WO2020203473A1

WO2020203473A1 - Two-pack curable laminating adhesive and laminate film

Info

Publication number: WO2020203473A1
Application number: PCT/JP2020/013060
Authority: WO
Inventors: 朗博今井; 英樹寺田; 太一上村; 祥城下川床; 祐也阿形
Original assignee: 三井化学株式会社
Priority date: 2019-03-29
Filing date: 2020-03-24
Publication date: 2020-10-08
Also published as: JPWO2020203473A1; JP7253043B2; JP7253043B6

Abstract

A two-pack curable laminating adhesive which is composed of a hardener comprising a polyisocyanate compound and a main ingredient comprising a compound containing an active-hydrogen group, wherein a starting-material ingredient for the polyisocyanate compound and/or a starting-material ingredient for the compound containing an active-hydrogen group has been combined with a silane coupling agent by covalent bonding.

Description

Two-component curable adhesive and laminate film

The present invention relates to a two-component curable laminate adhesive and a laminate film. Specifically, the present invention relates to a two-component curable laminate adhesive preferably used for producing a laminate film, and a laminate obtained by the two-component curable laminate adhesive. Regarding film.

Laminated films, which are made by adhering various films such as plastic films with a laminating adhesive, are widely used in the field of packaging materials.

As a laminating adhesive used in the production of a laminated film, for example, a two-component type laminating adhesive having a curing agent containing a polyisocyanate and a main agent containing a polyol, and blending them at the time of use, has been proposed. It has also been proposed that the curing agent contain a silane coupling agent (see, for example, Patent Document 1 below).

Further, as the laminating adhesive, for example, a one-component type composite laminating adhesive composition comprising a polyurethane having a free NCO group in the molecule and 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 Japanese Unexamined Patent Publication No. 56-57867

However, as in Patent Document 1, when the silane coupling agent is simply added to the curing agent and mixed, even if the obtained laminate adhesive is applied to the base material, the base material and the laminate adhesive adhere to each other. The sex may not be sufficient.

On the other hand, as in Patent Document 2 above, the adhesion between the base material and the laminate adhesive can be improved by chemically bonding the silane coupling agent in the molecular chain of the adhesive.

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

That is, in order to continuously mass-produce a laminated film such as a packaging material, if a one-component type laminated adhesive having excellent quick-curing properties is used, the storage stability is inferior. On the other hand, when a one-component type laminated adhesive having excellent storage stability is used, the quick curing property is inferior.

The present invention is a laminated adhesive having excellent storage stability and quick-curing properties, and also having excellent adhesion to a substrate, and a laminated film obtained by using the laminated adhesive.

The present invention [1] is a two-component curable laminate adhesive having a curing agent containing a polyisocyanate compound and a main agent containing an active hydrogen group-containing compound, and is a raw material component of the polyisocyanate compound and / or. It contains a two-component curable laminate adhesive in which a 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, and 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. The two-component curable laminate adhesive according to the above [1], which is covalently bonded, is contained.

In the present invention [3], the silane coupling agent has an isocyanate group, and 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. The two-component curable laminate adhesive according to the above [1], which is covalently bonded, is contained.

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

In the present invention [5], the content ratio of oxygen acid and / or a derivative thereof of the phosphorus is 1.0 to 5.0 parts by mass with respect to 100 parts by mass of the silane coupling agent. Contains the two-component curable laminate adhesive described in 1.

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

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

Further, in the two-component curable laminate 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 is used. Excellent adhesion to.

Further, the laminated film of the present invention has excellent adhesion between the base material and the adhesive layer, and also has excellent productivity.

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

In other words, the two-component curable laminate adhesive is a resin composition containing a main agent and a curing agent before mixing. In such a two-component curable laminated adhesive, the curing agent and the main agent are individually prepared and blended at the time of use.

Further, in the two-component curable laminated adhesive, as will be described in detail later, 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 a raw material component thereof. It has a covalent bond with a silane coupling agent (described later).

The curing agent contains a polyisocyanate compound.

Examples of the polyisocyanate compound include a polyisocyanate monomer and a polyisocyanate derivative.

Examples of the polyisocyanate monomer include polyisocyanates such as aliphatic polyisocyanate, aromatic polyisocyanate, and aromatic aliphatic polyisocyanate, and preferably diisocyanate.

Examples of the aliphatic polyisocyanate include ethylene diisocyanate, trimethylene diisocyanate, 1,2-propylene diisocyanate, and butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 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 Examples thereof include aliphatic diisocyanates such as ate and dodecamethylene diisocyanate.

In addition, the aliphatic polyisocyanate includes an alicyclic polyisocyanate. Examples of the alicyclic polyisocyanate include 1,3-cyclopentanediisocyanate, 1,3-cyclopentenediisocyanate, cyclohexanediisocyanate (1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (isoholodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'-or 2,2'-methylenebis (cyclohexylisocyanate, Trans, Transs of these) -Form, Trans, Cis-form, Cis, Cis-form, or a mixture thereof)) (H ₁₂ MDI), methylcyclohexanediisocyanate (methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate), norbornan Oil rings such as diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof) (H ₆ XDI) Group diisocyanate can be mentioned.

Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylenediisocyanate (m-, p-phenylenediisocyanate or a mixture thereof), 4, 4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-or 2,2'-diphenylmethane diisosinate or a mixture thereof) (MDI), Examples thereof include aromatic diisocyanates such as 4,4'-toluidine diisocyanate (TODI) and 4,4'-diphenyl ether diisocyanate.

Examples of the aromatic aliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylene diisocyanate or a mixture thereof) (XDI) and tetramethylxylene diisocyanate (1,3- or 1,4-tetra). Examples thereof include methylxylene diisocyanate (or a mixture thereof) (TMXDI), aromatic aliphatic diisocyanates such as ω, ω'-diisocyanate-1,4-diethylbenzene and the like.

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

Examples of the polyisocyanate derivative include multimers (for example, dimer and trimeric (for example, isocyanurate modified and iminooxadiazinedione modified)) of the above-mentioned polyisocyanate monomer. (7-mer, etc.), allophanate derivatives (for example, allophanate derivatives produced by the reaction of the above-mentioned polyisocyanate monomer with alcohol), biuret derivatives (for example, the above-mentioned polyisocyanate monomer, water, etc.) Biuret derivatives produced by reaction with amines, etc.), urea derivatives (for example, urea derivatives produced by reaction of the above-mentioned polyisocyanate monomer with diamine), oxadiazine trione derivatives (for example, described above). Oxadiazine trione derivatives produced by the reaction of polyisocyanate monomers with carbon dioxide gas, etc.), carbodiimide derivatives (carbodiimide derivatives produced by the decarbonate condensation reaction of the above-mentioned polyisocyanate monomers, etc.), polyol derivatives (, etc.) For example, from the reaction of an alcohol adduct produced by the reaction of the polyisocyanate monomer described above with a low molecular weight polyol described later, for example, the reaction of the polyisocyanate monomer described above with a high molecular weight polyol (and a low molecular weight polyol) described later. (Isocyanate group-terminated prepolymer to be produced, etc.) and the like.

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

The polyisocyanate compound can be used alone or in combination of two or more.

Examples of the polyisocyanate compound include a monomer of an aromatic polyisocyanate and a derivative thereof from the viewpoint of storage stability, quick curing and adhesion, and more preferably a monomer of an aromatic diisocyanate and a derivative thereof. Derivatives are mentioned, more preferably derivatives of aromatic diisocyanates, more preferably polyol derivatives of aromatic diisocyanates, and even more preferably isocyanate group-terminated prepolymers of aromatic diisocyanates, among others. Preferred is an isocyanate group-terminated prepolymer of MDI.

The isocyanate group-terminated prepolymer is a urethane prepolymer having two or more isocyanate groups at the molecular ends, and is composed of polyisocyanate as a raw material component of the isocyanate group-terminated prepolymer (hereinafter, first raw material polyisocyanate) 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 a first raw material polyol) at a ratio described later.

Examples of the first raw material polyisocyanate include the above-mentioned polyisocyanate monomer and / or polyisocyanate derivative, which can be used alone or in combination of two or more.

The first raw material polyisocyanate is preferably a polyisocyanate monomer, more preferably an aromatic polyisocyanate, further preferably an aromatic diisocyanate, and particularly preferably MDI. ..

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

As the first raw material polyol, preferably, a combination of a high molecular weight polyol (described later) and a low molecular weight polyol (described later) can be mentioned.

Further, as the high molecular weight polyol (described later), a polyether polyol (described later) is preferably mentioned, a polyoxyalkylene polyol is more preferable, and a polyoxypropylene glycol is more preferable.

Further, as the low molecular weight polyol (described later), a trihydric alcohol (described later) is preferably mentioned, and trimethylolpropane is more preferable.

Then, in order to synthesize the isocyanate group-terminated prepolymer, each of the above components is mixed with the ratio of the isocyanate group being excessive with respect to the active hydrogen group, that is, the isocyanate of the first raw material polyisocyanate with respect to the active hydrogen group of the first raw material polyol. The group is blended in an equivalent ratio (isocyanate group / active hydrogen group) of more than 1, preferably 2 or more and 100 or less.

In the reaction of each of the above components, for example, a known polymerization method such as bulk polymerization or solution polymerization is adopted. Preferably, solution polymerization is adopted, which makes it easier to adjust the reactivity and viscosity.

In 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 mixed with an organic solvent in a nitrogen atmosphere and 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 a solvent inert to the isocyanate group, but for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, for example, nitriles such as acetonitrile, methyl acetate, etc. Alkyl esters such as ethyl acetate, butyl acetate, isobutyl acetate, eg, aliphatic hydrocarbons such as n-hexane, n-heptane, octane, eg, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, eg. Aromatic hydrocarbons such as toluene, xylene and 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, eg, ethers such as diethyl ether, tetrahydrofuran, dioxane, eg methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide , Methylene iodide, halogenated aliphatic hydrocarbons such as dichloroethane, for example, polar aprotons such as N-methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, etc. Can be mentioned. These organic solvents can be used alone or in combination of two or more.

Further, in the above polymerization, for example, an amine-based, tin-based, lead-based or other reaction catalyst may be added, if necessary, and the obtained isocyanate group-terminated prepolymer is used as an unreacted first raw material polyisocyanate. Can also be removed by a known method such as distillation or extraction.

The isocyanate group-terminated prepolymer thus obtained is a compound having two or more free isocyanate groups at its molecular terminal.

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. It is 0 or less, more preferably 2.5 or less.

The number average molecular weight (number average molecular weight measured by GPC 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 5000 or less. ..

Further, the curing agent can contain the above-mentioned organic solvent, if necessary.

When the curing agent contains an organic solvent, the solid content concentration thereof 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, based on the total amount of the curing agent. For example, it is 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less.

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

The active hydrogen group-containing compound is a compound containing 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 specific examples thereof include a hydroxyl group, an amino group, a thiol group and a carboxy group, and a hydroxyl group and an amino group are preferable. 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.

Examples of the active hydrogen group-containing compound containing two or more hydroxyl groups in the molecule include polyol. Examples of the polyol include a low molecular weight polyol and a high molecular weight polyol.

The low molecular weight polyol is, for example, a compound having two or more hydroxyl groups in the molecule and having a molecular weight of 50 or more and 300 or less, preferably 400 or less, and for example, ethylene glycol, propylene glycol, 1,3-propanediol, and the like. 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-dimethylolheptan, alcoholic (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1, 4-Cyclohexanediol and their mixtures, bisphenol hydride 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, eg trihydric alcohols such as glycerin, trimethylolpropane, triisopropanolamine, eg tetrahydric alcohols such as tetramethylolmethane (pentaerythritol), diglycerin, eg pentahydric such as xylitol. Alcohols include, for example, hexahydric alcohols such as sorbitol, mannitol, aritol, iditor, darsitol, altritor, inositol, dipentaerythritol, for example, heptavalent alcohols such as persetol, eg, octahydric alcohols such as sucrose. ..

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

The high molecular weight polyol is an organic compound having two or more hydroxyl groups and having a number average molecular weight of more than 300, preferably more than 400, and is, for example, a polyether polyol (for example, a polyoxyalkylene such as polyoxypropylene glycol). Polyesters, polytetramethylene ether polyols, etc.), polyester polyols (eg, adipic acid-based polyester polyols, phthalic acid-based polyester polyols, lactone-based polyester polyols, and their acid-modified polyester polyols), polycarbonate polyols, polyurethane polyols (eg, etc.) , Polyester polyol, polyester polyol, polycarbonate polyol modified with urethane 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.

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

The polyol preferably includes a high molecular weight polyol, more preferably a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polyurethane polyol, and more preferably a polyurethane polyol.

The polyurethane polyol is a polyurethane resin having two or more hydroxyl groups at the molecular ends, and is a polyisocyanate as a raw material component of the polyurethane polyol (hereinafter, second raw material polyisocyanate) and a polyol as a raw material component of the polyurethane polyol (hereinafter,). , Second raw material polyol) can be obtained by reacting with the second raw material polyol) at a ratio described later.

Examples of the second raw material polyisocyanate include the above-mentioned polyisocyanate monomer and / or polyisocyanate derivative, which can be used alone or in combination of two or more.

The second raw material polyisocyanate is preferably a polyisocyanate monomer, more preferably an aromatic polyisocyanate, further preferably an aromatic diisocyanate, and particularly preferably TDI or MDI. Can be mentioned.

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

As the second raw material polyol, preferably, a combination of a high molecular weight polyol and a low molecular weight polyol can be mentioned.

Further, in the second raw material polyol, the high molecular weight polyol is preferably a polyether polyol, more preferably a polyoxyalkylene polyol, and further preferably a polyoxypropylene glycol.

Further, in the second raw material polyol, as the low molecular weight polyol, preferably, a dihydric alcohol is mentioned, and more preferably, 1,4-butanediol and dipropylene glycol are mentioned.

Then, in order to obtain the 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, 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 0.8. As described above, it is preferably formulated (mixed) so as to be 0.9 or more, for example, 1.2 or less, preferably 1.1 or less, and by a known polymerization method such as bulk polymerization or solution polymerization, for example, at room temperature. The curing reaction is carried out at ~ 250 ° C., preferably at room temperature to 200 ° C., for example, for 5 minutes to 72 hours, preferably 4 to 24 hours.

In the prepolymer method, first, the second raw material polyisocyanate is reacted with a part of the second raw material polyol (preferably, the high molecular weight polyol is used alone or the high molecular weight polyol is used in combination with the low molecular weight polyol). Synthesize isocyanate group-terminated prepolymers.

In this reaction, the equivalent ratio (isocyanate group / active hydrogen group) of the isocyanate group in the second raw material polyisocyanate component to the active hydrogen group in a part of the second raw material polyol is that the isocyanate group is the active hydrogen group. The ratio is excessive, 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, each of the above components is reacted by a known polymerization method such as the bulk polymerization or the solution polymerization, preferably the solution polymerization.

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

Further, in the above polymerization, for example, an amine-based, tin-based, lead-based or other reaction catalyst may be added, if necessary, and a second raw material polyisocyanate unreacted from the obtained isocyanate group-terminated prepolymer may be added. Can also be removed by a known method such as distillation or extraction.

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

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

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

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

The chain extender is reacted by dropping, and after the dropping is completed, the reaction is completed at room temperature, for example, with further stirring. The reaction time until the reaction is completed is, for example, 0.1 hour or more, and for example, 10 hours or less.

In this reaction, the blending ratio of each component is such that the active hydrogen group of the balance (chain extender) of the second raw material polyol is equal to or more than the isocyanate group 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 balance (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 end.

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 3.0 or less. Is 2.5 or less.

In addition, the main agent can contain an organic solvent.

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

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

The content ratio (solid content 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, preferably 30% by mass or more, based on the total amount of the main agent. It is 50% by mass or more, for example, 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less.

The active hydrogen group-containing compound in the main agent is not limited to the above-mentioned polyol, and for example, a thiol group-containing compound (polythiol), an amino group-containing compound (polyethyleneimine, etc.), and a carboxy group-containing compound (pyromellitic acid) are used. Etc.) and so on. As the active hydrogen group-containing compound, a polyol is preferable, and a polyurethane polyol is preferable.

In the two-component curable laminate adhesive, at least one of the polyisocyanate compound in the curing agent and the active hydrogen group-containing compound in the main agent is silane coupling in order to improve the adhesion. Has a covalent bond with the agent.

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 substrate (film or the like) described later in the molecule. ing.

The silane coupling agent is capable of reacting with an alkoxysilyl group capable of reacting with a base material (film or the like) 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 ratio 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 based on the polyisocyanate compound and the active hydrogen group-containing compound obtained by those reactions. For example, it is 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 the active hydrogen group-containing compound has an alkoxysilyl group in the molecule, the alkoxysilyl group is used when the two-component curable laminate adhesive is applied to a substrate (film or the like) described later. And the hydroxyl group on the surface of the base material (film, etc.) described later are dehydrated and condensed to form a strong bond.

Therefore, it is possible to improve the adhesion between the two-component curable laminate adhesive and the base material (described later).

Further, 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 the curing agent containing them are transported and stored in the state before mixing. Therefore, thickening is suppressed.

The form of the covalent bond with the silane coupling agent is not particularly limited, but for example, a urethane bond between an isocyanate group and a hydroxyl group, for example, a thiourethane bond between an isocyanate group and a thiol group, for example, an isocyanate group and a primary group. Alternatively, a urea bond with a secondary amino group and the like can be mentioned, and a urethane bond between an isocyanate group and a hydroxyl group is preferable.

Further, both the polyisocyanate compound (hardener) and the active hydrogen group-containing compound (main agent) may have a covalent bond with the silane coupling agent, but from the viewpoint of cost efficiency, the polyisocyanate compound is preferable. The raw material component of either (hardener) or the active hydrogen group-containing compound (main agent) has a covalent bond with the silane coupling agent.

That is, in a preferred embodiment of the two-component curable laminate adhesive, the raw material component of the polyisocyanate compound has a covalent bond with the silane coupling agent, and the raw material component of the active hydrogen group-containing compound is silane coupling. Examples include embodiments that do not have a covalent bond with the agent.

Further, as a preferred embodiment of the two-component curable laminate 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 Examples include embodiments that have a covalent bond with a silane coupling agent.

Further, in a particularly preferable 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. Examples thereof include.

The 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, in the production of the above-mentioned isocyanate group-terminated prepolymer, a silane coupling agent having an active hydrogen group is blended.

Examples of the silane coupling agent having an active hydrogen group include a mercapto group-containing silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, for example, N-2- (aminoethyl)-. A silane coupling agent having both a primary amino group and a secondary amino group such as 3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, for example, 3-aminopropyltri. Silane coupling that does not contain secondary amino groups such as methoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrialkoxysilane but contains primary amino groups Examples thereof include 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.

As the silane coupling agent having an active hydrogen group, preferably, an amino group-containing silane coupling agent can be mentioned, and more preferably, 3-aminopropyltriethoxysilane can be mentioned.

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 above-mentioned first raw material polyisocyanate and the above-mentioned first raw material polyol are used. , A silane coupling agent having an active hydrogen group is reacted.

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 reacted with the first raw material polyisocyanate at the same time (collective reaction) at a ratio in which the isocyanate group is excessive with respect to the active hydrogen group. ..

Further, for example, after reacting the first raw material polyisocyanate with the silane coupling agent at least at a ratio of the isocyanate group being excessive with respect to the active hydrogen group, the isocyanate group remaining in the obtained reaction product and the isocyanate group The first raw material polyol may be reacted at a ratio of an excess isocyanate group with respect to the active hydrogen group.

Further, for example, after reacting the first raw material polyol and the first raw material polyisocyanate at least at a ratio of an excess isocyanate group with respect to the active hydrogen group, the isocyanate group remaining in the obtained reaction product and the isocyanate group A silane coupling agent having an active hydrogen group may be reacted at a ratio of an excess isocyanate group to the active hydrogen group.

Preferably, from the viewpoint of suppressing cross-linking and thickening in the reaction process, first, the first raw material polyisocyanate and the silane coupling agent are reacted at least at a ratio in which the isocyanate group is excessive with respect to the active hydrogen group. After that, the isocyanate groups remaining in the obtained reaction product and the first raw material polyol are reacted at a ratio of the isocyanate groups being 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 a silane coupling agent are reacted at least at a ratio of an excess of isocyanate groups, and then the isocyanate remaining in the reaction product. Examples thereof include a method of reacting a group with a first raw material polyol at a ratio in which an isocyanate group becomes excessive. Further, as the polyisocyanate compound, preferably, an isocyanate group-terminated prepolymer obtained by this method can be mentioned.

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 the above-mentioned bulk polymerization or solution polymerization.

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

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

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 these active hydrogen groups and isocyanate The groups are covalently bonded.

In addition, 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 described above.

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

As a result, the free isocyanate group in the reaction product reacts with the active hydrogen group 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 the ratio in which the isocyanate group is excessive with respect to the active hydrogen group, and is more specific. Specifically, the equivalent ratio (isocyanate group / active hydrogen group) of the isocyanate group of the first raw material polyisocyanate to the total amount of the active hydrogen group of the first raw material polyol and the active hydrogen group of the silane coupling agent becomes larger than 1. The ratio, preferably 2 or more and 100 or less.

Further, in the above method, the blending 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, and for example, the silane cup having an active hydrogen group. The mass ratio of the ring agent is, for example, 0.01 part by mass or more, preferably 0.1 part by mass or more, and for example, 10 parts by mass or less, preferably 10 parts by mass, based on 100 parts by mass of the total amount of the first raw material polyol. 5, 5 parts by mass or less.

Further, with respect to 100 mol of active hydrogen derived from the first raw material polyol, the amount of active hydrogen derived from the silane coupling agent is, for example, 0.01 mol or more, preferably 0.1 mol or more, for example, 10. It is mol or less, preferably 5 mol or less.

Further, in the above polymerization, for example, an amine-based, tin-based, or lead-based reaction catalyst may be added, if necessary, and the first raw material polyisocyanate unreacted from the obtained isocyanate group-terminated prepolymer may be added. Can also be removed by a known method such as distillation or extraction.

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

For example, in the production of an isocyanate group-terminated prepolymer, a silane coupling agent having an isocyanate group 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. You can also do it.

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 present. , Covalent bond.

Further, although not described in detail, for example, in the production of an isocyanate group-terminated prepolymer, the above-mentioned silane coupling agent having an active hydrogen group 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 the active hydrogen group and the isocyanate group thereof. However, they are covalently combined. Further, 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. To do.

Even with such a method, an isocyanate group-terminated prepolymer in which the raw material component and the silane coupling agent are covalently bonded can be obtained.

The content ratio of the silane coupling agent covalently bonded to the raw material component of the isocyanate group-terminated prepolymer is, for example, 0.5% by mass or more, preferably 1.% by mass, based on the isocyanate group-terminated prepolymer obtained by these reactions. It is 0% by mass or more, for example, 20% by mass or less, preferably 10% by mass or less.

Further, the isocyanate group content (isocyanate group content in terms of solid content excluding the organic solvent) of the isocyanate group-terminated prepolymer (isocyanate group-terminated prepolymer in which the raw material component and the silane coupling agent are covalently bonded) is determined, 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 It is 10% by mass or less.

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. It is 0.0 or more, and for example, 3.5 or less, preferably 3.0 or less, and more preferably 2.5 or less.

Further, the obtained reaction product contains not only an isocyanate group-terminated prepolymer in which the raw material component and the silane coupling agent are covalently bonded, but also an isocyanate group-terminated prepolymer in which the silane coupling agent is not covalently bonded. May occur.

The content ratio 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, based on 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 in which a raw material component and a silane coupling agent are covalently bonded, as a curing agent, a base material of a two-component curing type laminate adhesive (described later). It is possible to improve the adhesion to the material.

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, in the production of the above-mentioned polyurethane polyol, the above-mentioned silane coupling agent having an active hydrogen group is blended.

The above-mentioned silane coupling agent having an active hydrogen group can be used alone or in combination of two or more. Examples of the silane coupling agent having an active hydrogen group include an amino group-containing silane coupling agent, and more preferably 3-aminopropyltriethoxysilane.

Then, 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 the polyurethane polyol, the above-mentioned second raw material polyisocyanate and the above-mentioned second raw material polyol are used. , A silane coupling agent having an active hydrogen group is reacted.

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

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

Further, for example, after reacting the second raw material polyisocyanate and the silane coupling agent at least at a ratio of the isocyanate group being excessive with respect to the active hydrogen group, the isocyanate group remaining in the obtained reaction product and the isocyanate group The second raw material polyol may be reacted at a ratio of an excess of active hydrogen groups to isocyanate groups.

Further, for example, after reacting the second raw material polyisocyanate and the second raw material polyol at least at a ratio of an excess isocyanate group with respect to the active hydrogen group, the isocyanate group remaining in the obtained reaction product and the isocyanate group The silane coupling agent may be reacted at a ratio of an excess of active hydrogen groups to isocyanate groups.

As shown in the production of the polyurethane polyol, the reaction product (raw material prepolymer) obtained after reacting a part of the second raw material polyol (and the silane coupling agent having an active hydrogen group). , The remainder of the second raw material polyol (chain extender) (and the silane coupling agent having an active hydrogen group) may be reacted.

Preferably, first, the second raw material polyisocyanate and a part of the second raw material polyol are reacted at least at a ratio of excess isocyanate groups, and then the isocyanate remaining in the obtained reaction product (raw material prepolymer). The group, the silane coupling agent having an active hydrogen group, and the balance (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 ratio in which the isocyanate group becomes excessive, and then the reaction obtained. Examples thereof include a method of reacting the isocyanate group remaining in the product (raw material prepolymer), the silane coupling agent having an active hydrogen group, and the balance (chain extender) of the second raw material polyol. 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. Further, as the active hydrogen group-containing compound, a polyurethane polyol obtained by this method is preferably mentioned.

More specifically, in this method, first, the second raw material polyisocyanate and a 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 the second raw material polyisocyanate and a part of the second raw material polyol is a ratio in which the isocyanate group is excessive with respect to the active hydrogen group, and more specifically, the active hydrogen group of the silane coupling agent. The equivalent ratio of isocyanate groups (isocyanate group / active hydrogen group) to the second raw material polyisocyanate is, for example, 1.05 or more, preferably 1.5 or more, for example, 10.0 or less, preferably 5. It is less than or equal to 0.0.

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

Next, in this method, the reaction product (raw material prepolymer) of the second raw material polyisocyanate and a part of the second raw material polyol, the silane coupling agent having an active hydrogen group, and the balance of the second raw material polyol ( (Chain extender) is added and reacted.

The blending ratio (total amount) of the reaction product with the balance of the silane coupling agent and the second raw material polyol is a ratio in which the amount of active hydrogen groups is equal to or more than that of the isocyanate groups, and more specifically, The equivalent ratio of isocyanate groups (isocyanate group / active hydrogen group) of the above reaction product (raw material prepolymer) to the total amount of active hydrogen groups in the balance 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 group of the reaction product (raw material prepolymer) and the active hydrogen group of the silane coupling agent having an active hydrogen group undergo a urethanization reaction to form a covalent bond.

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 these active hydrogen groups and isocyanate The groups are covalently bonded.

As a result, a polyurethane polyol having an active hydrogen group (hydroxyl group) at the molecular terminal can be obtained.

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

Further, in that case, the order of addition of the silane coupling agent and the balance (chain extender) of the second raw material polyol is not particularly limited. For example, first, the silane coupling agent having an active hydrogen group is added to the active hydrogen group. The isocyanate group may be added in an excess ratio with respect to the isocyanate group, and then the balance (chain extender) of the second raw material polyol may be added in a ratio in which the active hydrogen group is equal to or more than the isocyanate group. .. Further, for example, first, the remainder (chain extender) of the second raw material polyol is added at a ratio of the isocyanate group being excessive with respect to the active hydrogen group, and then the silane coupling agent having an active hydrogen group is activated. Hydrogen groups may be added in an amount equal to or more 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 at a ratio of an excess isocyanate group to the active hydrogen group, and then a second The balance of the raw material polyol (chain extender) is added at a ratio of active hydrogen groups equal to or more than the isocyanate groups.

Further, in the above method, the total ratio of the second raw material polyisocyanate to the second raw material polyol and the silane coupling agent (total amount) is the active hydrogen group of the second raw material polyol with respect to the isocyanate group of the second raw material polyisocyanate. And in the equivalent ratio (active hydrogen group / isocyanate group) of the total amount of active hydrogen groups of the silane coupling agent, the ratio is such that the amount of active hydrogen groups is equal or more, for example, 1.0 or more, preferably 1.05. As mentioned above, for example, it is 1.5 or less, preferably 1.2 or less.

Further, in the above method, the blending 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, and for example, silane having an active hydrogen group. The mass ratio of the coupling agent is, for example, 0.01 part by mass or more, preferably 0.1 part by mass or more, and for example, 10.0 parts by mass or less, based on 100 parts by mass of the total amount of the second raw material polyol. , Preferably 5.0 parts by mass or less.

Further, with respect to 100 mol of active hydrogen derived from the second raw material polyol, the amount of 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. 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 in which a raw material component and a silane coupling agent are covalently bonded, as a main agent, a base material of a two-component curable laminate adhesive is used. It is possible to improve the adhesion to (described later).

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 above polyurethane polyol.

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

Examples of the silane coupling agent having an isocyanate group include isocyanate group-containing silane coupling agents such as 3-trimethoxysilylpropyl succinic acid anhydride, tris- (trimethoxysilylpropyl) isocyanurate, and 3-isocyanatepropyltriethoxysilane. Agents are mentioned.

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

As the silane coupling agent having an isocyanate group, 3-isocyanatepropyltriethoxysilane is preferable.

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

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

The blending ratio of a part of the second raw material polyol and the second raw material polyisocyanate is a ratio in which the isocyanate group is excessive with respect to the active hydrogen group, and more specifically, with respect to the active hydrogen group of the second raw material polyol. The equivalent ratio of isocyanate groups (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.

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

The blending ratio of the isocyanate group-terminated prepolymer (raw material prepolymer) and the balance of the second raw material polyol (chain extender) is the ratio at which the amount of active hydrogen groups is equal to or more than that of the isocyanate groups.

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

This polyurethane polyol is a raw material polyurethane polyol as a raw material component of an active hydrogen group-containing compound.

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

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

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

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

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

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 these active hydrogen groups and isocyanate The groups are covalently bonded.

Therefore, by using such an active hydrogen group-containing compound, that is, an active hydrogen group-containing compound in which a raw material component and a silane coupling agent are covalently bonded, as a main agent, a base material of a two-component curable laminate adhesive ( It is possible to improve the adhesion to (described later).

Further, although not described in detail, for example, in the production of a polyurethane polyol, the above-mentioned silane coupling agent having an active hydrogen group and the above-mentioned 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 of the polyisocyanate compound (second raw material polyisocyanate) has an isocyanate group, and the active hydrogen group and the isocyanate group are present. , Covalent bond. Further, 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 these active hydrogen group and isocyanate The groups are covalently bonded.

Even with such a method, a polyurethane polyol obtained by covalently bonding the raw material component and the silane coupling agent can be obtained.

The content ratio of the silane coupling agent covalently bonded to the raw material component of the polyurethane polyol is, for example, 0.5% by mass or more, preferably 1.0% by mass or more, based on the polyurethane polyol obtained by those reactions. For example, it is 20% by mass or less, preferably 10% by mass or less.

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, more preferably 2. It is 0.0 or more, and for example, 3.0 or less, preferably 2.5 or less.

The obtained reaction product may contain a polyurethane polyol in which the raw material component and the silane coupling agent are covalently bonded, and a polyurethane polyol in which the silane coupling agent is not covalently bonded.

The content ratio of the polyurethane polyol in which the raw material component and the silane coupling agent are covalently bonded is, for example, 1.5% by mass or more, preferably 1.% by mass, 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.

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 above form.

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

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

The compounding ratio of the polyisocyanate compound is a ratio in which the isocyanate group of the polyisocyanate compound is excessive with respect to the amino group-containing silane coupling agent. More specifically, for example, the amino of the amino group-containing silane coupling agent. The equivalent ratio (isocyanate group / amino group) of the isocyanate group of the polyisocyanate compound to the 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, and more preferably 1.25 or less.

Further, the total amount of the polyisocyanate compound and the amino group-containing silane coupling agent is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, more preferably, with respect to 100 parts by mass of the high molecular weight polyol. 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 at the above ratio, the amino group of the amino group-containing silane coupling agent is first uread with the isocyanate group of the polyisocyanate compound. It reacts to form a urea group. After that, the excess isocyanate group of the urea-ized polyisocyanate compound and the hydroxyl group of the high molecular weight polyol undergo a urethanization reaction to form a urethanization group.

As a result, 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 between a high-molecular-weight polyol, a polyisocyanate compound, and an amino group-containing silane coupling agent as a main agent, two-component curing is performed. It is possible to improve the adhesion of the mold laminate adhesive to the base material (described later), and further to improve the retort resistance.

In the above reaction, the compounding ratio of the polyisocyanate compound is at least better than 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 1. In this case, although it is a competitive reaction between the urea conversion reaction of the amino group and the isocyanate group and the urethanization reaction of the isocyanate group and the hydroxyl group, the polyisocyanate compound is a high molecular weight polyol and an amino group-containing silane coupling agent. Includes cases where it reacts with both.

Further, the two-component curable laminated adhesive can contain an oxygen acid of phosphorus and / or a derivative thereof in either one or both of the curing agent and the main agent from the viewpoint of improving the adhesiveness. Preferably, the base agent contains an oxygen acid of phosphorus and / or a derivative thereof.

Examples of the oxygen acid of phosphorus include phosphoric acids such as hypophosphoric acid, phosphite, orthophosphoric acid, and hypophosphoric acid, and condensed phosphorus such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid. Acids and the like can be mentioned.

Examples of the oxygen acid derivative of phosphorus include phosphates such as sodium and potassium or condensed phosphates, such as monomethyl orthophosphoric acid, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphoric acid, and mono-orthophosphoric acid. Monoesters such as 2-ethylhexyl, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, monopropyl phosphite, monobutyl phosphite, mono-2-ethylhexyl phosphite, 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, sub Diethyl Phosphate, Dipropyl Phosphate, Dibutyl Phosphate, Di-2-ethylhexyl Phosphate, Diphenyl Phosphate, trimethyl Phosphate, Triethyl Phosphate, Tripropyl Phosphate, Tributyl Phosphate, Sub Examples thereof 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 oxygen acids or their derivatives can be used alone or in combination of two or more.

Examples of the oxygen acid of phosphorus or a derivative thereof include phosphoric acids, and more preferably orthophosphoric acid (phosphoric acid).

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

The proportion of phosphorus oxygen acid or its derivative is 100 mass by mass of the above-mentioned silane coupling agent (silane coupling agent covalently bonded to the raw material component of the polyisocyanate compound and / or the raw material component of the active hydrogen group-containing compound). From the viewpoint of adhesion (particularly, adhesive strength) to parts, 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, still more preferably. , 2.0 parts by mass or more. Further, from the viewpoint of suppressing deterioration of storage stability and adhesion (particularly, 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. More preferably, it is 3.5 parts by mass or less.

Further, the two-component curable laminated adhesive can contain a silane coupling agent that does not react with the raw material component 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 component of the polyisocyanate compound can be separately added and mixed with the curing agent of the two-component curing type laminate adhesive.

Examples of the silane coupling agent that can be added to the curing agent include silane coupling agents that do not react with isocyanate groups, and examples thereof include silane coupling agents that do not contain active hydrogen groups.

As such a silane coupling agent, more specifically, for example, a vinyl group-containing silane coupling agent such as vinyltrimethoxysilane, for example, an aromatic vinyl group-containing silane coupling agent such as p-styryltrimethoxysilane. , For example, a (meth) acrylic group-containing silane coupling agent such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Examples thereof include an epoxy group-containing silane coupling agent. Further, for example, the above-mentioned silane coupling agent having an isocyanate group can also be mentioned.

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

Further, examples of the silane coupling agent that can be added to the main agent include a silane coupling agent that does not react with an active hydrogen group, and examples thereof include a silane coupling agent that does not contain an isocyanate group.

Examples of such a silane coupling agent include the above-mentioned vinyl group-containing silane coupling agent, aromatic vinyl group-containing silane coupling agent, (meth) acrylic group-containing silane coupling agent, and epoxy group-containing silane coupling agent. And so on. Further, for example, the above-mentioned silane coupling agent having an active hydrogen group can also be mentioned.

The addition ratio of the silane coupling agent to the curing agent and / or the main agent is appropriately set as long as the excellent effect of the present invention is not impaired.

Further, in the two-component curable laminated adhesive, if necessary, one or both of the curing agent and the main agent may be used, for example, a defoaming agent, an epoxy resin, a catalyst, and an improvement in coatability. Additives such as agents, leveling agents, stabilizers (antioxidants, ultraviolet absorbers, etc.), plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, fungicides, etc. can be appropriately blended.

The blending amount of the additive is appropriately determined depending on the purpose and application.

In the two-component curing type laminate adhesive, the above-mentioned main agent and the above-mentioned curing agent are prepared and blended at the time of use.

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

Further, the two-component curable laminated adhesive can contain the above-mentioned organic solvent, if necessary. As described above, the organic solvent may be added to the curing agent and / or the main agent, or may be separately added when the curing agent and the main agent are mixed.

In the two-component curable laminated adhesive, the content ratio 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 becomes a predetermined ratio.

From the viewpoint of coating workability, the solid content concentration of the two-component curable laminate adhesive is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and for example, 50% by mass. % Or less, preferably 40% by mass or less, more preferably 30% by mass or less.

Such a two-component curable laminate adhesive has a curing agent containing a polyisocyanate compound and a main agent containing an active hydrogen group-containing compound, and is used by blending them at the time of use. Therefore, the polyisocyanate compound and the active hydrogen group-containing compound do not react before use (before compounding), and are excellent in quick curing property and storage stability.

Further, in the above-mentioned two-component curable laminate adhesive, 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 to each other. The liquid-curable laminate adhesive has excellent adhesion to the substrate.

Therefore, the above-mentioned two-component curable laminated adhesive is preferably used in the production of a laminated film.

In the production of laminate films, the main agent and the curing agent are separately prepared and stored in the above-mentioned two-component curable laminate adhesive, and they are mixed at the time of use. Then, the obtained mixture (laminate adhesive) is applied (coated) to the base material.

The environmental temperature in 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 with respect to 100 parts by mass of the main agent as the 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 (isocyanate group / active hydrogen group) of the isocyanate group of the curing agent to the active hydrogen group of the main agent is, for example, 0.3 or more, preferably 0.5 or more, and for example, 5.0. Hereinafter, it is preferably 3.0 or less.

Then, the two-component curable laminate adhesive is used as an adhesive for producing a laminate film (composite film) by laminating a film as a base material, for example, a film such as a barrier film or a plastic film.

More specifically, the two-component curable laminate adhesive is used, for example, for bonding plastic films to each other, barrier films, and plastic films.

The plastic film is, for example, an olefin polymer (for example, polyethylene, polypropylene, etc.), a polyester polymer (for example, polyalkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate, polyalkylene naphthalate, and their polyalkylene allylate units. Polyester (such as copolyester), polyamide-based polymer (for example, nylon (registered trademark) such as nylon 6 and nylon 66), and vinyl-based polymer (for example, polyvinyl chloride and 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-sealing unstretched film (unstretched polyethylene, polypropylene, etc.), uniaxially or biaxially stretched film (biaxially stretched polypropylene, polyalkylene terephthalate, nylon, etc.) can be used.

Further, the plastic film can be prepared as various coextruded films or a composite film in which plastic films are pre-attached to each other.

The barrier film is a layer having a barrier property against gas or liquid, and examples thereof include a film containing a metal or a metal oxide. Specific examples thereof include a metal foil or a plastic film containing a barrier layer.

The metal foil is made of, for example, aluminum, stainless steel, iron, copper, lead, etc., and its thickness is, for example, 5 μm or more, and for example, 100 μm or less, preferably 20 μm or less, more preferably 15 μm or less. is there.

Examples of the plastic film containing the barrier layer include a film in which an inorganic layer is formed on at least one surface of the above-mentioned plastic film.

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

For the plastic film containing the barrier layer, an overcoat layer can be laminated on the exposed side of the barrier layer.

Further, the surfaces of the plastic film and the barrier film may be surface-treated such as corona discharge treatment, or may be primer-treated with an anchor coating agent or the like. Further, the plastic film and the barrier film can be appropriately printed.

In the production of a laminated film, for example, when plastic films are bonded to each other, a two-component curable laminate 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 bonded to the surface of the other plastic film.

Further, for example, when a barrier film and a plastic film are bonded together, a two-component curable laminate adhesive containing a curing agent and a main agent is applied to the surface of either the barrier film or the plastic film, and the surface thereof is coated. The coated surface is attached to the surface of the other barrier film or plastic film, and in each case, then cured and cured at room temperature or under heating.

Further, as a laminated film, for example, when two plastic films are bonded to each other, two plastic films are bonded (primarily laminated), and when, for example, a barrier film and a plastic film are bonded to each other, a barrier is used. The film and the plastic film may be bonded (primarily laminated) to form a primary laminated composite film, and further, another plastic film may be bonded to at least one surface of the primary laminated composite film. (Secondary laminating) can also be made to produce a secondary laminated composite film.

In the primary laminating, usually either one of the barrier film and the plastic film is sent out from the sending roll, the other is bonded and wound on the winding roll, and if necessary, heating / curing (for example, 25 ° C. or higher) is performed. Curing at 60 ° C or lower).

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

In the production of the secondary laminate composite film, a two-component curable laminate adhesive may be used in both the primary laminate and the secondary laminate, or in either the primary laminate or the secondary laminate. A two-component curable laminate adhesive may be used, while other adhesives may be used.

The primary and secondary laminating temperatures (coating temperature) are usually 35 ° C. or higher, preferably 40 ° C. or higher. If it can be laminated, there is no upper limit to the temperature, but 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 laminating (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, more Preferably, the two-component curable laminated adhesive is heated at 80 ° C. or lower to adjust the viscosity to an appropriate level. The 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 in the above range.

If the heating temperature is 100 ° C. or lower, the reaction between the curing agent and the main agent can be suppressed before coating, so that excessive thickening can be prevented and good workability can be ensured.

The amount of the two-component curable laminate adhesive applied in each laminating step is, for example, 0.5 g / m ² or more, preferably 1 g / m ² or more, and more preferably 1.5 g / m ² or more. And, for example, 5 g / m ² or less, preferably 4.5 g / m ² or less. If the coating amount is equal to or more than the above lower limit, the adhesiveness is not sufficiently developed and it is possible to prevent the appearance from being poor. It is possible to prevent the agent from leaking and causing poor quality of the laminated film.

Further, as the laminating apparatus using the two-component curing type laminating adhesive, known apparatus such as a forward transfer type coating device and a reverse transfer type coating device (reverse coater) can be used.

Thereby, a laminate film can be produced by using the above-mentioned two-component curable laminate adhesive which is excellent in quick curing and storage stability and also has excellent adhesion to a substrate.

In other words, the laminated film contains an adhesive layer containing a cured product of the above-mentioned two-component curable laminated adhesive.

Therefore, the obtained laminated film is excellent in adhesion between the base material and the adhesive layer and also in productivity.

Therefore, the above-mentioned two-component curable laminated adhesive is used for various packaging materials such as refillable standing pouches in the toiletry field, for example, packaging materials for retort pouch foods and dried foods, for example, packaging materials for pharmaceuticals, electronic / electrical parts. , A battery member such as a solar cell or a fuel cell, for example, a living material such as a shopping bag, a book cover, or a sticker, for example, a building / industrial material such as a decorative sheet.

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

(1) First Embodiment <Manufacturing of curing agent>
Production Example 1 (Curing Agent A-1)
199 g of diphenylmethane diisocyanate (MDI, manufactured by Mitsui Chemicals SKC polyurethane, Cosmonate 300 MNB) 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 a urethanization reaction was carried out for 1 hour. Then, 0.056 g of tin octylate was added, and the urethanization reaction was further carried out at 80 ° C. for 1 hour.

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

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

12 g of 3-aminopropyltriethoxysilane was added thereto under a nitrogen stream, and the mixture was 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 the urethanization reaction was carried out for 1 hour. Then, 0.056 g of tin octylate was added, and the urethanization reaction was further 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 designated as a curing agent A-2.

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

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

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

<Preparation of main agent>
Preparation Example 1 (main agent B-1)
In a mixed solution of 220 g of polyoxypropylene glycol (molecular weight 1000, manufactured by Mitsui Chemicals SKC polyurethane, Actol D-1000) and 25 g of dipropylene glycol, tolylene diisocyanate (TDI, manufactured by Mitsui Chemicals SKC polyurethane) under a nitrogen stream, 85 g of Cosmonate T-80) was added and urethanized at 50 ° C. Then, the obtained reaction product was diluted with 150 g of ethyl acetate, 0.028 g of tin octylate was added, and the urethanization reaction was further 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, manufactured by 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 octylate was added, and the reaction was continued until the peak of isocyanate 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 having a solid content of 70% by mass. This was designated as the main agent B-1.

Preparation Example 2 (main agent B-2)
0.035 g of phosphoric acid was added to the main agent B-1, and the mixture was stirred at 60 ° C. for 30 minutes. As a result, the main agent B-2 was obtained. The amount of phosphoric acid added was 1.0 part 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 agent B-1, and the mixture was stirred at 60 ° C. for 30 minutes. As a result, the main agent 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 agent B-1, and the mixture was stirred at 60 ° C. for 30 minutes. As a result, the main agent 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 agent B-5)
0.35 g of phosphoric acid was added to the main agent B-1, and the mixture was stirred at 60 ° C. for 30 minutes. As a result, the main agent 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)
In a mixed solution of 220 g of polyoxypropylene glycol (molecular weight 1000, manufactured by Mitsui Chemicals SKC polyurethane, Actol D-1000) and 25 g of dipropylene glycol, tolylene diisocyanate (TDI, manufactured by Mitsui Chemicals SKC polyurethane) under a nitrogen stream, 85 g of Cosmonate T-80) was added and urethanized at 50 ° C. Then, the obtained reaction product was diluted with 150 g of ethyl acetate, 0.028 g of tin octylate was added, and the urethanization reaction was further carried out at 60 ° C. for 1 hour.

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. Then, 3-isocyanatepropyltriethoxysilane (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd., KBE-9007) was added, and the reaction was continued until the peak of isocyanate 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 having a solid content of 70% by mass. This was designated as the main agent B-6.

Preparation Example 7 (Main agent B-7)
0.35 g of phosphoric acid was added to the main agent B-6. The mixture was stirred at 60 ° C. for 30 minutes. As a result, the main agent 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)
In a mixed solution of 220 g of polyoxypropylene glycol (molecular weight 1000, manufactured by Mitsui Chemicals SKC polyurethane, Actol D-1000) and 25 g of dipropylene glycol, tolylene diisocyanate (TDI, manufactured by Mitsui Chemicals SKC polyurethane) under a nitrogen stream, 85 g of Cosmonate T-80) was added and urethanized at 50 ° C. Then, the obtained reaction product was diluted with 150 g of ethyl acetate, 0.028 g of tin octylate was added, and the urethanization reaction was further carried out at 60 ° C. for 1 hour.

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 until the peak of isocyanate 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 having a solid content of 70% by mass.

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

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

The main agent B-9 was simply a mixture of a polyurethane polyol and a silane coupling agent, and did not form a covalent bond between the raw material component and the silane coupling agent.

Examples 1 to 8 and Comparative Examples 1 to 3
-Manufacture of Laminate Adhesive A main agent and a curing agent were prepared according to the combinations shown in Table 1 to obtain a two-component curable laminated adhesive.

Next, the curing agent and the main agent in the combinations shown in Table 1 were added at a ratio of the main agent (polyurethane polyol) to 100 parts by mass based on the solid content with respect to 50 parts by mass based on the solid content of the curing agent (isocyanate group-terminated prepolymer). Was mixed, and the solid content concentration was adjusted to 75% by mass with ethyl acetate.

-Manufacture of laminated film Using the above-mentioned laminate adhesive (mixture containing a curing agent and a main agent), a polyethylene terephthalate film (PET) having a thickness of 12 μm / an aluminum foil (AL) having a thickness of 7 μm / A composite film composed of three layers of a polyethylene film (PE) having 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 at room temperature using a bar coater (# 8), the solvent is volatilized, and then the coated surface is coated. It was attached to an aluminum foil.

Next, in the same manner as above, a laminate adhesive (a mixture containing a curing agent and a main agent) is applied to the other surface of the aluminum foil, that is, the other surface of the aluminum foil with respect to the surface to be adhered to the polyethylene terephthalate film. After coating and volatilizing the solvent, the coated surface was bonded to a polyethylene film.

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

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

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

That is, among the laminated adhesives before mixing in each Example and each Comparative Example, 90 ml of the main agent or the curing agent forming a covalent bond between the raw material component and the silane coupling agent was put in a 100 ml glass bottle and sealed. , It was allowed to stand in a constant temperature room at 25 ° C.

Then, the viscosity change rate [100 × (viscosity after storage-viscosity before storage) / viscosity before storage) after 1 month at 25 ° C. was calculated.

The evaluation criteria are as follows.

⊚: Viscosity change after 1 month at 25 ° C less than 10% ○: Viscosity change after 1 month at 25 ° C 10% or more to less than 50% Δ: Viscosity change after 1 month at 25 ° C 50% or more to less than 200% ×: Cloudiness .. Viscosity change of 200% or more after 1 month at 25 ° C. (3) Fast-curing The time required for curing of the laminated adhesive in the production of the laminated film was measured. As a result, it was confirmed that in each example, it was cured within 24 hours and was excellent in quick curing.

(2) Second Embodiment <Production of acid-modified polyol>
Manufacturing 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 esterified at 180 to 220 ° C. under a nitrogen stream. After distilling a predetermined amount of water, 48.9 g of dimer acid and 250 g of adipic acid were added, and an esterification reaction was further carried out at 180 to 220 ° C. Then, the pressure inside the system was gradually reduced, and a 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-denatured) at 140 to 150 ° C., and then 920 g of ethyl acetate was added to obtain polyol A as a solution having a solid content of 60%.

The number average molecular weight of the polyester polyol in the obtained polyol A was about 6000.

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 XDI trimethylolpropane adduct (Takenate A-10, manufactured by Mitsui Chemicals) and 40 g of IPDI trimethylolpropane adduct (Takenate A-40E, manufactured by Mitsui Chemicals) are uniformly mixed at 50 ° C. under a nitrogen atmosphere. Then, a curing agent A2-1 having an isocyanate group content of about 11% was obtained.

<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% phosphoric acid solution with respect to 100 parts of solid content of acid-modified polyol, amino group-containing silane coupling agent A (3-aminopropyltriethoxy) The main agent B2-1 was prepared by blending silane, KBE-903, 0.60 part of Shin-Etsu Chemical Industry Co., Ltd. (hereinafter the same), and 0.30 part 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 agent B2-2)
By blending 100 parts of an acid-modified polyol (solution of polyol A), 0.60 parts of an amino group-containing silane coupling agent A with respect to 100 parts of the solid content of the acid-modified polyol, and 0.30 parts of IPDI. , The main agent B2-2 was prepared.

Preparation Example 3 (Main agent B2-3)
By blending 100 parts of an acid-modified polyol (solution of polyol A) and 0.60 parts of an amino group-containing silane coupling agent A and 0.60 parts of IPDI with respect to 100 parts of the solid content of the acid-modified polyol. , Main agent B2-3 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 2.0.

Preparation Example 4 (Main agent B2-4)
100 parts of acid-modified polyol (solution of polyol A), 0.012 parts of 85% phosphoric acid solution with respect to 100 parts of solid content of acid-modified polyol, amino group-containing silane coupling agent B (N-2- (amino) The main agent B2-4 was prepared by blending 0.60 parts of ethyl) -3-aminopropyltrimethoxysilane, KBM-603, manufactured by Shin-Etsu Chemical Industry Co., Ltd. (same below), and 0.30 parts of IPDI. ..

Preparation Example 5 (Main agent B2-5)
100 parts of acid-modified polyol (solution of polyol A), 0.012 parts of 85% phosphoric acid solution with respect to 100 parts of solid content of acid-modified polyol, amino group-containing silane coupling agent C (N-2- (amino) The main agent B2-5 is prepared by blending 0.60 parts of ethyl) -3-aminopropylmethyldimethoxysilane, KBM-602, manufactured by Shin-Etsu Chemical Industry Co., Ltd. (same below), and 0.32 parts of IPDI. did.

Preparation Example 6 (Main agent B2-6)
100 parts of acid-modified polyol (solution of polyol A), 0.012 parts of 85% phosphoric acid solution with respect to 100 parts of solid content of acid-modified polyol, 0.60 part of amino group-containing silane coupling agent A, and hexamethylene diisocyanate. The main agent B2-6 was prepared by blending 0.23 part of (HDI, second polyisocyanate compound).

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 part of amino group-containing silane coupling agent A, and By blending 0.55 parts of HDI trimer (D-170N, NCO group content: 20.7% by mass, solid content concentration: 100% by mass, Mitsui Chemicals, second polyisocyanate compound), The main agent B2-7 was prepared.

Preparation Example 8 (main agent B2-8)
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 part of amino group-containing silane coupling agent A, and HDI By blending 0.49 parts of a biuret derivative (D-165N, NCO group content: 23.3% by mass, solid content concentration: 100% by mass, Mitsui Chemicals, Inc., second polyisocyanate compound), the main agent B2 -8 was prepared.

Preparation Example 9 (Main agent B2-9)
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 part of amino group-containing silane coupling agent A, and HDI Alofanate derivative (D-178NL, NCO group content: 19.2% by mass, solid content concentration: 100% by mass, Mitsui Kagaku Co., Ltd., second polyisocyanate compound) 0.59 parts and the main agent B2 -9 was prepared.

Preparation Example 10 (main agent B2-10)
100 parts of acid-modified polyol (solution of polyol A), 0.012 parts of 85% phosphoric acid solution with respect to 100 parts of solid content of acid-modified polyol, 0.60 part of amino group-containing silane coupling agent A, and XDI The main agent B2-10 was prepared by blending 0.25 part 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 with respect to 100 parts of solid content of acid-modified polyol, 0.60 part of amino group-containing silane coupling agent A, and IPDI. Trimethylolpropane adduct (D-140N, NCO group content: 10.5% by mass, solid content concentration: 75% by mass, Mitsui Chemicals, Inc., second polyisocyanate compound) is mixed with 1.1 parts. To prepare the main agent B2-11.

Comparative Preparation Example 1 (Main Agent C2-1)
For 100 parts of acid-modified polyol (solution of polyol A) and 100 parts of solid content of acid-modified polyol, 0.050 parts of 85% phosphoric acid solution and 0.60 part of amino group-containing silane coupling agent A. The main agent C2-1 was prepared by blending with.

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

The obtained reaction product was added to 100 parts of acid-modified polyol 1 (solution of polyol A). As a result, the main agent C2-2 was prepared.

At this time, the adhesive could not be prepared and evaluated because the gel-like solid matter had settled in the main agent C2-2.

Examples 9-19 and Comparative Examples 4-5
・ Manufacturing of laminate adhesive

A main agent and a curing agent were prepared in the combinations shown in Table 2 to obtain a two-component curing type laminate adhesive.

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

-Manufacture of laminated film Using the above-mentioned laminate adhesive (mixture containing a curing agent and a main agent), polyethylene terephthalate film (thickness 12 μm) / nylon film (thickness 15 μm) / aluminum foil (thickness) can be obtained by the following method. A laminated film composed of four layers of 9 μm) / unstretched polypropylene film (thickness 60 μm: single-sided corona treatment) was obtained.

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

Next, the adhesive mixture of each Example and each Comparative Example was applied to the other surface of the nylon (registered trademark) film of the two-layer composite film in the same manner as described above, the solvent was volatilized, and then the coated surface was applied. It was attached to an aluminum foil.

Next, the adhesive mixture of each Example and each Comparative Example was applied to the other surface of the aluminum foil of the three-layer composite film in the same manner as described above, the solvent was volatilized, and then the applied surface was an unstretched polypropylene film. It was pasted on the corona-treated surface of.

After that, the 4-layer composite film was cured at 40 ° C. for 3 days to cure the adhesive mixture.

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

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

That is, among the laminated adhesives before mixing in 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 sealed at 25 ° C. It was left in a constant temperature room.

The evaluation criteria are as follows.

<Evaluation 2>
(1) Rotational retort evaluation Using a laminated film, a bag with a size of 9 x 14 cm was prepared, and a mixed sauce (1 /) in which vinegar / salad oil / ketchup was mixed at a volume ratio of 1/1/1 as the contents. 1/1 sauce) was filled.

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

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

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

The evaluation criteria are as follows.

◯: Delamination size less than 1 mm Δ: Delamination size 1 mm or more and less than 3 mm ×: Delamination size 3 mm or more

Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an example and should not be construed in a limited manner. Modifications of the invention that will be apparent to those skilled in the art are included in the claims.

The two-component curable laminated adhesive of the present invention includes various packaging materials such as refillable standing pouches in the toiletry field, packaging materials for retort pouch foods and dried foods, packaging materials for pharmaceuticals, electronic / electrical parts, solar cells, fuel cells, etc. It is preferably used in battery materials, daily life materials such as shopping bags, book covers, stickers, and construction / industrial materials such as decorative sheets.

Claims

A two-component curable laminate adhesive having a curing agent containing a polyisocyanate compound and a main agent containing an active hydrogen group-containing compound.
A two-component curable laminate adhesive, wherein the raw material component of the polyisocyanate compound and / or the raw material component of the active hydrogen group-containing compound and a silane coupling agent are covalently bonded.
The silane coupling agent has an active hydrogen group and
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.
The two-component curable laminate adhesive according to claim 1, wherein they are covalently bonded.
The silane coupling agent has an isocyanate group and
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.
The two-component curable laminate adhesive according to claim 1, wherein they are covalently bonded.
The two-component curable laminated adhesive according to claim 1, further comprising an oxygen acid of phosphorus and / or a derivative thereof.
The fourth aspect of the present invention, wherein the content ratio of the oxygen acid and / or its derivative of the phosphorus is 1.0 to 5.0 parts by mass with respect to 100 parts by mass of the silane coupling agent. Two-component curable laminate adhesive.
A laminate film comprising an adhesive layer containing a cured product of the two-component curable laminate adhesive according to claim 1.