JP5891766B2 - Barrier laminate film and packaging material using the same - Google Patents

Description

  The present invention relates to a packaging material for packaging food, medicine, industrial parts, etc., having barrier properties to oxygen, water vapor, aroma components, etc., easy tearability in both the vertical and horizontal directions, heat sealability, The present invention relates to a barrier laminate film having good packaging machine suitability and laminate suitability, and a packaging material using the film.

  Packaging materials used for packaging food and beverages have functions such as strength, resistance to cracking, retort resistance, and heat resistance to protect the contents from various distribution, storage such as refrigeration and heat sterilization. In addition to this, a wide variety of functions are required such as excellent transparency so that the contents can be confirmed. On the other hand, when the bag is sealed by heat sealing, an unstretched polyolefin film having excellent heat processability is essential, but the unstretched polyolefin film has many functions that are insufficient as a packaging material.

  For these reasons, a composite flexible film in which different polymer materials are combined is widely used as the packaging material. Generally, it consists of a thermoplastic film layer, etc., which becomes an outer layer having product protection and various functions, and a thermoplastic film layer, etc., which becomes a sealant layer. There is also a method in which three layers of thermoplastic resin for the sealant layer are melt-extruded and an unstretched laminated sheet is molded and then stretched (for example, see Patent Document 1). The dry lamination method (for example, refer patent document 2) which manufactures a multilayer film by adhere | attaching a layer is simple and has become mainstream. However, the adhesive used in this application generally has only a function of adhering between different films.

  Further, in recent years, there has been a demand for further enhancement of functionality for multilayer films. For the purpose of long-term storage of food, oxygen barrier properties that prevent the entry of oxygen from the outside in order to suppress oxidation, carbon dioxide barrier properties, various aroma components, etc. A barrier function is also required. When imparting a barrier function to a multilayer film, unstretched polyolefin films used for the inner layer (sealant side) have poor gas barrier properties and are difficult to impart a barrier function by coating or vapor deposition. Therefore, a barrier function is often imparted to various films (polyester resins such as polyethylene terephthalate (hereinafter referred to as PET), polyamide resins, stretched polyolefin resins, etc.) used on the outer layer side.

  When a barrier function is imparted to these outer layer side films by coating, as the barrier coating material, vinylidene chloride having a high oxygen barrier property and a high water vapor barrier property has been widely used, but dioxins are generated during incineration of waste, etc. There's a problem. In addition, when a polyvinyl alcohol resin or an ethylene-polyvinyl alcohol copolymer is used as a barrier coating material, the oxygen barrier property under low humidity is high, but the oxygen barrier property under high humidity, boil resistance, and retort resistance are inferior. There is a problem. On the other hand, a film in which a metal vapor deposition layer such as aluminum is provided as a gas barrier layer is opaque and has a problem that the inside cannot be visually recognized and a microwave oven cannot be used. Further, a film provided with a vapor deposition layer of a metal oxide such as silica or alumina as a gas barrier layer is expensive and has poor flexibility, and there is a problem that the barrier performance varies due to cracks or pinholes.

  On the other hand, a method for imparting an oxygen barrier function to an adhesive used during lamination is also known. This method has an advantage that a barrier film can be produced without using a film having a special gas barrier applied due to the steps and constitutions essential for producing a laminated film. On the other hand, gas permeability is generally high in a flexible molecular structure that is essential for developing adhesive performance. For this reason, the adhesive ability and the barrier ability are often in a trade-off relationship, and this elimination increases the technical difficulty.

  As such a gas barrier material that can be used as an adhesive for laminated films, for example, a thermosetting gas barrier polyurethane resin containing a resin cured product obtained by reacting an active hydrogen-containing compound and an organic polyisocyanate compound, 20% by mass or more of the skeleton structure derived from meta-xylene diisocyanate is contained in the cured resin, and the proportion of the trifunctional or higher functional compound in the active hydrogen-containing compound and the organic polyisocyanate compound is the active hydrogen-containing compound. There is provided a thermosetting gas barrier polyurethane resin characterized by being 7% by mass or more based on the total amount of the organic polyisocyanate compound (for example, see Patent Document 3).

  However, the resin provided in Patent Document 3 has a laminate strength when various films used on the outer layer side, particularly PET / CPP (cast polypropylene, hereinafter referred to as CPP) film widely used in food packaging, are used. There was a problem of being inferior.

  Further, for example, it is also provided that an epoxy resin cured product and / or a polyurethane resin cured product derived from metaxylylenediamine is used as an adhesive having excellent oxygen barrier properties (for example, Patent Documents 4 to 4). 5). However, in this technique, it is necessary to include a metaxylylene skeleton derived from an expensive monomer at a high content (at least 40% by mass, and an example in which 50% by mass or more is included in the examples). There was a problem. Furthermore, the barrier function by these adhesives is only oxygen barrier property and is not mentioned about water vapor barrier property, but generally has almost no barrier performance.

  Packaging materials for foods and pharmaceuticals need both oxygen and water vapor barrier functions. Therefore, as a practical product, a laminate component using an aluminum foil having a barrier property is used. Due to the recent emphasis on environmental issues, there is a strong demand from the market for laminated films that do not use aluminum foil, and that retain oxygen barrier properties, water vapor barrier properties, and even barrier properties to aroma components.

  Also, in the trend toward universal design, as a consideration for the socially vulnerable (elderly, infants, people with disabilities, etc.), methods that are easy for consumers to open, such as easy opening and tearing, are becoming important. is there. However, when trying to improve easy-openability and easy-tearability, the original functions of packaging materials, such as heat sealability, pinhole resistance, and impact resistance at low temperatures, are reduced during transportation and store display. There were problems such as broken bags and spilled contents.

  Bags made of a cellophane / polyethylene laminate have been put to practical use as films that are easily tearable. However, cellophane is hygroscopic, so the physical properties change due to humidity is large, dimensional stability is inferior, curling, blocking, etc. are suitable for laminating, printing, bag making, packaging machinery, etc. There was a problem.

  In order to protect the contents (improvement of moisture resistance and the like), a polyester film has been proposed as an alternative to cellophane (see, for example, Patent Document 6), but easy tearability in both the vertical and horizontal directions cannot be maintained. A packaging bag made of a syndiotactic polystyrene resin layer has also been proposed (see, for example, Patent Document 7). However, polystyrene is generally poor in moisture resistance, and packaging of contents with high hygroscopicity such as powders and tablets causes discoloration, deterioration of contents components, and the like, so that the storage period is limited. Furthermore, heat resistance, solvent resistance, and oil resistance were inferior, and there were problems with packaging suitability and printing workability.

  Since these materials having excellent easy tearability are mainly stretched, orientational crystallization proceeds, the melting point and the glass transition point rise, and the heat sealability is poor. Therefore, a sealant film made of a low melting point, low rigidity polyethylene-based resin or polypropylene-based resin having sealability is required to achieve a performance balance between moisture resistance and sealability. That is, a cellophane / sealant film, easily tearable polyester / sealant film, paper / easy tearable polystyrene / sealant film, etc. are required. Of course, easy tearability depends on the type and thickness of the sealant film, and depending on the structure, tearability is not easily or often not expressed in many cases.

  Furthermore, if the adhesion between the aluminum foil or aluminum vapor deposition layer and other resin layers is poor, delamination is likely to occur, and only the aluminum layer on the surface peels off when opened, making it difficult to take out the contents. Sometimes it becomes.

  In order to prevent such delamination, an anchor coat layer is usually provided between the aluminum layer and other resin layers (see, for example, Patent Document 8). Films have many production steps and are inferior in terms of production efficiency.

  From the viewpoint of environmental and social demands in recent years, packaging materials with oxygen, water vapor, and aroma component barrier performance without the use of aluminum foil that can be easily opened are compatible with universal design and have excellent packaging properties Considering that development is an urgent issue, laminate packaging materials that have easy tearability in both the vertical and horizontal directions, have good packaging machinery, have a good balance of sealing and laminating properties, and have good productivity. Is sought after.

JP 2006-341423 A JP 2003-013032 A JP 2004-010656 A JP 2004-195971 A JP 2008-188975 A JP 2001-233374 A JP 2002-240209 A JP 2009-166884 A

  An object of the present invention has been made in view of the above-described problems, and relates to a packaging material for packaging food, medicine, industrial parts, etc., having oxygen, water vapor, aroma component barrier performance, The object is to provide a barrier laminate film having no easy tearability in both directions, heat sealability, suitability for packaging machines, a decrease in laminate strength with time, poor appearance of laminate, and a packaging material using the film.

  As a result of intensive studies to solve the above problems, the present inventors have laminated a film having a resin layer containing a cyclic polyolefin resin and another resin film using an adhesive having a specific structure. The present inventors have found that the above problems can be solved and have completed the present invention.

  That is, the present invention provides a polyester polyol having two or more hydroxyl groups, a film (I) having a resin layer (i) containing 30% by mass or more of a cyclic polyolefin resin (i-1) as a resin component, and the resin film. A barrier laminate film characterized by being laminated using a barrier adhesive containing (A) and a polyisocyanate (B) having two or more isocyanate groups, and using the same A packaging material is provided.

  The barrier laminate film of the present invention has oxygen, water vapor, and aroma component barrier properties while having sufficient adhesion between substrates, and is easy to tear in both vertical and horizontal directions, heat sealability, and suitability for packaging machinery. It is a multilayer film that is excellent and has no decrease in laminate strength with time, poor appearance of laminate, and the like. Due to the above-described performance, this film can be suitably used as a packaging material for not only foods but also pharmaceuticals, precision industrial products and the like. Furthermore, the visibility of the contents can be imparted by using a transparent base film.

  The barrier laminate film of the present invention is formed by laminating a resin layer containing at least 30% by mass of a cyclic polyolefin resin (i-1) as a resin component with an adhesive having a specific structure. It is a multilayer film.

  As described above, the barrier laminate film of the present invention uses a single-layer or multilayer film (I) having a resin layer (i) containing 30% by mass or more of the cyclic polyolefin resin (i-1) as a resin component. It is essential. In the case of a multilayer film, the resin layer (i) may be included as a single layer or a plurality of layers. Examples of such a cyclic polyolefin resin (i-1) include a norbornene polymer, a vinyl alicyclic hydrocarbon polymer, and a cyclic conjugated diene polymer. Among these, norbornene-based polymers are preferable. The norbornene-based polymer includes a ring-opening polymer of a norbornene-based monomer (hereinafter referred to as “COP”), a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an olefin such as ethylene (hereinafter, referred to as “COP”). , “COC”). Furthermore, COP and COC hydrogenates are particularly preferred. The weight average molecular weight of the cyclic polyolefin resin is preferably 5,000 to 500,000, more preferably 7,000 to 300,000.

  The norbornene polymer and the norbornene monomer used as a raw material are alicyclic monomers having a norbornene ring. Examples of such norbornene-based monomers include norbornene, tetracyclododecene, ethylidene norbornene, vinyl norbornene, ethylidene tetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenyl norbornene, methoxycarbonyl norbornene, methoxycarbonyl And tetracyclododecene. These norbornene monomers may be used alone or in combination of two or more.

  The norbornene-based copolymer is a copolymer of the norbornene-based monomer and an olefin copolymerizable with the norbornene-based monomer, and examples of such olefin include the number of carbon atoms such as ethylene, propylene, and 1-butene. Examples thereof include olefins having 2 to 20; cycloolefins such as cyclobutene, cyclopentene, and cyclohexene; and non-conjugated dienes such as 1,4-hexadiene. These olefins can be used alone or in combination of two or more.

  As a commercially available product that can be used as the cyclic polyolefin resin (i-1), examples of the ring-opening polymer (COP) of the norbornene monomer include “ZEONOR” manufactured by Nippon Zeon Co., Ltd. Examples of the norbornene-based copolymer (COC) include “Appel” manufactured by Mitsui Chemicals, Inc., “TOPAS” manufactured by Polyplastics Co., Ltd., and the like.

  As described above, the content of the cyclic polyolefin-based resin (i-1) with respect to the resin component forming the resin layer (i) is such that the obtained barrier laminate film is easily tearable, suitable for packaging machinery, laminate strength, and its aging. From the viewpoint of the suppression of change and the barrier property to water vapor and aroma components, it is essential to be 30% by mass or more. If the content is lower than this, it is difficult to obtain a multilayer film having the intended performance. Particularly preferred is 50% by mass or more.

  In addition, the glass transition point (Tg) of the cyclic polyolefin resin (i-1) is 60 ° C. or higher from the viewpoints of suppression of adsorption of volatile components (fragrance components) from the contents of the resulting multilayer film, water vapor barrier properties, and the like. It is preferable that In the case of a multilayer film (I) in which other resin layers (ii) are laminated in order to further improve the packaging machine suitability as described later, the production by the coextrusion lamination method is possible, From the viewpoint of availability of industrial raw materials, Tg is preferably 200 ° C. or lower. The temperature is particularly preferably 70 ° C to 180 ° C. As the cyclic polyolefin resin (i-1) having such Tg, the content ratio of the norbornene monomer is preferably in the range of 30 to 90% by mass, more preferably 40 to 90% by mass, Preferably it is 50-85 mass%. When the content ratio is within this range, the rigidity, easy tearability, and processing stability of the film are improved. In addition, the glass transition point and melting | fusing point in this invention are measured by differential scanning calorimetry (DSC).

  On the other hand, norbornene copolymers having a high glass transition point (Tg) have low tensile strength, are extremely easy to break, and may tear easily. In view of the balance, it is also preferable to blend a high Tg product and a low Tg product having a glass transition point of less than 100 ° C. In addition, from the viewpoint of packaging mechanical properties (no wrinkles or shrinkage on the sealing surface during bag making and article filling, pinholes etc. from the heat seal part), a melting point or glass transition that is 20 ° C. lower than the melting point of the resin film to be laminated It is preferable to use the resin seed | species which has a point (Tg) individually or in mixture.

  Especially, the rigidity is so high that it easily tears or breaks when dropped during transportation, the sealing start temperature becomes too high, or the strength maintenance (hot tack property) immediately after heat sealing is improved. By blending, it is possible to improve the falling bag strength and the packaging machine suitability. Also, a polyethylene resin (i-2) and / or a polypropylene resin (i-3) that is compatible with COC and does not contain a cyclic structure, a rubber elastomer resin having a low melting point and a low Tg, and the like are blended. Is also effective.

The polyethylene-based resin (i-2) has a density for easy tearing, high heat seal strength, pinhole resistance, and maintenance of interlayer strength when the resin layer (ii) described later is laminated. preferably it has a 0.900~0.950g / cm ^3, more preferably at a density of 0.905~0.945g / cm ^3.

  Examples of the polyethylene resin (i-2) include polyethylene resins such as very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), and low density polyethylene (LDPE), and ethylene-vinyl acetate copolymer (EVA). ), Ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate (EMA) copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer (E-) EA-MAH), ethylene-acrylic acid copolymers (EAA), ethylene-based copolymers such as ethylene-methacrylic acid copolymer (EMAA); and ethylene-acrylic acid copolymer ionomers, ethylene-methacrylic acid Examples include copolymer ionomers, alone or in combination of two or more. Mixed and may also be used. Among these, VLDPE, LDPE, LLDPE, and MLDPE are preferable because of a good balance between sealing properties and easy tearability.

  The LDPE may be a branched low density polyethylene obtained by a high pressure radical polymerization method, and is preferably a branched low density polyethylene obtained by homopolymerizing ethylene by a high pressure radical polymerization method.

  As LLDPE and MLDPE, an ethylene monomer as a main component and a comonomer such as butene-1, hexene-1, octene-1, and 4-methylpentene are produced by a low-pressure radical polymerization method using a single site catalyst. -Copolymerized olefin. As a comonomer content rate in LLDPE, it is preferable that it is the range of 0.5-20 mol%, and it is more preferable that it is the range of 1-18 mol%.

  Examples of the single-site catalyst include various single-site catalysts such as metallocene catalyst systems such as combinations of metallocene compounds of Group IV or V transition metals and organoaluminum compounds and / or ionic compounds. In addition, the single-site catalyst has a uniform active site, so the molecular weight distribution of the resulting resin is sharper than a multi-site catalyst with a non-uniform active site. This is preferable because a resin having physical properties excellent in stability of sealing strength and anti-blocking property can be obtained.

As described above, the density of the polyethylene resin (i-2) is preferably 0.900 to 0.950 g / cm ³ . If the density is within this range, it has moderate rigidity, excellent mechanical strength such as heat seal strength and pinhole resistance, and film film formability and extrusion suitability are improved. Moreover, it is preferable that melting | fusing point is generally the range of 60-130 degreeC, and 70-125 degreeC is more preferable. If melting | fusing point is this range, processing stability and the extrusion workability at the time of using it mixed with the said cyclic polyolefin resin (i-1) will improve. Moreover, it is preferable that MFR (190 degreeC, 21.18N) of the said polyethylene-type resin (i-2) is 2-20 g / 10min, and it is more preferable that it is 3-10 g / 10min. When the MFR is within this range, the extrusion moldability of the film is improved.

  Since such a polyethylene resin (i-2) has good compatibility with the cyclic polyolefin resin (i-1), transparency as a film can be maintained. Further, without using an adhesive resin or the like, the interlayer adhesion strength between the resin layer (i) and the resin layer (ii) described later can be maintained, and since it has flexibility, the pinhole resistance is also improved. . Furthermore, when improving pinhole resistance, it is preferable to use LLDPE and MLDPE.

  Examples of the polypropylene resin (i-3) include propylene homopolymer, propylene / α-olefin random copolymer, such as propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene- An ethylene-butene-1 copolymer, a metallocene catalyst type polypropylene, etc. are mentioned. These may be used alone or in combination. A propylene-α-olefin random copolymer is desirable, and a propylene / α-olefin random polymer polymerized using a metallocene catalyst is particularly preferable. When these polypropylene resins are used, the heat resistance of the film is improved and the softening temperature can be increased, so that steam such as boiling at 100 ° C. or lower, hot filling, or retort sterilization at 100 ° C. or higher is used. -It can be suitably used as a packaging material excellent in high-pressure heat sterilization characteristics.

  In addition, these polypropylene resins (i-3) preferably have an MFR (230 ° C.) of 0.5 to 30.0 g / 10 minutes and a melting point of 110 to 165 ° C., more preferably MFR ( 230 ° C.) is 2.0 to 15.0 g / 10 min, and the melting point is 115 to 162 ° C. If MFR and melting | fusing point are this range, there will be little shrinkage | contraction of the film at the time of heat sealing, and also the film-forming property of a film will improve.

  Moreover, in order to improve the heat-sealability of the barrier laminate film of the present invention, and to provide easy-opening properties, etc., the resin layer (i) containing the cyclic polyolefin resin (i-1) as a main component is used. It can also be set as the multilayer film (I) formed by laminating | stacking the resin layer (ii) which has polyolefin-type resin (ii-1) as a main component further on the single side | surface or both surfaces. Here, the main component means that the resin component is contained in an amount of 50% by mass or more, preferably 80% by mass or more as the resin component forming the resin layer.

  As the polyolefin resin (ii-1), a polyethylene resin (ii-2) or a polypropylene resin (ii-3) is preferably used alone or in combination.

As said polyethylene-type resin (ii-2) and polypropylene-type resin (ii-3), the polyethylene-type resin (i-2) which can be used together with the above-mentioned cyclic polyolefin-type resin (i-1), polypropylene-type resin (i -3) can be mentioned, and preferred examples are also the same. When laminating the resin layer (ii) as the heat seal layer, a resin mixture in which the polyethylene resin (ii-2) and the polypropylene resin (ii-3) are used in combination facilitates cohesive failure. Openability can be imparted. The polyethylene-based resin (ii-2) when this, low density polyethylene having a density of 0.91~0.93g / cm ^3, or density using a high-density polyethylene 0.94~0.96g / cm ³ It is preferable. Furthermore, the melt flow rate (190 ° C., 21.18 N) is preferably 1 g / 10 min or more from the viewpoint of film formability.

  Furthermore, as a use ratio in the case of mixing and using the said polyethylene-type resin (ii-2) and the said polypropylene-type resin (ii-3), the mass represented by (ii-2) / (ii-3). The ratio is preferably in the range of 10 to 40/60 to 90 from the viewpoint that easy-openability can be easily expressed, and particularly preferably in the range of 15 to 30/70 to 85.

  Moreover, as a polypropylene resin (ii-3) used for the resin layer (ii) as a seal layer, from the viewpoint of easy adjustment of seal strength, an ethylene-propylene random copolymer, ethylene-propylene- It is preferable to use an ethylene-propylene copolymer polymerized using a butene-1 terpolymer or a single site catalyst.

  In addition, these polypropylene resins (ii-3) preferably have an MFR (230 ° C.) of 0.5 to 30.0 g / 10 min and a melting point of 120 to 165 ° C., more preferably MFR ( 230 ° C.) is 2.0 to 15.0 g / 10 min, and the melting point is 125 to 162 ° C. If MFR and melting | fusing point are this range, there will be little shrinkage | contraction of the film at the time of sealing, and also the film-forming property of a film will improve.

  In addition, the resin layer (ii) is used in combination with other olefin resins such as polybutene resins and the aforementioned cyclic polyolefin resins from the viewpoint of further facilitating easy opening and adjusting the sealing strength. May be. At this time, from the viewpoint of not impairing easy-openability, the total mass of the polyethylene resin (ii-2) and the polypropylene resin (ii-3) is 85% by mass in the resin component in the resin layer (B). It is preferable that it is contained above.

  In the film (I) used for the barrier laminate film of the present invention, the resin layer (ii) may be a single layer or may have a multilayer structure of two or more layers. In particular, from the viewpoint of maintaining the rigidity of the laminate film obtained, it is preferable to laminate two or more layers, and a polypropylene system synthesized using a metallocene catalyst as an intermediate layer between the resin layer (i) and the outermost layer. Use of a resin or linear low density polyethylene is preferable from the viewpoint of maintaining the mechanical strength of the film.

  For each of the resin layers (i) and (ii), if necessary, an antifogging agent, an antistatic agent, a heat stabilizer, a nucleating agent, an antioxidant, a lubricant, an antiblocking agent, a release agent, Components such as an ultraviolet absorber and a colorant can be added as long as the object of the present invention is not impaired. In particular, the friction coefficient on the surface of the film (I) is preferably 1.5 or less, more preferably 1.0 or less in order to impart processing suitability during film forming and packaging suitability of the filling machine. It is preferable to add a lubricant or an antiblocking agent as appropriate.

  Although it does not specifically limit as a manufacturing method of the said film (I), For example, each resin or resin mixture used for the resin layer (i) and the resin layer (ii) is heat-melted with a separate extruder, respectively, and coextrusion is carried out. Examples thereof include a method in which a film (I) is formed by a coextrusion method after being laminated in a molten state by a method such as a multilayer die method or a feed block method, by inflation, a T die / chill roll method or the like. The coextrusion method is preferable because the thickness ratio of each layer can be adjusted relatively freely, and a multilayer film excellent in hygiene and cost performance can be obtained. Furthermore, when the cyclic polyolefin resin and the low density polyethylene resin used in the present invention are used, the difference in melting point and Tg between the two is great, so that the film appearance deteriorates during the coextrusion process or a uniform layer. It may be difficult to form a configuration. In order to suppress such deterioration, a T-die / chill roll method that can perform melt extrusion at a relatively high temperature is preferable.

  The barrier laminate film of the present invention comprises a polyester polyol (A) having two or more hydroxyl groups and a polyisocyanate (B) having two or more isocyanate groups, the above-mentioned film (I) and other resin films. It is characterized by being laminated using a barrier adhesive contained therein.

[Polyester polyol having two or more hydroxyl groups (A)]
The polyester polyol (A) is a polyester polyol having two or more hydroxyl groups, and is obtained by polycondensation reaction between a polyvalent carboxylic acid and a polyhydric alcohol.

(Polyvalent carboxylic acid)
Specific examples of the polyvalent carboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and the like as aliphatic polyvalent carboxylic acid, and 1,3- Cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like as aromatic polyvalent carboxylic acid, orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and anhydrides or ester-forming derivatives of these dicarboxylic acids P-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and their di Polybasic acids such as ester-forming derivatives of hydroxycarboxylic acids can be used alone or in a mixture of two or more. These acid anhydrides can also be used. Among these, succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, orthophthalic acid anhydride, and isophthalic acid are preferably used from the viewpoint that the barrier property as an adhesive can be suitably expressed. And acid anhydrides thereof are preferably used.

(Polyhydric alcohol component)
Specific examples of the polyhydric alcohol 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., aromatic polyphenols such as hydroquinone, resorcinol, Catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and their ethylene oxide extensions, It can be exemplified 添化 and the like. In particular, the smaller the number of carbon atoms between oxygen atoms, the less likely the molecular chain will be excessively flexible and less likely to permeate oxygen, so ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol It is preferable to use, and it is particularly preferable to use ethylene glycol. The polycondensation reaction between the polyvalent carboxylic acid and the polyhydric alcohol can be performed by various methods.

As the polyester polyol (A) having two or more hydroxyl groups, more specifically,
A polyester polyol (A1) obtained by reacting a carboxylic acid anhydride or a polycarboxylic acid with a polyester polyol having three or more hydroxyl groups,
A polyester polyol (A2) having a polymerizable carbon-carbon double bond,
A polyester polyol (A3) having a glycerol skeleton,
A polyester polyol (A4) obtained by polycondensation of an ortho-oriented polyvalent carboxylic acid and a polyhydric alcohol,
-Polyester polyol (A5) having an isocyanuric ring,
Etc.
Hereinafter, each polyester polyol will be described.

[Polyester polyol (A1) obtained by reacting carboxylic acid anhydride or polycarboxylic acid with polyester polyol having 3 or more hydroxyl groups]
The polyester polyol (A1) has at least one carboxy group and two or more hydroxyl groups obtained by reacting a polyester polyol having three or more hydroxyl groups with a carboxylic acid anhydride or a polyvalent carboxylic acid. is there. The polyester polyol having three or more hydroxyl groups can be obtained by making a part of the polyvalent carboxylic acid or polyhydric alcohol trivalent or higher.

  The polyester polyol (A1) is preferably selected from the group consisting of a polyvalent carboxylic acid component containing at least one or more of orthophthalic acid and its anhydride, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. It is obtained by reacting a carboxylic anhydride or a polycarboxylic acid with a polyester polyol having three or more hydroxyl groups composed of a polyhydric alcohol component containing at least one kind.

(Orthophthalic acid and its anhydride)
Orthophthalic acid and its anhydride have an asymmetric structure in the skeleton. Therefore, it is presumed that the rotation of the molecular chain of the resulting polyester is suppressed, and it is presumed that this has excellent barrier properties. Further, it is presumed that due to this asymmetric structure, it exhibits non-crystallinity, imparts sufficient substrate adhesion, and is excellent in adhesive strength and barrier properties. Furthermore, when used as a dry laminate adhesive, the solvent solubility, which is essential, is also high, so that it has excellent handling characteristics.

(Polyvalent carboxylic acid and other components)
When synthesizing a polyester polyol having three or more hydroxyl groups, when a branched structure is introduced by a polyvalent carboxylic acid component, it is necessary to have at least part of a trivalent or higher carboxylic acid. Examples of these compounds include trimellitic acid and its acid anhydride, pyromellitic acid and its acid anhydride, etc. In order to prevent gelation during synthesis, trivalent or higher polyvalent carboxylic acids include three. Divalent carboxylic acids are preferred.

  As other components, the polyester polyol may be copolymerized with other polyvalent carboxylic acid components as long as the effects of the present invention are not impaired. Specifically, as the aliphatic polyvalent carboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc., as the unsaturated bond-containing polyvalent carboxylic acid, maleic anhydride, maleic acid, Fumaric acid etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc. as alicyclic polycarboxylic acid, terephthalic acid, isophthalic acid, pyromellitic as aromatic polyvalent carboxylic acid Acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p '-Dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- ( - it can be used in hydroxyethoxy) benzoic acid and alone or in mixture of two or more polybasic acids such as ester-forming derivatives of these dihydroxy carboxylic acids. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferably used.

(Polyhydric alcohol component)
The polyhydric alcohol preferably contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. Among them, ethylene glycol is most preferably used because it is presumed that the smaller the number of carbon atoms between oxygen atoms, the less the molecular chain becomes excessively flexible and the less oxygen permeates.

(Polyhydric alcohol and other ingredients)
When synthesizing a polyester polyol having three or more hydroxyl groups, when a branched structure is introduced by a polyhydric alcohol component, it is necessary to have at least part of a trihydric or higher polyhydric alcohol. Examples of these compounds include glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,4-butanetriol, pentaerythritol, and dipentaerythritol. In order to prevent gelation, trihydric alcohol is preferable as the trihydric or higher polyhydric alcohol.

  As the other components, the above-described polyhydric alcohol components may be copolymerized with other polyhydric alcohol components as long as the effects of the present invention are not impaired. Specifically, as the aliphatic diol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, Triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenols, hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and ethylene An oxide extension thing and a hydrogenation thing can be illustrated.

  The reaction between the polyester polyol and the carboxylic acid anhydride or polyvalent carboxylic acid can be carried out as follows.

  The polyester polyol is reacted with a polyvalent carboxylic acid or an acid anhydride thereof with a hydroxyl group of the polyester polyol. Since the ratio of the polyester polyol to the polyvalent carboxylic acid requires two or more hydroxyl groups of the polyester polyol (A1) after the reaction, the polyvalent carboxylic acid can be reacted with one third or less of the hydroxyl groups of the polyester polyol. preferable. Although there is no restriction | limiting in the carboxylic acid anhydride or polyvalent carboxylic acid used here, In consideration of the gelatinization at the time of reaction with polyvalent carboxylic acid and polyester polyol, a bivalent or trivalent carboxylic acid anhydride is used. It is preferable. Divalent carboxylic acid anhydrides include succinic anhydride, maleic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic acid Anhydride, phthalic anhydride, 2,3-naphthalenedicarboxylic acid anhydride and the like can be used, and trimellitic acid anhydride and the like can be used as the trivalent carboxylic acid anhydride.

  As a polyester polyol (A1) obtained, it is preferable that a hydroxyl value is 20-250 and an acid value is 20-200. The hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070, and the acid value can be measured by the acid value measuring method described in JIS-K0070. When the hydroxyl value is less than 20 mgKOH / g, the molecular weight is too large, the viscosity becomes high, and it may be difficult to obtain good coating suitability. On the other hand, when the hydroxyl value exceeds 250 mgKOH / g, the molecular weight becomes too small, so that the crosslinked density of the cured coating film becomes too high, and it is difficult to obtain good adhesive strength. When the acid value is less than 20 mgKOH / g, the interaction between molecules becomes small, and it may be difficult to obtain good barrier properties and good initial cohesive force. On the other hand, when the acid value exceeds 200 mgKOH / g, the reaction between the polyester polyol (A1) and the polyisocyanate (B) described later becomes too fast, and good coating suitability may not be obtained.

[Polyester polyol (A2) having a polymerizable carbon-carbon double bond]
Moreover, as a polyester polyol (A) which can be used by this invention, the polyester polyol (A2) which has a polymerizable carbon-carbon double bond in a molecule | numerator can be mentioned.

  The polyester polyol (A2) is obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol, and has a polymerizable carbon-carbon double bond as the polyvalent carboxylic acid or polyhydric alcohol. And the like may be those obtained by introducing a polysynthetic carbon-carbon double bond in the molecule.

(Polyvalent carboxylic acid)
Specific examples of the polyvalent carboxylic acid used as a raw material for the polyester polyol (A2) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and the like as the aliphatic polyvalent carboxylic acid. 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like as carboxylic acid, and orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4 as aromatic polyvalent carboxylic acid -Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and of these dicarboxylic acids Anhydrides or ester-forming derivatives; p-hydroxybenzoic acid, p- (2- Examples thereof include polybasic acids such as hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids, and these can be used alone or in a mixture of two or more. These acid anhydrides can also be used. Among these, succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydride of orthophthalic acid, and isophthalic acid are preferably used from the viewpoint that barrier properties in the obtained film can be easily expressed. It is more preferable to use an acid and its acid anhydride.

(Polyvalent carboxylic acid having a polymerizable carbon-carbon double bond)
In order to obtain the polyester polyol (A2), when a polyvalent carboxylic acid having a polymerizable carbon-carbon double bond is used, the polyvalent carboxylic acid includes maleic anhydride, maleic acid, fumaric acid, 4 -Cyclohexene-1,2-dicarboxylic acid and its anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid and its anhydride, etc. are mentioned. Among them, it is presumed that maleic anhydride, maleic acid, and fumaric acid are preferably used because it is presumed that the smaller the number of carbon atoms, the more the molecular chain does not become excessively flexible and the oxygen does not easily permeate.

(Polyhydric alcohol component)
Specific examples of the polyhydric alcohol 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, aromatic polyphenols, hydroquinone, resorcinol, catechol , Naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and these ethylene oxide extensions, It can be exemplified 添化 thereof. In particular, the smaller the number of carbon atoms between the oxygen atoms, the less the molecular chain becomes more flexible and the less likely it is to permeate oxygen, so ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol It is preferable to use, and it is more preferable to use ethylene glucol.

(Polyhydric alcohol with polymerizable carbon-carbon double bond)
In order to obtain the polyester polyol (A2), when a polyhydric alcohol having a polymerizable carbon-carbon double bond is used, examples of the polyhydric alcohol include 2-butene-1,4-diol.

  In addition to the above production method, the polyester polyol (A2) can also be obtained by a reaction between a polyester polyol having a hydroxyl group and a carboxylic acid having a polymerizable double bond or a carboxylic acid anhydride. As the carboxylic acid in this case, a carboxylic acid having a polymerizable double bond such as maleic acid, maleic anhydride or fumaric acid, an unsaturated fatty acid such as oleic acid or sorbic acid, or the like can be used. The polyester polyol in this case may be a polyester polyol having two or more hydroxyl groups, but it is more preferable to have three or more hydroxyl groups in consideration of molecular elongation by crosslinking with polyisocyanate (B) described later. When the polyester polyol has one or two hydroxyl groups, the polyester polyol (A2) obtained by reacting a carboxylic acid having a polymerizable double bond has 0 or 1 hydroxyl group, and reacts with the polyisocyanate (B). It becomes difficult to cause molecular elongation due to, and it becomes difficult to obtain properties such as laminate strength, seal strength, and heat resistance as an adhesive.

  The hydroxyl value of the polyester polyol (A2) is preferably 20 to 250 mgKOH / g and the acid value is preferably 0 to 100 mgKOH / g for the same reason as the polyester polyol (A1).

  Moreover, it is preferable that the monomer component which has a polymerizable carbon-carbon double bond is 5-60 mass parts with respect to 100 mass parts of all the monomer components which comprise polyester polyol (A2).

  By being in this range, the crosslinking point between the polymerizable double bonds is appropriate, the barrier property in the resulting film is easily expressed, the flexibility of the adhesive layer after curing is good, and the laminating property is improved. It will be excellent.

  In addition, the amount of monomer components having a polymerizable carbon-carbon double bond (double bond component ratio) in the polyester polyol (A2) is calculated using the formula (a).

  Here, the monomer refers to the polyvalent carboxylic acid or polyhydric alcohol used as the raw material.

  Further, the polyester polyol (A2) may be various drying oils having a carbon-carbon double bond or semi-drying oils.

[Polyester polyol having glycerol skeleton (A3)]
Examples of the polyester polyol (A) that can be used in the present invention include a polyester polyol (A3) having a glycerol skeleton represented by the following general formula (1).

［式（１）中、Ｒ_１〜Ｒ_３は、各々独立に、水素原子、又は下記一般式（２）

Wherein _(1), R 1 to R ₃ are each independently a hydrogen atom, or the following general formula (2)

〔式（２）中、ｎは１〜５の整数であり、Ｘは置換基を有してもよい１，２−フェニレン基、１，２−ナフチレン基、２，３−ナフチレン基、２，３−アントラキノンジイル基、又は２，３−アントラセンジイル基であって繰り返し単位ごとに同一であっても異なっていてもよく、Ｙは繰り返し単位ごとに同一であっても異なっていてもよい炭素原子数２〜６のアルキレン基である。〕
で表される基であって、Ｒ_１〜Ｒ_３のうち少なくとも一つは、一般式（２）で表される基である。］

[In formula (2), n is an integer of 1-5, X is a 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group which may have a substituent, 2, 3-anthraquinonediyl group or 2,3-anthracenediyl group, which may be the same or different for each repeating unit, and Y may be the same or different for each repeating unit It is an alkylene group of 2-6. ]
Wherein at least one of R _{1 to} R ₃ is a group represented by the general formula (2). ]

In the general formula (1), at least one of R ₁ , R ₂ and R ₃ needs to be a group represented by the general formula (2). Among them, it is preferable that all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (2).

In addition, a compound in which any _one of R ₁ , R ₂ and R _{3 in} the general formula (1) is a group represented by the general formula (2), and any one of R ₁ , R ₂ and R ₃ Any two or more of a compound in which two are groups represented by the general formula (2) and a compound in which all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (2) The compound may be a mixture.

  X in the general formula (2) is composed of 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group. It represents an arylene group which is selected from the group and may have a substituent. When X is substituted with a substituent, it may be substituted with one or more substituents, which are attached to any carbon atom on X that is different from the free radical. Examples of the substituent include chloro group, bromo group, methyl group, ethyl group, i-propyl group, hydroxyl group, methoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group, and a naphthyl group.

  In the general formula (2), Y represents ethylene group, propylene group, butylene group, neopentylene group, 1,5-pentylene group, 3-methyl-1,5-pentylene group, 1,6-hexylene group, methylpentylene. Represents an alkylene group having 2 to 6 carbon atoms, such as a len group or a dimethyl butylene group; Among them, Y is preferably a propylene group or an ethylene group, and most preferably an ethylene group.

  The polyester polyol (A3) having a glycerol skeleton represented by the general formula (1) includes glycerol, an aromatic polyvalent carboxylic acid in which a carboxylic acid is substituted at the ortho position, or an anhydride thereof (hereinafter referred to as an ortho-oriented aromatic). A polyhydric carboxylic acid) and a polyhydric alcohol component as essential components. Such an aromatic polyvalent carboxylic acid or anhydride thereof has an asymmetric structure in the skeleton. Therefore, it is presumed that the rotation of the molecular chain of the obtained polyester polyol is suppressed, and it is presumed that this has excellent barrier properties. In addition, it is presumed that due to this asymmetric structure, the crystallinity that inhibits the adhesion to the substrate is low, so that it exhibits high solubility in solvents such as ethyl acetate and methyl ethyl ketone and has excellent barrier properties.

  The aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted in the ortho position or its anhydride include orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid or its An anhydride, anthraquinone 2,3-dicarboxylic acid or its anhydride, 2,3-anthracene carboxylic acid or its anhydride, etc. are mentioned. These compounds may have a substituent on any other carbon atom of the aromatic ring. Examples of the substituent include chloro group, bromo group, methyl group, ethyl group, i-propyl group, hydroxyl group, methoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group, and a naphthyl group.

  Examples of the polyhydric alcohol component include alkylene diols having 2 to 6 carbon atoms. For example, diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, etc. Can be illustrated.

The content of the glycerol backbone in this application, based on the total solid content of the mass contained in the barrier adhesive, residues obtained by removing R ₁ to R ₃ in the general formula _{(1) (C 3 H 5} O ₃ = 89.07) is calculated using the following formula (b).

式中Ｐはグリセロール骨格を有するポリエステルポリオール（Ａ３）を表し、酸素バリア性接着剤用有機樹脂組成物固形分全重量は、バリア性接着剤の全質量から、希釈溶剤質量、硬化剤に含まれる揮発成分質量、無機成分を除いた質量を示す。

In the formula, P represents a polyester polyol (A3) having a glycerol skeleton, and the total solid content of the organic resin composition for oxygen barrier adhesive is included in the dilution solvent mass and the curing agent from the total mass of the barrier adhesive. The volatile component mass and the mass excluding inorganic components are shown.

  The content of the glycerol skeleton determined by this formula is preferably 5% by mass or more from the viewpoint that the effect as a barrier adhesive, particularly the oxygen barrier property can be suitably expressed.

(Other polyhydric alcohols)
The polyester polyol (A3) may be copolymerized with a polyhydric alcohol component other than an alkylene diol having 2 to 6 carbon atoms as a polyhydric alcohol as long as the effects of the present invention are not impaired. Specifically, aliphatic polyhydric alcohols such as erythritol, pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, tripropylene glycol, cyclohexane di Alicyclic polyhydric alcohols such as methanol and tricyclodecane dimethanol, hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, aromatic polyphenols such as tetramethylbiphenol, or ethylene oxides thereof An elongated product and a hydrogenated product can be exemplified.

(Other polycarboxylic acids)
In the polyester polyol (A3), an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted in the ortho position as a polyvalent carboxylic acid component or an anhydride thereof is essential, but in the range not impairing the effects of the present invention, Other polycarboxylic acids may be copolymerized. Specifically, as the aliphatic polyvalent carboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc., as the unsaturated bond-containing polyvalent carboxylic acid, maleic anhydride, maleic acid, Fumaric acid etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc. as alicyclic polycarboxylic acid, terephthalic acid, isophthalic acid, pyromellitic as aromatic polyvalent carboxylic acid Acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, diphenic acid and its anhydride, 1,2-bis ( Phenoxy) ethane-p, p′-dicarboxylic acid and anhydrides or ester-forming derivatives of these dicarboxylic acids; Polybasic acids such as droxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more.

  Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalic acid, and diphenic acid are preferable.

[Polyester polyol (A4) obtained by polycondensation of ortho-oriented polycarboxylic acid and polyhydric alcohol]
The polyester polyol (A4) used in the present invention is a polyester polyol (A4) obtained by polycondensation of a polyhydric alcohol with a polyhydric carboxylic acid containing at least one ortho-oriented polycarboxylic acid and anhydride thereof. It may be. Ortho-oriented polyvalent carboxylic acid and its anhydride include orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid or its anhydride, anthraquinone 2,3-dicarboxylic acid Preferably, it is at least one polyvalent carboxylic acid selected from the group consisting of an acid or its anhydride, and 2,3-anthracene dicarboxylic acid or its anhydride, particularly orthophthalic acid or its anhydride. It is preferable. In particular, the content of the orthophthalic acid and its anhydride with respect to all the components of the polyvalent carboxylic acid is preferably 70 to 100% by mass.

  The polyhydric alcohol is preferably a polyhydric alcohol containing at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. In particular, a polyester polyol having a content of 70 to 100% by mass of the orthophthalic acid and its anhydride with respect to all the components of the polyvalent carboxylic acid is preferable.

(Polyvalent carboxylic acid and other components)
In the polyester polyol (A4), it is essential to use an ortho-oriented polyvalent carboxylic acid and its anhydride as the polyvalent carboxylic acid. However, other polyvalent carboxylic acids may be used as long as the effects of the present invention are not impaired. It may be polymerized. Specifically, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc. are used as the aliphatic polycarboxylic acid, and maleic anhydride, maleic acid, fumaric acid are used as the unsaturated bond-containing polyvalent carboxylic acid. Acids etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc. as alicyclic polycarboxylic acid, terephthalic acid, isophthalic acid, pyromellitic acid as aromatic polyvalent carboxylic acid , Trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p ′ -Dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2- Polybasic acids such as hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferable.

[Polyester polyol having an isocyanuric ring (A5)]
The polyester polyol (A) used in the present invention may be a polyester polyol (A5) having an isocyanuric ring represented by the following general formula (3).

［式（３）中、Ｒ_１〜Ｒ_３は各々独立して、−（ＣＨ_２）_ｎ１−ＯＨ（但しｎ１は２〜４の整数である）、又は下記一般式（４）

[In formula (3), R _{1 to} R ₃ are each independently — (CH ₂ ) _n1 —OH (where n1 is an integer of 2 to 4), or the following general formula (4)

〔式（４）中、ｎ２は２〜４の整数であり、ｎ３は１〜５の整数であり、Ｘは置換基を有してもよい１，２−フェニレン基、１，２−ナフチレン基、２，３−ナフチレン基、２，３−アントラキノンジイル基、又は２，３−アントラセンジイル基であって繰り返し単位ごとに同一であっても異なっていてもよく、Ｙは繰り返し単位ごとに同一であっても異なっていてもよい炭素原子数２〜６のアルキレン基である。〕
で表される基であって、Ｒ_１、Ｒ_２及びＲ_３の少なくとも１つは前記一般式（４）で表される基である。］

[In Formula (4), n2 is an integer of 2-4, n3 is an integer of 1-5, X is a 1,2-phenylene group or a 1,2-naphthylene group which may have a substituent. 2,3-naphthylene group, 2,3-anthraquinonediyl group, or 2,3-anthracenediyl group, which may be the same or different for each repeating unit, and Y is the same for each repeating unit. It is an alkylene group having 2 to 6 carbon atoms which may be different or different. ]
Wherein at least one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (4). ]

In the general formula (3), the alkylene group represented by — (CH ₂ ) _n1 — may be linear or branched. n1 is preferably 2 or 3, and most preferably 2.

  In the general formula (4), when X is substituted with a substituent, it may be substituted with one or more substituents, and the substituent is any carbon atom on X different from the free radical. Is bound to. Examples of the substituent include chloro group, bromo group, methyl group, ethyl group, i-propyl group, hydroxyl group, methoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group, and a naphthyl group.

  As the substituent for X, among them, a hydroxyl group, a cyano group, a nitro group, an amino group, a phthalimide group, a carbamoyl group, an N-ethylcarbamoyl group, and a phenyl group are preferable, and a hydroxyl group, a phenoxy group, a cyano group, a nitro group, and a phthalimide group Most preferred is a phenyl group.

  In the general formula (4), Y is an alkylene group having 2 to 6 carbon atoms, specifically, ethylene group, propylene group, butylene group, neopentylene group, 1,5-pentylene group, 3-methyl- 1,5-pentylene group, 1,6-hexylene group, methylpentylene group, dimethylbutylene group and the like. Among these, a propylene group and an ethylene group are preferable, and an ethylene group is most preferable.

In the general formula (3), at least one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (4). Among these, it is preferable that all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (4).

_Further, R 1, _{R 2,} and the compound any one of _{R 3} is a group represented by the general formula _(4), R 1, _{R 2} and any two of the general formula _{R 3} (4) Or a mixture of any two or more compounds of the compound represented by formula (1) and the compound in which all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (4) Good.

  The polyester polyol (A5) having an isocyanuric ring represented by the general formula (3) includes a triol having an isocyanuric ring, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position, or an anhydride thereof, It is obtained by reacting a monohydric alcohol component as an essential component.

  Examples of the triol having an isocyanuric ring include alkylene oxide adducts of isocyanuric acid such as 1,3,5-tris (2-hydroxyethyl) isocyanuric acid and 1,3,5-tris (2-hydroxypropyl) isocyanuric acid. Etc.

  In addition, aromatic polyvalent carboxylic acids in which the carboxylic acid is substituted in the ortho position or anhydrides thereof include orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid. Or its anhydride, anthraquinone 2,3-dicarboxylic acid or its anhydride, 2,3-anthracene carboxylic acid or its anhydride, etc. are mentioned. These compounds may have a substituent on any other carbon atom of the aromatic ring.

  Examples of the substituent include chloro group, bromo group, methyl group, ethyl group, i-propyl group, hydroxyl group, methoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group, and a naphthyl group.

  Examples of the polyhydric alcohol component include alkylene diols having 2 to 6 carbon atoms. For example, diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, etc. Can be illustrated.

  Among them, 1,3,5-tris (2-hydroxyethyl) isocyanuric acid or 1,3,5-tris (2-hydroxypropyl) isocyanuric acid is used as the triol compound having an isocyanuric ring, and the carboxylic acid is in the ortho position. The polyester polyol (A5) having an isocyanuric ring using orthophthalic anhydride as the aromatic polyvalent carboxylic acid substituted with or an anhydride thereof and ethylene glycol as the polyhydric alcohol is particularly effective in barrier properties and adhesiveness. Excellent and preferred.

  The isocyanuric ring is highly polar and trifunctional. Therefore, the entire system can be made highly polar and the crosslinking density can be increased. From such a viewpoint, it is preferable to contain 5% by mass or more of the isocyanuric ring with respect to the solid content of the barrier adhesive.

  The reason why the barrier adhesive using the polyester polyol (A5) having an isocyanuric ring can ensure the barrier property and the dry laminate adhesiveness is estimated as follows.

  The isocyanuric ring is highly polar and does not form hydrogen bonds. In general, as a technique for improving adhesiveness, a method in which a highly polar functional group such as a hydroxyl group, a urethane bond, a ureido bond or an amide bond is blended is known, but a resin having these bonds forms intermolecular hydrogen bonds. It is easy to use, and it may impair the solubility in ethyl acetate and 2-butanone solvent, which are often used for dry laminate adhesives, but the polyester polyol having an isocyanuric ring does not impair the solubility, so it can be easily diluted. It is.

  In addition, since the isocyanuric ring is trifunctional, a polyester polyol compound having the isocyanuric ring as the center of the resin skeleton and a polyester skeleton having a specific structure in the branched chain can obtain a high crosslinking density. It is presumed that the gap through which a gas such as oxygen can be reduced by increasing the crosslinking density. Thus, since the isocyanuric ring is highly polar and does not form an intermolecular hydrogen bond and a high crosslinking density is obtained, it is presumed that the barrier property and the dry laminate adhesiveness can be ensured.

The content ratio of the isocyanuric ring in the present application, based on the total solid content of the mass of the barrier adhesive, except for _R 1 to R ₃ in the general formula (3) residues _{(C 3} N ₃ O 3 = 126 .05) is calculated using equation (c).

式中Ｐはイソシアヌル環を有するポリエステルポリオール（Ａ５）を表し、酸素バリア性接着剤用有機樹脂組成物固形分全重量は、バリア性接着剤の全質量から、希釈溶剤質量、硬化剤に含まれる揮発成分質量、無機成分を除いた質量を示す。

In the formula, P represents a polyester polyol (A5) having an isocyanuric ring, and the total solid content of the organic resin composition for oxygen-barrier adhesive is included in the dilution solvent mass and the curing agent from the total mass of the barrier adhesive. The volatile component mass and the mass excluding inorganic components are shown.

  The polyester polyol having an isocyanuric ring can be obtained by various polyester production methods. Specifically, it can be synthesized by a production method in which the reaction is carried out while removing produced water from the system at a reaction temperature of 200 to 220 ° C. in the presence of a catalyst.

  As a specific example, after the triol having an isocyanuric ring used as a raw material, an aromatic polycarboxylic acid in which the carboxylic acid is substituted in the ortho position, or an anhydride thereof, and a polyhydric alcohol component are collectively charged Then, the temperature is increased while stirring and mixing to cause dehydration condensation reaction. 1 mgKOH / g or less by the acid value measurement method described in JIS-K0070, and the hydroxyl value ZmgKOH / g obtained by the hydroxyl value measurement method described in JIS-K0070 is a numerical value on the right side of the following formula (d) (mgKOH / The target polyester polyol can be obtained by continuing the reaction until it falls within ± 5% of g).

（式（ｄ）中、Ｍｎは所定の３官能ポリエステル樹脂の設定数平均分子量を表す。）

(In formula (d), Mn represents the set number average molecular weight of a predetermined trifunctional polyester resin.)

  Alternatively, each raw material may be reacted in multiple stages. Moreover, you may prepare so that a hydroxyl value may enter into less than +/- 5%, adding the diol component which volatilized at reaction temperature.

  Examples of the catalyst used in the reaction include acids such as tin-based catalysts such as monobutyltin oxide and dibutyltin oxide, titanium-based catalysts such as tetra-isopropyl-titanate and tetra-butyl-titanate, and zirconia-based catalysts such as tetra-butyl-zirconate. A catalyst is mentioned. It is preferable to use a combination of the titanium-based catalyst such as tetra-isopropyl-titanate and tetra-butyl-titanate, which has high activity for ester reaction, and the zirconia catalyst. The catalyst amount is used in an amount of 1 to 1000 ppm, more preferably 10 to 100 ppm, based on the total mass of the reaction raw material used. If it is less than 1 ppm, it is difficult to obtain an effect as a catalyst, and if it exceeds 1000 ppm, the subsequent urethanization reaction tends to be inhibited.

  The number average molecular weight of these polyester polyols (A) is particularly preferably 450 to 5,000 because a crosslinking density with an excellent balance between adhesiveness and barrier property can be obtained. More preferably, the number average molecular weight is 500 to 3000. Further, as the curing agent, polyisocyanate (B) described later is most preferable, can provide an appropriate reaction time, and is particularly excellent in adhesion and barrier properties. When the molecular weight is less than 450, the cohesive force of the adhesive at the time of coating becomes too small, and the film tends to be displaced during lamination or the bonded film is lifted. Conversely, when the molecular weight is higher than 5000 , The viscosity at the time of coating becomes too high, making it difficult to coat, and the fact that the laminate is insufficient due to low adhesiveness. Here, the number average molecular weight is a value obtained by calculation from the obtained hydroxyl value and the number of functional groups of the designed hydroxyl group.

  The polyester polyol (A) used in the present invention preferably has a glass transition temperature in the range of -30 ° C to 80 ° C. More preferably, it is 0 degreeC-60 degreeC. More preferably, it is 25 degreeC-60 degreeC. If the glass transition temperature is too higher than 80 ° C., the flexibility of the polyester polyol near room temperature may be lowered, and the adhesion to the film (I) or the resin film may be insufficient, thereby reducing the adhesive force. is there. On the other hand, when the temperature is too lower than −30 ° C., there is a possibility that sufficient barrier properties may not be obtained due to intense molecular motion of the polyester polyol near normal temperature.

  Furthermore, a polyol having a number average molecular weight of 1000 to 15000 by urethane elongation by reaction of the polyester polyol (A) with a diisocyanate compound may be used as an adhesive. Since the polyol has a certain molecular weight component and a urethane bond, the polyol has excellent barrier properties, excellent initial cohesive force, and is further excellent as an adhesive used during lamination.

[Polyisocyanate (B)]
In the barrier adhesive of the present invention, a polyisocyanate (B) having two or more isocyanate groups is used as a curing agent capable of reacting with the hydroxyl group of the polyester polyol (A).

  Examples of the polyisocyanate (B) include aromatic and aliphatic diisocyanates, and trivalent or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds. For example, 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 excess of these isocyanate compounds Amounts and, for example, ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, Diethanolamine, triethanol Examples include adducts obtained by reacting low molecular active hydrogen compounds such as amines and metaxylylenediamines and their alkylene oxide adducts, various polyester resins, polyether polyols, and high molecular active hydrogen compounds of polyamides. .

  The polyisocyanate (B) may be a blocked isocyanate. As the isocyanate blocking agent, for example, phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime oximes, methanol, Alcohols such as ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; Examples include lactams such as caprolactam, δ-valerolactam, γ-butyrolactam, β-propylolactam, and other aromatic amines, imides, acetylacetate. , Acetoacetic ester, active methylene compounds such as malonic acid ethyl ester, mercaptans, imines, ureas, and also such as diaryl compounds sodium bisulfite. The blocked isocyanate can be obtained by subjecting the isocyanate compound and the isocyanate blocking agent to an addition reaction by various appropriate methods.

  Among these, xylylene diisocyanate and hydrogenated xylylene diisocyanate are preferable, and metaxylylene diisocyanate and metahydrogenated xylylene diisocyanate are most preferable.

  The glass transition temperature of the cured product of the polyester polyol (A) and polyisocyanate (B) of the present invention is preferably in the range of −30 ° C. to 80 ° C. More preferably, it is 0 degreeC-70 degreeC. More preferably, it is 25 degreeC-70 degreeC. When the glass transition temperature is higher than 80 ° C., the flexibility of the cured coating film near room temperature becomes low, and thus the adhesiveness to the substrate may be deteriorated due to poor adhesion to the substrate. On the other hand, when it is lower than −30 ° C., there is a possibility that sufficient fragrance retention may not be obtained due to intense molecular motion of the cured coating film at around room temperature.

  Among them, the polyisocyanate (B) is preferably a polyisocyanate having an aromatic ring. When the polyisocyanate includes the metaxylene skeleton, not only hydrogen bonds of urethane groups but also π-π stacking between aromatic rings. It is preferable because the barrier property can be improved.

  Examples of the polyisocyanate containing a metaxylene skeleton include xylene diisocyanate trimer, burette synthesized by reaction with amine, and adduct formed by reaction with alcohol. The adduct body is more preferable because the solubility of the polyisocyanate in the organic solvent used for the dry laminate adhesive is easily obtained. As the adduct, an adduct obtained by reacting with an alcohol appropriately selected from the above low molecular active hydrogen compounds can be used. Among them, addition of ethylene oxide of trimethylolpropane, glycerol, triethanolamine, metaxylenediamine, etc. Adduct bodies with objects are particularly preferred.

  In the polyester polyol (A) and the polyisocyanate (B), the ratio of the polyester polyol (A) and the polyisocyanate (B) is such that the hydroxyl group of the polyester polyol (A) and the reaction component of the polyisocyanate (B) are 1 It is preferable to mix | blend so that it may become /0.5-1/10 (equivalent ratio), More preferably, it is 1/1-1/5. If the polyisocyanate (B) is excessive beyond this range, excess polyisocyanate (B) may remain and bleed out from the adhesive layer after bonding. On the other hand, if the polyisocyanate (B) is insufficient May have insufficient adhesive strength.

  Moreover, when carboxylic acid remains in the terminal of the polyester polyol (A) used by this invention, an epoxy compound may also be used together with polyisocyanate (B) as a hardening | curing agent. Examples of epoxy compounds include diglycidyl ether of bisphenol A and oligomers thereof, diglycidyl ether of hydrogenated bisphenol A and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid diglyceride. Glycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol Cole diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether , Pentaerythritol tetraglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, and the like.

  When an epoxy compound is used in combination as a curing agent, various epoxy curing accelerators may be appropriately added for the purpose of accelerating curing as long as the barrier property that is the object of the present invention is not impaired.

  Moreover, the polymerization catalyst as a catalyst for promoting superposition | polymerization of a polymerizable carbon-double bond can be used. A transition metal complex is mentioned as a polymerization catalyst. Although a transition metal complex will not be specifically limited if it is a compound provided with the capability to oxidatively polymerize a polymerizable double bond, A various metal or its complex can be used. For example, metals such as cobalt, manganese, lead, calcium, cerium, zirconium, zinc, iron, copper, octyl acid, naphthenic acid, neodecanoic acid, stearic acid, resin acid, tall oil fatty acid, tung oil fatty acid, linseed oil fatty acid, A salt with soybean oil fatty acid or the like can be used. 0-10 mass parts is preferable with respect to polyester polyol (A), and, as for a transition metal complex, More preferably, it is 0-3 mass parts.

  Other curing agents or accelerators can also be used in combination. Examples of the adhesion promoter include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate coupling agents, aluminum coupling agents, and epoxy resins. Silane coupling agents and titanate coupling agents are also preferred in terms of improving the adhesive to the film.

(Adhesive and other ingredients)
Various additives may be blended in the barrier adhesive used in the present invention as long as the barrier property and adhesiveness are not impaired. Examples of additives include inorganic fillers such as silica, alumina, aluminum flakes, and glass flakes, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, and antiblocking agents. Examples include agents, colorants, fillers, crystal nucleating agents and the like.

(Plate-like inorganic compound)
The barrier adhesive used in the present invention may contain a plate-like inorganic compound. When using a plate-like inorganic compound, it has the effect of improving the laminate strength and barrier properties of an adhesive obtained by curing the adhesive because of its plate-like shape.

  The charge between the layers of the plate-like inorganic compound does not greatly affect the barrier property, but the dispersibility to the adhesive is greatly inferior with the ionic inorganic compound or the swellable inorganic compound with respect to water. Coating suitability becomes a problem because it increases the viscosity of the adhesive and imparts thixotropy. On the other hand, in the case of being uncharged (nonionic) or non-swelling with respect to water, even if the addition amount is increased, thickening and thixotropy are alleviated and coating suitability can be ensured. Examples of the plate-like inorganic compound used in the present invention include hydrous silicates (phyllosilicate minerals, etc.), kaolinite-serpentine clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.) Light, chrysotile, etc.), pyrophyllite-talc group (pyrophyllite, talc, kerolai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc.), vermiculite clay Minerals (vermiculite, etc.), mica or mica group clay minerals (mica, such as muscovite, phlogopite, margarite, tetrasilic mica, teniolite, etc.), chlorite group (cukeite, sudite, clinochlore, chamosite, nimite, etc.) , Hydro Lucite, tabular barium sulfate, boehmite, and aluminum polyphosphate and the like. These minerals may be natural clay minerals or synthetic clay minerals. The plate-like inorganic compounds may be used alone or in combination of two or more, and are preferably nonionic without interlayer electrification.

  Nonionic plate-like inorganic compounds include, for example, kaolinite-serpentine clay minerals (such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite, chrysotile, etc.), pyrophyllite-talc group (pyrolite) Phylite, talc, kerolai, etc.).

  The plate-like inorganic compound is preferably non-swellable with respect to water. Examples of such a plate-like inorganic compound include kaolinite-serpentine clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, antigolite, chrysotile, etc.), pyrophyllite-talc group (pyrophyll). Light, talc, kerolai, etc.), mica or mica group clay mineral (mica, muscovite, phlogopite, etc.), margarite, tetrasilic mica, teniolite, etc., chlorite group (kukeite, suduaite, clinochlore, chamosite, nimite) Etc.), hydrotalcite, plate-like barium sulfate and the like.

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

  The aspect ratio of the plate-like inorganic compound is preferably higher in order to improve the barrier property due to the maze effect such as oxygen, water vapor, and aroma components. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more. Moreover, although the content rate of a plate-shaped inorganic compound is arbitrary, it is preferable that it is 50 mass parts or less. If it exceeds 50 parts by mass, there is a possibility that the laminating operation becomes difficult or the adhesive force becomes insufficient.

  The content of the inorganic compound (PWC of the blended grains) can be obtained from the following formula (e).

  Various dispersion methods can be used as a method of dispersing the plate-like inorganic compound in the polyester polyol (A) or the barrier adhesive. For example, an ultrasonic homogenizer, a high-pressure homogenizer, a paint conditioner, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, a nano mill, an SC mill, a nanomizer, and the like can be mentioned, and even more preferably, a high shear force is generated. Examples of equipment that can be used include Henschel mixer, pressure kneader, Banbury mixer, planetary mixer, two-roll, three-roll. One of these may be used alone, or two or more devices may be used in combination.

  Moreover, an acid anhydride can also be used together as an additive as a method for improving the acid resistance of the adhesive layer. Examples of the acid anhydride include phthalic acid anhydride, succinic acid anhydride, het acid anhydride, hymic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, hexahydraphthalic acid anhydride, tetraprom phthalic acid Anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5- (2 , 5-oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, styrene maleic anhydride copolymer and the like.

  Moreover, you may add the compound etc. which have an oxygen trap function further as needed. Examples of the compound having an oxygen scavenging function include low molecular organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol, cobalt, manganese, nickel, iron, Examples include transition metal compounds such as copper.

  Moreover, in order to improve the adhesiveness with respect to the film immediately after application | coating, you may add tackifiers, such as a xylene resin, a terpene resin, a phenol resin, and a rosin resin, as needed. When adding these, the range of 0.01-5 mass parts is preferable with respect to 100 mass parts of total amounts of polyester polyol (A) and polyisocyanate (B).

  Moreover, an active energy ray can also be used as a method of reacting a polymerizable double bond. The active energy ray is not particularly limited, and can be cured by irradiation with ionizing radiation such as electron beam, ultraviolet ray, or γ ray. In the case of curing with ultraviolet rays, an ultraviolet irradiation device equipped with a high pressure mercury lamp, an excimer lamp, a metal halide lamp, or the like can be used.

  In the case of curing by irradiating with ultraviolet rays, if necessary, 0.1 to 20 parts by mass of a light (polymerization) initiator that generates radicals and the like by irradiation with ultraviolet rays with respect to 100 parts by mass of the polyester polyol (A). It is preferable to add a certain amount.

  Radical-generating photo (polymerization) initiators include hydrogen abstraction types such as benzyl, benzophenone, Michler's ketone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzoin ethyl ether, diethoxyacetophenone, benzylmethyl ketal, hydroxy Examples include photocleavage types such as cyclohexyl phenyl ketone and 2-hydroxy-2-methylphenyl ketone. These can be used alone or in combination.

(Adhesive form)
The barrier adhesive of the present invention may be either a solvent type or a solventless type. In the case of the solvent type, the solvent may be used as a reaction medium during the production of the polyester polyol (A) and the polyisocyanate (B). Furthermore, it is used as a diluent during painting. Examples of the solvent that can be used include esters such as ethyl acetate, butyl acetate, and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene. , Halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like. Of these, it is usually preferable to use ethyl acetate or methyl ethyl ketone. In addition, when used without a solvent, it is not always necessary to be soluble in an organic solvent, but considering the washing of a reaction kettle during synthesis and the washing of a coating machine during lamination, It is preferable that

  In the present invention, the above-mentioned barrier adhesive can be used by coating on the film (I) and / or a resin film described later. The coating method is not particularly limited. For example, in the case of a solvent type capable of adjusting the viscosity, it is often applied by a gravure roll coating method. Moreover, when it is a solventless type and has a high viscosity at room temperature and is not suitable for gravure roll coating, it can be coated with a roll coater while heating. When using a roll coater, it is preferable to apply in a state where the barrier adhesive is heated from room temperature to about 120 ° C. so that the viscosity of the barrier adhesive is about 500 to 2500 mPa · s.

  The barrier laminate film of the present invention is formed by laminating a resin film on the specific single layer or multilayer film (I) described above via the adhesive. The resin component of the film that can be used as a resin film here is a film from the viewpoint of packaging mechanical properties (such as no wrinkles or shrinkage on the surface during bag making and article filling, and the film does not fuse to the heat seal bar). It is preferably higher by 30 ° C. than the melting point or glass transition point of (I). The resin film may be a single layer or may be a laminate of two or more layers. Preferably, biaxially stretched resin films having high heat resistance, high rigidity, and high gloss are used alone or in combination.

  Examples of the biaxially stretched resin film include biaxially stretched polyester (PET), easily tearable biaxially stretched polyester (PET), biaxially stretched polypropylene (OPP), and biaxial from the viewpoints of easy tearing and laminating properties. Co-extruded biaxially stretched polypropylene with a stretched polyamide (PA), ethylene vinyl alcohol copolymer (EVOH) as the central layer, biaxially stretched ethylene vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC) coated Extruded biaxially oriented polypropylene and the like can be mentioned. These may be used alone or in combination. PET, PA, and OPP are preferable from the viewpoint of cost and availability, and PET and OPP are more preferable, and PET is most preferable.

  The method for laminating these resin films on the surface of the film (I) is not particularly limited, and examples thereof include dry lamination, wet lamination, non-solvent lamination, and extrusion lamination. Specifically, the dry lamination method is a method in which a barrier adhesive is applied to one of the films by a gravure roll method, and the other film is laminated and bonded by dry lamination (dry lamination method). The temperature of the laminate roll is preferably about room temperature to 60 ° C.

Non-solvent lamination is a method in which a barrier adhesive that has been heated to room temperature to 120 ° C in advance is applied to the film with a roll such as a roll coater that has been heated to room temperature to 120 ° C. It is a method of bonding. The laminating pressure is preferably about 10 to 300 kg / cm ² .

  In the case of the extrusion laminating method, a barrier adhesive (organic solvent solution) is applied to the film with a roll such as a gravure roll, dried at room temperature to 140 ° C. and subjected to a curing reaction, and then melted with an extruder. A laminated film can be obtained by laminating the polymer material. The polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.

  The barrier laminate film of the present invention is preferably subjected to aging after production. The aging condition is that the polyisocyanate is used as a curing agent, and is at room temperature to 80 ° C. for 12 to 240 hours. During this period, the polyester polyol and the polyisocyanate react to improve the adhesiveness.

  In the present invention, in order to give a higher barrier function, a film in which a vapor-deposited layer of a metal such as aluminum or a metal oxide such as silica or alumina is laminated, polyvinyl alcohol, or ethylene / vinyl alcohol as necessary. A barrier film containing a gas barrier layer such as a polymer or vinylidene chloride may be further laminated.

  Alternatively, aluminum may be deposited to form an aluminum layer. The vapor deposition means for this aluminum vapor deposition is not particularly limited as long as aluminum can be vapor deposited without causing deterioration such as shrinkage and yellowing to the above-mentioned film (I). (A) Vacuum vapor deposition method, sputtering method, Physical vapor deposition method (Physical Vapor Deposition method; PVD method) such as ion plating method, ion cluster beam method, (b) Plasma chemical vapor deposition method, thermal chemical vapor deposition method, photochemical vapor deposition method, etc. The chemical vapor deposition method (Chemical Vapor Deposition method; CVD method) and the like can be mentioned. Among these vapor deposition methods, a vacuum vapor deposition method and an ion plating method that can form a high-quality aluminum vapor deposition layer with high productivity are preferable.

  Usually, when aluminum vapor deposition is performed, an anchor coating agent is applied in order to maintain interlayer adhesion with the vapor deposition surface. However, applying the anchor coating agent uniformly on the surface of the film (I) formed and drying it removes the medium composed of organic components contained in the anchor coating agent in addition to the complexity of the work process. There is a need for an apparatus for preventing diffusion and application / drying of an anchor coat agent to the volatile components that are sometimes generated, and improvement is desired from the viewpoint of productivity. In the present invention, by performing vapor deposition on the resin layer (i) containing 30% by mass or more of the cyclic polyolefin resin (i-1) as a resin component, aluminum and aluminum can be used without using an anchor coat agent. Interlayer adhesion with the resin layer (i) can be maintained, and delamination can be prevented.

  In particular, when laminating a resin film, or when it is desired to improve interlayer adhesion in aluminum vapor deposition, or without continuously performing the laminating step, vapor deposition step, and film (I) manufacturing step, the film (I) When storing as it is, it is preferable that the surface of the film (I) is subjected to chemical and physical treatment. Examples of such surface treatment include corona treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, surface oxidation treatment such as ozone / ultraviolet treatment, and surface unevenness treatment such as sandblasting. Corona treatment is preferable.

The method of corona treatment is not particularly limited. For example, JP-B-39-12838, JP-A-47-19824, JP-A-48-28067, and JP-A-52-42114. It can be performed by the processing method described in the above. As the corona discharge treatment apparatus, a solid state corona treatment machine manufactured by Pillar, a LEPEL type surface treatment machine, a VETAPHON type treatment machine, or the like can be used. The treatment can be performed at normal pressure in air. The discharge frequency during the treatment is 5 kV to 40 kV, more preferably 10 kV to 30 kV, and the waveform is preferably an alternating sine wave. The gap transparent lance between the electrode and the dielectric roll is 0.1 mm to 10 mm, more preferably 1.0 mm to 2.0 mm. The discharge is processed above a dielectric support roller provided in the discharge zone, and the treatment amount is 0.34 kV · A · min / m ^{2 to} 0.4 kV · A · min / m ² , more preferably 0.344 kV. A · min / m ^{2 to} 0.38 kV · A · min / m ² .

  In the present invention, since the resin layer (i) of the film (I) contains the cyclic polyolefin resin (i-1), when this surface is corona-treated, the degree of treatment is a polyolefin having no cyclic structure. It improves compared with the case where a system resin is processed. The degree of treatment can be determined, for example, by measuring the surface tension with a wetting reagent. If the resin layer (i) is present on the surface of the film (I), the degree of treatment should be 45 mN / m or more. It is easy and can be 50 dyne / cm or more. Furthermore, there is little decrease in the processing degree with time. For these reasons, it contributes to the development of high laminate strength and has an effect of suppressing delamination when the seal portion is peeled off.

  As described above, the barrier laminate film of the present invention has a configuration of film (I) / adhesive layer / resin film. When the total thickness of the film (I) is in the range of 15 to 100 μm, the workability at the time of lamination is improved, and stable seal strength, suitability for packaging machinery, excellent pinhole resistance, easy tearing performance, etc. are obtained. It is done. More preferably, it is 30-130 micrometers. When film (I) is a single layer film of resin layer (i), the total thickness is preferably in the range of 20 to 50 μm. In the case of a multilayer film in which the resin layer (i) and the resin layer (ii) are laminated, the thickness ratio of the resin layer (i) to the film (I) is 20 to 80%, preferably 30 to 65. When the content is in the range of%, it is excellent in balance between tearability and sealability, further easy-openability, and the point of suppressing adsorption when the content contains a volatile component. In addition, the thickness of the resin film is appropriately selected according to the intended application, but in the range of 5 to 50 μm from the viewpoint of easily expressing effects such as easy tearability of the film (I). It is preferable to use one having a thickness in the range of 10 to 30 μm.

  The barrier laminate film of the present invention can be suitably used as a packaging material, and examples thereof include packaging bags, containers, and container lid materials used for foods, medicines, industrial parts, miscellaneous goods, magazines and the like. In particular, since there is little sorption / adsorption of aroma components contained in the contents on the film, and oxygen and water vapor barrier properties are excellent, there is also little decrease in seal strength over time, so foods, pharmaceuticals and industrial products containing volatile components It can be suitably used for chemicals.

  The packaging bag is heat-sealed by overlapping the films (I) of the barrier laminate film of the present invention inside, or heat-sealed by overlapping the film (I) side and the resin film side, so that the film ( A packaging bag formed with I) on the inside is preferred. For example, after cutting out two sheets of the barrier laminate film into a desired size of a packaging bag, overlapping them and heat-sealing three sides to form a bag, the contents are removed from one side that is not heat-sealed. It can be used as a packaging bag by filling, heat sealing and sealing. Furthermore, it is also possible to form a packaging bag by sealing the end of a roll-shaped film into a cylindrical shape by an automatic packaging machine and then sealing the top and bottom.

  It is also possible to form a lid of a packaging bag / container / container by heat-sealing with another film, sheet, or container heat-sealable with the film (I).

  The packaging material using the barrier laminate film of the present invention has an easy tear property and does not require any special device for opening, but weakens the initial tear strength, improves the opening property, In order to limit the portion to a specific location, an arbitrary tear start portion such as a V-notch, an I-notch, a perforation, or a micropore may be formed in the seal portion.

  Further, since the barrier laminate film of the present invention is characterized by having high oxygen and water vapor barrier properties, a PVDC coat layer, a polyvinyl alcohol (PVA) coat layer, an ethylene-vinyl alcohol copolymer (EVOH) film layer In addition, a very high level of barrier property is exhibited without using a commonly used barrier material such as a metaxylylene adipamide film layer, an inorganic vapor deposition film layer on which alumina, silica, or the like is vapor-deposited.

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

Production Example 1 Production Example of Polyester Polyol (A): Gly (OPAEG) 2MA This polyester polyol is the main agent of an adhesive having the structure of polyester polyols (A1), (A2), and (A3). In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., 1316.8 parts of phthalic anhydride, 573.9 parts of ethylene glycol, 409.3 parts of glycerin and titanium tetraisopropoxide are added. An amount corresponding to 100 ppm with respect to the total amount of the polyvalent carboxylic acid and the polyhydric alcohol was charged, and the inner temperature was maintained at 220 ° C. by gradually heating so that the upper temperature of the rectifying tube did not exceed 100 ° C. When the acid value reached 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a hydroxyl value of 339.9 mgKOH / g. Next, the temperature was lowered to 120 ° C., and 421.8 parts of maleic anhydride was added thereto, and maintained at 120 ° C. The esterification reaction was terminated when the acid value was approximately half of the acid value calculated from the charged amount of maleic anhydride, and the number average molecular weight was about 520, the hydroxyl value was 216.6 mgKOH / g, and the acid value was 96.2 mgKOH / g. A polyester polyol was obtained. Polyester polyol (A) Number of functional groups designed per molecule: 2 hydroxyl groups, 1 carboxy group.

(Production Example 2) Polyester polyol (A): Production example of OPAEG The present polyester polyol is a main component of an adhesive having a structure of polyester polyol (A4). A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc. was charged with 148.1 parts of phthalic anhydride, 84.2 parts of ethylene glycol, and 0.03 part of titanium tetraisopropoxide, The inner temperature was maintained at 205 ° C. by gradually heating so that the upper temperature of the rectifying tube did not exceed 100 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain an amorphous polyester polyol having a number average molecular weight of 600. This polyester polyol had a hydroxyl value of 190 mgKOH / g and an acid value of 1.0 mgKOH / g. The number of functional groups designed per polyester polyol molecule: hydroxyl group: 2 and carboxy group: 0, and the content of ortho-oriented aromatic dicarboxylic acid or its anhydride with respect to all polycarboxylic acid components Is 100% by mass.

(Production Example 3) Production Example of Amorphous Polyester Polyol OPASuAEG Composed of Phthalic Anhydride, Succinic Acid, and Ethylene Glycol This polyester polyol is the main agent of an adhesive having the structure of polyester polyol (A4). In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., 647.0 parts of phthalic anhydride, 277.8 parts of succinic acid, 575.2 parts of ethylene glycol, and titanium tetraisopropoxide 0.12 part was charged, and the inner temperature was maintained at 205 ° C. by gradually heating so that the temperature of the upper part of the rectifying tube did not exceed 100 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain an amorphous polyester polyol having a number average molecular weight of 600. This polyester polyol had a hydroxyl value of 190 mgKOH / g and an acid value of 1.0 mgKOH / g. The number of functional groups designed per polyester polyol molecule: hydroxyl group: 2 and carboxy group: 0, and the content of ortho-oriented aromatic dicarboxylic acid or its anhydride with respect to all polycarboxylic acid components Is 70% by weight.

(Production Example 4) Production Example of Polyester Polyol (A): THEI (OPAEG) 3 This polyester polyol is a main component of an adhesive having a structure of polyester polyol (A5). In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., 1136.5 parts of phthalic anhydride, 495.3 parts of ethylene glycol, 668.1 tris (2-hydroxyethyl) isocyanurate Part and titanium tetraisopropoxide are charged in an amount corresponding to 100 ppm with respect to the total amount of polyvalent carboxylic acid and polyhydric alcohol, and gradually heated so that the upper temperature of the rectification tube does not exceed 100 ° C. The temperature was kept at 220 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight of about 860, a hydroxyl value of 195.4 mgKOH / g, and an acid value of 0.9 mgKOH / g. Polyester polyol (A) Designed number of functional groups per molecule: hydroxyl groups: 3 and carboxy groups: 0.

(Polyisocyanate B-1)
“Takenate D-110N” manufactured by Mitsui Chemicals (trimethylolpropane adduct of metaxylylene diisocyanate) and “Takenate 500” (non-volatile content of metaxylylene diisocyanate) manufactured by Mitsui Chemicals were mixed at a ratio of 50/50 (mass ratio). It was set as polyisocyanate B-1. The nonvolatile content is 87.5% and NCO% is 28.1%.

(Polyisocyanate B-2)
“Desmodur N3200” (biuret of hexamethylene diisocyanate) manufactured by Sumika Bayer Urethane and “Takenate 500” manufactured by Mitsui Chemicals were mixed at a ratio of 33/67 to obtain polyisocyanate B-2. The non-volatile content is 99% or more, and the NCO% is 37.4%.

The polyester polyol and polyisocyanate obtained above were blended at a mass ratio shown in Table 1 to obtain barrier adhesives (A to E).

(Adhesive for comparative example)
100 parts of Dick Dry LX-703VL (manufactured by DIC Graphics: Polyester polyol, non-volatile content / about 62%), which is the main component of the solvent-type laminating adhesive, is mixed with 9 parts of the aforementioned polyisocyanate B-1. A comparative adhesive was obtained.

(Coating and aging method 1)
Adhesives A to D and comparative adhesives are solvent-type adhesives. Using a bar coater, apply the film (I) to a coating amount of 5.0 g / m ² (solid content), evaporate the diluting solvent with a drier set at a temperature of 70 ° C., and apply the adhesive. The adhesive layer surface of the film (I) was laminated with a resin film. Next, this laminate film was aged at 40 ° C. for 3 days, and the adhesive was cured to obtain a barrier laminate film.

(Coating and aging method 2)
The adhesive E is a solventless type. This is heated to about 80 ° C., and applied to a film (I) to a coating amount of 5.0 g / m ² using a solvent-free test coater polytype roll coater, and then the coated surface is laminated with a resin film. Then, a laminate film was prepared. Next, the laminate film was aged at 40 ° C. for 3 days to cure the adhesive, thereby obtaining a barrier laminate film.

<Evaluation method>
(1) Adhesive strength The laminated film after aging is cut to a width of 15 mm in parallel with the coating direction, and the space between the resin film and the film (I) is used using a Tensilon universal testing machine manufactured by Orientec Co., Ltd. The tensile strength at the time of peeling by the 180 ° peeling method was defined as the adhesive strength at an atmosphere temperature of 25 ° C. and a peeling speed of 300 mm / min. The unit of adhesive strength was N / 15 mm.
Those having an adhesive strength of 2N / 15 mm or more were marked with ◯, and those having an adhesive strength of less than 2N / 15 mm were marked with ×.
(2) Oxygen permeability The laminated film after aging was measured in an atmosphere of 23 ° C. and 90% RH in accordance with JIS-K7126 (isobaric method) using an oxygen permeability measuring device OX-TRAN2 / 21MH manufactured by Mocon. did. Note that RH represents humidity.
(3) Water Vapor Permeability The laminate film after aging was measured by leaving it in an atmosphere of 40 ° C. and 90% RH according to JIS-Z0208 (cup method). Note that RH represents humidity.
(4) Aroma retaining property The laminated film after aging was cut into 10 cm × 15 cm square. Fold the long side of the film in half, heat seal two sides of the 10cm x 7.5cm square at 160 ° C for 1 second, add 1cc of soy sauce, heat seal the other side, and seal in three directions Sealed with a mold. The bag was immediately placed in a mayonnaise bottle (M-70) manufactured by Koyo Glass Co., Ltd., sealed, and stored for 2 months or more at a temperature of 27 ° C. and a relative humidity of 60%. Each time, the presence or absence of odor leakage was confirmed by a sensory test. The case where the odor leaked within 3 days was evaluated as “X”, the case where the odor leaked within 7 days was indicated as “△”, the case where the odor leaked within 14 days was indicated as “◯”, and the case where no odor leaked was observed for 2 months or more.
(5) Laminate strength and appearance Laminate film after aging is overlaid with a sample of 10 cm × 10 cm square size on the surfaces of film (I), sealing temperature 200 ° C., sealing pressure 0.2 MPa, sealing time Three directions were sealed under the conditions of 1 second and a seal width of 8 mm to prepare a bag. 20 ml of 100% ethanol solution was poured into the bag and sealed under the above sealing conditions. The ethanol injection bag was left in a thermostatic chamber at 24 ° C. and 50% humidity for one month, and then the solution was taken out and the film appearance and the sealing strength (laminate strength) were measured. A sample having an intensity of 2N / 15 mm or more was marked with ◯ and a sample having a strength of less than 2N / 15 mm. As the evaluation of the film appearance, “O” indicates no change in the film appearance, and “X” indicates that a blistering float occurred between the film (I) and the resin film.
(6) Packaging machine characteristics The laminated film after the aging was subjected to the following horizontal pillow packaging with an automatic packaging machine to form a bag.
Horizontal sealing: The sealing layers were sealed while changing in increments of 10 ° C. from a rate of 30 bags / minute, a vertical heat sealing temperature of 150 ° C., an air gauge pressure of 4 kg / cm ² , and a horizontal heat sealing temperature of 140 ° C. to 190 ° C. A flat bag measuring 200 mm long and 150 mm wide was used.
Shrinkage / Wrinkle Test The appearance of the sealed portion of the flat bag which was subjected to horizontal (gap-attached) seal and vertical seal was evaluated by shrinkage and the state of film fusion to the heat seal bar and the condition of wrinkles.
○: There is no shrinkage of the seal part, fusion to the seal bar and wrinkles, etc. Δ: There is some shrinkage of the seal part, fusion to the seal bar and wrinkles, etc. ×: Shrinkage of the seal part, fusion to the seal bar and wrinkles Etc. Horizontal sealing property The film made under the above conditions was naturally cooled at 23 ° C., and then a test piece was cut into a strip of 15 mm width. The test piece was peeled 90 ° at a rate of 300 mm / min using a tensile tester (manufactured by A & D Co., Ltd.) in a thermostatic chamber at 23 ° C. and 50% RH, and the heat seal strength was measured. The heat sealability was evaluated according to the following criteria from the obtained heat seal strength value.
○: Heat seal strength is 300 g / 15 mm width or more.
X: Heat seal strength is less than 300 g / 15 mm width.
−: Measurement not possible due to shrinkage and wrinkling (7) Tear test Lamination film after aging was cut into test pieces each having a size of 63 mm × 76 mm in accordance with JIS K7128, and an Elmendorf tear tester (tester The tear strength was measured using Sangyo Co., Ltd. The tearability was evaluated from the obtained tear strength according to the following criteria.
○: Tear strength is less than 110. X: Tear strength is 110 or more.

Example 1
As a resin for the resin layer (i), a ring-opening polymer of a norbornene-based monomer [“Apel APL8008T” manufactured by Mitsui Chemicals, MFR: 15 g / 10 min (260 ° C., 21.18 N), glass transition point: 70 ° C. Hereinafter referred to as “COC (3)”. ] 70 parts and linear medium density polyethylene [density: 0.930 g / cm ³ , melting point 125 ° C., MFR: 5 g / 10 min (190 ° C., 21.18 N); hereinafter referred to as “LMDPE”. A resin mixture with 30 parts was used. This resin is supplied to (i) a layer extruder (50 mm in diameter) and melted at 200 to 230 ° C., and the melted resin is a T-die / chill roll co-extrusion multilayer film production apparatus (feed) (Block and T-die temperature: 250 ° C.) and melt extrusion was performed to obtain a single-layer film having a total thickness of 30 μm, and then the surface was subjected to corona treatment. The surface tension by the wetting reagent was 45 mN / m. After the adhesive A was applied to the treated surface side, biaxially stretched polyester (thickness: 12 μm) (melting point: 260 ° C., manufactured by Toyobo, hereinafter referred to as PET) was dry-laminated and then subjected to aging to obtain a barrier laminate film.

Example 2
As a resin for the resin layer (i), a ring-opening polymer of a norbornene monomer [“Apel APL6015T” manufactured by Mitsui Chemicals, MFR: 10 g / 10 min (260 ° C., 21.18 N), glass transition point: 145 ° C. Hereinafter referred to as “COC (1)”. Using a resin mixture of 50 parts and 50 parts of COC (3), a monolayer film having a total thickness of 30 μm was obtained in the same manner as in Example 1, and then the surface was subjected to corona treatment. The surface tension by the wetting reagent was 45 mN / m. After the adhesive B was applied to the treated surface side, biaxially stretched polyamide (thickness 15 μm) (melting point 260 ° C., manufactured by Toyobo, hereinafter referred to as ONY) was dry laminated, and then aging was performed to obtain a barrier laminate film.

Example 3
LMDPE was used as the resin layer (ii), and a resin mixture of 90 parts of COC (3) and 10 parts of LMDPE was used as the resin for the resin layer (i). These are supplied to an extruder for resin layer (i) and an extruder for resin layer (ii) and melted at 200 to 250 ° C., and the melted resin is co-extruded multilayer of T-die / chill roll method having a feed block. Each film is supplied to a film manufacturing apparatus (feed block and T die temperature: 250 ° C.) and co-melt extrusion is performed. The film has a two-layer structure (ii) / (i), and each layer has a thickness of 10 μm. A co-extruded multilayer film having a thickness of / 20 μm (total 30 μm) was obtained. The surface of the resin layer (i) was subjected to corona treatment. The surface tension by the wetting reagent was 45 mN / m. After the adhesive C was applied to the treated surface side, PET was dry laminated, and aging was performed to obtain a barrier laminate film.

Example 4
As a resin for the resin layer (i), 20 parts of COC (1), 70 parts of COC (3) and a propylene-α-olefin random copolymer polymerized using a metallocene catalyst [density: 0.900 g / cm ³ , Melting point 135 ° C., MFR: 4 g / 10 min (230 ° C., 21.18 N); hereinafter referred to as “MRCP”. ) Using 10 parts of resin mixture, using MRCP as the resin layer (ii), the film layer structure is a two-layer structure (ii) / (i), and the thickness of each layer is 10 μm / 20 μm (total 30 μm) A coextruded multilayer film was obtained. The surface of the resin layer (i) was subjected to corona treatment. The surface tension by the wetting reagent was 45 mN / m. After the adhesive D was applied to the treated surface side, ONY was dry laminated and aging was performed to obtain a barrier laminate film.

Example 5
A resin mixture of 90 parts of LMDPE and 10 parts of COC (3) is used as the resin layer (ii), and a resin mixture of 20 parts of COC (1), 60 parts of COC (3) and 20 parts of LMDPE is used as the resin for the resin layer (i). In the same manner as in Example 3, a coextruded multilayer film having a two-layer structure of (ii) / (i) and a thickness of each layer of 10 μm / 20 μm (total 30 μm) was obtained. . The surface of the resin layer (i) was subjected to corona treatment. The surface tension by the wetting reagent was 45 mN / m. After the adhesive A was applied to the treated surface side, ONY was dry laminated and aging was performed to obtain a barrier laminate film.

Example 6
As the resin layer (i) for the outer layer, a mixture of 20 parts of COC (1) and 80 parts of COC (3) is used, and LMDPE is used as the resin layer (ii) for the intermediate layer, and an adhesive is applied. As the resin for the inner resin layer (i), a resin mixture of 30 parts of COC (3) and 70 parts of LMDPE was used. These are supplied to an outer layer resin layer (i) extruder, an intermediate layer resin layer (ii) extruder, and an inner layer resin layer (ii) extruder and melted at 200 to 250 ° C. The resulting resin is fed to a T-die / chill roll co-extrusion multilayer film production apparatus (feed block and T-die temperature: 250 ° C.) having a feed block, and co-melt extrusion is performed. A co-extruded multilayer film having a three-layer configuration of layer / inner layer and a thickness of each layer of 10 μm / 30 μm / 20 μm (total 60 μm) was obtained. The surface of the inner resin layer (i) was subjected to corona treatment. The surface tension by the wetting reagent was 45 mN / m. After the adhesive A was applied to the treated surface side, PET was dry-laminated and aged to obtain a barrier laminate film.

Example 7
As a resin layer (i) for the outer layer, a mixture of 80 parts of COC (3) and 20 parts of LMDPE is used, and as a resin layer (ii) for the intermediate layer, a resin mixture of 50 parts of LMDPE and 50 parts of MRCP is used, and an adhesive is used. As the resin for the inner resin layer (i) to be applied, a resin mixture of 50 parts of COC (1) and 50 parts of COC (3) was used. Co-extrusion extrusion was carried out in the same manner as in Example 6 to obtain a co-extruded multilayer film having a film layer structure of 3 layers and a thickness of each layer of 10 μm / 30 μm / 20 μm (total 60 μm). The surface of the inner resin layer (i) was subjected to corona treatment. The surface tension by the wetting reagent was 45 mN / m. After the adhesive E was applied to the treated surface side, PET was dry-laminated and aged to obtain a barrier laminate film.

Example 8
As a resin for the surface layer, linear low density polyethylene [density: 0.920 g / cm ³ , melting point 115 ° C., MFR: 5 g / 10 min (190 ° C., 21.18 N); hereinafter referred to as “LLDPE”. As a resin layer (i) as a first intermediate layer laminated thereon, a resin mixture of 50 parts of COC (1) and 50 parts of COC (3) was used. Furthermore, as resin layer (ii) as the second intermediate layer, using LMDPE, as resin layer (i) of the inner layer to which the adhesive is applied, 70 parts of COC (1) and 30 parts of COC (3) A resin mixture was used. These are respectively supplied to four extruders and melted at 200 to 250 ° C., and the molten resin is a co-extruded multilayer film production apparatus (feed block and T-die temperature: 250) having a feed block. ) And co-melt extrusion is carried out, and the film has a four-layer structure of surface layer / intermediate layer-1 / intermediate layer-2 / inner layer, and each layer has a thickness of 3 μm / 6 μm / 15 μm / A coextruded multilayer film having a thickness of 6 μm (total 30 μm) was obtained. The surface of the inner resin layer (i) was subjected to corona treatment. The surface tension by the wetting reagent was 45 mN / m. After the adhesive A was applied to the treated surface, PET was dry laminated and aged to obtain a barrier laminate film.

Example 9
COPP was used as the resin for the surface layer, and a resin mixture of 50 parts of COC (1) and 50 parts of COC (3) was used as the resin layer (i) for the first intermediate layer laminated thereon. Further, a resin mixture of 50 parts of LMDPE and 50 parts of MRCP was used as the resin layer (ii) for the second intermediate layer. A resin mixture of 50 parts of COC (1) and 50 parts of COC (3) was used as the inner resin layer (i) to which the adhesive was applied. Co-extrusion extrusion was performed in the same manner as in Example 8 to obtain a co-extruded multilayer film having a film layer structure of 4 layers and a thickness of each layer of 3 μm / 9 μm / 15 μm / 3 μm (total 30 μm). The surface of the inner resin layer (i) was subjected to corona treatment. The surface tension by the wetting reagent was 45 mN / m. After the adhesive E was applied to the treated surface side, ONY was dry laminated and aged to obtain a barrier laminate film.

Example 10
LMDPE was used as the resin layer (ii) for the surface layer, and a resin mixture of 70 parts of LMDPE and 30 parts of COC (3) was used as the resin layer (i) as the intermediate layer. LMDPE was used as the resin layer (ii) as the inner layer. Co-extrusion extrusion was performed in the same manner as in Example 6 to obtain a co-extruded multilayer film having a film layer structure of 3 layers and a thickness of each layer of 7.5 μm / 15 μm / 7.5 μm (total 30 μm). . Corona treatment was applied to the surface of the inner layer. The surface tension by the wetting reagent was 45 mN / m. After the adhesive E was applied to the treated surface side, PET was dry laminated and aged to obtain a barrier laminate film.

Comparative Example 1
A corona treatment was applied to the surface of a single layer film made of LMDPE and having a total thickness of 30 μm. The surface tension by the wetting reagent was 40 mN / m. In the same manner as in Example 1, the treated surface was coated with the adhesive F to 5 g / m ² , and then PET was dry-laminated and aged to obtain a laminate film.

Comparative Example 2
LLDPE was used as the outer layer resin. Using LMDPE as the inner layer resin, a coextruded multilayer film having a two-layer structure and a thickness of 20 μm / 20 μm (total thickness 40 μm) was obtained in the same manner as in Example 3. The inner layer surface was subjected to corona treatment. The surface tension by the wetting reagent was 40 mN / m. A multilayer film without dry lamination was obtained.

Comparative Example 3
LMDPE was used as the outer layer resin. Using a resin mixture of LMDPE 95 and 5 parts of COC (3) as the inner layer resin, a coextruded multilayer film having a thickness of 20 μm / 20 μm (total thickness 40 μm) in a two-layer configuration in the same manner as in Example 3. Obtained. Corona treatment was applied to the surface of the inner layer. The surface tension by the wetting reagent was 40 dyne / cm. In the same manner as in Example 1, the treated surface was coated with the adhesive F to 5 g / m ² , then ONY was dry laminated and aged to obtain a laminated film.

  About the film obtained by the Example and the comparative example, it evaluated in accordance with the above-mentioned evaluation method. The results are shown in Tables 2-3.

Claims (19)

A film (I) having a resin layer (i) containing 30% by mass or more of a cyclic polyolefin resin (i-1) as a resin component, and a resin film ,
A laminated film laminated with an adhesive containing a polyester polyol (A) having two or more hydroxyl groups and a polyisocyanate (B) having two or more isocyanate groups ;
The polyester polyol (A) is
A polyester polyol obtained by polycondensation of a polyhydric alcohol with a polyhydric carboxylic acid containing at least one of an ortho-oriented polycarboxylic acid and an anhydride thereof,
Or, a polyester polyol having three or more hydroxyl groups composed of a polyhydric carboxylic acid containing at least one ortho-oriented polycarboxylic acid and anhydride and a polyhydric alcohol component, a carboxylic anhydride or a polycarboxylic acid Polyester polyol reacted with
Barrier laminate film, wherein the at. The ortho-oriented aromatic polyvalent carboxylic acid or its anhydride is orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid or its anhydride, anthraquinone 2,3 The barrier laminate film according to claim 1, which is at least one polyvalent carboxylic acid or its anhydride selected from the group consisting of -dicarboxylic acid or its anhydride and 2,3-anthracene dicarboxylic acid or its anhydride. Of ortho directing polycarboxylic acid or its anhydride, the barrier laminate film according to claim 1 or 2 content with respect to polycarboxylic acid entire component is 70 to 100 wt%. The barrier laminate film according to any one of claims 1 to 3, wherein the polyhydric alcohol contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. . The barrier laminate film according to claim 1, wherein the polyhydric alcohol contains glycerol. The polyester polyol (A) is a polyester polyol having three or more hydroxyl groups composed of a polyhydric carboxylic acid containing at least one or more of orthophthalic acid and its anhydride and a polyhydric alcohol component. The barrier laminate film according to any one of claims 1 to 5, which is a polyester polyol reacted with a carboxylic acid, having a hydroxyl value of 20 to 250 and an acid value of 20 to 200. The barrier laminate film according to any one of claims 1 to 6, wherein the polyester polyol (A) has an isocyanuric ring represented by the following general formula (3).

[In formula (3), R _{1 to} R ₃ are each independently — (CH ₂ ) _n1 —OH (where n1 is an integer of 2 to 4), or the following general formula (4)

[In Formula (4), n2 is an integer of 2-4, n3 is an integer of 1-5, X is a 1,2-phenylene group or a 1,2-naphthylene group which may have a substituent. 2,3-naphthylene group, 2,3-anthraquinonediyl group, or 2,3-anthracenediyl group, which may be the same or different for each repeating unit, and Y is the same for each repeating unit. It is an alkylene group having 2 to 6 carbon atoms which may be different or different. ]
Wherein at least one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (4). ] The barrier laminate film according to any one of claims 1 to 7 , wherein the polyisocyanate (B) contains a polyisocyanate having an aromatic ring. The barrier laminate film according to claim 8 , wherein the polyisocyanate having an aromatic ring is metaxylylene diisocyanate or a reaction product of metaxylylene diisocyanate and an alcohol having two or more hydroxyl groups. The barrier laminate film according to any one of claims 1 to 9 , wherein the cyclic polyolefin resin (i-1) is a norbornene polymer. The barrier laminate film according to any one of claims 1 to 10 , wherein the resin layer (i) further contains a polyethylene resin (i-2) and / or a polypropylene resin (i-3). . The film (I) is a multilayer film obtained by laminating a resin layer (ii) containing a polyolefin resin (ii-1) as a main component on one side or both sides of the resin layer (i) . 11. The barrier laminate film according to any one of 11 above. The barrier laminate film according to claim 12, wherein the polyolefin resin is a polyethylene resin (ii-2) or a polypropylene resin (ii-3). The barrier laminate film according to any one of claims 1 to 13 , wherein the film (I) has a thickness in a range of 15 to 100 µm. The barrier laminate film according to any one of claims 1 to 14 , wherein the film (I) is a multilayer film and is produced by a coextrusion lamination method. The barrier laminate film according to claim 1 , wherein the resin film is biaxially stretched polypropylene or biaxially stretched polyester. A packaging material comprising the barrier laminate film according to any one of claims 1 to 16 . The packaging material according to claim 17, which is a packaging bag formed so that the film (I) is inside. The packaging material according to claim 17 or 18, which is for foods, pharmaceuticals or industrial chemicals.