TW202302370A - Composite film, layered film, and layered product using same - Google Patents

Abstract

Provided are: a composite film having excellent low-temperature heat-sealing properties, excellent tight-sealing properties in conventional bags and at high filling speed, and excellent workability during layering of a function-imparting layer on a film surface; a layered film; and a layered product using same. This composite film comprises at least two layers, which are a base layer (A) and a heat-sealing layer (B). The base layer (A) is made of a resin composition obtained by mixing 100 parts by mass of a propylene random copolymer (a1) and 1-10 parts by mass of high-density polyethylene (a2) having a melt flow rate of less than 10 g/10 minutes at 190 DEG C. The heat-seal layer (B) is made of a resin composition obtained by mixing 100 parts by mass of a propylene random copolymer (b1) with 1-20 parts by mass of high-density polyethylene (b2) having a melt flow rate of less than 10 g/10 minutes at 190 DEG C. The resin composition has a melting point of 120 DEG C or higher and an extrapolated melting initiation temperature (Tim) of 110 DEG C or lower as measured by differential scanning calorimetry in accordance with JIS K 7121 (1987). This layered product uses the composite film.

Description

Composite film, laminated film and laminates using them

The present invention relates to composite films, laminated films and laminates using them. More specifically, it relates to a composite film with less cracks on a hot plate during heat sealing and tunneling (poor sealability due to lifting of the heat-sealed part) and good sealability, and to impart functionality to laminated layers A laminate on the composite film.

Polypropylene-based film as a sealing film is laminated on a base of polyethylene terephthalate (PET) film, nylon (Ny) film, especially stretched PET film, stretched nylon film (ONy) Laminates made of thin film materials are widely known as laminates for food packaging.

In particular, non-stretched polypropylene films are excellent as food packaging materials due to their low-temperature heat-sealability, heat resistance, and workability. Decorations, such as metal deposition and printing, can be provided to the non-stretched polypropylene film systems. Functionalities such as light-shielding properties are utilized, and they are used in a wide range of packaging applications.

Recently, in the context of the increase in marine plastic waste in the world, there is a trend to promote the recycling of used plastic packaging materials as a single material (single material) for reusing the entire package in the above-mentioned laminated body System structure, seeking to make a laminate of biaxially stretched polypropylene/non-stretched polypropylene-based sealing film.

A single-layer film comprising a propylene-α-olefin copolymer (see Patent Document 1), a base layer (A) and a heat-sealing layer (B) for the purpose of improving low-temperature sealability during bag making and high-speed filling are known. layer structure, and a film in which the melting point of the heat-sealing layer is lowered (Patent Document 2) and the like.

However, the films of Patent Document 1 and Patent Document 2 are used when making a packaging bag by heat sealing with a hot plate, or when heat sealing food or the like to a bag-making product (the end of the hot plate ), due to the lack of melting of the sealing resin and the insufficient bonding strength of the composite interface, that is, due to insufficient low-temperature heat-sealability and poor sealing performance, the problems of conventional bag-making and productivity at high-speed filling speeds have not been solved, and anti-blocking Sex is also bad. [Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Publication No. 6-68050 Patent Document 2: Japanese Patent Application Laid-Open No. 9-85912

[Problem to be solved by the invention]

The laminate system of biaxially stretched polypropylene/non-stretched polypropylene sealing film has poor heat resistance, and the laminate will melt at the high-speed filling temperature after conventional bag making. Therefore, it is necessary to lower the bag making temperature and the filling speed. Therefore, it becomes a big obstacle in application development.

The object of the present invention is to provide a film that has excellent low-temperature heat-sealing properties and anti-blocking properties, good sealing performance at conventional bag-making and high-speed filling speeds, and excellent processability when imparting functions to the laminated layer on the surface of the film. Composite films, laminated films and laminates using them. [Means to solve the problem]

In order to solve the above-mentioned problems, the present invention is as follows. (1) A composite film, which is a composite film having at least two layers of a base layer (A) and a heat-sealing layer (B), wherein the base layer (A) is composed of 100 parts by mass of propylene random copolymer (a1) It is made by mixing 1-10 parts by mass of a resin composition of high-density polyethylene (a2) with a melt flow rate of 190°C less than 10 g/10 minutes. The resin composition of the aforementioned heat-sealing layer (B) is made at 100 It is made by mixing 1-20 parts by mass of high-density polyethylene (b2) whose melt flow rate at 190°C is less than 10 g/10 minutes in 1-20 parts by mass of propylene-random copolymer (b1), and the heat-sealing layer (B ) resin composition is measured by differential scanning calorimetry of JIS K 7121 (1987), and the extrapolated melting onset temperature (Tim) is 110°C or lower, and the melting point (Tm) is 120°C or higher. (2) The composite film as described in (1), wherein the propylene-random copolymer (a1) of the base layer (A) is selected from the group consisting of ethylene-propylene random copolymer, propylene-1-butene random copolymer, and ethylene・One or more types of propylene/1-butene terpolymer group. (3) In the composite film described in (1) or (2), the propylene-random copolymer (b1) of the heat-sealing layer (B) is selected from the group consisting of ethylene-propylene random copolymer, propylene-1-butene random One or more of the group of copolymers and ethylene-propylene-1-butene terpolymers. (4) The composite film according to any one of (1) to (3), wherein the base layer (A) contains 30% by mass or less of the components of the heat-sealing layer (B) as self-recycling components of the composite film. (5) For the composite film as described in any one of (1) to (4), a biaxially stretched polypropylene film with a thickness of 20 μm or more is laminated on the composite film by dry lamination using an adhesive, and the heat sealing of the composite film is The layers (B) overlap each other, and the heat-sealing strength when heat-sealed by heating on one side at 120° C. is 6 N/15 mm or more. (6) A laminated film provided with a function-imparting layer for imparting a specific function on the surface of the base layer (A) of the composite film described in any one of (1) to (5). (7) The laminated film described in (6), wherein the specific function is at least one selected from the group consisting of gas barrier properties, light-shielding properties, gloss properties, wettability, ease of adhesion, and ease of printing. (8) The laminated film described in (6) or (7), which has an oxygen permeability of 50 cc/(m ² .day.atm) or less at 23°C and 0% humidity. (9) A laminate comprising the laminated film described in any one of (6) to (8) and another substrate, wherein the function-imparting layer is laminated so as to be on the side of the other substrate. (10) The laminate described in (9), wherein the other substrate is a biaxially stretched polypropylene film using a polypropylene resin with a stereoregularity of 90 to 98%. [Effect of Invention]

According to the constitution of the present invention, low-temperature heat-sealability and anti-blocking property are excellent, sealing properties at conventional bag-making and high-speed filling speeds are good, and processability when functionally imparted to the laminated layer on the surface of the film is excellent. In addition, by providing a functional layer on the surface of the base layer (A), and further laminating other base materials thereon to form a packaging laminate, it can have a high degree of high-speed filling suitability, and no problem and achieve excellent productivity.

[Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in further detail together with desired embodiments.

The propylene-random copolymer (a1) used in the base layer (A) of the present invention may be ethylene-propylene random copolymer, ethylene/propylene block copolymer, ethylene-propylene-1-butene terpolymer or the etc. From the viewpoint of adhesion to the functional imparting layer and secondary processability, ethylene-propylene-1-butene terpolymer is preferable.

The above-mentioned propylene-random copolymer (a1) has a melting point of 140°C or higher, preferably in the range of 145 to 155°C, and is excellent in high-speed filling when making bags, and also has excellent processability and adhesion when laminating the functional imparting layer. Sexual change is good, so it is better.

The melt flow rate of the above-mentioned propylene-random copolymer (a1) (hereinafter may be abbreviated as MFR) is 2 to 20 g/10 min, preferably 5 to 15 g/10 min. When the MFR is less than 2 g/10 minutes, the fluidity of the polymer during extrusion may be insufficient, and if it exceeds 20 g/10 minutes, there may be problems with film formation stability during film formation and casting.

By mixing 1 to 10 parts by mass of high-density polyethylene (a2) with respect to 100 parts by mass of the above-mentioned propylene-random copolymer (a1) in the base layer (A), rigidity of the film becomes high. If the blending amount of the high-density polyethylene (a2) is less than 1 part by mass, the rigidity-imparting effect will not be seen, and the rigidity-imparting effect will not change even if the blending ratio is more than 10 parts by mass. The above-mentioned high-density polyethylene (a2) has a density in the range of 0.935 to 0.965 g/cm ³ , and the blocking resistance and sliding properties of the film are improved, which is preferable. If the density is less than 0.935 g/cm ³ , the effect of the addition may not be seen, and if the density exceeds 0.965 g/cm ³ , the surface of the film may be too rough and the adhesion when the functional imparting layer is laminated may deteriorate.

The MFR of the above-mentioned high-density polyethylene (a2) is preferably less than 10 g/10 minutes, more preferably in the range of 1 to 8 g/10 minutes. When MFR exceeds 10 g/10 minutes, melt fracture may occur and film formation stability may fall.

The propylene-random copolymer (b1) used in the heat-sealing layer (B) of the present invention is preferably ethylene-propylene random copolymer, propylene-1-butene random copolymer, ethylene-propylene-1-butene ternary copolymer A copolymer or a mixture thereof, especially a mixture of an ethylene-propylene random copolymer and a propylene-1-butene random copolymer is preferable because it can balance anti-blocking properties and low-temperature heat-sealing properties.

The propylene-random copolymer (b1) may be the same as or different from the propylene-random copolymer (a1).

The resin composition of the heat-sealing layer (B) of the present invention is derived from the differential scanning calorimetry measurement of JIS K 7121 (1987), and the melting initiation temperature (Tim) is estimated to be 110°C or lower. If the extrapolated melting onset temperature (Tim) exceeds 110°C, the low-temperature sealability is not satisfied, and the extrapolated melting onset temperature (Tim) is preferably 95°C or less. Ethylene-propylene random copolymers, propylene-1-butene random copolymers, propylene/1-butene terpolymers, or mixtures thereof, when two or more of them are detected during melting by differential scanning calorimetry In the case of an endothermic peak, the extrapolated melting onset temperature at this time is the one with the larger endothermic peak being the extrapolated melting onset temperature (Tim) of the heat seal layer (B).

The resin composition of the heat-sealing layer (B) of the present invention has a melting point (Tm) measured by differential scanning calorimetry of JIS K 7121 (1987) of not less than 120°C, preferably not more than 145°C. When the melting point (Tm) is less than 120° C., blocking resistance deteriorates. In the case of 145°C or higher, the low-temperature sealing performance deteriorates. Ethylene-propylene random copolymers, propylene-1-butene random copolymers, propylene-1-butene terpolymers, or mixtures thereof, when two or more of them are detected during melting by differential scanning calorimetry In the case of an endothermic peak, the melting point is the melting point (Tm) of the heat-sealing layer (B) at the temperature of the peak maximum value of the one with a larger endothermic peak area.

The MFR of the above-mentioned propylene-random copolymer (b1) is preferably in the range of 3 to 20 g/10 minutes, more preferably in the range of 5 to 15 g/10 minutes. If the MFR is less than 3g/10min, the melt viscosity will be too high, and it will be difficult to stably extrude from the opening when forming a film. If it exceeds 20g/10min, there will be a problem of melt fracture, which will affect the film stability. problem situation.

The heat-sealing layer (B) of the present invention is made of a resin composition obtained by mixing 1 to 20 parts by mass of high-density polyethylene (b2) in 100 parts by mass of propylene-random copolymer (b1), which is anti-adhesive Connectivity becomes higher. When the blending amount of high-density polyethylene (b2) is less than 1 part by mass, the effect of imparting anti-blocking properties may not be seen, and if the blending ratio is more than 20 parts by mass, poor flow at the interface with the base layer (A) may occur. In this case, the stability of film formation is poor, the slack of the film becomes large, the secondary processability deteriorates, and the low-temperature heat sealability also deteriorates.

The density of the high-density polyethylene (b2) is in the range of 0.935-0.965 g/cm ³ , and the blocking resistance and sliding properties of the film are improved, which is preferable. If the density is less than 0.935 g/cm ³ , the effect of addition may not be seen, and if the density exceeds 0.965 g/cm ³ , low temperature heat sealing may deteriorate.

The MFR of the above-mentioned high-density polyethylene (b2) is less than 10 g/10 minutes, more preferably in the range of 5 to 10 g/10 minutes. When MFR exceeds 10 g/10 minutes, melt fracture may occur and film formation stability may fall.

The melting point of the above-mentioned high-density polyethylene (b2) is preferably 140° C. or lower. When the melting point exceeds 140° C., the curl of the film may become large, and problems may arise in secondary processing such as bag making and provision of a functional layer. Also, when packaging bags are made by laminating the composite film of the present invention with other substrates and heat-sealing with a hot plate, the sealing resin is insufficiently melted and filled when filling food, etc. into the bag-making products. In case of poor sealing. The lower limit of the melting point is not limited but is around 100°C. If it is less than that, the slipperiness of the film deteriorates to cause blocking easily, and when the content is filled into a bag-making product, the opening property of the bag decreases and a problem may arise. High-density polyethylene (b2) may be the same as high-density polyethylene (a2) or may be different.

As mentioned above, the base layer (A) of the present invention preferably comprises 30% by mass or less of the constituents of the heat-sealing layer (B) as a self-recycling component of the composite film of the present invention (i.e. as the composite film) Leftovers, components of recovered edge parts), more preferably 2 to 10% by mass. By being able to recover the self-recycling components of the composite film without greatly changing the composition and ratio of the main components of the base layer (A), it becomes possible to ensure the target performance of the composite film of the present invention while maintaining the production of the composite film of the present invention at a high degree yield.

The mixing method of the above-mentioned resin composition is not particularly limited, and it can be mixed by a conventionally known method. For example, it may be dry blending or melt blending.

On the composite film, 30 parts by mass of the adhesive "TAKELAC (registered trademark)" A969V type for polyether urethane dry lamination manufactured by Mitsui Chemicals Co., Ltd., and 10 parts by mass of dry Lamination curing agent "TAKELAC (registered trademark)" type A10 and 100 parts by mass of ethyl acetate were stirred for 30 minutes to prepare a dry lamination adhesive solution with a solid content concentration of 19% by mass. Next, the above-mentioned adhesive solution was coated on the base layer (A) surface of the composite film by bar coating, and dried at 80° C. for 45 seconds to form an adhesive layer with a thickness of 2 μm. Next, a 20 μm biaxially stretched polypropylene film (U-0 manufactured by Mitsui Chemicals Co., Ltd.) was laminated on the adhesive layer so that the corona-treated surface faced the adhesive layer. ) made "LAMIPACKER (registered trademark)" LPA330, heated the heat roll to 40 degreeC, and bonded together. This laminated film was stored in an oven heated to 40° C. for 2 days to obtain a laminated body.

Next, the heat-sealed layers (B) of the laminate were stacked on each other, and the sample was heat-sealed with a sealing temperature of 120°C, one-side heating, a sealing pressure of 0.1 MPa, and a sealing time of 1 second using a flat-plate heat-sealer. The heat seal strength was measured at a tensile speed of 300 mm/min using "TENSILON" manufactured by Orientec Corporation. When the heat-sealing strength at this time is 6 N/15 mm or more, the sealing property at bag making and high-speed filling speed is good and is preferable. If it is less than 6N/15mm, the temperature of bag making and sealing must be increased, and other substrates will melt and the appearance of the sealing part will obviously deteriorate.

In addition, in the base layer (A) and the heat-sealing layer (B), antioxidants, heat-resistant stabilizers, neutralizing agents, and antistatic agents can be contained within the range that does not hinder the heat-sealing property and the lamination property of the functional imparting layer. , hydrochloric acid absorbent, anti-blocking agent, lubricant, nucleating agent, etc. These additives may be used alone or in combination of two or more.

As mentioned above, if 300-5000ppm of inorganic particles or organic particles are added as an anti-blocking agent, then when the composite film of the present invention is wound into strips, the defects caused by wrinkles and poor ventilation will be reduced, so it is preferable. When the content of inorganic particles or organic particles is less than 300 ppm, the anti-blocking property imparting effect may not be seen, and when it exceeds 5000 ppm, the heat-sealing force may decrease.

Examples of the above-mentioned inorganic particles include silica, zeolite, calcium carbonate, etc., and examples of organic particles include cross-linked polystyrene particles, cross-linked polymethyl methacrylate particles, and the like. These average particle diameters are preferably in the range of 1 to 5 μm. When the average particle diameter is less than 1 μm, the effect of addition may not be seen, and when it exceeds 5 μm, the heat-sealing force may decrease.

Specific examples of antioxidants include hindered phenols such as 2,6-di-tertiary butylphenol (BHT), n-octadecyl-3-3',5'-di-tertiary butyl -4'-Hydroxyphenyl propionate ("Irganox" 1076, "Sumilizer" BP-76), tetrakis[methylene-3-(3,5-di-tertiary butyl-4-hydroxyphenyl) Propionate] Methane ("Irganox" 1010, "Sumilizer" BP-101), 3,5-di-tertiary butyl-4-hydroxybenzyl isocyanate ("Irganox" 3114, Mark AO-20) wait. In addition, examples of phosphite-based (phosphorus-based) antioxidants include: 2,4-di-tertiary butylphenyl phosphite ("Irgafos" 168, Mark 2112), 2,4-di- Tertiary butylphenyl-4-4'-biphenylene-diphosphonate ("Sandstab" P-EPQ), bis 2,4-di-tertiary butylphenyl neopentylthritol diphosphite ester ("Ultranox" 626, Mark PEP-24G), distearyl neopentylthritol diphosphite (Mark PEP-8), etc. Among them, 6-[3-(3-tertiary butyl-4-hydroxy-5-methyl)propoxy]-2,4 which has both the functions of these hindered phenols and phosphites is preferred. ,8,10-Tetra-tertiary butyldibenzo[d,f][1,3,2]-dioxaphosphine ("Sumilizer" GP), and acrylic acid 1'-hydroxy[2,2'- Ethylenebis[4,6-bis(1,1-dimethylpropyl)benzene]]-1-yl ("Sumilizer" GS), especially, the combined use of these two, when making thin films , exerts an effect on the inhibition of oxidation deterioration, and contributes to the balance of anti-blocking property and low-temperature heat-sealability, so it is preferable. Moreover, although the addition amount of an antioxidant also differs with the kind of antioxidant used, it should just set suitably in the range of 100-10000 ppm.

As the nucleating agent, well-known nucleating agents such as a phosphate metal salt-based nucleating agent, a sorbitol-based nucleating agent, and a carboxylate metal salt-based nucleating agent can be used.

The composite film of the present invention can contain a thermoplastic elastomer, further lowers the sealing initiation temperature, and improves productivity at bag making and high filling speeds. In addition, although the addition amount of a thermoplastic elastomer differs with the kind of thermoplastic elastomer used, it should just set suitably in the range of 5-30 mass parts.

The thermoplastic elastomer mentioned above refers to rubber elasticity at 25°C due to the presence of a hard segment phase and a soft segment phase. The phase exhibits fluidity, thereby becoming a high-molecular-weight body that can be molded and processed in the same way as general thermoplastic resins. As for the thermoplastic elastomer used in the sealing layer, it can be used alone or in combination. For example: polyester elastomer, polyolefin elastomer, polyamide elastomer, polyurethane elastomer , Styrene-based elastomers, and polyacrylic-based elastomers. Among these, polyolefin-based elastomers and hydrogenated styrene-based elastomers are preferably used from the viewpoint of the low-temperature sealability of the obtained film.

Preferable examples of the above-mentioned polyolefin-based elastomers include propylene-based elastomers and ethylene-based elastomers.

The propylene-based elastomer is an elastomer containing a structural unit derived from propylene, and a copolymer containing a structural unit derived from propylene is preferably exemplified. In the above-mentioned propylene-based elastomer, the content ratio of the structural units derived from propylene is preferably from 30 to 90% by mass, more preferably from 50 to 90% by mass. In the case of this range, since it is easy to obtain the composite film excellent in low-temperature sealing property, it is preferable.

As for other copolymerization components constituting the above-mentioned propylene-based elastomer, for example, ethylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1 Constituent units of monomers such as -hexene, 4-methyl-1-pentene, and 1-octene. Among them, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, etc. are preferable, and ethylene and 1-butene are particularly preferable. These can be used individually or in combination of 2 or more types. The above-mentioned propylene-based elastomer preferably contains a structural unit derived from ethylene. In the above-mentioned propylene-based elastomer, the content ratio of the constituent units derived from ethylene is preferably from 5 to 20% by mass, more preferably from 8 to 15% by mass.

The ethylene-based elastomer is preferably a low-crystallinity random copolymer of ethylene and an α-olefin having 3 to 8 carbons, more preferably a low-crystallinity random copolymer of ethylene and an α-olefin having 3 to 4 carbons. The low-crystallinity random copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms is preferably an ethylene-butene random copolymer excellent in low-temperature sealing properties, more preferably an ethylene-butene-1 random copolymer . The content of the α-olefin having 3 to 8 carbon atoms is in the range of 5 to 25% by mass, preferably 10 to 20% by mass, which is preferable because it can balance anti-blocking properties and low-temperature sealing properties.

The density of the ethylene-based elastomer is preferably 0.865-0.890 g/cm ³ , and the endothermic heat of melting during the heating process by a differential scanning calorimeter (DSC) according to JIS K7122 is in the range of 5-30 J/g. When the density is less than 0.865 g/cm ³ , the blocking resistance may deteriorate, and when the density exceeds 0.890 g/cm ³ , the impact resistance may deteriorate.

The hydrogenated styrene-based elastomer has a structure comprising a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one hydrogenated conjugated diene compound, such as Hydrogenated block copolymers including, for example, A-B-A, B-A-B-A, B-A-B-A-B, mixtures thereof, and the like. The hydrogenated block copolymer preferably contains 10 to 40% by mass of vinyl aromatic compounds.

Examples of the vinyl aromatic compound constituting the polymer block A include styrene and α-methylstyrene, especially styrene is preferred. Furthermore, the conjugated diene compound before hydrogenation of the hydrogenated conjugated diene compound constituting the polymer block B includes, for example, butadiene, isoprene, 1,3-pentadiene, especially Butadiene and isoprene are preferred. In vinyl aromatic compound-conjugated diene compound block copolymers, preferably 80%, preferably more than 90% of the aliphatic double bonds of the conjugated diene compound are hydrogenated to form an olefin compound polymer block B.

Typical hydrogenated styrene-based elastomers include: styrene-ethylene-butylene-styrene block copolymer (hereinafter referred to as SEBS), styrene-isoprene-styrene block copolymer Hydrides of substances (hereinafter referred to as SIS), etc., especially SEBS are preferred. Among SEBS, those with low styrene content and high ethylene and butene content have excellent compatibility with sea components including ethylene-propylene copolymers in the heat-sealing layer. Specifically, "DYNARON" 8601P manufactured by JSR Co., Ltd., "Tuftec" H1062 manufactured by Asahi Kasei Co., Ltd., G1660 manufactured by Kraton Polymers Japan Co., Ltd., etc. can be suitably used, and ethylene and butyl The total mass ratio of olefins is in the range of 12/88 to 67/33.

Moreover, 10-30 mass parts of ethylene-α-olefin copolymers can be contained in a heat-sealing layer (B). The α-olefin includes butene, hexene, octene, or a mixture thereof, and is preferably linear low-density polyethylene. The linear low-density polyethylene is preferably one produced by a metallocene catalyst from the viewpoint of sealing strength.

The density of the linear low-density polyethylene is preferably in the range of 0.900 to 0.935/cm ³ , more preferably in the range of 0.915 to 0.930/cm ³ . When the density of the linear low-density polyethylene is less than 0.900 g/cm ³ , the blocking resistance may be lowered, and when it is higher than 0.935 g/cm ³ , the dispersibility may be lowered.

The composite film of the present invention can be composed of two laminated layers of the base layer (A) and the heat-sealing layer (B) as described above, and can also be composed of three or more laminated layers in which the other intermediate layer (C) is interposed between the two layers. . The intermediate layer (C) is preferably a resin composition of the base layer (A), homopolypropylene, or the like that increases the strength and rigidity of the film. In addition, from the standpoint of quality stabilization and cost reduction, flakes or regenerated pellets obtained by crushing slit scraps generated during the production of the composite film of the present invention can be mixed and used.

The lamination method of the composite film having the base layer (A), the heat-sealing layer (B) and the middle layer (C) of the present invention is not particularly limited, but is generally melted and extruded separately using individual extruders to compound (pinol), feed block method and other pipe compounding, co-extrusion multi-layer mold method and other methods for lamination.

The thickness of the composite film of the present invention is not particularly limited, but it is usually about 15 μm to 80 μm, and especially 20 μm to 40 μm is preferably used from the viewpoint of handling. The thickness ratio of the heat seal layer (B) is preferably 10 to 50% of the overall thickness, more preferably 15 to 40%. When the thickness ratio of a heat-sealing layer (B) is less than 10%, heat-sealing force may fall and sealing property may be inferior. Also, if it exceeds 50%, the heat resistance may decrease, and the high-speed filling property, the lamination of the functional imparting layer, and the secondary processability at the time of lamination with other substrates may also deteriorate.

The composite film of the present invention can be formed as a laminated film in which a function-imparting layer imparting a specific function is provided on the surface of the base layer (A).

The so-called functional imparting layer in the present invention refers to the layer imparting specific functions in the aforementioned composite film. The specific functionality refers to at least one functionality selected from gas barrier properties, light-shielding properties, glossiness, ease of adhesion to other substrates, and ease of printing. The specific functionality may be only one function or several functions.

The so-called gas barrier properties in the present invention refer to the gas barrier properties of oxygen, water vapor, nitrogen, and carbon dioxide gas, preferably oxygen and water vapor. The oxygen barrier property can be measured by the method of JIS K 7126. The oxygen barrier property in the present invention refers to the oxygen transmission rate at a temperature of 23° C. and a relative humidity of 0%.

The water vapor barrier property can be measured by the method of JIS K 7129B, which refers to the water vapor transmission rate at a temperature of 40°C and a relative humidity of 90%. The oxygen permeability is preferably not more than 50 cc/(m ² .24 hr.atm), more preferably not more than 30 cc/(m ² .24 hr.atm).

The so-called light-shielding property in the present invention refers to the functionality that the total light transmittance measured by the method of JIS K 7361 is 5% or less. More preferably, the total light transmittance is 3% or less.

The so-called glossiness in the present invention refers to the glossiness of incident light and reflected light measured simultaneously at 60° by the method of JIS Z 8741. The glossiness of the function-imparting layer after aluminum vapor deposition is preferably at least 300%, more preferably at least 400%.

The ease of adhesion to other substrates referred to in the present invention refers to the ease of adhesion to other substrates described later. The ease of bonding refers to the ease of bonding to the base layer (A) of the composite film of the present invention. Examples include: the ease of adhesion of the adhesive used for bonding with other substrates to the base layer (A) of the composite film of the present invention; Ease of bonding of layer (A); Ease of bonding of extruded resin during extrusion coating processing to base layer (A) of the composite film of the present invention; Ease of adhesion of the base layer (A) of the composite film of the invention; ease of adhesion of the resin applied during coating processing to the base layer (A) of the composite film of the present invention, etc.

Although it does not specifically limit about the method of providing easy adhesion, The method of treating the surface of the base layer (A) of a composite film is mentioned. The surface treatment methods include: corona treatment, flame treatment, plasma treatment, ozone treatment, ion treatment, sputtering treatment, sand blasting treatment, surface modification treatment by resin such as anchor coating, etc.

Examples include: methods of forming chemically reactive functional groups on the surface of the base layer (A); adding particles to resins such as anchor coating; sputtering, sandblasting, etc. The method of roughening the surface to physically form surface irregularities having an anchoring effect on the surface of the base layer (A) may be any method, or may be a combination of any methods.

The method of treating the surface of the base layer (A) can be carried out in-line when the composite film of the present invention is formed, or can be carried out out-of-line after the composite film of the present invention is formed. Moreover, only the surface treatment may be performed, and the function-imparting layer may be formed continuously after surface-treating the base layer (A) when forming the function-imparting layer. The surface after forming the functional imparting layer may also be treated.

The so-called ease of printing in the present invention refers to the ease of printing on the base layer (A) of the composite film of the present invention. Printing is performed to express textual information, patterns, etc. that are necessary for packages such as packaging bags. The components used for printing are made by adding various pigments, plasticizers, drying The so-called printing easiness means that the printing components are easy to adhere during printing, and the missing dots of the ink are less likely to fall off.

Although it does not specifically limit about the method of providing easy printability, The method of treating the surface of the base layer (A) of a composite film is mentioned.

The method of surface treatment includes: corona treatment, flame treatment, plasma treatment, ozone treatment, ion treatment, surface modification treatment by resin such as anchor coating, etc. Examples include: a method of forming a highly reactive functional group with respect to printed ink on the surface of the base layer (A), a method of using an anchor coating resin to which printed ink is easily adhered, and a method of improving wettability. The method of adding wettability improver, etc. to the anchor coating, etc.

The timing of treating the surface of the base layer (A) may be carried out before printing, it may be carried out in-line when the composite film of the present invention is formed, or it may be carried out outside the line after the composite film is formed.

If the functions of gas barrier properties, light-shielding properties, glossiness, easy adhesion with other substrates, and easy printing properties of the present invention can be imparted, the function-imparting layer can be any of an inorganic layer, an organic layer, and an inorganic-organic mixture layer. one. In addition, these may be one layer, or multiple laminated layers. In the case of plural lamination, the order of lamination is not particularly limited as long as the intended function is satisfied. Examples of the inorganic layer include a metal layer, an inorganic oxide layer, and the like.

The metal layer is not particularly limited, but is preferably aluminum from the viewpoints of gas barrier properties, light-shielding properties, glossiness, and cost. The thickness of the metal layer is preferably not less than 20 nm and less than 100 nm, more preferably not less than 22 nm and less than 80 nm. In terms of optical density, 1.5 or higher is practical, and in terms of metallic luster, 600% or higher is practical. When the thickness of the metal layer is less than 20 nm, the optical density may be 1.5 or less, the glossiness may be 600% or less, light-shielding properties and metallic luster may not be obtained, and the appearance may become unsuitable for practical use. When the thickness of the metal layer is 100nm or more, there is no problem of light-shielding properties and metallic luster, but since the metal layer becomes thicker, the vapor deposition layer tends to dissipate heat, and the gas barrier performance and laminate strength may decrease.

When the contents can be visually recognized and gas barrier properties are imparted, an inorganic oxide layer is preferable. Inorganic oxides are not particularly limited, and include: alumina, silicon oxide, magnesium oxide, zinc oxide, silicon dioxide, and zinc oxide or zinc sulfide containing aluminum oxide, including zinc oxide-dioxide A layer of a coexisting phase of silicon-alumina, a layer of zinc sulfide and silicon dioxide, a layer containing a coexisting phase of zinc sulfide and silicon dioxide, diamond-like carbon, or a mixture thereof, but from the viewpoint of cost, it is relatively Aluminum oxide, silicon oxide, and magnesium oxide are preferable, and aluminum oxide and silicon oxide are more preferable.

The method for forming these metal layers and inorganic oxide layers is not particularly limited, and can be used: directly heating the metal to evaporate it, and forming the metal layer on the surface of the base layer (A) of the composite film of the present invention; Reactive evaporation method in which the metal evaporated by heating forms an inorganic oxide layer by reacting with oxygen; ion plating method in an oxygen environment; sputtering method using the target material as a target; sputtering in sputtering Well-known methods such as a reactive sputtering method in which the plating particles react with oxygen, a chemical vapor deposition method, and the like.

In addition, before forming the metal layer and the inorganic oxide layer, the surface of the base layer (A) of the composite film of the present invention may be subjected to a function-imparting treatment.

The thickness of the inorganic oxide layer is preferably not less than 10 nm and less than 30 nm. If the film thickness is less than 10 nm, the intended lamination strength may not be achieved, or the gas barrier performance may become insufficient. When the film thickness is 30 nm or more, the reaction heat also increases during the oxidation reaction of aluminum, and the base layer (A) may be deformed by the reaction heat, and the appearance may not be suitable for practical use. The thickness of the aluminum oxide layer and the metal aluminum layer can be calculated from the composition distribution (so-called depth profile) of the sputtering depth of aluminum and oxygen obtained by X-ray photoelectron spectroscopy and Auger electron spectroscopy.

For the organic material layer, an organic resin layer can be mentioned, such as vinylidene chloride resin, polyvinyl alcohol-based resin, polyurethane resin, polyepoxy resin, polyester resin, polyacrylic resin, vinyl vinyl alcohol copolymer, etc. When imparting oxygen barrier properties, it is preferable to apply an ethylene vinyl alcohol copolymer.

Examples of the inorganic-organic mixture layer include those in which an inorganic substance is mixed with the aforementioned organic resin, or those in which an organic resin and an inorganic component are combined. The inorganic substance to be mixed may be either a flat inorganic substance or a particulate inorganic substance. When imparting light-shielding properties, titanium oxide or the like is preferable as the particulate inorganic substance for the purpose of blocking light reflection.

In addition, these organic substances and organic-inorganic substances may contain materials such as oxygen absorbers.

The film thickness of the inorganic-organic mixture layer is preferably 0.5 to 1000 μm, more preferably 1 to 500 μm, further preferably 1 to 100 μm, particularly preferably 1 to 50 μm.

There are no particular limitations on the methods of forming these organic layers and inorganic-organic mixture layers, and they can be formed on the base layer (A) of the composite film of the present invention, the function-imparting layer and the base layer on the base layer (A) (A) Surface of functional processing. It can be formed using, for example, roll coating, dip coating, bar coating, die coating, knife edge coating, gravure coating, kiss coating, spin coating, spray coating, or a combination thereof.

Next, other substrates can be laminated on the base layer (A) of the composite film of the present invention, or the above-mentioned function-imparting laminated layer can be layered on the base layer (A) to further improve the functionality. The laminated structure of these laminates is based on the required characteristics of the packaging bag (for example: gas barrier properties during the quality maintenance period to meet the packaged food, size/impact resistance that can correspond to the quality of the contents, visual recognition of the contents sex, etc.) and choose appropriately.

The above-mentioned other substrates are not particularly limited as long as characteristics such as mechanical strength, heat resistance, and light resistance are considered depending on the application, and representative examples include: polyethylene terephthalate, polyethylene naphthalate polyester, butylene terephthalate, polybutylene 2,6-naphthalate and other polyesters; polyvinyl alcohol, saponified product of ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polyethylene, Polyolefins such as polypropylene; films and sheets containing homopolymers or copolymers such as polyamides such as nylon 6 and nylon 12, aromatic polyamides, and polyimides. From the viewpoint of strength retention and puncture resistance with respect to the contents, plastic films such as polyamide films, or paper substrates, film laminates obtained by laminating these plastic films with adhesives, etc., Paper laminates, etc. made by laminating polymer films and paper substrates with adhesives, etc. Among them, especially in the context of the increase in marine plastic waste in the world, the demand for recycling of used plastic packaging materials has become stronger. In the laminated body with the above-mentioned other substrates, as a way to make the entire packaging body The reused single material (single material) system structure is preferable from the viewpoint of reducing environmental load by making a laminate of biaxially stretched polypropylene and the composite film of the present invention, so that the same material can be recycled.

As mentioned above, the biaxially stretched polypropylene is preferably a polypropylene resin containing a stereoregularity in the range of 90 to 98%, which represents the ratio of the regular unidirectional arrangement of the methyl groups of propylene. If the stereoregularity is less than 90%, the rigidity of the film will decrease. When making a laminate with the above-mentioned composite film, the film will be stretched due to tension and wrinkles will easily occur. High-speed filling of bag-making products and functional imparting layer performance degradation. When the stereoregularity exceeds 98%, the crystallinity may become high, the surface roughness of the film may become large, and the adhesiveness with the function-imparting layer may decrease.

The methods for laminating the above-mentioned other substrates with the composite film of the present invention include dry lamination using an adhesive such as a two-component curable urethane resin, wet lamination, and solvent-free lamination without using a solvent. Known methods such as lamination method and extrusion sandwich lamination method by extruding resin.

A laminate obtained by laminating the above-mentioned other substrate and the composite film of the present invention can be suitably used as a packaging bag or a packaging container. In terms of packaging bags and packaging containers, examples include: gadget bag, stand-up pouch, brick type, flat type, etc., which can be used to fill and package various foods, beverages, adhesives, adhesives and other chemicals, cosmetics, etc. , pharmaceuticals and other miscellaneous goods.

An example of the method for producing the composite thin film of the present invention will be described. Using two extruders, from one extruder, 100 parts by mass of propylene-random copolymer (a1) with an MFR of 3 to 12 g/10 minutes as the resin of the base layer (A) was mixed for 1 to 10 minutes. The resin composition made of high-density polyethylene (a2) in parts by mass melts at a temperature of 220 to 270°C. A resin composition obtained by mixing 1 to 20 parts by mass of high-density polyethylene (b2) with 100 parts by mass of propylene-random copolymer (b1) as the heat-sealing layer (B) from another extruder The substance melts at a temperature of 220-270°C. The base layer (A) and the heat-sealing layer (B) are laminated with tube compounding and co-extrusion multi-layer dies, extruded from the opening to form a film, and cast with a cooling roll at 30-80°C to cool and solidify to form a composite film. At this time, it is preferable to set the thickness ratio of the gap at the end of the opening to the composite film that is cooled and solidified (gap at the end/thickness of the film=drawing ratio) to 20 to 50. By making the draft ratio, it can be melt-aligned in the long-side direction. Moreover, by applying heat treatment at 40-80° C. for 0.01-1 second with a mirror-surfaced roll that heats the cast film, the Young's type of the film can be made Modulus (rigidity) increased.

Next, as an example of a method of imparting functionality to the surface of the base layer (A) of the composite film, 20-60W is applied in an environment of a mixed gas of nitrogen and carbon dioxide gas (volume ratio of carbon dioxide 0.5-50%). Minutes/m ² of corona discharge treatment and coiled to obtain the composite film of the present invention.

In addition, as an example of the function-imparting layer in the above-mentioned composite film, it is installed in a vacuum evaporation device, and aluminum is applied to the surface of the base layer (A) of the above-mentioned film with a film thickness of 30 nm at a vacuum degree of 1.3 × 10 ^-2 Pa or higher. Pre-metal vapor deposition to obtain a metal vapor-deposited laminated film. [Example]

The present invention will be described using Examples and Comparative Examples.

Examples 1-12, Comparative Examples 1-16 Examples 1 to 12 and Comparative Examples 1 to 16 of the composite film of the present invention used the following polyolefin-based resins. (1) Ethylene-propylene random copolymer: melting point 141°C, extrapolated melting onset temperature 135°C, MFR 7.0g/10min, ethylene content 4 mol% (abbreviated as r-EPC). (2) Ethylene·propylene·1-butene terpolymer: melting point 140°C, extrapolated melting onset temperature 134°C, MFR 7.0g/10min, ethylene content 2 mole%, butene content 5 mole%( It will be referred to as r-EPBC for short). (3) Propylene-1-butene random copolymer: Melting point 125°C, extrapolated melting onset temperature 115°C, MFR 7.0g/10min, butene content 17 mol% (abbreviated as r-PBC(1) ). (4) Propylene-1-butene random copolymer: Melting point 125°C, extrapolated melting onset temperature 90°C, MFR 7.0g/10min, butene content 19 mol% (abbreviated as r-PBC(2) ). (5) Propylene-1-butene random copolymer: Melting point 125°C, extrapolated melting onset temperature 100°C, MFR 7.0g/10min, butene content 18 mol% (abbreviated as r-PBC(3) ). (6) Propylene-1-butene random copolymer: Melting point 110°C, extrapolated melting onset temperature 90°C, MFR 7.0g/10min, butene content 25 mol% (abbreviated as r-PBC(4) ). (7) High-density polyethylene: Novatec HD "HF562" manufactured by Nippon Polyethylene Co., Ltd. MFR 7.5 g/10 minutes, melting point 134° C. (this is abbreviated as HPDE (1)) was used. (8) High-density polyethylene: Novatec HD "HJ580N" manufactured by Nippon Polyethylene Co., Ltd. MFR 12.0 g/10 minutes, melting point 134° C. (this is abbreviated as HPDE (2)) was used.

The measured value of each evaluation item in the detailed description of this invention and an Example was measured by the following method.

Table 1 and Table 2 show the characteristics of each sample in each Example and Comparative Example.

(1) Melt flow rate (MFR) According to JIS K-7210-1999, the temperature of propylene-random copolymer, propylene-based elastomer and homopolypropylene is 230℃, and the temperature of high-density polyethylene, ethylene-α-olefin copolymer and ethylene-based elastomer is 190℃. Each measurement was performed with a load of 21.18N.

(2) Density According to JIS K-7112-1999, it is measured by the measurement method caused by density gradient tube.

(3) Melting point (Tm) Using a differential scanning calorimeter DSC (DSC-60A) manufactured by Shimadzu Corporation, the endothermic peak accompanying melting was measured when a 5 mg sample was heated to 250°C at a rate of 10°C/min under a nitrogen atmosphere. The peak temperature was taken as the melting point (Tm).

(4) The melting point (Tm) of the heat-sealing layer (B) of the composite film Under the same conditions as (3), obtain the sample obtained by cutting the surface of the heat-sealing layer (B) of the composite film with a diamond cutter, and detect more than 2 endothermic peaks, and the melting point at this time is the one with the larger endothermic peak Let it be the melting point (Tm) of a heat-sealing layer (B).

(5) Extrapolation of melting onset temperature (Tim) Assuming that the differential scanning calorimetry device DSC (DSC-60A) manufactured by Shimadzu Corporation was used, the temperature of 5 mg of the sample was raised to 250° C. at a rate of 10° C./min under a nitrogen atmosphere and held for 5 minutes, and then heated at 10° C. Cool down to 10°C at a cooling rate of °C/min, and when the temperature is raised again at a rate of 10°C/min, the point where the gradient of the straight line extending from the base line on the low temperature side to the high temperature side and the curve on the low temperature side of the melting peak becomes the largest The temperature at the point of intersection of the tangent lines drawn.

(6) The extrapolated melting start temperature (Tim) of the heat-sealing layer (B) of the composite film The sample obtained by cutting off the surface of the heat-sealing layer (B) of the composite film with a diamond cutter was obtained under the same conditions as (5). The extrapolated melting start temperature at this time is the one with a larger endothermic peak as the extrapolated melting start temperature (Tim) of the heat seal layer (B).

(7) Membrane stability In the film forming step of the composite film, the following evaluations were performed by observing the adhesion of the film to the processing roll and the appearance such as wrinkles of the film. ○ (good): There is no sticking to the processing roll in the film forming step, good film forming properties, and the film has no wrinkles, stains, etc., and has a good appearance with small curl. × (defective): There was adhesion to the processing roll in the film forming step, and the film forming property was unstable. In addition, the film had wrinkles and stains caused by roll adhesion, and the curl was large and the appearance was poor.

(8) Slack evaluation (curl) The composite film was wound into a roll, cut into a predetermined width to make a product, and a film of 2 m was pulled out from the product, stretched to about finger tension (3 to 4 kg with a spring balance) and checked. If slack is observable, measure its width with a tape measure. When the slack width was less than 100 mm, it was judged as a pass.

(9) Film thickness Using a dial gauge type thickness gauge (JIS B-7509: 1974, 5 mmφ flat type measuring pin), 10 points were measured at intervals of 10 cm in the longitudinal direction and width direction of the film, and the average value thereof was used.

(10) Thickness of each layer Cut out the cross section of the film with a microtome, use a digital microscope VHX-100 (manufactured by Keyence Co., Ltd.) to observe the cross section at a magnification of 1000 times, measure the distance in the thickness direction of each layer, and deduce it from the magnification And obtain the thickness of each layer. In addition, when obtaining the thickness of each layer, using a total of five cross-sectional photographs arbitrarily selected from mutually different measurement fields of view, the average value thereof was calculated.

(11) Heat seal strength Measure 30 parts by mass of Mitsui Chemicals Co., Ltd. polyetherurethane-based dry-lamination adhesive "TAKELAC (registered trademark)" type A969V, and 10 parts by mass of Mitsui Chemicals Co., Ltd.-manufactured dry-lamination hardener "TAKELAC (registered trademark)" type A10 and 100 parts by mass of ethyl acetate were stirred for 30 minutes to prepare an adhesive solution for dry lamination with a solid content concentration of 19% by mass. Next, the above-mentioned adhesive solution was coated on the base layer (A) surface of the composite film by bar coating, and dried at 80° C. for 45 seconds to form an adhesive layer with a thickness of 2 μm. Next, a 20 μm biaxially stretched polypropylene film (U-0 manufactured by Mitsui Chemicals Co., Ltd.) was laminated on the adhesive layer so that the corona-treated surface faced the adhesive layer. ) made "LAMIPACKER (registered trademark)" LPA330, heated the heat roll to 40 degreeC, and bonded together. This laminated film was stored in an oven heated to 40° C. for 2 days to obtain a laminated body.

Next, the heat-sealed layers (B) of the laminate were stacked on each other, and the sample was heat-sealed with a sealing temperature of 120°C, one-side heating, a sealing pressure of 0.1 MPa, and a sealing time of 1 second using a flat-plate heat-sealer. The heat seal strength was measured at a tensile speed of 300 mm/min using "TENSILON" manufactured by Orientec Corporation. The low-temperature heat-sealability was good when the heat-sealing strength at this time was 6 N/15mm or more.

(12) Anti-adhesion Prepare a film sample with a width of 30mm and a length of 100mm, overlap the sealing layers with each other in the range of 30mm×40mm, apply a load of 500g/ ^12cm2 , heat treatment in an oven at 40°C for 24 hours, and heat it at 23°C , After standing in an environment with a humidity of 65%RH for 30 minutes or more, the shear peeling force was measured at a tensile speed of 300 mm/min using TENSILON manufactured by Orientec Corporation. According to this measurement method, if the shear peeling force is less than 10N/12cm ² , the anti-blocking property is set as "○ (good)", and if the shear peeling force is more than 10N/12cm ² and less than 15N/12cm ² , it is set as "△ (possible)" , let 15N/12cm ² or more be "× (defective)".

(13) Oxygen permeability (gas barrier performance) As the function-imparting layer on the base layer (A) of the composite film, under the conditions of temperature 23° C. and humidity 0% RH, the U.S. Mocon (MOCON) company made Oxygen transmission rate measuring device (OXTRAN 2/20), according to B method (equal pressure method) recorded in JIS K7126 (2000 edition) to measure oxygen transmission rate as a method of metal vapor deposition, metal oxide vapor deposition, laminated organic layer Gas barrier properties of thin films. Samples were taken from three locations in the width direction of the film from both ends and the center, and the average value of the three measured values was taken as the value of the oxygen transmission rate in each Example and Comparative Example. The value of the oxygen permeability is 50 cc/(m ² .24 hr.atm) or less, and the gas barrier performance is good.

(14) Total light transmittance (shading) The total light transmittance was measured using a haze meter (NDH7000 manufactured by Nippon Denshoku Industries Co., Ltd.). Let the total light transmittance be 5% or less and make light-shielding property good.

(15) Surface gloss Gloss is measured using Suga Test Instruments Co., Ltd.'s variable angle gloss meter type: UGV-5D, in accordance with JIS Z8741 (1983), with an incident angle of 60°/reflection angle of 60° relative to the metal deposition surface. , the measured value is an average value obtained at three points in the width direction of the film. 600% or more was set as pass.

(16) Adhesion strength (easy adhesion) Measure 30 parts by mass of Mitsui Chemicals Co., Ltd. polyetherurethane-based dry-lamination adhesive "TAKELAC (registered trademark)" type A969V, and 10 parts by mass of Mitsui Chemicals Co., Ltd.-manufactured dry-lamination hardener "TAKELAC (registered trademark)" type A10 and 100 parts by mass of ethyl acetate were stirred for 30 minutes to prepare an adhesive solution for dry lamination with a solid content concentration of 19% by mass.

Next, the above-mentioned adhesive solution was coated on the function-imparting layer of the composite film by bar coating, and dried at 80° C. for 45 seconds to form an adhesive layer with a thickness of 2 μm.

Next, a 25 μm biaxially stretched polypropylene film ("Trefin (registered trademark)" YT42 manufactured by Toray Co., Ltd.) was overlaid on the adhesive layer as another base material so that the corona-treated surface faced the adhesive layer. , using "LAMIPACKER (registered trademark)" LPA330 manufactured by FUJITEC Co., Ltd., and bonding by heating the heat roll to 40°C. This laminated film was stored in an oven heated to 40° C. for 2 days to obtain a laminated body. Next, the laminate was cut into a width of 15 mm and a length of 150 mm to make a cut sample, and a tensile tester (RTG-1210 type) manufactured by A&D Co., Ltd. was used to make the interface between the composite film and the biaxially stretched polypropylene film. The strength was measured by peeling at a tensile speed of 300 mm/min by the T-peel method. Let the obtained value be adhesion strength (N/15mm). The adhesion strength was set to be good at 1 N/15 mm or more.

(17) Ease of printing Ink (LAMIC SR SC R White (M) manufactured by Dainichi Seika Co., Ltd.) and its dilution solvent (LAMIC SR Hardener) ink is applied to the functional layer, and dried in a hot air oven at 100°C for 30 seconds. After that, "Cellotape (registered trademark)" No. 405 (width 15mm) manufactured by NICHIBAN Co., Ltd. was attached to the printing surface with a rubber roller, and then peeled off to observe the peeling state of the ink. Ease of printing was evaluated. 5-stage evaluation "Easy printability (poor)" Level 1: Ink peeling 90% or more, Level 2: Ink peeling 50% or more and less than 90%, Level 3: Ink peeling 10% or more and less than 50%, 4 Grade: 1% or more to less than 10% of ink peeling off, Grade 5: less than 1% of ink peeling off "Easy printability (good)".

(18) Thickness of function imparting layer In the observation method of the transmission electron microscope, the thin film to be observed is sampled by the microsampling method, and then thinned using a focused ion beam processing device (FB-2000 manufactured by Hitachi, Ltd.). After that, a carbon and tungsten protective film is formed for protection. This sample was observed with a field emission type transmission electron microscope (HF-2200 manufactured by Hitachi, Ltd., hereinafter referred to as TEM).

Example 1 As the base layer (A) of the composite film, 95 parts by mass of the above-mentioned ethylene-propylene random copolymer (r-EPC) as the propylene-random copolymer (a1) was mixed with high-density polyethylene ( a2) 5 parts by mass of HDPE (1), 0.125 parts by mass of an antioxidant ("Irganox" 1010 manufactured by Ciba-Geigy), and 0.3 parts by mass of silica fine particles with an average particle diameter of 3 μm as an antiblocking agent The resin composition was supplied to an extruder heated to 240°C and melted, and as a heat-sealing layer (B), 97 parts by mass of the above-mentioned propylene-1-butene random copolymer (r-PBC(2 )), 3 parts by mass of HDPE (1) as a high-density polyethylene (b2), 0.125 parts by mass of an antioxidant ("Irganox" 1010 manufactured by Ciba-Geigy), and 0.2 parts by mass of an antiblocking agent. The resin composition made of silicon dioxide microparticles with a diameter of 3 μm is supplied to another extruder heated to 240°C to be melted, and then extruded in a multi-manifold opening for 2-layer lamination heated to 240°C. With a draft ratio of 25, it was cooled and solidified by casting with a cooling roll at 50°C. Next, apply 26W to the surface of the base layer (A). min/ ^m2 corona discharge treatment and coiling to obtain a co-extruded two-layer composite film with a base layer (A) thickness of 20 μm, a heat seal layer (B) thickness of 5 μm, and a total thickness of 25 μm. The extrapolated melting onset temperature of the heat-sealing layer (B) of the obtained composite film was 90°C, and the melting point was 125°C. Also, the resulting composite film has good film-forming properties, no film slack, and excellent blocking resistance and low-temperature heat-sealing properties.

Example 2 In addition to 95 parts by mass of ethylene-propylene-1-butene terpolymer (r-EPBC) as propylene-random copolymer (a1), 5 parts by mass of high-density polyethylene (a2) A coextruded two-layer composite film was obtained in the same manner as in Example 1, except that the resin composition made of HDPE (1) was used as the base layer (A) of the composite film. The extrapolated melting onset temperature of the heat-sealing layer (B) of the obtained composite film was 90°C, and the melting point was 125°C. Also, the resulting composite film has good film-forming properties, no film slack, and excellent blocking resistance and low-temperature heat-sealing properties.

Example 3 In addition to mixing 42 parts by mass of ethylene-propylene random copolymer (r-EPC) and 55 parts by mass of propylene-1-butene random copolymer (r-PBC(2)) as propylene-random copolymer (b1) , a resin composition composed of 3 parts by mass of HDPE (1) as high-density polyethylene (b2), and 0.3 parts by mass of silica microparticles with an average particle diameter of 3 μm as an anti-blocking agent as a sealant for a composite film Except for the layer (B), it carried out similarly to Example 2, and obtained the coextruded two-layer composite film. The extrapolated melting onset temperature of the heat-sealing layer (B) of the obtained composite film was 110°C, and the melting point was 130°C. Also, the resulting composite film has good film-forming properties, no film slack, and excellent blocking resistance and low-temperature heat-sealing properties.

Example 4 Except for 97 parts by mass of propylene-1-butene random copolymer (r-PBC(3)) as propylene-random copolymer (b1) and 3 parts by mass of HDPE as high-density polyethylene (b2) (1) Except for the sealing layer (B) which is a composite film, it carried out similarly to Example 2, and obtained the coextrusion two-layer composite film. The heat-sealing layer (B) of the obtained composite film had an extrapolated melting onset temperature of 100°C and a melting point of 125°C. Also, the resulting composite film has good film-forming properties, no film slack, and excellent blocking resistance and low-temperature heat-sealing properties.

Comparative example 1 In addition to using 97 parts by mass of the above-mentioned propylene-random copolymer (r-EPC) as a propylene-random copolymer (b1) and 3 parts by mass of HDPE (1) as a high-density polyethylene (b2), as an anti-adhesive A co-extruded two-layer composite film was obtained in the same manner as in Example 2, except that a resin composition comprising 0.3 parts by mass of silica fine particles with an average particle diameter of 3 μm was used as the sealing layer (B) of the composite film. The extrapolated melting onset temperature of the heat-sealing layer (B) of the obtained composite film was 135°C, and the melting point was 140°C. Since the extrapolated melting start temperature of the heat-sealing layer (B) is 135° C., the low-temperature heat-sealing property is poor.

Comparative example 2 In addition to using 97 parts by mass of the above-mentioned propylene-1-butene random copolymer (r-PBC(1)) as a propylene-random copolymer (b1) and 3 parts by mass of HDPE as a high-density polyethylene (b2) (1) A resin composition made of 0.3 parts by mass of silicon dioxide particles with an average particle diameter of 3 μm as an anti-blocking agent is used as the sealing layer (B) of the composite film, and the same procedure is carried out as in Example 2 to obtain a total Extrude 2-layer composite film. The extrapolated melting onset temperature of the heat-sealing layer (B) of the obtained composite film was 115°C, and the melting point was 125°C. Since the extrapolated melting start temperature of the heat-sealing layer (B) is 115° C., the low-temperature heat-sealing property is poor.

Comparative example 3 In addition to using 57 parts by mass of the above-mentioned ethylene-propylene random copolymer (r-EPC) as a propylene-random copolymer (b1), 40 parts by mass of a propylene-1-butene random copolymer (r-PBC(2) ), 3 parts by mass of HDPE (1) as high-density polyethylene (b2), and 0.3 parts by mass of silica particles with an average particle size of 3 μm as an anti-blocking agent. Except for the layer (B), it carried out similarly to Example 1, and obtained the coextruded two-layer composite film. The extrapolated melting onset temperature of the heat-sealing layer (B) of the obtained composite film was 117°C, and the melting point was 135°C. Since the extrapolated melting start temperature of the sealing layer (B) was 117° C., the low-temperature heat-sealability was poor.

Comparative example 4 Except for using a resin composition made of 100 parts by mass of ethylene-propylene-1-butene terpolymer (r-EPBC) as the base layer (A) of the composite film, it was carried out in the same manner as in Example 1. A coextruded 2-layer composite film was obtained. The resulting composite film has no high-density polyethylene (a2) mixed with the base layer (A), so the anti-blocking property is poor.

Comparative Example 5 Except having changed the high-density polyethylene (a2) of the base layer (A) of a composite film into HDPE (2), it carried out similarly to Example 2, and obtained the coextrusion two-layer composite film. The MFR of the high-density polyethylene (a2) in the base layer (A) of the obtained composite film is 10.0 g/min or more, so melt fracture occurs, the stability of film formation is poor, and the film sags are also large.

Comparative example 6 Except having changed the high-density polyethylene (b2) of the heat-sealing layer (B) of a composite film into HDPE (2), it carried out similarly to Example 2, and obtained the coextrusion two-layer composite film. The MFR of the high-density polyethylene (b2) in the heat-sealing layer (B) of the obtained composite film was more than 10.0 g/min, so melt fracture occurred, the stability of film formation was poor, and the film slack was large.

Comparative Example 7 In addition to the resin composition using 88 parts by mass of propylene-1-butene random copolymer (r-PBC (2)), 22 parts by mass of HDPE (1) as high-density polyethylene (b2) as Except for the heat-sealing layer (B) of the composite film, it carried out similarly to Example 2, and obtained the coextruded two-layer composite film. The resulting composite film has a large amount of high-density polyethylene (b2) mixed in the heat-sealing layer (B), so the lamination interface with the base layer (A) is disturbed and the film-forming stability is poor.

Comparative Example 8 In addition to using 97 parts by mass of the above-mentioned propylene-random copolymer (r-PBC (4)) as the propylene-random copolymer (b1) and 3 parts by mass of HDPE (1) as the above-mentioned high-density polyethylene (b1) , A resin composition formed of 0.3 parts by mass of silicon dioxide particles with an average particle diameter of 3 μm as an anti-blocking agent was used as the sealing layer (B) of the composite film, and co-extrusion 2 was obtained in the same manner as in Example 2. laminated film. The extrapolated melting onset temperature of the heat-sealing layer (B) of the obtained composite film was 90°C, and the melting point was 110°C. Since the melting point of the heat-sealing layer (B) is as low as 110° C., the blocking resistance is poor.

Example 5 Using the composite film described in Example 2, use a general roll-to-roll vapor deposition machine to evaporate aluminum at a vacuum of 1.3×10 ^-2 Pa to form a 40nm aluminum layer on the base layer of the composite film On the (A) side, a laminated film was obtained. The laminated film has an oxygen transmittance of 15cc/(m ² .24hr.atm) at 23°C and a humidity of 0%, a total light transmittance of 1.3%, and a gloss of 600%. good. In addition, the aluminum vapor-deposited layer is excellent in adhesiveness, ink printability, and low-temperature sealing properties.

Example 6 Using the composite film described in Example 4, use a general roll-to-roll vapor deposition machine to evaporate aluminum at a vacuum of 1.3×10 ^-2 Pa to form a 40nm aluminum layer on the base layer of the composite film On the (A) side, a laminated film was obtained. The laminated film has an oxygen transmittance of 15cc/(m ² .24hr.atm) at 23°C and a humidity of 0%, a total light transmittance of 1.3%, and a gloss of 600%. good. In addition, the aluminum vapor-deposited layer is excellent in adhesiveness, ink printability, and low-temperature sealing properties.

Comparative Example 9 Using the composite film described in Comparative Example 2, aluminum was evaporated at a vacuum degree of 1.3×10 ^-2 Pa with a general roll-to-roll vapor deposition machine, and a 40nm aluminum layer was formed on the base layer of the above-mentioned composite film. On the (A) side, a laminated film was obtained. The oxygen transmittance of this laminated film is measured. The oxygen transmittance of this laminated film is 15cc/(m ² .24hr.atm), the total light transmittance is 1.3%, and the gloss is 600% at 23°C and 0% humidity. , Good gas barrier properties, light-shielding properties, and gloss, but poor low-temperature sealing properties.

Comparative Example 10 Using the composite film described in Comparative Example 7, aluminum was evaporated at a vacuum degree of 1.3×10 ^-2 Pa with a general roll-to-roll vapor deposition machine to form a 40nm aluminum layer on the base layer of the above-mentioned composite film On the (A) side, a laminated film was obtained. In this laminated film, since the lamination interface between the base layer (A) and the heat-sealing layer (B) of the composite thin film system is disordered and the surface of the base layer (A) is rough, unevenness of the laminated aluminum vapor-deposited film occurs. The oxygen transmission rate of this laminated film was measured, and the oxygen transmission rate at 23°C and 0% humidity was 60cc/(m ² .24hr.atm), the total light transmission rate was 10%, and the glossiness was 450%. Due to the disorder of the lamination interface between the base layer (A) and the heat-sealing layer (B) of the composite film, the surface of the base layer (A) is rough, so the oxygen penetration rate is high, the adhesiveness of the aluminum vapor-deposited film layer is poor, and the gas barrier Sex, shading, gloss is also poor.

Example 7 Using the composite film described in Example 2, aluminum was evaporated at a vacuum degree of 1.3×10 ^-2 Pa with a general roll-to-roll vapor deposition machine, and a 10 nm aluminum oxide vapor-deposited layer was formed on the A laminated film was obtained on the base layer (A) side of the above composite film. The oxygen transmission rate of the above-mentioned laminated film was measured, and the oxygen transmission rate at 23°C and 0% humidity was 48cc/(m ² .24hr.atm), showing good gas barrier properties. In addition, a laminate was produced on the produced alumina by the method described in the evaluation of easy adhesion, and the adhesion strength was measured. Adhesion strength is 2.1N/15mm, and easy adhesion is good. Moreover, it is excellent in low-temperature heat-sealability.

Example 8 Using the composite film described in Example 4, aluminum was evaporated at a vacuum degree of 1.3×10 ^-2 Pa with a general roll-to-roll vapor deposition machine, and a 10 nm aluminum oxide vapor-deposited layer was formed on the A laminated film was obtained on the base layer (A) side of the above composite film. The oxygen transmission rate of the above-mentioned laminated film was measured, and the oxygen transmission rate at 23°C and 0% humidity was 48cc/(m ² .24hr.atm), showing good gas barrier properties. Also, a laminate of biaxially oriented polypropylene film was produced on the prepared alumina by the method described in the evaluation of easy adhesion, and the adhesion strength of the alumina vapor-deposited layer was measured. Adhesion strength is 2.1N/15mm, and easy adhesion is good. Moreover, it is excellent in low-temperature sealing property.

Comparative Example 11 Using the composite film described in Comparative Example 2, aluminum was evaporated at a vacuum degree of 1.3×10 ^-2 Pa with a general roll-to-roll vapor deposition machine, and a 10 nm aluminum oxide vapor-deposited layer was formed on the A laminated film was obtained on the base layer (A) side of the above composite film. The oxygen transmission rate of the above-mentioned laminated film was measured, and the oxygen transmission rate at 23°C and 0% humidity was 48cc/(m ² .24hr.atm), showing good gas barrier properties. In addition, a laminate was produced on the produced alumina by the method described in the evaluation of easy adhesion, and the adhesion strength was measured. Adhesion strength is 2.1N/15mm, good adhesion, but poor low temperature sealing.

Comparative Example 12 Using the composite thin film described in Comparative Example 7, aluminum was evaporated at a vacuum degree of 1.3×10 ^-2 Pa with a general roll-to-roll vapor deposition machine, and a 10 nm aluminum oxide vapor-deposited layer was formed on the A laminated film was obtained on the base layer (A) side of the above composite film. In this laminated film-based composite film, the laminated interface between the base layer (A) and the heat-sealing layer (B) is disturbed. This laminated film is due to the disorder of the lamination interface between the base layer (A) and the heat-sealing layer (B) of the composite film system, and the surface of the base layer (A) is rough, so the oxygen transmission rate at 23°C and 0% humidity is 78cc/(m ^2.24hr.atm ), the adhesion strength is 0.7N/15mm, the gas barrier property and the adhesion strength of the aluminum oxide vapor deposition layer are poor.

Example 9 As an organic layer, for the laminated layer on the base layer (A) of the composite film of Example 2, the ethylene content of 27 mol %, saponification degree of 99.8%, and MFR 4.0 g were melt-kneaded in separate extruders. Ethylene vinyl alcohol (hereinafter abbreviated as EVOH) ("EVAL" L171B manufactured by Kuraray Co., Ltd.) and interface adhesive resin (hereinafter abbreviated as AD) (ADMER QF500, Mitsui Chemical Co., Ltd.) using a 4-layer co-extruder at an extrusion temperature of 220°C to obtain a four-type four-layer multilayer film of EVOH/AD/base layer (A)/heat seal layer (B). The thicknesses of these are 10 μm/5 μm/20 μm/5 μm, respectively. The oxygen transmission rate of the above-mentioned laminated film was measured, and the oxygen transmission rate at 23°C and 0% humidity was 5cc/(m ² .24hr.atm), and the gas barrier property was good. Also, a laminate was produced on the produced EVOH by the method described in Adhesive Evaluation, and the adhesion strength was measured. The adhesion strength is 2.5N/15mm, the adhesion is good, and the low-temperature sealing property is also excellent.

Example 10 As an organic layer, for the laminated layer on the base layer (A) of the composite film of Example 4, the ethylene content of 27 mol %, saponification degree of 99.8%, and MFR 4.0 g were melt-kneaded in separate extruders. /10 minutes (2160g load, 210°C) of EVOH and AD, using a 4-layer co-extruder, at an extrusion temperature of 220°C, to obtain EVOH/AD/base layer (A)/heat seal layer (B) 4 types of 4-layer multilayer films. The thicknesses of these are 10 μm/5 μm/20 μm/5 μm, respectively. The oxygen transmission rate of the above-mentioned laminated film was measured, and the oxygen transmission rate at 23°C and 0% humidity was 5cc/(m ² .24hr.atm), and the gas barrier property was good. Also, a laminate was produced on the produced EVOH by the method described in Adhesive Evaluation, and the adhesion strength was measured. The adhesion strength is 2.5N/15mm, the adhesion is good, and the low-temperature sealing property is also excellent.

Comparative Example 13 As an organic layer, for the laminated layer on the base layer (A) of the composite film of Comparative Example 2, an ethylene content of 27 mol%, a degree of saponification of 99.8%, and MFR of 4.0 g were melt-kneaded in separate extruders. Ethylene vinyl alcohol (hereinafter abbreviated as EVOH) ("EVAL" L171B manufactured by Kuraray Co., Ltd.) and interface adhesive resin (hereinafter abbreviated as AD) (ADMER QF500, Mitsui Chemical Co., Ltd.) using a 4-layer co-extruder at an extrusion temperature of 220°C to obtain a four-type four-layer multilayer film of EVOH/AD/base layer (A)/heat seal layer (B). The thicknesses of these are 10 μm/5 μm/20 μm/5 μm, respectively. The oxygen transmission rate of the above-mentioned laminated film was measured, and the oxygen transmission rate at 23°C and 0% humidity was 5cc/(m ² .24hr.atm), and the gas barrier property was good. Also, a laminate was produced on the produced EVOH by the method described in Adhesive Evaluation, and the adhesion strength was measured. Adhesion strength is 2.5N/15mm, good adhesion, but poor low temperature sealing.

Comparative Example 14 Lamination as an organic layer on the base layer (A) of the composite film described in Comparative Example 7 was carried out in the same manner as in Example 10 above, and an EVOH layer/AD layer was laminated. The oxygen transmission rate of the above-mentioned laminated film was measured, and the oxygen transmission rate at 23°C and 0% humidity was 5cc/(m ² .24hr.atm), and the gas barrier property was good. However, because the composite film is the base layer (A) and The lamination interface of the heat-sealing layer (B) is disordered, the surface of the base layer (A) is rough, and the adhesion strength of the EVOH layer is as low as 0.7N/15mm.

Example 11 As the ease of printing on the base layer (A) of the composite film of Example 2, an organic-inorganic substance was produced by the following method to obtain a laminated film.

＜Organic component solution＞ As the vinyl alcohol-based resin, modified polyvinyl alcohol containing a γ-butyrolactone structure having a carbonyl group in the ring structure (hereinafter also referred to as modified PVA for short. The degree of polymerization is 1,700 and the degree of saponification is 93.0%), It poured into the solvent of water/isopropanol=97/3 by mass ratio, heated and stirred at 90 degreeC, and obtained the organic component solution of 10 mass % of solid content.

＜Inorganic component solution＞ Into a solution obtained by mixing 11.2 g of Ethyl Silicate 40 (an average pentameric ethyl silicate oligomer) manufactured by COLCOAT Co., Ltd. as a linear polysiloxane, and 16.9 g of methanol, drop 7.0 g of 0.06N hydrochloric acid aqueous solution to obtain pentameric ethyl silicate hydrolyzate.

<Organic and inorganic substances> _Mix /stir the _modified PVA and The inorganic component solution was diluted with water to obtain a coating solution having a solid content of 12% by mass. This coating solution was applied on the base layer (A) of the composite film described in Example 2, and dried to form an organic-inorganic substance with a thickness of 0.4 μm, thereby producing a laminated film. The five-stage evaluation of the printability of this laminated film was rated as five grades, which was good.

Example 12 As the ease of printing on the base layer (A) of the composite film of Example 4, organic and inorganic substances were formed in the same manner as in Example 12, and a laminated film was produced. The five-stage evaluation of the printability of this laminated film was rated as five grades, which was good. Moreover, it is also excellent in low-temperature sealing property.

Comparative Example 15 As the ease of printing on the base layer (A) of the composite film of Comparative Example 2, organic and inorganic substances were formed in the same manner as in Example 12, and a laminated film was produced. The five-step evaluation of the printability of this laminated film was good at rank 5, but poor in low-temperature sealing properties.

Comparative Example 16 As the ease of printing on the base layer (A) of the composite film described in Comparative Example 7, an organic-inorganic mixture was formed in the same manner as in Example 12, and a laminated film was produced. Since the surface of the base layer (A) was rough in this laminated film, the evaluation of printability was grade 3, and the printability was poor.

[Table 1] Melting point °C Extrapolated melting onset temperature °C Density g/cm ³ MFR g/min unit Example 1 2 3 4 functional endowment layer none none none none Basal layer (A) r-EPC 141 135 0.900 7 parts by mass 95 - - - r-EPBC 140 134 0.900 7 parts by mass - 95 95 95 HDPE(1) 134 - 0.960 7.5 parts by mass 5 5 5 5 Heat seal layer (B) r-EPC 141 135 0.900 7 parts by mass - - 42 - r-PBC(1) 125 115 0.900 7 parts by mass - - - - r-PBC(2) 125 90 0.900 7 parts by mass 97 97 55 - r-PBC(3) 125 100 0.900 7 parts by mass - - - 97 HDPE(1) 134 - 0.960 7.5 parts by mass 3 3 3 3 Extrapolated melting onset temperature of heat seal layer (B) [°C] 90 90 110 100 Melting point of heat seal layer (B) [°C] 125 125 130 125 film stability ○ ○ ○ ○ Anti-adhesion ○ ○ ○ ○ Heat seal strength [N/15mm] 120°C 8 7 7 6 Slack evaluation ○ ○ ○ ○ r-EPC: ethylene-propylene random copolymer (melting point 141°C, extrapolated melting onset temperature 135°C, ethylene content 4 mol%) r-EPBC: ethylene-propylene-1-butene terpolymer (melting point 140°C , the extrapolated melting onset temperature is 134°C, the ethylene content is 2 mol%, and the butene content is 5 mol%) r-PBC (1): Propylene·1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 115°C, butene content 17 mol%) r-PBC(2): Propylene・1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 90°C, butene content 19 mol%) r- PBC(3): Propylene-1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 100°C, butene content 18 mol%) HDPE (1): High-density polyethylene (melting point 134°C, density 0.960g/cm ³ )

[Table 2] Melting point °C Extrapolated melting onset temperature °C Density g/cm ³ MFR g/min unit comparative example 1 2 3 4 5 6 7 8 functional endowment layer none none none none none none none none Basal layer (A) r-EPC 141 135 0.900 7 parts by mass - - - - - - - - r-EPBC 140 134 0.900 7 parts by mass 95 95 95 100 95 95 95 95 HDPE(1) 134 - 0.960 7.5 parts by mass 5 5 5 - - 5 5 5 HDPE(2) 134 - 0.963 12 parts by mass - - - - 5 - - - Heat seal layer (B) r-EPC 141 135 0.900 7 parts by mass 97 - 57 - - - - - r-PBC(1) 125 115 0.900 7 parts by mass - 97 - - - - - - r-PBC(2) 125 90 0.900 7 parts by mass - - 40 97 97 97 78 - r-PBC(3) 125 100 0.900 7 parts by mass - - - - - - - - r-PBC(4) 110 90 0.900 7 parts by mass - - - - - - - 97 HDPE(1) 134 - 0.960 7.5 parts by mass 3 3 3 3 3 - twenty two 3 HDPE(2) 134 - 0.952 12 parts by mass - - - - - 3 - - Extrapolated melting onset temperature of heat seal layer (B) [°C] 135 115 117 90 90 90 90 90 Melting point of heat seal layer (B) [°C] 140 125 135 125 125 125 127 110 film stability ○ ○ ○ ○ x x x ○ Anti-adhesion ○ ○ ○ x ○ ○ ○ x Heat seal strength [N/15mm] 120℃ 0 1 2 8 8 8 8 9 Slack evaluation ○ ○ ○ ○ x x ○ ○ r-EPC: ethylene-propylene random copolymer (melting point 141°C, extrapolated melting onset temperature 135°C, ethylene content 4 mol%) r-EPBC: ethylene-propylene-1-butene terpolymer (melting point 140°C , the extrapolated melting onset temperature is 134°C, the ethylene content is 2 mol%, and the butene content is 5 mol%) r-PBC (1): Propylene·1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 115°C, butene content 17 mol%) r-PBC(2): Propylene・1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 90°C, butene content 19 mol%) r- PBC(3): Propylene・1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 100°C, butene content 18 mol%) r-PBC(4): Propylene・1-butene random copolymer (melting point 110°C, extrapolated melting start temperature 90°C, butene content 25 mol%) HDPE (1): high-density polyethylene (melting point 134°C, density 0.960g/cm ³ ) HDPE (2): high density Polyethylene (melting point 134°C, density 0.963g/cm ³ )

[Table 3-1] Melting point °C Extrapolated melting onset temperature °C Density g/cm ³ MFR g/min unit Example 5 Example 6 Comparative Example 9 Comparative Example 10 Example 7 Example 8 Comparative Example 11 Comparative Example 12 functional endowment layer functional layer - - - - Inorganic layer type Evaporated aluminum Evaporated alumina Laminate thickness μm 0.04 0.01 Basal layer (A) r-EPC 141 135 0.900 7 parts by mass - - - - - - - - r-EPBC 140 134 0.900 7 parts by mass 95 95 95 88 95 95 95 88 HDPE(1) 134 - 0.960 7.5 parts by mass 5 5 5 12 5 5 5 12 Heat seal layer (B) r-EPC 141 135 0.900 7 parts by mass - - - - - - - - r-PBC(1) 125 115 0.900 7 parts by mass - - 97 - - - 97 - r-PBC(2) 125 90 0.900 7 parts by mass 97 - - 97 97 - - 97 r-PBC(3) 125 100 0.900 7 parts by mass - 97 - - - 97 - HDPE(1) 134 - 0.960 7.5 parts by mass 3 3 3 3 3 3 3 3 Extrapolated melting onset temperature of heat seal layer (B) [°C] 90 100 115 90 90 100 115 90 Melting point of heat seal layer (B) [°C] 125 125 125 125 125 125 125 125 Oxygen transmission rate (23℃, 0%RH) cc/(m ² .24hr.atm) 15 15 15 60 48 48 48 78 Total light transmittance (shading) % 1.3 1.3 1.3 1.3 - - - - Surface gloss (evaporation surface) % 600 600 600 300 - - - - Adhesion Strength (Easy Adhesion) N/15mm 1 1 1 0.5 2.1 2.1 2.1 0.7 Heat seal strength 120°C N/15mm 7 6 1 8 7 6 1 8 Ease of printing class - - - - - - - - r-EPC: ethylene-propylene random copolymer (melting point 141°C, extrapolated melting onset temperature 135°C, ethylene content 4 mol%) r-EPBC: ethylene-propylene-1-butene terpolymer (melting point 140°C , the extrapolated melting onset temperature is 134°C, the ethylene content is 2 mol%, and the butene content is 5 mol%) r-PBC (1): Propylene·1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 115°C, butene content 17 mol%) r-PBC(2): Propylene・1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 90°C, butene content 19 mol%) r- PBC(3): Propylene-1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 100°C, butene content 18 mol%) HDPE (1): High-density polyethylene (melting point 134°C, density 0.960g/cm ³ ) EVOH: Ethylene vinyl alcohol with an ethylene content of 27 mol%, a degree of saponification of 99.8%, and an MFR of 4.0g/10 minutes (under a load of 2160g, at 210°C) AD: Interface adhesive resin (maleic anhydride modified Polypropylene, "ADMER" QF500)

[Table 3-2] Melting point °C Extrapolated melting onset temperature °C Density g/cm ³ MFR g/min unit Example 9 Example 10 Comparative Example 13 Comparative Example 14 Example 11 Example 12 Comparative Example 15 Comparative Example 16 functional endowment layer functional layer - - - - organic layer organic inorganic layer type EVOH/AD Modified PVA+silane Laminate thickness μm 10/5 2 Basal layer (A) r-EPC 141 135 0.900 7 parts by mass - - - - - - - - r-EPBC 140 134 0.900 7 parts by mass 95 95 95 95 95 95 95 88 HDPE(1) 134 - 0.960 7.5 parts by mass 5 5 5 5 5 5 5 12 Heat seal layer (B) r-EPC 141 135 0.900 7 parts by mass - - - - - - - - r-PBC(1) 125 115 0.900 7 parts by mass - - 97 - - - 97 - r-PBC(2) 125 90 0.900 7 parts by mass 97 - - 78 97 - - 97 r-PBC(3) 125 100 0.900 7 parts by mass - 97 - - 97 - - HDPE(1) 134 - 0.960 7.5 parts by mass 3 3 3 twenty two 3 3 3 3 Extrapolated melting onset temperature of heat seal layer (B) [°C] 90 100 115 90 90 100 115 90 Melting point of heat seal layer (B) [°C] 125 125 125 125 125 125 125 125 Oxygen transmission rate (23℃, 0%RH) cc/(m ² .24hr.atm) 5 5 5 5 - - - - Total light transmittance (shading) % - - - - - - - - Surface gloss (evaporation surface) % - - - - - - - - Adhesion Strength (Easy Adhesion) N/15mm 2.5 2.5 2.5 0.7 - - - - Heat seal strength 120°C N/15mm 7 6 1 8 7 6 1 8 Ease of printing class - - - - 5 5 5 3 r-EPC: ethylene-propylene random copolymer (melting point 141°C, extrapolated melting onset temperature 135°C, ethylene content 4 mol%) r-EPBC: ethylene-propylene-1-butene terpolymer (melting point 140°C , the extrapolated melting onset temperature is 134°C, the ethylene content is 2 mol%, and the butene content is 5 mol%) r-PBC (1): Propylene·1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 115°C, butene content 17 mol%) r-PBC(2): Propylene・1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 90°C, butene content 19 mol%) r- PBC(3): Propylene-1-butene random copolymer (melting point 125°C, extrapolated melting onset temperature 100°C, butene content 18 mol%) HDPE (1): High-density polyethylene (melting point 134°C, density 0.960g/cm ³ ) EVOH: Ethylene vinyl alcohol with an ethylene content of 27 mol%, a degree of saponification of 99.8%, and an MFR of 4.0g/10 minutes (under a load of 2160g, at 210°C) AD: Interface adhesive resin (maleic anhydride modified Polypropylene, "ADMER" QF500) [Possibility of industrial use]

By making the composite film of the present invention, there are few seal breakages and tunneling phenomena in heat sealing, good sealing performance, and excellent processability when the function-imparting layer is laminated on the surface of the film. Laminated on the surface of the base layer (A) and further laminated with other base materials to form a packaging laminate can have a high degree of high-speed filling suitability, and achieve excellent productivity without problems during packaging filling.

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Claims (10)

A composite film, which is a composite film having at least two layers of a base layer (A) and a heat-sealing layer (B), wherein, The base layer (A) is composed of 100 parts by mass of propylene-random copolymer (a1) mixed with 1 to 10 parts by mass of high-density polyethylene (a2) with a melt flow rate at 190°C of less than 10 g/10 minutes. made of composition, The heat-sealing layer (B) is made of mixing 1 to 20 parts by mass of high-density polyethylene (b2) with a melt flow rate at 190°C of less than 10 g/10 minutes in 100 parts by mass of propylene-random copolymer (b1). Made of resin composition, the resin composition of the heat-sealing layer (B) is derived from the differential scanning calorimetry measurement of JIS K 7121 (1987), and the extrapolated melting start temperature (Tim) is below 110°C, and the melting point is 120°C above. The composite film according to claim 1, wherein the propylene-random copolymer (a1) of the base layer (A) is selected from the group consisting of ethylene-propylene random copolymer, propylene-1-butene random copolymer, and ethylene-propylene・One or more kinds of groups of 1-butene terpolymers. The composite film as in claim 1, wherein the propylene-random copolymer (b1) of the heat-sealing layer (B) is selected from the group consisting of ethylene-propylene random copolymer, propylene-1-butene random copolymer, and ethylene-propylene random copolymer, and ethylene-propylene random copolymer. One or more types of propylene-1-butene terpolymer group. The composite film according to claim 1, wherein the base layer (A) contains 30% by mass or less of the components of the heat-sealing layer (B) as self-recycling components of the composite film. Such as the composite film of claim 1, wherein the biaxially stretched polypropylene film with a thickness of 20 μm or more is laminated on the composite film by dry lamination using an adhesive, and the heat-sealing layer (B) surfaces of the composite film are overlapped with each other, at 120 The heat seal strength when heat sealing is performed by heating on one side is 6N/15mm or more. A laminated film, which is provided with a function imparting layer imparting a specific function on the surface of the base layer (A) of the composite film as claimed in claim 1. The laminated film according to claim 6, wherein the specific function is at least one selected from the group consisting of gas barrier properties, light-shielding properties, gloss properties, wettability, ease of adhesion, and ease of printing. The laminated film according to Claim 6, wherein the oxygen permeability at 23°C and 0% humidity is 50cc/(m ² .24h.atm) or less. A laminated body formed by laminating the laminated film according to Claim 6 and another substrate, and the function imparting layer is laminated so as to be on the side of the other substrate. The laminate according to claim 9, wherein the other substrate is a biaxially stretched polypropylene film using a polypropylene resin with a stereoregularity of 90 to 98%.