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WO2018105440A1 - Composition de résine pour adhésif faisant barrière aux gaz, adhésif et stratifié - Google Patents

Composition de résine pour adhésif faisant barrière aux gaz, adhésif et stratifié Download PDF

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Publication number
WO2018105440A1
WO2018105440A1 PCT/JP2017/042550 JP2017042550W WO2018105440A1 WO 2018105440 A1 WO2018105440 A1 WO 2018105440A1 JP 2017042550 W JP2017042550 W JP 2017042550W WO 2018105440 A1 WO2018105440 A1 WO 2018105440A1
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Prior art keywords
group
acid
gas barrier
resin
resin composition
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PCT/JP2017/042550
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English (en)
Japanese (ja)
Inventor
下口　睦弘
正光 新居
正憲 林
耕司 白石
武田　博之
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DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2018517231A priority Critical patent/JPWO2018105440A1/ja
Publication of WO2018105440A1 publication Critical patent/WO2018105440A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

  • the present invention relates to a resin composition for gas barrier adhesive, an adhesive using the resin composition, and a gas barrier film.
  • a two-component reaction type polyurethane adhesive As an adhesive used for the laminate, a two-component reaction type polyurethane adhesive is known.
  • a two-component reaction type polyurethane adhesive there is an adhesive comprising a polyol component having a hydroxyl group at a polymer terminal and a polyisocyanate component having an isocyanate group, which forms a urethane bond and cures by the reaction between the hydroxyl group and the isocyanate group.
  • polyether polyurethane polyols polyester polyols whose aliphatic acid-derived polyester bond concentration is 2 to 4 mg equivalent / g based on the solid content of the adhesive, polyester polyurethane polyols, or mixtures of two or more thereof And a combination of polyisocyanate compounds are known (for example, see Patent Document 1).
  • a film provided with a metal oxide layer / adhesive / a film provided with a metal oxide layer exhibits a high barrier performance (for example, see Patent Document 2), and the coating amount is 4 g / m. 2.
  • Patent Document 2 Adhesive having an oxygen gas barrier performance of 90 ml / m 2 ⁇ day ⁇ MPa ( ⁇ 9.1 cc / m 2 ⁇ day ⁇ atm) or less when measured at a dry condition of 23 ° C. and 60% RH
  • Patent Document 2 Adhesive having an oxygen gas barrier performance of 90 ml / m 2 ⁇ day ⁇ MPa ( ⁇ 9.1 cc / m 2 ⁇ day ⁇ atm) or less when measured at a dry condition of 23 ° C. and 60% RH
  • Patent Document 2 Adhesive having an oxygen gas barrier performance of 90 ml / m 2 ⁇ day ⁇ MPa ( ⁇ 9.1 cc / m 2 ⁇ day
  • the problem to be solved by the present invention is to provide a resin composition for a gas barrier adhesive for laminate which has excellent barrier properties at high temperatures.
  • the present invention is a resin composition for a gas barrier adhesive comprising a resin (A) having two or more hydroxyl groups in one molecule and a polyisocyanate (B) having a divalent or higher isocyanate group.
  • a resin composition for a gas barrier adhesive is provided in which the cured product of the resin composition has a glass transition temperature in the range of 25 ° C to 150 ° C.
  • the present invention also provides an adhesive using the above-described resin composition for a gas barrier adhesive.
  • the present invention also provides a laminate using the above-mentioned adhesive as an adhesive layer.
  • the present invention also provides a laminate comprising a metal vapor-deposited film, a metal oxide vapor-deposited film, or an aluminum foil using the above-mentioned adhesive as an adhesive layer.
  • the present invention is a resin composition for a gas barrier adhesive comprising a resin (A) having two or more hydroxyl groups in one molecule and a polyisocyanate (B) having a divalent or higher isocyanate group.
  • the resin composition for gas barrier adhesives has a glass transition temperature of 25 ° C. to 150 ° C. of the cured product of the resin composition.
  • the glass transition temperature was measured using a differential scanning calorimetry “DSC822” manufactured by METLER TOLEDO (based on JIS K 7121, ISO 3146: 1985) (hereinafter, the glass transition temperature is Tg). May be abbreviated).
  • the rate of temperature increase was 20 ° C./min and was in the range of ⁇ 60 ° C. to 200 ° C.
  • the glass transition temperature is more preferably in the range of 30 ° C. to 100 ° C., and more preferably in the range of 35 ° C. to 80 ° C. If it is this range, the excessive softening of an adhesive bond layer can be suppressed even under high temperature, and the deterioration of barrier property can be reduced.
  • a resin (A) having two or more hydroxyl groups in one molecule to be used or a divalent or higher isocyanate group This can be realized by appropriately changing and combining the skeleton and the blending ratio of the polyisocyanate (B) having the above.
  • numerator as polyisocyanate (B) can satisfy
  • Polyisocyanate (B) The polyisocyanate (B) having a divalent or higher valent isocyanate group used in the present invention solidifies and bonds the adhesive by three-dimensionally cross-linking the resin (A) having two or more hydroxyl groups in one molecule. It has a function to let you. Therefore, if the divalent or higher polyisocyanate compound (b1) having an aromatic ring in the molecule is not included as a curing agent component, the adhesive layer is peeled off under conditions where heat is applied such as boiling and retorting. There is a risk of problems with lamination.
  • a divalent or trivalent polyisocyanate which is generally easily available, is preferably used because it can function as a crosslinking material if it is divalent or higher.
  • a divalent or higher polyisocyanate compound (b1) having an aromatic ring in the molecule is preferable.
  • the divalent or higher polyisocyanate compound (b1) having an aromatic ring in the molecule is not particularly limited, and known compounds can be used.
  • at least one diisocyanate selected from xylylene diisocyanate, metaxylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, methylphenylethane diisocyanate, a reaction product of the diisocyanate with a monohydric alcohol, or an alcohol having two hydroxyl groups Reaction products, carbodiimide modified products and the like can be mentioned.
  • an excess amount of the diisocyanate may be converted into a polyfunctional alcohol, for example, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, diethanolamine, triethanolamine, or other low molecular active hydrogen.
  • a polyfunctional alcohol for example, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, diethanolamine, triethanolamine, or other low molecular active hydrogen.
  • examples thereof include adducts which are reaction products of the compounds and their alkylene oxide adducts, various polyester resins, polyether polyols, and polymer active hydrogen compounds of polyamides.
  • the nurate body etc. which are the multimers of the said diisocyanate can also be used preferably.
  • metaxylylene diisocyanate metaxylylene diisocyanate, xylylene diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate are preferable, and metaxylylene diisocyanate is most preferable.
  • Polyisocyanate compounds that do not have an aromatic ring in the molecule In the present invention, it is more preferable to use a diisocyanate or higher polyisocyanate compound (b1) having an aromatic ring in the molecule and a polyisocyanate compound not having an aromatic ring in the molecule as a curing agent.
  • a diisocyanate or higher polyisocyanate compound (b1) having an aromatic ring in the molecule and a polyisocyanate compound not having an aromatic ring in the molecule as a curing agent.
  • Conventional polyisocyanates having an aromatic ring have hardened cured coatings, and it has been difficult to obtain good adhesive strength.
  • polyisocyanate compounds having no aromatic ring in the molecule especially allophanate While maintaining barrier properties by using diisocyanate in combination, flexibility is imparted to the coating film, adhesion to metal substrates such as aluminum foil, aluminum vapor deposition film, transparent vapor deposition film is improved, and barrier properties are also provided. improves.
  • Examples of the polyisocyanate compound having no aromatic ring in the molecule used in the present invention include hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, metaxylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated methylphenylethane diisocyanate, hydrogenated naphthalene- Examples include at least one diisocyanate selected from 1,5-disocyanate, a reaction product of the diisocyanate with a monohydric alcohol, a reaction product of an alcohol having two hydroxyl groups, and a carbodiimide modified product.
  • an excess amount of the diisocyanate may be converted into a polyfunctional alcohol, for example, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, diethanolamine, triethanolamine, or other low molecular active hydrogen.
  • a polyfunctional alcohol for example, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, diethanolamine, triethanolamine, or other low molecular active hydrogen.
  • examples thereof include adducts which are reaction products of the compounds and their alkylene oxide adducts, various polyester resins, polyether polyols, and polymer active hydrogen compounds of polyamides.
  • the nurate body etc. which are the multimers of the said diisocyanate can also be used preferably.
  • a polyisocyanate compound (b2) having a cyclic skeleton and having no aromatic ring in the molecule is preferable.
  • the cyclic skeleton include an alicyclic skeleton and a nurate skeleton.
  • the polyisocyanate having an alicyclic skeleton isophorone diisocyanate, norbornane diisocyanate, hydrogenated metaxylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated methylphenylethane diisocyanate, and hydrogenated naphthalene-1,5-disocyanate are preferable.
  • the mixing ratio of the polyisocyanate compound (b1) having two or more valences having an aromatic ring in the molecule and the polyisocyanate compound (b2) having no aromatic ring in the molecule is 1: 5 in terms of isocyanate content. It is preferably in the range of ⁇ 10: 1, more preferably 1: 3 to 5: 1.
  • the resin (A) used in the present invention may be any resin having substantially two or more hydroxyl groups, but if the number average molecular weight (Mn) is in the range of 400 to 3000, the time required for synthesis is short.
  • the process of forming an adhesive after synthesis is preferable because it can be simplified by being easily transferred.
  • polyester polyols examples include polyester polyols, polyether polyols, acrylic polyols, and the like, but polyester polyols are most preferable in order to impart gas barrier properties that are an additional important function.
  • the polyester polyol used in the present invention is a polyester polyol having two or more hydroxyl groups, and is substantially a plurality of hydroxyl groups obtained by polycondensation reaction between a polyvalent carboxylic acid component and a polyhydric alcohol component.
  • polycondensate that can exhibit the gas barrier properties of the present invention, but those having an aromatic ring are preferred, and those having an ortho-oriented aromatic ring are more gas barriers. Excellent in properties and preferable.
  • polyester polyol having a plurality of hydroxyl groups more specifically, -Polyester polyol (A0) obtained by polycondensation of an aromatic polyvalent carboxylic acid component, more preferably a polyvalent carboxylic acid component containing an ortho-oriented aromatic polyvalent carboxylic acid component and a polyhydric alcohol component, 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, -Polyester polyol (A4) having an isocyanuric ring,
  • a polyester polyol having a plurality of hydroxyl groups more specifically, -Polyester polyol (A0) obtained by polycondensation of an aromatic polyvalent carboxylic acid component, more preferably a polyvalent carboxylic acid component containing
  • polyester polyol (A0) used in the present invention is obtained by polycondensing an aromatic polyvalent carboxylic acid component, more preferably a polyvalent carboxylic acid component containing an ortho-oriented aromatic polyvalent carboxylic acid component and a polyhydric alcohol component. It is done.
  • Aromatic polyvalent carboxylic acids are preferably used in order to obtain gas barrier properties.
  • aromatic polycarboxylic acids include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, and 2,6-naphthalene.
  • Orthophthalic acid and its anhydride have an asymmetric structure in the skeleton. Therefore, it is presumed that the rotation of the molecular chain of the resulting polyester is suppressed, and thus it is presumed that the gas barrier property is excellent. Further, it is presumed that due to this asymmetric structure, it exhibits non-crystallinity, imparts sufficient substrate adhesion, and is excellent in adhesion and gas barrier properties. Furthermore, when used as a dry laminate adhesive, the solvent solubility, which is essential, is also high, so that it has excellent handling characteristics.
  • the polyester polyol (A0) preferably has a content of 70 to 100% by mass of the orthophthalic acid and its anhydride with respect to all the polyvalent carboxylic acid components.
  • polyhydric alcohol component is an aliphatic diol such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5.
  • -Pentanediol 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, hydroquinone as an aromatic polyphenol , Resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol and their ethylene oxide elongation It can be exemplified ones, the hydrogenated alicyclic.
  • ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane dimethanol are preferable because the number of carbon atoms between oxygen atoms is less likely to be excessively flexible. Is more preferable.
  • the polycondensation reaction between the polyvalent carboxylic acid component containing the aromatic polyvalent carboxylic acid component, more preferably the ortho-oriented aromatic polyvalent carboxylic acid component, and the polyhydric alcohol component can be performed by a known method.
  • polyester polyol (A1) obtained by reacting carboxylic acid anhydride or polycarboxylic acid with polyester polyol having 3 or more hydroxyl groups The polyester polyol (A1) used in the present invention comprises at least one carboxy group and two or more hydroxyl groups obtained by reacting a carboxylic acid anhydride or a polyvalent carboxylic acid with a polyester polyol having three or more hydroxyl groups. It is what has.
  • the polyester polyol having three or more hydroxyl groups can be obtained by making a part of the polyvalent carboxylic acid or polyhydric alcohol trivalent or higher.
  • polyester polyol (A1-1) having three or more hydroxyl groups when synthesizing a polyester polyol (A1-1) 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.
  • these compounds include trimellitic acid and its acid anhydride, pyromellitic acid and its acid anhydride, etc.
  • trivalent or higher polyvalent carboxylic acids include three. Divalent carboxylic acids are preferred.
  • the polyester polyol (A1-1) may be copolymerized with a polyvalent carboxylic acid component other than the above-mentioned orthophthalic acid and its anhydride, as long as the effects of the present invention are not impaired.
  • a polyvalent carboxylic acid component other than the above-mentioned orthophthalic acid and its anhydride such as the aliphatic polyvalent carboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc.
  • the unsaturated bond-containing polyvalent carboxylic acid maleic anhydride, maleic acid, Fumaric acid, etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc.
  • polyhydric alcohol and other ingredients When a branched structure is introduced by a polyhydric alcohol component when synthesizing the polyester polyol (A1-1), it is necessary to have at least part of a trihydric or higher polyhydric alcohol.
  • 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 preferred.
  • the polyhydric alcohol component containing at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol used for the synthesis of the polyester polyol (A1-1) is an oxygen atom Since it is estimated that the smaller the number of carbon atoms in the molecular chain, the more difficult the molecular chain becomes excessively flexible, it is most preferable to use ethylene glycol. On the other hand, in addition to the polyhydric alcohol components listed here, other polyhydric alcohol components may be copolymerized as long as the effects of the present invention are not impaired.
  • aliphatic diols include 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, Triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenols, hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and their ethylene oxides
  • An elongated product and a hydrogenated alicyclic group can be exemplified.
  • the reaction of the polyester polyol (A1-1) with a carboxylic acid anhydride or a polyvalent carboxylic acid can be performed by a known method.
  • the polyester polyol (A1-1) can be obtained by reacting a polyvalent carboxylic acid or an acid anhydride thereof with a hydroxyl group of the polyester polyol (A1-1). Since the ratio of the polyester polyol (A1-1) to the polyvalent carboxylic acid requires two or more hydroxyl groups of the polyester polyol (A1-1) after the reaction, the polyvalent carboxylic acid is a polyester polyol (A1-1). It is preferable to react with 1/3 or less of the hydroxyl group.
  • the carboxylic acid anhydride or polyvalent carboxylic acid used here is not limited, but in consideration of gelation during the reaction between the polyvalent carboxylic acid and the polyester polyol (A1-1), a divalent or trivalent carboxylic acid is used. It is preferred to use an anhydride.
  • 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 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.
  • 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.
  • the hydroxyl value exceeds 250 mgKOH / g, the molecular weight becomes too small, so that the crosslinked density of the cured coating film becomes too high and good adhesive strength may not be obtained.
  • polyester polyol having polymerizable carbon-carbon double bond (A2) The polyester polyol (A2) used in the present invention has a polymerizable carbon-carbon double bond in the molecule. Specifically, by using a component having a polymerizable carbon-carbon double bond as a component of the polyvalent carboxylic acid or polyhydric alcohol, a polysynthetic carbon-carbon double bond in the molecule of the polyester polyol (A2) is used. Is a polyester polyol into which is introduced.
  • polyvalent carboxylic acid Specific examples of the polyvalent carboxylic acid component include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and the like as the aliphatic polyvalent carboxylic acid, and 1, as the alicyclic polyvalent carboxylic acid.
  • 3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc., and aromatic polyvalent carboxylic acids include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and anhydrides or esters of these dicarboxylic acids
  • acid anhydrides can also be used.
  • succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydride of orthophthalic acid, and isophthalic acid are preferable, and orthophthalic acid and its acid anhydride are more preferable for obtaining gas barrier properties.
  • polyvalent carboxylic acid having a polymerizable carbon-carbon double bond examples include maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and its acid anhydride, 3-methyl-4- And cyclohexene-1,2-dicarboxylic acid and its anhydride.
  • maleic anhydride, maleic acid, and fumaric acid are preferred because it is estimated that the smaller the number of carbon atoms, the less likely the molecular chain becomes excessively flexible.
  • polyhydric alcohol component Specific examples of the polyhydric alcohol component include aliphatic glycol diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenols, hydroquinone, resorcinol, catechol , Naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and their ethylene oxide extensions It can be exemplified hydrogenated alicyclic.
  • aliphatic glycol diols such as
  • ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane dimethanol are preferred, since it is estimated that the smaller the number of carbon atoms between oxygen atoms, the more difficult the molecular chain becomes excessively flexible. More preferred is ethylene glucol.
  • polyhydric alcohol with polymerizable carbon-carbon double bond examples include 2-butene-1,4-diol.
  • a polyester polyol (A2) obtained by a reaction between a polyester polyol having a hydroxyl group and a carboxylic acid having a polymerizable double bond or a carboxylic acid anhydride may be used.
  • a carboxylic acid having a polymerizable double bond such as maleic acid, maleic anhydride or fumaric acid, an unsaturated fatty acid such as oleic acid or sorbic acid, or the like can be used.
  • the polyester polyol in this case is preferably a polyester polyol having two or more hydroxyl groups, but it is more preferable to have three or more hydroxyl groups in consideration of molecular elongation due to crosslinking with polyisocyanate.
  • the polyester polyol has one or two hydroxyl groups
  • the polyester polyol (A2) obtained by reacting a carboxylic acid having a polymerizable double bond has 0 or 1 hydroxyl group, and reacts with the polyisocyanate (B). It is difficult for molecular elongation to occur, and it is difficult to obtain properties such as laminate strength, seal strength, and heat resistance as an adhesive.
  • the polycondensation reaction between the polyvalent carboxylic acid component and the polyhydric alcohol component can be performed by a known and conventional method.
  • 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. If the hydroxyl value is less than 20 mgKOH / g, the molecular weight is too large, resulting in a high viscosity, which may result in poor coating suitability. Conversely, if the hydroxyl value exceeds 250 mgKOH / g, the molecular weight will be small. Therefore, the crosslinking density of the cured coating film becomes too high, and there is a possibility that good adhesive strength cannot be obtained.
  • the monomer component having a polymerizable carbon-carbon double bond is preferably 5 to 60 parts by mass with respect to 100 parts by mass of all monomer components constituting the polyester polyol (A2). If it is lower than this range, the number of crosslinking points between the polymerizable double bonds will decrease, making it difficult to obtain gas barrier properties. If it is higher, the number of crosslinking points will increase, and the flexibility of the cured coating will be significantly reduced, resulting in a laminate strength. There is a risk that it will be difficult.
  • the amount of monomer component having a polymerizable carbon-carbon double bond (double bond component ratio) in the polyester polyol (A2) is calculated using the formula (a).
  • the monomer refers to the polyvalent carboxylic acid and polyhydric alcohol.
  • polyester polyol (A2) of the present invention a known and commonly used drying oil having a carbon-carbon double bond or a semi-drying oil may be used.
  • polyester polyol having glycerol skeleton (A3) is a polyester polyol having a glycerol skeleton represented by the general formula (1).
  • R 1 to R 3 each independently represents a hydrogen atom, or a compound represented by the general formula (2)
  • n represents an integer of 1 to 5
  • 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
  • Y represents an alkylene group having 2 to 6 carbon atoms.
  • R 1 to R 3 represents a group represented by the general formula (2).
  • R 1 , R 2 and R 3 needs to be a group represented by the general formula (2). Among them, it is preferable that all of R 1 , R 2 and R 3 are groups represented by the general formula (2).
  • R 1, any one of R 2 and R 3 is a group represented by the general formula (2) compound, R 1, R 2, and any two of the general formula R 3 (2) Any two or more compounds of the compound represented by the general formula (2) and the compound in which all of R 1 , R 2 and R 3 are groups represented by the general formula (2) are mixed. Also good.
  • X is selected from the group consisting of 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group,
  • the arylene group which may have is represented.
  • X 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.
  • substituents examples 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.
  • 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.
  • Y is preferably a propylene group or an ethylene group, and most preferably an ethylene group.
  • the polyester resin compound having a glycerol skeleton represented by the general formula (1) is a reaction between glycerol, an aromatic polycarboxylic acid in which a carboxylic acid is substituted in the ortho position, or an anhydride thereof, and a polyhydric alcohol component. Let me get it.
  • Polyvalent carboxylic acid examples include orthophthalic acid or an anhydride thereof, naphthalene 2,3-dicarboxylic acid or an anhydride thereof, naphthalene 1,2-dicarboxylic acid, or Examples thereof include an anhydride thereof, anthraquinone 2,3-dicarboxylic acid or an anhydride thereof, and 2,3-anthracene carboxylic acid or an anhydride thereof. These compounds may have a substituent on any carbon atom of the aromatic ring.
  • substituents examples 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 polyvalent carboxylic acid component other than the aromatic polyvalent carboxylic acid or its anhydride substituted in the ortho position may be copolymerized within a range not impairing the effects of the present invention.
  • the aliphatic polyvalent carboxylic acid succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc.
  • the unsaturated bond-containing polyvalent carboxylic acid maleic anhydride, maleic acid, Fumaric acid, etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc.
  • p- Dorokishi benzoic acid can be used in p-(2-hydroxyethoxy) benzoic acid and alone or in mixture of two or more polybasic acids such as ester-forming derivatives of these dihydroxy carboxylic acids.
  • succinic acid 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalic acid and diphenic acid are preferred.
  • polyhydric alcohol component is an aliphatic diol such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5.
  • -Pentanediol 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, hydroquinone as an aromatic polyphenol , Resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol, ethylene oxide It can be exemplified Chobutsu, a hydrogenated alicyclic.
  • ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane dimethanol are preferred, since it is estimated that the smaller the number of carbon atoms between oxygen atoms, the more difficult the molecular chain becomes excessively flexible. More preferred is ethylene glycol.
  • the polycondensation reaction of the polyvalent carboxylic acid component and the polyhydric alcohol component can be performed by a known and usual method.
  • the content of the glycerol skeleton is the residue (C1) excluding R 1 to R 3 in the general formula (1) with respect to the total solid content of the organic resin composition for gas barrier adhesive of the present application.
  • P represents a polyester polyol (A3) having a glycerol skeleton.
  • the organic resin composition for gas barrier adhesive has 5% by mass or more of glycerol residues.
  • polyester polyol having an isocyanuric ring (A4) The polyester polyol (A4) used in the present invention is a polyester polyol (A4) having an isocyanuric ring represented by the general formula (3).
  • R 1 to R 3 are each independently — (CH 2 ) n1 —OH (where n1 represents an integer of 2 to 4), or the general formula (4)
  • n2 represents an integer of 2 to 4
  • n3 represents an integer of 1 to 5
  • 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
  • Y represents an alkylene group having 2 to 6 carbon atoms
  • the alkylene group represented by — (CH 2 ) n1 — may be linear or branched.
  • n1 is preferably 2 or 3, and most preferably 2.
  • n2 represents an integer of 2 to 4
  • 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.
  • X When X is substituted with a substituent, it may be substituted with one or more substituents, and the substituents are bonded to any carbon atom on X different from the free radical.
  • substituents 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.
  • Y represents an ethylene group, a propylene group, a butylene group, a neopentylene group, a 1,5-pentylene group, a 3-methyl-1,5-pentylene group, a 1,6-hexylene group, a methylpentyl group.
  • Y is preferably a propylene group or an ethylene group, and most preferably an ethylene group.
  • R 1 , R 2 and R 3 are a group represented by the general formula (4).
  • R 1 , R 2 and R 3 are groups represented by the general formula (4).
  • R 1, R 2, and the compound any one of R 3 is a group represented by the general formula (4), R 1, R 2 and any two of the general formula R 3 (4) Any two or more compounds of the compound represented by the formula and the compound in which all of R 1 , R 2 and R 3 are groups represented by the general formula (4) are mixed. Also good.
  • the polyester polyol (A4) having an isocyanuric ring represented by the general formula (3) includes a triol having an isocyanuric ring, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position, or an anhydride thereof, Obtained by reacting with a monohydric alcohol component.
  • triol having an isocyanuric ring examples 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.
  • 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 Alternatively, an anhydride thereof, anthraquinone 2,3-dicarboxylic acid or an anhydride thereof, and 2,3-anthracene carboxylic acid or an anhydride thereof may be used. These compounds may have a substituent on any carbon atom of the aromatic ring.
  • substituents examples 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 polyvalent carboxylic acid component other than the aromatic polyvalent carboxylic acid or its anhydride substituted in the ortho position may be copolymerized within a range not impairing the effects of the present invention.
  • the aliphatic polyvalent carboxylic acid succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc.
  • the unsaturated bond-containing polyvalent carboxylic acid maleic anhydride, maleic acid, Fumaric acid, etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc.
  • p- Dorokishi benzoic acid can be used in p-(2-hydroxyethoxy) benzoic acid and alone or in mixture of two or more polybasic acids such as ester-forming derivatives of these dihydroxy carboxylic acids.
  • succinic acid 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalic acid and diphenic acid are preferred.
  • polyhydric alcohol component is an aliphatic diol such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5.
  • -Pentanediol 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, hydroquinone as an aromatic polyphenol , Resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol, ethylene oxide It can be exemplified Chobutsu, a hydrogenated alicyclic.
  • ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane dimethanol are preferred, since it is estimated that the smaller the number of carbon atoms between oxygen atoms, the more difficult the molecular chain becomes excessively flexible. More preferred is ethylene glycol.
  • the polycondensation reaction between the polyvalent carboxylic acid and the polyhydric alcohol can be performed by a known and commonly used method.
  • 1,3,5-tris (2-hydroxyethyl) isocyanuric acid or 1,3,5-tris (2-hydroxypropyl) isocyanuric acid is used as a triol compound having an isocyanuric ring, and the carboxylic acid is in the ortho position.
  • Polyester polyol compounds having an isocyanuric ring using orthophthalic anhydride as the aromatic polyvalent carboxylic acid substituted with or an anhydride thereof and ethylene glycol as the polyhydric alcohol are particularly excellent in gas barrier properties and adhesion. .
  • 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 isocyanuric ring is highly polar and does not form hydrogen bonds.
  • 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 impair solubility in ethyl acetate and 2-butanone solvents 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.
  • the isocyanuric ring is trifunctional, a polyester polyol compound having the isocyanuric ring as the center of the resin skeleton and having a polyester skeleton with a specific structure in the branched chain can obtain a high crosslinking density. It is presumed that the gap through which a gas such as oxygen can be reduced by increasing the crosslinking density. Thus, since the isocyanuric ring is highly polar and does not form an intermolecular hydrogen bond and a high crosslink density is obtained, it is presumed that gas barrier properties and dry laminate adhesiveness can be secured.
  • P represents a polyester polyol (A4) having an isocyanuric ring.
  • the polyester polyol having an isocyanuric ring can be performed by a known and usual method.
  • 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
  • the temperature may be increased while stirring and mixing to cause a dehydration condensation reaction.
  • the number average molecular weight of the resin (A) is particularly preferably from 450 to 5,000 because a crosslinking density having an excellent balance between adhesive ability and barrier function can be obtained. More preferably, the number average molecular weight is 500 to 3,000.
  • 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.
  • 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 is a value obtained by calculation from the obtained hydroxyl value and the number of functional groups of the designed hydroxyl group.
  • the resin (A) may be used as a polyol having a number average molecular weight of 1000 to 15000 by urethane elongation by reaction with a diisocyanate compound within a range not impairing the effects of the present invention. Since the polyol has a certain molecular weight component and a urethane bond, the polyol has excellent gas barrier properties, excellent initial cohesive force, and is further excellent as an adhesive used during lamination.
  • the said resin (A) and the said polyisocyanate (B) are the isocyanate which the ratio of the said resin (A) and the said polyisocyanate (B) has the hydroxyl group which the said resin (A) has, and the said polyisocyanate (B) It is preferable to blend so that the group is 1 / 0.5 to 1/10 (equivalent ratio), more preferably 1 / 0.6 to 1/5. If the polyisocyanate (B) is excessive beyond this range, the excess polyisocyanate (B) may remain and bleed out from the adhesive layer after bonding, while the polyisocyanate (B) If it is insufficient, the adhesive strength may be insufficient.
  • the resin composition for gas barrier adhesives of the present invention contains a non-petroleum component, particularly a plant-derived component, it is preferable to be an environment-friendly material in addition to a low VOC material.
  • a monomer for synthesizing the resin (A) ethylene glycol, glycerin, propylene glycol, butylene glycol and the like are commercially available for polyhydric alcohol components, succinic acid is currently available for polyvalent carboxylic acid components, and currently plant-derived components are commercially available at industrial levels. ing. When these monomers are used, the gas barrier function is also high, which is particularly preferable.
  • the resin composition for gas barrier adhesives of the present invention may contain various additives as long as the suitability for lamination is not impaired.
  • additives include inorganic fillers such as silica, alumina, aluminum flakes, and glass flakes, coupling agents, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, Examples thereof include a lubricant, an antiblocking agent, a colorant, a filler, a crystal nucleating agent and the like.
  • the thermoplastic resin acrylic resin, ketone resin, epoxy resin, polyester resin or the like can be used.
  • the resin composition for a gas barrier adhesive of the present invention may contain a plate-like inorganic compound for the purpose of imparting a higher gas barrier function.
  • a plate-like inorganic compound used in combination, the laminate strength and barrier properties are improved due to the plate shape.
  • the plate-like inorganic compound used in the present invention include hydrous silicates (phyllosilicate minerals, etc.), kaolinite-serpentine clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.) antigolite.
  • the charge between the layers does not directly affect the barrier property, but the dispersibility to the resin is significantly inferior with the ionic inorganic compound, and the coating suitability becomes a problem when the addition amount is increased (becomes thixotropic). On the other hand, in the case of no charge, the coating suitability can be ensured even if the amount added is increased.
  • the particle size is larger than about 1 ⁇ m, the barrier property is likely to be exhibited, and a favorable barrier property cannot be obtained at the nm level.
  • the particle size is too large, in the case of gravure printing or the like, the plate-like inorganic compound does not enter the gravure plate, so that the coating suitability cannot be obtained.
  • the particle size is preferably from 0.1 to 100 ⁇ m. More preferably, it is 1 to 40 ⁇ m.
  • 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 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 the gas component molecules. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more. Moreover, although the content rate of a plate-shaped inorganic compound is arbitrary, it is preferable that it is 50 mass% or less. If it exceeds 50% by mass, the laminating operation may be difficult or the adhesive strength may be insufficient.
  • a known dispersion method can be used as a method for dispersing the inorganic compound used in the present invention in the resin composition for a gas barrier adhesive of the present invention.
  • a known dispersion method can be used.
  • 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.
  • 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.
  • a known acid anhydride can be used in combination as an additive as a method for improving the acid resistance of the resin composition layer for a gas barrier adhesive of the present invention.
  • 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.
  • a compound having an oxygen scavenging function may be added.
  • 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.
  • a tackifier such as a xylene resin, a terpene resin, a phenol resin, a rosin resin, or a petroleum resin may be added as necessary.
  • a tackifier such as a xylene resin, a terpene resin, a phenol resin, a rosin resin, or a petroleum resin may be added as necessary.
  • the range of 0.01 to 5 parts by mass is preferable with respect to 100 parts by mass of the total amount of the cured resin component.
  • the adhesive of the present invention when the number average molecular weight (Mn) of the resin (A) is in the range of 400 to 3000, the total solid content of the resin (A) and the polyisocyanate (B) is the total mass of the adhesive. It has the characteristic that it is easy to make a high solid type adhesive that is 40% by mass or more. Hereinafter, this may be referred to as a non-volatile component.
  • the content exceeds 80% by mass the viscosity in coating is generally high. It is not preferable because it improves too much.
  • a preferable range is 40 to 80% by mass.
  • the cured product of the adhesive of the present invention has a gas barrier function against various gases.
  • gases that can be shut off include oxygen, water vapor, inert gas, alcohol, scent components, various organic solvents, and the like.
  • the adhesive of the present invention may or may not use an adhesive solvent.
  • solvents for adhesives 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, toluene, Aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like.
  • ethyl acetate or methyl ethyl ketone it is usually preferable to use ethyl acetate or methyl ethyl ketone. These solvents may be used as a reaction medium during the production of the polyester polyol and the curing agent. Further, it may be used as a diluent during coating.
  • the adhesive of the present invention can be used as an adhesive for film lamination.
  • Laminated bodies such as laminated laminated films are excellent in gas barrier properties, and therefore can be used as laminated films for gas barriers.
  • 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.
  • a thermoplastic resin film can be appropriately selected according to a desired application.
  • PET film polystyrene film, polyamide film, polyacrylonitrile film
  • polyethylene film LLDPE: low density polyethylene film
  • HDPE high density polyethylene film
  • polypropylene film CPP: unstretched polypropylene film
  • OPP examples thereof include polyolefin films such as biaxially stretched polypropylene film), polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films. These may be subjected to stretching treatment.
  • 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.
  • sequential biaxial stretching it is common to first perform longitudinal stretching and then perform lateral stretching.
  • a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.
  • a film obtained by laminating a metal such as aluminum or a vapor deposition layer of a metal oxide such as silica or alumina on the laminating film may be used.
  • porous substrates such as paper, paperboard, coated paper, wood, and leather can be used. In this case, the adhesive penetrates the substrate, so the amount of adhesive applied is large. There is a need to.
  • the adhesive of the present invention can be preferably used as an adhesive for a laminated film formed by bonding a plurality of the same or different resin films.
  • the resin film may be appropriately selected depending on the purpose.
  • the outermost layer is a thermoplastic resin film selected from PET, OPP, and polyamide, and the innermost layer is unstretched polypropylene.
  • 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
  • LLDPE low density polyethylene film
  • 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 A thermoplastic resin film, a thermoplastic film forming a first intermediate layer selected from PET and nylon, a thermoplastic film forming a second intermediate layer selected from PET and polyamide, or a metal-deposited film thereof, metal A composite film composed of four layers using a thermoplastic resin film forming an innermost layer selected from an oxide vapor deposited film, LLDPE, and CPP can be preferably used as a food packaging material as a gas
  • the surface of the film may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer free from defects such as film breakage and repellency is formed.
  • Aging conditions are preferably from room temperature to 80 ° C., and preferably from 12 to 240 hours, during which adhesive strength occurs.
  • a gas barrier function may be further increased by using a plurality of films selected from barrier films containing a gas barrier layer such as vinylidene. In this case, the same film may be used for lamination, or different films may be laminated.
  • Polyester polyol (A1, A2, A3) Production example of Gly (OPAEG) 2MA Phthalic anhydride 1316 in a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, rectification tube, water separator, etc. .8 parts, ethylene glycol 573.9 parts, glycerin 409.3 parts and titanium tetraisopropoxide in an amount corresponding to 100 ppm with respect to the total amount of polycarboxylic acid and polyhydric alcohol, The internal temperature was kept at 220 ° C. by gradually heating so that the temperature did not exceed 100 ° C.
  • Polyester polyol (A4) Production example of THEI (OPAEG) 3
  • a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc. 1136.5 parts of phthalic anhydride, An amount corresponding to 100 ppm of ethylene glycol 495.3 parts, tris (2-hydroxyethyl) isocyanurate 668.1 parts and titanium tetraisopropoxide with respect to the total amount of the polyvalent carboxylic acid and the polyhydric alcohol,
  • the inner temperature was kept at 220 ° C. by gradually heating so that the upper temperature of the rectifying tube did not exceed 100 ° C.
  • HM6025 Made by HENGHAO, mica (KAL 2 (ALSi 3 O 10 ) (OH) 2 ), non-swelling, plate-like, average particle size 10 ⁇ m, aspect ratio 100 or more LX703VL: Dick Dry LX-703VL, DIC Graphics Manufactured (polyester polyol having an aromatic skeleton), non-volatile content / 62%, adhesive Takenate 500 having no oxygen barrier property: manufactured by Mitsui Chemicals, Inc .: xylylene diisocyanate (XDI), non-volatile content / 100% Takenate D110N: Takenate D-110N (Mitsui Chemicals Co., Ltd .: XDI polyisocyanate (having an aromatic ring), nonvolatile content / 75%
  • BASONAT HA-300 manufactured by BASF, HDI polyisocyanate (aliphatic, without alicyclic skeleton), non-vol
  • TDI polyisocyanate aromatic
  • KR90 manufactured by DIC Graphics, aliphatic polyisocyanate (aliphatic, without alicyclic skeleton), non-volatile content / 90%
  • VM-PET 1310: Toray Film Processing Co., Ltd., aluminum vapor-deposited PET film, 12 ⁇ m NCO compound: Polyisocyanate compound
  • the gas barrier adhesive resin composition prepared according to Table 1 is a 12 ⁇ m thick aluminum vapor-deposited PET film (Toray film processability) so that the coating amount is 3.5 g / m 2 (solid content).
  • a 12 ⁇ m aluminum vapor-deposited PET film (“1310” manufactured by Toray Film Processability Co., Ltd.) was laminated with an aluminum vapor-deposited surface to prepare a composite film having a layer structure of aluminum vapor-deposited PET film / adhesive layer / aluminum vapor-deposited PET film.
  • the composite film was aged at 25 ° C./1 day, further aged at 50 ° C./3 days, and the adhesive was cured to obtain a laminate of the present invention.
  • the gas barrier adhesive resin composition prepared according to Table 1 is applied to the non-corona-treated surface of the CPP film using an applicator, treated at a reduced pressure dryer at 25 ° C./1 day, and then treated at 50 ° C./3 days. Went.
  • the cured coating film was peeled off from the CPP film, and DSC822 manufactured by METTLER TOLEDO (based on JIS K 7121, ISO 3146: 1985). Differential scanning calorimetry was performed at a rate of temperature increase of 20 ° C./min, and the intersection of the baseline and the tangent at the inflection point was defined as the glass transition temperature (Tg).
  • the adhesive using the resin composition for gas barrier adhesives of the present invention has a good oxygen barrier property at high temperature, for example, for a protective film for solar cells, in addition to the adhesive for film laminate for the packaging material.
  • Desirable oxygen barrier properties such as adhesives for gas barrier substrates for display elements, adhesives for electronic materials such as adhesives for laminates for vacuum insulation materials, adhesives for building materials, adhesives for industrial materials, etc. If it is a use used, it can be used conveniently.

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Abstract

L'invention concerne une composition de résine pour adhésifs faisant barrière aux gaz qui comprend une résine (A) ayant deux groupes hydroxy ou plus dans la molécule et au moins un polyisocyanate (B) ayant deux groupes isocyanate ou plus, et qui donne un objet durci ayant une température de transition vitreuse dans la plage de 25 à 150 °C ; un adhésif comprenant la composition de résine ; et un stratifié comprenant une couche adhésive obtenue à partir de l'adhésif. Il est préférable que le polyisocyanate (B) comprenne un composé polyisocyanate (b1) ayant une fonctionnalité de deux ou plus et ayant un cycle aromatique dans la molécule. Il est préférable que la résine (A) ait une structure polyester, polyester-polyuréthane, polyéther ou polyéther-polyuréthane en tant que squelette principal.
PCT/JP2017/042550 2016-12-05 2017-11-28 Composition de résine pour adhésif faisant barrière aux gaz, adhésif et stratifié Ceased WO2018105440A1 (fr)

Priority Applications (1)

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JP2018517231A JPWO2018105440A1 (ja) 2016-12-05 2017-11-28 ガスバリア性接着剤用樹脂組成物、接着剤、及び積層体

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020084130A (ja) * 2018-11-30 2020-06-04 東洋インキＳｃホールディングス株式会社 複合フィルムからの脱離性を有するラミネート接着剤、積層体、及びシート状基材のリサイクル方法
CN116507691A (zh) * 2020-11-20 2023-07-28 东洋油墨Sc控股株式会社 无溶剂型反应性粘接剂、其硬化物及层叠体
WO2025041720A1 (fr) * 2023-08-23 2025-02-27 三井化学株式会社 Composition de polyisocyanate, composition polymérisable, résine, corps moulé, élément optique et lentille

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013027609A1 (fr) * 2011-08-24 2013-02-28 Dic株式会社 Composition de résine pour adhésifs contenant un composé inorganique en forme de plaque, et adhésif
JP2013123814A (ja) * 2011-12-13 2013-06-24 Dic Corp バリア性ラミネートフィルム及びこれを用いる包装材
JP2015016657A (ja) * 2013-07-12 2015-01-29 Dic株式会社 ガスバリア多層フィルム

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4534341B2 (ja) * 2000-11-07 2010-09-01 Ｊｓｒ株式会社 硬化性樹脂組成物および反射防止膜
WO2011162160A1 (fr) * 2010-06-21 2011-12-29 Dic株式会社 Film doté de propriétés de barrière d'oxygène, et adhésif
JP2012255096A (ja) * 2011-06-09 2012-12-27 Hitachi Chemical Co Ltd 熱硬化型バリア性ポリウレタン樹脂組成物及びそれを用いた硬化物、光学部材、光半導体装置
JP5201429B2 (ja) * 2011-07-13 2013-06-05 Ｄｉｃ株式会社 酸素バリア性接着剤用樹脂組成物、接着剤、及び積層体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013027609A1 (fr) * 2011-08-24 2013-02-28 Dic株式会社 Composition de résine pour adhésifs contenant un composé inorganique en forme de plaque, et adhésif
JP2013123814A (ja) * 2011-12-13 2013-06-24 Dic Corp バリア性ラミネートフィルム及びこれを用いる包装材
JP2015016657A (ja) * 2013-07-12 2015-01-29 Dic株式会社 ガスバリア多層フィルム

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020084130A (ja) * 2018-11-30 2020-06-04 東洋インキＳｃホールディングス株式会社 複合フィルムからの脱離性を有するラミネート接着剤、積層体、及びシート状基材のリサイクル方法
CN116507691A (zh) * 2020-11-20 2023-07-28 东洋油墨Sc控股株式会社 无溶剂型反应性粘接剂、其硬化物及层叠体
WO2025041720A1 (fr) * 2023-08-23 2025-02-27 三井化学株式会社 Composition de polyisocyanate, composition polymérisable, résine, corps moulé, élément optique et lentille

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