JP5074363B2 - Packaging film - Google Patents

Description

  The present invention is a packaging film mainly containing a lactic acid-based polymer, which is a resin derived from a natural plant, and is housed in a box equipped with a cutter blade, and is used in homes and the like. The present invention relates to a packaging film that can be suitably used as a film.

A so-called “wrap film” (also referred to as a “small roll wrap film” in the present invention to distinguish it from a commercial stretch wrap film) is used as a film for packaging cooked foods on earthenware or plastic containers. Yes.
Such a small wrap film is usually stored in a state of being wound around a cylinder in a paper box having a cutter blade. When packaging, pull the film out of the paper box to cover the food, press the film against the cutter blade provided in the paper box, open a perforated hole in the film with this cutter blade, and tear the film The film is cut so as to propagate the tear in the width direction, and the end of the film is used in close contact with the container for packaging. For this reason, in addition to transparency, the small roll wrap film is required to have various properties such as adhesion to the container and cut suitability when the film drawn from the box is cut.

Many of the wrapping films currently on the market are films mainly composed of stretched polyvinylidene chloride resin, extruded polyethylene resin, plasticized polyvinyl chloride resin, poly-4-methylpentene-1 system A film mainly composed of resin or the like.
In recent years, the effective use of depleting resources has become important due to increasing environmental problems, and natural plant-derived resins have attracted attention. Above all, lactic acid polymers are natural plant-derived resins obtained from starches such as corn and potatoes, and are not only mass-produced but also have excellent transparency, and are attracting attention as raw materials for packaging films. Research and development of packaging films using lactic acid polymers as raw materials has been conducted.

For example, in Patent Document 1, cut suitability, packaging suitability, which are characteristics of a household wrap film,
As a biodegradable wrap film having heat resistance at the same time, a storage elastic modulus value at 40 ° C. measured at a frequency of 10 Hz and a strain of 0.1% by a dynamic viscoelasticity measurement method of JIS K-7198 A method is 100 MPa. A lactic acid resin composition in a range of ˜3 GPa, a storage elastic modulus at 100 ° C. in a range of 30 MPa to 500 MPa, and a loss tangent (tan δ) peak value in a range of 0.1 to 0.8, For example, a biodegradable wrap film containing a lactic acid resin composition containing a lactic acid polymer and a plasticizer in a mass ratio of 60: 1 to 99: 1 as a main component is disclosed.

  In Patent Document 2, the outermost layer is a layer mainly composed of an olefin polymer, and a layer mainly composed of polylactic acid (lactic acid polymer) between the layers mainly composed of the olefin polymer. A shrink sheet-like material having at least one layer is disclosed, and an adhesive layer made of an acrylic-modified polyethylene resin is provided between a layer mainly composed of an olefin polymer and a layer mainly composed of polylactic acid. It is also disclosed that it can intervene.

However, as in Patent Document 1, in a system in which a plasticizer is blended with a lactic acid polymer, the glass transition point (Tg) of the lactic acid polymer is lowered to near room temperature, so that it is rapidly cooled by a casting method or the like. Then, when a wrap film is formed, the sheet is kept amorphous and the elastic modulus is lowered. If the wrap film is wound as it is, the roll may be blocked.
In addition, when the lactic acid polymer is exposed on the front and back layers of the wrap film, the molecular weight of the lactic acid polymer decreases with time due to hydrolysis, and thus there is a problem that blocking is more likely to occur.
Furthermore, in order to function as a small roll wrap film, as described above, in addition to transparency, various properties such as adhesion to the container and cut suitability when cutting the drawn film are required. It is not easy to produce a packaging film satisfying such various properties using as a main raw material, and in particular, in a multilayer film having a multilayer structure as in Patent Document 2, the adhesion to a container is improved. Making an excellent film has never been easier.

  Therefore, in packaging films that use lactic acid polymers as one of the main raw materials, there is no blocking even when the formed film is stored in a rolled state, and the degree of molecular weight reduction of lactic acid polymers is reduced. The following packaging film has been proposed as a packaging film that can satisfy various properties required for a small roll film (Patent Document 3).

  That is, Patent Document 3 discloses a packaging film composed of a laminated film of five or more layers having at least a surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer in this order. As a main component, the intermediate layer contains a lactic acid polymer as a main component, both adhesive layers contain an adhesive resin as a main component, and the adhesive resin is a modified olefin polymer. Or a copolymer of a soft aromatic hydrocarbon and a conjugated diene hydrocarbon, a hydrogenated derivative of these copolymers, or an ethylene-vinyl acetate copolymer having a vinyl acetate content of 30 to 80% by mass Alternatively, a lactic acid polymer, an acrylic block copolymer having a polymer block mainly composed of an acrylate unit and a polymer block mainly composed of a methacrylic ester unit, Any one of the lactic acid-acrylic mixed resin, or packaging film which is a resin composed of two or more thereof is disclosed having.

WO / 2005/082981 JP 2002-19053 A WO / 2008/004510

  As disclosed in Patent Document 3, a packaging film is formed from a laminated film having an adhesive layer between a surface layer mainly composed of an olefin polymer and an intermediate layer mainly composed of a lactic acid polymer. When producing, the important issue is ensuring the transparency of the adhesive layer.

  Therefore, the present invention further improves a packaging film having a laminated structure including an adhesive layer between a surface layer mainly composed of an olefin polymer and an intermediate layer mainly composed of a lactic acid polymer. In addition, even when stored in a state where the formed film is wound, blocking does not occur, the degree of decrease in the molecular weight of the lactic acid polymer can be reduced, and various properties required for the small-wrap film can be obtained. Moreover, the present invention intends to provide a new packaging film that can increase the transparency of the adhesive layer.

In view of such problems, the present invention provides both surface layers composed of a surface layer forming composition containing an olefin polymer (A) as a main component, and an intermediate layer formation containing a lactic acid polymer (B) as a main component. An adhesive layer comprising an intermediate layer made of the composition, and containing an olefin polymer (A), a lactic acid polymer (B) and a graft copolymer (D) as main components between the surface layer and the intermediate layer A packaging film provided with an adhesive layer comprising a forming composition,
The graft copolymer (D) is ethylene-α-olefin copolymer rubber, ethylene-α-olefin-nonconjugated polyene copolymer rubber, ethylene- (meth) acrylic acid alkyl ester copolymer, ethylene-acetic acid. A thermoplastic resin segment as a trunk component formed from one or more selected from the group consisting of vinyl copolymers, acid-modified olefin rubbers, olefin thermoplastic elastomers, and styrene thermoplastic elastomers; The present invention proposes a packaging film characterized by being a graft copolymer provided with an acrylic polymer segment as a branch component formed from a seed or two or more acrylic monomers.

If it is a film for packaging provided with such a configuration, since it has both surface layers mainly composed of the olefin polymer (A), it can be stored in a state in which the formed film is wound. The degree of molecular weight reduction of the lactic acid polymer can be reduced without blocking.
Further, by blending the olefin polymer (A) and the lactic acid polymer (B) with the graft copolymer (D), the compatibility between the olefin polymer (A) and the lactic acid polymer (B) is improved. Increases the transparency of the adhesive layer.
Moreover, since it can be made to contain additives, such as an antifogging agent and an adhesive, in both surface layers by setting it as the laminated film comprised from at least 5 layers, the antifogging property, adhesiveness, etc. of a film are improved. You can also.

  Furthermore, if the adhesive layer forming composition is composed of a surface layer forming composition, an intermediate layer forming composition, and a graft copolymer (D), trimming loss can be used as a raw material for the adhesive layer forming composition. Therefore, the packaging film can be manufactured at a lower cost.

  Hereinafter, a packaging film (hereinafter referred to as “the packaging film”) as an example of the embodiment of the present invention will be described. However, the scope of the present invention is not limited to the embodiments described below.

  The packaging film is a laminated film composed of at least five layers, both surface layers made of a surface layer forming composition containing an olefin polymer (A) as a main component, and a lactic acid polymer (B And an intermediate layer comprising an intermediate layer forming composition containing as a main component, and an adhesive layer forming containing as main components an olefin polymer (A), a lactic acid polymer (B) and a graft copolymer (D) A packaging film including an adhesive layer made of the composition.

  In this section, first, the olefin polymer (A) and the lactic acid polymer (B) will be described, then the surface layer, the intermediate layer, and the adhesive layer will be described, and then the laminated structure and physical properties of the packaging film will be described. Features, manufacturing methods, etc. will be described.

<Olefin polymer (A)>
The olefin polymer (A) is a main component of the surface layer and the adhesive layer. The olefin polymers (A) in both layers may be of different types, but from the viewpoint of reducing the difference in melt viscosity between layers, it is preferable to use the same type, particularly the same resin.

Examples of olefin polymers include ethylene polymers, butylene polymers, propylene polymers such as polypropylene and ethylene-propylene copolymers, poly-4-methylpentene, polybutene, and ethylene-vinyl acetate copolymers. be able to. These resins may be one type of the resins listed above, or may be a mixed resin composed of two or more types of resins.
As these olefin polymers, polyolefin thermoplastic elastomers in which ethylene / propylene rubber or the like is dispersed and composited can also be used.

  Among these, from the viewpoints of flexibility and transparency, mechanical properties and moldability, it is preferable to use a polyethylene resin, a polypropylene resin, or a mixture thereof. Among them, a propylene-ethylene random copolymer is preferably used because of its low crystallinity, balance between flexibility and heat resistance, and industrial availability at a relatively low cost.

Furthermore, among the above, the olefin polymer (A), particularly the olefin polymer (A) constituting the adhesive layer, preferably has a crystallization heat amount ΔHc of 5 to 80 J / g.
In this packaging film, since the mixed resin of the olefin polymer (A) and the lactic acid polymer (B) forms the main component of the adhesive layer, the mixed resin needs to have excellent transparency.
Transparency in the polymer blend is affected by the particle size of the dispersed phase and the average refractive index difference between the dispersed phase and the matrix phase. When the particle size of the dispersed phase is smaller than the wavelength of visible light, the resin composition exhibits excellent transparency. On the other hand, when the particle size of the dispersed phase is larger than the wavelength of visible light, the transparency is better as the average refractive index difference between the dispersed phase and the matrix phase is smaller. In general, the transparency of the resin composition and film obtained from the olefin polymer (A) and the lactic acid polymer (B) is greatly influenced by the difference in the average refractive index of both components.
Since the refractive index of a general olefin polymer is higher than that of a lactic acid polymer and the difference in refractive index between the two is large, a mixture of an olefin polymer (A) and a lactic acid polymer (B) is mixed. The transparency of the resin is not preferred. Therefore, in this packaging film, by using an olefin polymer having a lower crystallization heat amount than a general olefin polymer, the difference in refractive index from the lactic acid polymer (B) is reduced. Transparency of the mixed resin comprising the polymer (A) and the lactic acid polymer (B) is enhanced.
Therefore, from the viewpoint of transparency, the crystallization heat amount of the olefin polymer (A) is preferably 5 to 80 J / g, particularly 5 to 60 J / g, and particularly 5 to 40 J / g. Is particularly preferred.

On the other hand, when this packaging film is used as a small roll film, heat resistance is required because it may be heated in a microwave oven or the like. In order to improve heat resistance, it is preferable that the heat of crystallization is high, and it is particularly preferable that the heat of crystallization of the olefin polymer (A) constituting the surface layer is high.
Therefore, when the same olefin polymer (A) is used in the surface layer and the adhesive layer, the crystallization heat amount of the olefin polymer (A) is 20 in consideration of both ensuring transparency and heat resistance. It is preferably ˜80 J / g, and more preferably 30 to 60 J / g.

  The crystallization heat amount ΔHc of the olefin polymer (A) can be measured using a differential scanning calorimeter. Specifically, it can be expressed as the amount of heat when the temperature is raised to 200 ° C. at a heating rate of 10 ° C./min, held at 200 ° C. for 5 minutes, and then lowered to room temperature at a cooling rate of 10 ° C./min.

The refractive index of the olefin polymer (A) is preferably 1.48 to 1.49.
As described above, the transparency of the packaging film is greatly affected by the difference in average refractive index between the olefin polymer (A) and the lactic acid polymer (B). In general, the average refractive index of lactic acid polymers is about 1.45 to 1.46, and the average refractive index of olefin polymers is about 1.50 to 1.51, so the absolute value of the difference is 0.00. It is about 04 to 0.06. When this value exceeds 0.04, the resulting resin composition and film tend to become cloudy.
On the other hand, if the olefin polymer (A) is a relatively low crystalline olefin polymer and the average refractive index is 1.48 to 1.49, the lactic acid polymer (B) The average refractive index difference is small, and the transparency of the mixed resin composed of the olefin polymer (A) and the lactic acid polymer (B) can be enhanced. When the absolute value of the average refractive index difference between the olefin polymer (A) and the lactic acid polymer (B) is 0.04 or less, a resin composition and a film having further excellent transparency can be obtained. From this viewpoint, the absolute value of the average refractive index difference between the olefin polymer (A) and the lactic acid polymer (B) is more preferably 0.03 or less, and more preferably 0.02 or less. preferable.
Incidentally, the average refractive index of an olefin polymer is affected by its crystallinity, and the olefin polymer having a lower crystallization heat quantity ΔHc tends to decrease.

  As such an olefin polymer (A), from the viewpoints of flexibility and transparency, mechanical properties and moldability, an ethylene polymer, a propylene polymer having a crystallization heat amount ΔHc in the above range, or It is preferable to use a mixture thereof.

In the case of an olefin polymer, as a means for setting the crystallization heat amount ΔHc in the above range, a method of making a copolymer, a method of reducing stereoregularity, and the like can be suitably employed.
As the copolymer, a propylene-α-olefin copolymer or an ethylene-α-olefin copolymer is preferably used. Preferred examples of the α-olefin include those having 2 to 20 carbon atoms such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like. It can be illustrated. In this case, the α-olefin to be copolymerized may be used alone or in combination of two or more.
Specifically, it consists of a propylene-ethylene random copolymer, a propylene-ethylene-butene-1 copolymer and a polypropylene-based elastomer, or a combination of two or more of these. It is preferable to use a mixed resin.
Among them, a propylene-ethylene random copolymer is particularly preferable because of its low crystallinity, balance between flexibility and heat resistance, and industrial availability at a relatively low cost.

  In these copolymers, the content of α-olefin, particularly ethylene, is preferably 1.0% by mass or more from the viewpoints of crystallization heat quantity, flexibility, transparency, etc., among which 2.0-15% by mass. % Is particularly preferred. However, when the content of α-olefin, particularly ethylene, is increased, the refractive index tends to increase. When the content of α-olefin, particularly ethylene, exceeds 50% by mass, the refractive index becomes too high, which is not preferable.

  The melt flow rate (MFR) of the olefin polymer (A) is not particularly limited, but usually MFR (JISK7210, temperature: 230 ° C., load: 21.2 N) is 0.2 g / 10 min. As mentioned above, Preferably, it is 0.5-18 g / 10min, and it is more preferable that it is 1-15g / 10min.

  The production method of the olefin polymer (A) is not particularly limited, and a known polymerization method using a known olefin polymerization catalyst, for example, a multisite catalyst represented by a Ziegler-Natta type catalyst or a metallocene system. Examples include a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like using a single site catalyst typified by a catalyst, and a bulk polymerization method using a radical initiator.

<Lactic acid polymer (B)>
The lactic acid polymer (B) is a main component of the intermediate layer and the adhesive layer. The lactic acid polymers (B) in both layers may be of different types, but from the viewpoint of reducing the difference in melt viscosity between layers, it is preferable to use the same type, particularly the same resin.

As the lactic acid polymer (B), poly (L-lactic acid) whose structural unit is L-lactic acid, poly (D-lactic acid) whose structural unit is D-lactic acid, structural units that are L-lactic acid and D-lactic acid Poly (DL-lactic acid), a mixture thereof, or a copolymer containing these can be used.
However, poly (L-lactic acid) or poly (D-lactic acid) referred to here is ideally a polymer comprising 100% of L-lactic acid or D-lactic acid, but inevitably different lactic acid is included in the polymerization. Since there is a possibility, what contains 98% or more of L-lactic acid or D-lactic acid is intended.

The ratio (molar ratio) of D-lactic acid (D-form) to L-lactic acid (L-form) in the lactic acid-based polymer (B) is L-form / D-form = 100/0 to 85/15, or L-form / D. It is preferable that it is 0 / 100-15 / 85, More preferably, L-form / D-form = 99.5 / 0.5-85 / 15 or L-form / D-form = 0.5 / 99.5 15/85. If it exists in this range, the heat resistance of the film obtained will not be impaired.
In addition, you may blend the lactic acid-type polymer from which the copolymerization ratio of L body and D body differs. In that case, it is preferable that the average value of the copolymerization ratios of the L-form and D-form of a plurality of lactic acid polymers falls within the above range.

  From the viewpoint of suppressing bleed-out of plasticizers and the like, it is preferable that the crystallinity of the lactic acid polymer is low. Therefore, polylactic acid having a lower crystallinity than poly (L-lactic acid), such as poly (D-lactic acid), It is preferable to use poly (DL-lactic acid) or a mixture thereof as a main component. The ratio of D-form to L-form in the poly (DL-lactic acid) or the mixture is L-form / D-form = 85/15 to 95/5, or L-form / D-form = 5/95 to 15/85. Is preferred. If it exists in this range, since the crystallinity of a lactic acid-type polymer is low, bleeding out, such as a plasticizer, can be suppressed.

  Also, considering the balance between suppression of bleeding out of plasticizers and the like, heat resistance and cutability (depending on the type of olefin polymer (A) which is the main component of both surface layers), D Poly (L-lactic acid) having a body content of 0.5 to 5 mol% (hereinafter sometimes abbreviated as “B-1 component”) and poly (D, L-lactic acid) having a D body content of 10 to 15 mol% It is preferable to use a mixed resin composition (hereinafter sometimes abbreviated as “B-2 component”). Among them, the mixing mass ratio of the component (B-1) and the component (B-2) is (B− 1) / (B-2) = 10/90 to 80/20 is particularly preferable, and among them, (B-1) / (B-2) = 50/50 to 70/30 is particularly preferable. Is more preferable.

  The lactic acid-based polymer may contain other hydroxycarboxylic acid or the like as a small amount of a copolymer component, and may contain a small amount of a chain extender residue.

As a polymerization method for the lactic acid-based polymer, a condensation polymerization method, a ring-opening polymerization method, and other known polymerization methods can be employed.
For example, in the condensation polymerization method, L-lactic acid, D-lactic acid, or a mixture thereof can be directly subjected to dehydration condensation polymerization to obtain a lactic acid polymer having an arbitrary composition.
In the ring-opening polymerization method (lactide method), lactide, which is a cyclic dimer of lactic acid, has an arbitrary composition and crystallinity using an appropriate catalyst while using a polymerization regulator or the like as necessary. A lactic acid polymer can be obtained.
Lactide includes L-lactide, which is a dimer of L-lactic acid, D-lactide, which is a dimer of D-lactic acid, or DL-lactide composed of L-lactic acid and D-lactic acid. Accordingly, a lactic acid polymer having any composition and any crystallinity can be obtained by mixing and polymerizing.

  The mass average molecular weight of the lactic acid polymer is preferably in the range of 50,000 to 400,000, more preferably in the range of 100,000 to 250,000. If the mass average molecular weight of the lactic acid polymer is 50,000 or more, practical properties such as mechanical properties and heat resistance can be secured, and if it is 400,000 or less, the melt viscosity is too high and the molding processability may be inferior. Absent.

  As the lactic acid polymer used for the packaging film, a commercially available lactic acid polymer can be used. For example, a brand name “Lacia” series (manufactured by Mitsui Chemicals), a brand name “Nature Works” series (manufactured by NatureWorks), a brand name “U′z series” (manufactured by Toyota Motor Corporation), and the like can be given.

<Surface layer>
The inner and outer surface layers (hereinafter simply referred to as “surface layer”) can be formed from a surface layer forming composition containing the olefin polymer (A) as a main component.

  In addition to the above-mentioned olefin polymer (A), the surface layer can enhance the antifogging property of the film by blending an antifogging agent, and further improve the adhesion of the film by blending an adhesive. Can be increased.

More specifically, the following various additives can be appropriately blended in order to impart performances such as antifogging property, antistatic property, slipperiness and adhesiveness.
For example, an aliphatic alcohol fatty acid ester which is a compound of an aliphatic alcohol having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms and a fatty acid having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms, specifically, Monoglycerin oleate, polyglycerin oleate, polyglycerin polyricinoleate, glycerin triricinoleate, glyceryl acetyl ricinoleate, polyglyceryl stearate, polyglyceryl laurate, methyl acetyl lysylate, ethyl acetyl lysylate, butyl acetyl lysylate, Propylene glycol oleate, propylene glycol laurate, pentaerythritol oleate, polyethylene glycol oleate, polypropylene glycol oleate, sorbitan oleate, sorbitan laurate, polyethylene glycol Sorbitan oleate, polyethylene glycol sorbitan laurate, and the like, and polyalkylene ether polyols, specifically, polyethylene glycol, polypropylene glycol, etc., and at least one compound selected from paraffinic oil and the like constitute various types. 0.1 to 12 parts by mass can be added to 100 parts by mass of the resin component, and preferably 1 to 8 parts by mass is preferably added.

  The surface layer has a heat stabilizer, an antioxidant, a UV absorber, an anti-blocking agent, a light stabilizer, a nucleating agent, a hydrolysis inhibitor, a deodorant, etc. as long as the function of the packaging film is not impaired. These additives can be appropriately blended.

<Intermediate layer>
The intermediate layer can be formed from an intermediate layer forming composition containing the lactic acid polymer (B) as a main component.

  In addition to the lactic acid polymer (B), it is preferable to add a plasticizer capable of plasticizing the lactic acid polymer (B).

  Examples of the plasticizer include phthalic acid esters, adipic acid esters, trimellitic acid esters, phosphoric acid esters, adipic acid polyesters, glycerin fatty acid ester, and other plasticizers. From the viewpoint of good compatibility with the polymer, it is preferable to use glycerin fatty acid ester (C). Hereinafter, this glycerol fatty acid ester (C) is demonstrated.

(Glycerin fatty acid ester (C))
The glycerin fatty acid ester (C) can plasticize the lactic acid polymer (B). Such glycerin fatty acid esters are not particularly limited in their types, and examples include monoglycerides, diglycerides, triglycerides, acetylated monoglycerides, and polyglycerin fatty acid esters such as diglycerin, triglycerin, and tetraglycerin. Can do. Among these, an acetylated monoglyceride having a molecular structure represented by the following chemical formula (1) is particularly preferable from the viewpoint of good compatibility with a lactic acid polymer and high plasticizing ability.

  In the chemical formula (1), R1 represents an alkyl group, and R2 and R3 each represents an acetyl group or hydrogen. The number of carbon atoms of these alkyl groups is not particularly limited and is appropriately selected so as to achieve the purpose of improving adhesion and flexibility. In general, it is preferably 6 to 20.

  In order to obtain good compatibility with the lactic acid polymer (B), the molecular weight of the glycerin fatty acid ester (C) is preferably 2,000 or less, more preferably 1,500 or less.

  Among the glycerin fatty acid esters, a mixture of glycerin monoacetomonoester and glycerin diacetate monoester is preferable. Glycerin monoaceto monoester has good plasticizing performance and can substantially reduce the number of plasticizers added to the resin to be mixed. On the other hand, glycerin diacetate monoester can suppress volatilization of a plasticizer when mixed with a resin, and can exhibit stable plasticization performance. Therefore, the number of added parts can be determined and added depending on the application and the function required.

  The blending amount of the lactic acid polymer (B) and the glycerin fatty acid ester (C) is preferably blended so that the mass ratio is (B) / (C) = 90 / 10-60 / 40. By setting it within the above range, it is possible to suppress the bleed-out in which the glycerin fatty acid ester (C) is transferred to the surface with time and the surface becomes sticky by providing flexibility.

  In addition, from the viewpoint of processability, since it is preferable that the blending amount of glycerin fatty acid ester (C) is small, 1 to 20 parts by mass of glycerin fatty acid ester (C) with respect to 100 parts by mass of lactic acid polymer (B), Among these, it is more preferable to mix so as to include 3 to 18 parts by mass, particularly 5 to 18 parts by mass. By making the mixing amount of the glycerin fatty acid ester (C) 20 parts by mass or less, the melt viscosity of the lactic acid-based polymer (B) is not excessively decreased, and the difference in elastic modulus with the fluidity between the front and back layers. Can be reduced. That is, at the time of film formation, the workability at the time of co-pressing with the front and back layers (for example, the olefin polymer (A)) is improved, and a film excellent in appearance without striped pattern or whitening can be obtained.

The intermediate layer of the packaging film has a heat stabilizer, an antioxidant, a UV absorber, an anti-blocking agent, a light stabilizer, a nucleating agent, a hydrolysis inhibitor, as long as the function of the packaging film is not impaired. Additives such as thickeners and deodorants can be formulated.
For example, in order to maintain the practical properties of the packaging film, the carbodiimide compound is preferably added in an amount of 0.1 to 3 parts by mass, more preferably 0.5 to 1 part by mass, with respect to 100 parts by mass of the lactic acid polymer. By doing so, the mass average molecular weight can be increased. Below this range, the effect of increasing the mass average molecular weight is often small, and above this range, fish eyes and gels may be produced during film formation, which is not preferred.

<Adhesive layer>
The adhesive layer of the packaging film can be formed from an adhesive layer forming composition containing olefin polymer (A), lactic acid polymer (B) and graft copolymer (D) as main components.
As described above, the transparency in the polymer blend is affected by the particle size of the dispersed phase and the average refractive index difference between the dispersed layer and the matrix phase. In general, the compatibility between an olefin polymer and a lactic acid polymer is poor, but the present invention uses a graft copolymer (D) to form a phase between an olefin polymer (A) and a lactic acid polymer (B). By improving the solubility, excellent transparency can be achieved.

(Graft copolymer (D))
The graft copolymer is preferably a graft copolymer having a thermoplastic resin segment (a) as a trunk component and an acrylic polymer segment (b) as a branch component. In such a graft copolymer (D), the thermoplastic resin segment as a trunk component is compatible with the olefin polymer (A), while the acrylic polymer segment as a branch component is a lactic acid heavy polymer. Since it has compatibility with the polymer (B), the compatibility between the olefin polymer (A) and the lactic acid polymer (B) can be improved, and the particle size of the dispersed phase can be further refined. Therefore, the adhesive layer can be made more excellent in transparency.

  The thermoplastic resin segment (a) as the main component includes ethylene-α-olefin copolymer rubber, ethylene-α-olefin-nonconjugated polyene copolymer rubber, ethylene- (meth) acrylic acid alkyl ester copolymer. , Ethylene-vinyl acetate copolymer, acid-modified olefin rubber, olefin thermoplastic elastomer, and styrene thermoplastic elastomer. One of these may be used, or a combination of two or more may be used. By selecting a thermoplastic resin segment (a) that is a trunk component within this range, compatibility with the olefin polymer (A) can be improved.

  Among the thermoplastic resin segments (a), ethylene-propylene copolymer rubber or its acid-modified product, ethylene-octene copolymer rubber or its acid-modified product, ethylene-methyl acrylate copolymer, ethylene-acrylic Ethyl acid copolymer, ethylene-n-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene-nonconjugated polyene copolymer rubber or its acid-modified product, ethylene-ethyl acrylate-anhydrous A maleic acid copolymer, an olefin-based thermoplastic elastomer, and a styrene-based thermoplastic elastomer are preferable because of their high elastic recovery properties and, as a result, excellent impact resistance improving effects.

On the other hand, the acrylic polymer segment (b) as a branch component is formed from one or more acrylic monomers, and the acrylic monomer has a carbon number of alkyl chain length. 1 to 20 (meth) acrylic acid alkyl ester, acrylic monomer having acid group, acrylic monomer having hydroxyl group, acrylic monomer having epoxy group, acrylic monomer having cyano group, styrene Can be mentioned. One of these may be used, or a combination of two or more may be used. By selecting an acrylic polymer segment (b) that is a branch component within this range, compatibility with the lactic acid polymer (B) can be improved.
In this specification, acrylic and methacryl are collectively referred to as (meth) acrylic.

More specifically, as the acrylic monomer, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) lauryl acrylate, stearyl (meth) acrylate. (Meth) acrylic acid, maleic acid, maleic anhydride, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid glycidyl, (meth) acrylonitrile, styrene, etc. Can be mentioned. One of these may be used, or a combination of two or more may be used.
Among these, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid butyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic due to high affinity with polylactic acid resin Glycidyl acid, acrylonitrile and styrene are preferred.

The adhesive layer of the packaging film is preferably formed from an adhesive layer forming composition comprising a surface layer forming composition, an intermediate layer forming composition, and a graft copolymer (D).
The reason is that, for example, trimming loss that occurs when trimming by trimming both ends of the formed film can be used as a raw material for the adhesive layer, so that waste of material can be eliminated and material cost can be reduced. Because. Moreover, by making the adhesive layer a mixed composition of the surface layer component and the intermediate layer component, the difference in the melt viscosity of the resin in all layers can be brought close, and film formation stability can be obtained. And the compatibility of an olefin type polymer (A) and a lactic acid type polymer (B) can be improved by including a graft copolymer (D).

The mixing ratio of the olefin polymer (A) and the lactic acid polymer (B), and the mixing ratio of the surface layer forming composition and the intermediate layer forming composition surface layer component are 80/20 to 40/60. Preferably, it is 70/30 to 50/50. Within this range, the peel strength between the surface layer and the intermediate layer can be kept good.
In order to adjust to such a mixing ratio, when trimming loss is used, a resin having an insufficient component may be added according to the component composition of the trimming loss. If the entire trimming loss cannot be used up as the adhesive layer, the surplus may be provided as the reproduction layer. Moreover, you may use the mixture containing an olefin polymer (A) and a lactic acid-type polymer (B) as an alternative of trimming loss.

  The blending amount of the graft polymer (D) is preferably 1 to 50 parts by weight based on the amount of the mixture of the olefin polymer (A) and the lactic acid polymer (B) with respect to the adhesive layer forming composition. It is preferably 1 to 30 parts by mass, particularly 1 to 15 parts by mass.

In addition, the adhesive layer forming composition can contain a compatibilizing agent as long as it does not impair the function of the packaging film, and has performances such as antifogging properties, antistatic properties, slipping properties, and tackiness. In order to impart, the following various additives can be appropriately blended.
For example, an aliphatic alcohol fatty acid ester which is a compound of an aliphatic alcohol having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms and a fatty acid having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms, specifically, , Monoglycerin oleate, polyglycerin oleate, polyglycerin polyricinoleate, glycerin triricinoleate, glyceryl acetylricinoleate, glycerin monoacetomonostearate, glycerin diacetomonolaurate, glycerin diacetomonooleate, polyglycerin stearate, polyglycerin Laurate, methyl acetyl lysylate, ethyl acetyl lysylate, butyl acetyl lysylate, propylene glycol oleate, propylene glycol laurate, pentaerythritol oleate, polyethylene glycol acrylate , Polypropylene glycol oleate, sorbitan oleate, sorbitan laurate, polyethylene glycol sorbitan oleate, polyethylene glycol sorbitan laurate, etc., and polyalkylene ether polyols, specifically polyethylene glycol, polypropylene glycol, etc., and paraffinic oils , At least one compound selected from polybutene, terpene resin, petroleum resin, and the like can be blended in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of various resin components, preferably 3 to It is preferable to add 25 parts by mass.

  The thickness of the adhesive layer is preferably 0.3 μm to 5 μm because of its function. If the thickness of the adhesive layer is within such a range, the adhesiveness between the two surface layers and the intermediate layer can be expressed, and film forming stability is obtained during film formation, which is preferable. When it is desired to further secure the thickness ratio of the intermediate layer, the thickness is more preferably 0.5 μm to 3 μm.

<Laminated structure>
This packaging film is a laminated film comprising both surface layers, an intermediate layer, and an adhesive layer, and is a laminate of 5 or more layers having at least surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer in this order. Any film may be used, and other layers may be appropriately introduced as required, such as improvement of mechanical properties and interlayer adhesion. Further, a reproducing layer can be provided between the surface layer and the adhesive layer, or between the intermediate layer and the adhesive layer.

  For example, a layer having the same composition as the surface layer may be interposed in addition to both surface layers, and two or more layers having the same composition as the intermediate layer may be interposed between both surface layers. It doesn't matter. Specifically, in addition to a five-layer structure comprising surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer, surface layer / adhesive layer / intermediate layer / intermediate layer / adhesive layer / surface layer, surface layer / regeneration layer / Adhesive layer / intermediate layer / adhesive layer / surface layer, surface layer / adhesive layer / reproduction layer / intermediate layer / adhesive layer / surface layer, etc., surface layer / adhesive layer / intermediate layer / surface layer / intermediate Layer / adhesive layer / surface layer, surface layer / adhesive layer / intermediate layer / adhesive layer / intermediate layer / adhesive layer / surface layer, surface layer / reproduction layer / adhesive layer / intermediate layer / adhesive layer / reproduction layer / surface layer, A seven-layer structure composed of surface layer / adhesive layer / reproduction layer / intermediate layer / reproduction layer / adhesion layer / surface layer and the like can be exemplified. In this case, the resin composition and thickness ratio of each layer may be the same or different.

In the packaging film, the thickness ratio of the intermediate layer to the thickness of the entire film is preferably 35 to 90%. If the thickness ratio of the intermediate layer is within such a range, it becomes easy to design a film that satisfies the above characteristic values (E ′, tan δ) due to the dynamic viscoelasticity. For example, when the film is formed by the T-die method In addition to obtaining preferable film-forming stability, it is possible to relatively easily impart mechanical properties for expressing cut properties suitable for food packaging wrap films and relaxation properties for expressing container adhesion. it can. In addition, even when stored in a state where the formed film is wound, blocking does not occur, antifogging properties and container adhesion are good, and in addition to being difficult to cause molecular weight reduction due to hydrolysis over time, It can be set as the packaging film with favorable adhesiveness between layers.
Furthermore, in the case where more importance is attached to stable film forming workability and flexibility, the thickness ratio of the intermediate layer to the total film thickness is preferably 35 to 65%, more preferably 35 to 60%. preferable.
On the other hand, when more importance is attached to cutability and adhesion to a container, and further, the degree of planting, that is, CO ₂ reduction, the thickness ratio of the intermediate layer to the thickness of the entire film is preferably 60 to 90%. More preferably, it is 65 to 90%.
When there are two or more intermediate layers as described above, the thickness ratio may be calculated using the total thickness of all the intermediate layers.

(Reproduction layer)
As described above, the packaging film can have a reproduction layer as long as the effects of the present invention are not impaired. This is because, for example, trimming loss that occurs when trimming by trimming both ends of the formed film, it is possible to use a surplus after molding for the adhesive layer, defective molding, etc., eliminating waste of materials, Material costs can be reduced.
The reproduction layer can be provided between the surface layer and the adhesive layer, or between the intermediate layer and the adhesive layer. For example, the surface layer, the intermediate layer, or the adhesive layer is configured as a two-layer structure, and the trimming loss at both ends of the film is returned to one layer, so that between the surface layer and the adhesive layer or between the intermediate layer and the adhesive layer. A reproducing layer can be provided between the two. In this case, in addition to the thickness ratio and composition ratio of each layer, the mixing ratio of the three components can be adjusted depending on whether the layer containing the return is based on the surface layer, the intermediate layer, or the adhesive layer.

  The thickness (whole) of the present packaging film may be a range used as a food packaging wrap film, specifically 6 μm to 30 μm, and preferably 8 μm to 20 μm.

<Physical characteristics of the packaging film>
Next, physical characteristics of the packaging film will be described.

(Haze value)
The packaging film preferably has a total haze value of 3% or less in order to be suitably used as a small roll wrap film for household use, and the total haze value of the packaging film is 3% or less. Can do.

  If the total haze value of the film exceeds 3%, the packaged contents become difficult to see, and the value as a packaging film is lost. Therefore, the preferable total haze value is 2% or less, and more preferably 1.5% or less. In order to make the total film haze value within such a range, it can be adjusted by reducing the difference in refractive index between the olefin polymer (A) and the lactic acid polymer (B) as described above.

(Viscoelastic properties)
The packaging film has (1) a storage elastic modulus (E ′) measured by dynamic viscoelasticity measurement at a frequency of 10 Hz and a temperature of 20 ° C. of 1 to 4 GPa, and (2) a peak temperature of loss tangent (tan δ). Is 20 ° C. to 70 ° C., and (3) the peak value can be adjusted to be in the range of 0.1 to 0.8.
Incidentally, if it is a film provided with all of (1) to (3), it can be used as a small roll film.

That is, when the storage elastic modulus (E ′) is less than 1 GPa, the film is too soft and the stress is too small for deformation, so that, for example, the cutability when pulled out from a paper box and cut may be deteriorated. On the other hand, when E ′ exceeds 4 GPa, the film becomes hard and hardly stretched, and the drawability when pulled out from the paper box may deteriorate.
Further, if the peak temperature of tan δ is 70 ° C. or less and the peak value is 0.1 or more, the restoring behavior against deformation of the film does not occur instantaneously. It is preferable because the film is not restored and the adhesion to the container is improved. In addition, if the peak temperature of tan δ is 20 ° C. or higher and the peak value is 0.8 or lower, plastic deformation is not exhibited, and this is not a problem in a normal usage method.
The tan δ (loss tangent) is the ratio of the loss elastic modulus (E ″) to the storage elastic modulus (E ′), that is, the loss tangent (tan δ = E ″ / E ′). This means that the loss elastic modulus (E ″) of the material, that is, the contribution ratio of the viscosity is large among the viscoelastic properties. By evaluating the peak value and the peak temperature of tan δ, This is a great measure for judging the adhesiveness and stress relaxation behavior of the film in the packaging process.

  In order to produce a film that satisfies all of the above conditions (1) to (3), for example, selection of constituent components in the intermediate layer, the surface layer, and the adhesive layer (in some cases, the reproduction layer) (the type of resin as the main component) , Molecular weight and Tg, presence / absence and type of plasticizer, mixing ratio of components, LD ratio of lactic acid polymer, etc.), thickness ratio of intermediate layer, surface layer, and adhesive layer (recycled layer in some cases) It can be produced by appropriately adjusting the method and processing conditions (for example, heat treatment conditions after film formation, etc.) in a well-balanced manner.

<Manufacturing method>
Although the manufacturing method of this packaging film is demonstrated, it is not limited to the following manufacturing method.

  First, when the constituent material of each layer is a mixed composition, the constituent material of each layer is preferably mixed in advance and pelletized as necessary. As a mixing method at this time, for example, it may be pre-compounded in advance using a same-direction twin-screw extruder, a kneader, a Hayshell mixer, or the like. You may make it throw in. In any mixing method, it is necessary to consider a decrease in molecular weight due to decomposition of the raw material, but pre-compounding is preferable for uniform mixing. For example, in the case of an intermediate layer, the lactic acid-based polymer and additives as necessary are sufficiently dried to remove moisture, and then melt-mixed using a twin screw extruder, and a plasticizer is removed from the vent port. What is necessary is just to produce a pellet by extruding into a strand shape while adding a predetermined amount.

  The constituent materials for each layer are as described above, but the raw material for the adhesive layer forming resin can be obtained by adjusting the components such as adding a graft polymer (D) to the trimming loss of the packaging film. Pellets can be used.

Next, the constituent materials of each layer may be separately put into an extruder, melt extruded, and coextruded by T-die molding or inflation molding to be laminated.
At this time, it is preferable to form a film by practically pulling the melt extruded from the T die as it is while rapidly cooling it with a casting roll or the like.

When emphasizing the heat resistance and cutability of the film, after the melt-extruded sheet is cooled and solidified by a cooling roll, it is heated below the crystallization temperature of the resin, and the difference in speed between the nip rolls is used in the longitudinal direction of the film. It is preferable to employ a longitudinal stretching method in which the film is stretched 1.2 to 5.0 times, or a flat stretching method in which biaxial stretching and / or simultaneous biaxial stretching is sequentially performed 1.2 to 5.0 times in both the longitudinal and lateral directions of the film.
As the stretching temperature, the temperature of the extruded sheet is preferably set in the range of 30 to 90 ° C, and more preferably in the range of 40 to 60 ° C. If the stretching temperature is within such a range, it is preferable because both the intermediate layer forming composition and the ethylene copolymer (A) of the surface layer can be made close to the elastic modulus suitable for stretching. The draw ratio is preferably in the range of 1.2 to 5.0 times, and more preferably in the range of 1.5 to 4.0 times. As long as the draw ratio is within this range, the cut property can be improved without causing troubles such as breakage and whitening of the extruded sheet.

  Moreover, when importance is attached to productivity and / or economy, it is preferable to melt-extrude the material resin from an annular die and perform inflation molding. As a cooling method in that case, either a method of cooling from the outer surface of the tube, or a method of cooling from both the outer surface and the inner surface of the tube may be used.

The film thus obtained is reduced in heat shrinkage rate and natural shrinkage rate, depending on the purpose such as suppression of occurrence of width shrinkage, longitudinal stretching between heating rolls as required, various heat setting, Heat treatment such as aging may be performed.
As heat treatment conditions, the heat treatment temperature is preferably set in the range of 40 to 100 ° C, and more preferably in the range of 60 to 90 ° C. If the heat treatment temperature is 40 ° C. or higher, the effect of the heat treatment can be sufficiently obtained, and if it is 100 ° C. or lower, the problem of formability such as stickiness of the film on the roll does not occur.

  Further, for the purpose of imparting and promoting antifogging properties, antistatic properties, adhesiveness, and the like, treatments such as corona treatment and aging, and surface treatments and surface treatments such as printing and coating may be performed.

  The obtained film can be commercialized by trimming both ends and then slitting to the desired width.

<Explanation of terms>
In the present invention, the “main component” includes the meaning of allowing other components to be contained within a range that does not interfere with the function of the main component, unless otherwise specified. At this time, the content ratio of the main component is not specified, but the main component (when two or more components are main components, the total amount thereof) is 50% by mass or more, particularly 70% by mass in the composition. %, More preferably 90% by mass or more (including 100%).

  In general, “sheet” is a thin product as defined by JIS and generally has a thickness that is small and flat instead of length and width. In general, “film” refers to length and width. A thin flat product having an extremely small thickness and an arbitrarily limited maximum thickness, usually supplied in the form of a roll (Japanese Industrial Standard JISK6900). For example, in terms of thickness, in the narrow sense, a film having a thickness of 100 μm or more is sometimes referred to as a sheet, and a film having a thickness of less than 100 μm is sometimes referred to as a film. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.

  Further, in the present invention, when expressed as “X to Y” (X and Y are arbitrary numbers), unless otherwise specified, “X is preferably greater than X” and “ Is less than Y.

Hereinafter, although an Example and a comparative example demonstrate in more detail, this invention does not receive a restriction | limiting at all.
In addition, the various measured value and evaluation about the film displayed in this specification were performed as follows. Here, the flow direction of the film from the extruder is referred to as the vertical direction (hereinafter sometimes referred to as “MD”), and the perpendicular direction thereof is referred to as the horizontal direction (hereinafter sometimes referred to as “TD”).

(1) Heat of crystallization (ΔHc)
According to JIS K7121, 10 mg of olefin polymer was heated to 200 ° C. at a heating rate of 10 ° C./min using Pyris1 DSC manufactured by PerkinElmer Co., Ltd., held at 200 ° C. for 5 minutes, and then cooled at a rate of 10 The heat of crystallization ΔHc (J / g) was determined from the thermogram measured when the temperature was lowered to room temperature at ° C / min.

(2) Transparency Based on JISK7105, the total haze value of the film was measured at a film thickness of 10 μm.

(3) E ′, tan δ
JIS K-7198
Using the dynamic viscoelasticity measuring method described in Method A, using a dynamic viscoelasticity measuring device “DVA-200” manufactured by IT Measurement Control Co., Ltd., the vibration frequency is 10 Hz and the strain is 0 in the transverse direction (TD). .1%, measured from −50 ° C. to 150 ° C. at a rate of temperature increase of 1 ° C./min. From the obtained data, the storage elastic modulus (E ′) at a temperature of 20 ° C. and the loss tangent (tan δ) The peak temperature and its peak value were determined.

(4) Molecular weight retention (wet heat durability)
The obtained film was allowed to stand for 1 month in a constant temperature and humidity machine LH-112 manufactured by Tabay Espec adjusted to 40 ° C. × 90 mass%.
Gel Permeation Chromatography HLS-8120GPC manufactured by Tosoh Corporation is equipped with GPC-800CP of Shimadzu Corporation chroma column Shim-Pack series, solvent chloroform, solution concentration 0.2 wt / vol mass%. , The mass average molecular weight of the film before and after the test (that is, before and after standing for 1 month) was measured under the conditions of a solution injection amount of 200 μl, a solvent flow rate of 1.0 ml / min, and a solvent temperature of 40 ° C. This was shown by calculating the weight average molecular weight in terms of polystyrene. At this time, the mass average molecular weight of the standard polystyrene used is 20000, 670000, 110000, 35000, 10,000, 4000, 600.

The molecular weight retention rate (% by mass) was calculated from the calculated mass average molecular weight before and after the test, and the determination was made according to the following criteria.
○: The molecular weight retention is 60% by mass or more and 100% by mass or less, and the molecular weight after aging is 100,000 or more.
X: The molecular weight retention is 0% by mass or more and less than 60% by mass, and the molecular weight after aging is less than 100,000.

(5) Film-forming stability When forming a film, especially when the glass transition temperature (Tg) is around room temperature, it sticks to the casting roll during extrusion, preventing stable film formation. There is.

Therefore, when the film was formed by the T-die forming method, the casting stability and the degree of sticking to the roll were observed and evaluated according to the following criteria.
A: Extremely stable.
○: Stable.
X: Unstable.

(6) Production stability A: During production, thickness unevenness and breakage due to differences in fluidity during extrusion of each layer do not occur, and stable production can be achieved.
○: During production, there is thickness unevenness due to the difference in fluidity at the time of extrusion of each layer, but the film can be formed without breaking.
X: During production, the thickness unevenness is remarkable due to the difference in fluidity during extrusion of each layer, and breakage frequently occurs.

(7) Blocking resistance The obtained roll of film was stored in a temperature-controlled room under conditions of a temperature of 43 ° C. and a relative humidity of 40% for 5 days, and then the surface condition and roll-back property were observed and evaluated according to the following criteria. .
A: Level where there is no blocking between films.
○: A level where there is a little blocking between films, but does not cause a problem in practical use.
X: Level at which the film cannot be peeled off due to blocking between the films and cannot be rewound to cause a practical problem.

(8) Adhesion of container Adhesion to a container when packaged in a bowl-shaped ceramic container having a diameter of 10 cm and a depth of 5 cm was evaluated according to the following criteria.
A: Level that can be packaged appropriately.
○: Slightly widening from the shape of the container, but at a level where there is no practical problem.
X: Level at which the film spreads out of the container and causes a practical problem.

(9) Small roll applicability When producing small roll wrap films, considering the productivity, after first forming a film as a long raw material, it is wound around 20m, 50m, 100m, etc. It is normal to ship a replacement (small roll) in a box. Appropriateness in this rewinding process (small rewinding) is also important in the production of a small roll wrap film.

Then, the rewinding test of the formed film was performed at a winding speed of 200 m / min to 600 m / min, and the small rewinding suitability was evaluated according to the following criteria.
A: Small rewinding is possible without problems even at a winding speed of 600 m / min.
○: Small winding can be performed without any problem at a winding speed of 200 m / min or more and less than 600 m / min.
X: 200 m / min or more and less than 600 m / min In the course of rewinding, delamination and film breakage occur.

(10) Cut property The formed film was put into a carton box with a metal saw blade, and the film was pulled out and cut, and the ease of cutting at that time was evaluated according to the following criteria.
◎: Level that can be used without a sense of incompatibility when cutting.
○: A level where there is a slight practical resistance but no problem in practice.
X: Level at which the wrap bites into the metal saw blade and feels excessive resistance when cutting.

Example 1
About the surface layer forming composition, Nippon Polypro Co., Ltd. propylene / ethylene random copolymer “Novatech PP MG3F” (ethylene content: 3 mass%, heat of crystallization: Δ60 J / g, as the olefin polymer (A), Refractive index 1.49, MFR: 9 g / 10 minutes) (hereinafter abbreviated as “A-1”) 100 parts by mass and hydrogenated terpene resin “Clearon P125” manufactured by Yashara Chemical Company as an adhesive, The mixture was prepared by melting and kneading into a twin-screw extruder in the same direction set at an extrusion set temperature of 170 to 190 ° C.

On the other hand, for the intermediate layer forming composition, “Nature Works 4032D” (L-form / D-form = 98.6 / 1.4, refractive index 1.46, mass average molecular weight) manufactured by NatureWorks as the lactic acid-based polymer (B). : 200,000) (hereinafter abbreviated as “B-1”) and “NatureWorks 4060D” manufactured by NatureWorks (L-form / D-form = 87/13, refractive index 1.46, mass average molecular weight: 200,000) (hereinafter “B”) -2 ") is weighed so that the mass ratio is B-1 / B-2 = 60/40, and these are mixed into a co-directional twin-screw extruder set at an extrusion set temperature of 180 ° C. Then, a mixture of glycerin diacetomonoester (molecular weight 330) and glycerin monoacetomonoester (molecular weight 310) as glycerin fatty acid ester (C) ( The average molecular weight 320 (hereinafter abbreviated as “C-1”) is adjusted so that C-1 is 17 parts by mass with respect to the total of B-1 and B-2 (100 parts by mass). It melt-kneaded and prepared, inject | pouring using a fixed amount liquid feed pump from a vent port.
Furthermore, A-1, B-1, and C-1 were mixed in a mass ratio of A-1 / B-1 / C-1 = 45/46/9 in an extruder for an adhesive layer, and A- “Modiper A5200” manufactured by NOF Corporation as a graft copolymer (D) with respect to 100 parts by mass of the 1 / B-1 / C-1 mixture (70 parts by mass of ethylene / ethyl acrylate copolymer as a trunk component) %, 30 parts by mass of polymethyl methacrylate as a branching component) was added, and a resin composition pre-compounded in the same direction twin screw extruder was added in advance to prepare an adhesive layer forming composition.

  Then, the surface layer forming composition obtained by melt kneading as described above, the intermediate layer forming composition, and the adhesive layer forming composition are joined together from separate extruders, and the five-layer T Co-extruded at a die temperature of 190 ° C. and a die gap of 2 mm, and quenched with a cast roll set at a temperature of 30 ° C., resulting in a total thickness of 10 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 1.6 μm / A packaging film of 0.75 μm / 5.3 μm / 0.75 μm / 1.6 μm) was obtained. The results of evaluating the obtained film are shown in Table 1.

(Example 2)
Co-extrusion in the same manner as in Example 1 and a total thickness of 30 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 4.8 μm / 2.25 μm / 15.9 μm / 2.25 μm / 4.8 μm) An anti-film was obtained.
Subsequently, the film was uniaxially stretched in the MD by roll stretching at a stretching temperature of 60 ° C. and a stretching ratio of 3 times, and then heat treated at 90 ° C. to obtain a packaging film having a thickness of 10 μm. The results of evaluating the obtained film are shown in Table 1.

(Comparative Example 1)
Linear low density polyethylene “NUCG5361” (MFR: 4.0 g / 10 min, crystallization heat amount: Δ100 J / g, refractive index 1.51) (manufactured by Nippon Unicar Co., Ltd.) as the olefin polymer (A) (hereinafter “ Abbreviated as “A-2”) and linear low density polyethylene “NUCG5371” (MFR: 12.0 g / 10 min, refractive index: 1.51) manufactured by Nippon Unicar Co., Ltd. A-2 / A-3 = 50/50 by mass ratio and mixed into a surface layer extruder, and A-2, A-3, B-1 and C-1 are -2 / A-3 / B-1 / C-1 = 19/19/53/9 The resin composition pre-compounded in the same direction twin-screw extruder in advance was charged into the adhesive layer extruder. The total thickness was 10 μm (surface layer / adhesive layer / intermediate layer / adhesive) in the same manner as Example 2 except for Layer / surface layer = 1.6 μm / 0.75 μm / 5.3 μm / 0.75 μm / 1.6 μm). The results of evaluating the obtained film are shown in Table 1.

(Comparative Example 2)
A total thickness of 10 μm (surface layer) was obtained in the same manner as in Example 1 except that the resin to be fed into the adhesive layer extruder was changed to “Tuftec H1041” (styrene-ethylene-butadiene block copolymer) manufactured by Asahi Kasei Corporation. / Adhesive layer / intermediate layer / adhesive layer / surface layer = 1.6 μm / 0.75 μm / 5.3 μm / 0.75 μm / 1.6 μm). The results of evaluating the obtained film are shown in Table 1.

(Comparative Example 3)
The total thickness was the same as in Example 1 except that pellets pre-compounded in advance so as to have the same composition as the intermediate layer of Example 1 were put into the adhesive layer extruder, and a substantially three-layer film was formed. A packaging film of 10 μm (surface layer / intermediate layer / surface layer = 1.6 μm / 6.8 μm / 1.6 μm) was obtained. The results of evaluating the obtained film are shown in Table 1.

(Comparative Example 4)
In Comparative Example 3, Comparative Example 3 except that pellets pre-compounded in advance so as to have the same composition as the intermediate layer of Example 1 were put into an extruder for the surface layer to make a substantially single-layer film. Similarly, a packaging film having a total thickness of 10 μm was obtained. The results of evaluating the obtained film are shown in Table 1.

(Comparative Example 5)
In Comparative Example 3, an intermediate layer extruder was charged with pre-compounded pellets so as to have the same composition as both surface layers of Example 1 to obtain a substantially single layer film. In the same manner as in No. 3, a packaging film having a total thickness of 10 μm was obtained. The results of evaluating the obtained film are shown in Table 1.

  From Table 1, the film obtained in Example 1 can suppress a decrease in the molecular weight of the packaging film over time, and blocking does not occur even when the film formed is stored in a wound state. Furthermore, it was confirmed that the container adhesion was also good. In addition, it was confirmed that by providing a specific adhesive layer, a packaging film excellent in production stability and small rewindability was obtained, and a transparent packaging film having a good film appearance was obtained. In Example 2, it was excellent in cut property by performing a drawing process.

  On the other hand, in Comparative Examples 1 to 5, since a styrene-based elastomer was used as the adhesive layer between the front and back layers and the intermediate layer, the fluidity of each layer did not match during film formation, and film perforations were observed. (Comparative Example 1) and the case where the transparency (total haze value) is insufficient (Comparative Example 2) was confirmed because linear low density polyethylene was used for the front and back layers and the adhesive layer. Moreover, when it does not have adhesive layer resin (comparative example 3), it is confirmed that a problem arises in small rewinding suitability, and when it does not have front and back layer resin (comparative example 4), after film formation The blocking was remarkable, and the decrease in molecular weight with time was also significant. In the case where the intermediate layer containing a lactic acid polymer as a main component was not present (Comparative Example 5), the blocking and film-forming stability were good, but the container adhesion was insufficient.

“Modiper A5200” blended in Examples 1 and 2 is a graft copolymer containing an ethylene / ethyl acrylate copolymer as a trunk component and methyl methacrylate as a branch component. Since the thermoplastic resin segment as the trunk component is compatible with the olefin polymer (A), the acrylic polymer segment as the branch component is compatible with the lactic acid polymer (B). Since the compatibility of the polymer (A) and the lactic acid polymer (B) can be improved and the particle size of the dispersed phase can be further refined, the adhesive layer is more transparent. It is thought that it can be.
From such a viewpoint, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-nonconjugated polyene copolymer rubber, ethylene- (meth) acrylic acid alkyl ester copolymer, ethylene-vinyl acetate copolymer, acid A thermoplastic resin segment as a trunk component formed from one or more selected from the group consisting of a modified olefin rubber, an olefin thermoplastic elastomer, and a styrene thermoplastic elastomer, and one or two or more types It is considered that the same effect can be obtained if the graft copolymer includes an acrylic polymer segment as a branch component formed from an acrylic monomer.

Claims (7)

Both surface layers comprising a surface layer forming composition containing the olefin polymer (A) as a main component, and an intermediate layer comprising an intermediate layer forming composition containing the lactic acid polymer (B) as a main component And an adhesive layer comprising an adhesive layer forming composition containing olefin polymer (A), lactic acid polymer (B) and graft copolymer (D) as main components, between the surface layer and the intermediate layer. Packaging film,
The graft copolymer (D) is ethylene-α-olefin copolymer rubber, ethylene-α-olefin-nonconjugated polyene copolymer rubber, ethylene- (meth) acrylic acid alkyl ester copolymer, ethylene-acetic acid. A thermoplastic resin segment as a trunk component formed from one or more selected from the group consisting of vinyl copolymers, acid-modified olefin rubbers, olefin thermoplastic elastomers, and styrene thermoplastic elastomers; A graft copolymer comprising an acrylic polymer segment as a branch component formed from a seed or two or more acrylic monomers,
A packaging film having a total haze value of 3% or less . The packaging film according to claim 1, wherein the adhesive layer forming composition comprises a surface layer forming composition, an intermediate layer forming composition, and a graft copolymer (D). The packaging film according to claim 1 or 2 , wherein the intermediate layer forming composition contains a glycerin fatty acid ester (C) having a molecular weight of 2000 or less. Intermediate layer forming composition, packaging film according to claim 3, characterized in that it contains 1 to 20 parts by weight of glycerin fatty acid ester (C) with respect to the lactic acid polymer (B) 100 parts by weight. The packaging film according to any one of claims 1 to 4 , wherein the lactic acid polymer (B) is a mixed resin of two or more lactic acid polymers having different LD ratios. The olefin polymer (A) is one propylene polymer selected from propylene-ethylene random copolymer, propylene-ethylene-butene-1 copolymer and polypropylene elastomer, or two or more of these The packaging film according to claim 1 , wherein the packaging film is a mixed resin comprising a combination of the above. As measured by dynamic viscoelasticity, the storage elastic modulus (E ′) measured at a frequency of 10 Hz and a temperature of 20 ° C. is 1 to 4 GPa, the peak temperature of loss tangent (tan δ) is 20 to 70 ° C., and the peak value is 0.00. It is in the range of 1-0.8, The packaging film in any one of Claims 1-6 characterized by the above-mentioned.