JP7206888B2 - Reactive adhesives, laminated films, and packages - Google Patents

Description

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

Conventionally, various types of plastic films are laminated together, and laminates obtained by laminating plastic films with metal-deposited films or metal foils have been used in various applications, such as packaging materials for foods, pharmaceuticals, and daily necessities, as well as barriers. Materials, roofing 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, decoration used for injection molding simultaneous decoration methods, etc. It is used for various purposes.
For these laminates, various types of plastic films, metal vapor-deposited films, or metal foils are appropriately combined according to the properties required for each application, and an adhesive is selected according to the required properties. For example, in the case of food and daily necessities, functions such as strength, resistance to cracking, retort resistance, heat resistance, and resistance to contents are required to protect the contents from various distributions, storage such as refrigeration, and processing such as heat sterilization. is required.
Furthermore, these laminates are rarely distributed in the form of sheets, and for example, they are made into bags with heat-sealed ends, or they are sometimes subjected to molding for thermoforming, which requires heat-sealability and molding processability. Sometimes it is.

Reactive adhesives (also referred to as two-component curing adhesives) that react hydroxyl groups with isocyanate have been conventionally known as adhesives used for such lamination.
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) A polyisocyanate compound (b1) having a molecular weight (Mn) in the range of 400 to 3000, wherein the polyisocyanate (B) is a trivalent or higher polyisocyanate compound (b1), and a diisocyanate compound (b2) obtained by adding an isocyanate compound to a polyester diol. Adhesives are known which are mixtures of (See Patent Document 1, for example)

These reactive adhesives are required to have characteristics according to various uses, and in recent years, from the viewpoint of productivity, gravure coaters have been used. However, it is required to obtain a laminated film free from appearance defects. 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 that can be adjusted in viscosity using organic solvents. Also, there is a problem that depending on the base material, appearance defects such as citrus peel, blur, streaks, and bubbles are likely to occur.

JP 2014-101422 A JP 2010-264677 A

The problem to be solved by the present invention is that it can be applied as an adhesive for laminates in which various plastic films, metal vapor deposition films, or metal foils are appropriately combined, and even under high-speed coating conditions, high adhesion and lamination processing To provide a reactive adhesive with which a laminated film having an excellent appearance can be obtained.

The present inventors have solved the above problems by adding a specific amount of a siloxane compound having an aralkyl group.
As an adhesive for lamination used between a plastic substrate and a sealant layer, an isocyanate compound having 85% by weight or more of a difunctional or higher isocyanate group and 0.01 to 0.5% by weight of a polydimethylsiloxane compound. Such an adhesive is disclosed in US Pat. However, the problem of Patent Document 2 is that it has excellent initial lamination strength and the lamination strength does not decrease, and these excellent properties can be exhibited even with an extremely thin adhesive layer. was not

That is, the present invention provides a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein 0.001 of aralkyl-modified polymethylalkylsiloxane is added to the total solid content of the reactive adhesive. A two-part adhesive containing ~1% by weight is provided.

The present invention also provides a laminated film formed by laminating an adhesive layer between a first plastic film and a second plastic film, wherein the adhesive layer is a reactive adhesive layer according to any one of the above. A laminated film is provided.

The present invention also provides a laminated film formed by laminating a first plastic film, a printed layer, an adhesive layer, and a second plastic film in this order, wherein the adhesive layer is any one of claims 1 to 3. A laminated film is provided that is a layer of the reactive adhesive described.

The present invention also provides a package formed by molding the laminate film described above into a bag.

The present invention also provides a laminated film formed by laminating an adhesive layer between a first plastic film and a second plastic film, wherein the adhesive layer is a layer of the reactive adhesive described above. provide the film.

The present invention also provides a package formed by molding the laminate film described above into a bag.

The reactive adhesive of the present invention can be applied as an adhesive for laminates in which various types of plastic films, metal-deposited films, or metal foils are appropriately combined. A laminated film having an excellent appearance can be obtained. Furthermore, since it is excellent in heat resistance and content resistance, it can be suitably used as a food packaging bag and a sanitary refill bag.

In particular, 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, the above As the second plastic film, general-purpose CPP (unstretched polypropylene), VMCPP (aluminum-deposited unstretched polypropylene), LLDPE (linear low-density polyethylene), LDPE (low-density polyethylene), HDPE (high-density polyethylene), VMLDPE ( Since it has particularly high wettability to sealant films such as aluminum-deposited low-density polyethylene) and films such as nylon and polyethylene terephthalate (PET), it can be used particularly preferably in the production of laminated films 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 aralkyl-modified polymethylalkylsiloxane is added to the total solid content of the reactive adhesive. It is characterized by containing 0.002 to 1% by mass of.

(Aralkyl-modified polymethylalkylsiloxane)
The aralkyl-modified polymethylalkylsiloxane used in the present invention refers to a compound having a chain structure in which siloxane bonds are linearly connected, and an aralkyl group pendant to the Si group in the chain structure. . Specifically, it is a compound represented by the general formula (1). The molecular weight is preferably 500 to 20,000, more preferably 2,000 to 10,000 in terms of number average molecular weight.

In general formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² represents an aralkyl group, and x and y each independently represent an integer of 1 or more. Also, when x or y is each independently 2 or more, multiple x or y may be the same group or different groups. note that

In general formula (1), the number of carbon atoms in the alkyl group represented by R ¹ is, when x is 2 or more, an alkyl group having 1 to 6 carbon atoms and an alkyl group having 6 to 10 carbon atoms. A mixture is preferred. Among them, it is preferable that an alkyl group having 1 to 2 carbon atoms and an alkyl group having 8 to 10 carbon atoms are mixed.

Examples of the aralkyl group represented by R ² include groups in which the aryl moiety has 6 to 20 carbon atoms and the alkyl moiety has 1 to 10 carbon atoms. The number of carbon atoms in the aryl moiety is more preferably 6-14, more preferably 6-10. Examples of the aralkyl group represented by R ² include phenylmethyl group (benzyl group), phenylethyl group, phenylpropyl group, phenylbutyl group and the like. Among them, a phenylpropyl group is preferred.

The aralkyl-modified polymethylalkylsiloxane is preferably contained in an amount of 0.002 to 1% by mass based on the total solid content of the reactive adhesive of the invention. More preferably, it is in the range of 0.005 to 0.1% by mass.

In the reactive adhesive of the present invention, the aralkyl-modified polymethylalkylsiloxane is preferably used in combination with a polyhydric alcohol or polybasic acid having an alkyl side chain of 6 or more carbon atoms.
Examples of polyhydric alcohols or polybasic acids having alkyl side chains of 6 or more carbon atoms include dimer diol, castor oil, 1,2-octanediol, 1,2-decanediol, and dimer acid.

Here, the dimer acid is a product of the Diels-Alder dimerization reaction of unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, and various types such as those obtained by adding hydrogen to the unsaturated bond to saturate it. things are on the market. A representative one consists of 0-5% by weight of a monocarboxylic acid having 18 carbon atoms, 70-98% by weight of a dimer acid having 36 carbon atoms and 0-30% by weight of a trimer acid having 54 carbon atoms. Further, the dimer diol is obtained by reducing the dimer acid described above.

The polyhydric alcohol or polybasic acid having an alkyl side chain having 6 or more carbon atoms is 0.1 to 30.0% in the cured coating film of the polyol composition (A) and the polyisocyanate composition (B). It is preferably used in a percentage by weight, more preferably 0.2 to 20.0% by weight.
If the polyhydric alcohol or polybasic acid having an alkyl side chain having 6 or more carbon atoms is used as a reaction raw material for the polyol composition (A) of the reactive adhesive, the solid content of the polyol composition (A) It is preferably used in a proportion of 0.1 to 35.0% by weight, more preferably 0.2 to 25.0% by weight.
Further, if the polyhydric alcohol or polybasic acid having an alkyl side chain having 6 or more carbon atoms is used as a mixed raw material of the polyol composition (A) of the reactive adhesive, the polyol composition (A) solid It is preferably used in a proportion of 0.1 to 5.0% by weight, more preferably 0.2 to 3.0% by weight.

(Other raw materials polyol composition (A))
In the present invention, the reactive adhesive is not particularly limited except that the aralkyl-modified polymethylalkylsiloxane is added, and known polyols and polyisocyanates generally used in reactive adhesives that react hydroxyl groups and isocyanates are appropriately used. can do.
For example, as the polyol composition (A), known polyhydric alcohols and polyols can be used. Specifically, polyester polyol, polyether polyol, polyurethane polyol, polyether ester polyol, polyester (polyurethane) polyol, polyether (polyurethane) polyol, polyesteramide polyol, acrylic polyol, polycarbonate polyol, polyhydroxylalkane, castor oil or them may be mentioned polymer polyols selected from mixtures of Among them, polyester polyol is preferable.

(Polyol composition (A))
The polyol composition (A) used in the present invention is a composition containing a polyol compound as a main component. A polyol compound can be used individually or can also be used in mixture of multiple.
Specific examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. , neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1, Glycols such as 4-cyclohexanedimethanol; trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane and pentaerythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A and hydrogenated bisphenol F;

Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of polymerization initiators such as glycols and trifunctional or tetrafunctional aliphatic alcohols. a polyether urethane polyol obtained by further increasing the molecular weight of the polyether polyol with the aromatic or aliphatic polyisocyanate;

Polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, and the aforementioned glycols, glycerin, trimethylolpropane, pentaerythritol, etc. Polyester polyol (1) which is a reaction product with a polyhydric alcohol; Polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or bisphenol with a polyvalent carboxylic acid; A polyester polyol (3) obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polycarboxylic polyester polyol (4) obtained by reacting with an 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) are aromatic or aliphatic polyester polyurethane polyol obtained by polymerizing with group polyisocyanate; mixture of polyester polyols (1) to (5) and polyether polyol; castor oil, dehydrated castor oil, castor hardened oil which is hydrogenated castor oil, Castor oil-based polyols such as adducts of castor oil with 5 to 50 moles of alkylene oxide may be mentioned. The weight average molecular weight (Mw) of the polyol used is preferably 400-100,000.

Examples of polyvalent carboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. acids, aliphatic dicarboxylic acids such as tetrahydrophthalic anhydride; terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl dicarboxylic acids, aromatic dicarboxylic acids such as 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or aromatic dicarboxylic acids; p-hydroxybenzoic acid , p-(2-hydroxyethoxy)benzoic acid, ester-forming derivatives of these dihydroxycarboxylic acids, and polybasic acids such as dimer acid.

(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 ones can be used without any particular limitation, and they can be used singly or in combination.
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, xylylene diisocyanate, and NCO groups of these polyisocyanates partially modified with carbodiimide; isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl) polyisocyanate having an alicyclic structure in the molecular structure such as cyclohexane; Linear aliphatic polyisocyanates such as ,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate and trimethylhexamethylene diisocyanate, and compounds obtained by modifying some of the NCO groups of these polyisocyanates with carbodiimide;

isocyanurate forms of the various polyisocyanates; allophanate forms derived from the various polyisocyanates; biuret forms derived from the various polyisocyanates; adducts obtained by modifying the various polyisocyanates with trimethylolpropane; Examples include polyisocyanate which is a reaction product of isocyanate and polyol component.

Here, in the reaction ratio of the polyisocyanate compound and the polyol compound, the equivalent ratio [isocyanate group/hydroxyl group] between the isocyanate group and the hydroxyl group is in the range of 0.5 to 6.0. It is preferable from the viewpoint of the balance between cohesion and flexibility.

Specific examples of the polyol compound to be 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, cyclohexylene, etc. in the presence of a polymerization initiator such as the aforementioned glycol, trifunctional or tetrafunctional aliphatic alcohol; polyether polyols;
A 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 trifunctional or tetrafunctional aliphatic Polyester polyol (1) which is a reactant with alcohol;
A polyester polyol (2) obtained by reacting a polyol such as the linear aliphatic glycol, alicyclic glycol, dimer diol, bisphenol, or polyether polyol with a polyvalent carboxylic acid;
polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid;
A polyester polyol (4) obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid;
polyester polyols (5), which are polymers of hydroxyl acids such as dimethylolpropionic acid, castor oil fatty acid;
mixtures of the polyester polyols (1), (2), (3), (4), (5) and polyether polyols;
Castor oil, castor oil hydrogenated castor oil, and castor oil-based polyols such as adducts of 5 to 50 moles of alkylene oxide of castor oil.

Examples of the polyvalent carboxylic acid used for producing the polyester polyol (2), (3), (4) or (5) include succinic acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid. , maleic anhydride, non-cyclic aliphatic dicarboxylic acids such as fumaric acid; 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acids such as 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 of these Examples include polybasic acids such as ester-forming derivatives and dimer acids.

Polyisocyanates having an aromatic structure in the molecular structure, compounds obtained by modifying some of the NCO groups of these polyisocyanates with carbodiimide, polyisocyanates having an alicyclic structure in the molecular structure, and the linear aliphatic Isocyanurate, allophanate, biuret, and trimethylolpropane-modified adducts of polyisocyanate are preferred, and tolylene diisocyanate adduct, isocyanurate, biuret, allophanate, and 1,6-hexamethylene diisocyanate adduct. , isocyanurate, biuret, allophanate, xylylene diisocyanate adduct, isocyanurate, biuret, allophanate, or isophorone diisocyanate adduct, isocyanurate, biuret, allophanate. .

(solvent)
The reactive adhesive used in the present invention is an adhesive that cures through a chemical reaction between an isocyanate group and a hydroxyl group, and can be used as a solvent-type or non-solvent-type adhesive. In addition, the "solvent" of the solvent-free adhesive used in the present invention refers to a highly soluble organic solvent capable of dissolving the polyisocyanate compound and polyol compound used in the present invention. It means that it does not contain these highly soluble organic solvents. Examples of highly soluble organic solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, n-hexane, cyclohexane, and the like. mentioned. Among them, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are known as organic solvents with particularly high solubility.

In the reactive adhesive used in the present invention, the mixing ratio of the polyisocyanate composition (B) and the polyol composition (A) is The equivalent ratio [isocyanate group/hydroxyl group] between the isocyanate group and the hydroxyl group in the polyol compound contained in the polyol composition (A) is in the range of 0.5 to 6.0. The range of 1.0 to 4.0 is particularly preferred from the viewpoint that these performances become remarkable.

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

Examples of metal-based catalysts include metal complex-based, inorganic metal-based, and organic metal-based catalysts. ), Th (thorium), Ti (titanium), Al (aluminum) and Co (cobalt). Acetonate, zirconia acetylacetonate and the like can be mentioned, but among these, iron acetylacetonate (Fe(acac) ₃ ) or manganese acetylacetonate (Mn(acac) ₂ ) is preferable from the viewpoint of toxicity and catalytic activity. .

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

Examples of organometallic catalysts include stannus diacetate, stannus dioctoate, stannus dioleate, stannus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, bismuth naphthenate and the like. Preferred among these compounds are organic tin catalysts, and more preferred are stannous 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 preferred because of their excellent catalytic activity and industrial availability.

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.

Aliphatic cyclic amide compounds include, for example, δ-valerolactam, ε-caprolactam, ω-enanthollactam, η-capryllactam, β-propiolactam and the like.

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, in addition to aromatic or aliphatic diketones, those having alcohols having 2 to 10 carbon atoms as ligands are preferred from the viewpoint that the effects of the present invention are more pronounced.
In the present invention, the above catalysts may be used alone or in combination.

.
The mass ratio of the catalyst is preferably in the range of 0.001 to 3 parts per 100 parts of the mixture of the polyisocyanate composition (B) and the polyol composition (A), and more preferably in the range of 0.01 to 2 parts. more preferred.

The reactive adhesive of the present invention may be used in combination with a pigment, if desired. The pigments that can be used in this case are not particularly limited. Organic and inorganic pigments such as pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments and pearlescent pigments, and plastic pigments can be used. Specific examples of these coloring agents include various ones, and examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, Laked 4R; soluble pigments such as Laked C, Carmine 6B, and Bordeaux 10; Azo pigments; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant pigments such as quinoline lake and fast sky blue; vat dye-based pigments such as thioindigo-based pigments, perinone-based pigments; various quinacridone-based pigments such as Cincasia Red B; various dioxazine-based pigments such as dioxazine violet; pigments; aniline black and the like;

Examples of inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanic compounds such as Prussian blue; titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, and chromium oxide. various metal oxides such as green and zirconium oxide; various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types such as calcium silicate and ultramarine blue 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 and pearl pigments such as mica flake pigments coated with metal oxides and mica-like iron oxide pigments; graphite, carbon black and the like.

Extender pigments include, for example, precipitated barium sulfate, rice flour, precipitated calcium carbonate, calcium bicarbonate, Kansui stone, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.

Furthermore, examples of plastic pigments include “Glandol PP-1000” and “PP-2000S” manufactured by DIC Corporation.

As the pigments used in the present invention, inorganic oxides such as titanium oxide and zinc oxide as white pigments, and carbon black as black pigments 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, especially 10 to 300 parts by mass with respect to the total of 100 parts by mass of the isocyanate component B and the polyol component A. Adhesion, blocking resistance, etc. It is more preferable because it is excellent in

(adhesion promoter)
An adhesion promoter can also be used in combination with the reactive adhesive used in the present invention. Adhesion promoters include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and epoxy resins.

Silane coupling agents include, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ - aminosilanes such as N-phenyl-γ-aminopropyltrimethoxysilane; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxysilane; Epoxysilanes such as sidoxypropyltriethoxysilane; Vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane, γ-mercapto Propyltrimethoxysilane and the like can be mentioned.

Titanate-based coupling agents include, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, 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 epibis type, novolac 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, poly Various epoxy resins such as carboxylic acid ester type, aminoglycidyl type, resorcinol type, triglycidyl tris(2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acryl glycidyl compounds such as ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, pt-butylphenyl glycidyl ether, diglycidyl adipate, o-diglycidyl phthalate, glycidyl methacrylate, butyl glycidyl ether; mentioned.

(Other additives)
If necessary, the reactive adhesive used in the present invention may contain other additives than those mentioned above. Additives include, for example, leveling agents, inorganic fine particles such as colloidal silica and alumina sol, polymethyl methacrylate-based organic fine particles, antifoaming agents, anti-sagging agents, wetting and dispersing agents, viscosity modifiers, ultraviolet absorbers, metals Deactivators, peroxide decomposers, flame retardants, reinforcing agents, plasticizers, lubricants, rust inhibitors, fluorescent whitening agents, inorganic heat absorbers, flame retardants, antistatic agents, dehydrating agents, 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 within a range that does not impair the functions of the reactive adhesive used in the present invention.

These adhesion promoters and additives can be mixed with either the polyisocyanate composition (B) or the polyol composition (A), or used as a third component at the time of coating. can. Usually, the polyol composition (A) is premixed with components other than the polyisocyanate composition (B) in advance, and the premix and the polyisocyanate composition (B) are mixed immediately before coating. Prepared by mixing

(Laminated film)
The laminated film of the present invention is obtained by laminating an adhesive layer comprising the reactive adhesive between a first plastic film and a second plastic film. Specifically, it 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. Although any known method may be used for coating, gravure roll coating is generally used. The solid content of the adhesive is 1.0 to 5.0 g/m ² , preferably 1.5 to 4.0 g/m ² .

In addition, gravure, flexo, or offset printing of printing ink may be used on the first plastic film, and even in this case, a good laminate appearance can be exhibited. As the printing ink described above, solvent-based, water-based, or active energy ray-curable inks can be used.

When the reactive adhesive used in the present invention is used, the adhesive cures in 12 to 120 hours at room temperature or under heat after lamination, and exhibits practical physical properties.

The first plastic film used here includes PET (polyethylene terephthalate) film, nylon film, OPP (biaxially oriented polypropylene) film, K-coated film such as polyvinylidene chloride, base film such as various vapor deposition films, and aluminum foil. etc., and as the second plastic film, the other substrates include CPP (unstretched polypropylene) film, VMCPP (aluminum-deposited unstretched polypropylene) film, LLDPE (linear low-density polyethylene) film, Sealant films such as LDPE (low-density polyethylene) films, HDPE (high-density polyethylene) films, VMLDPE (aluminum-deposited non-low-density polyethylene) films, and the like.

(package)
The package of the present invention is formed by molding the laminated film into a bag shape, and specifically, the laminated film is heat-sealed to form the package. In addition, when considering the use as a package, the required performance (easily tearable and hand-cutting), the rigidity and durability required as a package (for example, impact resistance, pinhole resistance, etc.), Other layers may be laminated as desired. It is usually used with a substrate layer, a paper layer, a second sealant layer, a nonwoven layer, and the like. A well-known method can be used as a method of laminating other layers. For example, an adhesive layer may be provided between other layers and laminated by a dry lamination method, a heat lamination method, a heat sealing method, an extrusion lamination method, or the like. As the adhesive, the reactive adhesive may be used, or other one-liquid type urethane-based adhesive, epoxy-based adhesive, aqueous dispersion of acid-modified polyolefin, or the like may be used.

As a specific laminate structure, a first plastic film layer/adhesive layer/second plastic layer and a first plastic film, which can be suitably used for general packages, lids, refill containers, etc. Base material layer/adhesive layer/first plastic film layer/adhesive layer/second plastic layer, etc., in which a layer is used as a barrier layer. These laminates may have a printed layer, a topcoat layer, and the like, if necessary.

The first plastic film layer is, for example, polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polylactic acid (PLA); polyolefin resin films such as polypropylene; polystyrene resin films; Polyamide resin films such as p-xylylene adipamide (MXD6 nylon); polycarbonate resin films; polyacrylonitrile resin films; polyimide resin films; Ethylene-vinyl alcohol copolymer/nylon 6) and mixtures are used. Among them, those having mechanical strength and dimensional stability are preferable. In particular, among these, films arbitrarily stretched in biaxial directions are preferably used.

In addition, the first plastic film layer is a soft metal foil such as an aluminum foil in order to impart a barrier function, as well as a vapor deposition layer such as aluminum vapor deposition, silica vapor deposition, alumina vapor deposition, silica-alumina binary vapor deposition; vinylidene chloride resin , denatured polyvinyl alcohol, ethylene-vinyl alcohol copolymer, MXD nylon, or the like.

A conventionally known sealant resin can be used as the second plastic film layer. For example, polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), acid-modified polyethylene, polypropylene (PP), acid-modified polypropylene, copolymer polypropylene, VMCPP (aluminum vapor deposition) Polyolefin resins such as unstretched polypropylene), VMLDPE (aluminum-deposited low-density polyethylene), ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-(meth)acrylic acid copolymer, ionomer, etc. etc. Among them, polyethylene-based resins are preferable from the viewpoint of low-temperature sealability, and polyethylene is particularly preferable because it is inexpensive.

Examples of the paper layer include natural paper and synthetic paper. The first and second sealant layers can be formed of materials similar to the sealant layers described above. A printed layer may be provided on the outer surface or the inner surface side of the substrate layer and the paper layer, if necessary.

The "other layer" may contain known additives and stabilizers such as antistatic agents, easy-adhesion coating agents, plasticizers, lubricants and antioxidants. In addition, the "other layers" are pre-treated with corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. in order to improve adhesion when laminated with other materials. may

Embodiments of the package of the present invention include a three-side seal bag, a four-side seal bag, a gusset packaging bag, a pillow packaging bag, a gobel-top type bottomed container, a tetra classic, a Bruck type, a tube container, a paper cup, a lid material, and the like. There are various. Moreover, the package of the present invention may be appropriately provided with an easy-opening treatment or a resealing means.

EXAMPLES The contents and effects of the present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In addition, "parts" in the examples indicate "mass parts".
The "weight average molecular weight" was calculated using gel permeation chromatography using a standard polystyrene calibration curve.

(Method for producing polyol (A-1))
387.7 parts of isophthalic acid, 92.3 parts of adipic acid, 56.0 parts of dimer acid, and ethylene glycol were added to a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, water separator, etc. 92.6 parts of neopentyl glycol, 119.4 parts of neopentyl glycol, 72.0 parts of 1,6-hexanediol, and 0.03 parts of zinc acetate were charged and gradually heated so that the temperature at the top of the rectifying tube did not exceed 100°C. 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 maintained for 1.5 hours to complete the esterification reaction and obtain a polyol. This was diluted with ethyl acetate to obtain polyol (A-1) having a non-volatile content of 50%.

(Method for producing polyol (A-2))
394.2 parts of isophthalic acid, 135.0 parts of adipic acid, 96.8 parts of ethylene glycol, and neopentyl glycol were added to a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, water separator, etc. 95.1 parts, 45.0 parts of 1,6-hexanediol, 70.0 parts of diethylene glycol, and 0.03 parts of zinc acetate were charged, and gradually heated so that the temperature at the top of the rectification tube did not exceed 100°C. The temperature was held at 240°C. When the acid value reached 5 mgKOH/g, the pressure was reduced to 10 mmHg or less and maintained for 1.5 hours to complete the esterification reaction and obtain a polyol. This was diluted with ethyl acetate to obtain polyol (A-2) having a non-volatile content of 50%.

(Method for producing polyol (A-3))
35.2 parts of isophthalic acid, 20.9 parts of adipic acid, 8.5 parts of ethylene glycol, and neopentyl glycol are added to a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, water separator, etc. 15.7 parts of 1,6-hexanediol, 11.3 parts of 1,6-hexanediol, 8.4 parts of dimer acid (manufactured by Tsuno Foods Industry Co., Ltd., product name Tsunodigm 216), and 0.01 part of tetraisopropoxytitanium were charged, and a rectification tube was added. The inner temperature was maintained at 240°C by gradually heating so that the upper temperature did not exceed 100°C. When the acid value reached 5 mgKOH/g, the pressure was reduced to 10 mmHg or less and maintained for 1 hour 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 free NCO groups were substantially eliminated, diluted with ethyl acetate to give a nonvolatile content of 50. % of polyol (A-3) was obtained.

(siloxane compound)
Siloxane (D1): An aralkyl-modified dimethylsiloxane having a phenylpropyl group was used.

Siloxane (D2): Polyester-modified polymethylalkylsiloxane (product name: BYK-320 manufactured by BYK-Chemie Co., Ltd.) was used.

Siloxane (D3): Polyester-modified polymethylalkylsiloxane (product name: BYK-325 manufactured by BYK-Chemie Co., Ltd.) was used.

(Isocyanate composition (B-1))
An ethyl acetate solution of a TDI/TMP adduct (Coronate L, manufactured by Tosoh Corporation) was used.

(Example 1)
600 parts of polyol (A-1), 100 parts of isocyanate composition (B-1), 0.10 parts of siloxane (D1) (solid content ratio 0.02%) and 575 parts of ethyl acetate were blended and reacted. adhesive was prepared.

(Example 2)
600 parts of polyol (A-1), 100 parts of isocyanate composition (B-1), 1.00 parts of siloxane (D1) (0.2% solid content) and 575 parts of ethyl acetate were blended and reacted. adhesive was prepared.

(Example 3)
600 parts of polyol (A-2), 100 parts of isocyanate composition (B-1), 0.10 parts of siloxane (D1) (solid content ratio 0.02%) and 575 parts of ethyl acetate were blended and reacted. adhesive was prepared.

(Example 4)
500 parts of polyol (A-3), 50 parts of isocyanate composition (B-1), 0.10 parts of siloxane (D1) (solid content ratio 0.02%) and 600 parts of ethyl acetate were blended and reacted. adhesive was prepared.

(Comparative example 1)
A reactive adhesive was prepared by blending 600 parts of polyol (A-1), 100 parts of isocyanate composition (B-1) and 575 parts of ethyl acetate.

(Comparative example 2)
600 parts of polyol (A-1), 100 parts of isocyanate composition (B-1), 0.005 parts of siloxane (D1) (solid content ratio 0.001%), and 575 parts of ethyl acetate were blended and reacted. adhesive was prepared.

(Comparative Example 3)
600 parts of polyol (A-1), 100 parts of isocyanate composition (B-1), 0.1 part of each of siloxane (D2) (solid content ratio 0.02%), 575 parts of ethyl acetate, A reactive adhesive was prepared.

(Comparative Example 4)
600 parts of polyol (A-1), 100 parts of isocyanate composition (B-1), 0.1 part of each of siloxane (D3) (solid content ratio 0.02%), and 575 parts of ethyl acetate, A reactive adhesive was prepared.

<Evaluation method>
<Antifoaming> (Table evaluation)
For the adhesives of Examples and Comparative Examples, the viscosity was adjusted with ethyl acetate so as to be Zahn cup #15 (14 to 16 seconds). Put 40 ml of the adjusted adhesive in a 70 ml sealable bottle, stir the sample to be compared at once under the same conditions, stir (about 3 times per second for about 10 seconds (total 30 times), and immediately after that for 2 minutes Evaluated how the foam disappeared.
Evaluation ⊚ Bubbles completely disappeared within 30 seconds.
Evaluation ◯: Bubbles completely disappeared within 1 minute.
Evaluation Δ: Bubbles become almost inconspicuous after 2 minutes.
Evaluation × The foam hardly disappears even after 2 minutes have passed.

<Hajiki> (Table evaluation)
For the adhesives of Examples and Comparative Examples, the viscosity was adjusted with ethyl acetate so as to be Zahn cup #15 (14 to 16 seconds). The adhesive after adjustment was applied to an aluminum deposition film so that the coating amount was 3.0 g/m ² in terms of non-volatile matter. After the coated surface was dried with hot air, the appearance of the coating was visually confirmed.
Evaluation ⊚: No repelling was observed, and the surface was completely smooth.
Evaluation ◯: Repellence is not observed, but slight unevenness is observed on the coated surface.
Evaluation Δ: Some repelling is observed on the coated surface.
Evaluation x: The liquid is repelled on the entire surface, and the film is exposed.

<turbidity> (table evaluation)
The adhesives of Examples and Comparative Examples were adjusted with ethyl acetate to a Zahn cup #15 (14 to 16 seconds). 40 ml of the adhesive after preparation was placed in a 70 ml sealable bottle, stirred until completely dissolved, and after all bubbles were removed in a static state, turbidity was visually observed.
Evaluation ○ It looks completely transparent.
Evaluation Δ: Appears slightly muddy (slightly cloudy).
Evaluation x: Cloudy and opaque.

<Actual machine evaluation>
The adhesives of Examples and Comparative Examples were adjusted with ethyl acetate to a Zahn cup #3 (14-16 seconds). A chamber doctor was attached to a commercial machine size dry laminator (manufactured by Fuji Machinery Co., Ltd.), laminated films were prepared using the adhesives of Examples and Comparative Examples, and leveling and appearance abnormalities were evaluated by visual evaluation. rice field.
Application amount of adhesive: 2.8 (g/m ² ) in terms of solid content.
Laminator line speed: 150 m/min.
Structure of laminated film: PET/adhesive/VMPET/adhesive/LLDPE
PET: Espet E-5102 (polyethylene terephthalate film manufactured by Toyobo Co., Ltd.)
VMPET: 1310 (polyethylene terephthalate film with an aluminum deposition layer manufactured by Toray Advanced Film Co., Ltd.)
LLDPE: T.I. U.S.A. X-FCD100 (linear low-density polyethylene film manufactured by Mitsui Chemicals Tocello Co., Ltd.)

<Leveling property>
Evaluation ⊚ Completely smooth with no unevenness observed even when enlarged.
Evaluation ◯ It is smooth to the extent that unevenness cannot be recognized by normal visual observation.
Evaluation Δ: Slight unevenness can be observed.
Evaluation × The whole is rough.

<Appearance abnormality evaluation>
Evaluation ⊚: A uniform coating surface without air bubble-like appearance defects.
Evaluation ◯: Poor bubble-like appearance is partially confirmed.
Evaluation Δ: Bubble-like appearance defects are observed throughout.
Evaluation x: A large number of bubble-like appearance defects are observed throughout.

Tables 1 and 2 show the results.

In the table, blanks represent unblended.
As a result, the example using siloxane (D1) was good in all evaluation items. On the other hand, Comparative Example 1, in which no siloxane compound itself was used, was also inferior in antifoaming properties. Comparative Example 2, in which siloxane (D1) was used but the amount added was out of the range of the present invention, was inferior in leveling properties and caused abnormal appearance. Comparative Examples 3 and 4, which used siloxane compounds having no aralkyl group, were inferior in leveling properties and produced abnormal appearance.

Claims (5)

At least one polybasic acid selected from the group consisting of isophthalic acid, adipic acid, and dimer acid, and at least one selected from the group consisting of ethylene glycol, neopentyl glycol, 1,6-hexanediol, and diethylene glycol. A reaction product with a polyhydric alcohol, or at least one polybasic acid selected from the group consisting of isophthalic acid, adipic acid, and dimer acid, ethylene glycol, neopentyl glycol, 1,6-hexanediol, and diethylene glycol. - containing a polyol composition (A) which is a reaction product of at least one polyhydric alcohol selected from the group consisting of isophorone diisocyanate and isophorone diisocyanate, and a polyisocyanate composition (B) which is a TDI/TMP adduct 1. A two-component adhesive which is a reactive adhesive and contains 0.002 to 1% by mass of an aralkyl-modified polymethylalkylsiloxane having a phenylpropyl group relative to the total solid content of the reactive adhesive. The reaction ratio between the polyisocyanate compound in the polyisocyanate composition (B) and the polyol compound in the polyol composition (A) is such that the equivalent ratio of the isocyanate group to the hydroxyl group [isocyanate group/hydroxyl group] is 0.5 to 6. The reactive adhesive of claim 1 in the range of .0. A laminated film obtained by laminating an adhesive layer between a first plastic film and a second plastic film, wherein the adhesive layer is a layer of the reactive adhesive according to any one of claims 1 and 2 . A laminated film characterized by: A laminated film obtained by laminating a first plastic film, a printed layer, an adhesive layer, and a second plastic film in this order, wherein the adhesive layer is the reactive adhesive according to any one of claims 1 to 2 . A laminated film characterized by being a layer of an agent. A package formed by molding the laminated film according to claim 3 or 4 into a bag.