JP2021024986A - Gas barrier polyurethane resin composition and laminate - Google Patents

Abstract

To provide a gas barrier polyurethane resin composition capable of imparting excellent gas barrier properties to a gas barrier layer while suppressing occurrence of coating failure, and a laminate obtained by the gas barrier polyurethane resin composition.SOLUTION: A gas barrier polyurethane resin composition includes a polyisocyanate component containing an aromatic ring-containing polyfunctional isocyanate derivative and an active hydrogen group-containing component containing a polyol, and the aromatic ring-containing polyfunctional isocyanate derivative is modified with a monofunctional active hydrogen group-containing compound having 1 to 8 carbon atoms, alternatively, a monofunctional active hydrogen group-containing compound is further contained in the active hydrogen group-containing component, and the molar ratio of the monofunctional active hydrogen group-containing compound to the polyol is adjusted to 0.1 or more to 2.8 or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a gas barrier polyurethane resin composition and a laminate.

In the field of packaging materials, it is known that a gas barrier layer is formed on various films such as a plastic film to impart gas barrier properties to the packaging material.

As a material for such a gas barrier layer, for example, ethylene glycol as an active hydrogen-containing compound and a reaction product of xylylene diisocyanate and trimethylolpropane as an organic polyisocyanate compound are mixed, and the solid content concentration is adjusted with an organic solvent. A prepared polyurethane resin composition has been proposed (see, for example, Patent Document 1 (Example 11)).

Such a polyurethane resin composition is applied to a film as a coating liquid and then dried to form a gas barrier layer.

Japanese Unexamined Patent Publication No. 2004-10656

However, when the polyurethane resin composition described in Patent Document 1 is applied to a film, there is a problem that application defects such as streaks and omissions occur.

The present invention provides a gas barrier polyurethane resin composition capable of imparting excellent gas barrier properties to the gas barrier layer while suppressing the occurrence of coating defects, and a laminate obtained by the gas barrier polyurethane resin composition.

The present invention [1] contains a polyisocyanate component containing an aromatic ring-containing polyfunctional isocyanate derivative and an active hydrogen group-containing component containing a polyol, and the aromatic ring-containing polyfunctional isocyanate derivative has 1 to 1 carbon atoms. It has been modified with the monofunctional active hydrogen group-containing compound of 8, or the active hydrogen group-containing component further contains the monofunctional active hydrogen group-containing compound, and mol of the monofunctional active hydrogen group-containing compound with respect to the polyol. It contains a gas barrier polyurethane resin composition having a ratio of 0.1 or more and 2.8 or less.

In the present invention [2], the polyol contains the gas-barrier polyurethane resin composition according to the above [1], which contains a urethane-modified polyol.

The present invention [3] includes the gas barrier polyurethane resin composition according to the above [1] or [2], wherein the monofunctional active hydrogen group-containing compound contains a monoalcohol.

In the present invention [4], the monoalcohol contains the gas-barrier polyurethane resin composition according to the above [3], which contains an aromatic aliphatic monoalcohol.

In the present invention [5], the monoalcohol contains the gas-barrier polyurethane resin composition according to the above [3], which contains an aliphatic monoalcohol.

The present invention [6] includes a film and a cured product of the gas barrier polyurethane resin composition according to any one of the above [1] to [5], and a gas barrier layer arranged on the film. Includes a laminate.

In the gas barrier polyurethane resin composition of the present invention, the aromatic ring-containing polyfunctional isocyanate derivative is modified with a monofunctional active hydrogen group-containing compound, or the active hydrogen group-containing component contains a monofunctional active hydrogen group-containing compound. The mol ratio of the monofunctional active hydrogen group-containing compound to the polyol is equal to or higher than the above lower limit.

Therefore, it is possible to suppress the occurrence of coating defects when the gas barrier polyurethane resin composition is applied to the film.

Further, the carbon number of the monofunctional active hydrogen group-containing compound is in the above range, and the mol ratio of the monofunctional active hydrogen group-containing compound to the polyol is not more than the above upper limit.

Therefore, excellent gas barrier properties can be imparted to the gas barrier layer containing the cured product of the gas barrier polyurethane resin composition.

The laminate of the present invention includes a gas barrier layer containing a cured product of the above-mentioned gas barrier polyurethane resin composition. Therefore, it is possible to improve the gas barrier property while improving the adhesion of the gas barrier layer to the film.

FIG. 1A is a schematic configuration diagram of a laminated film as a first embodiment of the laminated body of the present invention. FIG. 1B is a schematic configuration diagram of a coated film as a second embodiment of the laminate of the present invention. FIG. 1C is a schematic configuration diagram of a coated film as a third embodiment of the laminated body of the present invention.

The gas-barrier polyurethane resin composition of the present invention (hereinafter, simply referred to as a polyurethane resin composition) contains a polyisocyanate component and an active hydrogen group-containing component.

<First Embodiment>
In the first embodiment of the polyurethane resin composition, the polyisocyanate component contains an aromatic ring-containing polyfunctional isocyanate derivative, and the active hydrogen group-containing component contains a polyol and a monofunctional active hydrogen group-containing compound.

In the first embodiment, the polyisocyanate component contains an aromatic ring-containing polyfunctional isocyanate derivative as an essential component.

The aromatic ring-containing polyfunctional isocyanate derivative contains an aromatic ring in its molecular skeleton and has two or more, preferably three or more isocyanate groups. Specifically, the aromatic ring-containing polyfunctional isocyanate derivative is derived from the aromatic ring-containing isocyanate monomer.

Examples of the aromatic ring-containing isocyanate monomer include an aromatic polyisocyanate monomer and an aromatic aliphatic polyisocyanate monomer.

As the aromatic polyisocyanate monomer, for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylenediisocyanate (m-, p-phenylenediisocyanate or a mixture thereof), 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI) ), Aromatic diisocyanate monomers such as 4,4'-toluidine diisocyanate (TODI) and 4,4'-diphenyl ether diisocyanate.

As the aromatic aliphatic polyisocyanate monomer, for example, xylylene diisocyanate (1,3- or 1,4-xylene diisocyanate or a mixture thereof) (XDI), tetramethylxylene diisocyanate (1,3- or 1,4). -Tetramethylxylene diisocyanate or a mixture thereof) (TMXDI), aromatic aliphatic diisocyanate monomers such as ω, ω'-diisocyanate-1,4-diethylbenzene and the like can be mentioned.

The aromatic ring-containing isocyanate monomer can be used alone or in combination of two or more.

As the aromatic ring-containing polyfunctional isocyanate derivative, for example, a multimer of the above-mentioned aromatic ring-containing isocyanate monomer (for example, a dimer or a trimeric (for example, an isocyanurate modified product or an iminooxadiazidinedione modified product)). A pentamer, a tetramer, etc.), an allophanate modified product (for example, an allophanate modified product which is a reaction product of the above-mentioned aromatic ring-containing isocyanate monomer and a monovalent alcohol or a divalent alcohol (described later)). Polypoly modified product (for example, polyol modified product (alcohol adduct) which is a reaction product of the above-mentioned aromatic ring-containing isocyanate monomer and trivalent or higher alcohol (described later)), biuret modified product (for example, described above). Biuret modified product, which is a reaction product of an aromatic ring-containing isocyanate monomer and water or amines), urea modified product (for example, urea, which is a reaction product of the above-mentioned aromatic ring-containing isocyanate monomer and diamine). Modified products (such as modified products), oxadiazine trione modified products (for example, oxadiazine trione which is a reaction product of the above-mentioned aromatic ring-containing isocyanate monomer and carbon dioxide gas), carbodiimide modified products (for example, the above-mentioned aromatic ring-containing isocyanate). Carbodiimide modified products, which are products of the decarbonation condensation reaction of monomers), uretdione modified products, uretonimine modified products, and the like. Further, examples of the aromatic ring-containing isocyanate derivative include polymethylene polyphenylene polyisocyanate (Crude MDI, Polymeric MDI) and the like.

Examples of the monohydric alcohol include monohydric alcohols having 1 to 8 carbon atoms such as methanol, ethanol, propanol, butanol, and isobutyl alcohol, and isobutyl alcohol is preferable.

Examples of the dihydric alcohol include alkylene diols having 1 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, and 1,2-butylene glycol. For example, ether diols having 1 to 8 carbon atoms such as diethylene glycol and dipropylene glycol can be mentioned, preferably alkylene diols having 1 to 8 carbon atoms, and more preferably 1,3-butylene glycol. Be done.

Examples of trihydric or higher alcohols include trihydric alcohols such as glycerin and trimethylolpropane, tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin, and pentahydric alcohols such as xylitol. , Preferably trihydric alcohols, and more preferably trimethylolpropane (TMP).

In the following, alcohols having a divalent value or higher may be collectively referred to as a low molecular weight polyol. The low molecular weight polyol is, for example, a compound having two or more hydroxyl groups in the molecule and having a molecular weight of 50 or more and less than 300, preferably less than 400.

The average number of functional groups of the isocyanate group in the aromatic ring-containing polyfunctional isocyanate derivative is, for example, 2 or more, preferably 2.5 or more, for example, 4 or less, preferably 3.5 or less.

The content (NCO%) of the isocyanate group in the aromatic ring-containing polyfunctional isocyanate derivative is, for example, 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, for example, 40% by mass. Hereinafter, it is preferably 30% by mass or less.

The aromatic ring-containing polyfunctional isocyanate derivative can be used alone or in combination of two or more.

The aromatic ring-containing polyfunctional isocyanate derivative preferably includes a polyol-modified product of an aromatic ring-containing isocyanate monomer, more preferably a polyol-modified product of an aromatic aliphatic polyisocyanate monomer, and further preferably. , TMP adduct of aromatic aliphatic polyisocyanate monomer. Further, as the aromatic aliphatic polyisocyanate monomer, xylylene diisocyanate (XDI) is preferable.

That is, the polyisocyanate component preferably contains a modified polyol of XDI, and more preferably contains a TMP adduct of XDI.

In addition, the polyisocyanate component may contain other polyisocyanate as an optional component as long as the excellent effects of the present invention are not impaired.

Examples of other polyisocyanates include the above-mentioned aromatic ring-containing isocyanate monomer, aromatic ring-free isocyanate monomer, and aromatic ring-free isocyanate derivative.

The aromatic ring-free isocyanate monomer is a polyisocyanate having no aromatic ring in its molecular skeleton, and examples thereof include an aliphatic polyisocyanate monomer.

As the aliphatic polyisocyanate monomer, for example, ethylene diisocyanate, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Butylene diisocyanis), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanis, 2,6-diisamethylene methyl Examples thereof include aliphatic diisocyanates such as caproate and dodecamethylene diisocyanate.

In addition, the aliphatic polyisocyanate monomer includes an alicyclic polyisocyanate monomer. Examples of the alicyclic polyisocyanate monomer include 1,3-cyclopentanediisocyanate, 1,3-cyclopentenediisocyanate, cyclohexanediisocyanate (1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate), and 3-isocyanatomethyl. -3,5,5-trimethylcyclohexylisocyanate (isoholodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'-or 2,2'-methylenebis (cyclohexylisocyanate, Trans of these) , Trans-form, Trans, Cis-form, Cis, Cis-form, or a mixture thereof)) (H ₁₂ MDI), methylcyclohexanediisocyanate (methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate) , Norbornan diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof) (H ₆ XDI), etc. Examples include alicyclic diisocyanate.

The aromatic ring-free isocyanate derivative is derived from the aromatic ring-free isocyanate monomer. Examples of the aromatic ring-free isocyanate derivative include those similar to the above-mentioned aromatic ring-containing polyfunctional isocyanate derivative.

Other polyisocyanates can be used alone or in combination of two or more.

The content ratio of other polyisocyanates is appropriately set according to the purpose and application.

From the viewpoint of gas barrier property, the polyisocyanate component particularly preferably contains 10% by mass or less of other polyisocyanates, and most preferably does not contain other polyisocyanates and is composed of an aromatic ring-containing polyfunctional isocyanate derivative.

In the first embodiment, the active hydrogen group-containing component contains a polyol and a monofunctional active hydrogen group-containing compound as essential components.

The polyol contains two or more hydroxyl groups. Examples of the polyol include the above-mentioned low molecular weight polyol and the above-mentioned modified polyol obtained by modifying the above-mentioned low molecular weight polyol.

The low molecular weight polyol preferably includes a diol having 2 to 8 carbon atoms, more preferably a diol having 2 to 6 carbon atoms, and further preferably an alkylene diol having 2 to 6 carbon atoms such as ethylene glycol. , Etherdiol having 2 to 6 carbon atoms such as diethylene glycol, and the like, and ethylene glycol is particularly preferable.

Examples of the modified polyol include urethane-modified polyol, urea-modified polyol, urethane urea-modified polyol, and the like, and urethane-modified polyol is preferable.

The urethane-modified polyol is, for example, a reaction product of a polyisocyanate and the above-mentioned low molecular weight polyol, and has a hydroxyl group at the molecular end.

Examples of the polyisocyanate in the urethane-modified polyol include the above-mentioned aromatic ring-containing isocyanate monomer (for example, aromatic polyisocyanate monomer, aromatic aliphatic polyisocyanate monomer, etc.) and the above-mentioned aromatic ring-free isocyanate single amount. Examples include the body (for example, an aliphatic polyisocyanate monomer) and derivatives thereof.

The polyisocyanate in the urethane-modified polyol can be used alone or in combination of two or more.

Among the polyisocyanates in the urethane-modified polyol, preferably an aromatic ring-containing isocyanate monomer is mentioned, more preferably an aromatic polyisocyanate monomer is mentioned, and particularly preferably an aromatic diisocyanate monomer is used. Among them, particularly preferably, tolylene diisocyanate (TDI) is mentioned.

Examples of the low molecular weight polyol in the urethane-modified polyol include the above-mentioned dihydric alcohols, preferably alkylene diols having 2 to 8 carbon atoms and ether diols, and more preferably alkylene diols having 2 to 4 carbon atoms. And ether diols, more preferably alkylene diols having 2 to 4 carbon atoms, and more preferably a combination of ethylene glycol (EG) and 1,4-butylene glycol (1,4-BG). Can be mentioned.

Among such urethane-modified polyols, the reaction of diisocyanate (for example, aromatic diisocyanate monomer such as TDI) and the above-mentioned dihydric alcohol (for example, EG and 1,4-BG) is preferable. Examples thereof include urethane-modified diols produced by.

The average hydroxyl value of the urethane-modified polyol is, for example, 100 mgKOH / g or more, preferably 150 mgKOH / g or more, for example, 500 mgKOH / g or less, preferably 300 mgKOH / g or less. The average number of functional groups of the urethane-modified polyol can be calculated from the charged components, and the average hydroxyl value can be obtained from a known titration method (the same applies hereinafter).

The average number of functional groups of the polyol is 2 or more and 3 or less, preferably 2.

Such polyols can be used alone or in combination of two or more.

Among such polyols, preferably, dihydric alcohol and urethane-modified polyol are mentioned, more preferably urethane-modified polyol is mentioned, and further preferably urethane-modified diol is mentioned. That is, the polyol preferably contains a dihydric alcohol and / or a urethane-modified polyol, more preferably a urethane-modified polyol, and even more preferably a urethane-modified diol.

When the polyol contains a urethane-modified polyol, the viscosity of the polyurethane resin composition can be improved, and the thickness of the coating film formed by applying the polyurethane resin composition to the film can be made relatively thick.

The content ratio of the polyol is, for example, 1 part by mass or more, preferably 3 parts by mass or more, for example, 60 parts by mass or less, preferably 40 parts by mass or less, based on 100 parts by mass of the polyisocyanate component.

The monofunctional active hydrogen group-containing compound is an organic compound having 1 to 8 carbon atoms and has one active hydrogen group (for example, a hydroxyl group, an amino group, a thiol group, etc.).

When the number of carbon atoms of the monofunctional active hydrogen group-containing compound is not more than the above upper limit, the gas barrier property of the gas barrier layer described later can be improved.

Examples of the monofunctional active hydrogen group-containing compound include monoalcohol (monool), monoamine, and monothiol.

A monoalcohol is an organic compound having one hydroxyl group, for example, an aliphatic monoalcohol such as methanol, ethanol, propanol, isopropanol, butanol, octanol, and an alicyclic monoalcohol such as cyclohexanol, for example, benzyl. Examples include aromatic aliphatic monoalcohols such as alcohol.

A monoamine is a compound having one amino group and includes a primary monoamine having one primary amino group and a secondary monoamine having one secondary amino group.

As the primary monoamine, for example, an aliphatic primary monoamine such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, and octylamine, and an alicyclic primary monoamine such as cyclohexylamine, for example, an aroma such as benzylamine. Aliphatic primary monoamines and the like can be mentioned.

Examples of the secondary monoamine include aliphatic secondary monoamines such as dimethylamine, diethylamine, methylethylamine, dipropylamine, and diisopropylamine.

A monothiol is an organic compound having one thiol group, for example, an aliphatic monothiol such as methanethiol, ethanethiol, propanethiol, isopropanethiol, butanethiol, octanethiol, and a fat such as cyclohexanethiol. Examples include cyclic monothiols, such as aromatic aliphatic monothiols such as benzylthiol.

The molecular weight of the monofunctional active hydrogen group-containing compound is, for example, 30 or more, preferably 40 or more, more preferably 50 or more, still more preferably 80 or more, for example 150 or less, preferably 130 or less.

The monofunctional active hydrogen group-containing compound can be used alone or in combination of two or more.

The monofunctional active hydrogen group-containing compound preferably contains a monoalcohol and / or a monoamine, and more preferably contains a monoalcohol.

Further, the monoalcohol preferably contains an aromatic aliphatic monoalcohol from the viewpoint of coating workability of the polyurethane resin composition.

When the monofunctional active hydrogen group-containing compound contains an aromatic aliphatic monoalcohol, the viscosity of the polyurethane resin composition can be further improved, and the coating film formed by applying the polyurethane resin composition to the film is made thicker. be able to.

Further, the monoalcohol preferably contains an aliphatic monoalcohol from the viewpoint of gas barrier property.

When the monofunctional active hydrogen group-containing compound contains an aliphatic monoalcohol, the gas barrier property of the gas barrier layer described later can be improved.

The mol ratio of the monofunctional active hydrogen group-containing compound to the polyol (preferably diol) is 0.1 or more, preferably 0.2 or more, more preferably 0.5 or more and 2.8 or less, preferably. It is 2.0 or less, more preferably 1.5 or less, still more preferably 1.0 or less.

When the mol ratio of the monofunctional active hydrogen group-containing compound to the polyol is at least the above lower limit, it is possible to suppress the occurrence of coating defects when the polyurethane resin composition is applied to the film. When the mol ratio of the monofunctional active hydrogen group-containing compound to the polyol is not more than the above upper limit, excellent gas barrier properties can be imparted to the gas barrier layer described later.

The content ratio of the monofunctional active hydrogen group-containing compound is, for example, 0.3 parts by mass or more, preferably 1.0 part by mass or more, and more preferably 2.0 parts by mass with respect to 100 parts by mass of the polyisocyanate component. The above is particularly preferably 5.0 parts by mass or more, for example, 25 parts by mass or less, preferably 20 parts by mass or less, and more preferably 15 parts by mass or less.

Further, the active hydrogen group-containing component can contain a high molecular weight polyol as an optional component as long as the excellent effects of the present invention are not impaired.

The high molecular weight polyol is an organic compound having two or more hydroxyl groups and having a number average molecular weight of 400 or more, preferably 500 or more, and is, for example, a polyether polyol (for example, a polyoxyalkylene polyol such as polypropylene glycol, or a polytetra). Polyester polyol (eg, methylene ether polyol, etc.), polyester polyol (for example, adipic acid-based polyester polyol, phthalic acid-based polyester polyol, lactone-based polyester polyol, etc.), polycarbonate polyol, polyurethane polyol (for example, polyether polyol, polyester polyol, polycarbonate polyol, etc.) Polyester modified with isocyanate), epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, vinyl monomer modified polyol and the like.

The high molecular weight polyol can be used alone or in combination of two or more.

From the viewpoint of gas barrier properties, the content ratio of the high molecular weight polyol is, for example, 10 parts by mass or less, preferably 0 parts by mass, based on 100 parts by mass of the total amount of the active hydrogen group-containing components. That is, the active hydrogen group-containing component preferably does not contain a high molecular weight polyol.

In other words, the active hydrogen group-containing component is particularly preferably not containing a high molecular weight polyol, but is composed of a polyol and a monofunctional active hydrogen group-containing compound from the viewpoint of gas barrier properties.

Further, in the polyurethane resin composition, if necessary, either one or both of the polyisocyanate component and the active hydrogen group-containing component may be used, for example, an oxygen acid of phosphorus or a derivative thereof, or a silane coupling. Agents, antifoaming agents, epoxy resins, catalysts, coatability improvers, leveling agents, stabilizers (antioxidants, UV absorbers, etc.), plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, Additives such as antifungal agents can be appropriately added. The blending amount of the additive is appropriately determined depending on the purpose and use thereof.

Such a polyurethane resin composition is prepared, for example, as a two-component polyurethane resin raw material or a one-component polyurethane resin raw material.

In the two-component polyurethane resin raw material, the agent A (main agent) containing the above-mentioned polyisocyanate component and the agent B (curing agent) containing the above-mentioned active hydrogen group-containing component are separately prepared and blended at the time of use. To.

When a two-component polyurethane resin raw material is used, the blending ratio of the agent A and the agent B is, for example, the equivalent ratio R (NCO / active hydrogen group) of the isocyanate group of the polyisocyanate component to the active hydrogen group of the active hydrogen group-containing component. ) Is, for example, 0.5 to 5, preferably 0.6 to 3.

Examples of the one-component polyurethane resin raw material include a moisture-curable adhesive that is cured by moisture or steam (amine vapor or the like).

The one-component polyurethane resin raw material contains, for example, a urethane prepolymer having an isocyanate group at the molecular terminal, which is obtained by reacting the above-mentioned polyisocyanate component and the above-mentioned active hydrogen group-containing component. In order to prepare a urethane prepolymer, a polyisocyanate component and an active hydrogen group-containing component are blended so that the isocyanate group of the polyisocyanate component is excessive with respect to the active hydrogen group of the active hydrogen group-containing component. If necessary, the reaction is carried out in the presence of a known urethanization catalyst.

In the one-component polyurethane resin raw material, the blending ratio of the active hydrogen group-containing component and the polyisocyanate component is, for example, the equivalent ratio R (NCO / active hydrogen) of the isocyanate group of the polyisocyanate component to the active hydrogen group of the active hydrogen group-containing component. The group) is, for example, a ratio of more than 1, preferably 1.1 to 8.0, and more preferably 1.2 to 5.0. The reaction conditions are, for example, a reaction temperature of 50 to 140 ° C. and a reaction time of 1 to 5 hours under vacuum.

The urethane prepolymer thus obtained has an isocyanate group at the molecular terminal, and the isocyanate group can be cured by reacting with moisture or vapor (amine vapor or the like) in the atmosphere.

The polyurethane resin composition (two-component polyurethane resin raw material and one-component polyurethane resin raw material) preferably contains an organic solvent.

When the polyurethane resin composition is a two-component polyurethane resin raw material, the organic solvent may be blended in the agent A and / or the agent B, or may be separately blended when the agents A and B are blended. ..

When the organic solvent is blended in the agent A, the solid content concentration of the agent A is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, for example, 90% by mass or less. , Preferably 80% by mass or less.

When the organic solvent is blended in the agent A, the content (NCO%) of the isocyanate group in the agent A is, for example, 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass. As mentioned above, for example, it is 30% by mass or less, preferably 20% by mass or less.

When the organic solvent is blended in the agent B, the solid content concentration of the agent B is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, for example, 95% by mass or less. , Preferably 90% by mass or less.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, nitriles such as acetonitrile, alkyl esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate, for example n-hexane. , N-Heptane, octane and other aliphatic hydrocarbons, such as cyclohexane, methylcyclohexane and other alicyclic hydrocarbons, such as toluene, xylene, ethylbenzene and other aromatic hydrocarbons, such as methyl cellosolve acetate, Glycol ether esters such as ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate , For example, ethers such as diethyl ether, tetrahydrofuran, dioxane, for example, halogenated aliphatic hydrocarbons such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dichloroethane, for example, N. Examples thereof include polar aprotons such as -methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide and hexamethylphosphonylamide. The organic solvent can be used alone or in combination of two or more.

Among the organic solvents, alkyl esters are preferable, and ethyl acetate is more preferable.

In the polyurethane resin composition, the content ratio of the organic solvent is appropriately set so that the total amount of the solid content (resin solid content) of the polyisocyanate component and the active hydrogen group-containing component becomes a predetermined ratio.

The solid content concentration of the polyurethane resin composition is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, for example, 50% by mass or less, from the viewpoint of coating workability described later. It is preferably 40% by mass or less, more preferably 30% by mass or less.

The Zahn cup viscosity of such a polyurethane resin composition (containing an organic solvent) is, for example, 10.0 seconds or longer, preferably 11.0 seconds or longer, more preferably 11.3 seconds or longer, particularly at 25 ° C. Preferably, it is 12.0 seconds or more, for example, 15.0 seconds or less. The Zahn cup viscosity can be measured according to the method described in Examples described later.

When the viscosity of the Zahn cup is at least the above lower limit, the thickness of the coating film formed by applying the polyurethane resin composition to the film can be made relatively thick. When the viscosity of the Zahn cup is not more than the above upper limit, the coating liquid does not level and becomes bubbles, and there is no problem such as clogging when the coating liquid is circulated by the pump, and the coating workability can be improved.

<Laminated body>
The polyurethane resin composition described above is suitably used as a coating raw material for, for example, paints and adhesives. Examples of the laminate obtained by using the polyurethane resin composition include the laminate film 1 shown in FIG. 1A, the coat film 2 shown in FIG. 1B, and the coat film 3 shown in FIG. 1C.

As shown in FIG. 1A, the polyurethane resin composition of the laminate film 1 is used as an adhesive for lamination. That is, the polyurethane resin composition is an adhesive for laminating. The laminated film 1 includes a first film 4, a second film 6, and a gas barrier layer 5. More specifically, in the laminated film 1, the first film 4 and the second film 6 are adhered to each other via the gas barrier layer 5.

The first film 4 includes a resin film. The first film 4 may further include an inorganic thin film (inorganic vapor deposition layer) to be vapor-deposited on one surface in the thickness direction of the resin film, if necessary. That is, the first film 4 may be a film having an inorganic thin film or a film not having an inorganic thin film.

Examples of the resin film include plastic films, and specifically, olefin-based polymers (for example, polyethylene, polypropylene, etc.), polyester-based polymers (for example, polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, and poly). Alkylene naphthalates and copolyesters containing these polyalkylene allylate units as the main components), polyamide-based polymers (for example, nylon 6, nylon 66, etc.), vinyl-based polymers (for example, polyvinyl chloride, ethylene-acetic acid, etc.) Examples thereof include a plastic film made of a polymer such as a vinyl copolymer, an ethylene-vinyl alcohol copolymer, etc.).

Further, the plastic film may be subjected to various treatments such as corona discharge treatment and primer treatment, if necessary.

Further, as the plastic film, either an unstretched film (unstretched polyethylene, unstretched polypropylene, etc.) or a uniaxially or biaxially stretched film (biaxially stretched polypropylene, biaxially stretched polyalkylene terephthalate, nylon, etc.) can be used. it can. Further, the plastic film can be prepared as various coextruded films or a composite film in which plastic films are attached in advance.

The thickness of the resin film is not particularly limited, but is, for example, 5 μm or more, preferably 10 μm or more, for example, 200 μm or less, preferably 100 μm or less.

The inorganic thin film is a thin film of an inorganic material. Examples of the inorganic material include magnesium, calcium, barium, group 2 of magnesium, calcium, barium, group 4 of titanium, zirconium, and group 13 according to the periodic table (according to the IUPAC Periodic Table of the Elements (version date 22 June 007). The same shall apply hereinafter). Inorganic substances containing metals such as aluminum, indium, group 14 silicon, germanium, and tin, such as inorganic oxides containing metal oxides such as magnesium oxide, titanium oxide, aluminum oxide, indium oxide, silicon oxide, and tin oxide. , Inorganic nitride oxides such as silicon oxide nitride and the like. From the viewpoint of gas barrier property and production efficiency, aluminum, silicon and oxides thereof are preferable. Further, these metals and their oxides may be combined in combination to form a layer composed of a metal and / or a metal oxide.

The inorganic thin film is formed on one side of the resin film in the thickness direction by, for example, a thin film deposition method (vacuum vapor deposition method, EB vapor deposition method, etc.), a sputtering method, an ion plating method, a lamination method, a plasma vapor deposition method (CVD method), or the like. It is formed. Among the methods for forming the inorganic thin film, a vacuum vapor deposition method is preferable.

The thickness of the inorganic thin film is appropriately selected depending on the type and composition of the inorganic material, and is, for example, 1 nm or more, preferably 2 nm or more, for example, 500 nm or less, preferably 300 nm or less.

The second film 6 has, for example, the same configuration as the first film 4.

In the laminated film 1, the gas barrier layer 5 is an adhesive layer. The gas barrier layer 5 contains a cured product of the polyurethane resin composition described above. The gas barrier layer 5 is arranged on the first film 4, and more specifically, is arranged between the first film 4 and the second film 6.

The thickness of the gas barrier layer 5 is not particularly limited, but is, for example, 5 μm or more, preferably 10 μm or more, for example, 200 μm or less, preferably 100 μm or less.

In order to prepare such a laminated film 1, first, the above-mentioned polyurethane resin composition is applied to one surface of the first film 4 in the thickness direction.

Specifically, the polyurethane resin composition is applied to one surface of the first film 4 in the thickness direction with a laminator. The laminating apparatus used for coating the polyurethane resin composition may be either a forward transfer type coating device or a reverse transfer type coating device (reverse coater).

The laminating temperature (coating temperature) is, for example, 35 ° C. or higher, preferably 40 ° C. or higher. If it can be laminated, there is no upper limit of temperature, but it is usually 100 ° C. or lower, preferably 90 ° C. or lower, and more preferably 85 ° C. or lower.

The coating amount of the polyurethane resin composition is, for example, 0.5 g / m ² or more, preferably 1.0 g / m ² or more, more preferably 1.5 g / m ² or more, for example, 5 g / m ² or less. is there.

Next, the second film 6 is attached to the coated surface and then cured at room temperature or under heating to volatilize the organic solvent from the polyurethane resin composition and cure the polyurethane resin composition. As a result, the gas barrier layer 5 is formed and the laminated film 1 is prepared.

Further, as shown in FIG. 1B, the polyurethane resin composition of the coat film 2 is used as a coating agent (paint). That is, the polyurethane resin composition is a coating agent. The coat film 2 includes the above-mentioned first film 4 and the above-mentioned gas barrier layer 5. In the coat film 2, the gas barrier layer 5 is a coat layer.

In order to prepare such a coat film 2, the polyurethane resin composition described above is applied to one surface of the first film 4 in the thickness direction in the same manner as described above.

Then, it is cured at room temperature or under heating to volatilize the organic solvent from the polyurethane resin composition and cure the polyurethane resin composition. As a result, the gas barrier layer 5 is formed and the coat film 2 is prepared.

As shown in FIG. 1C, the polyurethane resin composition of the coat film 3 is used as an anchor coating agent. That is, the polyurethane resin composition is an anchor coating agent. The coat film 3 includes the above-mentioned first film 4, the above-mentioned gas barrier layer 5, and the above-mentioned coat layer 7. In the coat film 3, the gas barrier layer 5 is an anchor coat layer.

In order to prepare such a coat film 2, the polyurethane resin composition described above is applied to one surface of the first film 4 in the thickness direction in the same manner as described above.

Then, it is cured at room temperature or under heating to volatilize the organic solvent from the polyurethane resin composition and cure the polyurethane resin composition. As a result, the gas barrier layer 5 is formed.

Next, a known coating agent (for example, a water-based coating agent) is applied to one surface of the gas barrier layer 5 in the thickness direction and cured at room temperature or under heating to volatilize the solvent from the coating agent and the coating agent. To cure. As a result, the coat layer 7 is formed and the coat film 3 is prepared.

<Effect>
In the above-mentioned polyurethane resin composition, the polyisocyanate component contains an aromatic ring-containing polyfunctional isocyanate derivative, and the active hydrogen group-containing component contains a polyol and a monofunctional active hydrogen group-containing compound. The mol ratio of the monofunctional active hydrogen group-containing compound to the polyol is equal to or higher than the above lower limit.

Therefore, it is possible to prevent the occurrence of coating defects when the polyurethane resin composition is applied to the film.

Further, the carbon number of the monofunctional active hydrogen group-containing compound is in the above range, and the mol ratio of the monofunctional active hydrogen group-containing compound to the polyol is not more than the above upper limit.

Therefore, excellent gas barrier properties can be imparted to the gas barrier layer formed from the polyurethane resin composition.

The "gas barrier property" is defined as having an oxygen permeability based on JIS K 7126 (2006) of 44.8 cc / m ² day atm or less in a ^{coating film having a dry thickness of 2 g / m 2 alone.} To.

It is presumed that such gas barrier properties are mainly exhibited by the molecular structure of the polyurethane resin, the ratio of the hard segment and the soft segment, and the cohesive force.

Further, when the polyol contains a urethane-modified polyol, the viscosity of the polyurethane resin composition can be improved. Therefore, the coating film formed by applying the polyurethane resin composition to the film can be made relatively thick.

Further, when the monoalcohol contains an aromatic aliphatic monoalcohol, the viscosity of the polyurethane resin composition can be further improved.

In particular, when the polyol contains a urethane-modified polyol and the monoalcohol contains an aromatic aliphatic monoalcohol, the viscosity of the polyurethane resin composition can be remarkably improved.

Further, when the monoalcohol contains an aliphatic monoalcohol, the gas barrier property of the gas barrier layer can be improved.

Further, as shown in FIGS. 1A to 1C, the laminate (laminate film 1, coat film 2 and coat film 3) includes a gas barrier layer 5 containing a cured product of the polyurethane resin composition described above. Therefore, the gas barrier property can be improved while the adhesion of the gas barrier layer 5 to the first film 4 can be improved.

Therefore, such a laminate is suitably used as a packaging material in various industrial fields such as foods, beverages, pharmaceuticals and quasi-drugs.

<Second Embodiment>
In the second embodiment of the polyurethane resin composition, the polyisocyanate component contains an aromatic ring-containing polyfunctional isocyanate derivative modified by a monofunctional active hydrogen group-containing compound, and the active hydrogen group-containing component contains a polyol.

That is, the aromatic ring-containing polyfunctional isocyanate derivative in the first embodiment is not modified by the monofunctional active hydrogen group-containing compound, while the aromatic ring-containing polyfunctional isocyanate derivative in the second embodiment contains a monofunctional active hydrogen group. It has been modified by the compound.

Therefore, in the following, the aromatic ring-containing polyfunctional isocyanate derivative not modified by the monofunctional active hydrogen group-containing compound is referred to as the first aromatic ring-containing polyfunctional isocyanate derivative, and the aromatic is modified by the monofunctional active hydrogen group-containing compound. Ring-containing polyfunctional isocyanate derivatives are distinguished as second aromatic ring-containing polyfunctional isocyanate derivatives.

In the second embodiment, the polyisocyanate component contains a second aromatic ring-containing polyfunctional isocyanate derivative as an essential component.

The second aromatic ring-containing polyfunctional isocyanate derivative is a reaction product of the above-mentioned first aromatic ring-containing polyfunctional isocyanate derivative and the above-mentioned monofunctional active hydrogen group-containing compound, and has an isocyanate group at the molecular terminal.

In order to prepare the second aromatic ring-containing polyfunctional isocyanate derivative, the first aromatic ring-containing polyfunctional isocyanate derivative and the monofunctional active hydrogen group-containing compound are mixed, and the isocyanate group of the first aromatic ring-containing polyfunctional isocyanate derivative is simple. The functional active hydrogen group-containing compound is blended so as to be excessive with respect to the active hydrogen group, and is reacted at 50 to 100 ° C. for 1 to 8 hours in an inert gas atmosphere, for example.

The average number of functional groups of the isocyanate group in the second aromatic ring-containing polyfunctional isocyanate derivative is, for example, 2 or more, preferably 2.5 or more, for example, 4 or less, preferably 3.0 or less.

The isocyanate group content (NCO%) in the second aromatic ring-containing polyfunctional isocyanate derivative is, for example, 2% by mass or more, preferably 5% by mass or more, for example, 30% by mass or less, preferably 20% by mass. % Or less.

The second aromatic ring-containing polyfunctional isocyanate derivative can be used alone or in combination of two or more.

The second aromatic ring-containing polyfunctional isocyanate derivative is preferably a reaction product of the first aromatic ring-containing polyfunctional isocyanate derivative and a monoalcohol, and more preferably a polyol modified product of an aromatic ring-containing isocyanate monomer and a monoalcohol. Reaction product with, more preferably, a polyol modified product of an aromatic aliphatic polyisocyanate monomer and a monoalcohol, particularly preferably a TMP adduct of an aromatic aliphatic polyisocyanate monomer and a monoalcohol. Reaction products with.

Further, as the aromatic aliphatic polyisocyanate monomer, xylylene diisocyanate (XDI) is preferable. Further, as the monoalcohol, preferably, an aliphatic alcohol and an aromatic aliphatic alcohol can be mentioned, and more preferably, an aromatic aliphatic alcohol can be mentioned.

That is, the polyisocyanate component preferably contains a reaction product of a polyol modified product of XDI and a monoalcohol, and more preferably a reaction product of a TMP adduct of XDI and an aromatic aliphatic alcohol, and / or , A reaction product of a TMP adduct of XDI and an aliphatic alcohol, and more preferably a reaction product of a TMP adduct of XDI and an aromatic aliphatic alcohol.

In addition, the polyisocyanate component may contain other polyisocyanate as an optional component as long as the excellent effects of the present invention are not impaired.

Examples of other polyisocyanates include the above-mentioned first aromatic ring-containing polyfunctional isocyanate derivative, the above-mentioned aromatic ring-containing isocyanate monomer, the above-mentioned aromatic ring-free isocyanate monomer, and the above-mentioned aromatic ring-free isocyanate derivative. Can be mentioned.

The polyisocyanate component is particularly preferably composed of a second aromatic ring-containing polyfunctional isocyanate derivative without containing other polyisocyanates.

In the second embodiment, the active hydrogen group-containing component contains the above-mentioned polyol as an essential component.

The active hydrogen group-containing component can contain other active hydrogen group-containing compounds as optional components as long as the excellent effects of the present invention are not impaired.

Examples of other active hydrogen group-containing compounds include the above-mentioned monofunctional active hydrogen group-containing compound and the above-mentioned high molecular weight polyol.

The active hydrogen group-containing component is particularly preferably free of other active hydrogen group-containing compounds and consists of a polyol.

Also in such a second embodiment, the mol ratio of the monofunctional active hydrogen group-containing compound to the polyol is in the above range.

Further, also in the second embodiment, the polyurethane resin composition is prepared as, for example, a two-component polyurethane resin raw material or a one-component polyurethane resin raw material, and is suitably used as a coating raw material in the same manner as described above.

Therefore, even in such a second embodiment, the same effect as that of the first embodiment described above can be obtained.

Further, in the second embodiment, since the polyisocyanate component contains an aromatic ring-containing polyfunctional isocyanate derivative modified by a monofunctional active hydrogen group-containing compound, the viscosity of the polyurethane resin composition can be improved. In particular, when the monofunctional active hydrogen group-containing compound contains an aromatic monoalcohol, the viscosity of the polyurethane resin composition can be remarkably improved, and the coating film formed by applying the polyurethane resin composition to the film can be used. The thickness can be made relatively thick.

Next, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are the compounding ratios corresponding to those described in the above-mentioned "Form for carrying out the invention". Substitute the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, and parameters. be able to.

Preparation Example 1
Takenate D-110N (XDI trimethylolpropane (TMP) adduct, isocyanate group content 11.5% by mass, solid content 75% by mass, solvent: ethyl acetate, manufactured by Mitsui Chemicals, Inc.) 952 g and ethanol (monofunctional activity) 48 g of a hydrogen group-containing compound) was mixed and reacted at 70 ° C. for 5 hours in a nitrogen atmosphere.

As a result, an ethanol-modified form of the TMP adduct of XDI (second aromatic ring-containing polyfunctional isocyanate derivative, hereinafter referred to as "XDI-TMP-ethanol") was produced.

From the above, agent A containing XDI-TMP-ethanol was obtained. In Agent A, the solid content concentration was 76.2% by mass, and the isocyanate group content was 6.8% by mass.

Preparation Example 2
Benzyl alcohol modified product of TMP adduct of XDI (second aromatic ring-containing polyfunctional isocyanate) in the same manner as in Preparation Example 1 except that 48 g of ethanol was changed to 106 g of benzyl alcohol (monofunctional active hydrogen group-containing compound). Agent A containing a derivative (hereinafter referred to as "XDI-TMP-benzyl alcohol") was obtained. In Agent A, the solid content concentration was 77.6% by mass, and the isocyanate group content was 6.4% by mass.

Preparation Example 3
Agent A containing XDI-TMP-ethanol was obtained in the same manner as in Preparation Example 1 except that 952 g of Takenate D-110N was changed to 914 g and 48 g of ethanol was changed to 86 g. In the polyisocyanate component, the solid content concentration was 77.1% by mass, and the isocyanate group content was 2.9% by mass.

Preparation Example 4
In a mixed solution of 182 g of ethylene glycol (EG) and 265 g of 1,4-butylene glycol (1,4-BG), 553 g of toluene diisocyanate (TDI) was added in a nitrogen atmosphere, and the solution temperature exceeded 70 ° C. The mixture was added dropwise and reacted at 70 ° C. for 2 hours.

As a result, a urethane-modified polyol in which EG and 1,4-BG were modified by TDI (hereinafter referred to as "TDI / EG / 1,4-BG") was produced.

Then, TDI / EG / 1,4-BG was dissolved in 250 g of ethyl acetate to prepare an ethyl acetate solution of TDI / EG / 1,4-BG. In the ethyl acetate solution, the solid content concentration was 75.0% by mass, and the hydroxyl value (OHv) was 186 mgKOH / g.

Examples 1-13
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, Inc.) was prepared as agent A containing a polyisocyanate component. ..

Further, the polyol shown in Table 1 and the monofunctional active hydrogen group-containing compound shown in Table 1 were mixed according to the formulation shown in Table 1 to prepare Agent B containing an active hydrogen group-containing component. The mol ratio of the monofunctional active hydrogen group-containing compound to the polyol is shown in Table 1.

In Examples 12 and 13, phosphoric acid was further added to Agent B so as to have the formulation shown in Table 1.

Next, ethyl acetate was added to the agent A so that the final solid content concentration of the coating liquid (polyurethane resin composition) was 30% by mass. In Tables 1 and 2, the solid content of the agent A is shown by mass as the mass part of the polyisocyanate component, and the total amount of ethyl acetate contained in the agent A and added ethyl acetate as the organic solvent is shown.

Next, the agent A and the agent B are added so that the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate component to the hydroxyl group of the active hydrogen group-containing component is 1.1, and the mixture is stirred and the coating liquid (polyurethane resin) is stirred. Composition) was prepared.

Next, the coating liquid (polyurethane resin composition) was applied to the first film (OPP thickness 20 μm, PET thickness 12 μm, LLDPE thickness 30 μm) shown in Table 1 by a dry laminator, and the solid content mass per unit area was 3. It was applied so as to be 0.0 g / m ^2.

Then, the second film (CPP thickness 20 μm, LDPE thickness 40 μm, VM-CPP 25 μm) shown in Table 1 was attached to the coated surface, and then ethyl acetate was volatilized. As a result, a laminate (laminate film) having a gas barrier layer as an adhesive layer was obtained. When using the aluminum-deposited CPP film, the vapor-filmed surface (VM surface) was brought into contact with the coated surface.

Examples 14-16
The coating liquid (polyurethane resin composition) prepared in the same manner as in Example 11 was applied to the first film (LLDPE thickness 30 μm, OPP thickness 20 μm, PET thickness 12 μm) shown in Table 2 by a dry laminator. After coating so as to have a mass of 3.0 g / m ² , ethyl acetate was volatilized to form a gas barrier layer.

As a result, a laminate (coat film) having a gas barrier layer as a coat layer was obtained.

Example 17
A laminate (coating) having a gas barrier layer as a coating layer in the same manner as in Example 14, except that the coating liquid was prepared in the same manner as in Example 12 and an aluminum-deposited CPP film was used as the first film. Film) was obtained.

Examples 18-20
The coating liquid (polyurethane resin composition) prepared in the same manner as in Example 11 was applied to the first film (LLDPE thickness 30 μm, OPP thickness 20 μm, PET thickness 12 μm) shown in Table 2 by a dry laminator in a unit area. After coating so that the solid content mass per hit was 3.0 g / m ² , ethyl acetate was volatilized. As a result, a gas barrier layer was formed.

Next, a water-based coating agent (manufactured by Mitsui Chemicals, trade name WPB-341A) is applied to the gas barrier layer with a dry laminator so that the solid content mass per unit area is 2.0 g / m ^2, and water is applied. It was volatilized.

As a result, a laminate (coat film) having a gas barrier layer as an anchor coat layer was obtained.

Example 21
A laminate having a gas barrier layer as an anchor coat layer in the same manner as in Example 18, except that the coating liquid was prepared in the same manner as in Example 12 and an aluminum-deposited CPP film was used as the first film. Coat film) was obtained.

Example 22 and Example 23
The monofunctional active hydrogen group-containing compound shown in Table 3 was mixed with the ethyl acetate solution of TDI / EG / 1,4-BG obtained in Preparation Example 4 according to the formulation shown in Table 3, and the active hydrogen group-containing component was mixed. A laminate (laminate film) was obtained in the same manner as in Example 2 except that the agent B containing the above was prepared.

In Table 3, the mass part of the solid content of Agent A is shown as the mass part of the polyisocyanate component, and the mass part of the active hydrogen group-containing component contains TDI / EG / 1,4-BG and a monofunctional active hydrogen group. A compound is shown, and the total amount of ethyl acetate contained in agent A, ethyl acetate contained in agent B, and added ethyl acetate as an organic solvent is shown.

Example 24
Same as Example 2 except that Takenate D-110N was changed to Agent A obtained in Preparation Example 1, only ethylene glycol was used as Agent B, and the formulation was changed to the values shown in Table 3. A laminate (laminate film) was obtained.

Example 25
Same as in Example 2 except that Takenate D-110N was changed to the agent A obtained in Preparation Example 2, ethylene glycol was used as the agent B, and the formulation was changed to the values shown in Table 3. , A laminate (laminate film) was obtained.

Example 26
A laminate (laminate film) was obtained in the same manner as in Example 24, except that the ethyl acetate solution of TDI / EG / 1,4-BG obtained in Preparation Example 4 was used as the agent B.

Example 27
A laminate (laminate film) was obtained in the same manner as in Example 25, except that the ethyl acetate solution of TDI / EG / 1,4-BG obtained in Preparation Example 4 was used as the agent B.

Comparative Example 1
A laminate (laminate film) was obtained in the same manner as in Example 1 except that ethanol was not added to Agent B and the formulation was changed to the values shown in Table 4.

Comparative Example 2
A laminate (laminate film) was obtained in the same manner as in Example 1 except that ethanol was changed to 4-hydroxymethylbiphenyl and the formulation was changed to the values shown in Table 4.

Comparative Example 3 and Comparative Example 4
A laminate (laminate film) was obtained in the same manner as in Example 1 except that the formulation was changed to the values shown in Table 4.

Comparative Example 5
A laminate (laminate film) was obtained in the same manner as in Example 24 except that the formulation was changed to the values shown in Table 4.

Comparative Example 6
A laminate (laminate film) was obtained in the same manner as in Example 11 except that ethanol was not added to Agent B and the formulation was changed to the values shown in Table 4.

Comparative Example 7
A laminate (laminate film) was obtained in the same manner as in Example 12 except that ethanol was not added to Agent B and the formulation was changed to the values shown in Table 4.

Comparative Example 8
A laminate (laminate film) was obtained in the same manner as in Example 13 except that ethanol was not added to Agent B and the formulation was changed to the values shown in Table 4.

Evaluation The laminate was evaluated according to the following method. The results are shown in Tables 1 to 4.

<Measurement of Zahn cup viscosity>
The viscosity of the coating liquid (polyurethane resin composition) prepared in each Example and each Comparative Example at 25 ° C. was measured using Zahn Cup # 3 (orifice diameter: about 3 mm, manufactured by Rigosha).

<Pot life>
The above-mentioned Zahn cup viscosity measurement was carried out 5 minutes after the compounding of the A and B agents and 6 hours after the compounding of the A and B agents, and the rate of change in the Zahn cup viscosity was measured by the following formula (1). did.

Potpolife = Zahn cup viscosity 6 hours after compounding (seconds) / Zahn cup viscosity 5 minutes after compounding (seconds) ... (1)
<Coatability (appearance)>
The appearance of the laminates of each Example and each Comparative Example was visually observed to confirm the presence or absence of coating defects such as missing lines and streaks.

<Oxygen barrier property (oxygen permeability)>
For the laminated body of each Example and each Comparative Example, the oxygen permeability based on JIS K 7126 (2006) was measured at 20 ° C. relative to the oxygen permeability measuring device (MOCON, OX-TRAN 2/20). It was measured under the condition of humidity 80% (80% RH). The oxygen permeation amount was measured as the permeation amount per 1 ^{m 2, 1 day and 1 atm.}

Further, in a laminated film provided with a PET film as a first film, a CPP film as a second film, and a gas barrier layer, oxygen permeability based on JIS K 7126 (2006) under the conditions of 20 ° C. and 80% relative humidity. The practical range of is 120 cc / m ² , day, atm or less.

<T-shaped adhesion>
From the laminate of each Example and each Comparative Example, a long test sample (width: 15 mm, length: 150 mm) was cut out from each of the samples prepared in each Example and each Comparative Example.

In the laminates of Examples 14 to 20, a mixture of Takenate A-969V (manufactured by Mitsui Chemicals, Inc.) and Takenate A-5 (manufactured by Mitsui Chemicals, Inc.) as an adhesive for dry lamination on the gas barrier layer ( Takenate A-969V / Takenate A-5 = 3/1 (mass ratio) was applied with a bar coater so as to ^{have a dry thickness of 3.0 g / m 2, and dried with a dryer.} Then, an unstretched polypropylene film (Tosero CP RXC-22 (CPP film, # 66), manufactured by Mitsui Chemicals Tohcello Co., Ltd.) was laminated and cured at 40 ° C. for 3 days.

Then, in accordance with JIS K 6854-3 (1999), a T-type peeling test was performed on the test sample using a universal tensile measuring device at a crosshead speed of 300 mm / min, and the laminated body was subjected to a T-type peeling test. Adhesive strength was measured.

The details of the abbreviations in the table are shown below.
XDI-TMP: Trimethylolpropane adduct of xylylene diisocyanate TDI: Tolylene diisocyanate EG: Ethylene glycol 1,4-BG: 1,4-Butanediol LLDPE: Linear low-density polyethylene film LDPE: Low-density polyethylene film OPP : Biaxially stretched polypropylene film CPP: Unstretched polypropylene film PET: Polyethylene terephthalate film VM-CPP: Aluminum vapor-deposited unstretched polypropylene film MF: Substrate cut (PET film breakage)

1 Laminate film 2 Coat film 3 Coat film 4 1st film 5 Gas barrier layer 6 2nd film

Claims (6)

A polyisocyanate component containing an aromatic ring-containing polyfunctional isocyanate derivative,
Contains active hydrogen group-containing components containing polyols,
The aromatic ring-containing polyfunctional isocyanate derivative is modified with a monofunctional active hydrogen group-containing compound having 1 to 8 carbon atoms, or the active hydrogen group-containing component further contains the monofunctional active hydrogen group-containing compound. ,
A gas barrier polyurethane resin composition, wherein the mol ratio of the monofunctional active hydrogen group-containing compound to the polyol is 0.1 or more and 2.8 or less. The gas barrier polyurethane resin composition according to claim 1, wherein the polyol contains a urethane-modified polyol. The gas barrier polyurethane resin composition according to claim 1 or 2, wherein the monofunctional active hydrogen group-containing compound contains a monoalcohol. The gas barrier polyurethane resin composition according to claim 3, wherein the monoalcohol contains an aromatic aliphatic monoalcohol. The gas barrier polyurethane resin composition according to claim 3, wherein the monoalcohol contains an aliphatic monoalcohol. With the film
A laminate comprising a cured product of the gas-barrier polyurethane resin composition according to any one of claims 1 to 5, and comprising a gas barrier layer arranged on the film.

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