Gas barrier composition, coating agent, and laminate

Abstract

[Solution] A gas barrier composition containing (A) a polyester polyol resin or polyurethane polyol resin having an acid value, (B) a divalent metal compound, and an organic solvent, the acid value of the polyester polyol resin or polyurethane polyol resin (A) in the composition is 150 mgKOH / g or less, the gas barrier coating agent contains the composition, and the laminate has a coating layer obtained by applying the coating agent. The divalent metal compound (B) is preferably at least one compound selected from the group consisting of zinc compounds, magnesium compounds, and calcium compounds.

Description

Technical Field

[0001] The present invention provides a composition having gas barrier properties. In addition, a coating agent containing the gas barrier composition and a laminate obtained by coating the coating agent are provided. Background Art

[0002] For packaging materials for packaging foods, pharmaceuticals, etc., it is required to prevent the deterioration of the contents, particularly oxidation caused by oxygen. In response to this requirement, conventionally, a barrier film made of a resin having relatively high oxygen barrier properties or a laminate (laminated film) using the barrier film as a film substrate has been used.

[0003] Conventionally, as oxygen barrier resins, resins containing highly hydrophilic hydrogen bonding groups in the molecule, such as polyacrylic acid or polyvinyl alcohol, have been used. Packaging materials made of these resins exhibit very excellent oxygen barrier properties under dry conditions. On the other hand, there is a problem that the oxygen barrier property is significantly reduced due to the hydrophilicity of the resin under high humidity.

[0004] To solve these problems, the following method is known: a gas barrier packaging material is prepared by laminating a polycarboxylic acid-based polymer layer and a layer containing a polyvalent metal compound adjacent to each other on a substrate and causing them to react between the two layers to generate a polyvalent metal salt of polycarboxylic acid. However, such a gas barrier packaging material requires a plurality of coating liquids during production and must be coated multiple times, which requires labor and time.

[0005] As a gas barrier composition that exhibits high barrier properties while reducing the coating process, the present applicants have previously found a gas barrier composition containing: a resin (A) having a carboxyl group, a divalent metal compound (B), and an alcohol (C), wherein the resin (A) is a homopolymer or copolymer of a monomer having a high acid value such as acrylic acid, methacrylic acid, maleic acid, or itaconic acid, and the content of the alcohol (C) in the composition is 85 to 98 wt%, and the water content in the composition is 1% or less (for example, refer to Patent Document 2). Although this composition exhibits high gas barrier properties and has good storage stability itself, there is a problem that the coating adaptability and stability when used as a coating agent are slightly poor.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2007-112114

[0009] Patent Document 2: International Publication WO20 / 203766 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] An object of the present invention is to provide a gas barrier composition that exhibits high barrier properties while reducing the coating process, and has excellent coating adaptability and stability when used as a coating agent.

[0012] Solutions to the Problems

[0013] The present inventors have found that: as a resin having a carboxyl group, homopolymers or copolymers of monomers having a high acid value such as acrylic acid, methacrylic acid, maleic acid, or itaconic acid having a high acid value disclosed in Patent Document 2 partially gel during the coating process as a coating agent, and this situation leads to a decrease in coating adaptability. It has been found that as an alternative resin, a gas barrier composition containing a specific polyester polyol resin or polyurethane polyol resin (A) having an acid value of 150 mgKOH / g or less, a divalent metal compound, and an organic solvent can solve the above problems.

[0014] That is, the present invention provides a gas barrier composition comprising: a polyester polyol resin or polyurethane polyol resin (A) having an acid value, a divalent metal compound (B), and an organic solvent, and the acid value of the polyester polyol resin or polyurethane polyol resin (A) in the composition is 150 mgKOH / g or less.

[0015] In addition, the present invention provides a gas barrier coating agent containing the above-described composition.

[0016] In addition, the present invention provides a laminate having a substrate and a coating layer obtained by coating the above-described coating agent.

[0017] In addition, the present invention provides a gas barrier coating agent which is a two-component type of the gas barrier coating agent containing the above composition, and the composition (CA) contains the above polyester polyol resin or polyurethane polyol resin (A) and an organic solvent, and the composition (CB) contains the above divalent metal compound (B) and an organic solvent.

[0018] In addition, the present invention provides a laminate having a substrate, a coating layer (CA) obtained by coating the above-described composition (CA), and a coating layer (CB) obtained by coating the composition (CB) described in claim 8.

[0019] In addition, the present invention provides a packaging material having the above-described laminate.

[0020] Effects of the Invention

[0021] The gas barrier composition of the present invention is a composition comprising a polyester polyol resin or a polyurethane polyol resin (A) having an acid value of 150 mgKOH / g or less, a divalent metal compound, and an organic solvent. During the process of coating it as a coating agent, even if the solvent evaporates, partial gelation is not likely to occur, and the coating adaptability is not reduced. Furthermore, the gas barrier composition of the present invention can be used in the form of a one-component coating agent containing all the compositions, or in the form of a two-component coating agent of composition (CA) and composition (CB). The above composition (CA) comprises the above polyester polyol resin or polyurethane polyol resin (A) and an organic solvent, and the above composition (CB) comprises the above divalent metal compound (B) and an organic solvent. High barrier properties can be exhibited by any of these methods, and it can be suitably used as a gas barrier coating agent.

[0022] In addition, since the laminate obtained by coating this composition on a substrate has excellent gas barrier properties, it can be suitably used as a packaging material, especially for packaging materials that require barrier properties such as foods, daily necessities, electronic materials, and medical uses.

[0023] Furthermore, since it also has excellent heat resistance and humidity resistance, it can also be suitably used as a packaging material for heat sterilization such as boiling or retorting. Detailed implementation mode

[0024] <Gas barrier composition>

[0025] The gas barrier composition of the present invention is a composition comprising a polyester polyol resin or a polyurethane polyol resin (A) having an acid value of 150 mgKOH / g or less, a divalent metal compound (B), and an organic solvent.

[0026] <Polyester polyol resin or polyurethane polyol resin (A) having an acid value>

[0027] The polyester polyol resin or polyurethane polyol resin (A) having an acid value used in the present invention (hereinafter sometimes referred to as resin (A)) is characterized in that the acid value is 150 mgKOH / g or less. It is preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less. It should be noted that the lower limit is only required to be 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.

[0028] (Method for measuring acid value)

[0029] The acid value refers to the number of milligrams of potassium hydroxide required to neutralize the acid components present in 1 g of the test sample. Specifically, it can be determined by the following method: Weigh the test sample and dissolve it in a suitable solvent for dissolving the test sample, such as a toluene / methanol = 70 / 30 mixture by volume. Add a few drops of 1% phenolphthalein alcohol solution in advance, and then add 0.1 mol / L potassium hydroxide alcohol solution dropwise. Determine it by confirming the color change point, and then it can be calculated by the following formula.

[0030] Acid Value Determination Method - 1

[0031] Acid value (mgKOH / g) = (V × F × 5.61) / S

[0032] V: The amount of 0.1 mol / L potassium hydroxide alcohol solution used (mL)

[0033] F: The titration factor of 0.1 mol / L potassium hydroxide alcohol solution

[0034] S: The amount of the test sample collected (g)

[0035] 5.61: The equivalent amount of potassium hydroxide in 1 mL of 0.1 mol / L potassium hydroxide alcohol solution (mg)

[0036] When the test sample is a resin solution, the resin acid value (mgKOH / g) can be calculated by the following formula. Resin acid value (mgKOH / g) = Resin solution acid value (mgKOH / g) / NV(%) × 100 NV: Non-volatile component (%)

[0037] In addition, when the solubility of the test sample in an organic solvent is low and precipitation makes it difficult to conduct the measurement, the acid value can also be determined by the following method.

[0038] Acid Value Determination Method - 2

[0039] The acid value (mgKOH / g-resin) refers to the value calculated by the following formula using FT-IR (manufactured by JASCO Corporation, FT-IR4200), the coefficient (f) obtained from the calibration curve made with the chloroform solution of maleic anhydride, the absorbance (I) of the stretching peak of the anhydride ring of maleic anhydride in the maleic anhydride-modified polyolefin solution (1780 cm -1 ), and the absorbance (II) of the stretching peak of the carbonyl group of maleic acid (1720 cm -1 ).

[0040] Acid value (mgKOH / g-resin) = [(Absorbance (I) × (f) × 2 × Molecular weight of potassium hydroxide × 1000 (mg) + Absorbance (II) × (f) × Molecular weight of potassium hydroxide × 1000 (mg)) / Molecular weight of maleic anhydride]

[0041] Molecular weight of maleic anhydride: 98.06, molecular weight of potassium hydroxide: 56.11

[0042] The molecular weight of the resin (A) used in the present invention is not particularly limited. From the viewpoint of film formability, the number average molecular weight is preferably 300 to 1,200,000, and particularly preferably 500 to 1,000,000.

[0043] The weight average molecular weight of the above resin (A) can be calculated by measuring it by a method using gel permeation chromatography (GPC).

[0044] (Polyester polyol resin having an acid value)

[0045] The polyester polyol resin having an acid value used in the present invention is not particularly limited, and known resins can be used. For example, polyester polyols obtained by polycondensing a polycarboxylic acid and a polyol by a known method can be mentioned.

[0046] The control of the acid value of the polyester polyol resin (A) used in the present invention is not particularly limited and can be carried out by a known method. For example, the following methods can be mentioned: after the start of the polycondensation reaction of esterification, a sample is taken to measure the acid value, and at the same time, the residual amount of the polycarboxylic acid is confirmed, and the reaction is stopped when the target acid value is reached.

[0047] As the polycarboxylic acid, for example, the following can be mentioned: aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid; polycarboxylic acids containing unsaturated bonds such as maleic anhydride, maleic acid, fumaric acid; alicyclic polycarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid and acid anhydride or ester-forming derivatives of these dicarboxylic acids; aromatic polycarboxylic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids; ortho-oriented polycarboxylic acids such as phthalic acid or its acid anhydride (phthalic anhydride), naphthalene 2,3-dicarboxylic acid or its acid anhydride, naphthalene 1,2-dicarboxylic acid or its acid anhydride, anthraquinone 2,3-dicarboxylic acid or its acid anhydride, and 2,3-anthracenedicarboxylic acid or its acid anhydride. These compounds may have substituents on any carbon atom of the aromatic ring. As the substituent, the following can be mentioned: chloro group, bromo group, methyl group, ethyl group, isopropyl group, hydroxy group, methoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group or naphthyl group, etc.

[0048] These polycarboxylic acids can be used alone or in combination of two or more.

[0049] As polyols, examples include: aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, etc.; polyols having three or more hydroxyl groups such as glycerol, trimethylolpropane, trimethylolethane, tris(2-hydroxyethyl)isocyanurate, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol, etc.; aromatic polyhydric phenols such as hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol, or ethylene oxide adducts thereof, hydrogenated alicyclic, etc. These polyols can be used alone or in combination of two or more.

[0050] When the polyester polyol has three or more hydroxyl groups, a part of the hydroxyl groups can be modified with acid groups. Such a polyester polyol can be obtained, for example, by first reacting a polycarboxylic acid with a polyol to obtain a polyester polyol, and then reacting a polycarboxylic acid or its acid anhydride with the obtained polyester polyol. The proportion of the hydroxyl groups modified with the polycarboxylic acid is preferably set to 1 / 3 or less of the hydroxyl groups possessed by the polyester polyol.

[0051] (Polyurethane polyol resin (A) having an acid value)

[0052] The polyurethane polyol resin having an acid value used in the present invention is not particularly limited, and known resins can be used. For example, polyurethane polyols obtained by polycondensing a polyol and an isocyanate compound by a known method can be cited.

[0053] As the polyol, the polyols described in the above polyester polyols can be used. Alternatively, the above polyester polyols can be directly used as the polyol. In this case, it becomes a polyester polyurethane polyol.

[0054] The control of the acid value of the polyurethane polyol resin (A) used in the present invention is not particularly limited and can be carried out by a known method. For example, it can be obtained by the following methods: selecting a polyester polyol, a polyol having a carboxyl group, etc. within the range of the target acid value, and subjecting them to a urethane reaction with an isocyanate compound.

[0055] Examples of the polyol having a carboxyl group include 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutyric acid, 2,2'-dimethylolbutanoic acid, 2,2'-dimethylolvaleric acid, etc. of a diol having one carboxyl group, or tartaric acid of a diol having two or more carboxyl groups.

[0056] As the isocyanate compound, those conventionally known ones can be used without particular limitation, and examples thereof include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or trimers of these isocyanate compounds, and adducts obtained by reacting an excessive amount of these isocyanate compounds with low-molecular active hydrogen compounds such as ethylene glycol, propylene glycol, m-xylene glycol, 1,3-bis(hydroxyethyl)benzene, 1,4-bis(hydroxyethyl)benzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, m-xylylenediamine, and epoxyalkane adducts thereof, various polyester resin types, polyether polyol types, and high-molecular active hydrogen compounds such as polyamides. A polyester polyisocyanate obtained by reacting a polyester polyol with a diisocyanate compound in such a manner that the ratio of the hydroxyl group to the isocyanate group is in an isocyanate-excessive state can also be used. One of these can be used, or two or more thereof can be used in combination.

[0057] As the isocyanate compound, blocked isocyanates can also be used. As the isocyanate blocking agent, for example, phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; oximes such as acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime; alcohols such as methanol, ethanol, propanol, and butanol; halogen-substituted alcohols such as chloroethanol and 1,3-dichloro-2-propanol; tertiary alcohols such as tert-butanol and tert-pentanol; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam can be cited. In addition, aromatic amines, imides, active methylene compounds such as acetylacetone, acetyl acetate, and ethyl malonate, thiols, imines, ureas, diaryl compounds, sodium bisulfite, etc. can also be cited. The blocked isocyanate is obtained by subjecting the above isocyanate compound and the isocyanate blocking agent to an addition reaction by a conventionally known and appropriate method.

[0058] <Divalent metal compound (B)>

[0059] The metal compound (B) used in the present invention is characterized in that it is a divalent metal compound.

[0060] The divalent metal compound (B) refers to a compound of a divalent metal. As the divalent metal compound (B), zinc compounds, magnesium compounds, calcium compounds, manganese compounds, iron compounds, cobalt compounds, nickel compounds, copper compounds, etc. can be cited, and zinc compounds, magnesium compounds, and calcium compounds are particularly preferred. These metal compounds can be used alone or in combination of two or more.

[0061] As the divalent metal compound (B), oxides, hydroxides, carbonates of divalent metals are preferred, and mixtures thereof may also be used.

[0062] Specific compounds of the divalent metal compound (B) are preferably zinc oxide, magnesium oxide, calcium oxide, and particularly preferably zinc oxide and magnesium oxide.

[0063] As the divalent metal compound (B), a particulate form is preferred. Further, fine particles having an average particle diameter of 500 nm or less and 10 nm or more are preferred. Particulate matter of 20 nm to 300 nm is particularly preferred.

[0064] The average particle diameter here can be measured using a dynamic light scattering type particle size distribution measuring device, such as LB-500 (manufactured by Kuroba Seisakusho).

[0065] <Organic solvent>

[0066] The organic solvent used in the present invention is not particularly limited, and a solvent generally used as an organic solvent can be used. For example, toluene, xylene, dichloromethane, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluene, mixed xylene, n-hexane, cyclohexane, methanol, ethanol, propanol, butanol, hexanol, pentanol, etc. can be used, and one kind or two or more kinds can be used in combination.

[0067] <Gas barrier composition>

[0068] The gas barrier composition of the present invention is characterized in that it contains the above resin (A), the above divalent metal compound (B), and an organic solvent.

[0069] The solid content is not particularly limited, and is preferably 5 to 20% by mass in the composition.

[0070] In addition, among all the solid components, the solid component of the above divalent metal compound (B) is preferably 20 to 90% by mass based on the total mass of all the solid components. More preferably, it is 60 to 80% by mass.

[0071] The total amount of the above resin (A) and the above divalent metal compound (B) is preferably 5 to 40% by mass. Particularly preferably, it is 5 to 20% by mass.

[0072] Within these ranges, particularly, the gas barrier property can be fully exhibited.

[0073] In addition, as the ratio of the above-mentioned resin (A) to the above-mentioned divalent metal compound (B), the above-mentioned divalent metal compound (B) is preferably 20 to 90% by mass based on the total amount of the above-mentioned resin (A) and the above-mentioned divalent metal compound (B). If it is within this range, gas barrier properties and coatability can be satisfactorily combined. Particularly preferably, it is 60 to 80% by mass.

[0074] The gas barrier composition of the present invention may also contain materials other than the above-mentioned resin (A), the above-mentioned divalent metal compound (B), and the organic solvent.

[0075] (Additive)

[0076] The gas barrier composition of the present invention may also contain various additives within a range that does not impair the effects of the present invention. Examples of the additives include: coupling agents, silane compounds, phosphoric acid compounds, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, nucleating agents, oxygen scavengers (compounds having an oxygen scavenging function), tackifiers, etc. These various additives may be used alone or in combination of two or more.

[0077] As the coupling agent, known and commonly used ones can be cited. For example, silane coupling agents, titanium coupling agents, zirconium coupling agents, aluminum coupling agents, etc. can be cited.

[0078] As the silane coupling agent, any known and commonly used one can be used. For example, epoxy group-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-γ-aminopropyltrimethoxysilane; (meth)acryloyl group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane, etc. can be cited.

[0079] Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloyl isostearoyl titanate, isopropyl isostearoyl diacryloyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, tetraoctyl bis(di-tridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl) bis(di-tridecyl) phosphite titanate, bis(dioctylpyrophosphate) oxyacetate titanate, bis(dioctylpyrophosphate) ethylene titanate, etc.

[0080] Examples of the zirconium coupling agent include zirconium acetate, ammonium zirconium carbonate, zirconium fluoride, etc.

[0081] Examples of the aluminum coupling agent include acetylalkoxydipropanol aluminum, diisopropoxymonoethyl acetoacetate aluminum, triethyl acetoacetate aluminum, aluminum triacetylacetonate, etc.

[0082] Examples of the silane compound include alkoxysilane, silazane, siloxane, etc. Examples of the alkoxysilane include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, 3,3,3-trifluoropropyltrimethoxysilane, etc. Examples of the silazane include hexamethyldisilazane, etc. Examples of the siloxane include siloxane containing a hydrolyzable group, etc.

[0083] Among the additives, examples of the inorganic filler include metals, metal oxides, resins, minerals and other inorganic substances and composites thereof. Specific examples of the inorganic filler include silica, alumina, titanium, zirconium oxide, copper, iron, silver, mica, talc, aluminum flakes, glass flakes, clay minerals, etc.

[0084] Examples of the compound having an oxygen scavenging function include hindered phenol compounds, vitamin C, vitamin E, organophosphorus compounds, gallic acid, pyrogallol and other low-molecular organic compounds that react with oxygen, or transition metal compounds such as cobalt, manganese, nickel, iron, copper, etc.

[0085] Examples of the tackifier include xylene resin, terpene resin, phenolic resin, rosin resin, etc. By adding a tackifier, the adhesiveness to various substrates immediately after coating can be improved. The addition amount of the tackifier is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin composition.

[0086] <Gas barrier coating agent>

[0087] The gas barrier coating agent of the present invention can be used as a one-component gas barrier coating agent or a two-component gas barrier coating agent, and either method exhibits high barrier properties. The one-component gas barrier coating agent is a single component composed of the resin (A), divalent metal compound (B), and organic solvent that constitute the above gas barrier composition. The two-component gas barrier coating agent is a combination of a composition (CA) containing the above polyester polyol resin or polyurethane polyol resin (A) and an organic solvent and a composition (CB) containing the above divalent metal compound (B) and an organic solvent.

[0088] (One-Component Gas Barrier Coating Agent and Laminate Using the Same)

[0089] The one-component gas barrier coating agent of the present invention can be obtained by mixing the above resin (A), divalent metal compound (B), and organic solvent. The one-component gas barrier coating agent can obtain a gas barrier coating layer only by directly coating it on a substrate and drying it. The laminate of the present invention is a laminate having a substrate and a coating layer obtained by coating the one-component gas barrier coating agent.

[0090] In the coating layer obtained by coating the gas barrier composition of the present invention, an ionic bond is formed between the resin (A) and the divalent metal compound (B). When the coating agent is coated on a substrate, the volatile components are removed, whereby an ionic bond is formed between the resin (A) and the divalent metal compound (B), and the barrier property is exhibited through this crosslinked structure.

[0091] Therefore, it is speculated that the one-component gas barrier coating agent exhibits gas barrier properties only by being coated and dried, and crosslinked elongation occurs three-dimensionally inside the coating layer, thereby exhibiting higher gas barrier properties.

[0092] In the one-component gas barrier coating agent of the present invention, the acid value of the polyester polyol resin or polyurethane polyol resin (A) is 150 mgKOH / g or less, and it is not easily gelated with the divalent metal compound (B) even when the organic solvent volatilizes, maintaining coating applicability.

[0093] (Substrate)

[0094] Regarding the base material used in the present invention, there are no particular limitations on its material, manufacturing method, or shape within the range where the effects of the present invention can be obtained. Mostly, those in the form of a thin film (sometimes also referred to as a sheet, which is called a thin film in the present invention) are used. As materials for these base materials, for example, materials containing the following substances can be cited: olefin resins such as polyethylene (PE), polypropylene (PP), cyclic olefin polymer (COP), cyclic olefin copolymer (COC), polyester, acrylic, polycarbonate, cellulose ester, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), nylon (NY), and components derived from biomass. In particular, as long as it is a thin film composed of a thermoplastic resin with an olefin resin as the main component, it can be used without particular limitation. Specifically, as olefin resins, the following can be cited: polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene (PP), ethylene-propylene copolymer, α-olefin polymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, cyclic olefin resin, ionomer resin, poly(methylpentene) and other olefin resins; modified olefin resins obtained by modifying olefin resins with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, and other unsaturated carboxylic acids.

[0095] The above-mentioned base material is not particularly limited as long as it is a base material with a thickness commonly used in packaging of foods, daily necessities, pharmaceuticals, etc. From the viewpoints of formability and transparency, a thin film within the range of 1 μm to 500 μm is sufficient, preferably 1 μm to 300 μm, and more preferably 1 μm to 100 μm. If it is less than 1 μm, the strength is insufficient, and if it exceeds 500 μm, the rigidity is too high, and there is a concern that processing will become difficult.

[0096] There are no particular limitations on the manufacturing method of these base materials. Various film-forming methods such as melt extrusion molding, solution casting molding, and calendering molding can be used for manufacturing, or those obtained by further subjecting these to biaxial stretching or uniaxial stretching treatment can also be used. In addition, a thin film that has been subjected to various surface treatments as needed can also be used.

[0097] An inorganic layer may also be formed on at least one side of the above-mentioned substrate. The inorganic substances for forming these inorganic layers are not particularly limited as long as the effects of the present invention can be obtained. Preferably, one or more selected from metals and metal oxides such as alumina, silica, aluminum, zinc oxide, magnesium oxide, calcium oxide, and zirconia are used. From the aspect of well exhibiting barrier properties, one or more selected from alumina, silica, aluminum, zinc oxide, and magnesium oxide are particularly preferably used. As a method for forming the inorganic layer, it is not particularly limited as long as the effects of the present invention can be obtained, and it can be formed by evaporation coating treatment, sputtering treatment, CVD treatment, or coating treatment. From the aspect of being able to uniformly form the inorganic layer, evaporation coating treatment and sputtering treatment are particularly preferably used.

[0098] Of course, examples include: woods, metals, metal oxides, papers, silicon or modified silicon, etc. other than the above, and substrates obtained by joining different raw materials can also be used. The shapes of these substrates are not particularly limited and can be any shape such as a flat plate, a sheet, or a shape having curvature on the entire surface or a part of a three-dimensional shape according to the purpose.

[0099] The method for coating the above-mentioned substrate with the one-component gas barrier coating agent of the present invention is not particularly limited, and known and commonly used coating methods can be used. For example, spraying method, spin coating method, dipping method, roll coating method, knife coating method, knife-over-roll method, doctor blade method, curtain coating method, slot coating method, screen printing method, inkjet method, dispensing method, etc. can be cited.

[0100] After coating the coating obtained by coating the one-component gas barrier coating agent of the present invention, it is dried, whereby the ionic bonds in the coating become denser and the gas barrier property is further improved. Therefore, it is preferable to provide a drying step after coating. As the drying step, normal temperature drying can be carried out, or forced drying such as heating, reduced pressure, or air supply can also be carried out.

[0101] (Other layers)

[0102] In the laminate of the present invention, various combinations of other substrate layers, printing layers, functional coating layers, adhesive layers, etc. can also be made.

[0103] (Other substrate layers)

[0104] As other base material layers, materials containing the following substances can be cited, for example: olefin resins such as polyethylene (PE) or polypropylene (PP), cyclic olefin polymer (COP), cyclic olefin copolymer (COC), polyester, acrylic, polycarbonate, cellulose ester, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), nylon (NY), and components derived from biomass. In particular, as long as it is a film composed of a thermoplastic resin having an olefin resin as a main component, it can be used without particular limitation. As the olefin resin, specifically, polyethylene such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, ethylene-propylene copolymer, α-olefin polymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, cyclic olefin resin, ionomer resin, poly-4-methyl-1-pentene and other olefin resins; modified olefin resins obtained by modifying olefin resins with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid and other unsaturated carboxylic acids. Among them, from the aspect that the effects of the present invention can be significantly obtained, it is preferable to use olefin resins such as polyethylene (PE) or polypropylene (PP), cyclic olefin polymer (COP), cyclic olefin copolymer (COC), and most preferably polyethylene (PE) or polypropylene (PP).

[0105] In addition, it can also be, for example, wood, metal, metal oxide, resin film other than the resin shown in the above layer (A), paper, silicon or modified silicon, etc., or a base material obtained by bonding different raw materials. The shape of the base material is not particularly limited and can be any shape such as a flat plate, a sheet, or a shape having a curvature on the entire surface or a part of a three-dimensional shape according to the purpose. In addition, the hardness, thickness, etc. of the base material are also not limited. In addition, when the laminate of the present invention is used as a packaging material, paper, plastic, metal, metal oxide, etc. can also be used as the base material.

[0106] (Printing layer)

[0107] The printing layer is a layer printed with characters, graphics, marks, other desired patterns, etc. The printing method or printing ink is not particularly limited, and known printing methods or printing inks can be used. Printing inks are mostly used for films used as the above base materials, such as gravure printing method, flexographic printing method, offset lithography printing method, inkjet recording printing method, etc. In addition, printing inks that combine these printing methods with methods cured by active energy rays such as ultraviolet (UV), LED, electron beam (EB), or methods cured by heat are also used. In addition, depending on the solvent used, it is sometimes called water-based ink or organic solvent-based ink.

[0108] Specifically, examples include: gravure printing ink or flexographic printing ink (sometimes in the industry, gravure printing ink and flexographic printing ink are referred to as liquid inks), ultraviolet curable ink for lithographic offset printing, electron beam curable ink for lithographic offset printing, ultraviolet curable ink for inkjet recording printing, electron beam curable ink for inkjet recording printing, and the like.

[0109] Set the position of the printed layer obtained by printing using these inks to any position. It can be set on the above-mentioned first substrate. In addition, the substrate provided with the printed layer can also be one of the components of the laminate of the present invention, and the position is arbitrary. In addition, the ink can be an ink containing resin, colorant, and solvent as essential components, or a so-called transparent ink containing resin and solvent and substantially free of colorant.

[0110] Hereinafter, the liquid ink most commonly used for printing on films will be described.

[0111] The resin used for the liquid ink is not particularly limited. For example, examples include: acrylic resin, polyester resin, styrene resin, styrene-maleic resin, maleic resin, polyamide resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl chloride resin, chlorinated polypropylene resin, cellulose-based resin, epoxy resin, alkyd resin, rosin-based resin, rosin-modified maleic resin, ketone resin, cyclized rubber, chlorinated rubber, butyraldehyde, petroleum resin, etc. One kind can be used, or two or more kinds can be used in combination. Preferably, at least one or two or more kinds selected from polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, and cellulose-based resin are used.

[0112] Examples of the colorant used for the liquid ink include: inorganic pigments such as titanium oxide, iron oxide red, antimony red, cadmium red, cadmium yellow, cobalt blue, iron blue, ultramarine blue, carbon black, and graphite; organic pigments such as soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments; extender pigments such as calcium carbonate, kaolin, barium sulfate, aluminum hydroxide, and talc.

[0113] The organic solvent used for the liquid ink preferably does not contain aromatic hydrocarbon-based organic solvents. More specifically, examples include: alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester-based organic solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; aliphatic hydrocarbon-based organic solvents such as n-hexane, n-heptane, and n-octane; alicyclic hydrocarbon-based organic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, and cyclooctane, etc. One kind can be used or two or more kinds can be used in combination.

[0114] (Functional coating layer)

[0115] As a functional coating layer, for example, coating agents added with various additives can be cited. As additives, for example, the following can be exemplified: modifiers, coupling agents, silane compounds, phosphoric acid compounds, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, anti-blocking agents, colorants, nucleating agents, oxygen scavengers (compounds having an oxygen scavenging function), tackifiers, etc. These various additives are used alone or in combination of two or more.

[0116] As a modifier, publicly known and commonly used ones can be cited. For example, various compounds such as diols, amine compounds, carbodiimides, or isocyanates can be added and used.

[0117] As a coupling agent, publicly known and commonly used ones can be cited. For example, silane coupling agents, titanium coupling agents, zirconium coupling agents, aluminum coupling agents, etc. can be cited.

[0118] As a silane coupling agent, publicly known and commonly used ones can be used. For example, epoxy group-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.; amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-γ-aminopropyltrimethoxysilane, etc.; (meth)acryloyl group-containing silane coupling agents such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.; isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane, etc. can be cited.

[0119] As a titanium coupling agent, for example, isopropyltriisostearoyl titanate, isopropyltrioctanoyl titanate, isopropyldimethylacryloylisostearoyl titanate, isopropylisostearyldiacryloyl titanate, isopropyltris(dioctylpyrophosphate) titanate, tetraoctylbis(di-tridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl) phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, etc. can be cited.

[0120] As a zirconium coupling agent, for example, zirconium acetate, ammonium zirconium carbonate, zirconium fluoride, etc. can be cited.

[0121] As an aluminum coupling agent, acetylalkoxydipropanol aluminum, diisopropoxymonoethylacetoacetate aluminum, triethylacetoacetate aluminum, triacetylacetone aluminum, etc. can be cited.

[0122] Examples of the silane compound include alkoxysilanes, silazanes, siloxanes, etc. Examples of the alkoxysilane include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, 3,3,3-trifluoropropyltrimethoxysilane, etc. Examples of the silazane include hexamethyldisilazane, etc. Examples of the siloxane include siloxanes having hydrolyzable groups, etc.

[0123] Among the additives, examples of the inorganic filler include inorganic substances such as metals, metal oxides, resins, minerals, and composites thereof. Specific examples of the inorganic filler include silica, alumina, titanium, zirconia, copper, iron, silver, mica, talc, aluminum flakes, glass flakes, clay minerals, etc.

[0124] Examples of the compound having an oxygen scavenging function include hindered phenol compounds, vitamin C, vitamin E, organophosphorus compounds, gallic acid, pyrogallol, etc., which are low molecular weight organic compounds that react with oxygen, or transition metal compounds such as cobalt, manganese, nickel, iron, copper, etc.

[0125] Examples of the tackifier include xylene resin, terpene resin, phenolic resin, rosin resin, etc. By adding a tackifier, the adhesiveness to various substrates just after coating can be improved. The addition amount of the tackifier is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin composition.

[0126] (Adhesive layer)

[0127] As the adhesive layer, for the purpose of laminating the laminate of the present invention with other substrates, etc., an adhesive that can be used for general lamination methods can be used. Examples of the lamination method include dry lamination, wet lamination, solventless lamination, extrusion lamination, etc.

[0128] As the adhesive used in the above dry lamination, for example, a single-component type or two-component type curable or non-curable adhesive of vinyl-based, (meth)acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, etc., which is solvent-based, water-based, or emulsion-based, etc., can be used. As the two-component curable adhesive, a two-component curable adhesive of polyol and isocyanate compound can be used. As the coating method of the above adhesive for lamination, for example, it can be coated by the following methods: direct gravure roll coating method, gravure offset roll coating method, kiss coating method, reverse roll coating method, injection method, transfer roll coating method, other methods.

[0129] In addition, various adhesives can be used, and a pressure-sensitive adhesive is preferably used. Examples of the pressure-sensitive adhesive include: a rubber-based adhesive obtained by dissolving polyisobutylene rubber, butyl rubber, or a mixture thereof in an organic solvent such as benzene, toluene, xylene, or hexane; or an adhesive obtained by blending a tackifier such as rosin ester of abietic acid, terpene-phenol copolymer, or terpene-indene copolymer into these rubber-based adhesives; or an acrylic-based adhesive obtained by dissolving an acrylic copolymer having a glass transition temperature of -20°C or lower, such as 2-ethylhexyl acrylate-n-butyl acrylate copolymer or 2-ethylhexyl acrylate-ethyl acrylate-methyl methacrylate copolymer, in an organic solvent, etc.

[0130] (Two-component gas barrier coating agent, and laminate using the same)

[0131] The two-component gas barrier coating agent of the present invention is composed of "composition (CA) obtained by mixing the above polyester polyol resin or polyurethane polyol resin (A) and an organic solvent" and "composition (CB) obtained by mixing the above divalent metal compound (B) and an organic solvent". Regarding the two-component coating agent, for example, composition (CA) can be coated on a substrate and dried to obtain a coating (CA) of composition (CA), and then composition (CB) can be coated on coating (CA) and dried to obtain a coating (CB).

[0132] In addition, the laminate of the present invention is a laminate having a substrate, a coating (CA) obtained by coating composition (CA) of the two-component gas barrier coating agent, and a coating (CB) obtained by coating composition (CB) of the two-component gas barrier coating agent.

[0133] Regarding the order of the laminate, in addition to the order of substrate / coating (CA) / coating (CB), the order of substrate / / coating (CB) / coating (CA) is also possible, and coating (CA) and coating (CB) must be in contact with each other.

[0134] That is, the coating formed by coating the gas barrier composition of the present invention forms an ionic bond between the above resin (A) and the above divalent metal compound (B), and thus exhibits barrier properties by using this crosslinked structure. Therefore, in the two-component gas barrier coating agent, coating (CA) and coating (CB) must be in contact with each other, and the gas barrier properties are exhibited by the contact of each layer.

[0135] In the laminate using the two-component gas barrier coating agent of the present invention, the same substrate or method as that of the laminate having a coating obtained by coating the one-component gas barrier coating agent of the present invention on a substrate can be used for the substrate or coating method, etc.

[0136] Regarding the timing of laminating the coating (CA) and the coating (CB), after the pre-set coating (CA) or coating (CB) is completely dried, the next-set coating (CA) or coating (CB) can be applied, or it can be applied without being completely dried.

[0137] In addition, regarding various other substrate layers, printing layers, functional coating layers, adhesive layers, etc. that can be combined, those the same as the laminate having the coating obtained by applying the one-component gas barrier coating agent of the present invention to a substrate can also be combined.

[0138] (Gas component types that can block permeation)

[0139] As the gases that the laminate of the present invention can block, in addition to oxygen, examples include: non-reactive gases such as carbon dioxide, nitrogen, argon, alcohol components such as methanol, ethanol, and propanol, phenols such as phenol and cresol, and aroma component types composed of low-molecular compounds, such as soy sauce, sauce, miso, limonene, menthol, methyl salicylate, coffee, cocoa, shampoo, conditioner, etc.

[0140] <Packaging material, and packaging material for heat sterilization>

[0141] Since the laminate of the present invention has excellent gas barrier properties, it can be suitably used as a packaging material that requires gas barrier properties. In particular, since high barrier properties are required for foods, daily necessities, electronic materials, medical uses, etc., the packaging material of the present invention can be suitably used.

[0142] Furthermore, since it also has excellent heat resistance and moisture-heat resistance, it can also be suitably used as a packaging material for heat sterilization such as boiling or steaming.

[0143] Examples of the filling content, such as food, include: snack foods such as rice cakes, bean pastries, nuts, biscuits, cookies, wafers, marshmallows, pies, semifinished cakes, candies, snacks, etc.; staple foods such as bread, snack noodles, instant noodles, dried noodles, pasta, aseptically packed rice, mixed porridge, congee, packed rice cakes, cereal foods, etc.; agricultural processed products such as pickled vegetables, boiled beans, natto, miso, frozen tofu, tofu, konnyaku threads, konnyaku blocks, processed wild vegetables, jams, peanut butter, salads, frozen vegetables, processed potato products, etc.; livestock processed products such as hams, bacon, sausages, processed chicken products, corned beef, etc.; fishery processed products such as fish ham and sausage, surimi products, fish cakes, nori, tsukudani, dried bonito, pickled seafood, smoked salmon, spicy pickled cod roe, etc.; fruit meats such as peaches, citrus fruits, pineapples, apples, pears, cherries, etc.; vegetables such as corn, asparagus, mushrooms, onions, carrots, daikon radishes, potatoes, etc.; processed foods such as frozen prefabricated foods and refrigerated prefabricated foods represented by hamburger patties, meatballs, fried aquatic products, dumplings, croquettes, etc.; dairy products such as butter, margarine, cheese, fresh cream, instant milk powder, formula milk for infants, etc.; food products such as liquid seasonings, bagged curries, pet foods, etc.

[0144] In addition, as non-food, it can also be used as various packaging materials such as cigarettes, disposable warmers, infusion bags, etc. for medicines, liquid detergents for washing, liquid detergents for kitchens, liquid detergents for bathing, liquid soaps for bathing, liquid shampoos, liquid hair conditioners, lotions or emulsions for cosmetics, vacuum insulation materials, batteries, etc.

[0145] (Recycled plastic)

[0146] The laminated body or packaging material of the present invention can also be directly processed by various known recycled plastic processing methods to manufacture recycled plastic. As an example of a specific form, recycled plastic can be obtained by having the following manufacturing method, that is: a step of separating the laminated body of the present invention into each base material to obtain a recyclate, or a step of crushing the laminated body and packaging material of the present invention; a step of melt-kneading the crushed film pieces; and a step of granulating the melt-kneaded kneaded product.

[0147] The crusher used in crushing (grinding) is not particularly limited as long as a known grinder is used.

[0148] The shredded film pieces are physically compounded by melt-kneading, solvent casting compounding, latex compounding, polymer compounding, etc. In particular, the melt-kneading method is usually used. As the device for kneading, the following can be cited: a roll, a Henschel mixer, a rotary mixer, a super mixer, a belt-type roll, a V-type compounding machine, etc. Melt-kneading is carried out by such a kneading device, and then pelletization is carried out. In melt-kneading and pelletization, a single-screw or multi-screw extruder is usually used, and the film pieces can be directly put in, or can be put in after being subjected to compression volume reduction treatment by heating or non-heating. Furthermore, in addition to these extruders, a Banbury mixer, a roll, a co-kneader, a jet mill, a Brabender plastograph, etc. can also be used, and these can be operated batchwise or continuously. In addition, the following method can also be adopted, that is, instead of melt-kneading, it is used as a molding resin, and melt-kneading is carried out in the heating cylinder of a molding machine.

[0149] Examples

[0150] The present invention will be described using the following examples, but the present invention is not limited to the examples. It should be noted that, unless otherwise specified, the units are in weight conversion.

[0151] (Production Example 1 Method for producing a polyester polyol resin having an acid value)

[0152] 100.0 parts of phthalic anhydride, 5.0 parts of ethylene glycol, 90.0 parts of glycerol, 85.0 parts of ethyl acetate, and 0.30 part of tetra-isopropoxy titanium were added to a polyester reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a rectifying pipe, a water separator, etc., and slowly heated so that the temperature at the upper part of the rectifying pipe did not exceed 100 °C, and the internal temperature was maintained at 220 °C. When the acid value reached the range of 40-50 mg / KOH / g, the esterification reaction was terminated, and an ethyl acetate solution of a polyester polyol resin: PEs1 with a number average molecular weight of 3000 was obtained. The acid value of PEs1 was 50 mg / KOH / g, and the solid content concentration was 60%.

[0153] (Production Example 2 Method for producing a polyester polyol resin having an acid value)

[0154] In the reaction vessel of Production Example 1, 200.0 parts of phthalic anhydride, 5.0 parts of ethylene glycol, 90.0 parts of glycerol, 125.0 parts of ethyl acetate, and 0.30 part of tetra-isopropoxy titanium were added, and slowly heated so that the temperature at the upper part of the rectifying pipe did not exceed 100 °C, and the internal temperature was maintained at 220 °C. When the acid value reached the range of 90-100 mg / KOH / g, the esterification reaction was terminated, and an ethyl acetate solution of a polyester polyol resin: PEs2 with a number average molecular weight of 4000 was obtained. The acid value of PEs2 was 100 mg / KOH / g, and the solid content concentration was 60%.

[0155] (Production Example 3: Method for Producing Polyester Polyol Resin with Acid Value)

[0156] In the reaction vessel of Production Example 1, 100.0 parts of terephthalic acid, 5.0 parts of ethylene glycol, 90.0 parts of glycerol, 85.0 parts of ethyl acetate, and 0.30 part of tetraisopropoxytitanium were added. It was slowly heated in such a way that the temperature at the upper part of the distillation tube did not exceed 100 °C, and the internal temperature was maintained at 220 °C. When the acid value reached the range of 40 - 50 mg / KOH / g, the esterification reaction was terminated to obtain a polyester polyol resin solution with a number average molecular weight of 3000: an ethyl acetate solution of PEs3. The acid value of PEs3 was 50 mg / KOH / g, and the solid content concentration was 60%.

[0157] (Production Example 4: Method for Producing Polyester Polyol Resin with Acid Value)

[0158] In the reaction vessel of Production Example 1, 200.0 parts of terephthalic acid, 5.0 parts of ethylene glycol, 90.0 parts of glycerol, 125.0 parts of ethyl acetate, and 0.30 part of tetraisopropoxytitanium were added. It was slowly heated in such a way that the temperature at the upper part of the distillation tube did not exceed 100 °C, and the internal temperature was maintained at 220 °C. When the acid value reached the range of 90 - 100 mg / KOH / g, the esterification reaction was terminated to obtain a polyester polyol resin with a number average molecular weight of 4000: an ethyl acetate solution of PEs4. The acid value of PEs4 was 100 mg / KOH / g, and the solid content concentration was 60%.

[0159] (Production Example 5: Method for Producing Polyester Polyol Resin with Acid Value)

[0160] In the reaction vessel of Production Example 1, 100.0 parts of phthalic anhydride, 95.0 parts of glycerol, 85.0 parts of ethyl acetate, and 0.30 part of tetraisopropoxytitanium were added. It was slowly heated in such a way that the temperature at the upper part of the distillation tube did not exceed 100 °C, and the internal temperature was maintained at 220 °C. When the acid value reached the range of 40 - 50 mg / KOH / g, the esterification reaction was terminated to obtain an ethyl acetate solution of polyester polyol resin PEs5 with a number average molecular weight of 3000. The acid value of PEs5 was 50 mg / KOH / g, and the solid content concentration was 60%.

[0161] (Production Example 6: Method for Producing Polyester Polyol Resin with Acid Value)

[0162] In the reaction vessel of Production Example 1, 200.0 parts of phthalic anhydride, 100.0 parts of glycerol, 85.0 parts of ethyl acetate, and 0.30 part of tetra isopropoxy titanium were added, and it was slowly heated in such a manner that the temperature at the upper part of the rectifying tube did not exceed 100 °C, and the internal temperature was maintained at 220 °C. When the acid value reached the range of 90 to 100 mg / KOH / g, the esterification reaction was terminated to obtain an ethyl acetate solution of a polyester polyol resin: PEs6 with a number average molecular weight of 3000. The acid value of PEs6 was 100 mg / KOH / g, and the solid content concentration was 60%.

[0163] (Method for producing a polyester polyol resin having an acid value in Production Example 7)

[0164] In Production Example 1, as the raw materials added, 150.0 parts of phthalic anhydride, 150.0 parts of terephthalic acid, 140.0 parts of adipic acid, 50.0 parts of ethylene glycol, 110.0 parts of diethylene glycol, 100.0 parts of neopentyl glycol, 300.0 parts of ethyl acetate, and 0.60 part of tetra isopropoxy titanium were added, and it was slowly heated in such a manner that the temperature at the upper part of the rectifying tube did not exceed 100 °C, and the internal temperature was maintained at 220 °C. When the acid value became 2 mg / KOH / g or less, the esterification reaction was terminated to obtain an ethyl acetate solution of a polyester polyol resin: PEs7 with a number average molecular weight of 6000. The acid value of PEs7 was 1 mg / KOH / g, and the solid content concentration was 60%.

[0165] (Method for producing a polyurethane polyol resin having an acid value in Production Example 8)

[0166] In the reaction vessel of Production Example 1, 90.0 parts by mass of DMPA (2,2 - dimethylolpropionic acid), 54.0 parts by mass of methyl ethyl ketone, and 81 parts by mass of tetrahydrofuran were added, and stirring was carried out under a nitrogen stream. Subsequently, 56.0 parts by mass of XDI (xylylene diisocyanate) was added, and the temperature was raised to 60 °C. After stirring for 1 hour, the temperature was lowered to 40 °C or lower, and then 56.0 parts by mass of XDI was further added, and the temperature was raised to 60 °C again. The reaction was continued until the disappearance of the isocyanate group was confirmed by infrared spectroscopy. Subsequently, 148.0 parts by mass of methanol was added as a diluting solvent to obtain a methyl ethyl ketone - tetrahydrofuran solution of a polyurethane resin containing a carboxyl group: Ure1. The acid value of Ure1 was 40 mg / KOH / g, and the solid content concentration was 60%.

[0167] (Method for producing a polyurethane polyol resin having an acid value in Production Example 9)

[0168] In the reaction vessel of Production Example 1, 252.8 parts of phthalic anhydride, 62.0 parts of ethylene glycol, 128.6 parts of neopentyl glycol, 105.8 parts of 1,6 - hexanediol, and 298.6 parts of ethyl acetate were added, and esterification was carried out. After the esterification was completed, 18.2 g of isophorone diisocyanate and 109.6 parts of ethyl acetate were added and aminocarbonylation was carried out. The aminocarbonylation reaction was terminated when the acid value became 1 mg / KOH / g or less, and a polyurethane polyol resin: an ethyl acetate solution of Ure2 was obtained. The acid value of Ure2 was 1 mg / KOH / g, and the solid content concentration was 60%.

[0169] (Method for producing a polyether polyurethane polyol resin having no acid value in Production Example 10)

[0170] In the reaction vessel of Production Example 1, 213.7 parts of a difunctional polypropylene glycol (hereinafter sometimes abbreviated as PPG) having a molecular weight of 400, 225.2 parts of a difunctional PPG having a molecular weight of 700, 69.0 parts of a difunctional PPG having a molecular weight of 2000, and 41.1 parts of a trifunctional PPG having a molecular weight of 430 were added, and while stirring, 152.6 parts of toluene diisocyanate were added simultaneously. After reaching 90 °C, 306.0 parts of ethyl acetate were added, and the reaction temperature was maintained at 90 °C and synthesis was carried out. When it was confirmed that NCO (%) was 0.1% or less and the viscosity measured by a B-type viscometer was in the range of 2000 - 3000 mPa, a polyether polyurethane polyol resin: Ether1 was obtained. The solid content concentration was 60%.

[0171] (Method for producing a polyvinyl alcohol solution (hereinafter sometimes abbreviated as PVA) in Production Example 11)

[0172] 5 g of KURARAY POVAL manufactured by KURARAY Co., Ltd., trade name: 28 - 98, and 95 g of water were mixed in a 200 ml vial and heated and stirred at 80 °C, whereby a PVA solution was obtained. The acid value of this solution was 0 mg / KOH / g.

[0173] (Method for producing a polyacrylic acid solution (hereinafter sometimes abbreviated as PAA) in Production Example 12)

[0174] 2 g of Aron A - 10H manufactured by Toagosei Co., Ltd., and 98 g of isopropyl alcohol were mixed in a 200 ml vial and heated and stirred at 80 °C, whereby a PAA solution was obtained. The acid value of this solution was 748 mg / KOH / g.

[0175] (Method for producing a dispersion of zinc oxide (ZnO) as a divalent metal compound in Production Example 13)

[0176] 200 g of ZnO with a primary particle size of 20 nm (manufactured by Sakai Chemical Industry Co., Ltd., FINEX-50) and 800 g of methyl ethyl ketone were mixed and dispersed for 1 hour using zirconia beads with a diameter of 0.3 mm in a bead mill (manufactured by Kotobuki Corporation: Ultra Apex Mill UAM-015). After that, the beads were screened to obtain a ZnO solution with a solid component concentration of 20%. This solution was designated as ZnO (MEK dispersion). The particle size of ZnO in this dispersion was 150 nm.

[0177] (Single-component gas barrier coating agent and method for producing and evaluating a laminate using the same)

[0178] (Examples 1 to 7, Comparative Examples 1 to 3)

[0179] Gas barrier compositions for Examples 1 to 7 and Comparative Examples 1 to 3 were prepared according to the formulation table in Table 1 and used as gas barrier coating agents. The coating agent was coated on a PET film (thickness: 12 μm) to obtain a laminate. The oxygen transmission rate, stability of the coating solution, and coating appearance were evaluated.

[0180] (Coating method of gas barrier coating agent)

[0181] Matsuo Sangyo Co., Ltd.'s K303 rods No.1 Yellow / 6 μm, No.2 Red / 12 μm, No.3 Green / 24 μm, and No.4 Black / 40 μm were prepared. The gas barrier coating agent was coated on a PET film (manufactured by TOYOBO Co., Ltd.: E5100, thickness: 12 μm), and then dried at 80 °C for 1 minute to form a coating, obtaining a laminate. The rod was selected in such a way that the weight of the coating when the sample was dried was approximately 1.0 g / m 2 .

[0182] <Evaluation of gas barrier properties of laminate: Oxygen transmission rate>

[0183] The laminate obtained in the previous item was used for evaluation. The oxygen transmission rate (hereinafter sometimes abbreviated as OTR) was measured in accordance with JIS-K7126 (isobaric method) using an oxygen transmission rate measuring device OX-TRAN1 / 50 manufactured by Mocon under an atmosphere of 23 °C and 0% RH and an atmosphere of 23 °C and 90% RH. RH represents relative humidity. The unit of OTR is cc / day·atm·m 2 , and the lower the value, the better the barrier properties. The evaluation was as follows.

[0184] 5: OTR: 20 cc or less

[0185] 4: OTR: 20 cc to 40 cc

[0186] 3: OTR: 40 cc to 60 cc

[0187] 2: OTR: 60 cc to 100 cc

[0188] 1: OTR: 100 cc or more

[0189] <Stability and Appearance Evaluation of Coating Solution>

[0190] Evaluate the smoothness during the coating of the gas barrier coating agent described in the formulation table of Table 1 according to the following criteria. Adjust so that the weight of the resin component contained in the coating solution is the same and the solid content during coating is fixed at about 8%.

[0191] (Smoothness Evaluation of Coating Film)

[0192] 1: A smooth coating film is obtained

[0193] 0: Due to the increase in the viscosity of the solution, a uniform coating film cannot be obtained. ZnO precipitation is found.

[0194] Show the results in Table 1.

[0195] [Table 1]

[0196]

[0197] In Examples 1 to 7, a smooth coating film with excellent oxygen barrier properties was obtained. Regarding this, it is speculated that after the coating solution is coated on the film and dried, the carboxyl groups present in the resin solution undergo an ionic crosslinking reaction with "Zn 2+ " generated by the ionization of ZnO, reducing the free volume in the coating film, thereby exhibiting excellent oxygen barrier properties. It is speculated that since the ionic crosslinking reaction does not occur in the state where the solution is allowed to stand, a smooth coating film is obtained. In Comparative Example 1, although a smooth coating film was obtained, the oxygen barrier properties were poor. It is speculated that the reason is that since PEs7 has almost no acid value, the ionic crosslinking reaction did not occur. In Comparative Example 2, although good oxygen barrier properties were obtained at 0% RH, the oxygen barrier properties were poor at 90% RH, and the smoothness of the coating film was also poor. It is speculated that the reason is that since PVA is a water-soluble resin, its compatibility with ZnO (MEK dispersion) is poor. In Comparative Example 3, the evaluation of all items was poor. Since the acid value of PAA is high and its reactivity with ZnO (MEK dispersion) is high, gel substances are generated, a uniform coating film cannot be obtained, and the oxygen barrier properties are also poor.

[0198] (Production and Evaluation Method of Two-Component Gas Barrier Coating Agent and Laminate Using the Same)

[0199] (Examples 8 to 12, Comparative Examples 4 to 5)

[0200] Prepare the compositions (CA) and (CB) of Examples 8 to 12 and Comparative Examples 4 to 5 according to the compounding table in Table 2, and use these to prepare a two-component gas barrier coating agent. Coating the coating agent on a PET film (thickness: 12 μm) to obtain a laminate. Evaluate the oxygen transmission rate under normal conditions and after cooking.

[0201] (Method for manufacturing a laminate of PET film / coating (CA) / coating (CB))

[0202] (Coating method for the first layer)

[0203] Using a bar coater, coat the composition (CA) described in Table 2 on a PET film (manufactured by TOYOBO Co., Ltd.: E5100, thickness: 12 μm) to obtain a coating (CA). A bar coater with a weight of about 1.0 g / m after drying at 80 °C for 1 minute was selected. 2 of the bar coater.

[0204] (Coating method for the second layer)

[0205] Using a bar coater, coat the composition (CB) described in Table 2 on the above-prepared coating (CA) to obtain a coating (CB). A bar coater with a weight of about 1.0 g / m after drying at 80 °C for 1 minute was selected. 2 of the bar coater.

[0206] (Manufacture of laminated film)

[0207] In the laminate of PET film / coating (CA) / coating (CB) obtained in the previous item, coat a laminating adhesive on the coating (CB) surface, and bond a CPP film (manufactured by Toray Advanced Film Co., Ltd.: ZK-93KM, thickness 70 μm) to produce a laminated film. A laminating adhesive mixed at a specified ratio with DICDRY: LX-703 (polyol material) and DICDRY: KR-90 (polyisocyanate material) manufactured by DIC Corporation was used, and the coating amount was coated in the range of 2.5 to 3.0 g / m. 2 The curing was carried out at 40 °C for 3 days.

[0208] (Cooking evaluation of laminated film)

[0209] The laminated film obtained in the previous item is cut into 150 mm × 300 mm, bent with CPP on the inside, heat-sealed at 1 atm and 210 °C for 1 second to produce a bag. Water is added as the content. For the filled bag, steam sterilization treatment is carried out under the conditions of 120 °C and 30 minutes. After taking out the bag, it is opened and the oxygen permeability is evaluated.

[0210] [Table 2]

[0211]

[0212] In Examples 8 to 12, excellent oxygen barrier properties were obtained both in the normal state and after retorting. It is speculated that the carboxyl group of the acid value-containing resin coated on the first layer undergoes an ionic crosslinking reaction with "Zn generated by the ionization of ZnO coated on the second layer", reducing the free volume in the coating film, thereby exhibiting excellent oxygen barrier properties. When retorting treatment is carried out, usually the laminated film is treated severely, so the barrier property deteriorates. It is speculated that in Examples 8 to 12 described in the present invention, by carrying out retorting treatment, the ionization of ZnO coated on the second layer is further promoted, and the ionic crosslinking with the first layer becomes stronger, thereby maintaining good oxygen barrier properties. 2+ In Comparative Example 4, since PEs7 coated on the first layer hardly has an acid value, no ionic crosslinking occurs and oxygen barrier properties cannot be obtained. In Comparative Example 5, although the PVA solution has good oxygen barrier properties at low humidity, it cannot obtain good oxygen barrier properties at high humidity and after retorting.

[0213] In Comparative Example 4, since PEs7 coated on the first layer hardly has an acid value, no ionic crosslinking occurs and oxygen barrier properties cannot be obtained. In Comparative Example 5, although the PVA solution has good oxygen barrier properties at low humidity, it cannot obtain good oxygen barrier properties at high humidity and after retorting.

Claims

1. A composition for gas barrier, characterized in that, it contains: a polyester polyol resin or a polyurethane polyol resin (A) having an acid value, a divalent metal compound (B), and an organic solvent, and the acid value of the polyester polyol resin or the polyurethane polyol resin (A) in the composition is 150 mgKOH / g or less.

2. The composition for gas barrier according to claim 1, wherein, the divalent metal compound (B) is at least one selected from zinc compounds, magnesium compounds, and calcium compounds.

3. The composition for gas barrier according to claim 1, wherein, the divalent metal compound (B) is fine particles having an average particle diameter of 500 nm or less.

4. The composition for gas barrier according to claim 1, wherein, the solid content of the divalent metal compound (B) is 20 to 90% by mass based on the total mass of all solid components in the composition.

5. A gas barrier coating agent, characterized in that, it contains the composition according to any one of claims 1 to 4.

6. A laminate having a substrate and a coating layer obtained by coating the coating agent according to claim 5.

7. A packaging material having the laminate according to claim 6.

8. A gas barrier coating agent, characterized in that, it contains the composition according to any one of claims 1 to 4 and is a two-component type of composition CA and composition CB, the composition CA contains the polyester polyol resin or the polyurethane polyol resin (A) and an organic solvent, the composition CB contains the divalent metal compound (B) and an organic solvent.

9. A laminate having a substrate, a coating layer (CA) obtained by coating the composition CA according to claim 8, and a coating layer (CA) obtained by coating the composition CB according to claim 8.

10. A packaging material having the laminate according to claim 9.

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