JP5982800B2 - Gas barrier adhesive using non-petroleum-derived component, and gas barrier multilayer film, container, and tube - Google Patents

Description

  The present invention relates to an adhesive using a non-petroleum-derived component in consideration of the global environment, and a barrier multilayer film, a container, and a tube using the same.

  Packaging materials such as food and beverages not only 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, etc. Various 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. More recently, from the viewpoint of saving resources, composite flexible films have been used for shampoos, rinses, liquid detergents, cosmetics, and the like that have been filled in plastics and glass bottles. In general, a composite flexible film is composed of a thermoplastic film layer as an outer layer having product protection and various functions, a thermoplastic film layer as a sealant layer, and the like. There is also a method in which an adhesive and a thermoplastic resin for a sealant layer are melt-extruded in three layers and an unstretched laminated sheet is molded and then stretched (for example, see Patent Document 1). A dry laminating method for producing a multilayer film by adhering layers (for example, see Patent Document 2) 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, and a gas barrier function for inert gases and the like is required in addition to oxygen for the purpose of extending the effective shelf life of foods and preventing oxidation degradation. 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 abbreviated as PET), polyamide resins, stretched polyolefin resins) used on the outer layer side.

In addition, there are strong social and industrial demands to change these multilayer film materials to “biomass”, which is defined as “renewable, bio-derived organic resources excluding fossil resources”. This is based on the value of saving oil resources and the value of preventing global warming by suppressing the increase in carbon dioxide. One way to meet this need is to use plant-derived raw materials. The reason is that there is an idea that CO ₂ can be counted as zero even if incinerated in order to absorb CO ₂ when the plant grows.

  In order to provide a barrier for a multilayer film, when a gas barrier function is imparted to the outer film by coating, vinylidene chloride having a high oxygen barrier property and a high water vapor barrier property has been widely used as a gas barrier coating material. There are problems with the global environment such as the generation of dioxins during firing. In addition, vinylidene chloride uses a petroleum-derived raw material as a starting raw material, and it is difficult to say that it is an environmentally friendly material that has become increasingly important in recent years. On the other hand, a film in which a metal vapor deposition layer such as aluminum is provided as a gas barrier layer has a problem that it is opaque and the inside cannot be visually recognized, and the 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 a problem of poor flexibility and performance variation due to cracks and pinholes. In addition, since a large facility using a vacuum deposition system is required, a large amount of manufacturing energy is required and it is difficult to say that the material is environmentally friendly.

  On the other hand, a method of imparting a gas barrier function to an adhesive used at the time of lamination is also known. This method has an advantage that a multi-layer film for gas barrier can be produced without using a film having a special gas barrier function imparted by a process and configuration essential for producing a laminated film. On the other hand, the flexible molecular structure essential for adhesives generally has high gas permeability. For this reason, the adhesive ability and the gas barrier function are often in a trade-off relationship, and this elimination increases the technical difficulty.

  As a container using such a gas barrier barrier laminate film, for example, in Patent Document 3 and Patent Document 4, an epoxy layer between an outer layer thermoplastic film layer and a thermoplastic film layer serving as a sealant layer is used. A bag-like container formed by bag-making a gas barrier laminated film bonded with an epoxy resin composition comprising a resin and an epoxy resin curing agent, wherein metaxylylenediamine or paraxylylenediamine is added to the epoxy resin curing agent A reaction product as an essential component, or the reactive biological bag-like container is described. However, there is no mention that a non-petroleum-derived component is used for these adhesive components, and it is estimated that the raw material monomer species of the used material is completely composed of a petroleum-derived material.

  On the other hand, as a resin produced from a non-petroleum-derived component, Patent Document 5 discloses that a polyol containing a plant-derived short-chain diol component (a) is reacted with an isocyanate component (d), resulting in a resin of 100 mass. There is a description relating to a biopolyurethane resin characterized in that the content of plant-derived components is 28 to 95% by mass relative to%. However, this document makes no mention of various gas barrier functions.

JP 2006-341423 A JP 2003-13032 A Japanese Patent No. 4092549 Japanese Patent No. 4366563 JP 2011-225863 A

  The problem to be solved by the present invention is to provide an adhesive mainly composed of polyester that can be used for packaging of contents for food packaging, etc., using non-petroleum-derived components in consideration of the global environment, and has excellent gas barrier properties. There is. Furthermore, it is providing the gas barrier multilayer film, gas barrier container, and gas barrier tube which use this adhesive agent.

The present inventors include a polyol component, a polyester polyol (A) having two or more hydroxyl groups synthesized from a polycarboxylic acid component, and a polyisocyanate (B) having two or more isocyanate groups. In the gas barrier adhesive,
A part of the polyol component is a non-petroleum-derived component short-chain polyol component (a1), or a part of the polycarboxylic acid component is a non-petroleum-derived component polycarboxylic acid component (a2). The above problems were solved by the gas barrier adhesive.

  According to the present invention, it is possible to provide a polyester-based adhesive excellent in gas barrier properties while having sufficient adhesion between substrates, and further to provide a gas barrier multilayer film, container, and tube by a multilayer film having the adhesive layer as an adhesive layer. It becomes possible. In addition, since the adhesive layer contains non-petroleum-derived components, the use of petroleum-derived components can be reduced, which can contribute to environmental problems such as the phenomenon of consumption of petroleum resources and the suppression of carbon dioxide increase. .

[Polyester polyol (A)]
The polyester polyol (A) used in the present invention has two or more hydroxyl groups synthesized from a polyol component and a polycarboxylic acid component, and a part of the polyol component is a short chain of a non-petroleum-derived component. It is a polyol component (a1) or a part of the polycarboxylic acid component is a non-petroleum-derived component polycarboxylic acid component (a2). In addition, the non-petroleum-derived component referred to in the present name refers to a renewable component derived from plants or animals. Among these, plant-derived materials are particularly preferable from the viewpoint of carbon neutral, since carbon dioxide absorbed during plant growth is used as a material.

(Non-petroleum-derived component short-chain polyol component (a1))
When the polyester polyol (A) of the present invention does not contain the non-petroleum component-derived monomer (a2) in the polycarboxylic acid component, the non-petroleum-derived component short-chain polyol component (a1) is used as a raw material monomer. On the other hand, the short-chain polyol component (a1) may also be contained when the polycarboxylic component (a2) is contained. Examples of the short-chain polyol component (a1) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerol and the like. For example, ethylene glycol is produced from bioethanol obtained by a conventional method via ethylene. 1,3-propanediol is produced from glycerol via 3-hydroxypropyl aldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant resources (for example, corn). 1,4-butanediol can be produced by obtaining succinic acid obtained by producing glycol from plant resources and fermenting it and hydrogenating it. Glycerol is obtained as an intermediate for obtaining the aforementioned 1,3-propanediol from plant resources. The reason why short-chain alkyl is preferably used as a gas, particularly as an oxygen-barrier skeleton, is that the smaller the number of carbon atoms between oxygen atoms, the less the molecular chain becomes excessively flexible and it is presumed that oxygen is less permeable. . These short-chain polyol components are currently in circulation as materials that can be mass-produced on a commercial basis. However, it is not limited to these polyols as long as they are short-chain polyols derived from non-petroleum components (having 6 or less carbon atoms).

(Non-petroleum-derived component polycarboxylic acid component (a2))
When the polyester polyol (A) of the present invention does not contain a non-petroleum component-derived monomer (a1) in the polyol component, the non-petroleum-derived component polycarboxylic acid component (a2) is used as an essential raw material monomer. On the other hand, also when the polyol component (a1) is contained, the polycarboxylic acid component (a2) may be contained.

  Examples of the non-petroleum-derived polycarboxylic acid component (b2) used in the present invention include sebacic acid and succinic acid. Sebacic acid is produced by alkaline pyrolysis of ricinoleic acid obtained from castor oil extracted from castor bean seeds. Succinic acid is produced as an intermediate of 1,4-butanediol described in the short-chain polyol component (a1). In particular, succinic acid is particularly preferably used since the short alkyl chain is suitable as a barrier skeleton, like the short-chain polyol component (a1). These polycarboxylic acid components are already distributed as materials that can be mass-produced on a commercial basis. However, it is not limited to these porils as long as they are derived from non-petroleum components.

(Polyol component derived from petroleum components)
The polyol used in the present invention may contain a petroleum-derived component in addition to the non-petroleum-derived component short-chain polyol component (a1). Specifically, as aliphatic diols generally produced from petroleum-derived components, 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, Examples thereof include bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide extension products, and hydrogenated alicyclic groups. Further, ethylene glycol, 1,3-propanediol, 1,4-butanediol, and glycerol derived from petroleum components may be contained. The polycondensation reaction between the polycarboxylic acid and the polyol can be performed by a known and usual method.

(Polycarboxylic acid derived from petroleum components)
If the polyester polyol (A) of the present invention contains a non-petroleum-derived component short-chain polyol component (a1) and / or a polycarboxylic acid component (a2), it may contain other petroleum-derived components. There is no problem. Specific examples of the polycarboxylic acid component include aliphatic polycarboxylic acids such as adipic acid, azelaic acid, and dodecanedicarboxylic acid, and alicyclic polycarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4. -Cyclohexanedicarboxylic acid and the like as aromatic polycarboxylic acid include 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 dihydroxycarboxylic acids Polybasic acids such as ester-forming derivatives of acids can be used alone or in a mixture of two or more. These acid anhydrides can also be used. Among them, in order to obtain barrier properties, in addition to the succinic acid mentioned in the polycarboxylic acid component (b2) derived from non-petroleum, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydride of orthophthalic acid, isophthalic acid Is more preferable, and orthophthalic acid and its acid anhydride are more preferable. Further, succinic acid and sebacic acid derived from petroleum components may be contained.

More specifically, as the polyester polyol (A) having two or more hydroxyl groups of the present invention, a part of the polyol component is a non-petroleum-derived component short-chain polyol component (a1) or the polycarboxylic acid. In addition to a part of the acid component being a non-petroleum-derived component polycarboxylic acid component (a2),
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 polycarboxylic acid component and a polyol component,
-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) used in the present invention comprises at least one carboxy group and two or more obtained by reacting a polyester polyol (I) having three or more hydroxyl groups with a carboxylic acid anhydride or polycarboxylic acid. It has a hydroxyl group. The polyester polyol (I) having three or more hydroxyl groups can be obtained by making a part of the polycarboxylic acid or polyol trivalent or higher.

  As the polyol component and polyol component of the polyester polyol (A1), preferably, a polycarboxylic acid component containing at least one or more of orthophthalic acid and its anhydride, ethylene glycol, 1,3-propanediol, 1,4-butanediol , A polyester polyol (I) having three or more hydroxyl groups comprising at least one polyol component selected from the group consisting of neopentyl glycol, and cyclohexane dimethanol, and a carboxylic anhydride or polycarboxylic acid. And having at least one carboxy group and two or more hydroxyl groups. At this time, when other non-petroleum-derived components are not included, at least a part thereof needs to contain non-petroleum-derived ethylene glycol, 1,3-propanediol, and 1,4-butanediol.

(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 thus it is presumed that the gas barrier property is excellent. Further, it is presumed that due to this asymmetric structure, it exhibits non-crystallinity, imparts sufficient substrate adhesion, and is excellent in adhesion and gas 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.

(Polycarboxylic acid and other components)
When synthesizing a polyester polyol (I) having three or more hydroxyl groups, when a branched structure is introduced by a polycarboxylic acid component, it is necessary to have at least a 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 polycarboxylic acids are trivalent. Carboxylic acid is preferred.
As other components, the polyester polyol (I) of the present invention may be copolymerized with other polycarboxylic acid components as long as the effects of the present invention are not impaired. Specifically, it is preferable to use an aliphatic polycarboxylic acid such as succinic acid or sebacic acid, which is a polycarboxylic acid derived from a non-petroleum component, because the content rate derived from the non-petroleum component in the polyester polyol can be increased. As other polycarboxylic acids, adipic acid, azelaic acid, dodecanedicarboxylic acid, etc., as unsaturated bond-containing polycarboxylic acids, maleic anhydride, maleic acid, fumaric acid, etc., as alicyclic polycarboxylic acids 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc., and aromatic polycarboxylic acids include 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 properties of these dicarboxylic acids Derivatives; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and Polybasic acids such as ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more.

(Polyol component)
The polyol used in the present invention preferably contains ethylene glycol derived from non-petroleum components, 1,3-propanediol, and 1,4-butanediol. In particular, the smaller the number of carbon atoms between oxygen atoms, the less likely the molecular chains are to be excessively flexible and the less likely to permeate oxygen, and ethylene glycol is used because plant-derived materials are widely distributed. Most preferably. As other polyol components, neopentyl glycol and cyclohexanedimethanol are preferably used from the viewpoint of low gas permeability.

(Polyol and other ingredients)
When synthesizing a polyester polyol (I) having three or more hydroxyl groups, when a branched structure is introduced by a polyol component, it is necessary to have at least part of a trivalent or higher polyol. As these compounds, it is preferable to use glycerol derived from non-petroleum components because the ratio of non-petroleum-derived components can be increased. Examples include trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol, etc., in order to prevent gelation during synthesis. The trihydric or higher polyol is preferably a trihydric alcohol.
As other components, in the present invention, the above-described polyol component may be copolymerized with other polycarboxylic acid 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 Examples thereof include an oxide extension product and a hydrogenated alicyclic group.

  Next, the reaction between the polyester polyol (I) of the present invention and the carboxylic acid anhydride or polycarboxylic acid is carried out as follows.

  That is, it can be obtained by reacting the polyester polyol (I) with a polycarboxylic acid or an acid anhydride thereof with a hydroxyl group of the polyester polyol (I). The ratio between the polyester polyol (I) and the polycarboxylic acid is that at least two hydroxyl groups of the polyester polyol (A) after the reaction are necessary, so that the polycarboxylic acid is 1/3 or less of the hydroxyl groups of the polyester polyol (I). It is preferable to react. Although there is no restriction | limiting in the carboxylic acid anhydride or polycarboxylic acid used here, when gelatinization at the time of reaction of polycarboxylic acid and polyester polyol (I) is considered, bivalent or trivalent carboxylic acid anhydride is used. It is preferable to do. 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.

  The polyester polyol (A1) preferably has a hydroxyl value of 20 to 250 and an acid value of 20 to 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 smaller than 20 mgKOH / g, the molecular weight is too large, the viscosity becomes high, and good coating suitability cannot be obtained. On the other hand, when the hydroxyl value exceeds 250 mgKOH / g, the molecular weight becomes too small, so that the crosslinking density of the cured coating film becomes too high, and good adhesive strength cannot be obtained. When the acid value is less than 20 mgKOH / g, the interaction between molecules becomes small, and good gas barrier properties and good initial cohesive force cannot be obtained. On the contrary, when the acid value exceeds 200 mgKOH / g, the reaction between the polyester polyol (A) and the polyisocyanate (B) becomes too fast, and good coating suitability cannot be obtained.

[Polyester polyol (A2) having a polymerizable carbon-carbon double bond]
Further, examples of the polyester polyol (A2) of the present invention include those having a polymerizable carbon-carbon double bond in the molecule.
The polyester polyol (A2) used in the present invention is obtained by reacting a polycarboxylic acid and a polyol, and by using a component having a polymerizable carbon-carbon double bond as a component of the polycarboxylic acid and polyol, A polysynthetic carbon-carbon double bond can be introduced into the molecule of the polyester polyol (A2).

(Polycarboxylic acid)
The polyester polyol (A2) of the present invention is derived from a non-petroleum component in a polyester polyol when an aliphatic polycarboxylic acid such as succinic acid or sebacic acid, which is a polycarboxylic acid derived from a non-petroleum component, is used as the polycarboxylic acid component. Since the content rate of can be raised, it is preferable. Other polycarboxylic acids include adipic acid, azelaic acid, dodecanedicarboxylic acid, etc., and alicyclic polycarboxylic acids include 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. As carboxylic acids, orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl Dicarboxylic acids, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and Polybases such as ester-forming derivatives of these dihydroxycarboxylic acids The acids can be used alone or in a mixture of two or more. These acid anhydrides can also be used. Among these, from the viewpoint of barrier properties, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, an acid anhydride of orthophthalic acid, and isophthalic acid are preferable, and orthophthalic acid and its acid anhydride are more preferable.

(Polycarboxylic acid having a polymerizable carbon-carbon double bond)
As polycarboxylic acid having a polymerizable carbon-carbon double bond in polycarboxylic acid, maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its acid anhydride, 3-methyl-4- And cyclohexene-1,2-dicarboxylic acid and its anhydride. Of these, maleic anhydride, maleic acid, and fumaric acid are preferred because it is presumed that the smaller the number of carbon atoms, the less the molecular chain becomes excessively flexible and the less oxygen permeates.

(Polyol component)
When the polyol used in the present invention does not contain any other non-petroleum-derived component, at least a part thereof must contain ethylene glycol derived from the non-petroleum component, 1,3-propanediol, 1,4-butanediol. is there. Other aliphatic diols include neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butyl Ethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenols, hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol Examples thereof include ethylene oxide elongated products and hydrogenated alicyclic groups. In particular, non-petroleum-derived materials are widely distributed, and the smaller the number of carbon atoms between oxygen atoms, the less the molecular chain is not excessively flexible, and it is estimated that it is difficult for oxygen to pass through. 1,3-propanediol and 1,4-butanediol are preferred, and ethylene glucol is more preferred.

(Polyol having a polymerizable carbon-carbon double bond)
Examples of the polyol having a polymerizable carbon-carbon double bond in the polyol include 2-butene-1,4-diol.

  In the polyester polyol (A2), a polycarboxylic acid having a polymerizable carbon-carbon double bond and a polyol are used to introduce a polymerizable double bond into the polyester polyol (A2). It may be a reaction between a polyol and a carboxylic acid having a polymerizable double bond, or a carboxylic 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 is preferably 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 due to crosslinking with polyisocyanate. When the polyester polyol has one or two hydroxyl groups, the polyester polyol (A2) obtained by reacting a carboxylic acid having a polysynthetic 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 polyester polyol (A2) preferably has a hydroxyl value of 20 to 250 mgKOH / g and an acid value of 0 to 100 mgKOH / g. 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 smaller than 20 mgKOH / g, the molecular weight is too large, the viscosity becomes high, and good coating suitability cannot be obtained. On the other hand, when the hydroxyl value exceeds 250 mgKOH / g, the molecular weight becomes too small, so that the crosslinking density of the cured coating film becomes too high, and good adhesive strength cannot be obtained.

  Moreover, it has the characteristics 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).

  If it is lower than this range, the number of crosslinking points between the polymerizable double bonds will be reduced, and it will be difficult to obtain barrier properties. If it is higher, the number of crosslinking points will be increased, and the flexibility of the cured coating will be significantly reduced, resulting in a laminate strength. This is not preferable because it is difficult to be performed.

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

  Here, the monomer refers to the above polycarboxylic acid and polyol.

  Moreover, as polyester polyol (A2) of this invention, the well-known usual drying oil which has a carbon-carbon double bond, or semi-drying oil can be mentioned.

[Polyester polyol having glycerol skeleton (A3)]
Examples of the polyester polyol (A3) of the present invention further include a polyester polyol having a glycerol skeleton represented by the general formula (1).

(In Formula (1), R < ₁ > -R < ₃ > is respectively independently a hydrogen atom or General formula (2).

(In the formula (2), n represents an integer of 1 to 5, and X represents an optionally substituted 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2 Represents an arylene group selected from the group consisting of 1,3-anthraquinonediyl group and 2,3-anthracenediyl group, and Y represents an alkylene group having 2 to 6 carbon atoms). However, at least one of R _{1 to} R ₃ represents 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).

_Further, R 1, any one of _{R 2} and _{R 3} is a group represented by the general formula (2) _compound, R 1, _{R 2,} and any two of the general formula _{R 3} (2) Any two or more compounds of the compound represented by the general formula (2) and the compound in which all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (2) are mixed. Also good.

  X is selected from the group consisting of 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group, The arylene group which may have is represented. 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 resin compound having a glycerol skeleton represented by the general formula (1) reacts with glycerol, an aromatic polycarboxylic acid substituted with carboxylic acid in the ortho position, or an anhydride thereof, and a polyol component as essential components. Let me get it. At this time, when other non-petroleum-derived components are not included, glycerol needs to be derived from non-petroleum components.

  Aromatic polycarboxylic 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. Products, anthraquinone 2,3-dicarboxylic acid or anhydride thereof, and 2,3-anthracene carboxylic acid or anhydride thereof. These compounds may have a substituent on any 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 polyol 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, with respect to gas barrier adhesive organic resin composition total solids of the mass of the present application, residues obtained by removing R ₁ to R ₃ in the general formula (1) (C _{The amount of 3} H ₅ O ₃ = 89.07) is calculated using equation (b).

P: represents a polyester polyol (A3) having a glycerol skeleton.

  The present invention is characterized by having a glycerol residue of 5% by mass or more in the organic resin composition for gas barrier adhesives in order to exhibit high barrier properties.

(Method for calculating mass of solid content of organic resin composition for gas barrier adhesive)
The mass excluding the dilution solvent mass, the volatile component mass contained in the curing agent, and the inorganic component from the mass part of the resin composition for gas barrier adhesive is the mass of the total solid content of the organic resin for gas barrier adhesive.

  On the other hand, an aromatic polycarboxylic acid in which an acyl group as a raw material for a polyester component is substituted in the ortho position or an anhydride thereof has an asymmetric skeleton. Therefore, it is presumed that the rotation of the molecular chain of the resulting polyester is suppressed, and thus it is presumed that the gas barrier property is excellent. 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 is excellent in gas barrier properties.

(Polyol)
In the polyester polyol (A3) used in the present invention, a polyol component other than an alkylene diol having 2 to 6 carbon atoms may be copolymerized as a polyol as long as the effects of the present invention are not impaired. At this time, it is preferable that a non-petroleum-derived raw material can be used because the ratio of non-petroleum-derived components can be increased. Specific examples of non-petroleum-derived materials include glycerol and erythritol. In addition, aliphatic polyols such as pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, tripropylene glycol, etc. Cyclohexanedimethanol, tricyclodecanedimethanol and other alicyclic polyols, hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol and other aromatic polyphenols or their ethylene oxide An elongated product and a hydrogenated alicyclic group can be exemplified.

(Polycarboxylic acid)
The polyester polyol (A3) of the present invention essentially comprises an aromatic polycarboxylic acid in which the carboxylic acid is substituted in the ortho position as a polycarboxylic acid component or an anhydride thereof, but within the range not impairing the effects of the present invention. The polycarboxylic acid component may be copolymerized. Specifically, it is preferable to use an aliphatic polycarboxylic acid such as succinic acid or sebacic acid, which is a polycarboxylic acid derived from a non-petroleum component, because the content rate derived from the non-petroleum component in the polyester polyol can be increased. Examples of other polycarboxylic acids include aliphatic polycarboxylic acids such as adipic acid, azelaic acid, and dodecanedicarboxylic acid, and unsaturated bond-containing polycarboxylic acids such as maleic anhydride, maleic acid, and fumaric acid. Examples of the alicyclic polycarboxylic acid include 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and examples of the aromatic polycarboxylic acid include terephthalic acid, isophthalic acid, pyromellitic 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 acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydride Polybasic acids such as loxybenzoic 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.

  Among them, succinic acid is a 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalic acid, diphen from the viewpoint of improving the gas barrier function and the content of non-petroleum-derived components. An acid is preferable from the viewpoint of improving the gas barrier function.

[Polyester polyol (A4) obtained by polycondensation of ortho-oriented polycarboxylic acid component and polyol component]
The polyester polyol (A4) used in the present invention comprises a polycarboxylic acid component containing at least one orthophthalic acid and its anhydride, ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol. And a polyol component containing at least one selected from the group consisting of cyclohexanedimethanol. In particular, a polyester polyol in which the usage rate of the orthophthalic acid and its anhydride with respect to all the components of the polycarboxylic acid is 70 to 100% by mass is preferable. At this time, if no other non-petroleum-derived component is contained, at least a part thereof must contain non-petroleum-derived ethylene glycol, 1,3-propanediol, and 1,4-butanediol.

(Polycarboxylic acid and other components)
The polyester polyol (A4) of the present invention requires the orthophthalic acid and its anhydride as a polycarboxylic acid component, but may be copolymerized with other polycarboxylic acid components within the range not impairing the effects of the present invention. Good. Specifically, it is preferable to use an aliphatic polycarboxylic acid such as succinic acid or sebacic acid, which is a polycarboxylic acid derived from a non-petroleum component, because the content rate derived from the non-petroleum component in the polyester polyol can be increased. Other polycarboxylic acids include aliphatic polycarboxylic acids such as adipic acid, azelaic acid, and dodecanedicarboxylic acid, and unsaturated bond-containing polycarboxylic acids such as maleic anhydride, maleic acid, and fumaric acid. Examples of the cyclic polycarboxylic acid include 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples of the aromatic polycarboxylic acid include 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 these dicarboxylic acids Anhydrides or ester-forming derivatives of p-hydroxybenzoic acid, p- (2- Polybasic acids such as droxyethoxy) 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.

  Examples of the polyol component and other components include those described above.

[Polyester polyol having an isocyanuric ring (A5)]
The polyester polyol (A) of the present invention more preferably includes a polyester polyol (A5) having an isocyanuric ring represented by the following general formula (3).

(In General Formula (3), R _{1 to} R ₃ are each independently — (CH ₂ ) _n1 —OH (where n1 represents an integer of 2 to 4), or General Formula (4)

(In General Formula (4), n2 represents an integer of 2 to 4, n3 represents an integer of 1 to 5, and X represents a 1,2-phenylene group, a 1,2-naphthylene group, or a 2,3-naphthylene group. , 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group, an arylene group which may have a substituent, and Y represents an alkylene group having 2 to 6 carbon atoms. Represent)
Represents a group represented by However, 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 said General formula (4), n2 represents the integer of 2-4, n3 represents the integer of 1-5.
X is selected from the group consisting of 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group, and has a substituent. Represents an arylene group which may be substituted.

  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.

  The substituent of X is preferably a hydroxyl group, a cyano group, a nitro group, an amino group, a phthalimide group, a carbamoyl group, an N-ethylcarbamoyl group, or a phenyl group, preferably a hydroxyl group, a phenoxy group, a cyano group, a nitro group, or a phthalimide group. A phenyl group is most preferred.

  In the general formula (4), 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 butylene group, a propylene group or an ethylene group, and most preferably an ethylene group.

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) Any two or more compounds of the compound represented by the formula and the compound in which all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (4) are mixed. Also good.

  The polyester polyol (A5) having an isocyanuric ring represented by the general formula (3) includes a triol having an isocyanuric ring, an aromatic polycarboxylic acid in which the carboxylic acid is substituted in the ortho position, or an anhydride thereof, and a polyol component. Obtained 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, the aromatic polycarboxylic acid in which the carboxylic acid is substituted in the ortho position or the anhydride thereof includes orthophthalic acid or an anhydride thereof, naphthalene 2,3-dicarboxylic acid or an anhydride thereof, naphthalene 1,2-dicarboxylic acid or The 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 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.

  Further, when the polyol component does not contain any other non-petroleum-derived component, at least a part thereof must contain non-petroleum component-derived ethylene glycol, 1,3-propanediol, and 1,4-butanediol. Examples of other polyol components include diols such as neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, and dimethylbutanediol. Can do.

  Among them, 1,3,5-tris (2-hydroxyethyl) isocyanuric acid or 1,3,5-tris (2-hydroxypropyl) isocyanuric acid is used as a triol compound having an isocyanuric ring, and the carboxylic acid is in the ortho position. A polyester polyol compound having an isocyanuric ring using orthophthalic anhydride as an aromatic polycarboxylic acid substituted with or an anhydride thereof and ethylene glycol as a polyol is particularly excellent in gas barrier properties and adhesiveness. At this time, it is preferable to use a non-petroleum component-derived material as ethylene glycol because the ratio of non-petroleum-derived components can be increased.

  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 mass% or more of the isocyanuric ring with respect to the total solid content of the adhesive resin.

  The reason why the adhesive of the present invention having an isocyanuric ring can secure gas barrier properties and dry laminate adhesiveness is presumed 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. Easily and may damage the solubility in ethyl acetate and 2-butanone solvent often used in dry laminate adhesives, but polyester resins with an isocyanuric ring do not impair the solubility and 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 crosslink density is obtained, it is presumed that gas barrier properties and dry laminate adhesiveness can be secured.

The content of isocyanuric rings in this application should be noted, with respect to the adhesive resin total solid mass of the present application, 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).

P: represents a polyester polyol (A5) having an isocyanuric ring.

(Method for calculating mass of resin composition organic total solid content of gas barrier adhesive)
The mass excluding the dilution solvent mass, the volatile component mass contained in the curing agent, and the inorganic component from the mass part of the resin composition for gas barrier adhesive is the mass of the total solid content of the organic resin for gas barrier adhesive.

  The polyester polyol having an isocyanuric ring can be obtained by a known polyester production method. 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, triol having an isocyanuric ring used as a raw material, aromatic polycarboxylic acid substituted with ortho-position of carboxylic acid or its anhydride, and a polyol component are collectively charged and mixed with stirring. While raising the temperature, a dehydration condensation reaction is performed. 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).

(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 1-1000 ppm, more preferably 10-100 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 from 450 to 5,000 because a crosslinking density with an excellent balance between adhesion and gas barrier function can be obtained. More preferably, the number average molecular weight is 500 to 3000. Further, as the curing agent, polyisocyanate described below is most preferable, can give an appropriate reaction time, and is particularly excellent in adhesive strength and gas barrier function. When the molecular weight is less than 450, the cohesive force of the adhesive at the time of coating becomes too small, causing the problem that the film shifts during lamination or the bonded film rises. Conversely, if the molecular weight is higher than 5000, The problem is that the viscosity at the time of construction is too high to be applied, and that the lamination is impossible due to low adhesiveness. The number average molecular weight was 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. When the glass transition temperature is too higher than 80 ° C., the flexibility of the polyester polyol near room temperature is lowered, and thus the adhesiveness to the substrate may be deteriorated due to poor adhesion to the substrate. On the other hand, when the temperature is too lower than −30 ° C., there is a possibility that sufficient gas 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 gas barrier properties, excellent initial cohesive force, and is further excellent as an adhesive used during lamination.

(Content of non-petroleum-derived components in polyester polyol)
In this invention, it is preferable that the content rate of a non-petroleum origin component is 20-80 mass% with respect to 100 mass% of polyester polyol (A). When this content is 20% by mass or less, the content derived from non-petroleum components in the entire adhesive layer is reduced. Therefore, contribution to the environment is reduced, and when it exceeds 80% by mass, a polyester polyol having a gas barrier function. There are restrictions on the structure, making it difficult to provide a good barrier function. The content rate of a non-petroleum origin component is calculated | required by following formula (e).

(Adhesive hardener)
The curing agent used in the present invention is not particularly limited as long as it is a curing agent capable of reacting with the hydroxyl group of the polyester polyol (A), and known curing agents such as polyisocyanates and epoxy compounds can be used. Among these, it is preferable to use polyisocyanate from the viewpoints of adhesiveness and retort resistance. In addition, it is more preferable to use a curing agent raw material using a non-petroleum-derived raw material at this time because the ratio of non-petroleum-derived components in the entire adhesive can be increased.

  Polyisocyanate compounds 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 isocyanate compound 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 above isocyanate compound and the isocyanate blocking agent to an addition reaction by a known and appropriate method.

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

  The glass transition temperature of the cured coating film 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 gas barrier properties may not be obtained due to intense molecular motion of the cured coating film at around room temperature.

  Among them, the curing agent is preferably a polyisocyanate having an aromatic ring, and if it is a polyisocyanate containing the metaxylene skeleton or the toluene skeleton, not only hydrogen bonds of urethane groups but also π-π stacking of aromatic rings. Is preferable because the gas 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.

Examples of the polyisocyanate containing a toluene skeleton include a trimer of toluene diisocyanate, a burette body synthesized by reaction with an amine, and an adduct body formed by reaction with alcohol, but compared with a trimer and a burette body. Adducts are more preferred because of their easy solubility in organic solvents used for polyisocyanate dry laminate adhesives. 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) curing agent, the ratio of the polyester polyol (A) and the curing agent is such that the hydroxyl group of the polyester polyol (A) and the reaction component of the curing agent are 1 / 0.5. It is preferable to mix | blend so that it may become ~ 1/10 (equivalent ratio), More preferably, it is 1 / 1-1 / 5. If the curing agent component is excessive beyond this range, the excess curing agent component may be left out and bleed out from the adhesive layer after bonding. On the other hand, if the curing agent component is insufficient, the adhesive strength is insufficient. There is a fear.

  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 diacid. 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. Also at this time, it is preferable that a non-petroleum-derived component is contained as a raw material for these epoxy compounds because the ratio of the non-petroleum-derived component can be increased. Examples of such compounds include succinic acid diglycidyl ester and sebacic acid diglycidyl ester.

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

  A known polymerization catalyst can be used as a catalyst for promoting polymerization of a polymerizable carbon-double bond. Examples of the polymerization catalyst include transition metal complexes. 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.

  The said hardening | curing agent can also use together the well-known hardening | curing agent or accelerator selected according to the kind. 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 various film materials.

(Adhesive and other ingredients)
The adhesive of this invention may mix | blend various additives in the range which does not impair gas barrier property. 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)
In the resin composition for adhesives of this invention, you may contain a plate-shaped inorganic compound.
When a plate-like inorganic compound is used in the present invention, it has an effect of improving the laminate strength and gas barrier properties of an adhesive obtained by curing a resin composition for an adhesive.

  When a plate-like inorganic compound is used in combination, the laminate strength and barrier properties are improved due to the plate shape. The charge between the layers of the plate-like inorganic compound does not greatly affect the barrier property directly, but the dispersibility to the resin composition is greatly inferior with the ionic inorganic compound or the swellable inorganic compound with respect to water, and the amount added is increased. As a result, the resin composition becomes thicker and thixotropic. On the other hand, in the case of being uncharged (nonionic) or non-swelling with respect to water, even if the addition amount is increased, it is difficult to become thickened or thixotropic, so that the coating suitability can be ensured. Examples of the plate-like inorganic compound used in the present invention include, for example, hydrous silicate (phyllosilicate mineral etc.), kaolinite-serpentine clay mineral (halloysite, kaolinite, ende Light, dickite, nacrite, etc., antigolite, chrysotile, etc.), pyrophyllite-talc group (pyrophyllite, talc, kerorai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, Sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite etc.), mica or mica group clay minerals (muscovite, phlogopite etc. mica, margarite, tetrasilic mica, teniolite, etc.), chlorite group (kukeite, sudite) , Clinocroix, sha Site Nimaito etc.), hydrotalcite, tabular barium sulfate, boehmite, and aluminum polyphosphate and the like. These minerals may be natural clay minerals or synthetic clay minerals. An inorganic layered compound is used individually or in combination of 2 or more types.

Moreover, it is preferable that the plate-like inorganic compound used in the present invention is nonionic without intercalation.

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

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

  Examples of the plate-like inorganic compound used in the present invention include kaolinite-serpentine clay minerals (such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite and chrysotile), and pyrophyllite. -Talc group (Pyrophyllite, Talc, Kerolai, etc.), Mica or Mica clay mineral (Mica, such as muscovite, phlogopite, etc.), Margarite, Tetrasilic mica, Teniolite, etc., Chlorite group (Kukueite, Sudokuite, (Clinochlor, chamosite, nimite, etc.), hydrotalcite, plate-like barium sulfate and the like.

  The average particle diameter in the present invention means a particle diameter having the highest appearance frequency when the particle size distribution of a certain plate-like inorganic compound is measured with a light scattering measurement device. The average particle diameter of the plate-like inorganic compound used in the present invention is not particularly limited, but is preferably 0.1 μm or more, and more preferably 1 μm or more. If the average particle size is 0.1 μm or less, the length of the long side is short, which causes a problem that it is difficult to improve the gas barrier function without lengthening the detour path of oxygen molecules. The side with a large average particle diameter is not particularly limited. When a large plate-like inorganic compound is contained by the laminating method and a defect such as a streak occurs on the coated surface, a material having an average particle diameter of 100 μm or less, more preferably 20 μm or less is preferably used.

The aspect ratio of the plate-like inorganic compound used in the present invention is preferably higher in order to improve the barrier ability due to the labyrinth effect of the scent component molecules. 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 the amount exceeds 50 parts by mass, the laminating operation may be difficult or the adhesive force may be insufficient.
The content of the inorganic compound (PWC of the blend) can be obtained from the following formula (f).

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

  Moreover, as a method for improving the acid resistance of the adhesive layer, a known acid anhydride can be used in combination as an additive. 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. It is preferable that a non-petroleum-derived component is contained as a raw material for these acid anhydrides because the ratio of the non-petroleum-derived component can be increased. An example of such a compound is succinic anhydride.

  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. It is preferable that a non-petroleum-derived component is contained as a raw material for these oxygen-supplementing compounds because the ratio of non-petroleum-derived components can be increased.

  Moreover, in order to improve the adhesiveness with respect to various film materials immediately after application | coating, you may add tackifiers, such as a xylene resin, a terpene resin, a phenol resin, 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 an epoxy resin and an epoxy resin hardening | curing agent. It is preferable that a non-petroleum-derived component is contained as a raw material for these adhesion improving compounds because the ratio of non-petroleum-derived components can be increased.

  Moreover, an active energy ray can also be used as a method of reacting a polymerizable double bond. A known technique can be used as the active energy ray, and it 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, a known 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 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 and the curing agent. 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, Sex is necessary. At this time, methyl lactate, ethyl lactate, soybean oil, linseed oil, tung oil, coconut oil, palm oil, etc., which are organic solvents of non-petroleum-derived components, do not affect the solubility and curability of polyester polyol and isocyanate. Use within the range is preferable because the ratio of non-petroleum-derived components in the entire adhesive can be increased.

  The adhesive of the present invention can be used by being applied to a substrate film or the like. The coating method is not particularly limited and may be performed by a known method. For example, in the case of a solvent type whose viscosity can be adjusted, it is often applied by a gravure roll coating method or the like. 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 of heating from room temperature to about 120 ° C. so that the viscosity of the adhesive of the present invention is about 500 to 2500 mPa · s.

  The adhesive of the present invention can be used as an adhesive for various applications that require gas barrier properties against polymers, paper, metals, etc. as a gas barrier adhesive.

  Hereinafter, an adhesive for film lamination will be described as one of specific applications.

  The adhesive of the present invention can be used as an adhesive for film lamination. Since the laminated film is excellent in gas barrier properties, it can be used as a laminated film for gas barrier.

The film for lamination used in the present invention is not particularly limited, and a thermoplastic resin film can be appropriately selected according to a desired application. For food packaging, for example, polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched polypropylene) Polyolefin film such as film, OPP (biaxially oriented polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, and the like. These may be subjected to stretching treatment. As the stretching treatment method, it is common to perform simultaneous biaxial stretching or sequential biaxial stretching after the resin is melt-extruded by extrusion film forming method or the like to form a sheet. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used. However, when a transparent vapor-deposited film having a high gas barrier property is used on both sides of the adhesive, polymerization of the polymerizable double bond of the polyester polyol (A2) as an adhesive component may be inhibited and good barrier properties may not be exhibited. is there. Therefore, as the gas barrier property of the laminated film for gas barrier, it is preferable that the oxygen permeability of at least one laminate film is 0.1 cc / m ² · day · atm or more. At this time, it is preferable that the film is derived from a compound derived from a non-petroleum component because the ratio of the non-petroleum-derived component as the whole multilayer film can be increased. As an example of such a film, for example, a PET film in which ethylene glycol, which is a raw material of PET, is derived from a petroleum component can be exemplified.

  The adhesive of the present invention can be preferably used as an adhesive for a laminated film formed by bonding a plurality of the same or different resin films. The resin film may be appropriately selected depending on the purpose. For example, when used as a packaging material, the outermost layer is a thermoplastic resin film selected from PET, OPP, and polyamide, and the innermost layer is unstretched polypropylene. (Hereinafter abbreviated as CPP), a composite film consisting of two layers using a thermoplastic resin film selected from a low density polyethylene film (hereinafter abbreviated as LLDPE), or an outermost layer selected from, for example, PET, polyamide and OPP A three-layer composite using a thermoplastic resin film, a thermoplastic resin film that forms an intermediate layer selected from OPP, PET, and polyamide, and a thermoplastic resin film that forms an innermost layer selected from CPP and LLDPE Heat to form an outermost layer selected from a film, for example, OPP, PET, polyamide Selected from a plastic film, a thermoplastic film forming a first intermediate layer selected from PET and nylon, and a thermoplastic film forming a second intermediate layer selected from PET and polyamide, LLDPE, and CPP A composite film composed of four layers using a thermoplastic resin film forming the innermost layer can be preferably used as a food packaging material as a gas barrier film.

  Moreover, you may perform various surface treatments, such as a flame treatment and a corona discharge treatment, as needed so that the adhesive layer without defects, such as a film | membrane piece and a repellency, may be formed in the film surface.

After the adhesive of the present invention is applied to one of the thermoplastic resin films, the other thermoplastic resin film is stacked and bonded together by lamination to obtain the laminated film for gas barrier of the present invention. As the lamination method, known lamination such as dry lamination, non-solvent lamination, extrusion lamination, etc. can be used.
Specifically, in the dry lamination method, the adhesive of the present invention is applied to one of the base films by the gravure roll method, and the other base film is stacked and bonded by dry lamination (dry lamination method). The temperature of the laminate roll is preferably about room temperature to 60 ° C.

In addition, non-solvent lamination is applied to the substrate film with a roll such as a roll coater heated to room temperature to 120 ° C., and then immediately applied to the surface after the adhesive of the present invention, which has been heated to room temperature to 120 ° C. in advance, is applied. A laminate film can be obtained by laminating various film materials. The laminating pressure is preferably about 10 to 300 kg / cm ² .

  In the case of the extrusion laminating method, the organic solvent solution of the adhesive of the present invention is applied to the base film as a bonding aid (anchor coating agent) with a roll such as a gravure roll, and the solvent is dried and cured at room temperature to 140 ° C. After the reaction, a laminate film can be obtained by laminating the polymer material melted by the extruder. 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.

  Moreover, it is preferable that the laminated | multilayer film for gas barriers of this invention perform aging after preparation. If polyisocyanate is used as a curing agent, the aging condition is from room temperature to 80 ° C., for 12 to 240 hours, during which adhesive strength is generated.

  Since the adhesive of the present invention is characterized by having a high gas barrier property, the laminate film formed by the adhesive is a PVDC coat layer, a polyvinyl alcohol (PVA) coat layer, an ethylene-vinyl alcohol copolymer ( EVOH) Film layer, metaxylylene adipamide film layer, inorganic vapor deposited film layer deposited with alumina, silica, etc. .

  In the present invention, in order to provide an even 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 can be used in combination to provide a higher barrier function.

(Gas component types that can block permeation)
Gas that can be shut off by the multilayer film for gas barrier of the present invention includes oxygen, inert gas such as carbon dioxide, nitrogen and argon, alcohol components such as methanol, ethanol and propanol, phenols such as phenol and cresol, Aroma components comprising low molecular weight compounds such as soy sauce, sauce, miso, lemonene, menthol, methyl salicylate, coffee, cocoa shampoo, rinse, etc. can be exemplified.
Further, the gas barrier adhesive of the present invention can be used as an adhesive layer of a gas barrier container. The said container can be used as containers, such as sauces, such as coffee, cocoa, miso, yoghurt, cooked cooked rice, sauces for grilled meat, dressings, cheese containers, and pizza.
Furthermore, the gas barrier adhesive of the present invention can be used as an adhesive layer for a gas barrier tube. The tube can be used as a tube for kneaded mustard, kneaded wasabi, condensed milk, fresh cream, bean plate soy, ketchup, mayonnaise, mustard, butter, toothpaste, hair dye, hand cream, detergent, hair cream.

  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 is a main component of an adhesive having the structures of polyesters (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 derived from plant components, and 409.3 of glycerol derived from plant components Part and titanium tetraisopropoxide in an amount corresponding to 100 ppm with respect to the total amount of polycarboxylic acid and polyol, and gradually heated so that the upper temperature of the rectification tube does not exceed 100 ° C. Held at 0C. 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 synthesized from plant-derived components was obtained. Polyester polyol (A) Number of functional groups designed per molecule: 2 hydroxyl groups, 1 carboxy group. Moreover, the content rate of the plant-derived component at this time is 39 mass%.

(Production Example 2) Production Example of Polyester Polyol (A): OPAEG This polyester is the main agent of an adhesive having a structure of polyester (A4).

  In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., 148.1 parts of phthalic anhydride, 84.2 parts of ethylene glycol derived from plant components, and 0.03 of titanium tetraisopropoxide 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, and an amorphous polyester polyol synthesized from a plant-derived component having a number average molecular weight of 600 was obtained. This polyester polyol had a hydroxyl value of 190 mgKOH / g and an acid value of 1.0 mgKOH / g. In addition, the number of functional groups designed per molecule of this polyester polyol is: hydroxyl group: 2 and carboxy group: 0, and the content of ortho-oriented aromatic dicarboxylic acid or its anhydride with respect to all components of polycarboxylic acid is 100% by mass. Moreover, the content rate of the plant-derived component at this time is 38 mass%.

(Production Example 3) Method for Producing Amorphous Polyester Polyol OPASuAEG Composed of Phthalic Anhydride, Succinic Acid, and Ethylene Glycol This polyester is the main agent of an adhesive having the structure of polyester (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 derived from plant components, and 575. 2 parts and 0.12 part of titanium tetraisopropoxide were charged, and the inner temperature was kept 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, and a polyester polyol synthesized from an amorphous plant-derived component having a number average molecular weight of 600 was obtained. This polyester polyol had a hydroxyl value of 190 mgKOH / g and an acid value of 1.0 mgKOH / g. In addition, the number of functional groups designed per molecule of this polyester polyol is: hydroxyl group: 2 and carboxy group: 0, and the content of ortho-oriented aromatic dicarboxylic acid or its anhydride with respect to all components of polycarboxylic acid is 70% by mass. Moreover, the content rate of the plant-derived component at this time is 62 mass%.

(Production Example 4) Production Example of Polyester Polyol (A): THEI (OPAEG) 3 This polyester is a main component of an adhesive having a structure of polyester (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 as a plant-derived component, tris (2-hydroxyethyl) isocyanate Charge 668.1 parts of nurate and titanium tetraisopropoxide in an amount corresponding to 100 ppm with respect to the total amount of polycarboxylic acid and polyol, and gradually heat so that the upper temperature of the rectification tube does not exceed 100 ° C. The internal temperature was kept at 220 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and a polyester polyol synthesized from a plant-derived component 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 Obtained. Polyester polyol (A) Designed number of functional groups per molecule: hydroxyl groups: 3 and carboxy groups: 0. Moreover, the content rate of the plant-derived component at this time is 22 mass%.

(Curing agent for solvent type adhesive a)
“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). Curing agent a. The non-volatile content of the hardener a is 87.5% and NCO% is 28.1%.

(Solvent-free adhesive curing agent b)
Sumika Bayer Urethane “Desmodur N3200” (hexuremethylene diisocyanate biuret) and Mitsui Chemicals “Takenate 500” were mixed at a ratio of 33/67 (mass ratio) to obtain curing agent b. The non-volatile content of the curing agent b is 99% or more, and the NCO% is 37.4%.

(Examples 2-3 ) Solvent-type adhesive for multilayer film for gas barrier
According to the compounding ratios of Examples 2 to 3 in Table 1, polyester polyol, solvent type curing agent a, and solvent were mixed to obtain a solvent type adhesive. The adhesive was applied and laminated by the following coating method 1 to obtain a laminated film for gas barrier of the present invention.

(Comparative Example 1)
Dick Dry LX-703VL (manufactured by DIC Graphics: polyester polyol, non-volatile content / about 62%, plant component-derived raw material in polyester polyol 0%), which is a solvent-based laminate adhesive, and curing for solvent-based adhesive Agent a was mixed as shown in Table 2 to obtain a solvent-type adhesive. The adhesive was applied and laminated by the following coating method 1 to obtain a comparative film for the present invention.

(Coating and aging method 1)
Corona treatment of stretched nylon (ONY) film ("Emblem ON" manufactured by Unitika) with a thickness of 15 μm using a bar coater to apply the solvent-type adhesive to a coating amount of 5.0 g / m ² (solid content) The film was applied to the surface, and the diluted solvent was volatilized and dried with a dryer set at a temperature of 70 ° C. The adhesive surface of the stretched nylon film to which the adhesive was applied, and an unstretched polyethylene (LLPDE) film having a thickness of 60 μm (East Cello ( A composite film having a layer structure of ONY film film / adhesive layer / LLPDE film was prepared by laminating with a corona-treated surface of “TUX-HC” manufactured by Co., Ltd. Next, this composite film was aged at 40 ° C. for 3 days, and the adhesive was cured to obtain a laminated film for gas barrier of the present invention.

(Evaluation method)
(1) The laminated film for gas barrier that has undergone adhesive strength aging is cut into a width of 15 mm parallel to the coating direction, and the space between the ONY film and the LLDPE film is measured 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.

(Evaluation method)
(2) Oxygen permeability The laminated film for gas barrier after aging was used in an atmosphere of 23 ° C. and 90% RH according to JIS-K7126 (isobaric method) using an oxygen permeability measuring device OX-TRAN2 / 21MH manufactured by Mocon. Measured with Note that RH represents humidity.

(3) Nitrogen gas permeability The various laminated films for which aging was completed were cut into 10 cm × 10 cm squares. This was set in a GTR tester “M-C1” (manufactured by Toyo Seiki Co., Ltd.) which is a differential pressure method type gas permeability measuring device, and nitrogen gas permeability was measured as a representative of inert gas. The measurement temperature is 25 ° C. Further, the humidity condition corresponds to measurement at 0% according to the measurement principle of the differential pressure method.

(4) Ethanol transmission rate Various laminated films after aging were cut into 10 cm × 15 cm squares. 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, then add 2.00g of ethyl alcohol and heat seal the remaining one side Sealed with a three-way seal. This was stored for 10 days in a thermostatic bath at a temperature of 30 ° C. and a relative humidity of 30%, and the weight after 10 days was measured. From the weight loss at this time, each alcohol permeability (unit m ² / g · day) was calculated.

(5) Incense properties Various laminated films after aging were cut into 10 cm × 15 cm squares. 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 Δ, the case where the odor leaked within 14 days was indicated as ○, and the case where the odor leaked over 2 months was indicated as ◎.

Table 1 shows the composition of the adhesive and the results of the film of each Example, and Table 2 shows the results of Comparative Example 1.

As a result, the gas barrier barrier laminated films of Examples 2 to 3 are environmentally friendly materials containing 38 to 62% by mass of a non-petroleum-derived component (plant component) in polyester polyol, in addition to oxygen and nitrogen. Each gas permeability was sufficiently smaller than that of the comparative example and showed a good gas barrier function. In addition, the ethanol permeability was less than half that of the comparative example, indicating an excellent barrier function. In addition, in addition to having an aroma retaining property for soy sauce, the laminate strength was in the practical range of 8 N / 15 mm .

On the other hand, in the laminated film of Comparative Example 1, in addition to being a non-environmentally compatible material that does not contain non-petroleum components in the polyester polyol, the oxygen transmission rate is 69 cc / day · m ² · atm and oxygen alone The transmittance was not greatly changed to 73 cc / day · m ² · atm, and substantially no oxygen barrier ability derived from the adhesive layer was exhibited. The same applies to nitrogen and ethanol, and the gas barrier ability derived from the adhesive layer was not exhibited. In addition, it did not show an incense function for soy sauce.

  The multilayer film, container, and tube of the present invention can contribute to the reduction of petroleum resources and the reduction of carbon dioxide emissions by using an adhesive layer containing non-petroleum-derived components, particularly plant raw material-derived components. It is an environmentally friendly material that can reduce the energy required for manufacturing by adding functions. In addition, since the laminated adhesive layer has various gas barrier properties, in addition to packaging materials for various foods and beverages, luxury products such as foods and teas having various fragrance components, shampoos, rinses, detergents, softeners, soaps, etc. Suitable for flexible packaging materials in the sanitary field, including pet food, insect repellents, fragrances, hair dyes, perfumes, pesticides, various organic solvents, etc. Can be used.

Claims (18)

In a gas barrier adhesive comprising a polyol component, a polyester polyol (A) having two or more hydroxyl groups synthesized from a polycarboxylic acid component, and a polyisocyanate (B) having two or more isocyanate groups ,
A part of the polyol component is a non-petroleum-derived component short-chain polyol component (a1), or a part of the polycarboxylic acid component is a non-petroleum-derived component polycarboxylic acid component (a2). A gas barrier adhesive,
Polyester polyol (A) is a polycarboxylic acid component containing at least one ortho-oriented aromatic dicarboxylic acid or anhydride thereof, ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, And a polyester polyol (A4) obtained by polycondensation of a polyol component containing at least one selected from the group consisting of cyclohexanedimethanol. Ortho-oriented aromatic dicarboxylic 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-dicarboxylic acid The gas barrier adhesive according to claim 1, which is at least one polycarboxylic acid selected from the group consisting of 2,3-anthracene dicarboxylic acid or an anhydride thereof, or an anhydride thereof, or an anhydride thereof. The gas barrier adhesive according to claim 1 or 2, wherein the usage rate of the ortho-oriented aromatic dicarboxylic acid or its anhydride is 70 to 100% by mass relative to all the components of the polycarboxylic acid. The gas barrier adhesive according to any one of claims 1 to 3, wherein the content of the non-petroleum-derived component is 20 to 80% by mass with respect to 100% by mass of the polyester polyol (A). The gas barrier adhesive according to any one of claims 1 to 3, wherein the polyisocyanate (B) contains a polyisocyanate having an aromatic ring. 6. The gas barrier adhesive according to claim 5, wherein the polyisocyanate having an aromatic ring is metaxylene diisocyanate or a reaction product of metaxylene diisocyanate and an alcohol having two or more hydroxyl groups. 6. The gas barrier adhesive according to claim 5, wherein the polyisocyanate having an aromatic ring is toluene diisocyanate or a reaction product of toluene diisocyanate and an alcohol having two or more hydroxyl groups. The gas barrier adhesive according to any one of claims 1 to 7, wherein the gas barrier adhesive further contains a crystalline polyester. The gas barrier adhesive according to any one of claims 1 to 8, wherein the gas barrier adhesive further comprises a plate-like inorganic compound (C) that is nonionic between layers or non-swellable with respect to water. Agent. When the coating amount of the cured coating film obtained from the polyester polyol (A) and the polyisocyanate (B) is about 5 g / m ² , the oxygen permeability of the cured coating film at 23 ° C. and 90% humidity is 50 cc / m ^2. The gas barrier adhesive according to any one of claims 1 to 9, which is not more than day · atm. When the total mass of the polyester polyol (A), polyisocyanate (B), and plate-like inorganic compound (C) is 100% by mass, the content of the plate-like inorganic compound (C) is 5 to 50% by mass. Item 11. The gas barrier adhesive according to Item 9 or 10. The gas barrier adhesive according to any one of claims 10 to 11, wherein the plate-like inorganic compound (C) contains particles having a particle size of 0.1 µm or more. The gas barrier adhesive according to any one of claims 1 to 12, which is obtained by dissolving the polyester polyol (A) in a ketone solvent, an ester solvent, or a mixed solvent containing a ketone solvent or an ester solvent. The gas barrier adhesive according to any one of claims 1 to 12, which is a solventless type. A gas barrier multilayer film using the gas barrier adhesive according to claim 1 as an adhesive layer. The gas barrier multilayer film according to claim 15, further comprising at least a base film layer or a sealant layer in addition to the gas barrier adhesive layer. A gas barrier container using the gas barrier adhesive according to claim 1 as an adhesive layer. A gas barrier tube using the gas barrier adhesive according to claim 1 as an adhesive layer.