JP7101933B2 - Hot melt adhesive for laminating and laminated film laminate using it - Google Patents

Description

The present invention is a hot melt adhesive having sufficient laminating strength against a plastic film on which aluminum, silicon oxide or metal oxide (alumina) is vapor-deposited even if it is a thin film, and having excellent transparency, and a composite film using the same. Regarding.

As a packaging film for foods, medical products, cosmetics, etc., a composite film in which several types of functional films are bonded is used, and it is common to composite the functional films with a laminating adhesive. Is the target. Further, oxidative deterioration due to oxygen in the air, aluminum, silicon oxide, and metal oxide (alumina) are vapor-deposited on the film in order to protect the contents wrapped in the film from deterioration such as ultraviolet rays. In recent years, solvent-free laminating adhesives have been developed from the viewpoint of reducing the environmental load and improving the working environment. Patent Document 1 does not require a chemical reaction and is environmentally and safety-friendly. A solvent-free hot-melt type adhesive for laminating has been proposed.

However, in the adhesive of Patent Document 1, when the thickness of the adhesive is less than 5 μm (less than about 5 g / m ² ), the laminate strength becomes very low, and especially for packaging film applications such as foods, medical products and cosmetics. The required performance could not be achieved.

Japanese Unexamined Patent Publication No. 2013-082827

An object of the present invention is to provide a hot melt adhesive which has sufficient laminating strength on the vapor-deposited surface of a polypropylene film and an aluminum-deposited film or an inorganic oxide-deposited film, and is excellent in transparency, coating suitability, and the like. That is. Another object of the present invention is to provide a laminated film laminate capable of maintaining excellent heat seal strength in a wide temperature range.

That is, the present invention relates to the following inventions [1] to [7].

[1] Ethylene-propylene copolymer (A) 20 to 50% by mass, hydrogenated rosin-based tackifier resin (B1) 1 to 20% by mass, hydrogenated tackifier resin other than (B1) in 100% by mass of adhesive (B1) B2) A hot melt adhesive for laminating containing 10 to 35% by mass and 1 to 20% by mass of an acid-modified olefin (C).

[2] The hot melt adhesive for laminating according to [1], which further contains an ethylene polymer (D) other than (A).

[3] Ethylene-propylene copolymer (A) 25 to 45% by mass, hydrogenated rosin-based tackifying resin (B1) 2 to 15% by mass, and hydrogenated tackifier resin other than (B1) in 100% by mass of the adhesive (B1). B2) The hot melt for lamination according to claim 2, which contains 15 to 30% by mass of an acid-modified olefin (C), 2 to 15% by mass of an acid-modified olefin (C), and 4 to 40% by mass of an ethylene polymer (D) other than (A). glue.

[4] The hot melt adhesive for laminating according to any one of [1] to [3], wherein the hydrogenated rosin-based tackifier resin (B1) has an acid value of 150 or more.

[5] A laminated film laminate obtained by laminating a first film base material and a second film base material with the hot melt adhesive for laminating according to any one of [1] to [4].

[6] The first film base material and / or the second film base material is an aluminum vapor deposition film or an inorganic oxide vapor deposition film, and the hot melt adhesive for lamination is an aluminum vapor deposition film or an inorganic oxide vapor deposition film. The laminated film laminate according to [5], which is laminated with a first film base material and / or a second film base material via a vapor-deposited surface.

[7] The laminated film laminate according to [5] or [6], wherein the amount of the hot melt adhesive for laminating applied to the laminated film laminate is less than 5 g / m ² .

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a hot melt adhesive which has sufficient laminating strength on the vapor-deposited surface of a polypropylene film and an aluminum-deposited film or an inorganic oxide-deposited film, and is excellent in transparency, coating suitability, and the like. can. Further, according to the present invention, it is possible to provide a laminated film laminate capable of maintaining excellent heat sealing strength in a wide temperature range.

Hereinafter, the constituent requirements of the hot melt adhesive of the present invention will be described in detail.

<Ethylene-propylene copolymer (A)>
The ethylene-propylene copolymer (A) used in the present invention has particularly good adhesion to the vapor-deposited surface of the polypropylene film, the aluminum-deposited film or the inorganic oxide-deposited film, and it takes time from the molten state to solidification. Therefore, it is most suitable for laminating a film after applying a thin film. If it does not contain ethylene, it becomes too hard and the adhesive strength is insufficient.

The ethylene-propylene copolymer (A) lacks adhesive strength to the polypropylene film when it is less than 20% by mass in 100% by mass of the hot melt adhesive for laminating, and 5 g / m ² when it exceeds 50% by mass. Since uniform coating cannot be performed with a thin film of less than 20% by mass, it is characterized by containing 20% by mass or more and 50% by mass or less (hereinafter, abbreviated as 20 to 50% by mass). It is preferably 25 to 45% by mass, more preferably 30 to 45% by mass. Further, the amount of propylene in the copolymer containing ethylene is preferably 50 mol% or more and 90 mol% or less, and more preferably 60 mol% or more and 85 mol% or less.

<Hydrogenated rosin adhesive resin (B1)>
By including the hydrogenated rosin-based tackifier resin (B1) in the present invention, the adhesive force of the aluminum-deposited film or the inorganic oxide-deposited film on the vapor-deposited surface can be further improved.
If the water-hydrated rosin-based tackifier resin (B1) is less than 1% by mass in 100% by mass of the hot-melt adhesive for laminating, the adhesive strength of the aluminum vapor-deposited film or the inorganic oxide-deposited film to the vapor-deposited surface is insufficient. If it exceeds 20% by mass, the hot melt adhesive becomes brownish due to thermal deterioration during heating during coating and the appearance deteriorates. Therefore, 1% by mass or more and 20% by mass or less (hereinafter, 1 to 20% by mass). (Abbreviated as) is included. 2 to 15% by mass is more preferable. Further, the higher the acid value of the hydrogenated rosin-based tackifier resin (B1), the more the adhesive force of the aluminum vapor-deposited film or the inorganic oxide-deposited film to the vapor-deposited surface can be further improved. The value is preferably 50 or more, more preferably 90 or more, and particularly preferably 150 or more.

The hydrogenated rosin-based tackifier resin (B1) is preferably hydrogenated with, for example, rosin, a rosin ester, an acid-modified rosin, or a polymerized rosin. When an unhydrogenated rosin-based tackifier resin is used, the transparency of the hot melt adhesive for laminating deteriorates.

<Hydrogenated adhesive resin (B2) other than hydrogenated rosin adhesive resin (B1)>
In the present invention, by containing a hydrogenated tackifier resin (B2) other than the hydrogenated rosin-based tackifier resin (B1), the adhesive force to the polypropylene base material, the aluminum vapor-deposited film, the inorganic oxide-deposited film, etc. can be increased. It can be improved further. The water-added adhesive resin (B2) lacks adhesive strength to the polypropylene film when it is less than 10% by mass in 100% by mass of the hot melt adhesive for laminating, and the hot melt adhesive becomes hard even when it exceeds 35% by mass. It is characterized by containing 10% by mass or more and 35% by mass or less (hereinafter, abbreviated as 10 to 35% by mass) because the adhesive force to the polypropylene film is insufficient. It is preferably 15 to 33% by mass, more preferably 15 to 30% by mass, and even more preferably 20 to 30% by mass.

The hydrogenated tackifier resin (B2) is, for example, a phenol resin, a modified phenol resin, a terpenphenol resin, a xylenephenol resin, a cyclopentadiene-phenol resin, a xylene resin, an aliphatic type, an alicyclic type, an aromatic type, or the like. Petroleum resin, phenol-modified petroleum resin, α-methylpolystyrene resin, and terpene resin are preferably hydrolyzed, and are preferably aliphatic, alicyclic, aromatic petroleum resin, and aromatic modified aliphatic petroleum resin. , Aromatically modified alicyclic petroleum resin hydrogenated is more preferable, and at least one petroleum resin hydrogenated from the group consisting of alicyclic and aromatic is particularly preferable. When an unhydrogenated tackifier resin is used, the transparency of the hot melt adhesive for laminating deteriorates.

<Acid-denatured olefin (C)>
In the present invention, the inclusion of the acid-modified olefin (C) can improve the adhesive force of the aluminum-deposited film or the inorganic oxide-deposited film on the vapor-deposited surface. Further, by using the hydrogenated rosin-based tackifier resin (B1) in combination, it becomes easy to be compatible with the ethylene-propylene polymer (A) and the like, and the transparency can be maintained. If the acid-modified olefin (C) is less than 1% by mass in 100% by mass of the hot melt adhesive for laminating, the adhesive force of the aluminum vapor deposition film or the inorganic oxide vapor deposition film to the vapor deposition surface becomes insufficient. On the other hand, if it exceeds 20% by mass, the hot melt adhesive becomes brownish due to thermal deterioration during coating heating and the appearance is deteriorated. Therefore, it is characterized by containing 1% by mass or more and 20% by mass or less. 2 to 18% by mass is more preferable, and 2 to 15% by mass is further preferable.

As the acid-modified olefin (C), for example, a polyolefin resin modified with an α, β-ethylenically unsaturated carboxylic acid is used. Examples of the polyolefin resin used as the base resin include polyethylene, polypropylene, polybutene, and an ethylene-propylene copolymer. Examples of the α, β-ethylenic unsaturated carboxylic acid to be added to these polyolefin resins include (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid and the like, and one or two anhydrides of these acids. The above is used. Among these, (meth) acrylic acid and maleic anhydride are preferable.
Specific examples of the acid-modified olefin (C) include a copolymer of ethylene and acrylic acid, a copolymer of ethylene and methacrylic acid, a modified product of maleic anhydride or maleic anhydride, and malein of an ethylene polypropylene high polymer. A modified product of acid or maleic anhydride is preferable, and it may be used alone or in combination of two or more.

<Ethylene polymer (D) other than (A)>
In the present invention, by using the ethylene-propylene polymer (A) and the ethylene-based polymer (D) other than (A) in combination, it is possible to prevent the hot melt adhesive for laminating from becoming hard and to suppress the hardening of the hot melt adhesive for lamination in a low temperature atmosphere. It is preferable because the adhesive strength can be maintained. Further, the ethylene-based polymer (D) other than (A) has the effect of facilitating the compatibility between the hydrogenated rosin-based tackifier resin (B1) and the ethylene-propylene polymer (A), and the transparency of the laminated adhesive. It is preferable to improve.

The ethylene polymer (D) other than (A) is preferably 4% by mass or more and 40% by mass or less (hereinafter, abbreviated as 4 to 40% by mass) in 100% by mass of the hot melt adhesive, and 6 to 35% by mass. % Is more preferable, and 10 to 35% by mass is further preferable. The ethylene-based polymer (D) other than (A) may be used alone or in combination of two or more.

Examples of the ethylene polymer (D) other than (A) include low-density polyethylene, ultra-low-density polyethylene, ethylene-butene copolymer, ethylene-heptene copolymer, ethylene-octene copolymer, and ethylene-acetic acid. Vinyl copolymers are preferable, and they may be used alone or in combination of two or more.

<Additives>
The hot-melt adhesive of the present invention includes additives such as waxes, antioxidants, ultraviolet absorbers, light stabilizers, anti-adhesive agents, antibacterial agents, deodorants, and fragrances as long as the object of the invention is not impaired. May include.

Examples of the wax include microcrystalline wax, paraffin wax, Fishertroph wax, polyethylene wax, polypropylene wax and the like. The wax may be used alone or in combination of two or more. Wax is a waxy solid substance. The melting point is preferably 40 ° C. or higher and 160 ° C. or lower, more preferably polyethylene wax or polypropylene wax, and the melting point of 120 ° C. or higher and 160 ° C. or lower is preferable.

Antioxidants include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl). ) Propionate, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylene bis (oxyethylene) Bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) Examples thereof include pentaerythritol diphosphite. These may be used alone or in combination of two or more.

As a phenolic antioxidant, hydrogen is donated to ROO (peroxy radical) generated in the chain growth process of autoxidation to stabilize it, and it itself becomes a stable phenoxy radical protected by an ortho-position substituent and chained. It has a function as a radical trapping agent that stops the reaction, thereby effectively suppressing thermal deterioration of the resin composition. In particular, it becomes more excellent by using a phenolic antioxidant in combination with a lactone-based antioxidant or a vitamin E-based antioxidant having a faster radical trap reaction than the phenolic antioxidant. In addition, the above-mentioned phosphorus-based antioxidant has a function of non-radically decomposing peroxides and ROOH to stop the chain reaction of the autoxidation process, which effectively deteriorates the heat of the resin composition. Suppress.

The ultraviolet absorber is not particularly limited, and examples thereof include commonly used ones such as benzophenone type and benzotriazole type. These may be used alone or in combination of two or more.

Examples of the light stabilizer include hindered amine-based light stabilizers that are usually used.

Examples of the anti-adhesive agent include fatty acid amides, long-chain alkyl grafts of polyethyleneimine, soybean oil-modified alkyd resins (for example, manufactured by Arakawa Chemical Industries, Ltd., trade name "Araquid 251", etc.), and tall oil-modified alkyd resins (for example,). Arakawa Chemical Industry Co., Ltd., trade name "Alkyd 6300", etc.) and the like can be mentioned. These may be used alone or in combination of two or more.

Antibacterial agents include benzylamine-based antibacterial agents such as butenafine and salts thereof, biphonazole, neticonazole, ketoconazole, lanoconazole, clotrimazole, miconazole, oxyconazole, thioconazole, croconazole, omoconazole, sulconazole and imidazoles such as salts thereof. Antibacterial agents, allylamine antibacterial agents such as terbinafine and its salts, morpholinic antibacterial agents such as amorolphin and its salts, thiocarbamic acid antibacterial agents such as lylanafate, tornafate and toluciclate, nystatin, tricomycin, variotin, siccanin, pyrrolnitri Examples thereof include antibacterial agents such as antibiotics such as miconazole. These may be used alone or in combination of two or more.

The deodorant is not particularly limited as long as it has a deodorizing effect, but lauryl methacrylate, geranyl chloride, film lonelyl senesionate, terpenaldehydes, pyruvate esters, zinc 2-ethylhexanoate, etc. Examples include zinc ricinoleate. These may be used alone or in combination of two or more.

As fragrances, hydrocarbon fragrances such as pinen and limonene, alcoholic fragrances such as linalol, geraniol, filmlonerol, menthol, borneol, benzyl alcohol, anis alcohol, β-phenethyl alcohol, and phenolic fragrances such as anetol and eugenol. , N-butylaldehyde, isobutylaldehyde, hexylaldehyde, filmlar, filmroneral, benzaldehyde, synamic aldehyde and other aldehyde-based fragrances, carboxylic, menton, cypress, acetphenone, ionone and other ketone-based fragrances, γ-butorlactone, coumarin , Aldehyde-based fragrances such as cineol, and ester-based fragrances such as octyl acetate, benzyl acetate, cinnamyl acetate, butyl propionate, and methyl benzoate. These may be used alone or in combination of two or more.

Since the blending amount of the above optional component varies in relation to the physical properties described later, the lower limit cannot be limited. However, the upper limit is preferably 20% by mass or less, more preferably 8% by mass or less, based on 100 parts by mass of the hot meltable composition. When the blending amount is 20% by mass or less, bleed-out or the like of an arbitrary component is less likely to occur.

<Manufacturing of hot melt adhesive>
The method for producing the hot melt adhesive of the present invention is not particularly limited, and heat-mixing is performed using either a melting kettle equipped with a roll, a Banbury mixer, a kneader, and a stirrer, or a single-screw or two-screw extruder. The hot melt method is desirable.

<Laminated film laminate (composite film laminate)>
Next, the configuration of the laminated film laminate using the hot melt adhesive for lamination of the present invention will be described. The film laminate of the present invention is a laminated film laminate obtained by laminating a first film base material and a second film base material with the hot melt adhesive for laminating of the present invention, and is a first film. / Hot melt adhesive layer / The composition of the second film may be included, and an undercoat layer may be provided between the first and second films and the hot melt adhesive or the like, or the first And a film or the like may be further laminated on the outside of the second film.
Further, the first film base material and / or the second film base material may be an aluminum vapor-deposited film or an inorganic oxide-deposited film, and examples of the inorganic oxide include silicon oxide and alumina. Either one or both of the first and the second may be a thin-film deposition film.

The first and second films are not particularly limited, but are film-like substrates produced from a thermoplastic resin that can be thermally molded by means such as extrusion molding, injection molding, blow molding, stretch blow molding, or draw molding. As the thermoplastic resin constituting the first and second films, there are olefin-based copolymers, polyesters, polyamides, styrene-based copolymers, vinyl chloride-based copolymers, acrylic-based copolymers, and the like. Examples thereof include polycarbonate, and olefin-based copolymers, polyesters, and polyamides are preferable.

Olefin-based copolymers include low-, medium- or high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene-polymer, ionomer, and ethylene-vinyl acetate copolymer. Combined, ethylene-vinyl alcohol copolymer and the like, as polyester, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate, polyethylene naphthalate and the like, and as polyamide, nylon 6, nylon 6, 6, nylon 6, etc. 10. Polypolymers such as metaxylylene adipamide and styrene-based copolymers include polystyrene, styrene-butadiene block copolymers, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers (ABS resin) and the like. However, examples of the vinyl chloride-based copolymer include polyvinyl chloride and vinyl chloride-vinyl acetate copolymer, and examples of the acrylic-based copolymer include polymethylmethacrylate and methylmethacrylate / ethylacrylate copolymer. Be done. These thermoplastic resins may be used alone or in combination of two or more.

Preferred thermoplastic resins include polyamide resins such as nylon 6, nylon 66 and nylon 46, aromatic polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polybutylene terephthalate and polybutylene naphthalate, and polylactic acid. Examples thereof include a polyolefin resin such as an aliphatic polyester resin, polypropylene and polyethylene, or a mixture thereof.

As the first film base material in the laminated film laminate of the present invention, a biaxially stretched thermoplastic resin film is preferable, and a biaxially stretched polypropylene (OPP) film is preferable. As the second film base material in the laminated film laminate of the present invention, one having a heat-sealing property in order to function as a heat-adhesive layer when forming a bag-shaped packaging bag or the like is preferable, and heat-sealing, high-frequency sealing, etc. Materials that can be used are used. For example, low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, polypropylene, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ethylene-acrylate copolymer. However, low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer film, and unstretched polypropylene are particularly preferably used.

Further, a gas barrier layer may be used for the purpose of long-term storage of the contents, and is not particularly limited, and has layers such as polyvinyl alcohol, a partial saponification of polyethylene-vinyl acetate, polyvinylidene chloride, and a polyacrylonitrile copolymer. You may be doing it.

The film laminate may have a print layer. The printing layer may be either the hot-melt adhesive layer side surface or the other surface of the first and second films, but the printed surface is printed on the adhesive layer side surface for designability and safety. Is preferable. Further, the first and second films may be subjected to corona treatment for the purpose of improving the adhesion of ink or the like.

The composite film laminate of the present invention is a first film base material such as OPP (biaxially stretched polypropylene film) by heating and melting a hot melt adhesive and using a gravure coater, a roll coater, a die coater, and a slit coater. It is preferable to apply it on top, attach it to a second film base material such as CPP (unstretched polypropylene film) that can be immediately heat-sealed, and press it with a pressure roll to produce it, but CPP (unstretched polypropylene film) ) And the like, the film may be immediately bonded to the first film of OPP (biaxially stretched polypropylene film) and pressure-bonded with a pressure roll. The vapor deposition of inorganic oxides such as aluminum, silicon oxide and alumina may be performed on either the first or second film. Further, the hot melt adhesive may be once applied to a transferable roll such as a silicon roll, and then transferred to a propylene film for bonding.

The amount of the hot melt adhesive applied is preferably less than 5 g / m ² , and more preferably 4 g / m ² or less from the viewpoint of flexibility. The composite film of the present invention can be used for packaging foods, medical products, cosmetics, etc. by heat sealing or the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but these Examples are merely one aspect of the present invention, and the present invention is not limited to these Examples.
In the example, "parts" and "%" represent "parts by mass" and "% by mass".

<Manufacturing method of hot melt adhesive>
[Examples 1 to 10, Comparative Examples 1 to 16]
A polymer, a tackifier resin, and the like were added to a kneader equipped with a stirrer in the number of parts shown in Tables 1 and 2, and the mixture was stirred at 180 ° C. for 3 hours to produce a hot melt adhesive.

<Evaluation of hot melt adhesive>
[Manufacturing of laminated laminate (composite film (1))]
The hot-melt adhesives obtained in Examples and Comparative Examples were applied to a biaxially stretched polypropylene film (OPP) at about 4 g / m ² using a gravure coater heated to 130 ° C., and immediately after that, aluminum-deposited unstretched polypropylene was applied. The composite film (1) having an OPP / VM-CPP structure was prepared by combining with the aluminum surface of the film (VM-CPP) and laminating and crimping at a roll pressure of 2.5 kgf.

[Manufacturing of laminated laminate (composite film (2))]
The hot melt adhesives obtained in Examples and Comparative Examples were applied to a biaxially stretched polypropylene film (OPP) at about 4 g / m ² using a gravure coater heated to 130 ° C., and immediately thereafter, a non-stretched polypropylene film (CPP) was applied. ), And bonded and crimped at a roll pressure of 2.5 kgf to prepare a composite film (2) having an OPP / CPP structure.

The obtained hot melt adhesives, laminated laminates (1) and (2) were evaluated as follows. The results are shown in Tables 1 and 2.

[transparency]
The transparency of the composite film (2) was visually determined. ○ and △ were judged to be practical.
○ (Good): Colorless and transparent △ (Yes): Colorless and translucent × (Bad): Opaque

[Uneven coating / foam residue]
With respect to the composite film (2), coating unevenness and foam residue were visually determined. ○ and △ were judged to be practical.
○ (Good): The coated surface is smooth and there are no bubbles that can be visually confirmed △ (Yes): The coated surface is slightly uneven, but there are no bubbles that can be visually confirmed × (Defective): The coated surface is uneven And there are scattered bubbles that can be visually confirmed.

[Laminate adhesive strength]
The composite film (1) is cut into a size of 25 mm × 100 mm, and a part of the adhesive portion between the biaxially stretched polypropylene and the non-stretched polypropylene vapor-deposited with aluminum is heated and peeled off so as to form a T shape in an atmosphere of 23 ° C. It was set in a tensile tester and peeled off in the T-shape at a speed of 200 mm / min, and the laminate adhesive strength was measured. ○ and △ were judged to be practical.
○ (Good): 2.0N / 25mm or more Δ (Yes): 1.5N / 25mm or more, less than 2.0N / 25mm × (Defective): Less than 1.5N / 25mm

[Peeling and floating during heat sealing]
The composite film (1) was cut into a size of 25 mm × 80 mm, and the non-aluminum surfaces of unstretched polypropylene vapor-deposited with aluminum were bonded together in pairs, and 25 mm × at 140 ° C., 1 kgf, and 1 second. A width of 20 mm was heat-sealed. The peeling and floating of the hot melt adhesive adhering the aluminum surfaces of the biaxially stretched polypropylene and the non-stretched polypropylene vapor-deposited with aluminum were visually determined. ○ and △ were judged to be practical.
○ (Good): No peeling or floating △ (Yes): Peeling or floating is less than 10% of the total × (Defective): Peeling or floating is 20% or more of the whole

[Heat seal strength: 23 ° C]
The heat-sealed sample was left at 23 ° C. 65% RH for 24 hours, and then set in a tensile tester in a T-shape under an atmosphere of 23 ° C. in the same manner as in the evaluation of laminate adhesive strength. The stretched polypropylenes were peeled off in the T-shape at a speed of 200 mm / min, and the heat seal strength thereof was measured. ○ and △ were judged to be practical.
○ (Good): 10N / 25mm or more Δ (Yes): 5N / 25mm or more and less than 10N / 25mm × (Defective): 5N / 25mm or less

[Heat seal strength: low temperature 0 ° C]
The heat seal strength in a 0 ° C atmosphere was measured in the same manner as in the above-mentioned [Heat seal strength: 23 ° C] evaluation except that the heat seal strength was measured in a 0 ° C atmosphere. ○ and △ were judged to be practical.
○ (Good): 10N / 25mm or more Δ (Yes): 5N / 25mm or more and less than 10N / 25mm × (Defective): 5N / 25mm or less

[Heat deterioration test]
20 g of the hot melt adhesive was weighed in a 50 ml steel can and heat-aged for 60 minutes in an oven at 180 ° C., and the change in the hue of the hot melt adhesive and the state of carbide generation were visually determined. ○ and △ were judged to be practical.
○ (Good): No change △ (Yes): Slightly yellow, no carbides generated × (Poor): Yellow, carbides generated

The abbreviations in Tables 1 and 2 are shown below.
Polymer 1: Ethylene-propylene copolymer containing 83 mol% propylene Polymer 2: Ethylene-propylene copolymer containing 78 mol% propylene Polymer 3: Ethylene-propylene copolymer containing 58 mol% propylene

Polymer 4: Low density polyethylene (melting point 118 ° C)
Polymer 5: Ethylene-butene copolymer polymer 6: Ethylene-octene copolymer polymer 7: Ethylene-vinyl acetate copolymer (vinyl acetate content 14 wt%)

Polymer 8: Polybutene homopolymer Polymer 9: Polypropylene homopolymer

Acid-modified olefin 1: Maleic acid-modified ethylene octene copolymer Acid-modified olefin 2: Ethylene acrylic acid copolymer Acid-modified olefin 3: Ethylene anhydride maleic acid copolymer Acid-modified olefin 4: Maleic acid-modified ethylene polypropylene co-weight Coalescence

Adhesive-imparting resin 1: Hydrogenated rosin (acid value 170)
Adhesive-imparting resin 2: Hydrogenated rosin ester (acid value 50)
Adhesive-imparting resin 3: Hydrogenated acid-modified rosin (acid value 240)

Adhesive-imparting resin 4: Water-added alicyclic petroleum resin Adhesive-imparting resin 5: Hydrated aromatic petroleum resin Adhesive-imparting resin 6: Hydrated terpene resin Adhesive-imparting resin 7: Hydroponic aliphatic resin adhesive Granting resin 8: Hydroponic aromatic-modified aliphatic petroleum resin Adhesive-imparting resin 9: Hydroponic aromatic-modified aliphatic petroleum resin

Adhesive-imparting resin 10: Unhydrogenated rosin ester Adhesive-imparting resin 11: Unhydrogenated α-methylstyrene resin Adhesive-imparting resin 12: Unhydrogenated alicyclic petroleum resin Adhesive-imparting resin 13: Unhydrogenated aromatic oil Resin adhesion-imparting resin 14: Copolymerization system of unhydrogenated alicyclic and aromatic Petroleum resin Adhesive-imparting resin 15: Unhydrogenated terpene resin Adhesive-imparting resin 16: Unhydrogenated aliphatic resin

Wax 1: Paraffin wax Melting point 70 ° C
Wax 2: Fischer-Tropsch wax Melting point 110 ° C
Wax 3: Polyethylene wax Melting point 110 ° C
Wax 4: Polyethylene wax Melting point 127 ° C
Wax 5: Polypropylene wax Melting point 156 ° C

From the results in Tables 1 and 2, 20 to 50% by mass of the ethylene-propylene copolymer (A), 1 to 20% by mass of the hydrogenated rosin-based tackifier resin (B1), and a hydroadhesive tackifier resin (B2) other than (B1). ) The hot melt adhesive for lamination of the present invention containing 10 to 35% by mass and 1 to 20% by mass of the acid-modified olefin (C) can be applied to the polypropylene film and the vapor deposition surface of the aluminum vapor deposition film or the inorganic oxide vapor deposition film. On the other hand, it was shown that it has sufficient laminating strength, maintains excellent heat-sealing strength in a wide temperature range, and is also excellent in transparency and coating suitability (coating unevenness).

Claims (7)

Ethylene-propylene copolymer (A) 20-50% by mass, hydrogenated rosin-based tackifier resin (B1) 1-20% by mass, hydrogenated tackifier resin (B2) 10 other than (B1) in 100% by mass of adhesive A hot melt adhesive for lamination containing up to 35% by mass and 1 to 20% by mass of acid-modified olefin (C). The hot melt adhesive for laminating according to claim 1, further comprising an ethylene polymer (D) other than (A). Ethylene-propylene copolymer (A) 25-45% by mass, hydrogenated rosin-based tackifier resin (B1) 2-15% by mass, hydrogenated tackifier resin (B2) 15 other than (B1) in 100% by mass of adhesive The hot melt adhesive for lamination according to claim 2, which contains ~ 30% by mass, 2 to 15% by mass of the acid-modified olefin (C), and 4 to 40% by mass of the ethylene polymer (D) other than (A). The hot melt adhesive for laminating according to any one of claims 1 to 3, wherein the hydrogenated rosin-based tackifier resin (B1) has an acid value of 150 or more. A laminated film laminate obtained by laminating a first film base material and a second film base material with the hot melt adhesive for laminating according to any one of claims 1 to 4. The first film base material and / or the second film base material is an aluminum vapor-deposited film or an inorganic oxide-deposited film, and the hot-melt adhesive for laminating forms a vapor-deposited surface of the aluminum-deposited film or the inorganic oxide-deposited film. The laminated film laminate according to claim 5, which is laminated with a first film substrate and / or a second film substrate via the film. The laminated film laminate according to claim 5 or 6, wherein the amount of the hot melt adhesive for laminating applied to the laminated film laminate is less than 5 g / m ² .