JP6002966B2 - Phosphate-modified compound-containing resin composition for adhesive and adhesive - Google Patents

Description

  The present invention relates to a resin composition that can provide a film having excellent laminate strength and oxygen barrier properties, and an adhesive obtained by curing the resin composition.

  As a food packaging material, a material obtained by laminating various plastic films, metals, glass-deposited films, metal foils and the like into a composite film has been used. As a method of laminating these various plastic films, metals, glass-deposited films, metal foils, etc., after applying an adhesive on one material surface, evaporating and removing the solvent, and laminating while heating and crimping the other material There is a technology called dry lamination. This technology is widely used in the manufacture of food packaging materials that require high performance because any film can be bonded together freely and a composite film having performance according to the purpose can be obtained. Yes.

  The adhesive used here is (1) adhesiveness to plastic film, aluminum vapor deposition film, alumina vapor deposition film, silica vapor deposition film, and aluminum foil, (2) initial adhesiveness to prevent tunneling, (3) adhesion High performance is required for the curing rate of the agent, (4) pot life, (5) content resistance, (6) boil, retort resistance and the like. More recently, importance has been placed on (7) low odor, in which various impurities derived from the adhesive migrate to the contents and do not adversely affect the aroma and taste.

  The adhesive used here is mainly a two-component reactive polyurethane adhesive. The main component of this adhesive is composed of a polyol component having a hydroxyl group at the polymer terminal and a polyisocyanate component having an isocyanate group, and a urethane bond is formed by the reaction between the hydroxyl group and the isocyanate group to be cured. Specifically, polyether polyurethane polyol, polyester polyol having a polyester bond concentration derived from aliphatic acid of 2 to 4 mg equivalent / g based on adhesive solid content, polyester polyurethane polyol, or a mixture of two or more of these. And a combination of polyisocyanate compounds are known (Patent Document 1).

  Furthermore, in recent years, attempts have been made to deal with the environment, and each adhesive manufacturer has been diligently developing high solid type and non-solvene and type adhesives that use a small amount of organic solvent. It has been a challenge to obtain a good balance of heat resistance, content resistance, printability and the like.

  In addition, the packaging materials used for packaging foods and beverages protect the contents from various distribution, storage such as refrigeration and heat sterilization, etc., so that the strength, resistance to cracking, retort resistance, heat resistance In addition to these functions, a wide variety of functions are required such as excellent transparency so that the contents can be confirmed. On the other hand, when the bag is sealed by heat sealing, an unstretched polyolefin film having excellent heat processability is essential, but the unstretched polyolefin film has many functions that are insufficient as a packaging material. In particular, high barrier properties are required for the purpose of maintaining the quality of the contents. Such a barrier packaging material is usually used as a composite flexible film in which different polymer materials are laminated.

  When imparting a barrier function to a multilayer film, unstretched polyolefin films used for the inner layer (sealant side) have poor oxygen barrier properties, and it is 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 the case of providing a barrier function to these outer layer side films by coating, vinylidene chloride having a high retort resistance and oxygen barrier property has been frequently used as a barrier coating material. However, problems such as generation of dioxin during firing of waste There is. In addition, when a polyvinyl alcohol resin or ethylene-polyvinyl alcohol copolymer is used as a barrier coating material, the oxygen barrier property is high at low humidity, but the oxygen barrier property is significantly reduced at high humidity, after boil treatment or after retort treatment. There was a problem to do. Further, a film provided with a vapor deposition layer of a metal oxide such as silica or alumina as an oxygen barrier layer is expensive and has a problem that the flexibility is poor and the barrier performance varies due to cracks and pinholes.

  As an oxygen barrier material, for example, in Patent Document 2, a thermosetting oxygen barrier polyurethane resin containing a resin cured product obtained by reacting an active hydrogen-containing compound (A) and an organic polyisocyanate compound (B), 20% by mass or more of a skeleton structure derived from meta-xylene diisocyanate is contained in the cured resin, and the proportion of trifunctional or higher functional compounds in (A) and (B) is (A) and (B The oxygen barrier composite film using the thermosetting oxygen barrier polyurethane resin, characterized in that it is 7% by mass or more with respect to the total amount of).

  However, since the composition must use a highly polar solvent, the workability is poor. For example, when a highly soluble solvent such as acetone is used, there is a problem that the viscosity of the preparation is likely to increase due to the reaction between water and isocyanate because the boiling point is low and the water in the outside air is easily taken up.

  Further, in Patent Document 3, the thin film layer surface of a transparent covering film in which a thin film layer of silicon oxide or aluminum oxide is formed on at least one surface of a polymer film substrate, and a heat-sealable resin film are inorganic. A barrier laminate obtained by adhering one or more particles selected from materials of silicon oxide or aluminum oxide by a dry laminate method through a barrier adhesive containing a polyester polyol and an isocyanate compound Have been described. However, in this laminate, the barrier property is expressed in combination with the barrier film, and the inorganic compound contained in the adhesive is a nano-order spherical or amorphous inorganic compound, There is a problem that the barrier property of the agent itself is not high.

  Further, Patent Document 4 discloses that a polyester outer layer, a polypropylene inner layer, and two adjacent layers of the laminate are bonded together, so that it is applied to at least one layer of the adjacent layer set of the laminate. A first solvent-free aliphatic polyurethane laminate adhesive comprising a peeled clay platelet that forms a functional barrier to the passage of gas through the at least one sheet. However, there is no description about the expression of barrier properties, and the barrier performance is unknown.

  Moreover, in patent document 5, it is the adhesive composition for plastic film laminated steel plates which added 0.1-10 weight part of phosphoric acid modified compounds with respect to 100 weight part of adhesive solid content, Comprising: Said adhesive solid content is ( a) Aliphatic and / or alicyclic blocked isocyanate compound solids as a curing agent on 100 parts by weight of polyester resin solids having a number average molecular weight of 8000 to 25000, a glass transition temperature of 0 ° C. to 40 ° C., and a hydroxyl value of 3 to 30 Blended at a ratio of 5 to 30 parts by weight, or (b) blended at a ratio of 10 to 40 parts by weight of phenol resin solids as a curing agent with 100 parts by weight of epoxy resin solids having a number average molecular weight of 3000 or more There is an adhesive composition for a plastic film laminated steel plate characterized by being, and adhesion is improved by using a phosphoric acid compound. Bets but is described, there is no description about the barrier property than it is steel sheet applications.

Patent Document 6 discloses a polyurethane prepolymer having an isocyanate group at some or all of the ends obtained by the reaction of a polyol and a diisocyanate and an alkanolamine having one primary or secondary amino group. The polyfunctional polyurethaneurea polyol resin composition having two or more hydroxyl groups at the terminal of the polymer molecule, and the polyurethane prepolymer in an amount of 0.001 in terms of the weight of phosphorus atoms relative to the solid content of the polyfunctional polyurethaneurea polyol resin composition. There is a polyfunctional polyurethaneurea polyol resin composition containing phosphoric acids or derivatives thereof in the range of 01 to 0.3% by weight, and there is a description that the initial adhesion to inorganic substances is improved, but the adhesive has barrier properties. And barrier properties such as improved barrier properties due to adhesives. It is not described that.

Patent Document 7 discloses a polyester resin containing two or more hydroxyl groups at the molecular terminals and an anhydrous aromatic polyvalent carboxylic acid in an amount that consumes 50 to 90% of the number of hydroxyl groups at the molecular terminals of the polyester resin. Polyester resin (1) containing 10 to 90% by weight of a polyester resin having a carboxyl group at the molecular end obtained by reaction, a mixture comprising 90 to 10% by weight of polyester polyurethane polyol, orthophosphoric acid or its ester compound and organic isocyanate Although there is an adhesive composition containing a compound, there is no description regarding the barrier property such that the adhesive has a barrier property or the barrier property is improved by the adhesive.

JP 2000-290631 A Japanese Patent No. 4054972 Japanese Patent No. 3829526 Japanese Patent No. 3906005 Japanese Patent No. 4006609 JP 2000-7748 A Japanese Patent No. 2848047

  In view of the above background art, the problem to be solved by the present invention is to provide a resin composition for an adhesive mainly composed of a resin having excellent laminate strength and oxygen barrier properties for an inorganic base material, and an adhesive. is there.

  Moreover, it is providing the multilayer film which has a layer formed with the adhesive agent of this invention.

The inventors have
Resin (A) having two or more hydroxyl groups in one molecule as a functional group, isocyanate compound (B) having two or more isocyanate groups in one molecule as a functional group, and general formula (1) or general formula (2) A resin composition for an adhesive containing a phosphoric acid-modified compound (C) represented by:

(Wherein, R ₁ to R ₃ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, (meth) acryloyl group, a phenyl group which may have a substituent, the carbon number having a (meth) acryloyloxy group A group selected from 1 to 4 alkyl groups, at least one of which is a hydrogen atom, and n represents an integer of 1 to 4.)

(In the formula, R _{4 to} R ₅ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth) acryloyl group, an optionally substituted phenyl group, or a carbon number having a (meth) acryloyloxy group. A group selected from 1 to 4 alkyl groups, n is an integer of 1 to 4, x is an integer of 0 to 30, and y is an integer of 0 to 30, but both x and y are 0. except.)
The above problem was solved by providing

  According to the present invention, it has a resin composition for an adhesive mainly composed of a resin excellent in laminate strength and oxygen barrier property, an adhesive obtained by applying the resin composition to a film, and a layer formed by the adhesive. A multilayer film can be provided.

[Resin having two or more hydroxyl groups in one molecule as a functional group (A)]
The resin (A) used in the present invention is a resin having a hydroxyl group in one molecule as a functional group, and the main skeleton contains polyester, polyester polyurethane, polyether, or polyether polyurethane. There is no particular limitation as long as the adhesive strength or oxygen barrier property of the present invention can be exhibited.

  A known technique can be used for the polyester used in the present invention, and for example, it can be obtained by a reaction between a polyhydric alcohol and a polycarboxylic acid. Polyester polyurethane can be obtained by a known technique, for example, by reaction of polyester polyol and diisocyanate. For the polyether, known techniques can be used. For example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, and a low molecular weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as an initiator. Obtained by polymerization. The polyether polyurethane can be obtained by a known technique, for example, by reaction of polyether with diisocyanate.

(Polyvalent carboxylic acid)
The resin (A) of the present invention is a polyvalent carboxylic acid component, specifically, an aliphatic polyvalent carboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc. Examples of the polyvalent carboxylic acid include 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and examples of the aromatic polyvalent carboxylic acid include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, and 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 B) Polybasic acids such as benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more. These acid anhydrides can also be used. Among them, succinic acid, 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 in order to obtain barrier properties.

(Polyhydric alcohol component)
Specifically, the polyhydric alcohol used in the present invention includes, as the aliphatic diol, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexane dimethanol, 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 polyphenol , Hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide De extension product, there can be mentioned hydrogenated alicyclic. In particular, the smaller the number of carbon atoms between oxygen atoms, the less likely the molecular chain to become excessively flexible and less oxygen permeation. Therefore, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane Methanol is preferred, and ethylene glycol is more preferred. The polycondensation reaction between the polyvalent carboxylic acid and the polyhydric alcohol can be performed by a known and commonly used method.

More specifically, as the resin (A) having two or more hydroxyl groups of the present invention,
A polyester polyol (A1) obtained by reacting a carboxylic acid anhydride or a polycarboxylic acid with a polyester polyol having three or more hydroxyl groups,
A polyester polyol (A2) having a polymerizable carbon-carbon double bond,
A polyester polyol (A3) having a glycerol skeleton,
A polyester polyol (A4) obtained by polycondensation of an ortho-oriented polyvalent carboxylic acid component and a polyhydric alcohol 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 has at least one carboxy group and two obtained by reacting a polyester polyol (I) having three or more hydroxyl groups with a carboxylic acid anhydride or a polyvalent carboxylic acid. It has the above hydroxyl groups. The polyester polyol (I) having three or more hydroxyl groups can be obtained by making a part of the polyvalent carboxylic acid or polyhydric alcohol trivalent or higher.

  As the polyhydric alcohol component and polyhydric alcohol 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, propylene glycol, butylene glycol, neopentyl Reacting a carboxylic acid anhydride or a polyvalent carboxylic acid with a polyester polyol (I) having three or more hydroxyl groups composed of a polyhydric alcohol component containing at least one selected from the group consisting of glycol and cyclohexanedimethanol And having at least one carboxy group and two or more hydroxyl groups.

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

(Polyvalent carboxylic acid and other components)
When synthesizing a polyester polyol (I) having three or more hydroxyl groups, when a branched structure is introduced by a polyvalent carboxylic acid component, it is necessary to have at least 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 polyvalent carboxylic acids include three. Divalent carboxylic acids are preferred.

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

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

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

  As other components, in the present invention, the above-mentioned polyhydric alcohol component may be copolymerized with other polyvalent carboxylic acid components as long as the effects of the present invention are not impaired. Specifically, as the aliphatic 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 of the polyester polyol (I) of the present invention with a carboxylic acid anhydride or a polyvalent carboxylic acid is carried out as follows.

  That is, the polyester polyol (I) can be obtained by reacting a polyvalent carboxylic acid or an acid anhydride thereof with a hydroxyl group of the polyester polyol (I). The ratio between the polyester polyol (I) and the polyvalent carboxylic acid is that at least two hydroxyl groups of the resin (A) after the reaction are required, so the polyvalent carboxylic acid is 1/3 or less of the hydroxyl groups of the polyester polyol (I). It is preferable to make it react with. Although there is no restriction | limiting in the carboxylic acid anhydride or polyhydric carboxylic acid used here, when gelatinization at the time of reaction with polyhydric carboxylic acid and polyester polyol (I) is considered, it is a bivalent or trivalent carboxylic acid anhydride. Is preferably used. 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 oxygen 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 resin (A) and the isocyanate compound (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 polyvalent carboxylic acid and a polyhydric alcohol, and has a polymerizable carbon-carbon double bond as a component of the polyvalent carboxylic acid and polyhydric alcohol. Can be used to introduce a polysynthetic carbon-carbon double bond into the molecule of the polyester polyol (A2).

(Polyvalent carboxylic acid)
The polyester polyol (A2) of the present invention is a polyvalent carboxylic acid component, specifically, an aliphatic polyvalent carboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc. Examples of the aromatic polycarboxylic acid include 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and examples of the aromatic polyvalent carboxylic acid include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimethyl Merit 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 Acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- Polybasic acids such as (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more. These acid anhydrides can also be used. Among them, succinic acid, 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 in order to obtain barrier properties.

(Polyvalent carboxylic acid having a polymerizable carbon-carbon double bond)
Maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and acid anhydrides thereof as polyvalent carboxylic acids having a polymerizable carbon-carbon double bond in the polyvalent carboxylic acid, 3-methyl- Examples include 4-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.

(Polyhydric alcohol component)
Specifically, the polyhydric alcohol used in the present invention includes, as the aliphatic diol, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexane dimethanol, 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 polyphenol , Hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide De extension product, there can be mentioned hydrogenated alicyclic. In particular, the smaller the number of carbon atoms between oxygen atoms, the less likely the molecular chain to become excessively flexible and less oxygen permeation. Therefore, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane Methanol is preferable, and ethylene glucol is more preferable.

(Polyhydric alcohol with polymerizable carbon-carbon double bond)
Examples of the polyhydric alcohol having a polymerizable carbon-carbon double bond in the polyhydric alcohol include 2-butene-1,4-diol.
Moreover, in the said polyester polyol (A2), although the polymerizable double bond was introduce | transduced into the polyester polyol (A2) by using the polyhydric carboxylic acid and polyhydric alcohol which have a polymerizable carbon-carbon double bond, It may be a reaction between a polyester polyol having a carboxylic acid having a polymerizable double bond, or a carboxylic acid anhydride. As the carboxylic acid in this case, a carboxylic acid having a polymerizable double bond such as maleic acid, maleic anhydride or fumaric acid, an unsaturated fatty acid such as oleic acid or sorbic acid, or the like can be used. The polyester polyol in this case 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 by crosslinking with an isocyanate compound. When the polyester polyol has 1 or 2 hydroxyl groups, the polyester polyol (A2) obtained by reacting with a carboxylic acid having a polysynthetic double bond has 0 or 1 hydroxyl group and reacts with the isocyanate compound (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 decreases, and it becomes difficult to obtain a barrier property. 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 polyvalent carboxylic acid and polyhydric alcohol.

  Moreover, as polyester polyol (A2) of this invention, a drying oil or a semi-drying oil can be mentioned. Examples of the drying oil or semi-drying oil include publicly known and commonly used drying oils having a carbon-carbon double bond, and semi-drying oils.

[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 (3).

(In Formula (3), R _{1 to} R ₃ are each independently a hydrogen atom or General Formula (4).

(In the formula (4), 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 (4). )

In the general formula (3), at least one of R ₁ , R ₂ and R ₃ needs to be 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.

  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 (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 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 (3) is essential for glycerol, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted in the ortho position, or an anhydride thereof, and a polyhydric alcohol component. Obtained by reacting as a component.

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

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

The content of the glycerol backbone in this application, with respect to the oxygen barrier adhesive organic resin composition total solids of the mass of the present application, except for R ₁ to R ₃ in the general formula (3) residues ( How much C ₃ H ₅ O ₃ = 89.07) is included 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 oxygen barrier adhesives in order to exhibit high barrier properties.

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

  On the other hand, the aromatic polyvalent carboxylic acid in which the acyl group, which is a raw material of the polyester component, is substituted in the ortho position, or its anhydride has an asymmetric structure. 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.

(Polyhydric alcohol)
In the polyester polyol (A3) used in the present invention, a polyhydric alcohol component other than an alkylene diol having 2 to 6 carbon atoms may be copolymerized as a polyhydric alcohol as long as the effects of the present invention are not impaired. Specifically, aliphatic polyhydric alcohols such as glycerol, erythritol, pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, tripropylene glycol, Cycloaliphatic polyhydric alcohols such as cyclohexanedimethanol and tricyclodecanedimethanol, aromatic polyhydric phenols such as hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, or the like Examples thereof include ethylene oxide elongated products and hydrogenated alicyclic groups.

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

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

[Polyester polyol (A4) obtained by polycondensation of ortho-oriented polyvalent carboxylic acid component and polyhydric alcohol component]
The polyester polyol (A4) used in the present invention comprises a polyvalent carboxylic acid component containing at least one orthophthalic acid and its anhydride, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. It consists of a polyhydric alcohol component containing at least one selected from the group. In particular, a polyester polyol having a content of 70 to 100% by mass of the orthophthalic acid and its anhydride with respect to all the components of the polyvalent carboxylic acid is preferable.

(Polyvalent carboxylic acid and other components)
The polyester polyol (A4) of the present invention essentially comprises the above-mentioned orthophthalic acid and its anhydride as a polyvalent carboxylic acid component. However, other polyvalent carboxylic acid components may be copolymerized within a range that does not impair the effects of the present invention. May be. Specifically, as the aliphatic polyvalent carboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc., as the unsaturated bond-containing polyvalent carboxylic acid, maleic anhydride, maleic acid, Fumaric acid etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc. as alicyclic polyvalent carboxylic acid, terephthalic acid, isophthalic acid, pyromellitic as aromatic polyvalent carboxylic acid Acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p '-Dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2 Polyhydroxy acids such as -hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferable.

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

[Polyester polyol having an isocyanuric ring (A5)]
The resin (A) of the present invention further preferably contains a polyester polyol (A5) having an isocyanuric ring represented by the following general formula (5).

(In General Formula (5), R _{1 to} R ₃ are each independently — (CH ₂ ) n 1 -OH (where n1 represents an integer of 2 to 4), or General Formula (6)

(In General Formula (6), 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 (6))

In the general formula (5), the alkylene group represented by — (CH ₂ ) n 1 — may be linear or branched. n1 is preferably 2 or 3, and most preferably 2.

In the general formula (6), n2 represents an integer of 2 to 4, and n3 represents an integer of 1 to 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 (6), Y represents an 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.

In the general formula (5), at least one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (6). Among them, it is preferable that all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (6).

_Further, R 1, any one of _{R 2} and _{R 3} is a group represented by the general formula (6) _compound, R 1, _{R 2,} and any two of the general formula _{R 3} (6) Any two or more compounds of the compound represented by the general formula (6) and the compound in which all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (6) are mixed. Also good.

  The polyester polyol (A5) having an isocyanuric ring represented by the general formula (5) includes a triol having an isocyanuric ring, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted in the ortho position, or an anhydride thereof, It is obtained by reacting a monohydric alcohol component as an essential component.

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

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

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

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

  Among them, 1,3,5-tris (2-hydroxyethyl) isocyanuric acid or 1,3,5-tris (2-hydroxypropyl) isocyanuric acid is used as the triol compound having an isocyanuric ring, and the carboxylic acid is in the ortho position. The polyester polyol compound having an isocyanuric ring using orthophthalic anhydride as the polyhydric aromatic polycarboxylic acid or anhydride and ethylene glycol as the polyhydric alcohol is particularly excellent in oxygen barrier properties and adhesiveness. preferable.

  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 the oxygen barrier property and the dry laminate adhesiveness is estimated as follows.

  The isocyanuric ring is highly polar and does not form hydrogen bonds. In general, as a technique for improving adhesiveness, a method in which a highly polar functional group such as a hydroxyl group, a urethane bond, a ureido bond or an amide bond is blended is known, but a resin having these bonds forms intermolecular hydrogen bonds. 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 crosslinking density is obtained, it is presumed that the oxygen barrier property and the 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 (5) residues _{(C 3 N 3 O 3 =} 126 .05) is calculated using equation (c).

Ｐ：イソシアヌル環を有するポリエステルポリオール（Ａ５）を表す。

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

(Method for calculating mass of resin composition organic total solid content of oxygen barrier adhesive)
The mass excluding the mass of the diluent solvent, the mass of the volatile component contained in the curing agent, and the inorganic component from the mass part of the resin composition for the oxygen barrier adhesive is the mass of the total solid content of the organic resin for the oxygen 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, after the triol having an isocyanuric ring used as a raw material, an aromatic polycarboxylic acid in which the carboxylic acid is substituted in the ortho position, or an anhydride thereof, and a polyhydric alcohol component are collectively charged Then, the temperature is increased while stirring and mixing to cause a dehydration condensation reaction. 1 mgKOH / g or less by the acid value measurement method described in JIS-K0070, and the hydroxyl value ZmgKOH / g obtained by the hydroxyl value measurement method described in JIS-K0070 is the 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.

  As the polyether polyol, active hydrogen such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. Addition polymerization of one or more monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, cyclohexylene, etc. by a conventional method using one or more compounds having two atoms as initiators If necessary, an alkyl alcohol having 1 to 4 carbon atoms as an initiator, ethylene oxide as an essential component, further propylene oxide, butylene oxide, styrene oxide, Pikuroruhidorin, may be used in combination of at least one and block or polyoxyalkylene monoalkyl ether obtained by random copolymerization of monomers such as cyclohexylene. Furthermore, polytetramethylene glycol is also exemplified as the polyether polyol. Here, polytetramethylene glycol is a polyol obtained by ring-opening polymerization of tetrahydrafuran. In the synthesis of polytetramethylene glycol, an analogous compound in which a part of tetrahydrofuran is substituted with ethylene oxide or propylene oxide can be used, or it can be used in combination with polytetramethylene glycol.

  The number average molecular weight of these resins (A) is particularly preferably from 450 to 5,000 because a crosslinking density with an excellent balance between adhesive ability and oxygen barrier ability can be obtained. More preferably, the number average molecular weight is 500 to 3000. As the curing agent, the polyisocyanate described below is most preferable, can give an appropriate reaction time, and is particularly excellent in adhesive strength and oxygen barrier ability. 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 resin (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 oxygen barrier properties may not be obtained due to intense molecular motion of the polyester polyol near room temperature.

  Furthermore, you may use the polyester polyurethane polyol and polyether polyurethane polyol which made the number average molecular weight 1000-15000 by urethane expansion | extension by reaction with a diisocyanate compound (A) as an adhesive agent. Since the polyol has a certain molecular weight component and a urethane bond, the polyol has an excellent oxygen barrier property, an excellent initial cohesive force, and is further excellent as an adhesive used during lamination. Moreover, the terminal can be made into an isocyanate group by making the ratio of the hydroxyl group and the isocyanato group in the resin (A) and the diisocyanate compound excessive in isocyanate, and this may be used as a curing agent.

(Adhesive hardener)
The curing agent used in the present invention is not particularly limited as long as it can react with the hydroxyl group of the resin (A), and known curing agents such as diisocyanate compounds, polyisocyanate compounds, and epoxy compounds can be used. Especially, it is preferable to use a polyisocyanate compound from a viewpoint of adhesiveness or retort resistance.

  Polyisocyanate compounds include aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanate compounds, 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.

  Of these, xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate are preferable, and metaxylylene diisocyanate and metahydrogenated xylylene diisocyanate are most preferable in order to obtain good oxygen barrier properties.

  The glass transition temperature of the cured coating film of the resin (A) and the isocyanate compound (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 the temperature is lower than −30 ° C., there is a fear that sufficient oxygen barrier properties may not be obtained due to intense molecular motion of the cured coating film at around room temperature, and there is a possibility that adhesive strength may be reduced due to insufficient cohesive force.

  Moreover, when carboxylic acid remains at the terminal of the resin (A) used in the present invention, an epoxy compound can be used as a 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.

  When using an epoxy compound as a curing agent, a general-purpose known epoxy curing accelerator may be appropriately added for the purpose of accelerating curing within the range in which the oxygen barrier property which is the object of the present invention is not impaired.

  Among them, it is preferable that the curing agent is a polyisocyanate compound having an aromatic ring. If the polyisocyanate compound includes the metaxylene skeleton, oxygen is not only generated by π-π stacking of aromatic rings but also hydrogen bonds of urethane groups. It is preferable because the barrier property can be improved.

  Examples of the polyisocyanate compound containing the meta-xylene skeleton include a trimer of xylylene diisocyanate, a burette synthesized by reaction with an amine, and an adduct obtained by reacting with an alcohol. The adduct body is more preferable because the solubility of the polyisocyanate compound in the organic solvent used for the dry laminate adhesive is easily obtained as compared with the body. 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 resin (A) and the curing agent, the ratio of the resin (A) and the curing agent is such that the hydroxyl group of the resin (A) and the reaction component of the curing agent are 1 / 0.5 to 1/10 (equivalent ratio). It is preferable to mix | blend so that it may become, 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.

  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 resin (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 the present invention may contain various additives as long as the adhesive strength and oxygen barrier properties are not impaired. Examples of additives include inorganic fillers such as silica, alumina, aluminum flakes, and glass flakes, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, and antiblocking agents. Examples include agents, colorants, fillers, crystal nucleating agents and the like.

(Phosphate-modified compound)
The present invention is characterized by containing the phosphoric acid-modified compound (C) represented by the general formula (1) or (2).

(Wherein, R ₁ to R ₃ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, (meth) acryloyl group, a phenyl group which may have a substituent, the carbon number having a (meth) acryloyloxy group A group selected from 1 to 4 alkyl groups, at least one of which is a hydrogen atom, and n represents an integer of 1 to 4.)

(In the formula, R _{4 to} R ₅ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth) acryloyl group, an optionally substituted phenyl group, or a carbon number having a (meth) acryloyloxy group. A group selected from 1 to 4 alkyl groups, n is an integer of 1 to 4, x is an integer of 0 to 30, and y is an integer of 0 to 30, but both x and y are 0. except.)

  The phosphoric acid-modified compound (C) has an effect of improving the laminate strength with respect to the inorganic base material of the present invention, and a known and conventional one can be used.

  More specifically, phosphoric acid, pyrophosphoric acid, triphosphoric acid, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxy Examples thereof include ethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, polyoxyethylene alkyl ether phosphate, and the like.

  As content of a phosphoric acid modification compound (C), 0.005-10 mass% is preferable in the resin composition for adhesive agents of this invention. More preferably, it is 0.01 to 1%. When it is less than 0.005%, good adhesion cannot be obtained. When it is more than 10%, the barrier property may be deteriorated.

(Plate-like inorganic compound)
The resin composition for adhesives of the present invention is characterized by containing a plate-like inorganic compound.
The plate-like inorganic compound used in the present invention has an effect of improving the laminate strength and oxygen barrier property of an adhesive obtained by curing a resin composition for an adhesive.

  The plate-like inorganic compound used in the present invention has a feature that the laminate strength and the barrier property are improved by the plate-like 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 (pyrophyllite, talc, kerolai, etc.), mica or mica clay mineral (mica, muscovite, phlogopite, etc.), margarite, tetrasilic mica, teniolite, etc. (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, so that the detour path of oxygen molecules does not become long, and there are problems that it is difficult to improve the oxygen barrier ability and adhesion force. . The side with a large average particle diameter is not particularly limited. When a large plate-like inorganic compound is contained by the coating 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 maze effect of oxygen. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.

In the present invention, when the total mass of the resin (A), the polyisocyanate compound (B), and the plate-like inorganic compound (C) is 100 parts by mass, the content of the plate-like inorganic compound is improved if the oxygen barrier ability is improved. Although there is no limitation in particular, it is preferable that it is 5-50 mass parts. In the case of 5 parts by mass or less, the barrier ability is difficult to improve, and in the case of 50 parts by mass or more, there is a possibility that the laminating operation becomes difficult due to a decrease in the adhesiveness of the coating surface, or the adhesive force may be insufficient. It is.
The content of the inorganic compound (PWC of the blend) can be obtained from the following formula (e).

  As a method for dispersing the inorganic compound described in the present invention in the resin (A) or the oxygen 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.

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

  Moreover, in order to improve the adhesiveness with respect to 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 resin (A) and the total amount of a hardening | curing agent.

  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, a light (polymerization) initiator that generates radicals and the like by irradiation with ultraviolet rays is about 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A). It is preferable to add.

  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. Solvents that can be used include, for example, 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.

  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 oxygen barrier adhesive for various applications that require oxygen barrier properties against polymers, paper, metals, and the like.

  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 oxygen barrier properties, it can be used as an oxygen barrier laminated film.

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 example, for food packaging, 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 film, OPP: Polyolefin film such as biaxially stretched 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 oxygen barrier property is used on both sides of an adhesive using polyester polyol (A2) as an adhesive component, polymerization of a polymerizable double bond of polyester polyol (A2) as an adhesive component May be inhibited and good barrier properties may not be exhibited. Therefore, when the polyester polyol (A2) is used as the adhesive component, the oxygen barrier property of the oxygen barrier laminate film is that the oxygen permeability of at least one laminate film is 0.1 cc / m ² · day · atm or more. It is preferable.

  A commercially available aluminum vapor deposition film can be used as the aluminum vapor deposition film. There is no limitation as a base film for vapor deposition, PET film, polyamide film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene) Polyolefin film such as film) can be used. As a deposition method, a known technique can be used, and a method of forming a thin film of aluminum by melting and evaporating aluminum under a high vacuum and attaching the aluminum to a film is generally used.

  Moreover, the vapor deposition film of metals other than aluminum can also be used. The metal to be deposited is zinc, gold, silver, copper, nickel, chromium, titanium, or the like, or the aluminum, zinc, gold, silver, copper, nickel, chromium, titanium, silicon, magnesium, titanium, tin Alternatively, zinc oxide can be used.

  A commercially available aluminum foil can be used as the aluminum foil. As a method for producing aluminum foil, a known technique can be used, and a method of performing annealing in a high-temperature electric furnace or the like in order to remove the rolling oil by rolling the aluminum foil ground with a rolling mill to adjust the thickness. It is common.

  Metal foils other than aluminum foil can also be used. As the metal foil other than the aluminum foil, a metal foil such as tin, iron, nickel, steel, lead or zinc and a metal foil of an alloy of these metals can be used.

As a transparent vapor deposition film used by this invention, the two-component vapor deposition film of an alumina vapor deposition film, a silica vapor deposition film, and a silica alumina can be illustrated. There is no limitation as a base film for vapor deposition, PET film, polyamide film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene) Polyolefin film such as film) can be used. As a deposition method, a known technique can be used. For example, in the case of an alumina vapor-deposited film, aluminum is melted and evaporated under a high vacuum, and aluminum is oxidized in the presence of oxygen to adhere to the film to form an aluminum thin film. The method of forming is common. Further, a protective coating layer may or may not be provided on the transparent vapor deposition film.

  Moreover, the vapor deposition film of the metal oxide containing metals other than aluminum and silicon can also be used. Zinc, copper, nickel, chromium, titanium, magnesium, calcium, etc. can be used as the metal to be deposited.

  The adhesive of the present invention can be preferably used as an adhesive for laminated films 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 an oxygen 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 applying the adhesive of the present invention to one of the thermoplastic resin films, the other thermoplastic resin film is overlaid and bonded by lamination to obtain the oxygen barrier laminate film 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.

  The oxygen barrier laminate film of the present invention is preferably subjected to aging after production. 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 oxygen 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) A very high level of gas barrier properties is achieved without using commonly used gas barrier materials such as film layers, metaxylylene adipamide film layers, and inorganic vapor deposited film layers deposited with alumina, silica, etc. To do.

  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 may be used in combination.

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

(Production Example 1) Production Example of Resin (A): Gly (OPAEG) 2MA In a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, rectification tube, water separator, etc., 1316.8 parts of phthalic anhydride, ethylene Glycol 573.9 parts, glycerin 409.3 parts and titanium tetraisopropoxide were charged in an amount corresponding to 100 ppm with respect to the total amount of polyvalent carboxylic acid and polyhydric alcohol, and the rectifying tube top temperature was 100 ° C. The internal temperature was maintained at 220 ° C. by gradually heating so as not to exceed. When the acid value reached 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a hydroxyl value of 339.9 mgKOH / g. Next, the temperature was lowered to 120 ° C., and 421.8 parts of maleic anhydride was added thereto, and maintained at 120 ° C. The esterification reaction was terminated when the acid value was approximately half of the acid value calculated from the charged amount of maleic anhydride, and the number average molecular weight was about 520, the hydroxyl value was 216.6 mgKOH / g, and the acid value was 96.2 mgKOH / g. A polyester polyol was obtained. The number of functional groups designed per resin (A) molecule: Hydroxyl group: 2, Carboxy group: 1, The solubility of the resin (A) was judged to be good.

(Production Example 2) Production Example of Resin (A): THEI (OPAEG) 3 In a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, rectification tube, water separator, etc., 1136.5 parts of phthalic anhydride, ethylene Glycine 495.3 parts, tris (2-hydroxyethyl) isocyanurate 668.1 parts, and titanium tetraisopropoxide were added in an amount corresponding to 100 ppm with respect to the total amount of polycarboxylic acid and polyhydric alcohol. The inner temperature was maintained at 220 ° C. by gradually heating so that the upper temperature of the distillation tube did not exceed 100 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight of about 860, a hydroxyl value of 195.4 mgKOH / g, and an acid value of 0.9 mgKOH / g. Resin (A) Number of functional groups designed per molecule Hydroxyl group: 3, Carboxy group: 0, Determination of solubility of resin (A) was ○.

(Production Example 3) Production method of resin (A): EGOPA (0.9K)
A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc. was charged with 148.1 parts of phthalic anhydride, 84.2 parts of ethylene glycol, and 0.03 part of titanium tetraisopropoxide, The inner temperature was maintained at 205 ° C. by gradually heating so that the upper temperature of the rectifying tube did not exceed 100 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight of 900 and a hydroxyl value of 126.2 mgKOH / g and an acid value of 0.36 mgKOH / g. Resin (A) Designed functional group number per molecule Hydroxyl group: 2, Carboxy group: 0, Resin (A) was judged to have good solubility.

(Adjustment of adhesive main agent)
The resin, inorganic compound, additive, and organic solvent described in the column of main agents in Tables 1 to 4 are mixed, and zirconia beads having the same mass as this compound are put in a container, and dispersed for about 1 hour with a paint conditioner. A main agent in which the compound was dispersed was prepared.

(Example 1) to (Example 7)
According to the examples in Tables 1, 3, and 4, an adhesive was obtained by mixing a resin, an inorganic compound, a curing agent, and a solvent. The coating method and the evaluation method were as follows.

(Comparative Example 1) to (Comparative Example 7)
According to the comparative examples in Tables 2 to 4, a resin, an inorganic compound, a curing agent and a solvent were mixed to obtain an adhesive. The coating method and the evaluation method were as follows.

(Coating method 1)
The solvent-type adhesive was applied to the corona-treated surface of the base film using a bar coater so that the coating amount was about 5.0 g / m ² (solid content), and diluted with a dryer set at a temperature of 70 ° C. Evaporate the solvent and dry it, and laminate it with the adhesive side of the base film coated with adhesive and the corona-treated side of the sealant film to create a composite film with the base film / adhesive layer / sealant film layer structure did. Next, this composite film was aged at 40 ° C. for 3 days, and the adhesive was cured to obtain a laminated film of the present invention. In addition, in the structure of the laminated body in a table | surface, the left side shows a base film and the right side shows a sealant film.

(Evaluation method)
(1) Laminate strength The laminated film after aging is cut into a width of 15 mm parallel to the coating direction, and the space between the base film and the sealant film is measured using a Tensilon universal testing machine manufactured by Orientec Co., Ltd. The atmosphere temperature was 25 ° C., the peeling speed was set to 300 mm / min, and the tensile strength when peeling by the 180 ° peeling method was defined as the laminate strength. The unit of laminate strength was N / 15 mm.

(2) Oxygen permeability (evaluation of oxygen barrier properties)
The laminated film after the aging was measured in an atmosphere of 23 ° C. and 90% RH in accordance with JIS-K7126 (isobaric method) using an oxygen permeability measuring device OX-TRAN2 / 21MH manufactured by Mocon. Note that RH represents humidity.

  Moreover, the oxygen barrier property of the adhesive-cured coating film alone was calculated using the formula (f) from the measurement results of the oxygen barrier laminate film, PET film, and CPP film.

P: Oxygen permeability of oxygen barrier laminate film P1: Oxygen permeability of coating film alone P2: Oxygen permeability of PET film (calculated as 100 cc / m ² · day · atm)
P3: Oxygen permeability of CPP film (calculated as 900 cc / m ² · day · atm)

(Solubility)
The resin (A) shown in the production example was mixed with ethyl acetate and methyl ethyl ketone (described as MEK) so as to have a nonvolatile content of 50%, and the solubility was confirmed. When the state of the liquid became transparent, it was judged that the solubility was good and judged as “◯”, and when turbidity occurred, the solubility was judged as poor and judged as “x”.

(Gelbo flex test (flexion test))
The laminated film after aging was adjusted to a size of 30 cm × 20 cm, and a bending test was performed with a gelbo flex tester (BE-1006 gelbo flex tester with a thermostatic bath, Tester Sangyo Co., Ltd.) according to ASTM F392. . The bending test was carried out under the conditions of 440 ° / 90 mm linear motion 65 mm, 23 ° C. and 10 times of bending, and the oxygen permeability after the gelboflex treatment was measured.

Hereinafter, the 5 g / m ² conversion of oxygen barrier property in each table is a conversion value when the application amount of the adhesive in the laminated film is 5 g / m ^2, and from the measured value and the application amount of the oxygen barrier property of the laminated film. Obtained by calculation.

The abbreviations in the table indicate the following.
BARRISURF HX: BARRISURF HX (manufactured by IMERYS, kaolin / non-swelling, interlayer nonionic, plate-like, average particle size / 1.5 μm, aspect ratio / about 100)
HM6025: HM6025 (manufactured by HENGHAO, mica / non-swellable, plate-like, average particle size 10 μm, aspect ratio 100 or more)
LX-703VL: Dick Dry LX-703VL (manufactured by DIC Graphics: polyester polyol having an aromatic skeleton), non-volatile content / about 62%, adhesive having no oxygen barrier property D-110N: Takenate D-110N (Mitsui Chemicals Co., Ltd .: XDI polyisocyanate, non-volatile content / about 75%)
Takenate 500: Takenate 500 (Mitsui Chemicals Co., Ltd .: XDI xylylene diisocyanate, nonvolatile content / about 100%)
KBM-403: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd .: 3-glycidoxypropyltrimethoxysilane, nonvolatile content / about 100%)
・ Phosphoric acid: Phosphoric acid (manufactured by Kanto Chemical, approximately 85% aqueous solution of phosphoric acid)
・ Pyrophosphate: Pyrophosphate (Kanto Chemical, Pyrophosphate 74.5-80.0% product)
AP-10: AP-10 (Daihachi Chemical Industry Co., Ltd., Isodecyl Acid Phosphate, nonvolatile content / about 100%)
PET: Polyester film, Toyobo Co., Ltd. E5102 12 μm
・ PET-AL: Aluminum bonded polyester film, aluminum foil / Toyo Aluminum Industry Co., Ltd. Aluminum haku C 9μm
CPP: unstretched polypropylene film, Toray Film Processing Co., Ltd. Treffan NO ZK93KM 70 μm
VM-CPP: Aluminum vapor-deposited unstretched polypropylene film, Toray Film Processing Co., Ltd. 2203 25 μm
VM-PE: Aluminum vapor deposited low density polyethylene film, Mitsui Chemicals Tosero Co., Ltd., TUX-F 30 μm

  As a result, in the laminated body of the adhesive resin composition using the phosphoric acid compound described in Examples 1 to 7, the adhesive body has a good adhesive strength as compared with the laminated body of the adhesive resin composition not using the phosphoric acid compound. Indicated. Furthermore, any adhesive had a good oxygen barrier property.

  Moreover, the oxygen barrier laminated film using the adhesive resin composition having oxygen barrier properties of Examples 1 to 4 has little deterioration of the oxygen barrier properties after the bending test and maintains a relatively good oxygen barrier property. It was. On the other hand, even if the adhesive which does not have oxygen barrier property has favorable adhesiveness, the oxygen barrier property after a bending test fell remarkably.

  Since the adhesive of the present invention has good adhesive strength and oxygen barrier properties, in addition to the above-mentioned film laminating adhesive for packaging materials, for example, adhesives for solar cell protective films and gas barrier substrates for display elements. Any application that requires oxygen barrier properties, such as an adhesive for electronic materials such as an adhesive, an adhesive for building materials, and an adhesive for industrial materials, can be suitably used.

Claims (21)

Resin (A) having two or more hydroxyl groups in one molecule as a functional group, isocyanate compound (B) having two or more isocyanate groups in one molecule as a functional group, and general formula (1) or general formula (2) In the resin composition for adhesives containing the phosphoric acid modified compound (C) represented by :
The main skeleton of the resin (A) is polyester or polyester polyurethane,
The resin composition for adhesives, wherein the content of ortho-oriented aromatic dicarboxylic acid or anhydride thereof is 70 to 100% by mass with respect to all the polyvalent carboxylic acid components of the polyester constituent monomer component.

(Wherein, R ₁ to R ₃ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, (meth) acryloyl group, a phenyl group which may have a substituent, the carbon number having a (meth) acryloyloxy group A group selected from 1 to 4 alkyl groups, at least one of which is a hydrogen atom, and n represents an integer of 1 to 4.)

(In the formula, R _{4 to} R ₅ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a (meth) acryloyl group, an optionally substituted phenyl group, or a carbon number having a (meth) acryloyloxy group. A group selected from 1 to 4 alkyl groups, n is an integer of 1 to 4, x is an integer of 0 to 30, and y is an integer of 0 to 30, but both x and y are 0. except.) Furthermore, the resin composition for adhesive agents of Claim 1 containing a plate-shaped inorganic compound (D). 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 resin composition for an adhesive according to claim 1 or 2, which is at least one selected from the group consisting of an anhydride thereof, and 2,3-anthracene dicarboxylic acid or an anhydride thereof. The resin composition for adhesives according to claim 1, wherein the resin (A) is a polyester polyol (A3) represented by the general formula (3).

(In Formula (3), R _{1 to} R ₃ are each independently a hydrogen atom or General Formula (4).

(In the formula (4), 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 (4). ) The resin composition for adhesives of Claim 4 which contains 5 mass% or more of glycerol residues of the polyester polyol (A3) represented by the said General formula (3) in an oxygen barrier property polyester resin composition. The resin composition for adhesives according to claim 1, wherein the resin (A) is a polyester polyol (A5) having an isocyanuric ring represented by the general formula (5).

(In General Formula (5), R _{1 to} R ₃ are each independently — (CH ₂ ) _n1 —OH (where n1 represents an integer of 2 to 4), or General Formula (6)

(In General Formula (6), 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. 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 (6). ) The resin composition for an adhesive according to any one of claims 1 to 6, wherein the isocyanate compound (B) contains a polyisocyanate having an aromatic ring. The resin composition for an adhesive according to claim 7, wherein the polyisocyanate having an aromatic ring is a reaction product of metaxylene diisocyanate or metaxylene diisocyanate and an alcohol having two or more hydroxyl groups. The resin composition for adhesives according to claim 2, wherein the plate-like inorganic compound (D) is nonionic between layers or non-swellable with respect to water. When the total mass of the resin (A), the isocyanate compound (B), the phosphoric acid-modified compound (C) and the plate-like inorganic compound (D) is 100 parts by mass, the content of the plate-like inorganic compound (D) is 5 to 5 parts. It is 50 mass parts, The resin composition for adhesives in any one of Claims 2-9. The resin composition for adhesives according to any one of claims 2 to 10, wherein the plate-like inorganic compound (D) contains particles having an average particle size of 0.1 µm or more. The resin composition for an adhesive according to any one of claims 1 to 11, wherein the resin (A) is dissolved in a ketone solvent, an ester solvent, or a mixed solvent containing a ketone solvent or an ester solvent. It is a solvent-free type, The resin composition for adhesives in any one of Claims 1-11. The resin composition for oxygen barrier adhesives in which the resin composition for adhesives in any one of Claims 1-13 has an oxygen barrier property. When the coating amount of the cured coating film obtained from the resin (A) and the isocyanate compound (B) is about 5 g / m ² , the oxygen permeability of the cured coating film at 23 ° C. and 90% humidity is 100 cc / m ^2. The resin composition for an oxygen barrier adhesive according to claim 14 , wherein the resin (A) and the isocyanate compound (B) are equal to or less than day · atm. When the coating amount of the cured coating obtained from the resin (A), the isocyanate compound (B), and the plate-like inorganic compound (D) is about 5 g / m ² , the cured coating at 23 ° C. and 90% humidity The oxygen-barrier adhesive according to claim 14, comprising a resin (A), an isocyanate compound (B), and a plate-like inorganic compound (D) having an oxygen permeability of 100 cc / m ² · day · atm or less. Resin composition. The adhesive agent which hardens the resin composition for adhesive agents in any one of Claims 1-16. An oxygen barrier adhesive obtained by curing the resin composition for an oxygen barrier adhesive according to claim 15 or 16. The adhesive according to claim 17 or 18, which is used as an adhesive for film lamination. Aluminum, zinc, gold, silver, copper, nickel, chromium, titanium, silicon, magnesium, titanium, tin, or zinc, or aluminum, zinc, gold, silver, copper, nickel, chromium, titanium, silicon, magnesium, titanium, A deposited film layer containing tin or zinc oxide,
Alternatively, the adhesive according to claim 19, which is used as an adhesive for film lamination in contact with any of metal foil layers of aluminum, zinc, gold, silver, copper, nickel, chromium, or titanium. A multilayer film having a layer formed by the adhesive according to claim 19 or 20.