JP4903370B2 - Gas barrier laminate - Google Patents

Description

  The present invention relates to a gas barrier film in which a gas barrier layer is laminated on a film.

  In the field of food and medicine packaging, packaging materials having excellent gas barrier properties such as oxygen gas barrier properties are used for the purpose of preventing quality deterioration of contents. As such a gas barrier film, a film in which polyvinylidene chloride is laminated, a film using a polyvinyl alcohol resin, and the like are known. In particular, a film in which the above-mentioned polyvinylidene chloride is laminated is widely used for food packaging.

  However, the film in which the polyvinylidene chloride is laminated tends to be refrained from use due to environmental problems such as dioxin in recent years. Moreover, since the film using the said polyvinyl alcohol-type resin contains a hydroxyl group, it has the problem that the gas barrier property under high humidity falls.

  On the other hand, as a method for improving the gas barrier property under high humidity, an example in which a composition comprising a composite polymer of an inorganic substance obtained by sol-gel polycondensation and a water-soluble resin is applied to a film, Patent Documents 1 and 2 disclose this.

  However, in the gas barrier composition described in these documents, when the composition is applied to a film, the gas barrier property under high humidity is not always sufficient when the heat treatment conditions are short-time drying and low-temperature drying. End up. For this reason, in order to actually perform mass production, it took too much time and energy required for heating, and it was not suitable for production of a gas barrier composition.

  Therefore, in Patent Document 3, an anchor layer containing a nitrogen-containing compound is first formed on the surface of a support such as a film having a polar group in order to improve gas barrier properties under high humidity and improve adhesion to a substrate. There is disclosed a gas barrier laminate in which a layer containing a reaction product of a hydrolysis condensate of a metal alkoxide and a hydrogen bonding resin and a flat pigment is provided thereon.

  Patent Document 4 discloses a composite polymer of an inorganic substance obtained by sol-gel polycondensation and a water-soluble resin, and a water dispersibility in order to achieve both a water vapor barrier property and an oxygen barrier property with small humidity dependency. A laminated film in which a layer containing a layered silicate is laminated is disclosed.

Japanese Patent No. 2556940 Japanese Patent No. 2880654 JP 2001-260269 A JP 2001-9974 A

  However, the gas barrier laminate disclosed in Patent Document 3 still has insufficient oxygen barrier properties under high humidity. Further, although the gas barrier layer contains a flat pigment providing a curved path effect, the water vapor barrier property largely depends on the film as the base material, and as a result, neither the oxygen barrier property nor the water vapor barrier property is sufficient.

  In addition, the laminated film disclosed in Patent Document 4 does not limit the order of lamination, and when the composite polymer layer is applied, the layer containing the lower water-dispersible layered silicate is dissolved in the upper composite polymer layer. Oxygen barrier properties may be reduced, and continuous coating to speed up the work may cause the composite polymer layer and the layer containing the water-dispersible layered silicate to react and cause cracks. It was. Furthermore, since the haze (cloudiness value) of the obtained barrier layer was increased, the transparency was insufficient.

  Therefore, an object of the present invention is to provide a gas barrier laminate having a small humidity dependency and excellent in water vapor barrier properties, oxygen barrier properties and transparency.

  The present invention comprises (A layer) a layer containing an organic base having a number average molecular weight of 5,000 to 1,000,000, (B layer) a first water-soluble polymer, on at least one surface of a substrate made of a polymer resin film, A layer containing a metal alkoxide hydrolyzate and / or a condensate thereof, an alkali metal salt and / or an alkaline earth metal salt, (C layer) a swellable synthetic fluoromica-based mineral and a second water-soluble polymer The above-mentioned problem was solved by the gas barrier laminate in which the layers to be formed were sequentially applied and formed from the substrate side.

  Even if a highly reactive first water-soluble polymer and a condensate of a metal alkoxide hydrolyzate are applied to the B layer by using a polymer organic base for the A layer in contact with the film, In order to cause a reaction with the organic base of the A layer, the swellable synthetic fluoromica-based mineral coated as the C layer and the second water-soluble polymer suppress the abrupt reaction that occurs between the B layer. , A decrease in gas barrier properties due to the reaction can be suppressed. Thereby, an oxygen barrier property and a water vapor barrier property are maintained, and a highly transparent gas barrier laminate can be obtained.

  The present invention will be described in detail below. In the present invention, as shown in FIG. 1, a gas barrier laminate in which an A layer 12, a B layer 13 and a C layer 14 are sequentially applied and formed on at least one surface of a substrate 11 made of a polymer resin film from the substrate 11 side. Is the body.

  The polymer resin film only needs to have strength as the base material 11 regardless of the presence or absence of gas permeability. Polyamide film made of polyamide resin such as nylon 6, nylon 66, nylon 46 or the like, polyethylene Polymer film comprising at least one resin selected from polyester films made of polyester resins such as terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyolefin films made of polyolefin resins such as polypropylene and polyethylene, and mixed resins thereof. Examples thereof include a resin film or a laminate of these polymer resin films. This polymer resin film may be an unstretched film or a stretched film. Among these, a polyolefin-based film is particularly desirable, and a biaxially stretched polypropylene film is most desirable.

  In addition, in order to improve adhesiveness, you may perform the well-known corona discharge process, a flame process, an ultraviolet-ray process, an anchor coating agent application | coating process, etc. on the surface of the said polymer resin film.

  The A layer 12 is obtained by coating and forming a coating agent containing an organic base having a number average molecular weight of 5,000 to 1,000,000. The organic base reacts in advance with the B layer 13 stacked on the A layer 12 to suppress the reaction that occurs when the C layer 14 is stacked on the B layer 13. Thus, it is possible to suppress a decrease in gas barrier properties of the obtained gas barrier laminate. If this number average molecular weight is less than 5,000 or exceeds 1,000,000, the film-forming property and the coating property are not sufficient, so that it is difficult to obtain a smooth coating film, and this suppression effect may not be sufficiently exhibited. . Examples of the organic base include polyethyleneimine. When the organic base is polyethyleneimine, the number average molecular weight is more preferably 10,000 to 200,000.

The coating amount after drying of the layer A 12 is preferably a 0.005~0.1g / m ^2, more desirably When it is 0.02~0.06g / m ^2. If it is less than 0.005 g / m ² , the coating amount is too small, so that it is difficult to uniformly apply to the base material 11. On the other hand, if it exceeds 0.1 g / m ² , the layer B When forming 13, the organic base constituting the A layer 12 is dissolved in a large amount and gelation occurs, and the coated surface becomes cloudy and gas barrier properties cannot be obtained.

  The B layer 13 includes a coating agent containing the first water-soluble polymer, a metal alkoxide hydrolyzate and / or a condensate thereof, and an alkali metal salt and / or an alkaline earth metal salt. It is obtained by coating on the layer 12. This is because the B layer 13 includes the case where the first water-soluble polymer and the metal alkoxide hydrolyzate are contained, and the condensate of the first water-soluble polymer and the metal alkoxide. Meaning either the case or both.

  The water-soluble polymer constituting the first water-soluble polymer refers to a water-soluble polymer substance, and as a functional group, a hydroxyl group, an amino group, an acid amide group, a thiol group, a carboxyl group, a sulfonic acid group, Those having a phosphate group and the like can be mentioned. Examples of the water-soluble polymer include polyvinyl alcohol polymer, ethylene-vinyl alcohol copolymer, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan, and polyacryl. Derivatives such as acid, sodium polyacrylate, polybenzene sulfonic acid, sodium polybenzene sulfonate, polyethyleneimine, polyallylamine, polyacrylamide, gelatin, polyvinyl pyrrolidone, and their copolymers and modified products are exemplified. At least one of these may be used, and only one may be used, or two or more may be mixed and used. Among these, as the first water-soluble polymer, a water-soluble polymer containing a nitrogen-containing functional group in the polymer is preferable, and polyacrylamide is particularly preferable. By using polyacrylamide, the adhesiveness with the A layer 12 is improved, and better performance can be obtained.

  Although the weight average molecular weight of the said water-soluble polymer is not specifically limited, 500-20 million are preferable and 5000-15 million are more preferable. If it is less than 500, the gas barrier property of the finally obtained coating agent tends to be poor. On the other hand, when it is larger than 20 million, the viscosity of the aqueous solution tends to be too high.

  The metal alkoxide used in the above metal alkoxide hydrolyzate or metal alkoxide condensate refers to a compound represented by the following chemical formula (1).

R ¹ _m M (OR ² ) _n (1)
In the above formula (1), M is a metal element, and is preferably at least one metal element selected from silicon, titanium, zirconium, aluminum and the like. R ¹ is preferably a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and R ² is preferably an alkyl group having 1 to 4 carbon atoms. R ¹ and R ² may be the same or different. M is an integer of 0 or more, n is an integer of 1 or more, and m + n corresponds to the valence of the metal element M.

  Since the said metal alkoxide uses the hydrolyzate and / or its condensate, if it hydrolyzes and condenses by the effect | action of a catalyst, it will not specifically limit. Examples of the metal alkoxide include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, n-propyltrimethoxysilane, and n-propyl. Triethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, trimethylmethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n- Alkoxysilane compounds such as butoxysilane, tetra-tert-butoxysilane, tetra-sec-butoxysilane, tetramethoxy titanium, tetraethoxy titanium, teto Titanium alkoxide compounds such as isopropoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-tert-butoxy titanium, tetra-sec-butoxy titanium, tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, Zirconium alkoxide compounds such as tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, tetra-tert-butoxyzirconium, tetra-sec-butoxyzirconium, trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, tri-n- Propoxyaluminum, tri-n-butoxyaluminum, tri-tert-butoxyaluminum, tri-sec-butoxyaluminum Aluminum alkoxide compounds such as beam and the like. Of these, alkoxysilane compounds are most preferred. At least one of these may be used, and only one may be used, or two or more may be used in combination.

  The amount of the metal alkoxide added is preferably 80 to 1000 parts by weight, preferably 140 to 800 parts by weight, and preferably 160 to 500 parts by weight in terms of the corresponding metal oxide with respect to 100 parts by weight of the water-soluble polymer. More preferable. When the amount is less than 80 parts by weight, sufficient gas barrier properties and hot water resistance tend to be hardly exhibited. On the other hand, when the amount is more than 1000 parts by weight, the brittleness of the resulting gas barrier coating layer made of the gas barrier coating agent increases, and the performance tends to deteriorate.

  In order to perform the hydrolysis reaction or condensation reaction for obtaining the metal alkoxide hydrolyzate and condensate from the metal alkoxide, water, a catalyst for performing the hydrolysis reaction or the condensation reaction, and an organic solvent are used. Furthermore, in order to further improve the binding property between the water-soluble polymer and the hydrolyzate of metal alkoxide and / or its condensate, it has an organic functional group and a hydrolyzable group represented by the following general formula (2). A silane compound (hereinafter referred to as “specific silane compound”) may be added.

R ³ _p Si (OR ⁴ ) _q (2)

In the above formula (2), R ³ contains at least one of at least one of a vinyl group, a mercapto group, an amino group, an epoxy group, and an isocyanate group, which are organic functional groups capable of reacting with the water-soluble polymer. It is desirable that it contains an epoxy group, and it is more desirable. R ⁴ is preferably an alkyl group having 1 to ⁴ carbon atoms. Note that p and q are integers of 1 or more, and the equation p + q = 4 holds.

  Further, when the first water-soluble polymer and the metal alkoxide hydrolyzate and / or the condensate thereof are contained in the B layer 13, they may be contained as compounds obtained by these polycondensation reactions. .

  The hydrolysis reaction of the metal alkoxide and the condensation reaction thereof, or the polycondensation reaction between the reaction product and the first water-soluble polymer are promoted under both acidic conditions and basic conditions. The gas barrier coating agent may be added with a generally known catalyst for causing the hydrolysis reaction and polycondensation reaction as long as the gas barrier property does not deteriorate.

  Examples of the acid catalyst that serves as the catalyst under acidic conditions include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as phosphoric acid, acetic acid, citric acid, oxalic acid, and p-toluenesulfonic acid. Examples of the catalyst under basic conditions include inorganic bases such as sodium hydroxide, calcium hydroxide and magnesium hydroxide, ammonia, pyridine, triethylamine, N, N-dimethylbenzylamine, tripropylamine, and tributylamine. And organic bases such as tripentylamine. Among these, acidic conditions are preferable, and hydrochloric acid is particularly preferable. Furthermore, these catalysts may use only 1 type and may use 2 or more types together. Furthermore, the catalyst may be divided into a catalyst for the hydrolysis reaction and a catalyst for the condensation reaction.

  The addition amount of said catalyst is not specifically limited, Arbitrary amounts can be added within the range in which a solution does not gel.

  The organic solvent used when performing the hydrolysis reaction or the condensation reaction is not particularly limited as long as it dissolves the metal alkoxide and is compatible with the aqueous solution of the first water-soluble polymer. Lower alcohols such as methanol, ethanol, propanol and butanol are preferred. These may use only 1 type and may use 2 or more types together.

  Although the addition amount of the organic solvent is not particularly limited, it is preferably 2 to 500 parts by weight and preferably 10 to 300 parts by weight with respect to 100 parts by weight of the metal alkoxide. When the amount is less than 2 parts by weight, the metal alkoxide is not sufficiently dissolved, and the hydrolysis reaction is suppressed. On the other hand, when the amount is more than 500 parts by weight, the solubility of the first water-soluble polymer tends to decrease.

  Among the alkali metal salts and alkaline earth metal salts contained in the B layer 13, examples of the alkali metal salt include salts containing lithium, sodium, potassium, rubidium, cesium, and the like. Examples of the alkaline earth metal salt include salts containing magnesium, calcium, strontium, barium and the like. These may be either a salt derived from a strong acid or a salt derived from a weak acid. That is, examples of the salt derived from the strong acid include sodium chloride and potassium chloride, which are alkali metal salts of hydrochloric acid, magnesium chloride and calcium chloride, which are alkaline earth metal salts, and sodium sulfate and potassium sulfate, which are alkali metal salts of sulfuric acid. And magnesium sulfate and calcium sulfate which are alkaline earth metal salts of sulfuric acid, sodium nitrate and potassium nitrate which are alkali metal salts of nitric acid, and magnesium nitrate and calcium nitrate which are alkaline earth metal salts of nitric acid. Examples of the salt derived from the weak acid include sodium carbonate and potassium carbonate which are alkali metal salts of carbonic acid, magnesium carbonate and calcium carbonate which are alkaline earth metal salts of carbonic acid, and phosphoric acid which is an alkali metal salt of phosphoric acid. Examples of the alkaline earth metal salt of sodium, potassium phosphate, and phosphoric acid include magnesium phosphate and calcium phosphate, and alkali metal salts and alkaline earth metal salts of carboxylic acids such as acetic acid, propionic acid, and butanoic acid. Further, it may be a composite salt containing a plurality of alkali metal elements or alkaline earth metal elements. Furthermore, the alkali metal salt and the alkaline earth metal salt may be either artificial or naturally derived. Among these salts, alkali metal salts are preferable, and sodium salts or potassium salts are more preferable. Most preferred is sodium or potassium hydrochloride, i.e. sodium chloride or potassium chloride.

  The addition amount of the alkali metal salt and / or alkaline earth metal salt should be 0.05 to 5 mol% with respect to the metal element contained in the hydrolyzate of metal alkoxide and / or the condensate thereof. 0.1 to 4 mol% is desirable, and 0.2 to 3 mol% is more desirable. If this addition amount is less than 0.05 mol% or exceeds 5 mol%, the gas barrier property of the resulting gas barrier laminate may not be sufficient under high humidity.

  A method for preparing the coating agent for forming the B layer 13 will be described. The coating agent for forming the B layer 13 is prepared by mixing the various raw materials described above. At this time, the metal alkoxide may be hydrolyzed in advance.

  The mixing order of various raw materials of the coating agent forming the B layer 13 is not particularly limited, but an example in the case of directly adding a metal alkoxide is shown below. First, the lower alcohol and the acid catalyst are added to the aqueous solution of the first water-soluble polymer, and then the metal alkoxide and, if necessary, the specific silane compound are mixed to completely dissolve the solution. Then, an alkali metal salt and / or an alkaline earth metal salt may be added, and an additive such as a crosslinking agent may be added as necessary. The coating agent thus prepared is applied onto the surface of the A layer 12 opposite to the polymer resin film to form the B layer 13.

  The C layer 14 is a surface formed on the surface of the B layer 13 opposite to the A layer 12, and is composed of a swellable synthetic fluoromica mineral and a second water-soluble polymer. Among these, the second water-soluble polymer is composed of a water-soluble polymer constituting the first water-soluble polymer, and is preferably a polyvinyl alcohol polymer. Further, in order to further improve the gas barrier property under high humidity of the obtained gas barrier laminate, a polyvinyl alcohol polymer having a saponification degree of 90 mol% or more is preferable, and a polyvinyl alcohol polymer having 97 mol% or more is preferable. More preferred.

  Moreover, when using the said polyvinyl alcohol-type polymer, 100-5000 are preferable and 200-2000 are more preferable. If it is less than 100, the gas barrier property tends to be lowered, and if it is more than 5000, the viscosity of the coating solution is large and coating becomes difficult, which is not preferable.

  Furthermore, among the polyvinyl alcohol polymers, modified polyvinyl alcohol containing a hydrophobic group in the molecule is preferable because it exhibits high gas barrier properties under high humidity.

The above-mentioned swellable synthetic fluoromica-based mineral is an artificial mineral that satisfies the following formula (3). This tetrahedron is based on a SiO ₄ regular tetrahedron and is connected to a hexagonal mesh plate. Ions having octahedral coordination are ion-bonded between the upper and lower two plates to form a sandwich layer. Between the sandwich layer and the sandwich layer, an alkali metal or alkaline earth metal ion called an interlayer ion is coordinated by a very weak ionic bond.

X _0.33 to _1.0 Y ₂ to ₃ Z ₄ O ₁₀ F ₂ (3)

Here, X represents a cation with a coordination number of 12, Y represents a cation with a coordination number of 6, and Z represents a cation with a coordination number of 4. Specifically, X is one or more cations selected from Na ⁺ , K ⁺ , Ca ²⁺ , Ba ²⁺ , Rb ²⁺ , Sr ²⁺ , and Li ⁺ , and Y is One or more cations selected from Mg ²⁺ , Fe ²⁺ , Ni ²⁺ , Mn ²⁺ , Al ³⁺ , Fe ³⁺ , Li ⁺ , and Z is Si ⁴⁺ , Ge ⁴ One or more cations selected from ⁺ , Al ³⁺ , Fe ³⁺ and B ³⁺ .

In addition, depending on the number of Si contained in Z in the general formula (3), the above-mentioned swellable synthetic fluoromica minerals include disilicon type (disilisic type), trisilicon type (trisilicic type), and tetrasilicon type. There are (Tetralithic) types. Among these, tetrasilicon mica, which is of the tetrasilicon type and has the above X, that is, the interlayer ion species is Na ⁺ or Li ⁺ and the interlayer ion compensates for the charge balance in the crystal structure, has swelling properties. It is particularly preferable.

Specific examples of this swellable synthetic fluoromica-based mineral include sodium tetralithic mica [NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ ], sodium or lithium teniolite [(Na or Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ ], sodium or lithium hectorite [(Na or Li) _0.33 Mg _2.67 Li _0.33 (Si ₄ O ₁₀ ) F ₂ ] and the like. Among these, sodium tetralithic mica, sodium or lithium hector A light is used more suitably. These can be used alone or in combination of two or more. In addition, about each composition formula about the specific example of said swellable synthetic fluorine mica system mineral, the ideal composition is shown and it is not necessary to correspond exactly | strictly.

  The swellable synthetic fluorinated mica-based mineral is used as a raw material so as to have the chemical composition of the desired swellable fluorinated mica, silica, magnesia, magnesium fluoride, sodium silicofluoride, sodium fluoride, lithium fluoride, sodium carbonate. And lithium carbonate and the like, and after melting this at 1400 to 1500 ° C. in an internal electric furnace, the melt is discharged into the mold and cooled, so that the fluoromica mineral is crystal-grown in the mold, so-called It can be synthesized by a known method called a melting method.

  As another synthesis method, as disclosed in JP-A-2-149415, talc is used as a starting material, alkali metal ions are intercalated therein, and the swellable fluorine mica before the above treatment is used. The method of obtaining a mineral can be mentioned. In this method, an alkali silicofluoride or alkali fluoride is mixed with talc and heat-treated at about 700 to 1200 ° C. for a short time in a magnetic crucible to obtain a swellable synthetic fluoromica-based mineral before the above treatment.

  When the swellable synthetic fluorinated mica-based mineral before the above treatment is produced by the above melting method, a by-product (hereinafter simply referred to as “by-product”) that is not a swellable synthetic fluorinated mica-based mineral or not. Reaction raw materials are mixed. Further, at the time of production by this melting method, large and good crystals are obtained, but cristobalite or the like is mainly mixed as the by-product.

  When the swellable synthetic fluoromica mineral before the treatment is produced by the intercalation method, a relatively high purity can be obtained with less by-products and unreacted raw materials compared to the melting method. However, by-products (hereinafter simply referred to as “by-products”) similar to the swellable synthetic fluoromica-based mineral before the treatment are mixed. An example of this by-product is a synthetic fluoromica-based mineral composed of a phase having poor swellability.

  The swellable synthetic fluoromica-based mineral produced as described above includes by-products such as cristobalite, unreacted raw materials, by-products such as the above non-swellable synthetic fluoromica-based minerals (hereinafter referred to as “impurities”). Containing). These impurities are contained in the resulting swellable synthetic fluoromica-based mineral by several volume% to several tens volume%. When the C-layer 14 is formed by mixing the swellable synthetic fluoromica-based mineral containing such impurities and the second water-soluble polymer, the resulting gas barrier laminate has a haze. (Haze value) becomes large, and it becomes difficult to obtain sufficient transparency, and smoothness and gas barrier properties, particularly gas barrier properties under high humidity tend to be insufficient. Therefore, it is desirable to use the purified swellable synthetic fluorinated mica-based mineral obtained by performing a purification treatment to remove the impurities from the swellable synthetic fluorinated mica-based mineral before coating on the C layer 14.

  The removal of the impurities can be performed by centrifugation or decantation.

  Specifically, in the centrifugation, the swellable synthetic fluoromica-based mineral before purification is 0.5 to 12% by weight, preferably 2 to 10% by weight, more preferably 3 to 10% by weight, using a homogenizer or the like. What is sufficiently dispersed in water so as to be 8% by weight is 200 to 100000 G, preferably 300 to 50000 G, more preferably 500 to 20000 G, under conditions of 10 seconds to 30 minutes, precipitated impurities, etc. Can be removed. If it is less than 200 G, it tends to be difficult to sufficiently separate impurities and the like. On the other hand, it may be larger than 100,000 G, but about 100,000 G is sufficient from the viewpoint of the performance and capacity of the centrifuge.

  As an example of a centrifugal separator, when the dispersion liquid in which the swellable synthetic fluoromica mineral is dispersed is continuously or intermittently supplied to a centrifugal separator that rotates and imparts centrifugal force, A centrifuge having a mechanism for intermittently discharging the impurities separated on the inner wall of the centrifuge unit to the outside of the centrifuge unit may be mentioned. As such a centrifuge, a disk-type centrifuge (also referred to as a DeLaval centrifuge or a separation plate centrifuge) can be given as an example.

  The frequency | count of performing the centrifugation process using said centrifuge is not limited to 1 time, You may perform two or more times as needed.

  Furthermore, in the decantation, the solid content concentration of the swellable synthetic fluoromica-based mineral before purification is 0.1 to 5% by weight, preferably 0.5 to 4.5% by weight, more preferably 1 to 4% by weight. %, Which is dispersed in a dispersion liquid to a concentration of 1%, and sufficiently dispersed using a homogenizer or the like, is allowed to stand for 1 to 120 hours, preferably 3 to 72 hours, more preferably 8 to 48 hours. Etc. can be removed. In any of these methods, the high-purity swellable synthetic fluorinated mica-based mineral can be obtained by recovering the swellable synthetic fluorinated mica-based mineral from the supernatant suspension. If it is shorter than 1 hour, it may not be sufficiently separated from impurities and the like. On the other hand, when the time is longer than 120 hours, not only the productivity is lowered but also the yield tends to be lowered.

  The centrifugal separation process and the decantation process may be performed only in one or both. In addition, as a dispersion medium used for the said dispersion liquid, ion-exchange water, distilled water, etc. are mentioned.

  When the decantation method is used, the average particle size of the swellable synthetic fluorinated mica-based mineral that is provided for the above purification treatment is preferably 6 to 50 μm, and more preferably 7 to 20 μm. If it is less than 6 μm, separation from impurities and the like is very bad, and it may be difficult to remove. On the other hand, those exceeding 50 μm are technically difficult to manufacture and expensive. When using the centrifugation method, it is preferable that it is 2-50 micrometers, and 4-20 micrometers is more preferable. If it is less than 2 μm, separation from impurities and the like is very bad and it may be difficult to remove. On the other hand, those exceeding 50 μm are technically difficult to manufacture and expensive.

  Before performing the centrifugal separation treatment or decantation treatment on the dispersion liquid containing the swellable synthetic fluoromica system mineral before the above treatment, as long as it does not impair the physical properties such as gas barrier properties, transparency and smoothness. A small amount of a dispersant or the like may be added. In this case, the swellable synthetic fluorinated mica-based mineral before the treatment can be dispersed in the dispersion medium to prepare a dispersion, and a dispersing agent can be added thereto for dispersion treatment.

  Examples of the dispersant include polymer type, surface active type, and inorganic type. Among them, it is more preferable to use a polymer type, particularly a polycarboxylic acid type polymer. By using this polycarboxylic acid type polymer, the yield at the time of centrifugation treatment is good, and furthermore, the gas barrier property, haze, and smoothness under high humidity of the finally obtained laminate are all good. Become.

  Examples of the polycarboxylic acid type polymer include sodium salts and ammonium salts of polycarboxylic acids having a weight average molecular weight of 1,000 to 1,000,000.

  In addition, if the swellable synthetic fluoromica-based mineral before the treatment is subjected to a mechanical pulverization treatment, the removal of the impurities is likely to be difficult even if the centrifugation treatment or the decantation treatment is performed. Even if a body is obtained, deterioration such as gas barrier properties and haze tends to occur.

  The purified swellable synthetic fluorinated mica-based mineral obtained by the above centrifugation or decantation treatment is dispersed uniformly in ion-exchanged water at a dispersion concentration of 0.5% by weight. Preferably satisfies the following formula (4).

(I / I ₀ ) × 100 ≧ 30 (4)

In the above formula (4), I ₀ represents the intensity of incident light (660 nm), and I represents the intensity of transmitted light. In addition, the measurement of this light transmittance can be measured using various photometers, and the optical path length at the time of the measurement is 1 cm.

Further, the value of the left side of the above formula (4) is preferably 30 or more, and more preferably 40 or more. When the value on the left side of the above formula (4) is smaller than 30, the gas barrier laminate containing the swellable synthetic fluoromica-based mineral cannot obtain sufficient gas barrier properties but also has transparency and smoothness. Remarkably worse. Furthermore, the upper limit of the value on the left side of the formula (4) is 100. Since theoretically I ≦ I ₀ , the value on the left side of the above formula (4) does not exceed 100.

  Presence of the impurities contained in the purified swellable synthetic fluorinated mica-based mineral obtained by the above centrifugation treatment or decantation treatment can be confirmed by a diffraction peak obtained by X-ray diffraction analysis. That is, the phase having a poor swelling property (non-swellable synthetic fluoric mica) can be confirmed with a peak having an interplanar spacing d of approximately 9.6 mm (9.4 to 9.8 mm). The cristobalite, which is a by-product, can be confirmed with a peak having an interplanar spacing d of about 4.0 mm (3.9 to 4.1 mm). Moreover, about a swelling synthetic fluorine mica type | system | group mineral, it can confirm with the peak whose surface space | interval d is about 12.4 (12.1-12.6). In either case, the intensity of the peak top is evaluated. The measurement is performed on a sample which is dried at 120 ° C. for 10 hours or more and then left at 23 ° C.-50% RH for 24 hours or more. The particle size of the sample was adjusted to pass through a 100 mesh screen.

(1) Powder X-ray diffraction analysis condition device: RINT2000 series manufactured by Rigaku Corporation, X-ray: Cu Kα ray (40 kV-30 mA)
Counter monochromator: fully automatic monochromator, divergence slit: 1 °, scattering slit: 1 °, light receiving slit: 0.15 mm, scan speed: 4 ° / min, scan step: 0.01 °, scan axis: 2θ / θ

(2) Smoothing conditions for calculating peak intensity I (score 9), background removal (curvature 0.00), Kα2 removal (Kα2 / Kα1 0.5)

Specifically, in the above powder X-ray diffraction analysis, the diffraction peak intensity [I _{d = 9.6 Å} ] indicating a phase with poor swellability (non-swellable synthetic fluorine mica) having an interplanar spacing d of approximately 9.6 ［was obtained, The diffraction peak intensity with an interplanar spacing d of approximately 4.0 ［is [I _{d = 4.0 Å} ], and the diffraction peak intensity with an interplanar spacing d of approximately 12.4 示 す indicating a swellable synthetic _fluoromica- based mineral is [I _{d = 12.4} when the _Å], the relative intensities of the diffraction _{peaks, [I d = 9.6Å] /} [I d = 12.4Å] × 100 ≦ 2, and _{[I d = 4.0Å] / [} I d = 12.4Å] _X100 ≦ 20 should be satisfied, and [I _{d = 9.6Å} ] / [I _{d = 12.4Å} ] = 0 and [I _{d = 4.0Å} ] / [I _{d = 12.4Å} ] × 100 ≦ 10 Preferably there is.

When the C layer 14 is formed by the purified swellable synthetic fluorinated mica-based mineral satisfying the above conditions and the second water-soluble polymer, oxygen barrier properties and water vapor barrier properties are sufficiently maintained even under high humidity conditions. The strength, transparency, and smoothness of the C layer 14 are improved. When [I _{d = 9.6 d} ] / [I _{d = 12.4Å} ] × 100> 2, or [I _{d = 4.0Å} ] / [I _{d = 12.4Å} ] × 100> 20, the gas barrier property May become insufficient, or the strength, transparency, and smoothness of the coating layer may be reduced.

  The purified swellable synthetic fluoromica-based mineral preferably has an average particle size of 0.05 to 10 μm, and more preferably 0.1 to 8 μm. When the thickness is less than 0.05 μm, the gas barrier property under high humidity is not sufficiently exhibited. On the other hand, when the thickness is more than 10 μm, the transparency and smoothness of the coated surface are lost, which is not preferable in practice. The average particle diameter can be measured using a laser diffraction / scattering particle size distribution measuring apparatus LA920 manufactured by Horiba, Ltd. and using ion-exchanged water as a dispersion medium. In addition, the average particle diameter as used in this invention means a median diameter (a particle diameter reference | standard is a volume).

  As the method for forming the C layer 14 on the B layer 13, the swellable synthetic fluorinated mica-based mineral (preferably the purified swellable synthetic fluorinated mica-based mineral) and the second water-soluble polymer are used. And a solution prepared by dissolving or suspending in a water-based solvent, and applying the composition. Here, ion-exchanged water or distilled water is desirable as the aqueous solvent, but methanol, ethanol, propanol, isopropanol, or the like may be added with these as the main components.

  The total solid content of the second water-soluble polymer and the swellable synthetic fluorinated mica-based mineral dissolved or suspended in the aqueous solvent is 0.5 to 15% by weight of the resulting solution or suspension. It is desirable to be. Further, if considering the viscosity, coating suitability, coating thickness, gas barrier properties, etc., 2 to 10% by weight is more preferable. If it is less than 0.5% by weight, drying may be insufficient during coating on the film. On the other hand, if it is more than 15% by weight, the viscosity of the coating solution may become too high.

  The addition ratio of the second water-soluble polymer and the swellable synthetic fluorinated mica-based mineral is arbitrary, but the second water-soluble polymer / the swellable synthetic fluorinated mica-based mineral (weight ratio) is 99.99. 5 / 0.5 to 20/80 is good, and 99/1 to 30/70 is preferable. When the swellable synthetic fluoromica system mineral is less than 0.5% by weight, the gas barrier property is not sufficient, and when it is more than 80% by weight, the strength of the coating film formed by the application of the C layer 14 is weakened. There is.

  The mixing method for obtaining the composition from the second water-soluble polymer and the swellable synthetic fluoromica-based mineral may be prepared by any procedure. That is, (1) after the swellable synthetic fluoromica mineral is dispersed in the aqueous solvent, the second water-soluble polymer is added and dissolved as a solid. (2) After the second water-soluble polymer is dissolved in the aqueous solvent, the swellable synthetic fluoromica-based mineral is added. (3) A mixture of the swellable synthetic fluoromica mineral and the second water-soluble polymer are mixed. You may mix by any procedure among these.

  You may add a crosslinking agent to the said B layer 13 as needed. By adding this crosslinking agent, hot water resistance can be improved. Examples of the crosslinking agent include carbodiimide compounds, epoxy compounds, isocyanate compounds, aldehyde compounds, oxazoline compounds, melamine compounds, aziridine compounds, organic metal salts such as titanium, zirconium, and aluminum, inorganic metals, silicon compounds, and the like. Among these, carbodiimide compounds, epoxy compounds, isocyanate compounds, and aldehyde compounds are particularly effective in improving performance.

  Moreover, you may add the crosslinking agent which has the effect of a film | membrane strength improvement to the said C layer 14 as needed. Examples of the crosslinking agent include carbodiimide compounds, epoxy compounds, isocyanate compounds, aldehyde compounds, organometallic compounds such as titanium, zirconium, and aluminum, inorganic metals, silicon compounds, and the like.

  Specific examples of the carbodiimide compound include monocarbodiimide compounds such as dicyclohexylcarbodiimide, diisobutylcarbodiimide, diisopropylcarbodiimide and diphenylcarbodiimide, and polycarbodiimide compounds obtained by decarboxylation of diisocyanate compounds known in the technical field of polyurethane. Diisocyanate compounds known in the polyurethane technical field include methylene diphenyl diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl. Examples include methane diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, and trimethylhexamethylene diisocyanate. Of these, hydrophilic carbodiimide compounds are particularly suitable, and specific examples include Nisshinbo Co., Ltd. product name: Carbodilite.

  Specific examples of the epoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and dipropylene glycol. Diglycidyl ether, tripropylidyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ethers such as glycerol diglycidyl ether, triglycidyl ethers such as glycerol triglycidyl ether, Tetraglycidyl ethers such as pentaerythritol tetraglycidyl ether Such as Le acids, and the like.

  Specific examples of the isocyanate compound include blocked isocyanate compounds (for example, trade names Elastrone, Elastolon BN series, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hexa Examples include methylene diisocyanate, 4,4′-methylenebiscyclohexyl diisocyanate, and isophorone diisocyanate.

  Specific examples of the aldehyde compounds include glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, hexane dial, heptane dial, octane dial, nonane dial, decandial, dodecandial, 2,4-dimethylhexane dial. 5-methylheptane dial, 4-methyloctane dial, 2,5-dimethyloctane dial, 3,6-dimethyldecandial, orthophthalaldehyde and the like.

Specific examples of the titanium compound, titanium acetylacetonate, titanium tetraacetyl acetonate, poly titanium acetylacetonate, titanium ethylacetoacetate, titanium octane diolate, titanium lactate, titanium triethanol aluminate, polyhydroxy titanium stearate Rate, etc.

Specific examples of the zirconium compound, di benzalkonium tetraacetyl acetonate, zirconium mono acetyl acetonate, zirconium bis acetyl acetonate, zirconium mono ethyl acetoacetate, zirconium acetyl acetonate bis ethyl acetoacetate acetonate, zirconium acetate, zirconium tri Organic zirconium compounds such as butoxy systemate, zirconium halides such as zirconium oxychloride, hydroxyzirconium chloride, zirconium tetrachloride and zirconium bromide, zirconium salts of mineral acids such as zirconium sulfate, basic zirconium sulfate and zirconium nitrate, ammonium zirconium carbonate , Sodium zirconium sulfate, ammonium zirconium acetate, sodium zirconium oxalate Zirconium citrate sodium, zirconium complex salts such as zirconium citrate ammonium and the like.

Examples of the aluminum compound, A Rumi pyridinium acetyl acetonate, aluminum organic chelate and the like.

Examples of the silicon compound, silicic containing acetylacetonate, silicon ethylacetoacetate, silicon octane dioleate, silicon lactate, silicon triethanolaminate, polyhydroxy silicon stearate, silicon n-propylate, silicon monoacetylacetonate , Silicon bisacetylacetonate, silicon monoethyl acetoacetate, silicon bisethylacetonate, silicon acetate, silicon tributoxy systemate and the like.

When the crosslinking agent is added to the B layer 13, the amount of addition is not particularly limited, but is preferably 0.1 × 10 ^{−3 to} 1 mol with respect to 1 mol of the reactive group in the water-soluble polymer. 0.5 × 10 ^{−3 to} 0.5 mol is preferable. When the amount is less than 0.1 × 10 ⁻³ mol, there is no particular effect in improving the performance of the layer formed from the gas barrier composition. On the other hand, when the amount is more than 1 mol, the solution tends to gel or the performance of the obtained gas barrier laminate tends to deteriorate.

When the above crosslinking agent is added to the C layer 14, the amount of addition is not particularly limited, but 1 × 10 ^{−3 to} 0.5 mol per 1 mol of the reactive group in the water-soluble polymer. Well, 2 × 10 ^{−3 to} 0.1 mol is more preferable. When the amount is less than 1 × 10 ⁻³ mol, the strength of the coating film is lowered. On the other hand, when the amount is more than 0.5 mol, the gas barrier property is lowered, or the coating agent is gelled and cannot be applied. There is.

  If necessary, various additives may be mixed in the B layer and the C layer as long as the gas barrier property, transparency, smoothness, and the like are not impaired. Examples of various additives include dispersants, antifoaming agents, antioxidants, weathering agents, lubricants, ultraviolet absorbers, colorants, plasticizers, and the like.

The coating amount after drying of the layer B 13 is preferably a 0.1 to 1.0 g / m ^2, more desirably When it is 0.25~0.60g / m ^2. If it is less than 0.1 g / m ² , the gas barrier property may not be sufficient, and if it exceeds 1.0 g / m ² , the drying may be poor, and the gas barrier property may not be sufficient. However, the gas barrier property is not significantly improved and it is not economical.

The coating amount after drying of the C layer 14 is preferably a 0.1 to 0.8 g / m ² in a dry state, more desirably When it is 0.2-0.4 g / m ^2. If it is less than 0.1 g / m ² , the gas barrier property may not be sufficient. On the other hand, if it exceeds 0.8 g / m ² , the film strength of this layer tends to be weak.

  The desirable coating amount of the B layer 13 and the C layer 14 is a value including these additives when an additive such as the crosslinking agent is added to the B layer 13 or the C layer 14. It is.

  The gas barrier laminate according to the present invention is obtained by sequentially applying and forming the A layer 12, the B layer 13 and the C layer 14 having the above composition on the polymer resin film as the base material 11.

  A method of sequentially applying and forming the A layer 12, the B layer 13, and the C layer 14 from the polymer resin film side on at least one surface of the polymer resin film that is the substrate 11 is not particularly limited. Usual coating methods such as gravure roll coating, reverse roll coating, wire bar coating, and die coating can be employed. The coating may be before or after stretching the film.

  Here, without providing the A layer 12 containing an organic base, the B layer 13 is applied and formed as a first layer on the surface of the polymer resin film, and then the C layer 14 is formed continuously. In such a case, the problem of whitening of the coating film occurs. Also, when a urethane resin layer is formed as a first layer on the surface of the polymer resin film instead of an organic base, and the B layer 13 and the C layer 14 are successively applied and formed thereon, The problem that a coating film whitens arises. These whitening phenomena remain in the B layer 13 when the C layer 14 is laminated on the B layer 13 because the C layer 14 includes a swellable synthetic fluorinated mica-based mineral and is basic. Condensation reaction of the metal alkoxide hydrolyzate having a silanol group or polycondensation reaction of the metal alkoxide hydrolyzate and its reaction product with the water-soluble polymer occurs rapidly, and the B layer 13 is excessively coated. Innumerable fine cracks are generated in the B layer 13 due to the shrinkage.

  On the other hand, after applying and forming the B layer 13 as the first layer on the surface of the polymer resin film as the base material 11, or forming a urethane resin layer as the first layer, the B layer is formed thereon. When the C layer 14 is laminated after several hours have passed after the layer 13 is formed by coating, a transparent laminate can be obtained without the B layer 13 whitening. Alternatively, when the B layer 13 is formed, if a drying process is applied with a large amount of heat, the C layer 14 is not whitened even if the C layer 14 is successively laminated. However, a coating operation that requires time until the C layer 14 is coated on the B layer 13 and a method that requires a large amount of heat treatment are poor in productivity.

  Therefore, by providing the A layer 12 containing an organic base as the first layer on the surface of the polymer resin film which is the base material 11, the B layer 13 and the C layer 14 are then formed. Even if the layers are laminated successively, that is, sequentially, whitening of the obtained laminate can be suppressed. The organic base is a high molecular weight organic base from the viewpoint of adhesion to the polymer resin film, adhesion to the B layer 13, ease of film formation during coating, and flexibility of the film. Among them, the polyethyleneimine exemplified above is preferable.

  When the coating is sequentially formed in the above order, the B layer 13 forms a dense structure and has water resistance due to a strong siloxane bond even in a drying process with a small amount of heat. When the layer 14 is coated on the B layer 13, since elution that collapses the dense structure formation of the B layer 13 does not occur, a stable gas barrier property can be obtained even under high humidity, and at the same time, transparency In addition, an excellent gas barrier laminate can be obtained.

  The C layer 14 contains a layered swellable synthetic fluorinated mica-based mineral and exhibits oxygen barrier properties due to its curved path effect, but the lamination of the C layer 14 on the B layer 13 is the above. The oxygen barrier improvement effect more than assumed from the curved path effect of the C layer 14 is exhibited, and a high oxygen barrier property is obtained.

  In addition to the curved path effect due to the swellable synthetic fluorine mica-based mineral contained in the C layer 14, the A layer 12 containing the organic base, and the alkali metal salt and / or alkaline earth metal salt Condensation reaction of the alkoxide hydrolyzate and polycondensation reaction of the metal alkoxide hydrolyzate and its reaction product with the first water-soluble polymer proceed, and the silanol group of the B layer 13 is basic. It is considered that the oxygen barrier improving effect is exhibited because the layer 14 gently causes the above condensation reaction to form a denser structure.

  When the coating order is different from the above, for example, the A layer 12, the C layer 14, and the B layer 13 are placed on the substrate 11 side on the surface of the polymer resin film that is the substrate 11. The performance of the laminated body sequentially formed by coating from the gas barrier laminate obtained by sequentially laminating the A layer 12, the B layer 13 and the C layer 14 according to the present invention is lowered. This is because, when the C layer 14 is applied earlier than the B layer 13, when the B layer 13 is applied, a part of the C layer 14 previously applied is newly formed. It is considered that the B layer 13 was eluted, and the B layer 13 could not form a dense structure, so that a permeation space for oxygen molecules was easily formed.

  The drying and curing method after applying each layer to the polymer resin film is not particularly limited, but can be performed at a temperature below the melting point and softening point of the polymer resin film as a substrate. The temperature at which the crosslinking reaction is sufficiently performed may be sufficient. Here, since each of the A layer 12 to the C layer 14 does not require heat treatment at a high temperature for a long time, drying and heat treatment at 150 ° C. or less and for a few seconds at a relatively low temperature in a short time are sufficient.

  Furthermore, by aging the gas barrier laminate obtained by coating and drying the above layers, the crosslink density of the formed gas barrier coating layer can be increased, and the barrier properties can be further improved. Although the temperature and time of this aging are not specifically limited, 1-150 hours are preferable at 20-120 degreeC, and 6-100 hours are more preferable at 30-70 degreeC. If the temperature is lower than 20 ° C., the aging time tends to be too long. On the other hand, if it exceeds 120 ° C., the polymer resin film as the base material may be damaged. If the time is shorter than 1 hour, the crosslinking density may not be increased sufficiently. On the other hand, although it may exceed 150 hours, it has no effect on performance improvement.

In the gas barrier laminate according to the present invention, the coating amount after drying from the A layer 12 to the C layer 14 is as described above, and the coating amount of the A layer 12 is 0.005 to 0.1 g / m ^2. The coating amount after drying the B layer 13 is 0.1 to 1.0 g / m ² , and the coating amount after drying the C layer 14 is 0.1 to 1.0 g / m ^2. , and the it is desirable that 0.1 to 0.8 g / m ^2. The ratio of the coating amount (solid content) between the A layer 12 and the B layer 13 is 2 ≦ (the coating amount of the B layer 13 / A layer 12), which satisfies the coating amount condition of each layer. Coating amount) ≦ 140, preferably 5 ≦ (coating amount of B layer 13 / coating amount of A layer 12) ≦ 40, excellent in transparency, even under high humidity conditions Stable oxygen barrier properties can be exhibited. If the above (the coating amount of the B layer 13 / the coating amount of the A layer 12) is smaller than 2, since the coating amount of the B layer 13 is small, a stable oxygen barrier property cannot be obtained, Since the coating amount of the A layer 12 is large, a large amount of the A layer 12 is melted when the coating of the B layer 13 is formed, and the coating film becomes white due to gelation, and a dense structure is not formed. It will become the laminated body film in which oxygen barrier property fell. On the other hand, when it is larger than 140, the oxygen barrier performance is not significantly improved even though the coating amount of the B layer 13 is large, which is economically undesirable.

  Furthermore, the ratio of the coating amount (solid content) of the B layer 13 and the C layer 14 is 0.25 ≦ (the coating amount of the B layer 13 / the coating amount of the C layer 14) ≦ 6.5. It is preferable that 0.35 ≦ (the coating amount of the B layer 13 / the coating amount of the C layer 14) ≦ 3.5. Within this range, the humidity dependency is small, and excellent oxygen barrier properties and water vapor barrier properties can be exhibited. Even if the above (the coating amount of the B layer 13 / the coating amount of the C layer 14) is smaller than 0.25, the water vapor barrier performance is not significantly improved, and sufficient oxygen barrier properties are obtained under high humidity. There is a possibility that it cannot be exhibited, and if it is larger than 6.5, even if sufficient oxygen barrier properties can be exhibited under high humidity, the water vapor barrier property may be insufficient, which is not preferable.

  The gas barrier laminate according to the present invention preferably has high transparency, more preferably has a haze of 4.0% or less, and more preferably 2.5% or less. This is because higher transparency means a wider range of use and is easier to handle.

The gas barrier laminate according to the present invention needs to have a high oxygen barrier property, that is, a low oxygen permeability. Specifically, for example, a biaxially stretched polypropylene having a thickness of 20 μm is used as the substrate 11. The gas barrier laminate obtained in this case preferably has an oxygen permeability in an environment of 23 ° C. and 90% RH of 5.0 cc / m ² · day · atm or less, and is 2.0 cc / m ² · day · atm. The following is more desirable. If it is greater than 5.0 cc / m ² · day · atm, the practicality of a gas barrier packaging material is lacking.

The gas barrier laminate according to the present invention needs to have a high water vapor barrier property, that is, a low water vapor permeability. Specifically, for example, a biaxially stretched polypropylene having a thickness of 20 μm is used as the substrate 11. The gas barrier laminate obtained in this case preferably has a water vapor permeability in an environment of 40 ° C. and 90% RH of 4.0 g / m ² · day or less, more preferably 2.0 g / m ² · day or less. desirable.

  The gas barrier laminate according to the present invention is used by forming a composite laminate by laminating at least one layer of this gas barrier laminate on another film or sheet, in addition to using it as a gas barrier film as it is. May be. This composite laminate can also be used as a laminate having gas barrier properties.

  Hereinafter, the present invention will be specifically described by way of examples. First, the chemical | medical agent to be used is demonstrated.

(Organic base)
Polyethyleneimine: Nippon Shokubai Co., Ltd .: Epomin P-1000, 30% polyethyleneimine aqueous solution, number average molecular weight: 70000
Polyethyleneimine: Wako Pure Chemical Industries, Ltd .: Reagent, Number average molecular weight: 1800
(Polyurethane resin)
Two-component curing urethane: Toyo Morton Co., Ltd .: EL-443A / EL-443C
(Water-soluble polymer)
Polyacrylamide: manufactured by Tokyo Chemical Industry Co., Ltd .: Reagent (10% aqueous solution, weight average molecular weight: 700,000 to 1,000,000, hereinafter abbreviated as “PAM”)
Polyvinyl alcohol: manufactured by Kuraray Co., Ltd .: PVA117 (average polymerization degree: 1700, hereinafter abbreviated as “PVA”)
(Metal alkoxide)
Tetraethoxysilane: Colcoat Co., Ltd .: ethyl silicate (hereinafter abbreviated as “TEOS”)
(Specific silane compounds: improved binding between alkoxides and water-soluble polymers)
3-Glycidoxypropyltrimethoxysilane: Shin-Etsu Silicone Co., Ltd .: KBM-403
(Carbodiimide compound: cross-linking agent)
Polycarbodiimide: Nisshinbo Industries, Inc .: Carbodilite V-02-L2 (active ingredient 40% by weight, carbodiimide equivalent 385)

(Swelling synthetic fluoromica-based mineral)
Alfa Laval Co., Ltd. disk type centrifuge BTPX205 (centrifuge section (bowl) capacity 3.1 liter, sludge space 1 liter), 5 wt% Na type tetralithic mica (Topy Industries, Ltd.) : NTS 10 wt% (sol), particle size: 13.5 μm, standard product) The dispersion was allowed to flow at a flow rate of 200 liters / hr for 1 hour. The solid content was discharged for 70 seconds, and impurities were discharged intermittently. The obtained supernatant was used as a purified swellable synthetic fluoromica-based mineral dispersion. Hereinafter, this supernatant is abbreviated as “P-NTS”. The average particle size of the P-NTS was measured by a laser diffraction / scattering particle size distribution measuring apparatus (Horiba, Ltd .: LA920) and found to be 0.9 μm. The relative intensity of the diffraction peak obtained by the powder X-ray diffraction method using a powder X-ray diffractometer (manufactured by Rigaku Denki Co., Ltd .: RINT2000) is [I _{d = 9.6 =} ] / [I _{d = 12.4 Å]} × 100 = 0, was _{[I d = 4.0Å] / [} I d = 12.4Å] × 100 = 0.
Purified montmorillonite …… Kunimine Kogyo Co., Ltd.:Kunipia P

(Film strength improver)
Zirconium ammonium carbonate solution: manufactured by Kishida Chemical Co., Ltd .: Reagent, solid content is 13 wt% in terms of zirconium oxide (hereinafter abbreviated as “AZC”).
(solvent)
2-propanol: Wako Pure Chemical Industries, Ltd .: Reagent (reagent)
Sodium chloride: Kishida Chemical Co., Ltd .: Reagent Magnesium chloride: Wako Pure Chemical Industries, Ltd .: Reagent

(Base material)
Polypropylene film: Toyobo Co., Ltd .: biaxially oriented polypropylene film: P2102, thickness: 20 μm, haze: 1.4%
Nylon film: Toyobo Co., Ltd .: Biaxially stretched nylon film: N2102, thickness: 15 μm, haze 2.2%
(Sealant)
LLDPE film: Idemitsu Unitech Co., Ltd .: LS-711C Thickness: 40 μm
(adhesive)
Polyurethane adhesive: Toyo Morton Co., Ltd .: TM-319 / CAT-11B

Next, each property evaluation method will be described.
(Oxygen barrier evaluation method)
According to JIS K 7126 B method, it measured using the oxygen permeability tester (made by Modern Control, OX-TRAN 2/20). The measurement conditions were 23 ° C. and 90% RH atmosphere.

(Water vapor barrier property evaluation method)
According to JIS K 7129 B method, it measured using the water-vapor-permeability tester (The product made by Modern Control, PERMATRAN-W3 / 30). The measurement conditions were 40 ° C. and 90% RH atmosphere.

(Haze measurement)
Murakami Color Research Laboratory product: HM-65W was used, and haze (cloudiness value) was measured according to JIS K 7105.

Next, preparation of the barrier coating agent using these will be described.
(Barrier coating agent 1)
As a first water-soluble polymer, 250 g (solid content 5 g) of a 2 wt% aqueous solution of PAM (manufactured by Tokyo Chemical Industry Co., Ltd .: reagent) was prepared, and then ethanol (manufactured by Wako Pure Chemical Industries, Ltd .: reagent) ) After adding 75 g, 10 g of 2N hydrochloric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd .: Reagent) is added. 0.5-g of 02-L was added sequentially, and stirred until the liquid became uniform. Then, 1 mol% of sodium chloride was stirred as an alkali metal salt to obtain a coating agent 1. In addition, mol% of addition amount is mol% with respect to the metal element contained in the hydrolyzate of TEOS which is a metal alkoxide, and / or its condensate.

(Barrier coating agent 2)
Purified swellable synthetic fluoromica-based mineral (P-NTS) and water-soluble polymer (PVA) in ion-exchanged water with a total solid concentration of 5% by weight and a solid content weight ratio of P-NTS: water-soluble The mixture was dispersed so that the polymer was 3: 7. 15% by weight of 2-propanol was added to 100 parts by weight of this dispersion. Next, AZC was added as a film strength improver so that the zirconium atom was 0.05 mol with respect to 1 mol of the hydroxyl group of the second water-soluble polymer to obtain a coating agent 2.

Example 1
A solution obtained by dissolving polyethyleneimine (number average molecular weight: 70,000) as an organic base in 2-propanol to a solid content ratio of 0.5% by weight is applied to the corona-treated surface of a polypropylene film (P2102 thickness: 20 μm). Then, coating with a Mayer bar so that the coating amount after drying is 0.03 g / m ^2, and drying with a hot air dryer (TABAI: SPHH-1000) at 100 ° C. for 1 minute to form A layer 12 I let you.
Next, the coating agent 1 is applied onto the A layer 12 so that the coating amount after drying is 0.3 g / m ² , dried at 100 ° C. for 1 minute and heat-treated to form the B layer 13. I let you.
Furthermore, the coating agent 2 is continuously applied thereon so that the coating amount after drying is 0.3 g / m ^2, and dried at 100 ° C. for 2 minutes to form the C layer 14. A gas barrier laminate was obtained. The evaluation results of the obtained gas barrier laminate are shown in Table 1.

(Example 2)
A gas barrier laminate was obtained by the same procedure as in Example 1 except that magnesium chloride was used as the sodium chloride used in preparing the coating agent 1. The evaluation results of the obtained gas barrier laminate are shown in Table 1.

Example 3
When preparing the coating agent 1, the gas-barrier laminated body was obtained by the procedure similar to Example 1 except having changed the 1st water-soluble polymer from PAM to PVA. The evaluation results of the obtained gas barrier laminate are shown in Table 1.

Example 4
When preparing the coating agent 2, the gas-barrier laminated body was obtained by the procedure similar to Example 1 except having changed the 2nd water-soluble polymer from PVA to PAM. The evaluation results of the obtained gas barrier laminate are shown in Table 1.

(Example 5)
A nylon film (N2102) is used as the polymer resin film, and a gas barrier laminate is obtained by the same procedure as in Example 1 except that a dry laminating method using a polyurethane adhesive is performed. An LLDPE film having a thickness of 40 μm was bonded to the surface of the C layer 14 of the obtained gas barrier laminate. The evaluation results of the obtained gas barrier laminate are shown in Table 1.

(Comparative Example 1)
A laminate was obtained by the same procedure as in Example 1 except that a two-component curable urethane was applied to the A layer 12 instead of polyethyleneimine. The evaluation results of the obtained laminate are shown in Table 1.

(Comparative Example 2)
A laminate was obtained by the same procedure as in Example 1 except that montmorillonite was used instead of P-NTS used for coating agent 2. The evaluation results of the obtained laminate are shown in Table 1.

(Comparative Example 3)
After applying the A layer 12 on the polypropylene film, a laminate was obtained by the same procedure as in Example 1 except that the order of applying the B layer 13 and the C layer 14 was reversed. The evaluation results of the obtained laminate are shown in Table 1.

(Comparative Example 4)
A laminate was obtained by the same procedure as in Example 1 except that polyethyleneimine having a number average molecular weight of 1800 was used as the organic base for the A layer 12 instead of polyethyleneimine having a number average molecular weight of 70000. The evaluation results of the obtained laminate are shown in Table 1. The coated polyethyleneimine was not sufficiently film-forming, and after drying, repelling occurred and it was scattered on the substrate 11. When the coating agent 1 was applied as the subsequent B layer 13, gelation occurred due to the scattered polyethyleneimine, and the coating film became white.

(Comparative Example 5)
A laminate was obtained by the same procedure as in Example 1 except that when the B layer 13 was applied and dried at 100 ° C. for 3 minutes, the C layer 14 was not applied. The evaluation results of the obtained laminate are shown in Table 1.

(Comparative Example 6)
The laminated body was formed by the same procedure as in Example 1 except that a biaxially stretched nylon film (N2102) was used for the polymer resin film and a two-component curable urethane was applied to the A layer 12 instead of polyethyleneimine. Obtained. Thereafter, an LLDPE film having a thickness of 40 μm was bonded by a dry laminating method using a polyurethane adhesive. The evaluation results of the obtained laminate are shown in Table 1.

(result)
In each of the examples, low oxygen permeability and water vapor permeability were realized, and haze could be suppressed. Compared with the Examples, the haze increased in all Comparative Examples other than Comparative Example 5 in which the C layer 14 was not simply applied. Further, in any of the comparative examples, at least one of the oxygen permeability and the water vapor permeability was higher than that of the examples, and the gas barrier property was not sufficient.

Sectional drawing of the gas-barrier laminated body concerning this invention

Explanation of symbols

11 Base material 12 A layer 13 B layer 14 C layer

Claims (4)

A gas barrier laminate in which the following A layer, B layer and C layer are sequentially applied and formed on at least one surface of a base material made of a polymer resin film from the base material side.
(A layer) a layer containing an organic base having a number average molecular weight of 5,000 to 1,000,000,
(B layer) Contains a first water-soluble polymer, a metal alkoxide hydrolyzate and / or condensate thereof, an alkali metal salt and / or an alkaline earth metal salt, and a swellable synthetic fluoromica mineral Do not layer,
(C layer) The average particle size is 0.05 to 10 μm, and the relative intensity of the diffraction peak obtained from the powder X-ray diffraction analysis is [I _{d = 9.6 Å} ] / [ _{Id = 12.4 Å} ] × 100 ≦ 2 and [I _{d = 4.0 雲} ] / [I _{d = 12.4} ］] × 100 ≦ 20, a swellable synthetic _fluoromica mineral and a second water-soluble polymer, and a metal alkoxide hydrolyzate And / or a layer containing no condensate thereof .   The gas barrier laminate according to claim 1, wherein the polymer resin film is a polyolefin film.   The gas barrier laminate according to claim 1 or 2, wherein the organic base of the A layer is made of polyethyleneimine. The coating amount after drying of the A layer is 0.005 to 0.1 g / m ² ,
The coating amount after drying of the B layer is 0.1 to 1.0 g / m ² ,
The coating amount after drying of the C layer is 0.1 to 0.8 g / m ² ,
And the ratio of the coating amount (solid content) of the A layer and the B layer is 2 ≦ (the coating amount of the B layer / the coating amount of the A layer) ≦ 140,
The ratio of the coating amount (solid content) of the B layer and the C layer is 0.25 ≦ (the coating amount of the B layer / the coating amount of the C layer) ≦ 6.5.
The gas barrier laminate according to any one of claims 1 to 3.

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