WO2023106097A1

WO2023106097A1 - Reactive adhesive, laminated film, and packaging

Info

Publication number: WO2023106097A1
Application number: PCT/JP2022/043264
Authority: WO
Inventors: 常行手島; 寛知永田; 千勇徳永
Original assignee: Dic株式会社
Priority date: 2021-12-09
Filing date: 2022-11-24
Publication date: 2023-06-15
Also published as: JPWO2023106097A1

Abstract

Provided are: a reactive adhesive satisfying (1) and (2); and a laminated film in which a plurality of olefinic resin-containing base films are laminated and adhered with a reactive adhesive, wherein the reactive adhesive satisfies (1) and (2). (1) After a polyolefinic resin and the reactive adhesive are blended in a ratio of 96:4 and melt-kneaded at 240°C for 3 minutes, the particle size of the adhesive is 20 μm or less. (2) E' at 200°C of a cured film obtained by curing the reactive adhesive at 40°C for 72 hours is in the range of 1.0×10⁵-3.0×10⁶.

Description

Reactive adhesives, laminated films, and packaging materials

The present invention relates to a reactive adhesive for laminated films suitable for recycled plastics, laminated films and packaging materials using the same.

Laminated films, which are conventionally manufactured by the lamination method using adhesives, are not only intended for packaging, but also provide various high-performance functions such as barrier properties, moisture resistance, and retort resistance with a single packaging material. It has been developed and evolved to laminate films of different resin types in order to meet the demands. (See Patent Document 1, for example)
However, in recent years, there have been voices that these different resin types of laminated films deteriorate the quality of recycled plastics, and there is a demand for highly functional and recyclable packaging materials.

As a method of improving the quality of recycled plastics without reducing the functionality of packaging materials as much as possible, there is a movement to ``compose packaging materials from a single type of raw material as much as possible'' (sometimes referred to as monomaterialization). , as a material of plastic, which is the main raw material, for example, a proposal to use a laminated film (sometimes called a mono-material film) composed only of polyolefin films such as polyethylene films laminated in multiple layers as a packaging material has begun. (See Patent Document 1, for example). As a global trend, the guidelines of CEFLEX (Circular Economy for Flexible Packaging), a consortium that promotes the realization of a circular economy in the flexible packaging field in Europe, contain less than 5% of impurities such as adhesives in mono-material films. decided to be As will be described later, even if the content of the adhesive, which is an impurity, is less than 5%, the recyclability of the monomaterial film is affected. Therefore, we must consider the development of adhesives that do not affect the recyclability of mono-material films.

As a method for laminating laminated films, there is a method in which each layer is formed by co-extrusion molding as described in paragraph 0070 of Patent Document 1, and a method in which each film is adhered with an adhesive to obtain a laminated film. In particular, a laminated film laminated using a thermosetting reactive adhesive obtained by a reaction between an isocyanate compound and a polyol compound has strong lamination adhesive strength because the adhesive layer after the reaction is crosslinked, heat resistance, It is excellent in chemical resistance and oil resistance, and is used, for example, as a retort food packaging material that requires retort resistance (see, for example, Patent Document 2). However, a laminated flexible film that consists of only a polyolefin film as a thermosetting reactive adhesive through the reaction of an isocyanate compound and a polyol compound may not have the strength, especially the tensile elongation, of recycled plastic after recycling. rice field.

JP 2020-55176 A Japanese Patent Application Laid-Open No. 2001-335771

The object of the present invention is to provide a reactive adhesive that can be applied to laminated flexible films composed only of polyolefin films, and that can maintain the strength, particularly the tensile elongation, of recycled plastics.

That is, the present invention provides a reactive adhesive that satisfies (1) and (2).
(1) A polyolefin resin and a reactive adhesive are blended in the range of 96:4, and the particle size of the adhesive after melt-kneading at 240° C. for 3 minutes is 20 μm or less.
(2) E′ at 200° C. of the cured coating film of the reactive adhesive cured at 40° C. for 72 hours is in the range of 1.0×10 ⁵ to 3.0×10 ⁶ ;

The present invention also provides a laminated film obtained by laminating and adhering base films made of a plurality of olefinic resins with a reactive adhesive, wherein the reactive adhesive is the reactive adhesive described above. .

The present invention also provides a packaging material comprising the laminated film described above.

According to the present invention, it can be applied to laminated flexible films composed only of polyolefin films, and the strength of recycled plastics, especially tensile elongation, can be maintained.

(reactive adhesive)
The reactive adhesive of the present invention is characterized by satisfying (1) and (2).
(1) A polyolefin resin and a reactive adhesive are blended in the range of 96:4, and the particle size of the adhesive after melt-kneading at 240° C. for 3 minutes is 20 μm or less.
(2) E′ at 200° C. of the cured coating film of the reactive adhesive cured at 40° C. for 72 hours is in the range of 1.0×10 ⁵ to 3.0×10 ⁶ ;

Currently, the general recycling method for waste plastics is to manually sort the collected waste plastics by type to a certain extent, and then undergo processes such as crushing, washing, melting, and extrusion to make recycled plastics. .
At this time, as described above, laminated films laminated using a thermosetting reactive adhesive or the like by the reaction of an isocyanate compound and a polyol compound have a strong laminating adhesive strength, so the adhesive cannot be easily removed by hand. It cannot be separated from film. Therefore, the reactive adhesive and the plastic resin (mostly polyolefin resin), which is the material of the laminated film, are mixed together and undergo the steps of crushing, washing, melting, extrusion, and the like.

(1) in the present invention simulates the "melting" process in this process. The present inventors found that even if the adhesive is mixed in the polyolefin resin, which is the material of the laminated film, in the melting process, (1) in the present invention, that is, the polyolefin resin and the reactive adhesive are in the range of 96:4. and having a particle size of 20 μm or less after melt-kneading at 230° C. for 3 minutes, it was found that the strength, especially tensile elongation, of recycled plastics can be maintained.

On the other hand, (2) in the present invention simulates the "crushing" process in this process. In the crushing process, even if the adhesive is mixed in the polyolefin resin that is the material of the laminated film, (2) in the present invention, that is, the cured coating film of the reactive adhesive cured at 40 ° C. for 72 hours at 200 ° C. An adhesive with E′ in the range of 1.0×10 ⁵ to 3.0×10 ⁶ facilitates pulverization of the adhesive during melt-kneading, and in the melting step following the pulverization step, the adhesive It becomes possible to further reduce the particle size, and it becomes easier to reduce the particle size of the adhesive to 20 μm or less in (1) above. As a result, it is estimated that the tensile elongation of the obtained recycled plastic can be maintained.

The above (1) will be explained.
In (1), a polyolefin resin and a reactive adhesive are blended in a ratio of 96:4, and the particle size of the adhesive after melt-kneading at 240° C. for 3 minutes is 20 μm or less.
The polyolefin resin used here refers to the raw material of the polyolefin resin film, which is frequently used for the laminated film produced by the lamination method, for which there is a high demand for recycling. Specific films frequently used for these laminated films include polyethylene films (LLDPE: linear low-density polyethylene film, LDPE: low-density polyethylene film, MDOPE: machine direction oriented polyethylene film, BOPE: biaxially oriented polyethylene film, HDPE: high-density polyethylene film) and polypropylene films (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film) and other polyolefin films. Ethylene and propylene, which are raw materials for the film, are commercially available, both petroleum-derived and bio-based raw materials.

The polyolefin resin and reactive adhesive are blended in the range of 96:4 in terms of mass ratio. Although the reactive adhesive may contain an organic solvent as described later, in the present invention, it is defined as a solid content.

In the above (1), the melt-kneading conditions were as follows.
20 μm OPP film (biaxially oriented polypropylene film) or 30 μm CPP film (non-stretched polypropylene film), the adhesive coating liquid is bar coater so that the solid content weight of the adhesive is about 2.0 g / m ² After the solvent is volatilized, it is laminated with a 30 μm CPP film using a desktop calender roll. Aging is performed at 40° C. for 72 hours to produce a laminated film.
The ratio of "the sum of the weight of the OPP film and the weight of the CPP film" to "the solid content weight of the adhesive" of the obtained laminated film is 96:4.
The laminated film is cut into strips having a width of 10 mm and a length of 300 mm, and the strips are melt-kneaded at 240° C. and 100 rpm for 3 minutes using a twin-screw kneading extruder (ULTnano 15TW manufactured by Technobell Co., Ltd.). The particle size of the adhesive after such melt-kneading conditions was measured.

Also, the particle size of the adhesive was a value measured by the following method.
The laminated film obtained under the same conditions as the melt-kneading was cut into strips of 10 mm in width and 300 mm in length, and extruded at 240° C. using a twin-screw kneading extruder (ULTnano 15TW manufactured by Technobell Co., Ltd.). , 100 rpm for 3 minutes, extruded from a nozzle, and immediately cooled with tap water to obtain a strand-like resin. The resulting strand was randomly cut out at 10 locations with a microtome, and each cross section was observed with a SEM backscattered electron image at 15 KV and 150 magnifications to obtain an image with a field of view of 400 μm×600 μm. The adhesive particles are extracted from the obtained image using image processing analysis software ImageJ. In this process, 2×2 pixels or less were determined to be noise, and the diameter calculated from the area was calculated assuming that the particle was a circle, and a histogram was created. From the obtained histogram, the maximum value of the area that occupies 90% of the whole was taken as the adhesive particle size.

In the present invention, the particle size of the adhesive is preferably 20 µm or less, more preferably 10 µm or less. On the other hand, the lower limit is preferably 1 μm or more, most preferably 3 μm or more.

The above (2) will be explained.
In (2) above, the cured coating film of the reactive adhesive cured at 40° C. for 72 hours has an E′ at 200° C. in the range of 1.0×10 ⁵ to 3.0×10 ⁶ .
In the present invention, the E′, E″ and tan δ peaks were values obtained by measuring by the following method.
Using a dynamic viscoelasticity measuring device (RSA G2 manufactured by TA Instruments), a test piece for viscoelasticity measurement was measured under the following conditions, and E′ (storage elastic modulus), E″ (loss elastic modulus), tan δ (Loss tangent) is obtained under the following conditions.
Sample: length 20 mm (excluding gripping allowance) x width 5 mm x thickness 0.3 mm
Measurement temperature range: -50 to 200°C
Frequency: 1.0Hz
Heating rate 5°C/min

The range of E′ is preferably in the range of 2.0×10 ⁵ to 2.0×10 ⁶ , more preferably in the range of 3.0×10 ⁵ to 1.0×10 ⁶ . .

In the present invention, the reactive adhesive to be used preferably has a tan δ peak of 0°C or higher and 40°C or lower after heating at 240°C. Since the tan δ peak is within this range, the tensile elongation can be further maintained.
The tan δ peak is preferably in the range of 2°C to 36°C, more preferably in the range of 2°C to 25°C.

(reactive adhesive)
The adhesive used in the present invention is a reactive adhesive, and contains a polyisocyanate composition (A) containing an isocyanate compound and a polyol compound, which are frequently used in laminated films produced by a lamination method with a high demand for recycling. A reactive adhesive containing a polyol composition (B).

(Polyisocyanate composition (A))
The polyisocyanate composition (A) contains a polyisocyanate compound (A1). A known polyisocyanate compound (A1) can be used without particular limitation. 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, isocyanate groups of these polyisocyanates (may be abbreviated as NCO group) partially modified with carbodiimide;

Polyisocyanates having an alicyclic structure in the molecular structure such as isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane; 1,6-hexamethylene diisocyanate, 1,5 -Linear aliphatic polyisocyanates such as pentamethylene diisocyanate, lysine diisocyanate and trimethylhexamethylene diisocyanate, compounds obtained by modifying some of the NCO groups of these polyisocyanates with carbodiimide; isocyanurate forms of these polyisocyanates; these polyisocyanates biuret forms of these polyisocyanates; adducts obtained by modifying these polyisocyanates with trimethylolpropane; and polyurethane polyisocyanates which are reaction products of these polyisocyanates and polyols.

When polyurethane polyisocyanate is used as the polyisocyanate compound (A1), from the viewpoint of the balance between the cohesive force and flexibility of the adhesive coating film, the above-mentioned polyisocyanate and polyol are adjusted to the equivalent ratio [NCO] of the isocyanate group to the hydroxyl group. /[OH] is preferably obtained by reacting at a ratio of 0.5 to 5.0.

Examples of polyols that are reactive components of polyurethane polyisocyanate include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Chains such as 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and bishydroxyethoxybenzene aliphatic glycols;

Alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; Heterocyclic glycols such as tris(2-hydroxyethyl) isocyanurate; Trifunctional or tetrafunctional aliphatic alcohols; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A and hydrogenated bisphenol F; dimer diol;

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 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, hydrogenated castor oil, which is a hydrogenated castor oil, and castor oil-based polyols such as adducts of 5 to 50 mol of alkylene oxide of castor oil, etc., can be used alone or in combination.
Examples of polyvalent carboxylic acids that are reaction components of polyester polyols (2) to (5) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1, Aliphatic dicarboxylic acids such as 3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic 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 anhydride or ester-forming derivatives of these aliphatic or dicarboxylic acids; p- Polybasic acids such as hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, ester-forming derivatives of these dihydroxycarboxylic acids, and dimer acid can be mentioned.

Examples of the polyisocyanate compound (A1) include polyisocyanates having an aromatic structure in the molecular structure, polyisocyanates having an aromatic structure in the molecular structure and some of the NCO groups of the polyisocyanate modified with carbodiimide, and polyisocyanates having an aromatic structure in the molecular structure. Any isocyanurate, allophanate, biuret, or adduct of a polyisocyanate having a cyclic structure is preferable, and isocyanurate or allophanate of tolylene diisocyanate, 1,6-hexamethylene diisocyanate, xylylene diisocyanate, or isophorone diisocyanate. Body, billet body and adduct body are preferred.

(Polyol composition (B))
The polyol composition (B) used in the present invention is a composition containing a polyol compound (B1) as a main component. The polyol compound (B1) may be used alone or in combination.
Specifically, various polyols exemplified as reaction components when polyurethane polyisocyanate is used as the polyisocyanate compound (A1) can be used.
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 chain aliphatic glycols;

Alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol;
trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol;
Bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F;
dimer diall;

(Other components of adhesive)
The reactive adhesive of the present invention may contain ingredients other than those mentioned above. These components may be contained in either or both of the polyisocyanate composition (A) and the polyol composition (B), or may be prepared separately from these and the polyisocyanate may be added immediately before coating the adhesive. It may be used by mixing with the composition (A) and the polyol composition (B). Each component will be described below.

(Organic solvent)
The reactive adhesives of the present invention may be in either solvent-based or solvent-free form. The "solvent type" adhesive referred to in the present invention is a method of applying the adhesive to a base material, heating it in an oven or the like to volatilize the organic solvent in the coating film, and then bonding it to another base material. , refers to a form used in a so-called dry lamination method. Either one or both of the polyisocyanate composition (A) and the polyol composition (B) are used in the present invention by dissolving the constituent components of the polyisocyanate composition (A) and the polyol composition (B) ( containing organic solvents that can be diluted).

Examples of organic solvents include esters such as ethyl acetate, butyl acetate and cellosolve acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; and aromatic hydrocarbons such as toluene and xylene. , methylene chloride, halogenated hydrocarbons such as ethylene chloride, dimethylsulfoxide, dimethylsulfamide and the like. The organic solvent used as a reaction medium during the production of the components of the polyisocyanate composition (A) or the polyol composition (B) may also be used as a diluent during coating.

As used herein, the term "solvent-free" adhesive means that the polyisocyanate composition (A) and the polyol composition (B) are substantially The form of the adhesive used in the so-called non-solvent lamination method, which is a method in which the adhesive is applied to the base material and then laminated to another base material without the process of heating in an oven or the like to volatilize the solvent. point to The constituent components of the polyisocyanate composition (A) or the polyol composition (B) and the organic solvent used as the reaction medium during the production of the raw materials cannot be completely removed, resulting in the polyisocyanate composition (A) or the polyol composition ( If a small amount of organic solvent remains in B), it is understood that the organic solvent is not substantially contained. Further, when the polyisocyanate composition (A) contains a low-molecular-weight alcohol, the low-molecular-weight alcohol reacts with the polyol composition (B) and becomes part of the coating film, so it is not necessary to volatilize after coating. Such forms are therefore also treated as solventless adhesives and low molecular weight alcohols are not considered organic solvents.

(catalyst)
The curing reaction of the reactive adhesive of the present invention can be accelerated by using a catalyst as necessary. The catalyst is not particularly limited as long as it promotes the urethanization reaction between the polyisocyanate composition (A) and the polyol composition (B), and includes metal catalysts, amine catalysts, aliphatic cyclic amide compounds, and titanium chelates. Complexes and the like are exemplified.

Metal-based catalysts include metal complex-based, inorganic metal-based, and organic metal-based catalysts. As the metal complex catalyst, a group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), Co (cobalt) Examples include acetylacetonate salts of metals selected from the above, such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate and the like. From the point of view of toxicity and catalytic activity, iron acetylacetonate (Fe(acac) ₃ ) or manganese acetylacetonate (Mn(acac) ₂ ) are preferred.

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

Organometallic catalysts include organozinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; , dioctyltin dilaurate, dibutyltin oxide, dibutyltin dichloride and other organic tin compounds, nickel octylate, nickel naphthenate and other organic nickel compounds, cobalt octylate, cobalt naphthenate and other organic cobalt compounds, bismuth octylate, neodecanoic acid Examples include organic bismuth compounds such as bismuth and bismuth naphthenate, and titanium compounds such as tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride.

Amine catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl Propylenediamine, 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-hydroxyethyl)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-methyl imidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1- (2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)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. Among these, ε-caprolactam is more effective in accelerating hardening.

The titanium chelate complex is a compound whose catalytic activity is enhanced by ultraviolet irradiation, 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.

These catalysts can be used alone or in combination of two or more. The amount of the catalyst compounded is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the total solid content of the polyisocyanate composition (A) and the polyol composition (B). is more preferable.

(pigment)
The reactive adhesive of the present invention may contain a pigment if necessary. The pigments used are not particularly limited, and extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, and blue pigments described in the 1970 edition of the Handbook of Paint Materials (edited by the Japan Paint Manufacturers Association). Organic and inorganic pigments such as pigments, metal powder pigments, luminescent pigments, and pearlescent pigments, and plastic pigments can be used.

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.

Specific examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R; soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10; various (copper) pigments such as phthalocyanine blue and phthalocyanine green. Phthalocyanine pigments; various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant pigments such as quinoline lake and fast sky blue; various pigments such as anthraquinone pigments, thioindigo pigments and perinone pigments vat dye-based pigments; various quinacridone-based pigments such as Cincasia Red B; various dioxazine-based pigments such as dioxazine violet; various condensed azo pigments such as chromophtal;

Examples of inorganic pigments include various chromates such as yellow lead, zinc chromate, molybdate orange; various ferrocyanic compounds such as Prussian blue; Various metal oxides such as 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 of silicon such as calcium silicate and ultramarine blue. acid salts; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder; These metal flake pigments and mica flake pigments; metallic pigments and pearl pigments such as mica-like iron oxide pigments and mica-like iron oxide pigments coated with metal oxides; graphite, carbon black and the like.

Examples of plastic pigments include "Grandol PP-1000" and "PP-2000S" manufactured by DIC Corporation.

The pigment to be used may be appropriately selected according to the purpose. For example, inorganic oxides such as titanium oxide and zinc oxide are preferably used as white pigments because they are excellent in durability, weather resistance, and design. Carbon black is preferably used as the pigment.

The amount of the pigment compounded is, for example, 1 to 400 parts by mass with respect to 100 parts by mass of the total solid content of the polyisocyanate composition (A) and the polyol composition (B), in order to improve adhesion. More preferably 10 to 300 parts by mass.

(adhesion promoter)
The reactive adhesive of the present invention may contain an adhesion promoter. Examples of adhesion promoters include coupling agents such as silane coupling agents, titanate coupling agents and aluminum coupling agents, and epoxy resins.

Silane coupling agents include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-amino Aminosilanes such as propyltrimethyldimethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy epoxysilanes such as propyltriethoxysilane; vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane, γ-mercaptopropyltrisilane; methoxysilane and the like.

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. are mentioned.

Examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.

As the epoxy resin, generally commercially available epibis 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, 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.

(Antioxidant)
The reactive adhesive of the invention may contain an antioxidant. Phosphorus-based antioxidants or bindered phenol-based antioxidants are particularly preferred as antioxidants. Phosphorus-based antioxidants include, for example, triphenyl phosphite (Johoku Chemical Co., Ltd., JP-360), trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, trioleyl phosphite, diphenylmono ( 2-ethylhexyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, bis(decyl) pentaerythritol diphosphite, tristearyl phosphite etc. Binderd phenol antioxidants include, for example, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (BASF Japan Ltd., Irganox1010), thiodiethylene bis[3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-hydroxyphenyl)propionate, 3,5-bis(1,1-dimethylethyl)benzylacetate -4-hydroxy-C7-C9 branched alkyl esters and the like.
The amount of the phosphorus-based antioxidant added is most preferably 0.1 to 1.0% by mass, and the amount of the bindered phenol-based antioxidant added is most preferably 0.1 to 5.0% by mass. Phosphorus-based antioxidants or bindered phenol-based antioxidants may be used alone or in combination.

(Other additives)
In addition to the components described above, the reactive adhesive of the present invention includes a leveling agent, inorganic fine particles such as colloidal silica and alumina sol, polymethyl methacrylate-based organic fine particles, an antifoaming agent, an anti-sagging agent, a wetting and dispersing agent, a viscosity Regulators, UV absorbers, metal deactivators, peroxide decomposers, flame retardants, reinforcing agents, plasticizers, lubricants, rust inhibitors, fluorescent brighteners, inorganic heat absorbers, flame retardants , antistatic agents, dehydrating agents, known and commonly used thermoplastic elastomers, tackifiers, phosphoric compounds, melamine resins, reactive elastomers, and the like. The blending amount of these additives is appropriately adjusted within a range that does not impair the desired properties of the reactive adhesive of the present invention.

(Laminated film)
The reactive adhesive of the present invention is particularly useful as a reactive adhesive for laminated films obtained by laminating and adhering base films made of a plurality of olefinic resins with a reactive adhesive. In the laminated film having this structure, the effect of the present invention, particularly the maintenance of the tensile elongation of the recycled plastic, can be maximized.

Specifically, the olefin resin is a polyethylene film (LLDPE: linear low density polyethylene film, LDPE: low density polyethylene film, MDOPE: machine direction oriented polyethylene film, BOPE: biaxially oriented polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), etc., but not limited thereto. Ethylene and propylene, which are raw materials for the film, may be derived from petroleum or biomaterials, and are not particularly limited, and any commercially available olefin resin film can be used. These films are obtained by laminating them by a dry lamination method or a non-solvent lamination method.

The film may be stretched. As a stretching treatment method, it is common to melt-extrude a resin into a sheet by an extrusion film-forming method or the like, and then subject the sheet to simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then laterally stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.

As a more specific structure of the laminated film,
(1) Base film 1/adhesive layer 1/sealant film (2) Base film 1/adhesive layer 1/unstretched film (3) Base film 1/adhesive layer 1/stretched film (4) Transparent evaporated stretched film /adhesive layer 1/sealant film (5) base film 1/adhesive layer 1/base film 2/adhesive layer 2/sealant film (6) base film 1/adhesive layer 1/stretched film/adhesive layer 2/sealant Examples include, but are not limited to, films. The sealant film, unstretched film, and stretched film may be subjected to metal vapor deposition, transparent vapor deposition, or the like.

An OPP film is mentioned as the base film 1 used in the configuration (1). Further, as the base film 1, a film coated for the purpose of improving gas barrier properties, ink receptivity when providing a printing layer described later, and the like may be used. Commercially available coated base film 1 includes A-OPP film. The adhesive layer 1 is a cured coating film of the reactive adhesive of the present invention. Examples of sealant films include CPP films and LLDPE films. A printed layer may be provided on the surface of the substrate film 1 on the adhesive layer 1 side (when a coated substrate film 1 is used, the surface of the coating layer on the adhesive layer 1 side). The printed layer is formed by a general printing method conventionally used for printing on polymer films using various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, and inkjet ink.

The base film 1 used in the configurations (2) and (3) includes an OPP film. The adhesive layer 1 is a cured coating film of the reactive adhesive of the present invention. As an unstretched film, a CPP film can be mentioned, but a VM-CPP film to which aluminum or the like has been vapor-deposited can also be used. An OPP film can be used as the stretched film, but a VM-OPP film on which aluminum or the like is vapor-deposited can also be used. A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

Examples of transparent vapor-deposited stretched films used in configuration (4) include films obtained by vapor-depositing silica or alumina on an OPP film. For the purpose of protecting the inorganic deposition layer of silica or alumina, etc., a film obtained by coating the deposition layer may be used. The adhesive layer 1 is a cured coating film of the reactive adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the transparent vapor deposited stretched film (when using a film having a coated inorganic vapor deposited layer, the surface of the coating layer on the adhesive layer 1 side). The method of forming the printed layer is the same as that of configuration (1).

Examples of the base film 1 used in configuration (5) include an OPP film and the like. Examples of the base film 2 include an OPP film and the like. Adhesive layers 1 and 2 are cured coating films of the reactive adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

Examples of the base film 1 of configuration (6) include the same ones as those of configurations (2) and (3). Examples of stretched films include OPP films, and examples include VM-OPP films deposited with metal such as aluminum, and films deposited with silica, alumina, or the like. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the reactive adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

In addition, of course, the reactive adhesive of the present invention can also be applied to general-purpose films other than the olefin films. For example, food packaging includes polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film and the like.

Alternatively, a barrier film containing a vapor-deposited layer of a metal such as aluminum, a metal oxide such as silica or alumina, or a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used in combination. good too. By using such a film, a laminated film having barrier properties against water vapor, oxygen, alcohol, inert gas, volatile organic matter (aroma) and the like can be obtained.

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

Examples of the base film 1 used in configuration (1) include OPP film, PET film, nylon film (hereinafter also referred to as Ny film), and the like. Further, as the base film 1, a film coated for the purpose of improving gas barrier properties, ink receptivity when providing a printing layer described later, and the like may be used. Commercially available coated base film 1 includes A-OPP film. The adhesive layer 1 is a cured coating film of the reactive adhesive of the present invention. Examples of sealant films include CPP films and LLDPE films. A printed layer may be provided on the surface of the substrate film 1 on the adhesive layer 1 side (when a coated substrate film 1 is used, the surface of the coating layer on the adhesive layer 1 side). The printed layer is formed by a general printing method conventionally used for printing on polymer films using various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, and inkjet ink.

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

Examples of transparent vapor-deposited stretched films used in configuration (4) include films obtained by vapor-depositing silica or alumina on OPP films, PET films, nylon films, or the like. For the purpose of protecting the inorganic deposition layer of silica or alumina, etc., a film obtained by coating the deposition layer may be used. The adhesive layer 1 is a cured coating film of the reactive adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the transparent vapor deposited stretched film (when using a film having a coated inorganic vapor deposited layer, the surface of the coating layer on the adhesive layer 1 side). The method of forming the printed layer is the same as that of configuration (1).

Examples of the base film 1 used in the configuration (5) include PET film and the like. Examples of the base film 2 include a nylon film. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the reactive adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

Examples of the base film 1 of configuration (6) include the same ones as those of configurations (2) and (3). Examples of the metal-deposited oriented film include VM-OPP film and VM-PET film obtained by subjecting an OPP film or PET film to metal deposition such as aluminum. At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the reactive adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

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

Examples of the base film 1 of configuration (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 reactive adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on the adhesive layer 1 side of the base film 1 in the same manner as in the configuration (1).

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

When the laminated film 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, and the adhesive layer in contact with the metal layer are formed by curing the reactive adhesive of the present invention. It is preferably a coating film.

When the reactive adhesive of the present invention is a solvent type, the reactive adhesive of the present invention is applied to the film material as a substrate using a roll such as a gravure roll, and the organic solvent is volatilized by heating in an oven or the like. After that, the other substrate is laminated to obtain the laminated film of the present invention. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably room temperature to 80° C., and the aging time is preferably 12 to 240 hours.

When the reactive adhesive of the present invention is solvent-free, the reactive adhesive of the present invention preheated to about 40° C. to 100° C. is applied to the base film material using a roll such as a gravure roll. Immediately after coating with the other substrate, the laminate film of the present invention is obtained by laminating the other substrate. It is preferable to perform an aging treatment after lamination. The aging temperature is preferably room temperature to 70° C., and the aging time is preferably 6 to 240 hours.

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

The amount of adhesive to be applied is appropriately adjusted. In the case of a solvent-based adhesive, for example, the solid content is adjusted to 1 g/m ² or more and 10 g/m ² or less, preferably 2 g/m 2 ^or more and 5 g/m ² or less. In the case of a solventless adhesive, the coating amount of the adhesive is, for example, 1 g/m ² or more and 5 g/m ² or less, preferably 1 g/m ² or more and 3 g/m ² or less.

When the reactive adhesive of the present invention is used as an adhesion aid, the coating amount is, for example, 0.1 g/m ² or more and 2 g/m ² or less (solid content).

The laminated film of the present invention may further contain other films and substrates in addition to the above-described configurations (1) to (10). As other substrates, in addition to the stretched film, unstretched film, and transparent vapor-deposited film described above, porous substrates such as paper, wood, and leather, which will be described later, can also be used. These can be removed as foreign matter by a mesh filter during melting and kneading in the recycling process, making it easier than separating different types of plastic. The adhesive used when bonding other substrates may or may not be the reactive adhesive of the present invention.

As the paper, a known paper base material can be used without any 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 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. The types of pulp that can be used include chemical pulp, ground pulp, chemi-grand pulp, thermomechanical pulp, and the like prepared by sulfate cooking, acidic/neutral/alkaline sulfite cooking, soda salt cooking, and the like.

In addition, various commercially available high-quality papers, coated papers, lined papers, impregnated papers, cardboards, paperboards, etc. can also be used. A printed layer may be provided on the outer surface or the inner surface of the paper layer, if necessary.

"Other layers" 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

The laminated film of the present invention can be used in various applications, such as packaging materials for foods, pharmaceuticals, and daily necessities, lid materials, paper straws, paper napkins, paper tableware such as paper spoons, paper plates, and paper cups, barrier 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 methods, etc. It can be suitably used as packaging materials for liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and the like.

<Packaging material>
The laminated film of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, pharmaceuticals, and the like. When used as a multilayer packaging material, the layer structure may vary depending on the contents, usage environment, and usage pattern. Moreover, 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 laminated film of the present invention, stacking the laminated films with their sealant film surfaces facing each other, and then heat-sealing the peripheral edges to form a bag. As a bag-making method, the laminated film of the present invention is folded or overlapped so that the inner layer surface (surface of the sealant film) faces each other, and the peripheral edge is sealed, for example, with a side seal type, a two-sided seal type, There are three-side seal type, four-side seal type, envelope-type seal type, joint-type seal type, fold-type seal type, flat-bottom seal type, square-bottom seal type, gusset type, and other heat-sealing methods. be done. The packaging material of the present invention can take various forms depending on the contents, environment of use, and form of use. A self-supporting packaging material (standing pouch) or the like is also possible. As a heat sealing method, known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing and ultrasonic sealing can be used.

After the packaging material of the present invention is filled with contents through its opening, the opening is heat-sealed to manufacture a product using the packaging material of the present invention. Examples of filling contents include foods such as rice confectionery, bean confectionery, nuts, biscuits and cookies, wafer confectionery, marshmallows, pies, half-baked cakes, candy, snacks, bread, snack noodles, and instant noodles. , dried noodles, pasta, aseptic packaged rice, rice porridge, rice porridge, packaged mochi, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, mushrooms, konjac, processed wild plants, jams, peanut cream, Salads, frozen vegetables, processed agricultural products such as potato processed products, hams, bacon, sausages, processed chicken products, processed livestock products such as corned beef, fish hams and sausages, fish paste products, kamaboko, seaweed, tsukudani, Processed marine products such as bonito flakes, salted fish, smoked salmon, and mustard cod roe; fruits such as peaches, oranges, pineapples, apples, pears, and cherries; vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, and potatoes. , hamburgers, meatballs, fried seafood, gyoza, croquettes, and other frozen and chilled prepared foods; butter, margarine, cheese, cream; instant creamy powder; Foods such as seasonings, retort pouch curry, and pet food can be mentioned.

Non-food items include cigarettes, disposable body warmers, medicines such as infusion packs, liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, cosmetics such as lotions and milky lotions, and vacuum cleaners. It can also be used as various packaging materials such as heat insulators, batteries and the like.

(recycled plastic)
In the laminated film, especially the laminated film obtained by laminating and adhering a base film made of a plurality of olefinic resins with the reactive adhesive of the present invention can be reused as a recycled plastic whose tensile elongation is maintained.
Here, an example of a processing method for making the laminated film into a recycled plastic is shown. Of course, the present invention is not limited to this, and various known recycled plastic processing methods can be applied.

The laminated film is crushed with a crusher or the like. A known grinder may be used as the grinder, and there is no particular limitation.
After pulverization, the film pieces are physically blended by melt kneading, solvent cast blending, latex blending, polymer complexing, and the like. A melt-kneading method is particularly common. Apparatuses for kneading include a tumbler, a Henschel mixer, a rotary mixer, a super mixer, a ribbon tumbler, a V-blender and the like. After being melted and kneaded by such a kneading device, the mixture is pelletized. Single or multi-screw extruders are generally used for melt-kneading and pelletization, and in addition to these extruders, Banbury mixers, rollers, co-kneaders, blast mills, Plabender brautographs, etc. can also be used. They can be run batchwise or continuously. Alternatively, the resin may be used as a molding resin and melt-kneaded in a heating cylinder of a molding machine without melt-kneading.

The present invention will be described in more detail below with specific examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" represent "mass parts" and "mass%", respectively, unless otherwise specified.

(Synthesis of polyol)
(Polyol B1)
640 parts of isophthalic acid, 670 parts of sebacic acid, 350 parts of ethylene glycol, 700 parts of diethylene glycol, and 2.1 parts of dibutyltin dilaurate are charged into a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, etc. , and an internal temperature of 250°C. After the dehydration reaction, an intermediate polyester polyol having an acid value of 1 mgKOH/g was obtained. This was dissolved and diluted with ethyl acetate to form a 60% by mass non-volatile solution to obtain a polyester polyol having a hydroxyl value of 7 mgKOH/g. The number average molecular weight of this polyester polyol was about 9,500.

(Synthesis of polyol)
(Polyol B2)
800 parts of isophthalic acid, 700 parts of sebacic acid, 150 parts of ethylene glycol, 700 parts of neopentyl glycol, and 0.3 parts of dioctyltin dilaurate are placed in a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, etc. was charged, and an ester reaction was carried out at an internal temperature of 250°C. After the dehydration reaction, an intermediate polyester polyol having an acid value of 1 mgKOH/g was obtained. This was dissolved and diluted with ethyl acetate to obtain a non-volatile content 60% by mass solution. Furthermore, 4 parts of isophorone diisocyanate was added to 100 parts of the obtained intermediate polyester polyol solid content, and the mixture was heated to 80° C. to carry out a urethanization reaction until free NCO groups were substantially eliminated, resulting in a hydroxyl value of 7 mg KOH. / g of polyester urethane polyol was obtained. The number average molecular weight of this polyester urethane polyol was about 9,000.

(Synthesis of polyol)
(Polyol B3)
600 parts of isophthalic acid, 300 parts of phthalic anhydride, 325 parts of sebacic acid, 1275 parts of neopentyl glycol, and 2.1 parts of dibutyltin dilaurate are added to a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, etc. A portion was charged, and an ester reaction was carried out at an internal temperature of 250°C. After the dehydration reaction, an intermediate polyester polyol having an acid value of 1 mgKOH/g was obtained. This was dissolved and diluted with ethyl acetate to obtain a solution of 57% by mass of non-volatile matter to obtain a polyester polyol having a hydroxyl value of 12 mgKOH/g. The number average molecular weight of this polyester polyol was about 5,500.

(Synthesis of polyol)
(Polyol B4)
425 parts of terephthalic acid, 250 parts of isophthalic acid, 525 parts of adipic acid, 925 parts of ethylene glycol, bisphenol A propylene oxide (2 mol) were placed in a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, etc. 400 parts of the adduct and 2.1 parts of dibutyltin dilaurate were charged, and an ester reaction was carried out at an internal temperature of 260°C. After the dehydration reaction, an intermediate polyester polyol having an acid value of 1 mgKOH/g was obtained. This was dissolved and diluted with ethyl acetate to obtain a solution of 51% by mass of non-volatile matter to obtain a polyester polyol having a hydroxyl value of 9 mgKOH/g. The number average molecular weight of this polyester polyol was about 7,500.

(Synthesis of polyol)
(Polyol B5)
900 parts of isophthalic acid, 689 parts of 1,4-cyclohexanedicarboxylic acid, 525 parts of adipic acid, 1596 parts of ethylene glycol, and neopentyl glycol are placed in a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, etc. 749 parts of dioctyltin dilaurate and 0.35 parts of dioctyltin dilaurate were charged, and an ester reaction was carried out at an internal temperature of 260°C. After the dehydration reaction, an intermediate polyester polyol having an acid value of 1 mgKOH/g was obtained. This was dissolved and diluted with ethyl acetate to obtain a 60% by mass non-volatile solution to obtain a polyester polyol having a hydroxyl value of 8 mgKOH/g. The number average molecular weight of this polyester polyol was about 8,300.

(Synthesis of polyol)
(Polyol B6)
666 parts of succinic acid, 361 parts of ethylene glycol, and 1474 parts of tris(2-hydroxyethyl) isocyanurate were charged into a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, rectifying tube, etc., and the internal temperature was 220°C. The ester reaction was carried out at After the dehydration reaction, an intermediate polyester polyol having an acid value of 1 mgKOH/g was obtained. 0.2 part of phosphoric acid was added to this to obtain a polyester polyol having a hydroxyl value of 410 mgKOH/g. The number average molecular weight of this polyester polyol was about 420.

(Adjustment of polyisocyanate)
(Polyisocyanate A1)
A flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube was charged with 90 parts of Desmodur N3210A (a hexamethylene diisocyanate biuret structure, manufactured by COVESTRO) and 10 parts of ethyl acetate to prepare a 90% by mass non-volatile solution. The isocyanate (hereinafter sometimes referred to as NCO) content is 20.7% by mass.

(Adjustment of polyisocyanate)
(Polyisocyanate A2)
Put 1260 parts of xylylene diisocyanate in a flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube and stir while heating to 70 ° C., drop 750 parts of polyol B6 over 2 hours using a dropping funnel, After further stirring for 4 hours, a polyisocyanate was obtained. Its NCO content was 15.7%.

(Preparation of adhesive coating solution)
(Example 1)
10 parts of polyol B and 0.8 parts of polyisocyanate A were blended, and the solid content was adjusted to 30% with ethyl acetate to prepare an adhesive coating solution of Example 1.

(Example 2) to (Example 5)
Adhesive coating solutions of Examples 2 to 5 were prepared in the same manner as in Example 1, except that the formulations of polyol B and polyisocyanate A used were changed to those shown in Table 1.

(Comparative Example 1) to (Comparative Example 2)
Adhesive coating solutions of Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 except that the formulations of polyol B and polyisocyanate A used were changed to those shown in Table 1.

(evaluation)
(Viscoelasticity measurement of cured coating film)
The adhesive coating liquid was dropped onto a petri dish so as to have a film thickness of 2 mm, ethyl acetate was volatilized at room temperature, and then aging was performed at 40° C. for 72 hours.
Using a dynamic viscoelasticity measuring device (RSA G2 manufactured by TA Instruments), the cured coating film for viscoelasticity measurement was measured under the following conditions to obtain E' at 200°C.
Cured coating film: length 20 mm (excluding gripping allowance) x width 5 mm x thickness 0.3 mm
Measurement temperature range: -50 to 200°C
Frequency: 1.0Hz
Heating rate 5°C/min

(Viscoelasticity measurement after heating the cured coating film at 240°C)
The adhesive coating liquid was dropped onto a petri dish so as to have a film thickness of 2 mm, ethyl acetate was volatilized at room temperature, and then aging was performed at 40° C. for 72 hours. The resulting cured coating film was heated in an electric oven to 230°C for 45 minutes, and after reaching 240°C, it was held for 15 minutes.
Using a dynamic viscoelasticity measuring device (RSA G2, manufactured by TA Instruments), the cured coating film for viscoelasticity measurement was measured under the following conditions to determine the tan δ peak temperature.
Cured coating film: length 20 mm (excluding gripping allowance) x width 5 mm x thickness 0.3 mm
Measurement temperature range: -50 to 200°C
Frequency: 1.0Hz
Heating rate 5°C/min

(Adhesive particle size after melt-kneading)
A 30 μm CPP film is coated with an adhesive coating liquid using a bar coater so that the solid content weight of the adhesive is about 2.0 g / m ² , and after volatilizing the solvent, a desktop calendar roll is applied. A CPP film having a thickness of 30 μm was laminated using this. A laminated film was produced by aging at 40° C. for 72 hours.
The ratio of "the sum of the weight of the OPP film and the weight of the CPP film" to "the solid content weight of the adhesive" of the obtained laminated film is 96:4.
The laminated film is cut into strips with a width of 10 mm and a length of 300 mm, and is melted and kneaded at 240 ° C. and 100 rpm for 3 minutes using a twin-screw kneading extruder (ULTnano 15TW manufactured by Technobell Co., Ltd.), and then extruded into a nozzle. and immediately cooled with tap water to obtain a strand-like resin.
The resulting strand was randomly cut out at 10 locations with a microtome, and each cross section was observed with a SEM backscattered electron image at 15 KV and 150 magnifications to obtain an image with a field of view of 400 μm×600 μm.
Adhesive particles were extracted from the obtained image using image processing analysis software ImageJ. In this process, 2×2 pixels or less were determined to be noise, and the diameter calculated from the area was calculated assuming that the particle was a circle, and a histogram was created. The maximum value of the area that occupies 90% of the entire histogram was taken as the adhesive particle size. The following CPP films were used.
CPP film: Pyrene P1128 30 μm manufactured by Toyobo Co., Ltd.
The evaluation was as follows.
○: Adhesive particle size ≤ 20 μm
×: Adhesive particle size>20 μm

(Tensile elongation of recycled plastic)
A 30 μm CPP film is coated with an adhesive coating liquid using a bar coater so that the solid content weight of the adhesive is about 2.0 g / m ² , and after volatilizing the solvent, a desktop calendar roll is applied. A CPP film having a thickness of 30 μm was laminated using this. A laminated film was produced by aging at 40° C. for 72 hours.
The laminated film is cut into strips with a width of 10 mm and a length of 300 mm, and is melted and kneaded at 240 ° C. and 100 rpm for 3 minutes using a twin-screw kneading extruder (ULTnano 15TW manufactured by Technobell Co., Ltd.), and then extruded into a nozzle. and immediately cooled with tap water to obtain a strand-shaped resin, which was cut to obtain a repellet sample.
9 g of the repellet sample was put into a stainless steel press picture frame mold (inner dimension 100 mm square, thickness 1 mm), sandwiched between stainless steel plates (thickness 2 mm), and compression molded at 210 ° C., 30 MPa, for 3 minutes, A plastic plate with a thickness of 1 mm was prepared, and a 1/3 size test piece of JIS K6251-5 was punched out using a Super Dumbbell Cutter SDK500 1/3 manufactured by Dumbbell Co., Ltd. and used for a tensile test. The tensile test was performed at 50 mm/min and the distance between chucks was 30 mm, and the tensile elongation was measured.

The results of Examples are shown in Table 1, and the results of Comparative Examples are shown in Table 2. In addition, a blank indicates unblended.

Claims

A reactive adhesive characterized by satisfying (1) and (2).
(1) A polyolefin resin and a reactive adhesive are blended in the range of 96:4, and the particle size of the adhesive after melt-kneading at 240° C. for 3 minutes is 20 μm or less.
(2) E′ at 200° C. of the cured coating film of the reactive adhesive cured at 40° C. for 72 hours is in the range of 1.0×10 5 to 3.0×10 6 ;
The reactive adhesive according to claim 1, wherein the reactive adhesive has a tan δ peak of 0°C or higher and 40°C or lower after heating at 240°C.
The reactive adhesive is a reactive adhesive containing a polyisocyanate composition (A) containing a polyisocyanate compound (A1) and a polyol composition (B) containing a polyol (B1). Reactive adhesive as described.
A laminated film obtained by laminating and bonding base films made of a plurality of olefinic resins with a reactive adhesive, wherein the reactive adhesive is the reactive adhesive according to any one of claims 1 to 3. A laminated film characterized by:
A packaging material made of the laminated film according to claim 4.