JP7253043B6 - Two-liquid curing laminating adhesive and laminating film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a two-component curing lamination adhesive and a laminate film, and more particularly, a two-component curing lamination adhesive suitably used for manufacturing a laminate film, and a laminate obtained from the two-component curing lamination adhesive. Regarding film.

2. Description of the Related Art Laminated films obtained by bonding various films such as plastic films with a laminating adhesive are widely used in the field of packaging materials.

As a lamination adhesive used for producing a laminate film, for example, a two-liquid lamination adhesive containing a curing agent containing a polyisocyanate and a main agent containing a polyol, which are blended at the time of use, has been proposed. It has also been proposed to incorporate a silane coupling agent into the curing agent (see, for example, Patent Document 1 below).

Further, as the laminate adhesive, for example, a one-liquid type adhesive composition for composite lamination comprising polyurethane having a free NCO group in the molecule and containing a silane coupling agent having an active hydrogen atom in the molecular chain. A product has also been proposed (see, for example, Patent Document 2 below).

Japanese Patent Application Laid-Open No. 2003-113359 JP-A-56-57867

However, when the silane coupling agent is simply added to and mixed with the curing agent as in Patent Document 1, even if the obtained laminate adhesive is applied to the base material, adhesion between the base material and the laminate adhesive does not occur. Sexuality may not be enough.

On the other hand, by chemically bonding a silane coupling agent to the molecular chain of the adhesive as in Patent Document 2, it is possible to improve the adhesion between the substrate and the lamination adhesive.

However, since the composite laminate adhesive composition described in Patent Document 2 is a one-liquid type, there is a trade-off relationship between storage stability and curing speed.

In other words, if a one-liquid type laminating adhesive with excellent rapid curing properties is used for the continuous mass production of laminated films such as packaging materials, storage stability is poor. On the other hand, if a one-liquid type lamination adhesive with excellent storage stability is used, the rapid curing is inferior.

INDUSTRIAL APPLICABILITY The present invention provides a lamination adhesive which is excellent in storage stability and rapid curing property and which is also excellent in adhesion to a substrate, and a laminate film obtained using the lamination adhesive.

The present invention [1] is a two-component curable laminating adhesive comprising a curing agent containing a polyisocyanate compound and a main component containing an active hydrogen group-containing compound, wherein the raw material component of the polyisocyanate compound and/or It contains a two-liquid curing lamination adhesive in which the raw material component of the active hydrogen group-containing compound and a silane coupling agent are covalently bonded.

In the present invention [2], the silane coupling agent has an active hydrogen group, the raw material component of the polyisocyanate compound and/or the raw material component of the active hydrogen group-containing compound has an isocyanate group, and It contains the two-part curable lamination adhesive according to [1] above, which is characterized by covalent bonding.

In the present invention [3], the silane coupling agent has an isocyanate group, the raw material component of the active hydrogen group-containing compound and/or the raw material component of the polyisocyanate compound has an active hydrogen group, and It contains the two-part curable lamination adhesive according to [1] above, which is characterized by covalent bonding.

The present invention [4] further comprises the two-component curable lamination adhesive according to any one of [1] to [3] above, which further contains an oxyacid of phosphorus and/or a derivative thereof. there is

The present invention [5] is the above [4], wherein the content of the oxygen acid of phosphorus and/or its derivative is 1.0 to 5.0 parts by mass with respect to 100 parts by mass of the silane coupling agent. contains the two-part curable laminating adhesive described in .

The present invention [6] includes a laminate film comprising an adhesive layer containing a cured product of the two-component curing laminating adhesive according to any one of [1] to [5] above.

The two-component curable laminating adhesive of the present invention is a two-component curable laminating adhesive that has a curing agent containing a polyisocyanate compound and a main component containing an active hydrogen group-containing compound, and is used by blending at the time of use. Therefore, the polyisocyanate compound and the active hydrogen group-containing compound do not react before use (before compounding), but they react immediately after compounding, resulting in excellent rapid curing and storage stability.

In addition, in the two-component curing lamination adhesive of the present invention, since the raw material component of the polyisocyanate compound and/or the raw material component of the active hydrogen group-containing compound and the silane coupling agent are covalently bonded, the base material Excellent adhesion to

In addition, the laminate film of the present invention is excellent in adhesion between the substrate and the adhesive layer, and is also excellent in productivity.

The two-component curable laminating adhesive of the present invention is a two-component curable laminating adhesive comprising a curing agent containing a polyisocyanate compound and a main component containing an active hydrogen group-containing compound.

In other words, the two-pack curable lamination adhesive is a resin composition comprising a main agent and a curing agent before mixing. In such a two-liquid curing lamination adhesive, the curing agent and the main agent are separately prepared and blended at the time of use.

Further, in the two-liquid curing laminating adhesive, as will be described later in detail, at least one of the polyisocyanate compound in the curing agent and the active hydrogen group-containing compound (described later) in the main agent is the raw material component. It has a covalent bond with a silane coupling agent (described later).

The curing agent contains a polyisocyanate compound.

Examples of polyisocyanate compounds include polyisocyanate monomers and polyisocyanate derivatives.

Polyisocyanate monomers include, for example, polyisocyanates such as aliphatic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates, preferably diisocyanates.

Examples of aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, ), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcapro and aliphatic diisocyanates such as ate and dodecamethylene diisocyanate.

Aliphatic polyisocyanates also include alicyclic polyisocyanates. Alicyclic polyisocyanates include, for example, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3 ,5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis(cyclohexylisocyanate) (4,4′-, 2,4′- or 2,2′-methylenebis(cyclohexylisocyanate), these Trans, Trans -, Trans, Cis-, Cis, Cis-, or mixtures thereof)) (H ₁₂ MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane Alicyclics such as diisocyanates (various isomers or mixtures thereof) (NBDI), bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof) (H ₆ XDI) group diisocyanates.

Examples of aromatic polyisocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixtures thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or mixtures thereof), 4, 4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof) (MDI), aromatic diisocyanates such as 4,4'-toluidine diisocyanate (TODI) and 4,4'-diphenylether diisocyanate;

Examples of araliphatic polyisocyanates include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixtures thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra araliphatic diisocyanates such as methylxylylene diisocyanate (or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, and the like.

These polyisocyanate monomers can be used singly or in combination of two or more.

Examples of polyisocyanate derivatives include multimers (e.g., dimers, trimers (e.g., isocyanurate modified products, iminooxadiazinedione modified products), pentamers, and polyisocyanate monomers of the above polyisocyanate monomers. Heptamers, etc.), allophanate derivatives (e.g., the above-described polyisocyanate monomers and allophanate derivatives produced by reaction with alcohols, etc.), biuret derivatives (e.g., the above-described polyisocyanate monomers, water and biuret derivatives produced by reaction with amines, etc.), urea derivatives (for example, urea derivatives produced by reaction of the above-mentioned polyisocyanate monomers and diamines, etc.), oxadiazinetrione derivatives (for example, the above-mentioned Oxadiazinetrione derivative generated by reaction of polyisocyanate monomer and carbon dioxide gas, etc.), carbodiimide derivative (carbodiimide derivative generated by decarboxylation condensation reaction of the above-described polyisocyanate monomer, etc.), polyol derivative ( For example, an alcohol adduct produced by the reaction of the above-described polyisocyanate monomer and a low-molecular-weight polyol described later, for example, from the reaction of the above-described polyisocyanate monomer and a high-molecular-weight polyol (and a low-molecular-weight polyol) described later generated isocyanate group-terminated prepolymer, etc.).

These polyisocyanate derivatives can be used alone or in combination of two or more.

Polyisocyanate compounds can be used alone or in combination of two or more.

Polyisocyanate compounds preferably include aromatic polyisocyanate monomers and derivatives thereof, more preferably aromatic diisocyanate monomers and derivatives thereof, from the viewpoints of storage stability, rapid curing and adhesion. derivatives, more preferably derivatives of aromatic diisocyanates, more preferably polyol derivatives of aromatic diisocyanates, still more preferably isocyanate group-terminated prepolymers of aromatic diisocyanates, especially Preferably, an isocyanate group-terminated prepolymer of MDI is used.

The isocyanate group-terminated prepolymer is a urethane prepolymer having two or more isocyanate groups at the molecular ends, and is composed of a polyisocyanate (hereinafter referred to as the first raw material polyisocyanate) as a raw material component of the isocyanate group-terminated prepolymer and an isocyanate group. It can be obtained by reacting a polyol as a raw material component of the terminal prepolymer (hereinafter referred to as first raw material polyol) in the ratio described later.

Examples of the first raw material polyisocyanate include the above polyisocyanate monomers and/or polyisocyanate derivatives, which can be used alone or in combination of two or more.

The first raw material polyisocyanate preferably includes a polyisocyanate monomer, more preferably an aromatic polyisocyanate, still more preferably an aromatic diisocyanate, and most preferably MDI. .

Examples of the first raw material polyol include low-molecular-weight polyols described later and high-molecular-weight polyols described later, and they can be used alone or in combination of two or more.

As the first raw material polyol, a combination of a high-molecular-weight polyol (described later) and a low-molecular-weight polyol (described later) is preferably used.

As the high-molecular-weight polyols (described later), polyether polyols (described later) are preferred, polyoxyalkylene polyols are more preferred, and polyoxypropylene glycols are even more preferred.

As the low-molecular-weight polyol (described later), trihydric alcohol (described later) is preferred, and trimethylolpropane is more preferred.

Then, in order to synthesize an isocyanate group-terminated prepolymer, each of the above components is added to the active hydrogen group at a ratio at which the isocyanate group is excessive, that is, the isocyanate of the first raw material polyisocyanate to the active hydrogen group of the first raw material polyol. The group equivalent ratio (isocyanate group/active hydrogen group) is blended at a rate exceeding 1, preferably at a rate of 2 or more and 100 or less.

For the reaction of each of the above components, for example, known polymerization methods such as bulk polymerization and solution polymerization are employed. Preferably, solution polymerization is employed as it is easier to control reactivity and viscosity.

In the bulk polymerization, for example, the above components are blended in a nitrogen atmosphere and reacted at a reaction temperature of 75 to 85° C. for about 1 to 20 hours.

In solution polymerization, for example, the above components are blended in an organic solvent under a nitrogen atmosphere, and the mixture is reacted at a reaction temperature of 20 to 80° C. for about 1 to 20 hours.

The organic solvent is not particularly limited as long as it is inert to isocyanate groups. Examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, nitriles such as acetonitrile, methyl acetate, Alkyl esters such as ethyl acetate, butyl acetate and isobutyl acetate; aliphatic hydrocarbons such as n-hexane, n-heptane and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, such as methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3 -glycol ether esters such as methoxybutyl acetate, ethyl-3-ethoxypropionate, ethers such as diethyl ether, tetrahydrofuran, dioxane, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide , methylene iodide, dichloroethane and other halogenated aliphatic hydrocarbons, e.g., N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide and other polar aprotons, etc. mentioned. These organic solvents can be used alone or in combination of two or more.

In addition, in the above polymerization, if necessary, a reaction catalyst such as an amine-based, tin-based, or lead-based reaction catalyst may be added. can also be removed by known methods such as, for example, distillation or extraction.

The isocyanate group-terminated prepolymer obtained in this manner is a compound having two or more free isocyanate groups at the molecular end.

The average number of isocyanate groups (average number of functional groups) of the isocyanate group-terminated prepolymer is, for example, 1.9 or more, more preferably 2.0 or more, and for example, 3.5 or less, preferably 3.5. 0 or less, more preferably 2.5 or less.

In addition, the number average molecular weight (number average molecular weight by GPC measurement using standard polystyrene as a calibration curve) is, for example, 500 or more, preferably 800 or more, and, for example, 10,000 or less, preferably 5,000 or less. .

Moreover, the curing agent can contain the above-described organic solvent, if necessary.

When the curing agent contains an organic solvent, its solid content concentration is appropriately set according to the purpose and application.

The content ratio (solid content concentration) of the polyisocyanate compound (preferably isocyanate group-terminated prepolymer) in the curing agent is, for example, 30% by mass or more, preferably 50% by mass or more, relative to the total amount of the curing agent, For example, it is 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less.

The main agent contains an active hydrogen group-containing compound.

Active hydrogen group-containing compounds are compounds that contain two or more active hydrogen groups in the molecule.

In the active hydrogen group-containing compound, the active hydrogen group is a substituent capable of reacting with an isocyanate group, and specifically includes a hydroxyl group, an amino group, a thiol group, a carboxy group, etc., preferably a hydroxyl group and an amino group. and more preferably a hydroxyl group.

In other words, the active hydrogen group-containing compound is preferably a compound containing two or more hydroxyl groups in the molecule.

Active hydrogen group-containing compounds containing two or more hydroxyl groups in the molecule include, for example, polyols. Polyols include, for example, low-molecular-weight polyols and high-molecular-weight polyols.

The low-molecular-weight polyol is, for example, a compound having two or more hydroxyl groups in the molecule and a molecular weight of 50 or more and 300 or less, preferably 400 or less, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C7-20) diols, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1, 4-cyclohexanediol and mixtures thereof, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, di dihydric alcohols such as propylene glycol, trihydric alcohols such as glycerin, trimethylolpropane and triisopropanolamine, tetramethylolmethane (pentaerythritol), tetrahydric alcohols such as diglycerin, pentahydric alcohols such as xylitol Alcohols, for example, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol; heptahydric alcohols, such as perseitol; and octahydric alcohols, such as sucrose. .

These low-molecular-weight polyols can be used alone or in combination of two or more.

High-molecular-weight polyols are organic compounds having two or more hydroxyl groups and a number-average molecular weight exceeding 300, preferably exceeding 400, such as polyether polyols (e.g., polyoxyalkylenes such as polyoxypropylene glycol). polyols, polytetramethylene ether polyols, etc.), polyester polyols (e.g., adipic acid-based polyester polyols, phthalic acid-based polyester polyols, lactone-based polyester polyols, and their acid-modified polyester polyols, etc.), polycarbonate polyols, polyurethane polyols (e.g., , polyether polyol, polyester polyol, polycarbonate polyol, etc. urethane-modified with polyisocyanate), epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, vinyl monomer-modified polyol, polybutadiene polyol, and the like.

These high molecular weight polyols can be used alone or in combination of two or more.

Polyols can be used singly or in combination of two or more.

Polyols preferably include high molecular weight polyols, more preferably polyether polyols, polyester polyols, polycarbonate polyols and polyurethane polyols, and more preferably polyurethane polyols.

Polyurethane polyol is a polyurethane resin having two or more hydroxyl groups at the molecular ends, and is composed of a polyisocyanate (hereinafter referred to as a second raw material polyisocyanate) as a raw material component of the polyurethane polyol and a polyol as a raw material component of the polyurethane polyol (hereinafter , second raw material polyol) in the ratio described later.

Examples of the second raw material polyisocyanate include the above polyisocyanate monomers and/or polyisocyanate derivatives, which can be used alone or in combination of two or more.

The second raw material polyisocyanate preferably includes a polyisocyanate monomer, more preferably an aromatic polyisocyanate, still more preferably an aromatic diisocyanate, and particularly preferably TDI and MDI. mentioned.

Examples of the second raw material polyol include the high-molecular-weight polyols described above and the low-molecular-weight polyols described above, which may be used alone or in combination of two or more.

A combination of a high-molecular-weight polyol and a low-molecular-weight polyol is preferably used as the second raw material polyol.

In the second raw material polyol, the high-molecular-weight polyol is preferably polyether polyol, more preferably polyoxyalkylene polyol, and still more preferably polyoxypropylene glycol.

In the second raw material polyol, the low-molecular-weight polyol is preferably a dihydric alcohol, more preferably 1,4-butanediol and dipropylene glycol.

Then, in order to obtain polyurethane polyol, the second raw material polyisocyanate and the second raw material polyol are reacted by a known method such as a one-shot method or a prepolymer method.

In the one-shot method, for example, each of the components described above is added so that the equivalent ratio (isocyanate group/active hydrogen group) of the isocyanate group in the second raw material polyisocyanate to the active hydrogen group in the second raw material polyol is, for example, 0.8. above, preferably 0.9 or more, for example, 1.2 or less, preferably 1.1 or less, is formulated (mixed), by a known polymerization method such as bulk polymerization or solution polymerization, for example, at room temperature Curing reaction is carried out at a temperature of up to 250° C., preferably room temperature to 200° C., for example, for 5 minutes to 72 hours, preferably 4 to 24 hours.

In the prepolymer method, first, a second raw material polyisocyanate and a part of the second raw material polyol (preferably, a single use of a high molecular weight polyol, or a combination of a high molecular weight polyol and a low molecular weight polyol) are reacted, An isocyanate group-terminated prepolymer is synthesized.

In this reaction, the equivalent ratio of the isocyanate groups in the second raw material polyisocyanate component to the active hydrogen groups in a portion of the second raw material polyol (isocyanate groups/active hydrogen groups) is It is an excessive ratio, for example, 1.2 or more, preferably 1.3 or more, for example, 3.0 or less, preferably 2.5 or less.

In this method, the components are reacted by a known polymerization method such as the bulk polymerization or the solution polymerization, preferably the solution polymerization.

In the bulk polymerization, for example, the above components are blended in a nitrogen atmosphere and reacted at a reaction temperature of 75 to 85° C. for about 1 to 20 hours.

In the solution polymerization, for example, the above components are added to the above organic solvent under a nitrogen atmosphere, and the mixture is reacted at a reaction temperature of 20 to 80° C. for about 1 to 20 hours.

In addition, in the above polymerization, if necessary, a reaction catalyst such as an amine-based, tin-based, or lead-based reaction catalyst may be added. can also be removed by known methods such as, for example, distillation or extraction.

The isocyanate group-terminated prepolymer thus obtained is a raw material prepolymer used as a raw material component of polyurethane polyol.

Thereafter, in this method, the isocyanate group-terminated prepolymer (raw material prepolymer) obtained above is reacted with the remainder of the second raw material polyol (preferably low-molecular-weight polyol) to obtain a polyurethane polyol.

The remainder of the second raw material polyol is a chain extender.

The reaction between the isocyanate group-terminated prepolymer (raw material prepolymer) and the remainder of the second raw material polyol (chain extender) is not particularly limited, and a known method is employed. For example, the remainder of the second raw material polyol (chain extender) is added to the solution or dispersion of the isocyanate group-terminated prepolymer obtained above.

The chain extender is allowed to react by being added dropwise, and after the completion of the dropwise addition, the reaction is completed at, for example, room temperature while further stirring. The reaction time until completion of the reaction is, for example, 0.1 hours or more and, for example, 10 hours or less.

In this reaction, the blending ratio of each component is such that the active hydrogen groups of the remainder (chain extender) of the second raw material polyol are equal to or more than the isocyanate groups of the isocyanate group-terminated prepolymer (raw material prepolymer). is.

More specifically, the equivalent ratio (active hydrogen group/isocyanate group) of the active hydrogen group in the remainder (chain extender) of the second raw material polyol to the isocyanate group of the isocyanate group-terminated prepolymer (raw material prepolymer) is For example, it is 1.0 or more, preferably 1.05 or more, for example, 1.5 or less, preferably 1.2 or less.

The polyurethane polyol thus obtained is a polyurethane resin having two or more free hydroxyl groups at its molecular ends.

The average number of hydroxyl groups (average number of functional groups) of the polyurethane polyol is, for example, 1.5 or more, preferably 1.9 or more, more preferably 2.0 or more, and for example, 3.0 or less, preferably is less than or equal to 2.5.

In addition, the number average molecular weight (number average molecular weight by GPC measurement using standard polystyrene as a calibration curve) is, for example, 500 or more, preferably 800 or more, and, for example, 10,000 or less, preferably 5,000 or less. .

Moreover, the main agent can contain an organic solvent.

Examples of the organic solvent include the above-described organic solvents. These organic solvents can be used alone or in combination of two or more.

In addition, when the main agent contains an organic solvent, its solid content concentration is appropriately set according to the purpose and application.

The content ratio (solid concentration) of the active hydrogen group-containing compound (preferably high molecular weight polyol, more preferably polyurethane polyol) in the main agent is, for example, 30% by mass or more relative to the total amount of the main agent, preferably 50% by mass or more, for example, 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less.

In addition, the active hydrogen group-containing compound in the main agent is not limited to the above polyols. etc.). Active hydrogen group-containing compounds are preferably polyols, preferably polyurethane polyols.

In the two-liquid curing lamination adhesive, in order to improve adhesion, at least one of the raw material components of the polyisocyanate compound in the curing agent and the active hydrogen group-containing compound in the main agent is subjected to silane coupling. agent and a covalent bond.

That is, the raw material component of the polyisocyanate compound and/or the raw material component of the active hydrogen group-containing compound and the silane coupling agent are covalently bonded.

As a result, at least one of the polyisocyanate compound and the active hydrogen group-containing compound has a group (alkoxysilyl group) capable of silane coupling reaction with the base material (film etc.) described later in the molecule. ing.

The silane coupling agent is an alkoxysilyl group that can react with a base material (such as a film) described later, a raw material component of a polyisocyanate compound, and/or a raw material component of an active hydrogen group-containing compound. It is a compound having a reactive functional group (isocyanate group, active hydrogen group).

The content of the raw material component of the polyisocyanate compound and/or the silane coupling agent covalently bonded to the raw material component of the active hydrogen group-containing compound is relative to the polyisocyanate compound and the active hydrogen group-containing compound obtained by their reaction. , for example, 0.5% by mass or more, preferably 1.0% by mass or more, and for example, 20% by mass or less, preferably 10% by mass or less.

If the polyisocyanate compound and/or active hydrogen group-containing compound has an alkoxysilyl group in the molecule, when the two-component curing lamination adhesive is applied to a substrate (such as a film) described later, the alkoxysilyl group and hydroxyl groups on the surface of a base material (such as a film) to be described later form a strong bond through dehydration condensation.

Therefore, it is possible to improve the adhesion between the two-liquid curing lamination adhesive and the substrate (described later).

In addition, even if the silane coupling agent is covalently bonded to the raw material component of the polyisocyanate compound and/or the raw material component of the active hydrogen group-containing compound, the main agent and curing agent containing them are transported and stored in a state before mixing. thickening is suppressed.

The form of the covalent bond by the silane coupling agent is not particularly limited. Alternatively, a urea bond with a secondary amino group, etc., and preferably a urethane bond with an isocyanate group and a hydroxyl group are included.

Both the polyisocyanate compound (curing agent) and the active hydrogen group-containing compound (main agent) may have a covalent bond formed by a silane coupling agent, but from the viewpoint of cost, preferably the polyisocyanate compound One raw material component of the (curing agent) and the active hydrogen group-containing compound (main agent) has a covalent bond with the silane coupling agent.

That is, as a preferred embodiment of the two-component curing lamination adhesive, the raw material component of the polyisocyanate compound has a covalent bond with a silane coupling agent, and the raw material component of the active hydrogen group-containing compound is a silane coupling agent. Embodiments that do not have a covalent bond with the agent are included.

Further, as a preferred embodiment of the two-component curing lamination adhesive, the raw material component of the polyisocyanate compound does not have a covalent bond with the silane coupling agent, and the raw material component of the active hydrogen group-containing compound is An embodiment having a silane coupling agent and a covalent bond is included.

In a particularly preferred embodiment, the raw material component of the polyisocyanate compound does not have a covalent bond with the silane coupling agent, and the raw material component of the active hydrogen group-containing compound has a covalent bond with the silane coupling agent. An embodiment having

A covalent bond between the raw material component of the polyisocyanate compound and the silane coupling agent is formed, for example, as follows.

That is, in this method, for example, a silane coupling agent having an active hydrogen group is blended in the production of the isocyanate group-terminated prepolymer described above.

Silane coupling agents having an active hydrogen group include, for example, mercapto group-containing silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, N-2-(aminoethyl)- Silane coupling agents having both primary and secondary amino groups such as 3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, such as 3-aminopropyltrimethoxysilane. Silane coupling containing no secondary amino group but containing primary amino group such as methoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrialkoxysilane and amino group-containing silane coupling agents such as agents.

These silane coupling agents having active hydrogen groups can be used alone or in combination of two or more.

The silane coupling agent having an active hydrogen group is preferably an amino group-containing silane coupling agent, more preferably 3-aminopropyltriethoxysilane.

Then, in order for the raw material component of the polyisocyanate compound to form a covalent bond with the silane coupling agent, for example, in the production of the isocyanate group-terminated prepolymer, the first raw material polyisocyanate and the first raw material polyol , with a silane coupling agent having an active hydrogen group.

In the production of the isocyanate group-terminated prepolymer, the order of blending the first raw material polyisocyanate, the first raw material polyol and the silane coupling agent is not particularly limited.

That is, for example, the first raw material polyol and the silane coupling agent may be simultaneously reacted (batch reaction) with respect to the first raw material polyisocyanate at a ratio in which the isocyanate group is excessive with respect to the active hydrogen group. .

Further, for example, the first raw material polyisocyanate and the silane coupling agent are reacted at least at a ratio in which the isocyanate groups are excessive with respect to the active hydrogen groups, and the isocyanate groups remaining in the reaction product obtained, The first raw material polyol may be reacted in such a ratio that the isocyanate groups are excessive with respect to the active hydrogen groups.

Furthermore, for example, the first raw material polyol and the first raw material polyisocyanate are reacted at least at a ratio in which the isocyanate groups are excessive with respect to the active hydrogen groups, and the isocyanate groups remaining in the reaction product obtained, A silane coupling agent having an active hydrogen group may be reacted at a ratio in which the isocyanate group is excessive with respect to the active hydrogen group.

Preferably, from the viewpoint of suppressing thickening due to cross-linking in the reaction process, first, the first raw material polyisocyanate and the silane coupling agent are reacted at least at a rate in which the isocyanate group is excessive with respect to the active hydrogen group. After that, the isocyanate groups remaining in the resulting reaction product are reacted with the first raw material polyol in such a ratio that the isocyanate groups are excessive with respect to the active hydrogen groups.

That is, as a method for producing a polyisocyanate compound, preferably, first, the first raw material polyisocyanate and the silane coupling agent are reacted at least at a rate in which the isocyanate groups are excessive, and then the isocyanate remaining in the reaction product A method of reacting the groups and the first raw material polyol at a ratio in which the isocyanate groups are excessive is exemplified. Further, the polyisocyanate compound preferably includes an isocyanate group-terminated prepolymer obtained by this method.

More specifically, in this method, first, the first raw material polyisocyanate and a silane coupling agent having an active hydrogen group are reacted by a known polymerization method such as bulk polymerization or solution polymerization.

The blending ratio of the first raw material polyisocyanate and the silane coupling agent is a ratio at which the isocyanate group is excessive relative to the active hydrogen group, more specifically, the first raw material relative to the active hydrogen group of the silane coupling agent The isocyanate group equivalent ratio (isocyanate group/active hydrogen group) of the polyisocyanate is, for example, 1.05 or more, preferably 1.5 or more, and for example, 4.0 or less, preferably 3.0 or less. be.

As a result, the isocyanate groups of the first raw material polyisocyanate (preferably TDI, MDI) and the active hydrogen groups of the silane coupling agent undergo a urethanization reaction to form covalent bonds.

That is, in this method, the silane coupling agent has an active hydrogen group, and the raw material component of the polyisocyanate compound (first raw material polyisocyanate) has an isocyanate group, and the active hydrogen group and the isocyanate The groups are covalently bonded.

Moreover, the reaction product obtained thereby has a free isocyanate group.

Next, in this method, the reaction product of the first raw material polyisocyanate and the silane coupling agent is reacted with the first raw material polyol by a known polymerization method such as bulk polymerization or solution polymerization.

The blending ratio of the reaction product and the first raw material polyol is the ratio at which the isocyanate group is excessive with respect to the active hydrogen group. The isocyanate group equivalent ratio (isocyanate group/active hydrogen group) in the product is, for example, 1.05 or more, preferably 1.5 or more, and, for example, 4.0 or less, preferably 3.0 or less. is.

As a result, the free isocyanate groups in the reaction product react with the active hydrogen groups of the first raw material polyol to obtain an isocyanate group-terminated prepolymer as a polyisocyanate compound.

Further, in the above method, the total ratio of the first raw material polyisocyanate, the first raw material polyol and the silane coupling agent (total amount) is a ratio in which the isocyanate groups are excessive with respect to the active hydrogen groups, and more specifically Specifically, the equivalent ratio (isocyanate group/active hydrogen group) of the isocyanate groups of the first raw material polyisocyanate to the total amount of the active hydrogen groups of the first raw material polyol and the active hydrogen groups of the silane coupling agent is greater than 1. It is a ratio, preferably a ratio of 2 or more and 100 or less.

In the above method, the mixing ratio of the silane coupling agent having an active hydrogen group and the first raw material polyol is appropriately set according to the purpose and application. The mass ratio of the ring agent is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 10 parts by mass or less, preferably , 5 parts by mass or less.

Further, the active hydrogen derived from the silane coupling agent is, for example, 0.01 mol or more, preferably 0.1 mol or more, relative to 100 mol of active hydrogen derived from the first raw material polyol. mol or less, preferably 5 mol or less.

Also in the above polymerization, if necessary, a reaction catalyst such as an amine-based, tin-based, or lead-based reaction catalyst may be added. can also be removed by known methods such as, for example, distillation or extraction.

In addition, the polyisocyanate compound in which the raw material component and the silane coupling agent are covalently bonded is not limited to the isocyanate group-terminated prepolymer described above.

For example, in the production of an isocyanate group-terminated prepolymer, a silane coupling agent having an isocyanate group, which will be described later, is blended, and the first raw material polyisocyanate, the silane coupling agent having an isocyanate group, and the first raw material polyol are reacted. can also

In this method, the silane coupling agent has an isocyanate group, and the raw material component (first raw material polyol) of the polyisocyanate compound has an active hydrogen group, and the active hydrogen group and the isocyanate group are , to covalently bond.

Furthermore, although not described in detail, for example, in the production of an isocyanate group-terminated prepolymer, the silane coupling agent having an active hydrogen group described above and the silane coupling agent having an isocyanate group described later can be used in combination.

In this method, the silane coupling agent has an active hydrogen group, and the raw material component of the polyisocyanate compound (first raw material polyisocyanate) has an isocyanate group, and those active hydrogen groups and isocyanate groups is covalently bonded. Furthermore, the silane coupling agent has an isocyanate group, and the raw material component (first polyol) of the polyisocyanate compound has an active hydrogen group, and the active hydrogen group and the isocyanate group are covalently bonded. do.

Such a method also yields an isocyanate group-terminated prepolymer in which the raw material components and the silane coupling agent are covalently bonded.

The content of the silane coupling agent covalently bonded to the raw material components of the isocyanate group-terminated prepolymer is, for example, 0.5% by mass or more, preferably 1.0% by mass or more, based on the isocyanate group-terminated prepolymer obtained by their reaction. It is 0% by mass or more, for example, 20% by mass or less, preferably 10% by mass or less.

In addition, the isocyanate group content of the isocyanate group-terminated prepolymer (the isocyanate group-terminated prepolymer in which the raw material component and the silane coupling agent are covalently bonded) (the isocyanate group content in terms of solid content excluding the organic solvent) is, for example, 0.3% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and for example, 15% by mass or less, preferably 12% by mass or less, more preferably , 10% by mass or less.

In addition, the average number of isocyanate groups (average number of functional groups) of the isocyanate group-terminated prepolymer in which the raw material component and the silane coupling agent are covalently bonded is, for example, 1.5 or more, preferably 1.9 or more, more preferably 2. 0.0 or more and, for example, 3.5 or less, preferably 3.0 or less, more preferably 2.5 or less.

In addition, the number average molecular weight (number average molecular weight by GPC measurement using standard polystyrene as a calibration curve) is, for example, 500 or more, preferably 800 or more, and, for example, 10,000 or less, preferably 5,000 or less. .

In addition, the resulting reaction product contains an isocyanate group-terminated prepolymer in which the raw material components and the silane coupling agent are covalently bonded, and an isocyanate group-terminated prepolymer to which the silane coupling agent is not covalently bonded. may occur.

The content of the isocyanate group-terminated prepolymer in which the raw material component and the silane coupling agent are covalently bonded is, for example, 90% by mass or more, preferably 95% by mass or more, relative to the polyisocyanate compound (solid content). Yes, for example, 99.99% by mass or less, preferably 99.9% by mass or less.

Then, by using such a polyisocyanate compound, that is, a polyisocyanate compound obtained by covalently bonding a raw material component and a silane coupling agent, as a curing agent, a base material of a two-component curing lamination adhesive (described later) It is possible to improve the adhesion to.

On the other hand, the covalent bond between the raw material component of the active hydrogen group-containing compound and the silane coupling agent is formed, for example, as follows.

That is, in this method, for example, the above-described silane coupling agent having an active hydrogen group is blended in the production of the above-described polyurethane polyol.

The above silane coupling agents having active hydrogen groups can be used alone or in combination of two or more. The silane coupling agent having an active hydrogen group is preferably an amino group-containing silane coupling agent, more preferably 3-aminopropyltriethoxysilane.

In order to form a covalent bond between the raw material component of the active hydrogen group-containing compound and the silane coupling agent, for example, in the production of polyurethane polyol, the second raw material polyisocyanate and the second raw material polyol , with a silane coupling agent having an active hydrogen group.

In the production of polyurethane polyol, the order of mixing the second raw material polyisocyanate, the second raw material polyol and the silane coupling agent is not particularly limited.

That is, for example, the second raw material polyol and the silane coupling agent may be simultaneously reacted (batch reaction) with respect to the second raw material polyisocyanate at a ratio in which the active hydrogen groups are excessive with respect to the isocyanate groups. .

Further, for example, the second raw material polyisocyanate and the silane coupling agent are reacted at least at a ratio in which the isocyanate groups are excessive with respect to the active hydrogen groups, and the isocyanate groups remaining in the reaction product obtained, The second raw material polyol may be reacted in such a ratio that the active hydrogen groups are excessive with respect to the isocyanate groups.

Furthermore, for example, the isocyanate groups remaining in the reaction product obtained after the second raw material polyisocyanate and the second raw material polyol are reacted at least at a ratio in which the isocyanate groups are excessive with respect to the active hydrogen groups, The silane coupling agent may be reacted in such a ratio that the active hydrogen groups are excessive with respect to the isocyanate groups.

In addition, as shown in the production of the polyurethane polyol, after reacting a part of the second raw material polyol (and the silane coupling agent having an active hydrogen group), the obtained reaction product (raw material prepolymer) and , with the remainder of the second raw material polyol (chain extender) (and the silane coupling agent having an active hydrogen group).

Preferably, first, the second raw material polyisocyanate and a part of the second raw material polyol are reacted at least at a rate in which the isocyanate groups are excessive, and then the isocyanate remaining in the resulting reaction product (raw material prepolymer) A group, a silane coupling agent having an active hydrogen group, and the remainder (chain extender) of the second raw material polyol are reacted.

That is, as a method for producing an active hydrogen group-containing compound, preferably, first, a part of the second raw material polyol and the second raw material polyisocyanate are reacted at least at a rate in which the isocyanate group is excessive, and then the resulting reaction A method of reacting an isocyanate group remaining in the product (raw material prepolymer), a silane coupling agent having an active hydrogen group, and the remainder of the second raw material polyol (chain extender) may be mentioned. Preferably, as will be described later, the silane coupling agent having an active hydrogen group and the remainder of the second raw material polyol are sequentially reacted. Moreover, the active hydrogen group-containing compound preferably includes a polyurethane polyol obtained by this method.

More specifically, in this method, first, the second raw material polyisocyanate and part of the second raw material polyol are reacted by a known polymerization method such as bulk polymerization or solution polymerization.

In addition, in the above polymerization, if necessary, a reaction catalyst such as an amine-based, tin-based, or lead-based reaction catalyst may be added. can also be removed by known methods such as, for example, distillation or extraction.

The blending ratio of the second raw material polyisocyanate and part of the second raw material polyol is a ratio at which the isocyanate group is excessive with respect to the active hydrogen group, more specifically, the active hydrogen group of the silane coupling agent is, for example, 1.05 or more, preferably 1.5 or more, for example, 10.0 or less, preferably 5 .0 or less.

As a result, an isocyanate group-terminated prepolymer (raw material prepolymer) is obtained as a reaction product of the second raw material polyisocyanate and part of the second raw material polyol.

Next, in this method, a silane coupling agent having an active hydrogen group and the remainder of the second raw material polyol ( chain extender) is added and allowed to react.

The blending ratio (total amount) of the reaction product, the silane coupling agent, and the remainder of the second raw material polyol is a ratio at which the active hydrogen groups are equal to or greater than the isocyanate groups, and more specifically, The equivalent ratio (isocyanate group/active hydrogen group) of the isocyanate group of the reaction product (raw material prepolymer) to the total amount of the remaining active hydrogen groups of the silane coupling agent and the second raw material polyol is, for example, 0.2 or more, It is preferably 0.3 or more, for example, 0.95 or less, preferably 0.7 or less.

As a result, the free isocyanate groups of the reaction product (raw material prepolymer) and the active hydrogen groups of the silane coupling agent having active hydrogen groups undergo a urethanization reaction to form covalent bonds.

That is, in this method, the silane coupling agent has an active hydrogen group, and the raw material component (raw material prepolymer) of the active hydrogen group-containing compound has an isocyanate group, and the active hydrogen group and the isocyanate The groups are covalently bonded.

As a result, a polyurethane polyol having active hydrogen groups (hydroxyl groups) at the ends of the molecules is obtained.

In this method, the silane coupling agent and the remainder of the second raw material polyol (chain extender) may be added simultaneously or sequentially.

In that case, the order of addition of the silane coupling agent and the remainder of the second raw material polyol (chain extender) is not particularly limited. and then the remainder of the second raw material polyol (chain extender) may be added at a ratio in which the active hydrogen groups are equal to or greater than the isocyanate groups. . Alternatively, for example, first, the remainder of the second raw material polyol (chain extender) is added at a ratio in which the isocyanate group is excessive with respect to the active hydrogen group, and then the silane coupling agent having an active hydrogen group is added to the active hydrogen group. Hydrogen groups may be added in a proportion equal to or greater than that of isocyanate groups.

Preferably, from the viewpoint of improving the viscosity stability during storage, first, a silane coupling agent having an active hydrogen group is added in a proportion in which the isocyanate group is excessive with respect to the active hydrogen group, and then the second The rest of the raw material polyol (chain extender) is added in such a proportion that the active hydrogen groups are equal to or greater than the isocyanate groups.

In the above method, the total ratio of the second raw polyisocyanate, the second raw polyol and the silane coupling agent (total amount) is the active hydrogen groups of the second raw polyol with respect to the isocyanate groups of the second raw polyisocyanate. and the equivalent ratio (active hydrogen group/isocyanate group) of the total amount of active hydrogen groups in the silane coupling agent, the ratio at which the active hydrogen groups are equal or more, for example, 1.0 or more, preferably 1.05 For example, it is 1.5 or less, preferably 1.2 or less.

In the above method, the mixing ratio of the silane coupling agent having an active hydrogen group and the second raw material polyol is appropriately set according to the purpose and application. The mass ratio of the coupling agent is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 10.0 parts by mass or less with respect to 100 parts by mass of the total amount of the second raw material polyol. , preferably 5.0 parts by mass or less.

Further, the active hydrogen derived from the silane coupling agent having an active hydrogen group is, for example, 0.01 mol or more, preferably 0.1 mol or more with respect to 100 mol of active hydrogen derived from the second raw material polyol. Yes, for example, 10.0 mol or less, preferably 5.0 mol or less.

Then, by using such an active hydrogen group-containing compound, that is, an active hydrogen group-containing compound obtained by covalently bonding a raw material component and a silane coupling agent, as a main agent, a base material of a two-component curing laminating adhesive can be obtained. (described later) can be improved.

In addition, the active hydrogen group-containing compound in which the raw material component and the silane coupling agent are covalently bonded is not limited to the polyurethane polyol described above.

For example, in the production of polyurethane polyol, a silane coupling agent having an isocyanate group may be blended, and the second raw polyisocyanate, the silane coupling agent having an isocyanate group, and the second raw polyol may be reacted.

Examples of the silane coupling agent having an isocyanate group include isocyanate group-containing silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride, tris-(trimethoxysilylpropyl)isocyanurate, and 3-isocyanatopropyltriethoxysilane. agents.

These isocyanate group-containing silane coupling agents can be used alone or in combination of two or more.

The silane coupling agent having an isocyanate group is preferably 3-isocyanatopropyltriethoxysilane.

In the production of polyurethane polyol, the order of mixing the second raw material polyisocyanate, the silane coupling agent and the second raw material polyol is not particularly limited.

For example, in the production of the polyurethane polyol described above, first, the second raw material polyisocyanate and part of the second raw material polyol are reacted, and then the resulting isocyanate group-terminated prepolymer (raw material prepolymer) and the second raw material polyol (chain extender), the resulting polyurethane polyol can be further reacted with a silane coupling agent having an isocyanate group.

More specifically, in this method, first, the second raw material polyisocyanate and part of the second raw material polyol are reacted by a known polymerization method such as bulk polymerization or solution polymerization.

The blending ratio of a part of the second raw material polyol and the second raw polyisocyanate is a ratio at which the isocyanate group is excessive with respect to the active hydrogen group, more specifically, with respect to the active hydrogen group of the second raw material polyol The isocyanate group equivalent ratio (isocyanate group/active hydrogen group) of the second raw material polyisocyanate is, for example, 1.2 or more, preferably 1.3 or more, for example, 3.0 or less, preferably 2.5 or less. is.

In addition, in the above polymerization, if necessary, a reaction catalyst such as an amine-based, tin-based, or lead-based reaction catalyst may be added. can also be removed by known methods such as, for example, distillation or extraction.

As a result, an isocyanate group-terminated prepolymer (raw material prepolymer) is obtained as a reaction product of the second raw material polyisocyanate and part of the second raw material polyol.

Next, in this method, the isocyanate group-terminated prepolymer (raw material prepolymer) obtained above is reacted with the remainder of the second raw material polyol (preferably a low molecular weight polyol (chain extender)) to produce a polyurethane polyol. obtain.

The mixing ratio of the isocyanate group-terminated prepolymer (raw material prepolymer) and the remainder of the second raw material polyol (chain extender) is such that the active hydrogen groups are equal to or more than the isocyanate groups.

More specifically, the equivalent ratio (active hydrogen group/isocyanate group) of the active hydrogen group in the remainder (chain extender) of the second raw material polyol to the isocyanate group of the isocyanate group-terminated prepolymer (raw material prepolymer) is For example, it is 1.0 or more, preferably 1.05 or more, for example, 1.5 or less, preferably 1.2 or less.

As a result, the isocyanate group-terminated prepolymer (raw material prepolymer) reacts with the remainder of the second raw material polyol (chain extender) to obtain a polyurethane polyol.

In addition, this polyurethane polyol is a raw material polyurethane polyol as a raw material component of the active hydrogen group-containing compound.

Thereafter, in this method, the raw material polyurethane polyol obtained above and a silane coupling agent having an isocyanate group are blended and reacted.

The blending ratio of the raw material polyurethane polyol and the silane coupling agent having an isocyanate group is such that the active hydrogen groups are excessive with respect to the isocyanate groups.

More specifically, the equivalent ratio of the active hydrogen groups of the polyurethane polyol to the isocyanate groups of the silane coupling agent (active hydrogen groups/isocyanate groups) is, for example, 1.05 or more, preferably 1.05 or more. , for example, 10.0 or less, preferably 5.0 or less.

Thereby, the raw material component (raw material polyurethane polyol) of the active hydrogen group-containing compound and the silane coupling agent form a covalent bond.

As a result, a polyurethane polyol (polyurethane polyol obtained by covalently bonding a raw material polyurethane polyol and a silane coupling agent) is obtained as an active hydrogen group-containing compound.

That is, in this method, the silane coupling agent has an isocyanate group, and the raw material component (raw material polyurethane polyol) of the active hydrogen group-containing compound has an active hydrogen group, and the active hydrogen group and the isocyanate The groups are covalently bonded.

Therefore, by using such an active hydrogen group-containing compound, that is, an active hydrogen group-containing compound obtained by covalently bonding a raw material component and a silane coupling agent, as a main agent, a base material ( (to be described later) can be improved.

Furthermore, although not described in detail, for example, in the production of polyurethane polyol, the above-described silane coupling agent having an active hydrogen group and the above-described silane coupling agent having an isocyanate group can be used in combination.

In this method, the silane coupling agent has an active hydrogen group, and the raw material component (second raw material polyisocyanate) of the polyisocyanate compound has an isocyanate group, and the active hydrogen group and the isocyanate group are , to covalently bond. Furthermore, the silane coupling agent has an isocyanate group, and the raw material component of the polyisocyanate compound (second raw material polyol, raw material prepolymer, etc.) has an active hydrogen group, and the active hydrogen group and the isocyanate The groups are covalently bonded.

Such a method also yields a polyurethane polyol in which the raw material component and the silane coupling agent are covalently bonded.

The content of the silane coupling agent covalently bonded to the raw material components of the polyurethane polyol is, for example, 0.5% by mass or more, preferably 1.0% by mass or more, relative to the polyurethane polyol obtained by their reaction. , for example, 20% by mass or less, preferably 10% by mass or less.

In addition, the average number of hydroxyl groups (average number of functional groups) of the polyurethane polyol (polyurethane polyol in which the raw material component and the silane coupling agent are covalently bonded) is, for example, 1.5 or more, preferably 1.9 or more, and more preferably 2. 0.0 or more and, for example, 3.0 or less, preferably 2.5 or less.

In addition, the number average molecular weight (number average molecular weight by GPC measurement using standard polystyrene as a calibration curve) is, for example, 500 or more, preferably 800 or more, and, for example, 10,000 or less, preferably 5,000 or less. .

The resulting reaction product may contain polyurethane polyols in which raw material components and silane coupling agents are covalently bonded, as well as polyurethane polyols in which silane coupling agents are not covalently bonded.

The content of the polyurethane polyol obtained by covalently bonding the raw material components and the silane coupling agent is, for example, 1.5% by mass or more, preferably 1.5% by mass or more, based on the active hydrogen group-containing compound (solid content). It is 9% by mass or more, for example, 80% by mass or less, preferably 70% by mass or less.

Then, by using such an active hydrogen group-containing compound, that is, an active hydrogen group-containing compound obtained by covalently bonding a raw material component and a silane coupling agent, as a main agent, a base material of a two-component curing laminating adhesive can be obtained. (described later) can be improved.

Furthermore, the covalent bond between the raw material component of the active hydrogen group-containing compound and the silane coupling agent is not limited to the form described above.

For example, an amino group-containing silane coupling agent and a polyisocyanate compound are added to a high-molecular-weight polyol, and the amino-group-containing silane coupling agent is covalently bonded to the high-molecular-weight polyol via the polyisocyanate compound. can also

More specifically, in this method, a high-molecular-weight polyol (preferably polyester polyol), the above polyisocyanate compound (e.g., polyisocyanate monomer, polyisocyanate derivative), and an amino group-containing silane coupling agent is added.

The blending ratio of the polyisocyanate compound is a ratio at which the isocyanate groups of the polyisocyanate compound are excessive relative to the amino group-containing silane coupling agent. The equivalent ratio of the isocyanate group of the polyisocyanate compound to the group (isocyanate group/amino group) is, for example, more than 1.00, preferably 1.10 or more, more preferably 1.20 or more, for example, It is 2.00 or less, preferably 1.50 or less, more preferably 1.25 or less.

Further, the total amount of the polyisocyanate compound and the amino group-containing silane coupling agent is, with respect to 100 parts by mass of the high molecular weight polyol, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, for example, 10.0 parts by mass or less, preferably 5.0 parts by mass or less, more preferably 2.0 parts by mass or less, More preferably, it is 1.5 parts by mass or less.

When the polyisocyanate compound and the amino group-containing silane coupling agent are added to the high-molecular-weight polyol in the above proportions, the amino group of the amino group-containing silane coupling agent first urea with the isocyanate group of the polyisocyanate compound. react to form urea groups. Thereafter, excess isocyanate groups of the urea-modified polyisocyanate compound and hydroxyl groups of the high-molecular-weight polyol undergo a urethanization reaction to form urethane groups.

Thereby, the amino group-containing silane coupling agent can be covalently bonded to the high molecular weight polyol via the polyisocyanate compound.

Then, by using such an active hydrogen group-containing compound, that is, an active hydrogen group-containing compound containing a covalent bond of a high molecular weight polyol, a polyisocyanate compound and an amino group-containing silane coupling agent as a main agent, two-liquid curing can be achieved. It is possible to improve the adhesion of the mold lamination adhesive to the substrate (described later), and further improve the retort resistance.

In addition, in the above reaction, the mixing ratio of the polyisocyanate compound is preferably at least the above ratio. For example, the equivalent ratio (isocyanate group/amino group) of the isocyanate group of the polyisocyanate compound to the amino group-containing silane coupling agent may be one. In this case, the urea formation reaction of amino groups and isocyanate groups and the urethanization reaction of isocyanate groups and hydroxyl groups are competing reactions, but the polyisocyanate compound is a high-molecular-weight polyol and an amino group-containing silane coupling agent. This includes the case of reacting with both.

In addition, from the viewpoint of improving adhesion, the two-liquid curing laminating adhesive may contain an oxyacid of phosphorus and/or a derivative thereof in either or both of the curing agent and the main agent. Preferably, the main agent contains an oxyacid of phosphorus and/or a derivative thereof.

Examples of oxyacids of phosphorus include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid and hypophosphoric acid; acids and the like.

Examples of oxyacid derivatives of phosphorus include phosphates or condensed phosphates of sodium and potassium, such as monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, and mono-orthophosphate. 2-ethylhexyl, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, monopropyl phosphite, monobutyl phosphite, mono-2-ethylhexyl phosphite, monoesters such as monophenyl phosphite, For example, di-2-ethylhexyl orthophosphate, diphenyl orthophosphate, trimethyl orthophosphate, triethyl orthophosphate, tripropyl orthophosphate, tributyl orthophosphate, tri-2-ethylhexyl orthophosphate, triphenyl orthophosphate, dimethyl phosphite, nitrite diethyl phosphate, dipropyl phosphite, dibutyl phosphite, di-2-ethylhexyl phosphite, diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, tributyl phosphite Examples include di- and triesters such as tri-2-ethylhexyl phosphate and triphenyl phosphite, and mono-, di- and triesters obtained from condensed phosphoric acid and alcohols.

These phosphorus oxyacids or derivatives thereof can be used alone or in combination of two or more.

Phosphorus oxyacids or derivatives thereof preferably include phosphoric acids, more preferably orthophosphoric acid (phosphoric acid).

The ratio of the oxygen acid of phosphorus or its derivative is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, or, for example, 3.0 parts per 100 parts by mass of the total amount of the curing agent and the main agent. It is not more than 2.5 parts by mass, preferably not more than 2.5 parts by mass.

In addition, the ratio of the oxygen acid of phosphorus or a derivative thereof is 100 masses of the above-described silane coupling agent (the raw material component of the polyisocyanate compound and/or the silane coupling agent that covalently bonds with the raw material component of the active hydrogen group-containing compound). part, from the viewpoint of adhesion (especially adhesive strength), for example, 0.5 parts by mass or more, preferably 1.0 parts by mass or more, more preferably 1.5 parts by mass or more, more preferably , 2.0 parts by mass or more. In addition, from the viewpoint of suppressing deterioration of storage stability and adhesion (especially heat seal strength), for example, 10 parts by mass or less, preferably 8.0 parts by mass or less, more preferably 5.0 parts by mass or less , and more preferably 3.5 parts by mass or less.

Furthermore, the two-component curing laminating adhesive may contain a silane coupling agent that does not react with the raw material components in either one or both of the curing agent and the main agent.

That is, a silane coupling agent that has not reacted with the raw material components of the polyisocyanate compound can be separately added and mixed with the curing agent of the two-component curing lamination adhesive.

Silane coupling agents that can be added to the curing agent include silane coupling agents that do not react with isocyanate groups, such as silane coupling agents that do not contain active hydrogen groups.

Examples of such silane coupling agents include, more specifically, vinyl group-containing silane coupling agents such as vinyltrimethoxysilane, and aromatic vinyl group-containing silane coupling agents such as p-styryltrimethoxysilane. (Meth)acrylic group-containing silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. and epoxy group-containing silane coupling agents. Further, for example, silane coupling agents having the above-described isocyanate groups are also included.

These silane coupling agents can be used alone or in combination of two or more.

Examples of the silane coupling agent that can be added to the main agent include silane coupling agents that do not react with active hydrogen groups, such as silane coupling agents that do not contain isocyanate groups.

Such silane coupling agents include, for example, the above vinyl group-containing silane coupling agents, aromatic vinyl group-containing silane coupling agents, (meth)acrylic group-containing silane coupling agents, and epoxy group-containing silane coupling agents. etc. Further, for example, silane coupling agents having an active hydrogen group as described above may also be used.

These silane coupling agents can be used alone or in combination of two or more.

The addition ratio of the silane coupling agent to the curing agent and/or main agent is appropriately set within a range that does not impair the excellent effects of the present invention.

Furthermore, in the two-liquid curing lamination adhesive, if necessary, either one or both of the curing agent and the main agent may include, for example, an antifoaming agent, an epoxy resin, a catalyst, and a coatability improving agent. Additives such as agents, leveling agents, stabilizers (antioxidants, ultraviolet absorbers, etc.), plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, antifungal agents, etc., can be appropriately added.

The amount of the additive to be added is appropriately determined according to its purpose and application.

In the two-liquid curing laminating adhesive, the main agent and the curing agent are separately prepared and blended at the time of use.

When using a two-component curing lamination adhesive, the mixing ratio of the main agent and the curing agent is, for example, the equivalent ratio of the isocyanate group of the curing agent to the active hydrogen group of the main agent (isocyanate group/active hydrogen group) is, for example, The ratio is 0.5 to 5, preferably 0.6 to 3.

In addition, the two-liquid curing lamination adhesive can contain the above organic solvent, if necessary. The organic solvent may be blended with the curing agent and/or the main agent as described above, or may be blended separately when the curing agent and the main agent are mixed.

In the two-liquid curing lamination adhesive, the content of the organic solvent is appropriately set so that the total amount of the solid content (resin solid content) of the curing agent and the main agent is at a predetermined rate.

From the viewpoint of coating workability, the solid content concentration of the two-liquid curing lamination adhesive 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, preferably 40 mass % or less, more preferably 30 mass % or less.

And such a two-component curing lamination adhesive has a curing agent containing a polyisocyanate compound and a main component containing an active hydrogen group-containing compound, and is a two-component curing lamination adhesive that is blended at the time of use. Therefore, the polyisocyanate compound and the active hydrogen group-containing compound do not react before use (before compounding), and the rapid curing and storage stability are excellent.

In addition, in the two-component curing lamination adhesive described above, the silane coupling agent, the raw material component of the polyisocyanate compound, and/or the raw material component of the active hydrogen group-containing compound are covalently bonded. A liquid curing laminating adhesive has excellent adhesion to a substrate.

Therefore, the two-liquid curing lamination adhesive described above is suitable for use in the production of laminate films.

In the production of laminate films, the above-described two-component curing lamination adhesive is prepared and stored separately as a main agent and a curing agent, and these are mixed at the time of use. Then, the resulting mixture (laminate adhesive) is applied (coated) to the substrate.

The ambient temperature for mixing and coating is not particularly limited, but is, for example, 30° C. or higher, preferably 40° C. or higher, and for example, 100° C. or lower, preferably 90° C. or lower.

The mixing ratio of the curing agent and the main agent is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, of the curing agent to 100 parts by mass of the main agent, as a mass ratio of the curing agent to the main agent. Also, for example, it is 500 parts by mass or less, preferably 300 parts by mass or less.

Further, for example, the equivalent ratio of the isocyanate group of the curing agent to the active hydrogen group of the main agent (isocyanate group/active hydrogen group) is, for example, 0.3 or more, preferably 0.5 or more, or, for example, 5.0. Below, it is preferably 3.0 or less.

The two-liquid curable lamination adhesive is used as an adhesive for producing a laminate film (composite film) by laminating a film as a substrate, such as a barrier film or a plastic film.

More specifically, the two-liquid curing laminating adhesive is used, for example, for laminating plastic films together or laminating a barrier film and a plastic film.

Plastic films include, for example, olefin polymers (e.g., polyethylene, polypropylene, etc.), polyester polymers (e.g., polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, polyalkylene naphthalates, and their polyalkylene arylate units (e.g., nylon (registered trademark) such as nylon 6, nylon 66, etc.), vinyl polymers (e.g., polyvinyl chloride, ethylene-vinyl acetate copolymer , ethylene-vinyl alcohol copolymer, etc.). The thickness of the plastic film is usually 5 μm or more and usually 200 μm or less.

As the plastic film, any of heat-sealable unstretched films (unstretched polyethylene, polypropylene, etc.), uniaxially or biaxially stretched films (biaxially stretched polypropylene, polyalkylene terephthalate, nylon, etc.) can be used.

Also, the plastic film can be prepared as various coextruded films or as a composite film in which plastic films are adhered in advance.

A barrier film is a layer having barrier properties against gases or liquids, and includes, for example, films containing metals or metal oxides. Specifically, a metal foil or a plastic film containing a barrier layer can be used.

The metal foil is made of, for example, aluminum, stainless steel, iron, copper, lead, or the like, and has a thickness of, for example, 5 μm or more and, for example, 100 μm or less, preferably 20 μm or less, more preferably 15 μm or less. be.

As the plastic film containing the barrier layer, for example, a film in which an inorganic layer is formed on at least one surface of the above-mentioned plastic film can be mentioned.

The inorganic layer can be formed by vapor deposition, sputtering, sol-gel method, or the like. The inorganic layer can be formed, for example, from a simple substance such as titanium, aluminum, or silicon, or an inorganic compound (such as an oxide) containing those elements. As the inorganic layer, preferably, aluminum alone, alumina alone, silica alone, or both alumina and silica are vapor-deposited on a plastic film.

In addition, the plastic film including the barrier layer can also be laminated with an overcoat layer on the exposed side of the barrier layer.

Furthermore, the surfaces of the plastic film and the barrier film may be subjected to surface treatment such as corona discharge treatment, or may be subjected to primer treatment with an anchor coating agent or the like. Also, the plastic film and the barrier film can be printed as appropriate.

In the production of a laminate film, for example, when bonding plastic films together, a two-component curing lamination adhesive containing a curing agent and a main agent is applied to the surface of either one of the two plastic films, The coated surface is attached to the surface of the other plastic film.

Further, for example, when bonding a barrier film and a plastic film together, a two-component curing lamination adhesive containing a curing agent and a main agent is applied to the surface of either the barrier film or the plastic film. The coated side is laminated to the surface of the other barrier film or plastic film and, in each case, subsequently cured and cured at room temperature or under elevated temperature.

As the laminate film, for example, when the plastic films are laminated together, two plastic films are laminated together (primary lamination), and when a barrier film and a plastic film are laminated together, for example, a barrier film is used. A film and a plastic film may be laminated together (primarily laminated) to produce a primary laminated composite film, and another plastic film may be laminated to at least one surface of the primary laminated composite film. (Secondary lamination) to produce a secondary laminated composite film.

In the primary lamination, either one of the barrier film and the plastic film is usually sent out from a delivery roll, the other is laminated, wound on a take-up roll, and if necessary, heated and cured (for example, 25 ° C. or higher Curing at 60°C or less).

In the secondary lamination, the primary laminate composite film is usually sent out from the winding roll, another plastic film is laminated, wound on the winding roll, and if necessary, heated and cured (for example, 25 ° C. or higher Curing at 60°C or less).

In the production of the secondary laminate composite film, both the primary laminate and the secondary laminate may use a two-component curable laminate adhesive, or either the primary laminate or the secondary laminate may be Two-part curing laminating adhesives can be used, while other adhesives can be used.

The primary and secondary lamination temperature (coating temperature) is usually 35°C or higher, preferably 40°C or higher. Although there is no upper limit for the temperature as long as lamination can be performed, it is usually 100° C. or lower, preferably 90° C. or lower, and more preferably 85° C. or lower. As the upper and lower limits of the temperature, at the time of lamination (coating), for example, 35 ° C. or higher, preferably 35 ° C. or higher, more preferably 40 ° C. or higher, and, for example, 100 ° C. or lower, preferably 90 ° C. or lower. Preferably, the two-component curing laminating adhesive is heated at 80° C. or lower to adjust the viscosity to an appropriate value. Appropriate viscosity is, for example, 100 mPa·s or more, preferably 300 mPa·s or more, and for example, 5000 mPa·s or less, preferably 3000 mPa·s or less, at a temperature within the above range.

If the temperature is set to 100° C. or less, the reaction between the curing agent and the main agent can be suppressed before coating, thereby preventing excessive thickening and ensuring good workability.

The coating amount of the two-liquid curing lamination adhesive is, for example, 0.5 g/m ² or more, preferably 1 g/m ² or more, more preferably 1.5 g/m ² or more in each lamination step. and, for example, 5 g/m ² or less, preferably 4.5 g/m ² or less. If the coating amount is at least the above lower limit, the adhesion is not sufficiently expressed, and it is possible to prevent appearance defects. It is possible to prevent the agent from leaking out and causing poor quality of the laminate film.

Further, as a lamination device using a two-liquid curing lamination adhesive, known devices such as a forward transfer coating device and a reverse transfer coating device (reverse coater) can be used.

As a result, a laminate film can be produced using the above-described two-component curing lamination adhesive that is excellent in fast curing property, storage stability, and adhesion to the substrate.

In other words, the laminate film includes an adhesive layer containing a cured product of the two-component curing laminating adhesive described above.

Therefore, the laminate film obtained is excellent in adhesion between the substrate and the adhesive layer and also in productivity.

Therefore, the above-mentioned two-liquid curing laminating adhesive can be used, for example, for various packaging materials such as refillable standing pouches in the field of toiletries, packaging materials for retort foods and dry foods, packaging materials for pharmaceuticals, electronic/electrical parts, etc. , battery members such as solar cells and fuel cells, household materials such as shopping bags, book covers and stickers, and construction and industrial materials such as decorative sheets.

Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited by the following examples. "Parts" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are the corresponding mixing ratios ( Content ratio), physical properties, parameters, etc. be able to.

(1) First embodiment <Production of curing agent>
Production Example 1 (Curing Agent A-1)
199 g of diphenylmethane diisocyanate (MDI, Mitsui Chemicals SKC Polyurethane, Cosmonate 300MNB) was dissolved in 141 g of ethyl acetate at 45°C.

348 g of polyoxypropylene glycol was added thereto under a nitrogen stream and heated to 65° C., then 13 g of trimethylolpropane was added and the temperature was raised to 75° C., and the urethanization reaction was carried out for 1 hour. After that, 0.056 g of tin octylate was added, and the urethanization reaction was carried out at 80° C. for 1 hour.

As a result, an isocyanate group-terminated prepolymer was obtained as a polyisocyanate compound without blending a silane coupling agent. The isocyanate group-terminated prepolymer was obtained as a solution having a solid content of 80% by mass. This was used as Curing Agent A-1.

Production Example 2 (curing agent A-2)
199 g of diphenylmethane diisocyanate (MDI, Mitsui Chemicals SKC Polyurethane, Cosmonate 300MNB) was dissolved in 141 g of ethyl acetate at 45°C.

12 g of 3-aminopropyltriethoxysilane was added thereto under a nitrogen stream and heated to 65°C.

Further, 336 g of polyoxypropylene glycol was added and heated to 65° C., then 13 g of trimethylolpropane was added and the temperature was raised to 75° C., and urethanization reaction was carried out for 1 hour. After that, 0.056 g of tin octylate was added, and the urethanization reaction was carried out at 80° C. for 1 hour.

As a result, an isocyanate group-terminated prepolymer in which the raw material component and the silane coupling agent were covalently bonded was obtained. The isocyanate group-terminated prepolymer was obtained as a solution having a solid content of 80% by mass. This was used as curing agent A-2.

Production Example 3 (curing agent A-3)
12 g of 3-isocyanatopropyltriethoxysilane was added to the curing agent A-1 and stirred at 25° C. for 30 minutes.

As a result, a mixture of the isocyanate group-terminated prepolymer and the silane coupling agent was obtained. The obtained mixed liquid was used as a curing agent A-3.

The curing agent A-3 was simply a mixture of an isocyanate group-terminated prepolymer and a silane coupling agent, and did not form a covalent bond between the raw material components and the silane coupling agent.

<Preparation of main agent>
Preparation Example 1 (main agent B-1)
Tolylene diisocyanate (TDI, Mitsui Chemicals SKC Polyurethane, Cosmonate T-80) (85 g) was added and urethanized at 50°C. Then, after diluting the obtained reaction product with 150 g of ethyl acetate, 0.028 g of tin octylate was added, and further urethanization reaction was carried out at 60° C. for 1 hour.

As a result, an isocyanate group-terminated prepolymer (raw material prepolymer) was obtained.

After that, 3.5 g of 3-aminopropyltriethoxysilane (silane coupling agent, Shin-Etsu Chemical Co., Ltd., KBE-903) was added to the isocyanate group-terminated prepolymer (raw material prepolymer) and reacted for 30 minutes. Further, 16 g of 1,4-butanediol (chain extender) was added and urethanized for 3 hours. Then 0.065 g of tin octoate was added and the reaction continued until the isocyanate peak disappeared in the IR spectrum.

As a result, a polyurethane polyol in which the raw material component and the silane coupling agent were covalently bonded was obtained. The polyurethane polyol was obtained as a solution with a solid content of 70% by mass. This was designated as main agent B-1.

Preparation Example 2 (main ingredient B-2)
0.035 g of phosphoric acid was added to the main ingredient B-1, and the mixture was stirred at 60° C. for 30 minutes. As a result, a main component B-2 was obtained. The amount of phosphoric acid added was 1.0 parts by mass with respect to 100 parts by mass of the silane coupling agent.

Preparation Example 3 (main agent B-3)
0.087 g of phosphoric acid was added to the main ingredient B-1, and the mixture was stirred at 60° C. for 30 minutes. As a result, a main component B-3 was obtained. The amount of phosphoric acid added was 2.5 parts by mass with respect to 100 parts by mass of the silane coupling agent.

Preparation Example 4 (main agent B-4)
0.175 g of phosphoric acid was added to the main ingredient B-1, and the mixture was stirred at 60° C. for 30 minutes. As a result, a main component B-4 was obtained. The amount of phosphoric acid added was 5 parts by mass with respect to 100 parts by mass of the silane coupling agent.

Preparation Example 5 (main ingredient B-5)
0.35 g of phosphoric acid was added to the main ingredient B-1, and the mixture was stirred at 60° C. for 30 minutes. As a result, a main component B-5 was obtained. The amount of phosphoric acid added was 10 parts by mass with respect to 100 parts by mass of the silane coupling agent.

Preparation Example 6 (main agent B-6)
Tolylene diisocyanate (TDI, Mitsui Chemicals SKC Polyurethane, Cosmonate T-80) (85 g) was added and urethanized at 50°C. Then, after diluting the obtained reaction product with 150 g of ethyl acetate, 0.028 g of tin octylate was added, and further urethanization reaction was carried out at 60° C. for 1 hour.

As a result, an isocyanate group-terminated prepolymer (raw material prepolymer) was obtained.

After that, 16 g of 1,4-butanediol (chain extender) was added to the isocyanate group-terminated prepolymer (raw material prepolymer) and urethanized for 3 hours. Further, 0.065 g of tin octylate was added and the reaction was continued for 1 hour. After that, 3-isocyanatopropyltriethoxysilane (a silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd., KBE-9007) was added, and the reaction was continued until the isocyanate peak disappeared in the IR spectrum.

As a result, a polyurethane polyol in which the raw material component and the silane coupling agent were covalently bonded was obtained. The polyurethane polyol was obtained as a solution with a solid content of 70% by mass. This was designated as main agent B-6.

Preparation Example 7 (main agent B-7)
0.35 g of phosphoric acid was added to the main ingredient B-6. Stirred at 60° C. for 30 minutes. As a result, a main component B-7 was obtained. The amount of phosphoric acid added was 10 parts by mass with respect to 100 parts by mass of the silane coupling agent.

Preparation Example 8 (main agent B-8)
Tolylene diisocyanate (TDI, Mitsui Chemicals SKC Polyurethane, Cosmonate T-80) (85 g) was added and urethanized at 50°C. Then, after diluting the obtained reaction product with 150 g of ethyl acetate, 0.028 g of tin octylate was added, and further urethanization reaction was carried out at 60° C. for 1 hour.

As a result, an isocyanate group-terminated prepolymer (raw material prepolymer) was obtained.

After that, 16 g of 1,4-butanediol (chain extender) was added to the isocyanate group-terminated prepolymer (raw material prepolymer) and urethanized for 3 hours. Further, 0.065 g of tin octoate was added and the reaction was continued until the isocyanate peak disappeared in the IR spectrum.

As a result, a polyurethane polyol was obtained without adding a silane coupling agent. The polyurethane polyol was obtained as a solution with a solid content of 70% by mass.

Further, 0.35 g of phosphoric acid was added thereto and stirred at 60° C. for 30 minutes. As a result, a main agent B-8 was obtained. The amount of phosphoric acid added was the same amount as that of the main agent B-5 (equivalent to 10 parts by mass with respect to 100 parts by mass of the silane coupling agent of B-5).

Preparation Example 9 (main ingredient B-9)
3.5 g of 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) was added to the main ingredient B-8, and the mixture was stirred at room temperature for 30 minutes. As a result, a main component B-9 was obtained.

The main component B-9 was obtained by simply mixing a silane coupling agent with a polyurethane polyol, and did not form a covalent bond between the raw material components and the silane coupling agent.

Examples 1-6, Comparative Example 17, Comparative Examples 1-8 and Comparative Examples 1-3
Production of Laminate Adhesive A main agent and a curing agent were prepared in the combination shown in Table 1 to obtain a two-liquid curable lamination adhesive.

Next, the curing agent (isocyanate group-terminated prepolymer) of 50 parts by mass based on the solid content of the curing agent (isocyanate group-terminated prepolymer) and the main component (polyurethane polyol) of 100 parts by mass based on the solid content of the curing agent and the main component are combined as shown in Table 1. were mixed, and the solid content concentration was adjusted to 75% by mass with ethyl acetate.

・Production of laminate film Using the laminate adhesive obtained above (a mixture containing a curing agent and a main agent), a polyethylene terephthalate film (PET) with a thickness of 12 μm / an aluminum foil (AL) with a thickness of 7 μm / A composite film consisting of three layers of polyethylene film (PE) with a thickness of 40 μm was produced.

That is, a laminate adhesive (a mixture containing a curing agent and a main agent) is first applied to a polyethylene terephthalate film using a bar coater (#8) at room temperature, the solvent is volatilized, and then the coated surface is It was pasted on aluminum foil.

Next, on the other side of the aluminum foil, that is, on the other side of the aluminum foil to the surface to be attached to the polyethylene terephthalate film, a lamination adhesive (a mixture containing a curing agent and a main agent) is applied in the same manner as described above. After coating and volatilizing the solvent, the coated surface was attached to a polyethylene film.

After that, the obtained composite film was aged at 40° C. for 2 days to cure the laminate adhesive.

<Evaluation>
(1) Adhesion The obtained composite film was measured at 24° C. with a test piece width of 15 mm, and the adhesive strength (peel strength) between the aluminum foil and polyethylene was measured at a tensile speed of 300 mm / min by T-type peeling. .

The heat seal strength (HS strength) was evaluated by heat sealing the composite films together under the conditions of 180° C., 0.1 MPa, and 0.6 seconds.
(2) Storage stability Storage stability was evaluated as follows.

That is, 90 ml of the main agent or curing agent forming a covalent bond between the raw material component and the silane coupling agent of the laminate adhesive before mixing of each example and each comparative example was placed in a 100 ml glass bottle and sealed. , and placed in a constant temperature room at 25°C.

Then, the rate of change in viscosity after one month at 25° C. [100×(viscosity after storage−viscosity before storage)/viscosity before storage)] was calculated.

In addition, the evaluation criteria are described below.

◎: Less than 10% change in viscosity after 1 month at 25°C ○: Change in viscosity from 10% to less than 50% after 1 month at 25°C △: Change in viscosity from 50% to less than 200% after 1 month at 25°C ×: Cloudy . Viscosity change of 200% or more after 1 month at 25°C (3) Rapid Curing In the production of laminate films, the time required for curing of the laminate adhesive was measured. As a result, it was confirmed that each example cured within 24 hours and had excellent rapid curability.

(2) Second embodiment <Production of acid-modified polyol>
Production example 1
568 g of isophthalic acid, 142 g of terephthalic acid, 205 g of ethylene glycol, 306 g of neopentyl glycol, 234 g of 1,6-hexanediol and 0.29 g of zinc acetate were subjected to an esterification reaction at 180 to 220° C. under a nitrogen stream. After a predetermined amount of water was distilled off, 48.9 g of dimer acid and 250 g of adipic acid were added, and esterification reaction was carried out at 180-220°C. After that, the pressure in the system was gradually reduced, and the condensation reaction was carried out at 220 to 230° C. for 6 hours.

Further, 6.83 g of trimellitic anhydride was added and reacted (acid-modified) at 140 to 150° C., and 920 g of ethyl acetate was added to obtain polyol A as a solution having a solid content of 60%.

In addition, the number average molecular weight of the polyester polyol in the obtained polyol A was about 6,000.

The obtained solution of polyol A was designated as acid-modified polyol 1.

<Preparation of curing agent>
Preparation example 1 (curing agent A2-1)
60 g of the trimethylolpropane adduct of XDI (Takenate A-10, manufactured by Mitsui Chemicals) and 40 g of the trimethylolpropane adduct of IPDI (Takenate A-40E, manufactured by Mitsui Chemicals) were uniformly mixed at 50 ° C. under a nitrogen atmosphere. to obtain a curing agent A2-1 having an isocyanate group content of about 11%.

<Preparation of main agent>
Preparation Example 1 (main agent B2-1)
100 parts of acid-modified polyol (solution of polyol A), 0.012 parts of 85% solution of phosphoric acid with respect to 100 parts of solid content of acid-modified polyol, amino group-containing silane coupling agent A (3-aminopropyltriethoxy A main agent B2-1 was prepared by blending 0.60 parts of silane, KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter the same), and 0.30 parts of IPDI (second polyisocyanate compound).

The equivalent ratio (isocyanate group/amino group) of the isocyanate group of the second polyisocyanate compound to the amino group of the amino group-containing silane coupling agent was 1.0.

Preparation Example 2 (main ingredient B2-2)
By blending 100 parts of acid-modified polyol (solution of polyol A), 0.60 parts of amino group-containing silane coupling agent A with respect to 100 parts of solid content of acid-modified polyol, and 0.30 parts of IPDI , to prepare the main agent B2-2.

The equivalent ratio (isocyanate group/amino group) of the isocyanate group of the second polyisocyanate compound to the amino group of the amino group-containing silane coupling agent was 1.0.

Preparation Example 3 (main agent B2-3)
By blending 100 parts of acid-modified polyol (solution of polyol A), 0.60 parts of amino group-containing silane coupling agent A with respect to 100 parts of solid content of acid-modified polyol, and 0.60 parts of IPDI , to prepare the main agent B2-3.

The equivalent ratio (isocyanate group/amino group) of the isocyanate group of the second polyisocyanate compound to the amino group of the amino group-containing silane coupling agent was 2.0.

Preparation Example 4 (main agent B2-4)
100 parts of acid-modified polyol (solution of polyol A), 0.012 parts of 85% solution of phosphoric acid per 100 parts of solid content of acid-modified polyol, amino group-containing silane coupling agent B (N-2-(amino Ethyl)-3-aminopropyltrimethoxysilane, KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter the same)) 0.60 parts, and IPDI 0.30 parts were blended to prepare a main agent B2-4. .

The equivalent ratio (isocyanate group/amino group) of the isocyanate group of the second polyisocyanate compound to the amino group of the amino group-containing silane coupling agent was 1.0.

Preparation Example 5 (main agent B2-5)
100 parts of acid-modified polyol (solution of polyol A), 0.012 parts of 85% solution of phosphoric acid per 100 parts of solid content of acid-modified polyol, amino group-containing silane coupling agent C (N-2-(amino Ethyl)-3-aminopropylmethyldimethoxysilane, KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd. (hereinafter the same)) 0.60 parts, and 0.32 parts of IPDI were blended to prepare main agent B2-5. bottom.

The equivalent ratio (isocyanate group/amino group) of the isocyanate group of the second polyisocyanate compound to the amino group of the amino group-containing silane coupling agent was 1.0.

Preparation Example 6 (main agent B2-6)
100 parts of acid-modified polyol (solution of polyol A), 0.012 parts of 85% solution of phosphoric acid per 100 parts of solid content of acid-modified polyol, 0.60 parts of amino group-containing silane coupling agent A and hexamethylene diisocyanate (HDI, second polyisocyanate compound) was blended with 0.23 parts to prepare a main component B2-6.

The equivalent ratio (isocyanate group/amino group) of the isocyanate group of the second polyisocyanate compound to the amino group of the amino group-containing silane coupling agent was 1.0.

Preparation Example 7 (main agent B2-7)
100 parts of acid-modified polyol (solution of polyol A), 0.012 parts of 85% solution of phosphoric acid with respect to 100 parts of solid content of acid-modified polyol, 0.60 parts of amino group-containing silane coupling agent A, and HDI trimer (D-170N, NCO group content: 20.7% by mass, solid concentration: 100% by mass, manufactured by Mitsui Chemicals, second polyisocyanate compound) 0.55 parts, A main agent B2-7 was prepared.

The equivalent ratio (isocyanate group/amino group) of the isocyanate group of the second polyisocyanate compound to the amino group of the amino group-containing silane coupling agent was 1.0.

Preparation Example 8 (main ingredient B2-8)
100 parts of acid-modified polyol (solution of polyol A), 0.012 part of 85% solution of phosphoric acid per 100 parts of solid content of acid-modified polyol, 0.60 part of amino group-containing silane coupling agent A, and HDI Biuret derivative (D-165N, NCO group content: 23.3% by mass, solid concentration: 100% by mass, manufactured by Mitsui Chemicals, the second polyisocyanate compound) 0.49 parts of the main agent B2 -8 was prepared.

The equivalent ratio (isocyanate group/amino group) of the isocyanate group of the second polyisocyanate compound to the amino group of the amino group-containing silane coupling agent was 1.0.

Preparation Example 9 (main agent B2-9)
100 parts of acid-modified polyol (solution of polyol A), 0.012 part of 85% solution of phosphoric acid per 100 parts of solid content of acid-modified polyol, 0.60 part of amino group-containing silane coupling agent A, and HDI Allophanate derivative (D-178NL, NCO group content: 19.2% by mass, solid content concentration: 100% by mass, manufactured by Mitsui Chemicals, second polyisocyanate compound) 0.59 parts, the main agent B2 -9 was prepared.

The equivalent ratio (isocyanate group/amino group) of the isocyanate group of the second polyisocyanate compound to the amino group of the amino group-containing silane coupling agent was 1.0.

Preparation Example 10 (main agent B2-10)
100 parts of acid-modified polyol (solution of polyol A), 0.012 parts of 85% solution of phosphoric acid per 100 parts of solid content of acid-modified polyol, 0.60 parts of amino group-containing silane coupling agent A, and XDI A main component B2-10 was prepared by blending 0.25 parts of the monomer (second polyisocyanate compound) of

Preparation Example 11 (main agent B2-11)
100 parts of acid-modified polyol (solution of polyol A), 0.012 parts of 85% solution of phosphoric acid per 100 parts of solid content of acid-modified polyol, 0.60 parts of amino group-containing silane coupling agent A, and IPDI 1.1 parts of trimethylolpropane adduct (D-140N, NCO group content: 10.5% by mass, solid concentration: 75% by mass, Mitsui Chemicals, second polyisocyanate compound) to prepare the main agent B2-11.

The equivalent ratio (isocyanate group/amino group) of the isocyanate group of the second polyisocyanate compound to the amino group of the amino group-containing silane coupling agent was 1.0.

Comparative Preparation Example 1 (main component C2-1)
Acid-modified polyol (solution of polyol A) 100 parts and 0.050 parts of an 85% solution of phosphoric acid per 100 parts of the solid content of the acid-modified polyol, and 0.60 parts of amino group-containing silane coupling agent A By blending, the main agent C2-1 was prepared.

Comparative Preparation Example 2 (main ingredient C2-2)
In 8.5 parts of ethyl acetate, 0.60 parts of amino group-containing silane coupling agent A and 0.34 parts of MDI were reacted to obtain reaction product X.

The resulting reaction product was blended with 100 parts of acid-modified polyol 1 (solution of polyol A). Thus, main agent C2-2 was prepared.

At this time, since gel-like solids precipitated in the main agent C2-2, the adhesive could not be prepared and evaluated.

Comparative Examples 4-16
・Manufacture of laminating adhesives

A main agent and a curing agent were prepared according to the combination shown in Table 2 to obtain a two-component curing laminating adhesive.

Next, the curing agent and the main agent in the combination shown in Table 2 are mixed at a ratio of 60 parts by mass of the main agent (based on solid content) to 9.4 parts by mass of the curing agent (based on solid content), and The solid concentration was adjusted to 25% by mass with ethyl acetate.

・Production of laminate film Using the laminate adhesive obtained above (mixture containing curing agent and main agent), polyethylene terephthalate film (thickness 12 μm)/nylon film (thickness 15 μm)/aluminum foil (thickness 9 μm)/unstretched polypropylene film (thickness: 60 μm: one side treated with corona).

That is, the adhesive mixture was first applied to a polyethylene terephthalate film using a bar coater (#8) at room temperature, the solvent was evaporated, and then the coated surface was laminated to a nylon (registered trademark) film.

Next, on the other side of the nylon (registered trademark) film of the two-layer composite film, in the same manner as described above, the adhesive mixture of each example and each comparative example was applied, and after the solvent was volatilized, the coated surface was peeled off. It was pasted on aluminum foil.

Next, on the other side of the aluminum foil of the three-layer composite film, in the same manner as described above, the adhesive mixture of each example and each comparative example was applied, and after the solvent was volatilized, the coated side was covered with an unstretched polypropylene film. was attached to the corona-treated surface of the

The four-layer composite film was then cured at 40° C. for 3 days to cure the adhesive mixture.

<Evaluation 1>
(1) Adhesion A test piece with a width of 15 mm was taken out from the laminate film, and the adhesive strength between aluminum foil (AL) and unstretched polypropylene (CPP) was measured by T-type peeling at 24 ° C. and a tensile speed of 300 mm / min. It was measured.

Also, the heat seal strength (HS strength) was evaluated by heat sealing the composite films under the conditions of 220° C., 0.15 MPa, and 1.0 seconds.
(2) Storage stability Storage stability was evaluated as follows.

That is, of the laminate adhesives before mixing of each example and each comparative example, 90 ml of the main agent forming a covalent bond between the raw material component and the silane coupling agent was placed in a 100 ml glass bottle, sealed, and heated to 25°C. was placed in a constant temperature room.

Then, the rate of change in viscosity after one month at 25° C. [100×(viscosity after storage−viscosity before storage)/viscosity before storage)] was calculated.

In addition, the evaluation criteria are described below.

◎: Less than 10% change in viscosity after 1 month at 25°C ○: Change in viscosity from 10% to less than 50% after 1 month at 25°C △: Change in viscosity from 50% to less than 200% after 1 month at 25°C ×: Cloudy . Viscosity change of 200% or more after 1 month at 25°C (3) Rapid Curing In the production of laminate films, the time required for curing of the laminate adhesive was measured. As a result, it was confirmed that each example cured within 24 hours and had excellent rapid curability.

<Evaluation 2>
(1) Rotating retort evaluation Using a laminated film, a bag with a size of 9 × 14 cm was prepared, and the content was a mixed sauce (1/ 1/1 sauce).

The bag was then placed on a 210×520×105 mm tray and heat-treated at 125° C. for 30 minutes at 8 revolutions per minute under a pressure of 0.25 MPa.

Thereafter, the adhesive strength between the aluminum foil and the unstretched polypropylene was measured in the same manner as in (1) above. The results are shown in Table 1.

In addition, the peeling state (delamination) at the corner portion of the bag was observed.

Evaluation criteria are described below.

○: Delamination size less than 1 mm △: Delamination size 1 mm or more and less than 3 mm ×: Delamination size 3 mm or more

It should be noted that although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an illustration and should not be construed as a limitation. Variations of the invention that are obvious to those skilled in the art are included in the following claims.

The two-liquid curing lamination adhesive of the present invention can be used for various packaging materials such as refillable standing pouches in the field of toiletries, packaging materials for retort food and dry foods, packaging materials for pharmaceuticals, electronic and electrical parts, solar cells, fuel cells, etc. battery members, household materials such as shopping bags, book covers and stickers, and architectural and industrial materials such as decorative sheets.

Claims (5)

A two-component curable laminating adhesive comprising a curing agent containing a polyisocyanate compound and a main component containing an active hydrogen group-containing compound,
A raw material component of the active hydrogen group-containing compound and a silane coupling agent having an active hydrogen group are covalently bonded,
The active hydrogen group-containing compound is a reaction product of a raw material prepolymer and the silane coupling agent, and a chain extender,
A two-component curing laminating adhesive , wherein the raw material prepolymer is an isocyanate group-terminated prepolymer that is a reaction product of polyisocyanate and polyether polyol. 2. The two-liquid curing laminating adhesive according to claim 1, further comprising an oxyacid of phosphorus and/or a derivative thereof. The content ratio of the phosphorus oxyacid and/or derivative thereof is 1.0 to 5.0 parts by mass with respect to 100 parts by mass of the silane coupling agent, according to claim 2 . Two-liquid curing lamination adhesive. A laminate film comprising an adhesive layer containing a cured product of the two-liquid curing laminating adhesive according to claim 1 . A method for producing a two-component curable laminating adhesive comprising a curing agent containing a polyisocyanate compound and a main component containing an active hydrogen group-containing compound,
preparing the curing agent;
A step of preparing the main agent ,
The step of preparing the main agent includes the step of reacting polyisocyanate and polyether polyol to produce a raw material prepolymer that is an isocyanate group-terminated prepolymer;
reacting the raw material prepolymer with a silane coupling agent having an active hydrogen group;
a step of covalently bonding the raw material components of the active hydrogen group-containing compound and the silane coupling agent;
A method for producing a two-component curable lamination adhesive, comprising reacting a reaction product of the raw material prepolymer and the silane coupling agent with a chain extender.