Two-component curing gas barrier composition, coating agent, adhesive, film and laminate

Abstract

To provide a two-component curable gas barrier composition that allows for improved gas barrier properties such as an oxygen barrier property and a water vapor barrier property as well as improved adhesion, a coating agent and an adhesive each including the two-component curable gas barrier composition, a film including a cured product of the two-component curable gas barrier composition, and a laminate that includes a barrier layer including a cured product of the two-component curable gas barrier composition.SOLUTION: A two-component curable gas barrier composition includes an A agent and a B agent. The A agent includes a polythiol adduct of an aromatic ring-containing polyisocyanate. The B agent includes a polyol and / or polythiol.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a two-component curing gas barrier composition, a coating agent and adhesive comprising the two-component curing gas barrier composition, and a film and laminate comprising a cured product of the two-component curing gas barrier composition. [Background technology]

[0002] Two-component polyurethane resin raw materials have been widely used in the fields of coating agents and adhesives. Two-component polyurethane resin raw materials contain a curing agent containing polyisocyanate and a base agent containing macropolyol separately. The curing agent and base agent are mixed immediately before use, then applied to an object and cured. This forms a polyurethane resin on the object.

[0003] As a curing agent for such a two-component polyurethane resin raw material, for example, a polyisocyanate composition containing an isocyanate derivative obtained by reacting xylylene diisocyanate with a methylolalkane has been proposed (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2015 / 115291 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the polyisocyanate composition described in Patent Document 1 has the drawback that its gas barrier properties, such as oxygen barrier property and water vapor barrier property, are insufficient.

[0006] The present invention provides a two-component curing gas barrier composition that can improve gas barrier properties such as oxygen barrier property and water vapor barrier property, a coating agent and adhesive comprising the two-component curing gas barrier composition, and a film and laminate that include a cured product of the two-component curing gas barrier composition. [Means for solving the problem]

[0007] The present invention [1] is a two-component curing gas barrier composition comprising a component A and a component B, wherein the component A comprises a polythiol adduct of an aromatic ring-containing polyisocyanate, and the component B comprises a polyol and / or a polythiol.

[0008] The present invention [2] includes the two-component curing gas barrier composition according to the above [1], in which the reaction product of the polythiol adduct of the aromatic ring-containing polyisocyanate with the polyol and / or polythiol contains 20 mass % or more of a thiourethane skeleton [—NH—CO—S—].

[0009] The present invention [3] includes a coating agent containing the two-component curing gas barrier composition described in [1] or [2] above.

[0010] The present invention [4] includes an adhesive containing the two-component curing gas barrier composition described in [1] or [2] above.

[0011] The present invention [5] includes a film comprising a cured product of the two-component curing gas barrier composition described in [1] or [2] above.

[0012] The present invention [6] includes a laminate comprising a substrate and a barrier layer, wherein the barrier layer comprises a cured product of the two-component curing gas barrier composition described in [1] or [2] above. [Effects of the Invention]

[0013] The two-component curing gas barrier composition of the present invention has a thiourethane skeleton [—NH—CO—S—] in the polythiol adduct of an aromatic ring-containing polyisocyanate. Therefore, the two-component curing gas barrier composition of the present invention can improve gas barrier properties such as oxygen barrier property and water vapor barrier property, and can also improve adhesive strength. Furthermore, because the two-component curing gas barrier composition of the present invention can improve gas barrier properties and adhesive strength, the coating agent and adhesive of the present invention can also achieve excellent gas barrier properties and improved adhesive strength. Furthermore, the film and laminate of the present invention contain a cured product of the two-component curing gas barrier composition, which can achieve excellent gas barrier properties and improved adhesive strength, and can therefore achieve excellent gas barrier properties and improved adhesive strength. DETAILED DESCRIPTION OF THE INVENTION

[0014] The two-component curing gas barrier composition of the present invention contains component A and component B.

[0015] Agent A contains, as an essential component, a polythiol adduct of an aromatic ring-containing polyisocyanate.

[0016] The polythiol adduct of an aromatic ring-containing polyisocyanate is an adduct in which an aromatic ring-containing polyisocyanate is added to a polythiol.

[0017] The polythiol adduct of aromatic ring-containing polyisocyanate can be obtained, for example, by subjecting aromatic ring-containing polyisocyanate to an addition reaction with polythiol.

[0018] The aromatic ring-containing polyisocyanate is a polyisocyanate that contains an aromatic ring in the molecular skeleton, and examples thereof include aromatic polyisocyanates and aromatic aliphatic polyisocyanates.

[0019] Examples of aromatic polyisocyanates include aromatic diisocyanates, such as tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), and 4,4'-diphenyl ether diisocyanate.

[0020] Examples of araliphatic polyisocyanates include araliphatic diisocyanates, such as xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or 1,4-tetramethyl xylylene diisocyanate or a mixture thereof) (TMXDI), and ω,ω'-diisocyanato-1,4-diethylbenzene.

[0021] These aromatic ring-containing polyisocyanates can be used alone or in combination of two or more kinds.

[0022] The aromatic ring-containing polyisocyanate is preferably an araliphatic polyisocyanate, more preferably an araliphatic diisocyanate, still more preferably xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), and particularly preferably 1,3-xylylene diisocyanate.

[0023] The polythiol has two or more mercapto groups (thiol groups), for example, six or less, preferably four or less mercapto groups (thiol groups).The polythiol most preferably has three mercapto groups (thiol groups).

[0024] The molecular weight of the polythiol is, for example, 50 or more, and, for example, 500 or less, preferably 400 or less, and more preferably 300 or less.

[0025] Examples of polythiols include difunctional thiols having two mercapto groups, trifunctional thiols having three mercapto groups, tetrafunctional thiols having four mercapto groups, pentafunctional thiols having five mercapto groups, hexafunctional thiols having six mercapto groups, and octafunctional thiols having eight mercapto groups.

[0026] Examples of bifunctional thiols include aliphatic bifunctional thiols, aromatic bifunctional thiols, heterocycle-containing bifunctional thiols, and bifunctional thiols containing a sulfur atom in addition to a mercapto group in one molecule.

[0027] Examples of aliphatic bifunctional thiols include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis(mercaptomethyl)-2,3-dithiol, and 1,1-bis(mercaptomethyl)-2,3-dithiol. bis(2-mercaptomethyl)cyclohexane, 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, bis(2-mercaptoethyl)ether, diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), 1,4-cyclohexanediol bis(2-mercaptoacetate), and 1,4-cyclohexanediol bis(3-mercaptopropionate).

[0028] Examples of aromatic bifunctional thiols include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2-bis(mercaptomethyleneoxy)benzene, 1,3-bis(mercaptomethyleneoxy)benzene, 1,4-bis(mercaptomethyleneoxy)benzene, 1,2-bis(mercaptoethyleneoxy)benzene, 1,3-bis(mercaptoethyleneoxy)benzene, 1,4-bis(mercaptoethyleneoxy)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, and 1,3-di(p-methoxyphenyl) Propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di(p-mercaptophenyl)pentane, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-dimethylbenzene Examples of suitable mercaptodiphenyls include 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,5-dichlorobenzene-1,3-dithiol, 1,3-di(p-chlorophenyl)propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene, and 2,3,4,6-tetrachloro-1,5-bis(mercaptomethyl)benzene.

[0029] Examples of heterocycle-containing bifunctional thiols include 2-methylamino-4,6-dithiol-sym-triazine, 2-ethylamino-4,6-dithiol-sym-triazine, 2-amino-4,6-dithiol-sym-triazine, 2-morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, and 2-thiobutyloxy-4,6-dithiol-sym-triazine.

[0030] Examples of bifunctional thiols containing a sulfur atom other than a mercapto group include bis(mercaptomethyl) sulfide, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) sulfide (bis(2-mercaptoethyl) sulfide (MES)), bis(mercaptoethyl) disulfide, bis(mercaptopropyl) sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2 -Bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydro Hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxypropyl sulfide bis(2-mercaptoacetate), hydroxypropyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3 -mercaptopropionate), hydroxypropyl disulfide bis(2-mercaptoacetate), hydroxypropyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol bis(3-mercaptopropionate), thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), 4,4-Thiodibutyric acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), 4,4-dithiodibutyric acid bis(2-mercaptoethyl ester), thiodiglycolic acid bis(2,3-dimercaptopropyl ester), 3,4-thiophenedithiol, bismuthiol, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(4,5-dimercaptopropyl ester) 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclopentane, 1,5-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2-(1,3-dithietanyl)]methyl-2,4-dithiapentane, 4,6-bis{3-[2-(1,3-dithietanyl)]methyl-5-mercapto-2,4-dithiapentylthio}-1,3-dithiane, 3,7-bis[2-(1,3-dithietanyl)]methyl ethanyl)]methyl-1,9-dimercapto-2,4,6,8-tetrathianonane, 4,5-bis{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-1,3-dithiolane, 2-{bis[4-(5-mercaptomethylthio-1,3-dithiolanyl)thio]methyl}-1,3-dithietane, 4-[4-(5-mercaptomethylthio-1,3-dithiolanyl)thio]-5-{1-[2-(1,3-dithietanyl)]-3-mercapto-2- Examples of the mercaptomethylthio include {mercaptopropylthio}-1,3-dithiolane, 2,4-bis(mercaptomethylthio)-1,3,5-trithiacyclohexane, bis(mercaptomethyl)methylthio-1,3,5-trithiacyclohexane, 2,4-bis(mercaptomethylthio)-1,3-dithiacyclopentane, 2-mercaptoethylthio-4-mercaptomethyl-1,3-dithiacyclopentane, and 2-(2,3-dimercaptopropylthio)-1,3-dithiacyclopentane.

[0031] Examples of trifunctional thiols include aliphatic trifunctional thiols, aromatic trifunctional thiols, and trifunctional thiols containing a sulfur atom in addition to a mercapto group in one molecule.

[0032] Examples of aliphatic trifunctional thiols include 1,2,3-propanetrithiol, 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), thiomalic acid bis(2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptopropionate), 3-mercapto-1,2-propanediol bis(2-mercaptoacetate), 3-mercapto- Examples include 1,2-propanediol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(2-mercaptoacetate), trimethylolethane tris(3-mercaptopropionate), glycerin tris(2-mercaptoacetate), and glycerin tris(3-mercaptopropionate).

[0033] Examples of aromatic trifunctional thiols include 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5 -tris(mercaptoethyl)benzene, 1,2,3-tris(mercaptomethyleneoxy)benzene, 1,2,4-tris(mercaptomethyleneoxy)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, 1,2,3-tris(mercaptoethyleneoxy)benzene, 1,2,4-tris(mercaptoethyleneoxy)benzene, and 1,3,5-tris(mercaptoethyleneoxy)benzene.

[0034] Examples of trifunctional thiols containing a sulfur atom in addition to a mercapto group include 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST), 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 4,6-bis[4-(6-mercaptomethylthio)-1,3- dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, tris(mercaptomethylthio)methane, tris(mercaptoethylthio)methane, 2,4,6-tris(mercaptomethylthio)-1,3,5-trithiacyclohexane, tris[(4-mercaptomethyl-2,5-dithiacyclohexyl-1-yl)methylthio]methane, 4-mercaptomethyl-2-(2,3-dimercaptopropylthio)-1,3-dithiacyclopentane, and 4-mercaptomethyl-2-(1,3-dimercapto-2-propylthio)-1,3-dithiacyclopentane.

[0035] Examples of tetrafunctional thiols include aliphatic tetrafunctional thiols, aromatic tetrafunctional thiols, and tetrafunctional thiols containing a sulfur atom in addition to a mercapto group in one molecule.

[0036] Aliphatic tetrafunctional thiols include, for example, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), and tetrakis(mercaptomethyl)methane.

[0037] Examples of aromatic tetrafunctional thiols include 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene, 1,2,3,5-tetrakis(mercaptomethyl)benzene, 1,2,4,5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptoethyl)benzene, 1,2, Examples include 4,5-tetrakis(mercaptoethyl)benzene, 1,2,3,4-tetrakis(mercaptomethyleneoxy)benzene, 1,2,3,5-tetrakis(mercaptomethyleneoxy)benzene, 1,2,4,5-tetrakis(mercaptomethyleneoxy)benzene, 1,2,3,4-tetrakis(mercaptoethyleneoxy)benzene, 1,2,3,5-tetrakis(mercaptoethyleneoxy)benzene, and 1,2,4,5-tetrakis(mercaptoethyleneoxy)benzene.

[0038] Examples of aliphatic tetrafunctional thiols containing a sulfur atom in addition to a mercapto group include 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimethylamino ... mercaptopropyl) sulfide, thiodipropionic acid bis(2,3-dimercaptopropyl ester), dithiodiglycolic acid bis(2,3-dimercaptopropyl ester), thiodipropionic acid bis(2,3-dimercaptopropyl ester), dithiodipropionic acid bis(2,3-dimercaptopropyl ester), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)propane Trachys(mercaptomethylthio)-3,4-dithiahexane, 2,5-bis(4,4-bis(mercaptomethylthio)-2-thiabutyl)-1,4-dithiane, 2,2-bis(mercaptomethylthio)-1,3-propanedithiol, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithiahexane Nylthio]-1,3-bis(mercaptomethylthio)propane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, 1,1,5,5-tetrakis(mercaptomethylthio)-2,4-dithiapentane, and 1,1,3,3-tetrakis(mercaptomethylthio)-2-thiapropane.

[0039] An example of the pentafunctional thiol is a pentafunctional thiol containing a sulfur atom in addition to a mercapto group in one molecule.

[0040] Examples of pentafunctional thiols containing a sulfur atom in addition to a mercapto group include 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane and bis[4,4-bis(mercaptomethylthio)-1,3-dithiabutyl]-(mercaptomethylthio)methane.

[0041] An example of the hexafunctional thiol is a hexafunctional thiol containing a sulfur atom in addition to a mercapto group in one molecule.

[0042] Examples of hexafunctional thiols containing a sulfur atom in addition to a mercapto group include 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,4,8,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl ...5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-5 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl ]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithietane, 2-[3,4,8, 9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, tris[4,4-bis(mercaptomethylthio)-1,3-dithiabutyl]methane, tris[2,2-bis(mercaptomethylthio)-2-thiapropyl]methane, tris[4,4-bis(mercaptomethylthio)-3-thiabutyl]methane and 2,4,6-tris[3,3-bis(mercaptomethylthio)-2-thiapropyl]-1,3,5-trithiacyclohexane.

[0043] An example of the octafunctional thiol is an octafunctional thiol containing a sulfur atom in addition to a mercapto group in one molecule.

[0044] Examples of octafunctional thiols containing sulfur atoms in addition to mercapto groups include tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, and tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane. Examples include tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, and tetrakis[3,3-bis(mercaptomethylthio)-2-thiapropyl]methane.

[0045] Furthermore, the polythiol may be a halogen-substituted product of the above-mentioned polythiol. Examples of the halogen-substituted product of the above-mentioned polythiol include a chlorine-substituted product of the above-mentioned polythiol and a bromine-substituted product of the above-mentioned polythiol.

[0046] The polythiol is not limited to the above-mentioned exemplary compounds.

[0047] The polythiol is preferably a difunctional thiol, a trifunctional thiol, or a tetrafunctional thiol, more preferably a trifunctional thiol or a tetrafunctional thiol, even more preferably a trifunctional thiol, particularly preferably a trifunctional thiol containing a sulfur atom in addition to a mercapto group in one molecule, and most preferably 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST).

[0048] These polythiols can be used alone or in combination of two or more kinds.

[0049] The addition reaction of the aromatic ring-containing polyisocyanate to the polythiol is carried out, for example, by subjecting the aromatic ring-containing polyisocyanate and the polythiol to a thiourethanization reaction in the presence of a zinc-containing catalyst so that the equivalent ratio of isocyanate groups to mercapto groups ([NCO] / [SH]) falls within the range described below.

[0050] The equivalent ratio of isocyanate groups to mercapto groups ([NCO] / [SH]) is greater than 1, 2.0 or more, preferably 3.0 or more, and for example, 12.0 or less, preferably 8.0 or less, more preferably 7.0 or less.

[0051] The thiourethanization reaction is carried out, for example, in an inert gas atmosphere such as nitrogen gas under normal pressure (atmospheric pressure). The reaction temperature is, for example, 50° C. or higher, preferably 70° C. or higher, and, for example, 100° C. or lower, preferably 90° C. or lower. The reaction time is, for example, 2 hours or higher, preferably 4 hours or higher, and, for example, 72 hours or lower, preferably 24 hours or lower.

[0052] In this reaction, preferably, unreacted aromatic ring-containing polyisocyanate is removed from the reaction mixture.

[0053] Examples of methods for removing unreacted aromatic ring-containing polyisocyanate include distillation methods such as thin film distillation and extraction purification methods such as liquid-liquid extraction.

[0054] In the thin film distillation method, the reaction liquid containing the remaining aromatic ring-containing polyisocyanate is distilled using a thin film still.

[0055] In the liquid-liquid extraction method, an extraction solvent (for example, an organic solvent) is brought into contact with the reaction liquid containing the remaining aromatic ring-containing polyisocyanate. This separates the aromatic ring-containing polyisocyanate from the reaction product. The liquid-liquid extraction method can be carried out in accordance with the description in paragraphs

[0026] to

[0034] of JP 2010-265364 A.

[0056] A preferred method for removing the unreacted aromatic ring-containing polyisocyanate is liquid-liquid extraction. Note that a portion of the extraction solvent may be used as it is to dilute the reaction product (adduct).

[0057] The isocyanate group concentration (isocyanate group content) of the polythiol adduct of aromatic ring-containing polyisocyanate obtained in this manner is, for example, 5.0 mass% or more, preferably 10.0 mass% or more, and for example, 30.0 mass% or less, preferably 20.0 mass% or less, more preferably 15.0 mass% or less. The isocyanate group concentration can be measured using a potentiometric titrator by the n-dibutylamine method in accordance with JIS K-1556 (the same applies hereinafter).

[0058] The average number of functional groups in the polythiol adduct of aromatic ring-containing polyisocyanate is, for example, 2.0 or more, preferably 2.5 or more, and for example, 6 or less, preferably 4 or less, more preferably 3 or less. The average number of functional groups corresponds to the number of functional groups in the polythiol.

[0059] When prepared as a solution as described below, the content of the polythiol adduct of aromatic ring-containing polyisocyanate in Component A is, for example, 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, and for example, 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less.

[0060] The component A may contain unreacted aromatic ring-containing polyisocyanate as an optional component. The content of unreacted aromatic ring-containing polyisocyanate in the component A is, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less. Most preferably, the component A does not contain unreacted aromatic ring-containing polyisocyanate.

[0061] Agent A can be prepared as a solution. When preparing it as a solution, the polythiol adduct of aromatic ring-containing polyisocyanate is diluted with a known organic solvent.

[0062] Examples of the organic solvent include ketones, nitriles, alkyl esters, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, glycol ether esters, ethers, halogenated aliphatic hydrocarbons, and polar aprotic solvents. The organic solvent is preferably an alkyl ester or an aliphatic hydrocarbon, more preferably ethyl acetate or hexane.

[0063] The solids concentration of agent A is, for example, 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, and for example, 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less.

[0064] In the solid content of Agent A, the thiourethane skeleton (described below) is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 12% by mass or more, and for example, 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less.

[0065] The agent B contains a polyol and / or a polythiol as an essential component.

[0066] The polyol has two or more hydroxy groups (hydroxyl groups), for example, four or less, preferably three or less hydroxy groups, and most preferably two hydroxy groups.

[0067] The molecular weight of the polyol is, for example, 50 or more, and, for example, 500 or less, preferably 400 or less, and more preferably 300 or less.

[0068] Examples of polyols include dihydric alcohols, trihydric alcohols, and tetrahydric alcohols.

[0069] Dihydric alcohols include alkanediols, etherdiols, and alkenediols.

[0070] Examples of alkanediols include ethylene glycol (EG), propylene glycol (1,2- or 1,3-propanediol or a mixture thereof), butylene glycol (1,2-, 1,3-, or 1,4-butanediol or a mixture thereof), 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 1,3- or 1,4-cyclohexanediol.

[0071] Ether diols include, for example, diethylene glycol, triethylene glycol, and dipropylene glycol.

[0072] Alkenediols include, for example, 1,4-dihydroxy-2-butene.

[0073] Examples of trihydric alcohols include glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolpropane, and 2,2-bis(hydroxymethyl)-3-butanol.

[0074] Examples of tetrahydric alcohols include tetramethylolmethane (pentaerythritol) and diglycerin.

[0075] The polyol is preferably a dihydric alcohol or a trihydric alcohol, more preferably a dihydric alcohol, further preferably an alkanediol, and particularly preferably ethylene glycol (EG).

[0076] Such polyols can be used alone or in combination of two or more kinds.

[0077] The polythiol may be any of the polythiols described above.

[0078] When a polythiol is used in Agent B, preferably, a bifunctional thiol, a trifunctional thiol, and a tetrafunctional thiol are used, more preferably, a bifunctional thiol and a trifunctional thiol are used, even more preferably, a bifunctional thiol is used, particularly preferably, a bifunctional thiol containing a sulfur atom other than a mercapto group is used, and most preferably, bis(2-mercaptoethyl) sulfide (MES) is used.

[0079] The component B contains a polyol and / or a polythiol, and preferably contains a polyol.

[0080] The polyol and / or polythiol contained in component B may be used as is without diluting with a known organic solvent. In this case, the content of the polyol and / or polythiol in component B is, for example, 90% by mass or more, preferably 95% by mass or more, and more preferably 100%.

[0081] The component B may be prepared as a solution. When preparing the component B as a solution, the polyol and / or polythiol is diluted with a known organic solvent. The solids concentration of the component B prepared as a solution is the same as the solids concentration of the component A.

[0082] In the two-component curing gas barrier composition, known additives such as phosphorus oxyacids or derivatives thereof, silane coupling agents, antifoaming agents, epoxy resins, catalysts, coatability improvers, leveling agents, stabilizers (antioxidants, ultraviolet absorbers, etc.), plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, and antifungal agents may be appropriately blended into component A and / or component B as needed.

[0083] The additives may be added to the above-mentioned agent A and / or agent B in advance, or may be added to the agent A and agent B after mixing them. After mixing, the mixture can be added to the mixture.

[0084] The amount of the additives to be added is determined appropriately depending on the purpose and application.

[0085] In the two-component curing gas barrier composition, component A (curing agent) and component B (main component) are prepared separately and mixed together at the time of use.

[0086] When the component A (curing agent) and the component B (main component) are mixed at the time of use, an organic solvent may be mixed at the time of use.

[0087] In the two-component curing gas barrier composition, the content of the organic solvent is appropriately set so that the total amount of the solid content of the components A and B is a predetermined ratio.

[0088] When using a two-component curing gas barrier composition, the blending ratio of component A (curing agent) to component B (main component) is, for example, the equivalent ratio R(NCO / (OH and SH)) of the isocyanate groups (NCO) in component A (curing agent) to the total of the hydroxyl groups (OH) and mercapto groups (SH) in component B (main component), of, for example, 0.6 or more, preferably 0.8 or more, more preferably more than 1.0, and for example, 1.4 or less, preferably 1.2 or less.

[0089] When components A and B are blended, the polythiol adduct of aromatic ring-containing polyisocyanate in component A and the polyol and / or polythiol in component B undergo a curing reaction to produce a cured product.

[0090] The curing temperature in the curing reaction is, for example, 20°C or more, preferably 40°C or more, and for example, 100°C or less, preferably 80°C or less.

[0091] The curing time in the curing reaction is, for example, 2 hours or more, preferably 4 hours or more, and for example, 72 hours or less, preferably 48 hours or less.

[0092] The concentration of the thiourethane skeleton [—NH—CO—S—] (hereinafter sometimes referred to as the thiourethane group concentration) in the reaction product (cured product) of the polythiol adduct of aromatic ring-containing polyisocyanate (Component A) and the polyol and / or polythiol (Component B) is, for example, 20% by mass or more, preferably 22.5% by mass or more, more preferably 25% by mass or more, and for example, 50% by mass or less, more preferably 40% by mass or less, even more preferably 39% by mass or less, particularly preferably 35% by mass or less, and most preferably 30% by mass or less. If the concentration of the thiourethane skeleton [—NH—CO—S—] is within the above range, it is possible to improve gas barrier properties such as oxygen barrier property and water vapor barrier property, and to improve adhesive strength.

[0093] The thiourethane group concentration is determined by the ratio of the raw material components (Equivalent ratio of component A and component B), solid content and isocyanate group concentration of component A It can be calculated from

[0094] The thiourethane skeleton [-NH-CO-S-] is formed by replacing some of the oxygen atoms in the urethane bond with sulfur.

[0095] The cured product thus obtained can have improved gas barrier properties such as oxygen barrier property and water vapor barrier property, and improved adhesive strength.

[0096] In addition, the "gas barrier property" of a two-component curing gas barrier composition means that the oxygen permeability based on JIS K 7126 (2006) is 40 cc / m for a coating film alone with a dry thickness of 3 μm. 2·day·atm or less, and the water vapor permeability based on JIS K 6404-15 (1999) is 45 g / m for a dry thickness of 3 μm. 2 It is defined as being less than or equal to d.

[0097] The two-component curing gas barrier composition can be used in various industrial fields without any particular limitation. Specifically, it can be used for coating agents, adhesives, films, and laminates. It can be preferably used for coating agents and adhesives.

[0098] Such a coating agent includes, and preferably consists of, a two-component curing gas barrier composition, and is applied to a substrate, followed by drying and curing to form a coating layer on the substrate.

[0099] The coating layer thus formed is a film obtained by drying and curing the two-component curing gas barrier composition. In other words, the film contains a cured product of the two-component curing gas barrier composition, and preferably consists of a cured product of the two-component curing gas barrier composition. The film may be separated from the substrate.

[0100] The adhesive contains a two-component curing gas barrier composition, preferably a two-component curing gas barrier composition, which is applied to one adherend, dried, and then attached to the other adherend, followed by curing.

[0101] The laminate includes a substrate and a barrier layer. The barrier layer includes a cured product of a two-component curing gas barrier composition, and preferably consists of a cured product of a two-component curing gas barrier composition. In this laminate, the coating layer corresponds to the barrier layer in the laminate of the substrate and the coating layer described above.

[0102] The substrate is not particularly limited, but examples thereof include paper, cloth, leather, resin sheets, rubber sheets, foams, metal foils, and wood. [Example]

[0103] The present invention will be specifically described below with reference to examples. The present invention is not limited to the examples. In addition, the specific amounts (contents), physical properties, parameters, etc. described below The objective values correspond to those described in the "Description of the Invention" above. The upper limit of the compounding amount (content), physical property value, parameter, etc. (as "less than" or "less than") a defined number) or a lower limit (a number defined as "greater than or equal to" or "exceeds" ) can be substituted.

[0104] [Synthesis Example 1] In the presence of zinc bis(dibutyldithiocarbamate) zinc (ZnBTC) as a zinc-containing catalyst, 4-mercaptomethyl-1,8-dimercapto-3,6-diaoctane (GST) as a polythiol and m-xylene diisocyanate (XDI) were subjected to thiourethanation. The equivalent ratio of the isocyanate groups of XDI to the mercapto groups of GST ([NCO] / [SH]) was set to 6.0. Specifically, 650.2 parts by mass of XDI was charged into a four-neck flask equipped with a stirrer, thermometer, nitrogen inlet line, and dropping funnel, and stirring was initiated. Next, 7.5 parts by mass of a propylene glycol dimethyl ether solution of ZnBTC (concentration 0.1% by mass) was added to the flask, and the reaction solution was heated to an internal temperature of 80°C. 100 parts by mass of GST was added to the flask using the dropping funnel over 30 minutes, and the internal temperature was maintained at 80°C and stirred for 24 hours. Next, 200 parts by mass of ethyl acetate was added and stirred for 30 minutes while maintaining the internal temperature at 50°C. 575 parts by mass of hexane was added to the mixed solution and stirred for another 30 minutes. As a result, the residual monomer XDI was dissolved in hexane, and the isocyanate derivative (aromatic ring-containing polyisocyanate polythiol adduct) was dissolved in ethyl acetate. After that, the stirring was stopped and the mixture was left to stand for 30 minutes, and the upper layer (hexane layer) of the separated two layers was aspirated. After repeating the same procedure 10 times, the lower layer (ethyl acetate layer) was collected. Thereafter, the collected ethyl acetate layer was diluted with ethyl acetate to obtain a thiourethane group-containing polyisocyanate composition PI-1 (isocyanate group content: 6.7% by mass, solid content: 53% by mass). 。

[0105] Example 1 The polyisocyanate composition PI-1 prepared in Synthesis Example 1 was used as Agent A. Ethylene glycol was also prepared as Agent B. Next, components A and B were added and stirred so that the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate composition PI-1 to the hydroxyl groups of the ethylene glycol (EG) was 1.1, to prepare a coating liquid (two-component curing gas barrier composition). The coating solution was then applied to a 12 μm thick PET film using a dry laminator so that the dry solid thickness was 3 μm, and the film was then placed in an oven at 110°C for 1 minute to volatilize the ethyl acetate and form a gas barrier layer. The film was then cured at room temperature under a nitrogen atmosphere for 1 week. This resulted in a laminate (coated film) with a gas barrier layer as the coating layer. In this case, the coating solution was a coating agent. The coating liquid was then applied to a first film (OPP (biaxially oriented polypropylene film) 20 μm thick, PET 12 μm thick) so that the dry solid thickness would be 3 μm, and the solvent was then evaporated using a dryer. A second film (CPP (unoriented polypropylene film) 20 μm thick) was then attached, and the ethyl acetate was evaporated to obtain a laminate (laminate film) with a gas barrier layer as an adhesive layer. The film was then aged at 40°C for 2 days. In this case, the coating liquid was the adhesive. In this case, if the mass proportion of thiourethane groups in the solid components of PI-1 is 27.3%, the mass proportion of thiourethane groups contained in the obtained gas barrier layer is 25.1% by mass.

[0106] Example 2 A laminate (coated film, laminate film) having a gas barrier layer was obtained in the same manner as in Example 1, except that the agent B was changed to bis(2-mercaptoethyl) sulfide (MES). In this case, if the mass proportion of thiourethane groups in the solid components of PI-1 is 27.3%, the mass proportion of thiourethane groups contained in the obtained gas barrier layer is 39.5% by mass.

[0107] Comparative Example 1 A laminate (coated film, laminated film) having a gas barrier layer was obtained in the same manner as in Example 1, except that the agent A was changed to Takenate D-110N (TMP (trimethylolpropane) adduct of XDI, isocyanate group content 11.5 mass%, solid content 75 mass%, solvent: ethyl acetate, manufactured by Mitsui Chemicals, Inc.). The mass proportion of thiourethane groups contained in the obtained gas barrier layer was 0 mass %.

[0108] Comparative Example 2 A laminate (coated film, laminated film) having a gas barrier layer was obtained in the same manner as in Example 1, except that Agent A was changed to Takenate D-110N and Agent B was changed to bis(2-mercaptoethyl) sulfide (MES). The mass proportion of thiourethane groups contained in the obtained gas barrier layer was 19.6 mass %.

[0109] Table 1 shows the mass proportions of thiourethane groups contained in the agents A and B used, and in the gas barrier layers obtained in each example and comparative example.

[0110] In Example 2 and Comparative Example 2, it was assumed that thiourethane groups were ideally formed from thiol groups contained in Agent B, and the thiourethane group concentration was calculated from the sum of the weight of thiourethane groups contained in Agent A and the weight of thiourethane groups formed by the reaction of Agent A and Agent B, and the sum of the solid weight of Agent A and Agent B.

[0111] [Evaluation Method] The laminate was evaluated according to the following method. The results are shown in Table 1.

[0112] <Coatability (Appearance)> The appearance of the laminate of each example and each comparative example was visually observed to confirm the presence or absence of coating defects such as peeling and streaks. In Table 1, the case without coating defects is indicated as "good".

[0113] <Oxygen Barrier Property (OTR)> Regarding the coating film of each example and each comparative example, the oxygen permeability based on JIS K 7126 (2006) was measured using an oxygen permeability measuring device (manufactured by MOCON, OX-TRAN 2 / 20) under the conditions of 20 °C and relative humidity of 80% (80% RH). The oxygen permeation amount was measured as the permeation amount per 1 m 2 , per day and per atmospheric pressure.

[0114] <Water Vapor Barrier Property (WVTR)> Regarding the coating film of each example and each comparative example, the water vapor permeability was measured in accordance with JIS K 6404-15 (1999). The test conditions were 40 °C and relative humidity of 90% (90% RH), and the water vapor permeation amount was measured as the permeation amount per 1 m 2 , per day.

[0115] <T-Peel Adhesion> Test samples in the form of long strips (width: 15 mm, length: 150 mm) were cut out from the laminate films of each example and each comparative example. Then, in accordance with JIS K 6854-3 (1999), a T-peel test was performed on the test samples using a universal tensile measuring device at a crosshead speed of 300 mm / min to measure the adhesion strength of the laminate. In Table 1, "MF" indicates substrate breakage (film breakage).

[0116] The details of the abbreviations in the table are as follows. Takenate D-110N: TMP adduct of XDI, isocyanate group content 11.5% by mass, solid content 75% by mass, solvent: ethyl acetate, manufactured by Mitsui Chemicals EG: Ethylene glycol MES: Bis(2-mercaptoethyl) sulfide OPP: Biaxially oriented polypropylene film CPP: Unstretched polypropylene film PET: Polyethylene terephthalate film

[0117] [Table 1]

Claims

1. A two-component curing gas barrier composition comprising a component A and a component B, The agent A is It contains a polythiol adduct of an aromatic ring-containing polyisocyanate, The agent B is containing a polyol and / or a polythiol, the reaction product of the polythiol adduct of the aromatic ring-containing polyisocyanate with the polyol and / or polythiol contains 20 mass% or more of a thiourethane skeleton [—NH—CO—S—], The concentration of the thiourethane skeleton [—NH—CO—S—] is calculated from the charge ratio of the raw material components (equivalent ratio of component A and component B), the solids concentration of component A, and the isocyanate group concentration. A two-component curing gas barrier composition.

2. A coating agent comprising the two-component curing gas barrier composition according to claim 1.

3. An adhesive comprising the two-component curing gas barrier composition according to claim 1.

4. A film comprising a cured product of the two-component curing gas barrier composition according to claim 1.

5. a substrate and a barrier layer, A laminate, wherein the barrier layer comprises a cured product of the two-component curing gas barrier composition according to claim 1.

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