JP6733835B1 - Reactive adhesive, laminate, and package - Google Patents

Abstract

A reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) is coated on a polyethylene terephthalate film at a solid content of 3.0 g/m ^2. A reactive adhesive having a water contact angle of 65 degrees or more on the surface of the dried coating film, and a laminate obtained by laminating a plurality of films or papers with an adhesive, wherein the adhesive is the reactive adhesive. Which is a laminate or a package. The polyol composition (A) is (1) a reaction product of a polyvalent alcohol and a polybasic acid having an alkyl side chain having 6 or more carbon atoms, or a polybasic acid and an alkyl side chain having 6 or more carbon atoms. Or a reaction product of a polyvalent alcohol having
(2) A mixture of a reaction product of a polyhydric alcohol and a polybasic acid with a polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or a polybasic acid having an alkyl side chain having 6 or more carbon atoms. Is preferred.

Description

TECHNICAL FIELD The present invention relates to a reactive adhesive, a laminate and a package using the same.

BACKGROUND ART Conventionally, a laminated body in which various plastic films are bonded to each other or a plastic film and a metal vapor deposition film or a metal foil are laminated (laminated) has been used for various applications such as packaging materials for foods, pharmaceuticals, daily necessities, and barriers. Materials for roofing materials, roofing materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive parts, signboards, stickers and other outdoor industrial applications, and injection molding simultaneous decoration methods. It is used for various purposes.
In these laminates, various plastic films, metal vapor deposition films or metal foils are appropriately combined according to the required properties for each application, and an adhesive agent is selected according to the required properties. For example, in the case of food and daily necessities, in order to protect the contents from various distribution, storage such as refrigeration and treatment such as heat sterilization, strength and resistance to cracking, retort resistance, heat resistance, content resistance Is required.
Furthermore, these laminates rarely circulate in a sheet form, and for example, they may be heat-sealed at the ends to form a bag, or may be molded by thermoforming, which requires heat-sealing properties and molding processability. It may be done.

As an adhesive used for such a laminate, a reactive adhesive (also referred to as a two-component curing adhesive) that reacts a hydroxyl group with an isocyanate has been conventionally known.
For example, in food applications, in an adhesive containing a diol compound (A) having two hydroxyl groups and a polyisocyanate (B) having two or more isocyanate groups, the number average of the diol compound (A) is The molecular weight (Mn) is in the range of 400 to 3000, the polyisocyanate (B) is a triisocyanate or higher polyisocyanate compound (b1), and a diisocyanate compound (b2) obtained by adding an isocyanate compound to polyester diol. An adhesive which is a mixture of (See, for example, Patent Document 1)

These reactive adhesives are required to have properties according to various uses, and in recent years, a gravure coater has been used from the viewpoint of productivity, and for example, the coating speed is 200 m/min or more. However, it is required to obtain a laminate that does not cause a defective appearance. However, under such high-speed coating (also called high-speed processing) conditions, not only solvent-free reactive adhesives that do not use organic solvents but also dry-laminate reactive adhesives whose viscosity can be adjusted using organic solvents However, depending on the base material, there is a problem that a defective appearance such as orange peel, scrape, streaks or bubbles is likely to occur.

JP, 2014-101422, A

The problem to be solved by the present invention is that it can be applied as an adhesive for a laminated body in which various plastic films, metal vapor deposition films or metal foils are appropriately combined, and has high adhesiveness and lamination even under high-speed coating conditions. An object of the present invention is to provide a reactive adhesive capable of obtaining a laminate having an excellent appearance later.

Since the plastic film is laminated on the adhesive coating surface in the uncured state, the present inventors have found that the wettability of the adhesive in the uncured state with respect to the plastic film substrate is such that the adhesiveness and the laminate under high-speed coating conditions are high. As a result of having determined that it has an influence on the appearance after processing and conducted diligent studies, it was found that an adhesive having a high wettability with respect to the plastic film substrate, that is, the surface tension of the uncured adhesive surface tends to be lower.
On the other hand, since the water contact angle with respect to a substance surface having a low surface tension is generally large, this is used to simulate the surface tension of an uncured adhesive at the water contact angle, and specify it when a coating film is formed. It has been found that a reactive adhesive using a polyol composition having a water contact angle in the range solves the problem.

That is, the present invention is a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) is coated on a polyethylene terephthalate film at a solid content of 3.0 g. /M ^{2 The} reactive adhesive has a water contact angle of 65 degrees or more on the surface of the dried coating film.

The present invention also provides a laminate in which a plurality of films or papers are bonded together with an adhesive, wherein the adhesive is the reactive adhesive described above.

The present invention also provides a laminate obtained by laminating a film or paper provided with a plurality of printing layers with an adhesive, wherein the adhesive is the reactive adhesive described above.

The present invention also provides a package formed by molding the above-mentioned laminated body into a bag shape.

INDUSTRIAL APPLICABILITY The reactive adhesive of the present invention can be applied as an adhesive for a laminate in which various kinds of plastic films, metal vapor deposition films or metal foils, papers, etc. are appropriately combined, and has high adhesiveness even under high-speed coating conditions. A laminate having an excellent appearance after lamination can be obtained. Furthermore, since it has excellent heat resistance and content resistance, it can be suitably used especially as a food packaging bag.

Particularly, when the reactive adhesive of the present invention is obtained by applying the reactive adhesive to a first plastic film, then laminating a second plastic film on the coated surface, and curing the adhesive layer, General-purpose CPP (unstretched polypropylene), VMCPP (aluminum vapor-deposited unstretched polypropylene), LLDPE (linear low-density polyethylene), LDPE (low-density polyethylene), HDPE (high-density polyethylene), VMLDPE (second plastic film) Since it has particularly high wettability to a sealant film such as aluminum vapor-deposited low-density polyethylene) or a film such as nylon or polyethylene terephthalate (PET), it can be particularly preferably used for producing a laminate using these films.

The reactive adhesive of the present invention is a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) is coated on a polyethylene terephthalate film in a solid content. An amount of 3.0 g/m ² applied and dried, the water contact angle of the coating film surface is 65 degrees or more.

The water contact angle is preferably 65 degrees or more, and more preferably 70 degrees or more in order to further enhance the effect of the present application. The upper limit is 110 degrees or less, preferably 100 degrees or less.

The water contact angle represents a static contact angle measured 1 second after the contact of 3 μl of water drop with the coating film surface. In the present invention, 3 μL of purified water was dropped onto the adhesive dry coating film on the polyester film obtained above using a fully automatic contact angle meter “DropMaster DMo-701” manufactured by Kyowa Interface Science Co., Ltd. After that, the contact angle after 1 second was measured.

(Polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or polybasic acid having an alkyl side chain having 6 or more carbon atoms)
As the reactive adhesive of the present invention, a known material can be used without particular limitation except that the water contact angle of the coating film surface is 65 degrees or more, but a material having too high hydrophilicity has a water contact angle. Since it tends to be low, it is preferable to use a polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or a polybasic acid having an alkyl side chain having 6 or more carbon atoms in combination.
Examples of the polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or the polybasic acid having an alkyl side chain having 6 or more carbon atoms include, for example, dimer diol, castor oil, 1,2-octanediol, 1,2-decane. Examples thereof include diol and dimer acid.

Here, dimer acid is a product of Diels-Alder type dimerization reaction of unsaturated fatty acid having 18 carbon atoms (C) such as oleic acid and linoleic acid, which is saturated by adding hydrogen to unsaturated bond. And so on. Typical examples are 0 to 5% by weight of monocarboxylic acid having 18 carbon atoms (C), 70 to 98% of dimer acid having 36 carbon atoms (C), and 0 to trimer acid having 54 carbon atoms (C). It is composed of 30% by weight. The dimer diol is obtained by reducing the dimer acid described above.

The polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or the polybasic acid having an alkyl side chain having 6 or more carbon atoms may be used as it is as one component of a reactive adhesive, or a polyol. Alternatively, it may be used as one component of the raw material of polyisocyanate.
Among them, it is preferable to use it as one component of the polyol raw material and to use it as a reaction product of a polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or a polybasic acid having an alkyl side chain having 6 or more carbon atoms. ..
Specifically, the reaction product is a polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or a polybasic acid having an alkyl side chain having 6 or more carbon atoms, and an alkyl side chain having 6 or more carbon atoms. A polyester polyol which is a reaction product of a polyhydric alcohol having a chain or a polyhydric alcohol other than the polybasic acid having an alkyl side chain having 6 or more carbon atoms or a polybasic acid is preferable.

The polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or the polybasic acid having an alkyl side chain having 6 or more carbon atoms is a cured coating of a polyol composition (A) and a polyisocyanate composition (B). It is preferably used in a proportion of 0.1 to 30.0% by weight in the film, and more preferably 0.2 to 20.0% by weight.

In addition, a polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or a polybasic acid having an alkyl side chain having 6 or more carbon atoms may be used as a polyol contained in the polyol composition (A) of the reactive adhesive. When used as a reaction raw material, it is preferably used in a proportion of 0.1 to 35.0% by weight in the solid content of the polyol composition (A), and more preferably 0.2 to 25.0% by weight. ..

Further, the polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or the polybasic acid having an alkyl side chain having 6 or more carbon atoms is used as a mixed raw material for the polyol composition (A) of the reactive adhesive. If so, it is preferably used in a proportion of 0.1 to 5.0% by weight, and more preferably 0.2 to 3.0% by weight in the solid content of the polyol composition (A).

(Polyol composition (A))
The reactive adhesive of the present invention is not particularly limited, except that the polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or the polybasic acid having an alkyl side chain having 6 or more carbon atoms is used. Well-known polyols and polyisocyanates generally used in reactive adhesives for reacting hydroxyl groups with isocyanates can be appropriately used.

For example, as the polyol composition (A), known polyhydric alcohols and polyols can be used.
Specifically, polyhydric alcohols, polyester polyols obtained by reacting polyhydric alcohols with other reaction monomers, polyether polyols, polyurethane polyols, polyether ester polyols, polyester (polyurethane) polyols, polyether (polyurethane) polyols. Polymer polyols selected from polyester amide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyl alkanes, castor oil or mixtures thereof.

Specific examples of the polyhydric alcohol include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1 ,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4- Glycols such as cyclohexanediol and 1,4-cyclohexanedimethanol; trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane and pentaerythritol; bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, etc. Bisphenol and the like.
Among them, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol And other polyhydric alcohols having 2 to 6 carbon atoms are preferred.

Further, the above-mentioned glycol which is the above-mentioned polyhydric alcohol, trifunctional or tetrafunctional aliphatic alcohol and the like are added to ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene and the like in the presence of a polymerization initiator. Polyether polyol obtained by addition-polymerizing alkylene oxide; Polyether urethane polyol obtained by further polymerizing the polyether polyol with the aromatic or aliphatic polyisocyanate;

Polyester obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone and the glycol, glycerin, trimethylolpropane, pentaerythritol, etc. Polyester polyol (1) which is a reaction product with polyhydric alcohol; Polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or bisphenol with a polycarboxylic acid; Polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid; a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polycarboxylic acid. Polyester polyol (4) obtained by reacting with acid; polyester polyol (5), which is a polymer of hydroxyl acid such as dimethylolpropionic acid and castor oil fatty acid;

A polyester polyether polyol obtained by reacting the polyester polyols (1) to (5) with the polyether polyol and an aromatic or aliphatic polyisocyanate; the polyester polyols (1) to (5) being aromatic or aliphatic. Polyester polyurethane polyol obtained by polymerizing with a group polyisocyanate; a mixture of polyester polyols (1) to (5) and a polyether polyol; castor oil, dehydrated castor oil, castor hydrogenated oil which is a hydrogenated product of castor oil, Castor oil-based polyols such as adducts of castor oil with 5 to 50 mol of alkylene oxide can also be preferably used.
The weight average molecular weight (Mw) of the polyol used is preferably 400 to 100,000.

Among them, polyester polyol is preferable, and polyester polyol obtained by reacting the polyhydric alcohol with polybasic acid is preferable. Examples of polybasic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and tetrahydroanhydride. Aliphatic dicarboxylic acids such as phthalic acid; terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1 , 2-bis(phenoxy)ethane-p,p'-dicarboxylic acid and other aromatic dicarboxylic acids; and anhydrides or ester-forming derivatives of these aliphatic or aromatic dicarboxylic acids; p-hydroxybenzoic acid, p-( Examples thereof include 2-hydroxyethoxy)benzoic acid, ester-forming derivatives of these dihydroxycarboxylic acids, and polybasic acids having an alkyl side chain having 6 or more carbon atoms, such as dimer acid. These can be used alone or as a mixture of two or more kinds.
Among them, phthalic acid such as orthophthalic acid, terephthalic acid and isophthalic acid, adipic acid and sebacic acid are preferable.

A polyester polyurethane polyol obtained by reacting the polyester polyol with polyisocyanate is also preferable. Examples of the polyisocyanate include diphenylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, tolylene diisocyanate, aromatic diisocyanates such as prepolymers of low molecular glycols and the aromatic diisocyanates, 1,6-hexamethylene diisocyanate, and 2 , 2,4-Trimethylhexamethylene diisocyanate, lysine diisocyanate, aliphatic diisocyanates such as prepolymers of low molecular glycols such as ethylene glycol, propylene glycol and the above aliphatic diisocyanates, isophorone diisocyanate, hydrogenated 4,4′- Examples thereof include diphenylmethane diisocyanate, methylcyclohexylene diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, alicyclic diisocyanates such as prepolymers of low-molecular glycols and the alicyclic diisocyanates, and mixtures of two or more thereof. .. At the time of urethanization, the above-mentioned polyhydric alcohol and polyether polyol can be used in addition to the above-mentioned polyester polyol. Further, these polyesters and polyurethanes can be used by blending the above-mentioned polyhydric alcohol and polyether polyol components.

As described above, the polyol composition (A) is
(1) A reaction product of a polyvalent alcohol and a polybasic acid having an alkyl side chain having 6 or more carbon atoms, or a polybasic acid and a polyvalent alcohol having an alkyl side chain having 6 or more carbon atoms. Is it a reaction product?
(2) A mixture of a reaction product of a polyhydric alcohol and a polybasic acid with a polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or a polybasic acid having an alkyl side chain having 6 or more carbon atoms. Is preferred.

The reaction product of the above (1) polyvalent alcohol and a polybasic acid having an alkyl side chain of 6 or more carbon atoms, or a polyvalent alcohol having a polybasic acid and an alkyl side chain of 6 or more carbon atoms. In the reaction product of, the reaction product may be a reaction product obtained by appropriately combining the above raw materials, but as a more preferable reaction product, a polyester polyol is preferable, and as a specific embodiment of a more preferable combination,
-Polyester polyol which is a reaction product of dimer acid and polyhydric alcohol-Polyester polyol which is a reaction product of dimer diol and polybasic acid-Reaction product of dimer acid, polyhydric alcohol and polyisocyanate And a polyester urethane polyol which is a reaction product of a polybasic acid and a polyisocyanate.

(2) a reaction product of a polyhydric alcohol and a polybasic acid, and a polyhydric alcohol having an alkyl side chain having 6 or more carbon atoms or a polybasic acid having an alkyl side chain having 6 or more carbon atoms. In the mixture, the above raw materials may be appropriately combined, but specific examples of a more preferable combination include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol. , 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol and other polyhydric alcohols having 2 to 6 carbon atoms, and phthalic acid such as orthophthalic acid, terephthalic acid and isophthalic acid, A mixture of a polyester polyol obtained by reacting a polybasic acid such as adipic acid or sebacic acid with a dimer diol or castor oil can be mentioned.

(Polyisocyanate composition (B)
The polyisocyanate composition (B) used in the present invention is a composition containing a polyisocyanate compound as a main component. As the polyisocyanate compound used in the present invention, known compounds can be used without particular limitation, and they can be used alone or in combination of two or more.
For example, polyisocyanates having an aromatic structure in the molecular structure such as tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and xylylene diisocyanate, and NCO groups of these polyisocyanates. A part of which is modified with carbodiimide; polyisocyanate having an alicyclic structure in the molecular structure such as isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane; 1 Linear aliphatic polyisocyanates such as 6,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate and trimethylhexamethylene diisocyanate, and compounds obtained by modifying a part of the NCO groups of these polyisocyanates with carbodiimide;

Isocyanurate bodies of the various polyisocyanates; Allophanate bodies derived from the various polyisocyanates; Burette bodies derived from the various polyisocyanates; Adduct bodies obtained by modifying the various polyisocyanates with trimethylolpropane; Examples thereof include polyisocyanate, which is a reaction product of an isocyanate and a polyol component.

Here, the reaction ratio between the polyisocyanate compound and the polyol compound is that the equivalent ratio of the isocyanate group and the hydroxyl group [isocyanate group/hydroxyl group] is in the range of 1.5 to 5.0. It is preferable in terms of the balance between cohesive strength and flexibility.

Specific examples of the polyol compound reacted with the polyisocyanate having an alicyclic structure or an aromatic structure in the molecular structure include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene Chain aliphatic glycols such as glycol, dipropylene glycol, tripropylene glycol and bishydroxyethoxybenzene; alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; glycerin, trimethylolpropane, penta Trifunctional or tetrafunctional aliphatic alcohols such as erythritol;
Bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F;

Dimer diol; addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and cyclohexylene in the presence of a polymerization initiator such as the glycol, trifunctional or tetrafunctional aliphatic alcohol. Polyether polyols;
Polyester obtained by a ring-opening polymerization reaction of a cyclic ester compound such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, and the glycol or the trifunctional or tetrafunctional aliphatic Polyester polyol (1) which is a reaction product with alcohol;
A polyester polyol (2) obtained by reacting a polyol such as a chain aliphatic glycol, an alicyclic glycol, a dimer diol, a bisphenol or the polyether polyol with a polyvalent carboxylic acid;
A polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid;
Polyester polyol (4) obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid;
Polyester polyol (5), which is a polymer of hydroxyl acid such as dimethylolpropionic acid and castor oil fatty acid;
A mixture of the above polyester polyols (1), (2), (3), (4) and (5) and a polyether polyol;
Examples include castor oil, castor hydrogenated oil that is a hydrogenated product of castor oil, and castor oil-based polyol such as 5 to 50 mol adduct of castor oil with alkylene oxide.

Here, examples of the polycarboxylic acid used for producing the polyester polyol (2), (3), (4) or (5) include succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid. , Acyclic aliphatic dicarboxylic acids such as maleic anhydride and fumaric acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and tetrahydrophthalic anhydride; terephthalic acid, isophthalic acid , Phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'- Aromatic dicarboxylic acids such as dicarboxylic acids; anhydrides or ester-forming derivatives of these aliphatic or aromatic dicarboxylic acids; p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and dihydroxycarboxylic acids thereof. Examples thereof include ester-forming derivatives and dibasic acids such as polybasic acids having an alkyl side chain having 6 or more carbon atoms.

Polyisocyanates having an aromatic structure in the molecular structure, compounds obtained by modifying a part of NCO groups of these polyisocyanates with carbodiimide, polyisocyanates having an alicyclic structure in the molecular structure, and the linear aliphatic compounds Polyisocyanate isocyanurates, allophanates, burettes, and trimethylolpropane-modified adducts are preferable. Tolylene diisocyanate adducts, isocyanurates, biurets, allophanates, 1,6-hexamethylene diisocyanate adducts. , Isocyanurate body, biuret body, allophanate body, xylylene diisocyanate adduct body, isocyanurate body, biuret body, allophanate body, or isophorone diisocyanate adduct body, isocyanurate body, biuret body, allophanate body is preferably used. ..

(solvent)
The reactive adhesive used in the present invention is an adhesive that is cured by a chemical reaction between an isocyanate group and a hydroxyl group, and can be used as a solvent type or solventless type adhesive. The "solvent" of the solvent-free adhesive in the present invention refers to a highly soluble organic solvent capable of dissolving the polyisocyanate compound and the polyol compound used in the present invention, "solvent-free" Means that these highly soluble organic solvents are not included. Specific examples of the highly soluble organic solvent include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, n-hexane and cyclohexane. Can be mentioned. Of these, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are known as particularly soluble organic solvents.

In the reactive adhesive used in the present invention, the blending ratio of the polyisocyanate composition (B) and the polyol composition (A) is such that the polyisocyanate compound (B) contains the polyisocyanate compound. Adhesive strength and heat-sealing that the equivalent ratio [isocyanate group/hydroxyl group] of the isocyanate group and the hydroxyl group in the polyol compound contained in the polyol composition (A) is in the range of 0.6 to 5.0. It is preferable from the viewpoint that it is excellent in heat resistance at the time, and it is particularly preferable that it is in the range of 1.0 to 3.5 from the viewpoint that these properties become remarkable.

(catalyst)
In the present invention, a curing reaction can be promoted by using a catalyst.
The catalyst used in the present invention is not particularly limited as long as it promotes the urethanization reaction, and examples thereof include metal catalysts, amine catalysts, diazabicycloundecene (DBU), and aliphatic cyclic amide compounds. A catalyst such as a titanium chelate complex can be used.

Examples of the metal-based catalyst include metal complex-based, inorganic metal-based, and organic metal-based catalysts. Specific examples of the metal complex-based catalyst include Fe (iron), Mn (manganese), Cu (copper), and Zr (zirconium). ), Th (thorium), Ti (titanium), Al (aluminum), and Co (cobalt), a metal acetylacetonate salt selected from the group consisting of iron acetylacetonate, manganese acetylacetonate, and copper acetyl. Examples thereof include acetonate and zirconia acetylacetonate. Of these, iron acetylacetonate (Fe(acac) ₃ ) or manganese acetylacetonate (Mn(acac) ₂ ) are preferable from the viewpoints of toxicity and catalytic activity. ..

Examples of the inorganic metal-based catalyst include a catalyst selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co and the like.

As the organometallic catalyst, stannas diacetate, stannas dioctoate, stannas dioleate, stannas dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, Examples thereof include nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, and bismuth naphthenate. Of these, preferred compounds are organotin catalysts, and more preferred are stannas dioctoate and dibutyltin dilaurate.

The tertiary amine catalyst is not particularly limited as long as it is a compound having the above structure, and examples thereof include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, and 2-methylquinuclidine. Among these, triethylenediamine and 2-methyltriethylenediamine are preferable because they have excellent catalytic activity and are industrially available.

Other tertiary amine catalysts include N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N. "-Pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N, N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxy Ethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanolamine, 3-quinuclidinol, N,N,N', N′-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8-diazabicyclo[5.4.0]undecene-7,N-methyl-N '-(2-Dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2 -Methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxy Propyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole and the like can be mentioned.

Examples of the aliphatic cyclic amide compound include δ-valerolactam, ε-caprolactam, ω-enanthollactam, η-capryllactam, β-propiolactam and the like. Among these, ε-caprolactam is more effective in promoting curing.

The titanium chelate complex is a compound whose catalytic activity is enhanced by irradiation with ultraviolet rays, and a titanium chelate complex having an aliphatic or aromatic diketone as a ligand is preferable from the viewpoint of excellent curing acceleration effect. Further, in the present invention, those having an alcohol having 2 to 10 carbon atoms in addition to the aromatic or aliphatic diketone as a ligand are preferable because the effect of the present invention becomes more remarkable.
In the present invention, the above catalysts may be used alone or in combination.

..
The mass ratio of the catalyst is preferably 0.001 to 3 parts, and preferably 0.01 to 2 parts, when the mixed liquid of the polyisocyanate composition (B) and the polyol composition (A) is 100 parts. More preferable.

The reactive adhesive of the present invention may be used in combination with a pigment, if necessary. In this case, the pigment that can be used is not particularly limited, and examples thereof include extender pigments, white pigments, black pigments, gray pigments, and red pigments described in Handbook of Paint Materials 1970 edition (edited by Japan Paint Industry Association). Examples thereof include organic pigments such as pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments and pearlescent pigments, inorganic pigments, and plastic pigments. Various examples are given as specific examples of these colorants, and as the organic pigment, for example, various insoluble azo pigments such as benzine yellow, Hansa yellow, and laked 4R; solubility of laked C, carmine 6B, bordeaux 10 and the like. Azo pigments; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorine dyed lakes such as rhodamine lake and methyl violet lake; various mordant dye pigments such as quinoline lake and fast sky blue; anthraquinone Various vat dye pigments such as pigments, thioindigo pigments, perinone pigments; various quinacridone pigments such as Shincacia Red B; various dioxazine pigments such as dioxazine violet; various condensed azo such as chromophthal Pigments; aniline black and the like can be mentioned.

Examples of the inorganic pigments include various chromates such as yellow lead, zinc chromate and molybdate orange; various ferrocyan compounds such as dark blue; titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, chrome oxide. Various metal oxides such as green and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; calcium silicate, ultramarine blue, etc. Silicates; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powders such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder Pigments; flake pigments of these metals, mica flake pigments; metallic pigments such as mica flake pigments coated with metal oxides, mica-like iron oxide pigments, and pearl pigments; graphite, carbon black and the like.

Examples of extender pigments include precipitated barium sulfate, rice flour, precipitated calcium carbonate, calcium bicarbonate, cryolite, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (aerosil), and silica sand (silica). Sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess and the like.

Furthermore, examples of the plastic pigment include “Grandall PP-1000” and “PP-2000S” manufactured by DIC Corporation.

As the pigment used in the present invention, titanium oxide as a white pigment, an inorganic oxide such as zinc white, and carbon black as a black pigment are more preferable because they are excellent in durability, weather resistance, and design.

The mass ratio of the pigment used in the present invention is 1 to 400 parts by mass, and especially 10 to 300 parts by mass, based on 100 parts by mass of the isocyanate component B and the polyol component A. It is more preferable because it is excellent.

(Adhesion promoter)
Further, an adhesion promoter may be used in combination with the reactive adhesive used in the present invention. Examples of the adhesion promoter include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and an epoxy resin.

Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-β(aminoethyl)-γ. -Aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and other aminosilanes; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-gly Epoxy silanes such as cidoxypropyltriethoxysilane; vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and other vinylsilanes; hexamethyldisilazane, γ-mercapto Examples include propyltrimethoxysilane and the like.

Examples of titanate coupling agents include, for example, tetraisopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy. Titanium etc. can be mentioned.

Examples of the aluminum-based coupling agent include acetoalkoxyaluminum diisopropylate.

As the epoxy resin, generally commercially available Ebisusu type, novolak type, β-methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, many Various epoxy resins such as carboxylic acid ester type, aminoglycidyl type and resorcin type, triglycidyl tris(2-hydroxyethyl)isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acrylglycidyl Compounds such as ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, p-t-butylphenyl glycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, glycidyl methacrylate, butyl glycidyl ether, etc. Can be mentioned.

(Other additives)
If necessary, the reactive adhesive used in the present invention may contain other additives than the above. Examples of the additives include leveling agents, inorganic fine particles such as colloidal silica and alumina sol, polymethylmethacrylate-based organic fine particles, defoaming agents, anti-sagging agents, wetting and dispersing agents, viscosity modifiers, ultraviolet absorbers, and metals. Inactivating agent, peroxide decomposing agent, flame retardant, reinforcing agent, plasticizer, lubricant, rust preventive agent, fluorescent brightening agent, inorganic heat ray absorber, flameproofing agent, antistatic agent, dehydrating agent, Known and commonly used thermoplastic elastomers, tackifiers, phosphoric acid compounds, melamine resins, or reactive elastomers can be used. The content of these additives can be appropriately adjusted and used within a range that does not impair the function of the reactive adhesive used in the present invention.

These adhesion promoters and additives may be mixed with either of the components of the polyisocyanate composition (B) or the polyol composition (A), or may be blended as a third component at the time of application and used. it can. Usually, a premix prepared by previously mixing a component other than the polyisocyanate composition (B) with the polyol composition (A) is prepared, and the premix and the polyisocyanate composition (B) are prepared immediately before coating. Are prepared by mixing.

(Laminate)
The laminate of the present invention can be obtained, for example, by laminating a plurality of films or papers using the adhesive of the present invention by a dry laminating method or a non-solvent laminating method.
There is no particular limitation on the film used, and a film can be appropriately selected depending on the application. For example, for food packaging, polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched). Examples thereof include a polypropylene film, a polyolefin film such as OPP: biaxially oriented polypropylene film), a polyvinyl alcohol film, and a plastic film (also referred to as a polymer film) such as an ethylene-vinyl alcohol copolymer film.

The film may be stretched. As a stretching treatment method, a resin is melt-extruded by an extrusion film forming method or the like to form a sheet, and then simultaneous biaxial stretching or sequential biaxial stretching is performed. Further, in the case of sequential biaxial stretching, it is general to first perform a longitudinal stretching treatment and then perform a transverse stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and lateral stretching using a tenter is often used.

Alternatively, a barrier film containing a metal such as aluminum, a vapor-deposited layer of a metal oxide such as silica or alumina, a polyvinyl alcohol or ethylene/vinyl alcohol copolymer, or a barrier film containing a gas barrier layer such as vinylidene chloride is used together. Good. By using such a film, a laminate having a barrier property against water vapor, oxygen, alcohol, inert gas, volatile organic substances (fragrance), etc. can be obtained.

The surface of the film may be subjected to various surface treatments such as flame treatment and corona discharge treatment, if necessary, so that an adhesive layer free from defects such as film breakage and cissing is formed.

Alternatively, the laminate of the present invention is obtained by applying the adhesive of the present invention as an adhesion aid (anchor coating agent) to a film by a laminator, carrying out a curing reaction, and then laminating a polymer material melted by an extruder. Can be obtained (extrusion lamination method). As the film, the same films as those used in the dry laminating method and the non-solvent laminating method described above can be used. As the polymer material to be melted, a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin or an ethylene-vinyl acetate copolymer resin is preferable.

As a more specific structure of the laminated body,
(1) Substrate film 1/adhesive layer 1/sealant film (2) Substrate film 1/adhesive layer 1/metal-deposited unstretched film (3) Substrate film 1/adhesive layer 1/metal-deposited stretched film (4) Transparent vapor-deposited stretched film/adhesive layer 1/sealant film (5) substrate film 1/adhesive layer 1/substrate film 2/adhesive layer 2/sealant film (6) substrate film 1/adhesive layer 1/metal vapor-deposited stretched film /Adhesive layer 2 /Sealant film (7) Substrate film 1 /Adhesive layer 1 /Transparent vapor deposition stretched film /Adhesive layer 2 /Sealant film (8) Substrate film 1 /Adhesive layer 1 /Metal layer /Adhesive layer 2 /Sealant Film (9) Base film 1/adhesive layer 1/base film 2/adhesive layer 2/metal layer/adhesive layer 3/sealant film (10) base film 1/adhesive layer 1/metal layer/adhesive layer 2/ Examples thereof include base film 2/adhesive layer 3/sealant film, but are not limited thereto.

Examples of the base film 1 used in the configuration (1) include OPP film, PET film, nylon film and the like. Further, as the base film 1, a film coated for the purpose of improving gas barrier properties and ink receptivity when a printing layer described later is provided may be used. Examples of commercially available coated substrate film 1 include K-OPP film and K-PET film. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include CPP film and LLDPE film. A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side (when the coated base film 1 is used, the surface of the coating layer on the adhesive layer 1 side). The printing layer is formed by various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink by a general printing method that has been conventionally used for printing on a polymer film.

Examples of the base film 1 used in the configurations (2) and (3) include OPP films and PET films. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. As the metal vapor-deposited unstretched film, use a VM-CPP film obtained by vapor-depositing a metal such as aluminum on a CPP film, and use the VM-OPP film obtained by vapor-depositing a metal such as aluminum on an OPP film as the metal vapor-deposited stretched film. You can A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as the configuration (1).

Examples of the transparent vapor-deposited stretched film used in the constitution (4) include a film obtained by vapor-depositing silica or alumina on an OPP film, a PET film, a nylon film or the like. For the purpose of protecting the inorganic vapor deposition layer of silica or alumina, a film coated on the vapor deposition layer may be used. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. As the sealant film, the same one as the constitution (1) can be mentioned. A printing layer may be provided on the surface of the transparent vapor-deposited stretched film on the side of the adhesive layer 1 (the surface of the coating layer on the side of the adhesive layer 1 when a coating is applied on the inorganic vapor-deposited layer). The method of forming the print layer is the same as that of the configuration (1).

Examples of the base film 1 used in the configuration (5) include a PET film and the like. Examples of the base film 2 include a nylon film and the like. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. As the sealant film, the same one as the constitution (1) can be mentioned. A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as the configuration (1).

Examples of the base film 1 having the structure (6) include the same as those of the structures (2) and (3). Examples of the metal vapor-deposited stretched film include a VM-OPP film and a VM-PET film obtained by vapor-depositing a metal such as aluminum on an OPP film or a PET film. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. As the sealant film, the same one as the constitution (1) can be mentioned. A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as the configuration (1).

Examples of the base film 1 having the configuration (7) include a PET film and the like. Examples of the transparent vapor-deposited stretched film include those similar to the structure (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. As the sealant film, the same one as the constitution (1) can be mentioned. A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as the configuration (1).

Examples of the base film 1 having the structure (8) include a PET film and the like. Aluminum foil etc. are mentioned as a metal layer. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. As the sealant film, the same one as the constitution (1) can be mentioned. A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as the configuration (1).

Examples of the base film 1 having the configurations (9) and (10) include PET films. Examples of the base film 2 include a nylon film and the like. Aluminum foil etc. are mentioned as a metal layer. At least one layer of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present invention. As the sealant film, the same one as the constitution (1) can be mentioned. A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as the configuration (1).

When the laminate of the present invention includes at least one of a metal vapor deposition film, a transparent vapor deposition film, and a metal layer, the metal vapor deposition layer, the transparent vapor deposition layer, the adhesive layer in contact with the metal layer is a cured coating film of the adhesive of the present invention. Is preferred.

When the adhesive of the present invention is a solvent type, the adhesive of the present invention is applied to the film material serving as a substrate using a roll such as a gravure roll, and after evaporating the organic solvent by heating in an oven or the like, The other base material is attached to obtain the laminate of the present invention. After laminating, aging treatment is preferably performed. The aging temperature is preferably room temperature to 80° C., and the aging time is preferably 12 to 240 hours.

When the adhesive of the present invention is a solventless type, after applying the adhesive of the present invention which has been heated in advance to about 40° C. to 100° C. to a film material as a base material using a roll such as a gravure roll Immediately, the other base material is attached to obtain the laminate of the present invention. After laminating, aging treatment is preferably performed. The aging temperature is preferably room temperature to 70° C., and the aging time is preferably 6 to 240 hours.

When the adhesive of the present invention is used as an adhesive auxiliary, the adhesive auxiliary of the present invention is applied to a film material as a base material by using a roll such as a gravure roll, and the organic solvent is volatilized by heating in an oven or the like. Then, the polymer material melted by the extruder is laminated to obtain the laminate of the present invention.

The amount of adhesive applied is adjusted appropriately. In the case of a solvent-type adhesive, for example, the solid content is adjusted to 1 g/m ² or more and 10 g/m ² or less, preferably 1 g/m ² or more and 5 g/m ² or less. In the case of a solventless adhesive, the amount of the adhesive applied is, for example, 1 g/m ² or more and 10 g/m ² or less, preferably 1 g/m ² or more and 5 g/m ² or less.

When the adhesive of the present invention is used as an adhesion auxiliary agent, the coating amount is, for example, 0.03 g/m ² or more and 0.09 g/m ² or less (solid content).

The laminated body of the present invention may further contain other film or base material in addition to the above-mentioned constitutions (1) to (10). As the other base material, in addition to the above-mentioned stretched film, unstretched film and transparent vapor deposition film, it is also possible to use a porous base material such as paper, wood and leather described later. The adhesive used for laminating other base materials may or may not be the adhesive of the present invention.

As the paper, a known paper base material can be used without particular limitation. Specifically, it is produced by a known paper machine using natural fibers for papermaking such as wood pulp, but the papermaking conditions are not particularly specified. Examples of the natural fibers for papermaking include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as manila hemp pulp, sisal pulp and flax pulp, and pulp obtained by chemically modifying these pulps. As the type of pulp, it is possible to use a chemical pulp, a ground pulp, a chemi-ground pulp, a thermomechanical pulp, etc. prepared by a sulfate digestion method, an acidic/neutral/alkaline sulfite digestion method, a soda salt digestion method or the like.

Further, various commercially available high-quality papers, coated papers, backing papers, impregnated papers, cardboards, paperboards and the like can also be used. A printing layer may be provided on the outer surface or the inner surface side of the paper layer, if necessary.

The "other layer" may contain known additives and stabilizers such as an antistatic agent, an easily adhesive coating agent, a plasticizer, a lubricant, and an antioxidant. The "other layer" is a layer in which the surface of the film is subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. as a pretreatment in order to improve adhesion when laminated with other materials. May be.

As described above, in order to maximize the effect of the present invention that it is possible to obtain a laminate having high adhesiveness and excellent appearance after laminating even under high-speed coating conditions, The adhesive is first applied to a plastic film, and then the adhesive surface and another plastic film or a non-plastic film, for example, a transparent substrate, a porous substrate such as paper, wood, leather, etc. It is preferable to obtain a laminate by laminating.

The laminate of the present invention has various uses, for example, packaging materials for foods, pharmaceuticals, and household items, lid materials, paper straws, paper napkins, paper spoons, paper plates, paper dishes such as paper cups, wall materials, and roofs. Materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive parts, signboards, outdoor industrial applications such as stickers, decorative sheets used for injection molding simultaneous decoration method, etc. It can be suitably used as a packaging material such as a liquid detergent for laundry, a liquid detergent for kitchen, a liquid detergent for bath, a liquid soap for bath, a liquid shampoo, a liquid conditioner and the like.

<Packaging material>
The laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, medicines and the like. When it is used as a multi-layer packaging material, its layer structure may change depending on the contents, environment of use, and form of use. Further, the package of the present invention may be appropriately provided with an easy-opening treatment or a resealing means.

The packaging material of the present invention is obtained by using the laminate of the present invention, and stacking the sealant films of the laminate so as to face each other, and then heat-sealing the peripheral edges thereof to form a bag. As the bag-making method, the laminate of the present invention is folded, or the surfaces of the inner layers of the laminate are opposed to each other (the surface of the sealant film), and the peripheral edges thereof are, for example, a side seal type, a two-side seal type, Examples include heat sealing methods such as three-sided seal type, four-sided seal type, envelope-attached seal type, joint-sealed seal type, pleated seal type, flat bottom seal type, square bottom seal type, gusset type, and other heat seal types. To be The packaging material of the present invention can take various forms depending on the contents, the use environment, and the use form. Self-supporting packaging materials (standing pouches) are also possible. As a heat sealing method, a known method such as bar sealing, rotating roll sealing, belt sealing, impulse sealing, high frequency sealing, or ultrasonic sealing can be used.

After filling the contents of the packaging material of the present invention through the opening, the opening is heat-sealed to manufacture a product using the packaging material of the present invention. As the contents to be filled, for example, as foods, rice confectionery, bean confectionery, nuts, biscuits and cookies, wafer confectionery, marshmallows, pies, half-cakes, candy, snacks such as confectionery, bread, snack noodles, instant noodles, etc. , Dried noodles, pasta, aseptic packed rice, elephant, rice porridge, packed rice, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, nameko mushrooms, konjac, wild vegetable products, jams, peanut cream, Agricultural processed products such as salads, frozen vegetables, potato processed products, hams, bacon, sausages, chicken processed products, livestock processed products such as corned beef, fish ham/sausage, marine products, kamaboko, paste, boiled fish paste, Seafood products such as dried bonito, salted fish, smoked salmon, and spicy cod roe, peaches, tangerines, pineapples, apples, pears, flesh such as cherries, corn, asparagus, mushrooms, onions, carrots, radishes, potatoes and other vegetables. , Hamburger, meatballs, fried fish, gyoza, croquette and other prepared foods, chilled prepared foods such as prepared foods, butter, margarine, cheese, cream, instant creamy powders, dairy products such as infant formula, liquids Examples include foods such as seasonings, retort curry, and pet food.

Non-food items include tobacco, disposable body warmers, medical products such as infusion packs, liquid detergent for washing, liquid detergent for kitchen, liquid detergent for bath, liquid soap for bath, liquid shampoo, liquid conditioner, cosmetics such as lotion and emulsion, vacuum. It can also be used as various packaging materials such as heat insulating materials and batteries.

Hereinafter, the contents and effects of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following examples. In the examples, “part” means “part by weight”.

(Method for producing polyol (A1))
A polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a rectification tube, a water separator, etc., was charged with 46.1 parts of isophthalic acid, 16.9 parts of adipic acid, 10.5 parts of ethylene glycol, neopentyl glycol. 10.1 parts, 1,6-hexanediol 16.4 parts, and zinc acetate 0.03 parts were charged and gradually heated so that the upper temperature of the rectification tube did not exceed 100°C, and the internal temperature was kept at 240°C. .. When the acid value became 5 mgKOH/g, the pressure was reduced to 10 mmHg or less, and the pressure was maintained for 1.5 hours to complete the esterification reaction to obtain a polyol. This was diluted with ethyl acetate to obtain a polyol (A1) having a nonvolatile content of 50%.

(Method for producing polyol (A2))
35.2 parts of isophthalic acid, 20.9 parts of adipic acid, 8.5 parts of ethylene glycol, neopentyl glycol were placed in a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction pipe, a rectification pipe, a water separator, etc. Charge 15.7 parts, 1,6-hexanediol 11.3 parts, dimer acid (Tsunodime 216 manufactured by Tsukino Food Industry Co., Ltd., product name 8.4 parts), zinc acetate 0.03 parts, and rectification tube upper temperature. Was gradually heated so that the temperature did not exceed 100°C, and the internal temperature was kept at 240°C. When the acid value reached 5 mgKOH/g, the pressure was reduced to 10 mmHg or less and kept for 1.5 hours to obtain an intermediate polyol. To 100 parts of the obtained intermediate polyol, 2.1 parts of isophorone diisocyanate was added and heated to 120° C. to carry out a urethanization reaction until the free NCO groups were substantially eliminated, and diluted with ethyl acetate to obtain a nonvolatile content of 50%. % Polyol (A2) was obtained.

(Method for producing polyol (A3))
A polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., was charged with 36.1 parts of isophthalic acid, 17.0 parts of adipic acid, 8.2 parts of ethylene glycol, neopentyl glycol. Charge 17.3 parts, 8.2 parts of 1,6-hexanediol, 13.2 parts of dimer acid (Tsunodime 216 manufactured by Tsukino Food Industry Co., Ltd.), 0.03 parts of zinc acetate, and the upper temperature of the rectification tube. Was gradually heated so that the temperature did not exceed 100°C, and the internal temperature was kept at 240°C. When the acid value reached 5 mgKOH/g, the pressure was reduced to 10 mmHg or less and kept for 1.5 hours to obtain an intermediate polyol. To 100 parts of the obtained intermediate polyol, 2.1 parts of isophorone diisocyanate was added and heated to 120° C. to carry out a urethanization reaction until the free NCO groups were substantially eliminated, and diluted with ethyl acetate to obtain a nonvolatile content of 50%. % Polyol (A3) was obtained.

(Polyol (A4))
As the polyol (A4), dimer diol (Product name Pripol 2033 manufactured by Croda Japan Co., Ltd.: referred to as A4-a in the table), castor oil (Product name castor oil manufactured by Ito Oil Co., Ltd.: referred to as A4-b in the table), 2 -Ethyl-1,3-hexanediol (KH Neochem Co., Ltd. product name octanediol: referred to as A4-c in the table) was used.

(Isocyanate composition (B))
As the isocyanate composition (B), a biuret body of hexamethylene diisocyanate (HDI) (manufactured by BASF Japan Ltd., HB-100) was used.

(Method for adjusting reactive adhesive)
The polyols (A1), (A2), (A3), (A4) and (isocyanate composition (B)) were blended as shown in Table 1 to prepare reactive adhesives 1 to 11.
Using these reactive adhesives, the contact angle of water on the adhesive surface and the appearance of the laminated film were evaluated by the methods described below.

(Evaluation method of water contact angle)
Using a fully automatic contact angle meter “DropMaster DMo-701” manufactured by Kyowa Interface Science Co., Ltd., a polyol composition used in the reactive adhesives 1 to 11 was formed into a polyethylene terephthalate film (E-5100: Toyobo) having a thickness of 50 μm. Co., Ltd.) at a processing speed of 10 m/min so that the coating amount was 3.0 g (solid content)/m ² . Then, it was dried with a dryer at 60° C. to obtain a dried coating film of the polyol composition.
After 3 μL of purified water was dropped on the dried coating film, the water contact angle after 1 second was measured.

(Laminated appearance evaluation method)
Using a dry laminator (manufactured by Orient Co., Ltd.: DL-600 type), an adhesive compounding liquid prepared by mixing the reactive adhesives 1 to 11 with ethyl acetate as a diluting solvent was gravure-printed to a thickness of 20 μm. An axially stretched polypropylene film (OPP: manufactured by Toyobo Co., Ltd., PYREN OT P-2161) was coated at a processing speed of 200 m/min so that the coating amount was 3.0 g (solid content)/m ² , and a drier (60 C./70.degree. C./80.degree. C.), after drying ethyl acetate, a 25 .mu.m thick aluminum vapor-deposited polypropylene film (VMCPP: Toray Film Co., Ltd., 2203) overlaps the aluminum vapor-deposited surface and the adhesive coated surface. Thus, a laminate was obtained.
The ink portion of the obtained laminate was observed and the appearance was evaluated.
◯: Number of bubbles in 1 cm ² scale: 0 to 4 Δ: Number of bubbles in 1 cm ² scale: 5 to 9 x: Number of bubbles in 1 cm ² scale: 10 or more

In Table 1, the abbreviations represent the following.
A4-a: Dimer diol (Product name Pripol 2033 manufactured by Croda Japan Co., Ltd.)
A4-b: Castor oil (Product name castor oil manufactured by Ito Oil Co., Ltd.)
A4-c: 2-ethyl-1,3-hexanediol (KH Neochem Co., Ltd. product name octanediol)

As a result, by introducing an alkyl side chain having 6 or more carbon atoms and increasing the water contact angle of the dried coating film of the polyol composition (A) (decreasing the surface tension), the uncured resin film base material is uncured. The wettability of the adhesive in the state was improved, and it became possible to obtain a laminate excellent in laminate appearance even under high-speed coating conditions.

Claims (6)

A reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), comprising:
The polyol composition (A) is a mixture of a reaction product of polyhydric alcohol and polybasic acid, dimer diol, castor oil, or dimer acid ,
The dimer diol, castor oil, or dimer acid is contained in the polyol composition (A) in a solid content of 0.1 to 5.0% by weight,
A reactive adhesive having a water contact angle of 65 degrees or more on the surface of a dry coating film obtained by coating the polyethylene terephthalate film with the polyol composition (A) at a solid coating amount of 3.0 g/m ² . The reactive adhesive according to claim 1, wherein the dimer diol, castor oil, or dimer acid is contained in the polyol composition (A) in a solid content of 0.2 to 3.0% by weight. The reactive adhesive according to claim 1, wherein the reaction product of the polyhydric alcohol and the polybasic acid is a polyester polyol obtained by reacting the polyhydric alcohol and the polybasic acid. A laminate obtained by laminating a plurality of films or papers with an adhesive, wherein the adhesive is the reactive adhesive according to any one of claims 1 to 3. A laminate obtained by laminating a film or paper provided with a plurality of printing layers with an adhesive, wherein the adhesive is the reactive adhesive according to any one of claims 1 to 4. Laminate. A package formed by forming the laminate according to claim 4 or 5 into a bag shape.