a high level to a laminated body can be manufactured suitably. There is an effect.

  The manufacturing method of the laminated body of Claim 10 which concerns on this invention is a manufacturing method of the laminated body provided with the base material and the layer which consists of a resin composition formed on this base material as mentioned above. A step of preparing a mixed solution containing at least a high hydrogen bonding resin, an inorganic layered compound, a metal organic compound capable of undergoing a crosslinking reaction with the high hydrogen bonding resin, and a liquid at a pH of 5 or less; A step of coating the mixed solution on at least one surface of the substrate, and a step of forming a layer made of the resin composition by removing the liquid from the mixed solution coated on the substrate.

  As described above, the method for producing a laminate according to claim 11 of the present invention is the method for producing a laminate according to claim 10, wherein the thickness of the layer made of the resin composition is in the range of 1 nm to 10 μm. It is.

  According to said structure, there exists an effect that the laminated body which is excellent in water resistance, such as boil resistance and retort resistance, and has gas barrier property in a high level can be manufactured suitably.

  The method for producing the laminate can be suitably used as a method for producing, for example, a packaging material in many fields such as the food field, cosmetic field, agricultural chemical field, and medical field.

  One embodiment of the present invention will be described with reference to FIGS. 1 to 7 as follows.

  The method for producing a resin composition according to the present invention comprises a resin composition prepared from at least a high hydrogen bonding resin, an inorganic layered compound, and a metal organic compound capable of undergoing a crosslinking reaction with the high hydrogen bonding resin. It is for manufacturing. Moreover, the manufacturing method of the laminated body concerning this invention is for manufacturing the laminated body which has the structure provided with at least 1 layer of barrier layers 3 which consist of said resin composition as shown in FIG. It is. As shown in FIG. 1, for example, the barrier layer 3 may be laminated on the base material 1 via the anchor layer 2, or may be laminated directly on the base material 1.

  As shown in FIG. 2, the barrier layer 3 is formed so that the inorganic layered compound has a layered shape so that the layers, for example, the unit crystal layers 31 face each other and are substantially parallel to the surface direction of the barrier layer 3. The resin 32 which is a crosslinked product formed by crosslinking the high hydrogen bonding resin and the metal organic compound is interposed between the inorganic layered compounds, for example, between the unit crystal layers 31 and 31. have.

  In the present invention, the high hydrogen bond resin used in the resin composition as a barrier material constituting the barrier layer 3 is a compound having a hydrogen bond group or an ionic group as a crosslinkable functional group. The content of hydrogen bonding groups or ionic groups in the high hydrogen bonding resin (the total amount of both when both are included) is usually in the range of 20 mol% to 60 mol%, preferably It exists in the range of 30 mol%-50 mol%. The content of these hydrogen bonding groups and ionic groups can be measured by, for example, nuclear magnetic resonance (for example, 1H-NMR, 13C-NMR, etc.).

  Specific examples of the hydrogen bonding group possessed by the high hydrogen bonding resin include a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Examples of the ionic group include ionic groups such as a carboxylate group, a sulfonate ion group, a phosphate ion group, an ammonium group, and a phosphonium group. Among these hydrogen bonding groups and ionic groups, particularly preferred functional groups include a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonic acid ion group, and an ammonium group.

  Although it does not specifically limit as said high hydrogen bond resin, Specifically, for example, polyvinyl alcohol, polysaccharide, the ethylene-vinyl alcohol copolymer mentioned later, polyacrylic acid, its ester, poly Examples thereof include sodium acrylate, polybenzenesulfonic acid, sodium polybenzenesulfonate, polyethyleneimine, polyallylamine and its quaternary ammonium salt, polyvinyl thiol, polyglycerin, polyvinylidene chloride, polyacrylonitrile and the like.

The polyvinyl alcohol (PVA) is, for example, a copolymer of vinyl alcohol and vinyl acetate, and a polymer obtained by hydrolysis or transesterification (saponification) of the acetate portion of the vinyl acetate polymer; trifluoro And polymers obtained by saponifying vinyl acetate polymer, vinyl formate polymer, vinyl pivalate polymer, t-butyl vinyl ether polymer, trimethylsilyl vinyl ether polymer, and the like. For details of the polyvinyl alcohol, for example, “World of PVA” edited by Poval Association (1992, Kobunshi Publishing Co., Ltd.); “Poval” (1981, Kobunshi Publishing Co., Ltd., Nagano et al. ); Etc., it will become clearer.

  The saponification rate of the polyvinyl alcohol is preferably 70 mol% or more, more preferably 85 mol% or more, particularly preferably 98 mol% or more, and most preferably a complete saponified product. The degree of polymerization of the polyvinyl alcohol is preferably in the range of 100 to 5,000, more preferably in the range of 200 to 3,000. Moreover, as said PVA, unless the objective of this invention is inhibited, you may modify | denature with a small amount of copolymerization monomers.

  Polysaccharides are biopolymers synthesized in biological systems by condensation polymerization of various monosaccharides, and in the present invention, those obtained by chemically modifying the biopolymers are also included. Specific examples of the polysaccharide include cellulose; cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose; amylose; amylopectin; pullulan; curdlan; xanthan; chitin;

  The ethylene-vinyl alcohol copolymer (EVOH) is EVOH having a vinyl alcohol fraction in the range of 40 mol% to 80 mol%, and preferably has a vinyl alcohol fraction of 45 mol% to 75 mol. EVOH in the range of mol%. The melt index (MI) of the EVOH is not particularly limited, but is preferably 0.1 g / 10 min to 50 g / 10 min under conditions of a temperature of 190 ° C. and a load of 2,160 g. The above EVOH may be modified with a small amount of a copolymerization monomer as long as the object of the present invention is not impaired.

  These high hydrogen bond resins may be used alone or in a suitable combination of two or more. Among these highly hydrogen bonding resins, polyvinyl alcohol, polysaccharides, and ethylene-vinyl alcohol copolymers are particularly suitable.

  In addition, the metal organic compound used in the present invention is a compound capable of undergoing a crosslinking reaction with the high hydrogen bond resin through a coordination bond, a hydrogen bond, an ionic bond, or the like. The metal organic compound crosslinks with the high hydrogen bond resin as a cross-linking agent for the high hydrogen bond resin, and maintains the flexibility of the high hydrogen bond resin with the boil property on the barrier layer 3. And a high level of water resistance such as retortability.

  Moreover, the organometallic compound has high cross-linking reactivity with the high hydrogen bonding resin, and can improve the cross-linking efficiency as compared with, for example, an inorganic metal salt. Moreover, when laminating | stacking the said barrier layer 3 by coating of the coating liquid containing the said resin composition, for example, when reactivity is too high, a crosslinking reaction will advance in a coating liquid and it will become unsuitable for coating. However, organometallic compounds are suitable for coating because their reactivity can be easily controlled by changing their ligands.

  Preferable examples of the metal organic compound include a titanium organic compound, a zirconium organic compound, an aluminum organic compound, and a silicon organic compound. Only one kind of these metal organic compounds may be used, or two or more kinds may be appropriately mixed and used.

Specific examples of the titanium organic compound include, for example, titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate; titanium acetylacetonate, titanium tetra Titanium chelates such as acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium triethanolamate, titanium ethylacetoacetate; titanium acylates such as polyhydroxytitanium stearate; It is done.

  Specific examples of the zirconium organic compound include, for example, zirconium normal propyrate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium acetylacetonate bisethylacetoacetate and the like. Can be mentioned.

  Specific examples of the aluminum organic compound include aluminum acetylacetonate and aluminum organic acid chelate.

  Specific examples of the silicon organic compound include compounds having the ligands exemplified for the titanium organic compound and the zirconium organic compound described above.

  One type of the metal organic compound may be used, or two or more types may be appropriately mixed and used. Among the metal organic compounds, a metal organic compound having a chelating ligand such as an acetylacetonate and having a coordination bond with the high hydrogen bonding resin has an appropriate crosslinking reactivity. Among them, a titanium chelate compound is particularly preferable from the viewpoint of stability in a coating solution when the resulting resin composition is applied. In addition, the titanium chelate compound exhibits a particularly excellent effect in improving water resistance.

  The inorganic layered compound used in the present invention is an inorganic compound in which the unit crystal layers 31 are stacked to have a layered structure. In the present invention, the inorganic layered compound having an oxygen permeation preventing effect is dispersed in the resin 32 of the barrier layer 3 so as to swell or swell and cleave so that the unit crystal layers 31 face each other. Therefore, a labyrinth effect can be produced and an excellent gas barrier property can be obtained.

  In the cleaved state, the inorganic layered compound preferably has a particle size of 5 μm or less and an aspect ratio in the range of 50 to 5,000 from the viewpoint of gas burr properties, and an aspect ratio in the range of 200 to 3,000. It is more preferable that If the aspect ratio is less than 50, the gas barrier property is not sufficient, and if it is greater than 5,000, it is technically difficult and economically expensive. Further, if the particle size is 3 μm or less, the transparency is better, and if the particle size is 1 μm or less, it is more preferable for applications in which transparency is important.

  The average particle size of the inorganic layered compound can be measured by a method using a diffraction / scattering method, a method using a dynamic light scattering method, a method using a change in electrical resistance, a method using image processing after photographing in a liquid microscope, or the like.

  For example, as a method for measuring the average particle size of the inorganic layered compound in a pure solvent such as water, a dynamic light scattering method is suitably used.

  However, the dynamic light scattering method is difficult to evaluate when the resin coexists because the apparent liquid viscosity changes from that of a pure solvent, and the electric resistance change method is limited in the electrolyte concentration of the liquid. The method based on image processing after medium microscope photography has a problem of resolution and is limited in use.

For this reason, when the average particle size of the inorganic layered compound is measured in the presence of the resin, the solution containing the resin, for example, the resin aqueous liquid is transparent and substantially less scattered, and scattering derived from the particles of the inorganic layered compound is dominant. In this case, since only information on the particle size distribution of the inorganic layered compound particles can be obtained regardless of the presence or absence of the resin, a method using a diffraction / scattering method is preferably used.

  Therefore, the particle size of the inorganic layered compound used in the present invention indicates the particle size obtained by the diffraction / scattering method in the dispersion medium. Although it is extremely difficult to measure the true particle size in the barrier layer 3, it is sufficiently swollen and cleaved with the same kind of dispersion medium as used in the diffraction / scattering method, and is combined with the resin 32 used in the barrier layer 3. In this case, the particle size of the cleaved inorganic layered compound in the barrier layer 3 shown in FIG. 2 can be considered to correspond to the particle size of the cleaved inorganic layered compound in the dispersion medium.

  Below, the method to measure the average particle diameter of an inorganic layered compound with the said diffraction / scattering method is demonstrated.

  The particle size distribution and average particle size of the inorganic layered compound by the diffraction / scattering method are determined from the diffraction / scattering pattern obtained when light passes through the inorganic layered compound dispersion by the Mie scattering theory and the like. It can be obtained by calculating the particle size distribution that is most consistent with the scattering pattern.

  A commercially available apparatus can be used as a diffraction / scattering pattern measuring apparatus used in the diffraction / scattering method. Specifically, for example, laser diffraction / light scattering method particle size measuring devices LS230, LS200, LS100 manufactured by Coulter, Inc .; laser diffraction particle size distribution measuring devices SALD2000, SALD2000A, SALD3000 manufactured by Shimadzu Corporation; laser diffraction manufactured by Horiba, Ltd. -Scattering type particle size distribution measuring apparatus LA910, LA700, LA500; Nikkiso Microtrac SPA, Microtrac FRA, etc.

  Next, a method for measuring the aspect ratio (aspect ratio (Z)) of the inorganic layered compound will be described.

  The aspect ratio (Z) is a ratio obtained from the relationship represented by Z = L / a. Here, L represents the particle size (volume-based median diameter) of the inorganic layered compound obtained by the particle size measurement method by the diffraction / scattering method described above in the dispersion, and a represents the cleaved inorganic material shown in FIG. The unit thickness of the layered compound, that is, the thickness of the unit crystal layer 31 of the inorganic layered compound is shown.

  The “unit thickness a” of the inorganic layered compound is, for example, a powder X-ray diffraction method described later (“Guide to Instrumental Analysis (a)” (1985, published by Kagaku Dojinsha, supervised by Jiro Shiokawa), page 69), etc. Is a value determined based on the measurement of the inorganic layered compound alone. More specifically, as schematically shown in the graph shown in FIG. 3, the Bragg equation (nλ = n) is calculated from the angle θ corresponding to the peak at the lowest angle among diffraction peaks observed by X-ray diffraction. (2Dsin θ, n = 1, 2, 3...) Is defined as “unit thickness a”.

  When the resin composition corresponding to the barrier layer 3 obtained by removing the solvent from the dispersion is subjected to powder X-ray diffraction, the interplanar spacing of the inorganic layered compound in the resin composition is usually shown in FIG. It can be obtained as “surface distance d”.

  More specifically, as schematically shown in the graph of FIG. 4, the diffraction peaks observed on the lower angle (larger interval) side than the diffraction peak position corresponding to the “unit thickness a” described above. The interval corresponding to the peak on the lowest angle side is “surface interval d” (where a <d).

As a result of the powder X-ray diffraction, as schematically shown in the graph of FIG. 5, it is difficult to detect the peak corresponding to the “plane distance d” overlapping with the halo (or background). , The area of the portion excluding the base line on the lower angle side than 2θd is defined as a peak corresponding to the “plane distance d”. Here, “θd” is a diffraction angle corresponding to “(unit thickness a) + (width of single resin chain)”. For details of the method for determining the “plane distance d”, see, for example, pages 35 and 271 and pages 271 and below of “Encyclopedia of Clay” (1985, Asakura Shoten Publishing, Shuichi Iwao, etc.). It will become clearer.

  Thus, the integrated intensity of the diffraction peak observed in the powder X-ray diffraction of the resin composition is 2 as a relative ratio with respect to the integrated intensity of the reference diffraction peak (that is, the diffraction peak corresponding to “plane spacing d”). Preferably, it is preferably 10 or more.

  Usually, the difference k (k = (d−a)) between the “surface distance d” and the “unit thickness a” is the length of the resin single chain constituting the resin composition when converted to a length. It is equal to or greater than the width (k = (da) ≧ width of single resin chain). Such “resin single chain width” can be determined by simulation calculation (for example, see “Introduction to Polymer Chemistry” (1981, pp. 103-110)). In the case of alcohol, it is 4 to 5 cm (2 to 3 cm for water molecules).

  It is extremely difficult to directly measure the “true aspect ratio” of the inorganic layered compound in the resin 32 of the barrier layer 3. Therefore, the “aspect ratio (Z)” described above is not necessarily equal to the “true aspect ratio” of the inorganic layered compound in the resin 32 of the barrier layer 3. It is valid to approximate "true aspect ratio" with (Z) ".

  That is, a <d between the “plane distance d” obtained by the powder X-ray diffraction method of the resin composition and the “unit thickness a” obtained by the powder X-ray diffraction measurement of the inorganic layered compound alone. In the case where there is a relationship and the value of k ((da) value) is equal to or greater than the width of the single resin chain in the resin composition, in the resin composition, between the layers of the inorganic layered compound. The resin is inserted. Accordingly, the thickness of the inorganic layered compound in the resin 32 of the barrier layer 3 is approximated by the above “unit thickness a”, that is, the “true aspect ratio” of the inorganic layered compound in the barrier layer 3 is the above-described inorganic There is sufficient validity to approximate the “aspect ratio (Z)” in the dispersion of the layered compound.

  As described above, it is extremely difficult to measure the true particle size of the inorganic layered compound in the resin 32 of the barrier layer 3, but the particle size of the inorganic layered compound in the resin 32 of the barrier layer 3 is determined in the dispersion liquid. It can be considered that this corresponds to the particle size L of the inorganic layered compound.

  However, since the particle size L of the inorganic layered compound in the dispersion obtained by the diffraction / scattering method is considered to have a very low possibility of exceeding the major axis (Lmax) of the inorganic layered compound, “true aspect ratio ( The possibility that “Lmax / a)” is lower than the “aspect ratio (Z)” used in the present invention (Lmax / a <Z) is theoretically quite low.

  Therefore, for the two reasons described above, the definition of “aspect ratio (Z)” used in the present invention is considered to have sufficient validity. In the present embodiment, the “aspect ratio” indicates the “aspect ratio (Z)” defined above, and the “particle diameter” indicates the “particle diameter L determined by the diffraction / scattering method”. .

Specific examples of the inorganic layered compound include graphite, phosphate derivative compounds (such as zirconium phosphate compounds), chalcogenides, and clay minerals. The chalcogenide is a dichalcogenide of group IV (Ti, Zr, Hf), group V (V, Nb, Ta) and group VI (Mo, W), which has the chemical formula MX2 (where M is It represents a group IV and group VI element, and X represents a chalcogen (S, Se, Te)).

  One kind of the inorganic layered compound may be used, or two or more kinds may be appropriately mixed and used. Among the inorganic layered compounds, those having a property of swelling or cleaving in a solvent are preferable from the viewpoint of easily giving a large aspect ratio, and those having a property of cleaving in a solvent (swelling in a solvent and cleaving) are more preferable. . The swelling property and cleavage property of the inorganic layered compound in a solvent can be evaluated by a swelling property test and a cleavage property test described later.

(Swellability test)
100 ml of solvent is put into a 100 ml graduated cylinder, and 2 g of inorganic layered compound is slowly added thereto. After standing at 23 ° C. for 24 hours, the volume (ml) of the inorganic layered compound dispersion layer is read as a swelling value from the scale of the interface between the inorganic layered compound dispersion layer and the supernatant in the graduated cylinder. It shows that swelling property is so high that this figure is large.

[Cleavage test]
Slowly add 30 g of the inorganic layered compound to 1,500 ml of solvent, and disperse (Asada Tekko Co., Ltd., Despa MH-L, blade diameter 52 mm, rotation speed 3,100 rpm, container capacity 3 L, bottom-blade distance 28 mm) After dispersing at a peripheral speed of 8.5 m / min for 90 minutes at 23 ° C., 100 ml of this dispersion was collected in a graduated cylinder. After standing for 60 minutes, the volume (ml) of the inorganic layered compound dispersion layer is read as a cleavage value from the scale of the interface between the inorganic layered compound dispersion layer and the supernatant in the graduated cylinder. The larger this value, the higher the cleaving property.

  The solvent used in the swellability measurement test and the cleavage property measurement test is a solvent having a density smaller than that of the inorganic layered compound. When the inorganic layered compound is a natural swellable clay mineral, it is preferable to use water as the solvent.

  The swelling property of the inorganic layered compound is determined by the above-described swelling property measurement test when the volume of the inorganic layered compound dispersion layer (that is, the volume after swelling of 2 g of the inorganic layered compound) is about 5 ml or more (ie, the swelling value is 5 or more). It is preferably about 20 ml or more (that is, a swelling value of 20 or more).

  On the other hand, the cleavage property of the inorganic stratiform compound is determined by the volume of the inorganic stratiform compound dispersion layer (that is, the volume after swelling of the inorganic stratiform compound (corresponding to about 2 g) contained in 100 ml of the dispersion) in the above-described cleavage property test. Is preferably about 5 ml or more (that is, a cleavage value of 5 or more), more preferably about 20 ml or more (that is, a cleavage value of 20 or more).

  Among the inorganic layered compounds, as the inorganic layered compound that swells or cleaves in a solvent, a clay mineral having swelling property and cleavage property in a solvent is particularly preferably used. The clay mineral generally has (i) a type having a two-layer structure having an octahedral layer mainly composed of aluminum, magnesium, or the like on the upper part of a tetrahedral layer of silica, and (ii) a tetrahedral layer of silica. In addition, it is classified into a type having a three-layer structure in which an octahedral layer having aluminum or magnesium as a central metal is narrowed from both sides. Examples of the former (i) two-layer structure type include clay minerals such as kaolinite group and antigolite group. The latter (ii) three-layer structure type includes clay minerals such as smectite group, vermiculite group and mica group depending on the number of interlayer cations.

More specifically, these clay minerals include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite hectorite, Examples include tetrasilic mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite. In addition, those obtained by treating these clay minerals with organic substances (see Asakura Shoten, “Encyclopedia of Clay”; hereinafter may be referred to as organically modified clay minerals) can also be used as the inorganic layered compound.

  Among the clay minerals, smectite group, vermiculite group, and mica group clay minerals are preferable and smectite group is more preferable from the viewpoint of swelling or cleavage. Specific examples of the smectite clay mineral include montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, and hectorite, but are not particularly limited.

  Examples of the dispersion medium for swelling or cleaving the inorganic layered compound include water; alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, and diethylene glycol when the inorganic layered compound is a natural swellable clay mineral. Dimethylformamide; dimethyl sulfoxide; acetone; and the like. Among them, water and alcohols such as methanol are more preferable. When the inorganic layered compound is an organically modified clay mineral, examples of the dispersion medium include aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as ethyl ether and tetrahydrofuran; acetone, methyl ethyl ketone, and methyl isobutyl. Ketones such as ketones; Aliphatic hydrocarbons such as n-pentane, n-hexane and n-octane; Halogenated hydrocarbons such as chlorobenzene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and perchloroethylene Ethyl acetate; methyl methacrylate (MMA); dioctyl phthalate (DOP); dimethylformamide; dimethyl sulfoxide; methyl cellosolve;

  The blending ratio of the high hydrogen bonding resin, the inorganic layered compound, and the metal organic compound in the resin composition is not particularly limited, but for example, the inorganic layered compound with respect to the high hydrogen bonding resin The weight ratio (inorganic layered compound / high hydrogen bonding resin) is preferably in the range of 1/100 to 100/1, more preferably in the range of 1/20 to 10/1, and 1/20 to 2 More preferably within the range of / 1. The higher the weight ratio of the inorganic layered compound, the better the barrier properties. However, in view of the bending resistance, the weight ratio is preferably in the range of 1/20 to 2/1.

  The blending ratio of the metal organic compound to the high hydrogen bond resin is the number of moles of crosslinkable functional groups in the high hydrogen bond resin (that is, the total number of moles of hydrogen bond groups and ionic groups). Is the number of moles of the crosslinkable group of the metal organic compound with respect to the number of moles of the crosslinkable functional group of the high hydrogen bonding resin. The ratio K (K = CN / HN) is preferably in the range of 0.001 to 10, and more preferably in the range of 0.01 to 1.

  Further, the resin composition preferably contains a surfactant for improving the adhesion between the barrier layer 3 and the anchor layer 2. The surfactant is not particularly limited as long as it can improve the adhesion between the anchor layer 2 and the barrier layer 3, and examples thereof include an anionic surfactant and a cationic surfactant. , Zwitterionic surfactants and nonionic surfactants.

Examples of the anionic surfactant include aliphatic monocarboxylates, carboxylic acid types such as N-acyloyl glutamate, alkylbenzene sulfonates, naphthalene sulfonate-formaldehyde condensates, and sulfonic acids such as sulfosuccinic acid dialkyl esters. Hydrocarbon anionic surfactants, such as sulfuric acid ester type such as alkyl sulfate, alkyl sulfate polyoxyethylene salt, phosphoric acid ester type such as alkyl phosphate, boric acid ester type such as alkyl borate, Fluorine anionic surfactants such as sodium perfluorodecanoate and sodium perfluorooctyl sulfonate, and silicone anionic surfactants having an anionic group such as a polymer having a polydimethylsiloxane group and a carboxylic acid metal salt Is mentioned.

  Examples of the cationic surfactant include amine salt types such as alkylamine salts, quaternary ammonium salt types such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, and alkyldimethylbenzylammonium salts.

  Examples of the zwitterionic surfactant include carboxybetaine types such as N, N-dimethyl-N-alkylaminoacetic acid betaine, and glycine types such as 1-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine. It is done.

  Nonionic surfactants include ester types such as glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester, polydimethylsiloxane group and alkylene oxide adduct condensation polymer, polysiloxane-polyoxyalkylene copolymer, Ether type such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether and polyoxyethylene polyoxypropylene block polymer, ester ether type such as polyethylene glycol fatty acid ester and polyoxyethylene sorbitan fatty acid ester, alkanol such as aliphatic alkanolamide Examples include amide type, fluorine type such as perfluorodecanoic acid-diglycerin ester and perfluoroalkylalkylene oxide compounds.

  Among the above surfactants, in particular, ether type nonionic surfactants such as alkali metal salts of carboxylic acids having an alkyl chain of 6 to 24 carbon atoms, polydimethylsiloxane-polyoxyethylene copolymer, etc. (Silicone-based nonionic surfactants) and fluorine-type nonionic surfactants (fluorine-based nonionic surfactants) such as perfluoroalkylethylene oxide compounds are preferred.

  When the barrier layer 3 is formed, for example, when a coating solution is used, the content of the surfactant is 0.001 to 5% by weight in the coating solution from the viewpoint of effects. Is preferably set to be 0.003% by weight to 0.5% by weight, more preferably 0.005% by weight to 0.1% by weight. Particularly preferred.

  Since the resin composition further contains a surfactant, the affinity of the barrier layer 3 with respect to the anchor layer 2, that is, the wettability can be improved. Adhesion with the barrier layer 3 can be improved.

  Moreover, the said resin composition may contain conventionally well-known various additives, such as a ultraviolet absorber, a coloring agent, and antioxidant, in the range which does not impair the effect of this invention.

  The laminate of the present invention forms a coating film by coating a coating liquid (composition liquid mixture) containing the resin composition and a liquid on the substrate 1 or the anchor layer 2 by coating. The film can be easily obtained by drying and heat-treating the film to remove the liquid from the coating film and laminating the barrier layer 3 made of the resin composition on the substrate 1 or the anchor layer 2. A film made of the resin composition may be laminated on the substrate 1 or the anchor layer 2, and the former is particularly preferable.

Thus, by laminating the barrier layer 3 by coating, the formation of the barrier layer 3 can be facilitated. When the anchor layer 2 is laminated by coating, the barrier layer 3 is continuously formed. It can be formed on the anchor layer 2. Therefore, it is suitable for mass production.

  The coating liquid used in the present invention is a liquid obtained by dispersing or dissolving the resin composition in a liquid such as a solvent or a dispersion medium. From the viewpoint of gas barrier properties of the resulting laminate, the liquid is preferably a dispersion medium that swells or cleaves the inorganic layered compound described above. When the liquid is a dispersion medium, the inorganic layered compound is dispersed in the liquid in a swollen or cleaved state.

  The concentration of the high hydrogen bonding resin and the inorganic stratiform compound in the coating solution is generally in the range of 0.1 wt% to 70 wt%, and 4 wt% to 15 wt%. It is preferable to be within the range, and within the range of 4 wt% to 10 wt% is more preferable from the viewpoint of productivity.

  In addition, as a method used for coating the above-described coating liquid, a gravure method such as a direct gravure method, a reverse gravure method, or a micro gravure method; a roll coating such as a two roll beat coat method or a bottom feed three reverse coat method Various conventionally known methods such as a method; a doctor knife method; a die coating method; a dip coating method; a bar coating method;

  The method for preparing the coating liquid and the method for blending the high hydrogen bonding resin, the inorganic layered compound, and the metal organic compound are not particularly limited. For example, as a method of blending the high hydrogen bond resin and the inorganic layered compound, from the viewpoint of uniformity during blending or easy operation, for example, (1) the high hydrogen bond resin is dissolved in a solvent. (2) A dispersion obtained by swelling or cleaving an inorganic layered compound with a dispersion medium is added to the high hydrogen bonding resin. A method of dissolving the high hydrogen bonding resin in the dispersion; (3) adding an inorganic layered compound to a solution obtained by dissolving the high hydrogen bonding resin in a solvent; A method of swelling or cleaving to obtain a dispersion is preferably used. Finally, the above solution or dispersion is removed.

  The metal organic compound is preferably added and mixed after mixing the high hydrogen bonding resin and the inorganic layered compound. However, the metal organic compound is added simultaneously with the high hydrogen bonding resin or the inorganic layered compound, or in advance, It may be used by dissolving or dispersing in the above solvent or dispersion medium. The metal organic compound is preferably added after being dissolved in alcohols. Moreover, it is preferable to make the said coating liquid acidic from the surface of the stability of the coating liquid containing the said metal organic compound, pH 5 or less is more preferable, and 3 or less is especially preferable. There is no particular lower limit to the pH of the coating solution, but it is usually 0.5 or more. By including the mixing step of the high hydrogen bonding resin and the metal organic compound, the barrier layer 3 in which the high hydrogen bonding resin is crosslinked can be obtained.

  Furthermore, as a suitable blending method of the high hydrogen bonding resin and the inorganic layered compound, in addition to the methods (1) to (3), for example, (4) the high hydrogen bonding resin and the inorganic layered compound, And a method of heat-kneading a metal organic compound.

  Among the methods described above, the methods (1) to (3) are more preferable because a large aspect ratio of the inorganic layered compound can be easily obtained. Moreover, when employ | adopting the method of said (1)-(3), it is preferable from a viewpoint of the dispersibility of an inorganic layered compound to process using a high voltage | pressure dispersion apparatus.

Examples of the high-pressure dispersing device include an ultrahigh-pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidics Corporation or a nanomizer manufactured by Nanomizer, and other examples include a Manton Gorin type high-pressure dispersing device such as a homogenizer manufactured by Izumi Food Machinery. . Resin in which the inorganic layered compound and the resin are uniformly dispersed by subjecting the composition mixture containing the inorganic layered compound and the resin to a high pressure dispersion treatment, in particular, a high pressure dispersion treatment under a pressure condition of 100 kgf / cm 2 or more. A coating liquid containing the composition and the resin composition can be obtained.

  As shown in FIG. 7, the high-pressure dispersion treatment in the present invention means that a high-shearing or high-pressure dispersion treatment is performed by causing a composition mixed solution mixed with particles to be dispersed or a dispersion medium to pass through and collide with a plurality of thin tubes 11. Dispersion treatment is performed under special conditions such as high pressure.

  In such a high-pressure dispersion treatment, the composition mixed solution is preferably passed through a narrow tube 11 having a tube diameter of 1 μm to 1,000 μm, and the maximum pressure condition is 100 kgf when passing through the thin tube 11. It is preferable to apply a pressure of not less than / cm 2, more preferable to apply a pressure of not less than 500 kgf / cm 2, and particularly preferable to apply a pressure of not less than 1,000 kgf / cm 2. Further, when the composition mixed solution passes through the narrow tube 11, the maximum arrival speed of the composition mixed solution preferably reaches 100 m / s or more, and the heat transfer rate is preferably 100 kcal / hr or more.

  The principle of the high-pressure treatment in the high-pressure dispersion treatment apparatus used for the high-pressure dispersion treatment will be schematically explained. First, the composition mixture is sucked by the pump 12 into the feeder tube 13 having a tube diameter larger than that of the thin tube 11. It is captured. Subsequently, a high pressure is applied to the composition mixture in the feeder tube 13 by the pump 12. At this time, the composition mixed solution in the feeder tube 13 is pushed out toward the thin tube 11 by a backflow prevention valve (not shown) provided in the feeder tube 13. Accordingly, the composition mixed solution is in a high pressure and high speed state in the thin tube 11, and the inorganic layered compound particles of the composition mixed solution collide with each other and the inner wall of the thin tube 11, so that the diameter of each inorganic layered compound particle is increased. And the thickness, particularly the thickness, is subdivided and more uniformly dispersed and taken out from the discharge pipe 14.

  For example, when the flow velocity at the point where the maximum velocity is instantaneously reached is 300 m / s with respect to the composition liquid mixture that is the processing sample in the thin tube 11 portion, for example, 1 / (3 X105) When passing in sec and the temperature of the composition mixture rises by 35 ° C., energy is transferred to the composition mixture by pressure loss. The heat transfer rate is 3.8 × 10 4 kcal / hr when the specific gravity of the composition mixture is 1 g / cm 3 specific heat 1 cal / g ° C.

  In the above methods (1) to (3), the solvent and the dispersion medium are removed from the coating film formed by coating the coating liquid on the substrate 1 or the anchor layer 2, and the resultant lamination is performed. Heat aging of the body at, for example, 110 ° C. or more and 220 ° C. or less is particularly preferable since the water resistance of the laminate, that is, the gas barrier property after the water resistance environment test can be improved. There is no limitation on the aging time, but it is necessary that the laminate reaches at least the set temperature.

  The heat source is not particularly limited, and various methods such as hot roll contact, heat medium contact (air, oil, etc.), infrared heating, microwave heating and the like can be applied.

  The aging treatment exhibits a particularly excellent effect in improving water resistance when the inorganic layered compound is a clay mineral having swelling properties.

What is necessary is just to set suitably the coating thickness with respect to the base material 1 or the anchor layer 2 of the said coating liquid according to the kind of the base material 1 or the anchor layer 2 which should be coated, the target barrier performance, a use, etc., especially Although not limited, the dry thickness (that is, the barrier layer 3) from the viewpoints of dryness and adhesion.
Is preferably set to be 1 μm or less, since the transparency of the resulting barrier layer 3 is remarkably enhanced. Although the minimum of the film thickness of the said barrier layer 3 is not specifically limited, In order to acquire effective gas barrier property on the relationship of the unit thickness a of the said inorganic layered compound, it is 1 nm or more. preferable.

  The base material 1 used in the film laminate is not particularly limited, and can be appropriately selected and set according to the application. Specific examples of the substrate 1 include general substrates such as resin (hereinafter referred to as substrate resin), paper, aluminum foil, wood, cloth, and nonwoven fabric.

  Examples of the base resin include polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene, and ethylene-acetic acid. Polyolefin resins such as vinyl copolymer, ethylene-methyl methacrylate copolymer and ionomer resin; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Nylon-6, Nylon-6,6, Metaxylenediamine -Amide resin such as adipic acid condensation polymer and polymethylmethacrylamide; Acrylic resin such as polymethyl methacrylate; Polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, poly Styrene-acrylonitrile resins such as rilonitrile; Hydrophobized cellulose resins such as cellulose triacetate and cellulose diacetate; Halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and Teflon; polyvinyl alcohol, ethylene-vinyl alcohol Hydrogen bonding resins such as copolymers and cellulose derivatives; engineering plastic resins such as polycarbonate resins, polysulfone resins, polyether sulfone resins, polyether ether ketone resins, polyphenylene oxide resins, polymethylene oxide resins, liquid crystal resins; etc. Is given.

  Among the base materials 1 using these base resins, films formed by biaxial stretching of base resins such as polypropylene, polyethylene terephthalate, nylon, etc .; biaxial stretching of base resins such as polypropylene, polyethylene terephthalate, nylon, etc. Thereafter, a film formed by coating polyvinylidene chloride called K coat; a film obtained by biaxially stretching a base resin such as polypropylene, polyethylene terephthalate, and nylon, and further depositing aluminum, silica, alumina, or the like. OPP (AS-OP) for strong antistatic use is suitable. The base material 1 using the base resin may be, for example, a film shape or a sheet shape.

  When the base material 1 is made of a base resin, the anchor layer 2 described above is preferably provided in order to improve the adhesion between the base material 1 and the barrier layer 3 made of the resin composition according to the present invention. The anchor layer 2 can be formed using various compounds (anchor coating agents) such as a polyethyleneimine compound, a titanium compound, a polybutadiene compound, and a urethane compound, but from the viewpoint of water resistance. Those obtained by reacting an isocyanate compound and an active hydrogen compound are preferred.

  Specific examples of the isocyanate compound used in the anchor layer 2 include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), and hexamethylene diisocyanate (HDI). 4,4′-methylenebiscyclohexyl isocyanate (H12MDI), isophorone diisocyanate (IPDI), and the like.

Specific examples of the active hydrogen compound include low molecular weight polyols such as ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and trimethylolpropane; polyethylene Polyether polyol such as glycol, polyoxypropylene glycol, ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol; poly-β-methyl-δ-valerolactone, polycaprolactone, polyester from diol / dibasic acid, etc. Polyester polyols; and the like.

  As the active hydrogen compound, a low molecular weight polyol is particularly preferable, and a diol is more preferable. Here, the diol is ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and the like, and as a dibasic acid, adipic acid, azelaic acid, sebacic acid, Isophthalic acid, terephthalic acid and the like. Other polyols include active hydrogen compounds such as castor oil, liquid polybutadiene, epoxy resin, polycarbonate diol, acrylic polyol, and neoprene.

  The mixing ratio of the isocyanate compound and the active hydrogen compound is not particularly limited, but the addition amount should be determined in consideration of the equivalent relationship between the isocyanate group and the active hydrogen group, for example, —OH group, —NH group, and —COOH group. Is preferred. For example, assuming that the number of moles of isocyanate groups is AN and the number of moles of active hydrogen groups in the active hydrogen compound is BN, the ratio R (R = AN / BN) of the number of moles of isocyanate groups to the number of moles of active hydrogen groups is From the viewpoint of adhesive strength, it is preferably 0.001 or more, and from the viewpoint of tackiness and blocking, it is preferably 10 or less. The mole ratio R is more preferably in the range of 0.01 or more and 1 or less. The number of moles of isocyanate group and active hydrogen group can be determined by 1H-NMR and 13C-NMR.

  The method for laminating the anchor layer 2 on the substrate 1 is not particularly limited, but an anchor coating agent prepared by dissolving the above-described anchor coating agent, for example, an anchor coating agent containing an isocyanate compound and an active hydrogen compound in a solvent is used. Preferred coating methods. Examples of the coating method include gravure methods such as direct gravure method, reverse gravure method, and micro gravure method; roll coating methods such as two roll beat coat method and bottom feed three reverse coat method; doctor knife method; die coating method A dip coating method; a bar coating method; or a coating method combining these;

  The solvent component in the anchor coating agent solution is mainly an organic solvent, for example, alcohols, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, esters, ketones, ethers, halogens. Hydrocarbons and mixed solvents thereof.

  Although the coating (application) thickness with respect to the base material 1 of the said anchor coating agent solution is not specifically limited, It should be set so that dry thickness (film thickness of the anchor layer 2) may exist in the range of 0.01 micrometer-5 micrometers. Is preferred. The greater the coating thickness, the better the heat seal strength, but the lower the gelboflex resistance. For this reason, the coating thickness is more preferably in the range of 0.03 μm to 2.0 μm, and particularly preferably in the range of 0.05 μm to 1.0 μm.

Moreover, you may laminate | stack the sealant layer 4 for improving a heat seal intensity | strength on the said laminated body on the said barrier layer 3, as shown in FIG. As the material of the sealant layer 4, polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene due to problems of desorption such as heat seal strength, food fragrance, and resin odor. -Hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate A copolymer, an ethylene-acrylic acid copolymer, a polyolefin resin such as an ionomer resin, a polyacrylonitrile resin (PAN), a polyester resin, or an ethylene-vinyl alcohol copolymer is preferably used.

  The method of laminating the sealant layer 4 on the barrier layer 3 is not particularly limited. For example, a method of dissolving a resin used for the sealant layer 4 in a solvent and coating the barrier layer 3; Preferred examples include a method of extrusion laminating on the barrier layer 3; a method of dry laminating the sealant layer 4 on the barrier layer 3, and the like. Further, the interface between the sealant layer 4 and the barrier layer 3 may be subjected to treatment such as corona treatment, ozone treatment, electron beam treatment, and application of an anchor coating agent.

  In addition, within the range not impairing the effects of the present invention, each of the various materials such as an ultraviolet absorber, a colorant, and an antioxidant is used for at least one of the base material 1, the anchor layer 2, the barrier layer 3, and the sealant layer 4. Additives may be mixed. Furthermore, the said laminated body may have the structure further provided with layers other than the layer mentioned above as needed.

  According to the present invention, a laminate having both a high level of water resistance such as boil resistance and retort resistance and a high level of gas barrier properties and a resin composition used as a barrier material for the laminate are preferably produced. be able to.

  The method for producing a film laminate according to the present invention can be suitably used, for example, as a method for producing a packaging material or the like in many fields such as the food field, cosmetic field, agricultural chemical field, and medical field.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these. Moreover, the various physical properties of the film laminated body obtained by the Example and the comparative example were measured as follows.

[Thickness measurement]
The thickness of 0.5 μm or more was measured with a commercially available digital thickness gauge (contact thickness gauge, trade name: ultra-high precision deci-micro head MH-15M, manufactured by Nippon Optical Co., Ltd.). On the other hand, when the thickness is less than 0.5 μm, the film thickness of the actual coating film is determined by gravimetric analysis (the weight measurement value of a certain area of film is divided by the area and further divided by the specific gravity of the resin composition) or IR method. A calibration curve of thickness and IR absorption was prepared and obtained from the calibration curve. Furthermore, in the case of measurement relating to the film thickness of the coating film of the resin composition of the present invention, the elemental analysis method (the ratio of the specific inorganic element analysis value of the laminate (derived from the barrier layer) and the specific element fraction of the inorganic layered compound alone) The method for determining the ratio between the barrier layer and the base film of the present invention).

(Particle size measurement)
Using a laser diffraction / scattering particle size distribution analyzer (LA910, manufactured by Horiba, Ltd.), the volume-based median diameter of particles considered to be inorganic layered compounds present in the resin matrix of the medium was measured as the particle size L. . The dispersion stock solution was measured with a paste cell at an optical path length of 50 μm, and the diluted solution of the dispersion was measured with a flow cell method at an optical path length of 4 mm.

[Aspect ratio calculation]
Using an X-ray diffractometer (XD-5A, manufactured by Shimadzu Corporation), diffraction measurement was performed by a powder method of the inorganic layered compound alone and the resin composition. Thereby, the unit thickness a of the inorganic layered compound was determined, and further, from the diffraction measurement of the resin composition, it was confirmed that there was a portion where the interplanar spacing d of the inorganic layered compound was widened. Using the particle diameter L obtained by the above method, the aspect ratio Z is set to Z = L / a
It was calculated by the following formula.

[Boil test]
A heat sealer (FUJIIMPULSET230: manufactured by FUJIIMPULSECO.LTD) was used between the sealant layers of the film laminate to heat seal at a temperature of 208 ° C., a time of 0.5 seconds, and a heat seal width of 10 mm to produce a 105 mm × 150 mm bag. . 50 cc of water was put into this bag and boiled at 95 ° C. for 60 minutes, and changes in the appearance such as end surface delamination, whitening, and bag deformation were visually confirmed.

[Retort test]
A heat sealer (FUJIIMPULSET230: manufactured by FUJIIMPULSECO.LTD) was used between the sealant layers of the film laminate to heat seal at a temperature of 208 ° C., a time of 0.5 seconds, and a heat seal width of 10 mm to produce a 105 mm × 150 mm bag. . 50 cc of water was put into this bag, and it was retorted at 120 ° C. for 30 minutes, and changes in the appearance such as end surface delamination, whitening, and bag deformation were visually confirmed.

(Oxygen permeability measurement)
Based on JISK7126, measurement was performed under conditions of 23 ° C. and 50% RH with an ultrasensitive oxygen permeability measuring device (OX-TRANML, manufactured by MOCON).

[Gelbo flex resistance test]
Based on ASTMF392, the obtained film laminate was aged in an environment of 23 ° C. and 50% RH for 24 hours, and then the above-mentioned film laminate held in a cylindrical shape was subjected to a gel bath flex tester with a thermostatic bath (tester industry ( Co., Ltd.), and the test was performed 100 times repeatedly after twisting 440 ° using the cylindrical central axis as the rotation axis.

[Example 1]
In a dispersion kettle (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.), 1,410 g of ion-exchanged water (specific electric conductivity 0.7 μs / cm or less) and polyvinyl alcohol (high hydrogen bonding resin) PVA117H; Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1,700) 80 g was charged, and the temperature was raised to 95 ° C. under low speed stirring (1,500 rpm, peripheral speed 4.10 m / min). Then, the solution was stirred for 1 hour to obtain a solution (B).

  On the other hand, after 92 g of 1-butanol and 277 g of isopropyl alcohol were mixed, 0.18 g of a nonionic surfactant (trade name: SH3746, manufactured by Toray Dow Corning Co., Ltd.) was further added and mixed liquid (A) Got. The nonionic surfactant is a polydimethylsiloxane-polyoxyethylene copolymer.

  Next, the temperature of the solution (B) in the dispersion kettle was lowered to 60 ° C. while stirring, and then the previously prepared mixed solution (A) was added to the solution (B). Furthermore, 40 g of natural montmorillonite (trade name: Kunipia F; manufactured by Kunimine Kogyo Co., Ltd.) as an inorganic layered compound was added as powder, and after confirming that the natural montmorillonite (Kunipia F) was almost precipitated in the liquid, High-speed stirring (3,100 rpm, peripheral speed 8.47 m / min) was performed for 90 minutes to obtain a mixed liquid (C) having a total solid content concentration of 6.3% by weight. At this time, the cleaved natural montmorillonite (Kunipia F) had a particle size of 560 nm, an a value obtained from powder X-ray diffraction of 1.2156 nm, and an aspect ratio (Z) of 461.

In the above mixed liquid (C), 5.3 g of titanium acetylacetonate (trade name: TC100, manufactured by Matsumoto Pharmaceutical Co., Ltd.) as a metal organic compound was stirred (1,500 rpm, peripheral speed 4.10 m). / Min), the coating solution (1) containing the resin composition and the solvent according to the present invention was prepared by gradually adding the mixture with hydrochloric acid so that the pH of the system was 3 or less.

  A biaxially stretched polypropylene (OPP) film (trade name: Pyrene P2102; manufactured by Toyobo Co., Ltd.) having a thickness of 20 μm is used as a base material (base film), and an anchor coating agent ( ADCOAT AD335AE / CAT10 = 15/1 (weight ratio): manufactured by Toyo Morton Co., Ltd.) using a test coater (manufactured by Yasui Seiki Co., Ltd.) by a microgravure coating method, a coating speed of 3 m / min, and a drying temperature of 80 Gravure coating was performed at ℃. The dry thickness of the coating layer (film thickness of the anchor layer) was 0.05 μm.

  Further, as the TOP coating solution, the above coating solution (1) is subjected to gravure coating at a coating speed of 3 m / min and a drying temperature of 100 ° C. by a microgravure coating method using a test coater (manufactured by Yasui Seiki). And the coating film (laminated body) in which the film (barrier layer) based on the said coating liquid (1) was formed on the base material through the anchor layer was obtained. The film thickness of the barrier layer, that is, the dry thickness of the coating layer formed by coating the coating liquid (1) on the anchor layer was 0.5 μm.

  Next, on the barrier layer of the coated film, linear polyethylene ((LLDPE), product name: KF101, Seki, which has been surface corona-treated using a urethane-based adhesive (product name: Eunoflex J3, manufactured by Sanyo Chemical Industries). Film Co., Ltd., thickness 40 μm) was dry laminated as an outer layer (sealant layer) to obtain a film laminate as a laminate according to the present invention. The film laminate was subjected to a boil test by the method described above. As a result, there was no change in appearance before and after boiling, and the appearance was good.

[Comparative Example 1]
In Example 1, a melamine-formalin-based crosslinking agent (trade name: Sumitex Resin M-3, manufactured by Sumitomo Chemical Co., Ltd.) was used instead of the metal organic compound in the same manner as in Example 1 for comparison. A film laminate was obtained. The film laminate was subjected to a boil test in the same manner as in Example 1. As a result, delamination (film lifting) was observed on the end face of the film laminate after boiling, and the appearance was poor.

[Example 2]
In a dispersion kettle (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.), 1,860 g of ion exchange water (specific electric conductivity 0.7 μs / cm or less) and polyvinyl alcohol (high hydrogen bonding resin) PVA117H; manufactured by Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1,700) 128, and heated to 95 ° C. under low speed stirring (1,500 rpm, peripheral speed 4.10 m / min) Then, the solution was stirred for 1 hour to obtain a solution (D).

  On the other hand, 125 g of 1-butanol and 375 g of isopropyl alcohol were mixed, and then 0.25 g of a nonionic surfactant (trade name: SH3746, manufactured by Toray Dow Corning Co., Ltd.) was added and mixed liquid (E) Got. The nonionic surfactant is a polydimethylsiloxane-polyoxyethylene copolymer.

  Next, the temperature of the solution (D) in the dispersion kettle is lowered to 60 ° C. with stirring, and then the previously prepared mixed solution (E) is added to the solution (D) to add a mixed solution (F )

Next, 1,960 g of the mixed liquid (F) was charged into a stirring emulsifier (trade name: vacuum emulsifier PVQ-3UN, manufactured by Mizuho Industry Co., Ltd.), and the high hydrogen bonding resin, the inorganic layered compound, The natural montmorillonite (trade name: Kunipia F; manufactured by Kunimine Kogyo Co., Ltd.) as an inorganic layered compound was added in an amount of 50 g in a powder form so that the weight ratio was 2: 1. continue,
After confirming that the natural montmorillonite (Kunipia F) was almost precipitated in the liquid, it was stirred at 600 mmHg and 5,000 rpm for 10 minutes at high speed to obtain a mixed liquid (G).

  Next, by passing 2,000 g of the above mixed solution (G) through a high-pressure dispersion device (trade name: ultrahigh-pressure homogenizer M110-E / H, manufactured by Microfluidics Corporation), the mixture is processed once at 1,750 kgf / cm 2. A uniform dispersion (G ′) having good dispersibility was obtained. The solid content concentration of the dispersion (G ′) was 7.5% by weight. A dispersion composed of PVA and montmorillonite was cast into a film and subjected to X-ray analysis, and the surface spacing d of the natural montmorillonite (Kunipia F) swollen and cleaved was measured. The natural montmorillonite (Kunipia F) was sufficiently cleaved. The aspect ratio of the natural montmorillonite (Kunipia F) at this time was 450 or more. In the above dispersion (G ′), 5.33 g of titanium acetylacetonate (trade name: TC100, manufactured by Matsumoto Pharmaceutical Co., Ltd.) as a metal organic compound was stirred at a low speed (1,500 rpm, peripheral speed 4. 10 m / min), a coating liquid (2) containing the resin composition and the solvent according to the present invention was prepared by gradually adding while adjusting with hydrochloric acid so that the pH of the system was 3 or less.

  A biaxially stretched polyethylene terephthalate (OPET) film (trade name: Espet T4102; manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm is used as a base material (base film), and an anchor coat is formed on the base material. Coating agent (Adcoat AD503 / CAT10 = 15/1 (weight ratio): manufactured by Toyo Morton Co., Ltd.) using a test coater (manufactured by Yasui Seiki Co., Ltd.) by a microgravure coating method, drying rate of 3 m / min. Gravure coating was performed at a temperature of 80 ° C. The dry thickness of the coating layer (film thickness of the anchor layer) was 0.05 μm.

  Further, as the TOP coating solution, the above coating solution (2) is subjected to gravure coating at a coating speed of 3 m / min and a drying temperature of 100 ° C. by a microgravure coating method using a test coater (manufactured by Yasui Seiki). And the coating film (laminated body) in which the film (barrier layer) based on the said coating liquid (2) was formed on the base material through the anchor layer was obtained. The film thickness of the barrier layer, that is, the dry thickness of the coating layer formed by coating the coating liquid (2) on the anchor layer was 0.5 μm.

  Next, on the barrier layer of the coating film, an anchor coat agent (ADCOAT AD503 / CAT10 = 15/1 (weight ratio): manufactured by Toyo Morton Co., Ltd.) was used as an adhesive for retort treatment. CPP (trade name: P1156, manufactured by Toyobo Co., Ltd .: thickness 50 μm) was dry laminated as an outer layer (sealant layer) to obtain a film laminate as a laminate according to the present invention. The film laminate was subjected to a retort test by the method described above. As a result, the appearance was not changed before and after the retort, and the appearance was good.

[Comparative Example 2]
In Example 2, a melamine-formalin crosslinking agent (trade name: Sumitex Resin M-3, manufactured by Sumitomo Chemical Co., Ltd.) was used in place of the metal organic compound in the same manner as in Example 2 for comparison. A film laminate was obtained. A retort test was performed on the film laminate in the same manner as in Example 1. As a result, delamination (film lift) was observed on the end face of the film laminate after retorting, and the appearance was poor.

Example 3
In a dispersion kettle (trade name: Despa MH-L, manufactured by Asada Tekko Co., Ltd.), 1,410 g of ion-exchanged water (specific electric conductivity 0.7 μs / cm or less) and polyvinyl alcohol (high hydrogen bonding resin) PVA117H; Kuraray Co., Ltd., saponification degree: 99.6%, polymerization degree 1,700) 50 g were charged, and the temperature was raised to 95 ° C. under low speed stirring (1,500 rpm, peripheral speed 4.10 m / min). And stirred for 1 hour to dissolve.

  Next, after the temperature in the dispersion kettle is lowered to 60 ° C. while stirring, 15 g of 1-butanol is dropped into the solution, and the final 1-butanol fraction is 1% by weight. It was made to become. Then, 25 g of natural montmorillonite (trade name: Kunipia F; manufactured by Kunimine Kogyo Co., Ltd.) as an inorganic layered compound was added in powder form, and after confirming that the natural montmorillonite (Kunipia F) was almost precipitated in the liquid, High-speed stirring (3,100 rpm, peripheral speed 8.47 m / min) was performed for 90 minutes to obtain a mixed liquid (H) having a total solid content concentration of 5 wt%. At this time, the cleaved natural montmorillonite (Kunipia F) had a particle size of 560 nm, an a value obtained from powder X-ray diffraction of 1.2156 nm, and an aspect ratio (Z) of 461.

  On the other hand, after 92 g of 1-butanol and 277 g of isopropyl alcohol were mixed, 0.18 g of a nonionic surfactant (trade name: SH3746, manufactured by Toray Dow Corning Co., Ltd.) was further added and mixed liquid (A) Got. The nonionic surfactant is a polydimethylsiloxane-polyoxyethylene copolymer.

  Next, the mixed solution (A) is gradually added to the mixed solution (H) under low-speed stirring (1,500 rpm, peripheral speed 4.10 m / min), and titanium acetylacetate as a metal organic compound is further added. 3.3 g of Naruto (trade name: TC100, manufactured by Matsumoto Pharmaceutical Co., Ltd.) is adjusted with hydrochloric acid so that the pH of the system is 3 or less under low speed stirring (1,500 rpm, peripheral speed 4.10 m / min). The coating liquid (3) containing the resin composition concerning this invention and a solvent was prepared by adding gradually, adding.

  A biaxially stretched polypropylene (OPP) film (trade name: Pyrene P2102; manufactured by Toyobo Co., Ltd.) having a thickness of 20 μm is used as a base material (base film), and an anchor coating agent ( Adcoat AD335 / CAT10 = 15/1 (weight ratio: manufactured by Toyo Morton Co., Ltd.) using a test coater (manufactured by Yasui Seiki Co., Ltd.) by a microgravure coating method, a coating speed of 3 m / min, and a drying temperature of 80 Gravure coating was performed at ℃. The dry thickness of the coating layer (film thickness of the anchor layer) was 0.15 μm.

  Further, as the TOP coating liquid, the above-mentioned coating liquid (3) is subjected to gravure coating at a coating speed of 3 m / min and a drying temperature of 100 ° C. by a microgravure coating method using a test coater (manufactured by Yasui Seiki). And the coating film (laminated body) in which the film (barrier layer) based on the said coating liquid (3) was formed on the base material through the anchor layer was obtained. The film thickness of the barrier layer, that is, the dry thickness of the coating layer formed by coating the coating liquid (3) on the anchor layer was 0.5 μm. The coated film before performing the above-described gelboflex resistance test (described as 0 times in the table) and the coated film after performing the gelboflex resistance test 100 times on the coated film. And oxygen permeability was measured. The results are shown in Table 1.

It is a schematic sectional drawing which shows an example of the laminated body manufactured using this invention. It is a schematic sectional drawing which shows the barrier layer of the said laminated body. 4 is an X-ray diffraction graph of an inorganic layered compound for calculating “unit thickness a” of the inorganic layered compound in the laminate. 4 is an X-ray diffraction graph of an inorganic layered compound for calculating “plane spacing d” of the inorganic layered compound in the laminate. In the graph of FIG. 4, when calculating the “plane spacing d” of the inorganic layered compound when the peak corresponding to the “plane spacing d” overlaps with the halo (or background) and is difficult to detect, It is a line diffraction graph. It is a schematic sectional drawing which shows the other example of the laminated body manufactured using this invention. It is explanatory drawing which shows typically the high-speed dispersion | distribution process used in one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 2 Anchor layer 3 Barrier layer 4 Sealant layer 11 Narrow pipe 12 Pump 13 Feeder pipe 14 Discharge pipe 31 Unit crystal layer 32 Resin

Claims (9)

At least one kind of high hydrogen bonding resin selected from polyvinyl alcohol and ethylene-vinyl alcohol copolymer , an inorganic layered compound, a metal organic compound capable of crosslinking reaction with the high hydrogen bonding resin, water and / or A step of preparing a mixed solution containing alcohols at a pH of 5 or less, and a step of removing water and / or alcohols from the mixed solution ,
The metal organic compound is at least one compound selected from the group consisting of titanium organic compounds, zirconium organic compounds, aluminum organic compounds, and silicon organic compounds, and the metal organic compound is a chelate compound. A method for producing a resin composition.   The method for producing a resin composition according to claim 1, wherein the mixed solution is adjusted to a pH of 3 or less. The method for producing a resin composition according to claim 1 or 2 , wherein a ratio of the crosslinkable functional group in the high hydrogen bondable resin is in a range of 20 mol% to 60 mol%. The ratio of the number of moles of crosslinked product group metal organic compound to the number of moles of the crosslinkable functional group in the high-hydrogen bonding resin, according to claim 1 to 3, characterized in that in the range of 0.001 to 10 The manufacturing method of the resin composition of any one. The method for producing a resin composition according to any one of claims 1 to 4 , wherein an aspect ratio of the inorganic layered compound is in a range of 50 to 5,000. The method for producing a resin composition according to any one of claims 1 to 5 , wherein the inorganic layered compound is a compound that swells or cleaves in a solvent. The weight ratio of the inorganic laminar compound on the high hydrogen bond resin, the resin composition according to any one of claim 1 to 6, characterized in that in the range of 1 / 20-10 / 1 Production method. A method for producing a laminate comprising a substrate and a layer made of a resin composition formed on the substrate,
At least one kind of high hydrogen bonding resin selected from polyvinyl alcohol and ethylene-vinyl alcohol copolymer , an inorganic layered compound, a metal organic compound capable of crosslinking reaction with the high hydrogen bonding resin, water and / or A step of preparing a mixed solution containing alcohols at a pH of 5 or less,
A step of coating the mixed solution on at least one surface of the substrate, and forming a layer made of a resin composition by removing water and / or alcohols from the mixed solution coated on the substrate Including the steps of :
The metal organic compound is at least one compound selected from the group consisting of titanium organic compounds, zirconium organic compounds, aluminum organic compounds, and silicon organic compounds, and the metal organic compound is a chelate compound. A method for manufacturing a laminate. The method for producing a laminate according to claim 8 , wherein the thickness of the layer made of the resin composition is in the range of 1 nm to 10 µm.

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