JPWO2008023721A1 - Multi-layered lactic acid soft film - Google Patents

Abstract

Providing a lactic acid-based soft film that can be incorporated into a small-wrap film without causing blocking even when stored in a rolled state in a lactic acid-based soft film that uses lactic acid-based polymers as the main raw material. Therefore, it is a multilayer lactic acid-based soft film provided with at least three layers, both surface layers contain a polyolefin-based polymer (A) as a main component, and the intermediate layer is a lactic acid-based polymer (B-1). A multilayer lactic acid-based soft film characterized by containing a lactic acid-based mixed resin composition (B) composed of a lactic acid-based copolymer (B-2) as a main component is proposed.

Description

  The present invention is a multilayer lactic acid-based soft film mainly composed of a lactic acid-based polymer, which is a resin derived from a natural plant, and more specifically, for example, suitable as a wrap film for food packaging, especially a small roll wrap film used at home, etc. The present invention relates to a multilayer lactic acid-based soft film that can be used for the above.

  Speaking of flexible films, there are various types such as shopping bags, garbage bags, wrap films for packaging food, confectionery, cosmetics, pharmaceuticals, agricultural and horticultural films, greenhouse films, platemaking films, adhesive tapes, and waterproof sheets. It is used for purposes.

Wrapping film for food packaging, especially packaging film that can easily wrap food cooked at home etc. on a ceramic dish (in order to distinguish it from commercial wrapping film, Since a special condition is required for the “wrapped wrap film” as compared to other uses, it is not easy to produce a film suitable for this use.
Such a small roll wrap film is stored in a paper box provided with a cutter blade in a state of being wound around a cylinder, and when packaging, the film is drawn out from the paper box so as to cover the food, and the film is covered. The film is cut by pressing against the cutter blade provided in the paper box, perforating the film with this cutter blade and tearing the film so that the tear propagates in the width direction, and the end of the film It is common to pack the container in close contact with the container. For this reason, in addition to transparency, the small wrap film requires various conditions such as adhesion to the container, drawability that allows the film to be pulled out smoothly from the paper box, and cutability when the drawn film is cut. Is done.

  As a small roll film currently on the market, in addition to a film mainly composed of stretched polyvinylidene chloride resin, extruded cast polyethylene resin, plasticized polyvinyl chloride resin, poly-4-methylpentene-1 Examples thereof include a film mainly composed of a 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. Among these, lactic acid polymers are natural plant-derived resins obtained from starches such as corn and potatoes, and are not only mass-produced but also excellent in transparency, and thus are attracting attention as raw materials for flexible films. . However, since lactic acid polymers have high rigidity, it is not easy to commercialize soft films made from lactic acid polymers as main raw materials, especially food packaging wrap films, especially small roll wrap films. It was.

  As a soft film mainly composed of a lactic acid polymer, for example, in Patent Document 1, a lactic acid resin, a copolymer of a lactic acid resin and a diol / dicarboxylic acid, and a plasticizer having a molecular weight of 2,000 or less are used. A lactic acid-based soft film comprising the lactic acid-based resin composition, wherein the lactic acid-based resin composition has a single Tg, and further has a storage elastic modulus at 20 ° C. of 1 to 4 GPa and storage at 100 ° C. A lactic acid soft film having an elastic modulus of 10 to 100 MPa and a loss tangent at 20 ° C. of 0.1 to 0.8 is disclosed as a household wrap film.

  Patent Document 2 discloses that a biodegradable wrap film having the characteristics of cut, packaging, and heat resistance, which are the characteristics of a household wrap film, has a frequency of 10 Hz according to the dynamic viscoelasticity measurement method of JIS K-7198 A method. The value of the storage elastic modulus at 40 ° C. measured at a strain of 0.1% is in the range of 100 MPa to 3 GPa, the value of the storage elastic modulus at 100 ° C. is in the range of 30 MPa to 500 MPa, and the loss tangent (tan δ) The main component is a lactic acid resin composition having a peak value in the range of 0.1 to 0.8, for example, a lactic acid resin composition containing a lactic acid resin and a plasticizer in a mass ratio of 60: 1 to 99: 1. A biodegradable wrap film is disclosed.

  Patent Document 3 discloses a lactic acid-based soft film formed by using a lactic acid-based resin composition comprising a lactic acid-based resin and a copolymer of a lactic acid-based resin and a diol / dicarboxylic acid. Lactic acid having a single Tg, a storage elastic modulus at 20 ° C. of 1 to 4 GPa, a storage elastic modulus at 100 ° C. of 10 to 100 MPa, and a loss tangent at 20 ° C. of 0.1 to 0.8. Based soft films have been disclosed as household wrap films.

  In Patent Document 4, the outermost layer is a layer mainly composed of a polyolefin-based resin in order to provide a shrinkable sheet-like material that can obtain a high shrinkage rate at a relatively low temperature by an inflation method excellent in productivity. A shrinkable sheet-like material having at least one layer mainly composed of polylactic acid between layers composed mainly of the polyolefin-based resin is disclosed. Further, it is disclosed that an acrylic-modified polyethylene resin is used as an adhesive layer between a layer mainly composed of a polyolefin resin and a layer mainly composed of polylactic acid.

JP 2006-16605 A WO / 2005/082981 JP 2005-336468 A JP 2002-19053 A

  The lactic acid-based soft film disclosed in Patent Document 1 can be incorporated into a small wrap film, and a plasticizer is added to a completely compatible polymer blend system of a lactic acid-based resin and a copolymer. Bleed-out can also be suppressed. However, if the film is stored in a rolled state, the molecular weight of the lactic acid resin will decrease over time, or the film will block and the films will stick together. It was.

  Further, as described in Patent Documents 2 and 3, lactic acid-based resin composition crystals are also used for lactic acid-based polymers blended with a plasticizer, and for lactic acid-based resins, lactic acid-based resins, and diol / dicarboxylic acids. The glass transition point (Tg) of the lactic acid polymer is lowered to near room temperature, and when a wrap film is formed by rapid cooling using a casting method or the like, the sheet is kept amorphous. As a result, the elastic modulus is lowered, and if the roll is wound as it is, the scroll may be blocked by a winding force or the like.

  In view of such problems, the present invention provides a lactic acid-based soft film mainly composed of a lactic acid-based polymer, and does not cause blocking even when stored in a state where the formed film is wound. It is intended to provide a lactic acid-based soft film that can suppress the degree of molecular weight reduction of the coalescence and that can be incorporated to satisfy various conditions required for food packaging wrap films, particularly small roll wrap films. is there.

  In view of this problem, the present invention is a multilayer lactic acid-based soft film having at least three layers, both surface layers containing the polyolefin polymer (A) as a main component, and the intermediate layer comprising a lactic acid-based heavy film. Proposed is a multilayer lactic acid-based soft film characterized by containing a lactic acid-based mixed resin composition (B) composed of a combination (B-1) and a lactic acid-based copolymer (B-2) as a main component.

  In the multilayer lactic acid-based soft film of the present invention, the intermediate layer serving as the nucleus of the multilayer lactic acid-based soft film is divided into a lactic acid-based polymer (B-1) and a lactic acid-based copolymer (B-2), preferably further a plasticizer. (C) is a flexible film that is excellent in plantiness, flexibility, transparency and biodegradability, and can satisfy various conditions required for food packaging wrap films, particularly small roll wrap films. Can be built. Moreover, the molecular weight of the lactic acid-based resin composition can be obtained by covering the intermediate layer with a surface layer mainly composed of the polyolefin-based polymer (A) and storing the film formed in a wound state. The decrease can be suppressed, and the problem of the films sticking to each other by suppressing the blocking of the film can be solved. Furthermore, since the surface layer can contain an antifogging agent, the antifogging property of the film can be improved.

(Glossary of terms)
In general, "film" is a thin flat product whose thickness is extremely small compared to the length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll. (Japanese Industrial Standard JISK6900), and “sheet” generally refers to a product that is thin according to the definition in JIS, and usually has a thickness that is small instead of length and width. 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.
In addition, in the present invention, the expression “main component” includes the intention of allowing other components to be contained within a range that does not hinder the function of the main component unless otherwise specified. Although the content ratio of the main component is not particularly specified, the main component (when two or more components are main components, the total amount thereof) is 50% by mass or more, preferably 70% by mass or more, particularly preferably Includes 80% by mass or more (including 100%).
Further, when described as “X to Y” (X and Y are arbitrary numbers), “preferably greater than X” or “preferably less than Y” with the intention of “X or more and Y or less” unless otherwise specified. Is also included.

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

  The lactic acid-based soft film is a multilayer film having at least three layers, both surface layers are layers containing the polyolefin-based polymer (A) as a main component, and the intermediate layer is a lactic acid-based polymer ( This is a layer containing B-1) and a lactic acid copolymer (B-2) as main components.

The lactic acid-based soft film only needs to be a multilayer film having at least three layers of the above-described intermediate layer and both surface layers. As a preferable laminated structure, for example, surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer The laminated film of 5 layers or more which have these in this order can be mentioned. At this time, for example, a reproducing layer may be interposed between the layers.
Therefore, in the following description, a surface layer, an intermediate layer, an adhesive layer, and a reproduction layer that can be constituent elements of the lactic acid-based soft film will be described in this order, and then the laminated structure, characteristic values, manufacturing method, etc. of the lactic acid-based soft film Will be described.

<Surface layer>
In this lactic acid-based soft film, the front and back layers are layers that can increase the airtightness when forming a package by heat sealing or adhesion, and can also increase the mechanical strength such as tear strength, puncture strength, impact strength, etc. It is. Moreover, in the case of film forming by inflation molding or tubular stretching, it is possible to impart to the film a function of improving stability during molding. It can also serve as an antiblocking layer for the packaging film. When an additive such as a plasticizer is added to the intermediate layer, these bleed-outs can be prevented. Since an antifogging agent, an antistatic agent, a lubricant and the like can be added to the surface layer, various functions can be imparted to the film. Furthermore, it can also play a role of suppressing a temporal decrease in molecular weight due to hydrolysis of the lactic acid-based polymer (B-1) or the lactic acid-based copolymer (B-2).

(Polyolefin polymer (A))
Examples of polyolefin polymers include ethylene polymers, butylene polymers, propylene polymers such as polypropylene and ethylene-propylene copolymers, poly-4-methylpentene, polybutene, ethylene-vinyl acetate copolymers, and the like. be able to. These resins may be one kind of the resins listed above, or may be a mixed resin composed of two or more kinds of resins.
Polyolefin thermoplastic elastomers in which ethylene / propylene rubber or the like is dispersed and combined with these polyolefin polymers can also be used.

  Among the above, the role of the surface layer, that is, blocking prevention of the packaging film, an appropriate balance between slip and surface adhesiveness, surface properties such as antifogging property, molding processing stability during film formation, and further hydrolysis In view of the role of suppressing the decrease in the molecular weight of the lactic acid-based mixed resin composition (B) with time, the main component of the surface layer is preferably an ethylene polymer.

The ethylene polymer may be one ethylene polymer selected from low density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, medium density polyethylene and high density polyethylene, or a combination of two or more of these. A mixed resin comprising a combination or a copolymer having ethylene as a main component, that is, ethylene and propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, etc. 10 α-olefins, vinyl esters such as vinyl acetate and vinyl propylene acid, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, conjugated dienes and non-conjugated dienes A copolymer with one or more comonomers selected from compounds, or Terpolymer, or can include the ethylene polymer, the copolymer, two or more combinations mixed resin consisting of said multicomponent copolymer. The ethylene unit content of these ethylene polymers is usually more than 50% by mass.
Among them, 1 selected from low density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer and ethylene-methacrylic acid ester copolymer A mixed resin composed of a seed ethylene polymer or a combination of two or more of these is particularly preferable.
Examples of the acrylic acid ester of the ethylene-acrylic acid ester copolymer include methyl acrylate and ethyl acrylate. Examples of the acrylic acid ester of the ethylene-methacrylic acid ester copolymer include methyl methacrylate. And ethyl methacrylate.

Among the polyolefin-based polymers (A), in the case where importance is attached to surface properties such as balance of surface tackiness, antifogging properties, and molding processing stability during film formation, the vinyl acetate content is 10 to 60% by mass. Melt flow rate (hereinafter sometimes abbreviated as “MFR”. MFR measurement conditions are 190 ° C., load 21.18 N based on JIS K 7210, and the same applies to other MFRs). An ethylene-vinyl acetate copolymer that is 2 to 20 g / 10 min is particularly preferred.
In this ethylene-vinyl acetate copolymer, if the vinyl acetate content is 10% by mass or more, the film is not hard because the crystallinity is low, the flexibility and elastic recovery are good, and surface tackiness is also exhibited. It is preferable in that it is easy. On the other hand, if it is 60% by mass or less, heat resistance, film strength, etc. can be secured, bleed-out can be suppressed even if an antifogging agent is added, and the film is unwound because the surface tackiness is not too strong. It is preferable at the point that property and an external appearance can be made favorable. From such a viewpoint, the vinyl acetate content of the ethylene-vinyl acetate copolymer is more preferably 10 to 58% by mass, and particularly preferably 12 to 56% by mass.
Further, if the MFR of the ethylene-vinyl acetate copolymer is 0.2 g / 10 min or more, the extrusion processability is stable, and if it is 20 g / 10 min or less, stable film formation at the time of molding becomes possible. It is preferable because thickness unevenness, decrease in mechanical strength, variation, and the like are reduced. From such a viewpoint, the MFR of the ethylene-vinyl acetate copolymer is more preferably 0.5 to 18 g / 10 minutes, and more preferably 1 to 15 g / 10 minutes.

On the other hand, when importance is attached to microwave heat resistance that can withstand microwave heating, linear low density polyethylene having a density of 0.90 to 0.95 g / cm ³ and an MFR of 0.2 to 20 g / 10 min is used. Particularly preferred.
If the density of the polyolefin-based polymer (A) is within such a range, the film does not become hard because it has appropriate crystallinity, and the flexibility and elastic recovery are good, and the polyolefin-based polymer (A) The melting point of the wrap will be higher than the actual operating temperature range of the wrap, specifically the atmospheric temperature when heated in a microwave oven, etc. This is preferable because it does not cause a problem that the film melts and sticks. From this point of view, particularly preferred that the density of the polyolefin-based polymer (A) is a 0.90~0.94g / cm ^3, even more preferably among them 0.91~0.94g / cm ³ .
Also, if the MFR of the polyolefin polymer (A) is 0.2 g / 10 min or more, the extrusion processability is stable, and if it is 20 g / 10 min or less, stable film formation at the time of molding becomes possible. This is preferable because spots, a decrease in mechanical strength, variations, and the like are reduced. From such a viewpoint, the MFR of the polyolefin polymer (A) is particularly preferably 0.5 to 18 g / 10 minutes, and more preferably 1 to 15 g / 10 minutes.

  The method for producing the polyolefin 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. Examples thereof include a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method using a single site catalyst typified by a catalyst, and a bulk polymerization method using a radical initiator.

<Intermediate layer>
The intermediate layer of the lactic acid-based flexible film contains, as main components, a lactic acid-based polymer (B-1) and a lactic acid-based copolymer (B-2), in other words, a lactic acid-based polymer (B-1) and This layer contains a lactic acid-based mixed resin composition (B) composed of a lactic acid-based copolymer (B-2) as a main component, and further contains a plasticizer (C) as necessary.

(Lactic acid polymer (B-1))
Examples of the lactic acid polymer (B-1) include 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 -Poly (DL-lactic acid) which is lactic acid, or a mixture thereof can be used.
From the viewpoint of suppressing bleed-out of the plasticizer, it is preferable that the lactic acid-based polymer has low crystallinity. Therefore, when the intermediate layer contains a plasticizer, the crystallinity is lower than that of poly (L-lactic acid). It is preferable to use polylactic acid such as poly (D-lactic acid), poly (DL-lactic acid), or a mixture thereof.
The poly (L-lactic acid) or poly (D-lactic acid) referred to here is ideally a polymer composed of 100% L-lactic acid or D-lactic acid, but inevitably different lactic acid is included in the polymerization. Since there is a possibility, it contains 98% or more of L-lactic acid or D-lactic acid.

The ratio (molar ratio) between D-lactic acid (D-form) and L-lactic acid (L-form) in the lactic acid-based polymer (B-1) is L-form: D-form = 100: 0 to 85:15, or L-form: D-form = 0: 100 to 15:85, 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.
Also in this case, from the viewpoint of suppressing bleed-out of the plasticizer, it is preferable that the crystallinity of the lactic acid polymer is low. Therefore, L-form: D-form = 50: 50 to 94: 6 is preferable.
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, what is necessary is just to make it the average value of the copolymerization ratio of the L body and the D body of a some lactic acid type polymer fall in the said range. For example, by blending poly (L-lactic acid) or poly (D-lactic acid) and poly (DL-lactic acid), it is possible to balance the difficulty of bleeding and the development of heat resistance.

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 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.

  The lactic acid polymer preferably has a weight average molecular weight in the range of 50,000 to 400,000, more preferably in the range of 100,000 to 250,000. If the weight average molecular weight of the lactic acid-based polymer is 50,000 or more, practical physical 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.

  A commercially available lactic acid polymer can also be used as the lactic acid polymer (B-1). For example, the brand name “Lacia” series (manufactured by Mitsui Chemicals), the brand name “Nature Works” series (manufactured by NatureWorks), the brand name “U'z series” (manufactured by Toyota Motor Corporation), etc. Can do.

(Lactic acid copolymer (B-2))
The lactic acid copolymer (B-2) is a resin obtained by copolymerizing a lactic acid polymer. Especially, what makes a perfect compatible polymer blend with a lactic acid-type polymer (B-1) is preferable. In other words, a polymer blend composition obtained by mixing the lactic acid copolymer (B-2) and the lactic acid polymer (B-1) is measured at a heating rate of 10 ° C./min in differential scanning calorimetry. A lactic acid copolymer (B-2) having a single glass transition temperature is preferred.

  Here, the glass transition temperature of the mixed resin composition is single when the glass transition temperature of the polymer blend composition is measured using a differential scanning calorimeter at a heating rate of 10 ° C./min according to JIS K7121. This means that only one peak indicating the glass transition temperature appears. From another viewpoint, when the polymer blend composition is measured by dynamic viscoelasticity measurement (dynamic viscoelasticity measurement of JISK-7198A method) at a strain of 0.1% and a vibration frequency of 10 Hz, a loss tangent is obtained. This means that there is one maximum value of (tan δ). The fact that the glass transition temperature (or the maximum value of the loss tangent) of the polymer blend composition is single means that the lactic acid polymer (B-1) and the lactic acid copolymer (B-2) are on the nanometer order. It means being in a compatible state at the (molecular level), and a level of transparency that cannot be obtained with an incompatible polymer blend can be obtained.

  As a preferred example of the lactic acid copolymer (B-2), for example, a copolymer of the above lactic acid polymer and a diol / dicarboxylic acid can be exemplified.

  The lactic acid polymer constituting the copolymer of the lactic acid polymer and the diol / dicarboxylic acid may be any of L-lactic acid, D-lactic acid, and DL-lactic acid, but the lactic acid polymer (B From the viewpoint of forming a completely compatible polymer blend with -1), those having the same structure as the structural unit of the lactic acid polymer (B-1) are particularly preferred.

  On the other hand, the diol component in the diol / dicarboxylic acid is not particularly limited. For example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol. Linear diols such as 1,7-peptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, Propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,3-pentanediol, 2,4-pentane Diol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol Branched diols such as 1,5-hexanediol, polyethylene glycol, polypropylene glycol, polybutylene glycol, can be mentioned polyol polytetramethylene glycol, and among them polypropylene glycol.

In addition, the dicarboxylic acid component in the diol / dicarboxylic acid is not particularly limited. For example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, maleic acid, fumaric acid, Linear dicarboxylic acids such as citraconic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, methylsuccinic acid, dimethylsuccinic acid, ethylsuccinic acid, 2-methylglutaric acid, 2-ethylglutaric acid, 3-methylglutaric acid, 3-ethylglutar Acids, branched dicarboxylic acids such as 2-methyladipic acid, 2-ethyladipic acid, 3-methyladipic acid, 3-ethyladipic acid, methylglutaric acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, Naphthalene dicarboxylic acid, phthalic anhydride Bisphenol A, can be mentioned aromatic dicarboxylic acids such as biphenol, inter alia succinic acid is preferred.
Therefore, as a copolymer of a lactic acid polymer constituting a lactic acid copolymer (B-2) and a diol / dicarboxylic acid, a copolymer of a lactic acid polymer, a (poly) propylene glycol, and succinic acid is used. Is the most preferred example.

  Among the above-mentioned types of lactic acid-based polymers and diol / dicarboxylic acid copolymers, the lactic acid-based polymer can be operated at a strain of 0.1% and a vibration frequency of 10 Hz from the viewpoint of softening the lactic acid-based polymer. It is preferable to select and use a copolymer having one maximum value of loss tangent (tan δ) measured by dynamic viscoelasticity measurement (dynamic viscoelasticity measurement of JISK-7198A method). This point will be described in detail below.

  Here, a copolymer having two maximum values of loss tangent is referred to as “A type”, and a copolymer having one maximum value of loss tangent is referred to as “B type”. Blending a copolymer (A type) having two local maximum values of loss tangent does not allow the lactic acid polymer (B-1) to be softened due to a decrease in glass transition temperature, but the maximum value of loss tangent By blending a copolymer (B type) in which one is present, the lactic acid polymer (B-1) can be softened due to a decrease in the glass transition temperature. From this, it can be said that the component (B) is preferably a copolymer (B type) having one maximum value of loss tangent (tan δ).

  By the way, examples of the structure of a copolymer of a lactic acid-based polymer and a diol / dicarboxylic acid include a random copolymer, a block copolymer, and a graft copolymer. In general, when the structure of the copolymer is a block copolymer, it becomes a type (A type) in which there are two local maximum values of loss tangent measured under the above conditions, and the structure of the copolymer is In the case of a random copolymer, since there is a type (B type) in which there is one local maximum of loss tangent measured under the same conditions, the structure of the lactic acid copolymer (B-2) is as follows: A random copolymer is preferred.

  In a copolymer of a lactic acid polymer and a diol / dicarboxylic acid, the content ratio of the lactic acid polymer and the diol / dicarboxylic acid is preferably a storage elastic modulus at 20 ° C., a peak temperature of loss tangent, and a loss tangent value. It is preferable to adjust to be in the range. As a guideline, the mass ratio of the lactic acid polymer to the diol / dicarboxylic acid is adjusted to be 10:90 to 70:30, particularly 30:70 to 70:30, and particularly 40:60 to 60:40. It is preferable to do this.

  The copolymer of lactic acid-based polymer and diol / dicarboxylic acid can be adjusted to a predetermined molecular weight using an isocyanate compound or a carboxylic acid anhydride. However, the weight average molecular weight of the lactic acid-based polymer and the diol / dicarboxylic acid copolymer is preferably in the range of 50,000 to 300,000, more preferably in the range of 100,000 to 250,000 from the viewpoint of processability and durability. .

  The method for producing a copolymer of a lactic acid-based polymer and a diol / dicarboxylic acid is not particularly limited, but a polyester or polyether polyol having a structure obtained by dehydration condensation of a diol and a dicarboxylic acid is converted into lactide and ring-opening polymerization. Alternatively, a method obtained by transesterification, a method in which a polyester or polyether polyol having a structure obtained by dehydration condensation of a diol and a dicarboxylic acid is subjected to dehydration / deglycolization condensation or transesterification with a lactic acid polymer, etc. .

  Commercially available lactic acid polymers and copolymers with diol / dicarboxylic acid can also be used. Specifically, the product name “Plamate PD-350” (manufactured by Dainippon Ink & Chemicals, Inc.) can be mentioned.

  As mentioned above, as the lactic acid-based mixed resin composition (B) comprising the lactic acid-based polymer (B-1) and the lactic acid-based copolymer (B-2), both polymer blends (mixed resin composition) ) Are completely compatible, that is, those having a single glass transition temperature measured by differential scanning calorimetry at a heating rate of 10 ° C./min. Among these, the glass transition temperature is preferably 0 ° C. to 30 ° C. What becomes the range of 20 to 30 degreeC is more preferable. Because the glass transition temperature is in the range of 0 ° C. to 30 ° C., the film will not be too hard under the actual use environment temperature and will stretch appropriately, so that it can be packaged well along the shape of the container etc. Therefore, it is particularly suitable as a household wrap film.

  In addition, the other lactic acid-type copolymer which makes a completely compatible polymer blend with the lactic acid-type polymer (B-1) can also be used. For example, a copolymer of a lactic acid polymer and polyethylene glycol can be given as a preferred example.

  The total molecular weight of the lactic acid polymer (B-1) and the lactic acid copolymer (B-2) is preferably 100,000 or more. For this purpose, it is preferable to increase the overall molecular weight by blending the lactic acid polymer (B-1) having a high molecular weight. If the total molecular weight is 100,000 or more, it is possible to easily form a wrap film. .

The blending ratio of the lactic acid polymer (B-1) and the lactic acid copolymer (B-2) is the total of the lactic acid polymer (B-1) and the lactic acid copolymer (B-2). It is preferable that the ratio of the lactic acid-type polymer (B-1) to 50 to 80 mass% and the ratio of the lactic acid-type copolymer (B-2) is 50 to 20 mass%.
In this lactic acid-based soft film, if the proportion of the lactic acid-based copolymer (B-2) is increased, flexibility can be imparted without impairing the transparency, but the lactic acid-based copolymer (B-2) ) Increases, the weight average molecular weight may decrease to 100,000 or less, and practical physical properties, for example, mechanical properties when left in a humid state for a long time may not be expressed. Moreover, when the ratio of a lactic acid-type copolymer (B-2) increases, melt viscosity will become low and moldability will fall. From these points, the proportion of the lactic acid copolymer (B-2) in the total of the lactic acid polymer (B-1) and the lactic acid copolymer (B-2) is 50% by mass as the upper limit. It is necessary to make it 40% by mass or less. On the other hand, if the proportion of the lactic acid copolymer (B-2) is small, the plasticizing effect is lowered and the film becomes poor in flexibility. From this point, the lactic acid polymer (B-1) and the lactic acid polymer The ratio of the lactic acid copolymer (B-2) in the total of the copolymer (B-2) needs to be 20% by mass, and more preferably 30% by mass or more.

(Plasticizer (C))
Even if the intermediate layer of the lactic acid-based soft film is composed mainly of the lactic acid-based mixed resin composition (B), the transparency may be impaired if the proportion of the lactic acid-based copolymer (B-2) is increased. The film can be made flexible. However, when the proportion of the lactic acid copolymer (B-2) is increased, the practical physical properties, for example, the mechanical properties when placed in a humid state for a long time are lowered, or the melt viscosity is lowered and the molding processability is lowered. In some cases, the plasticizer (C) is preferably blended as necessary. At this time, the lactic acid copolymer (B-2) and the plasticizer (C) are in a relationship to compensate for each other's problems, and the mechanical properties when placed in a humid state for a long time by blending the plasticizer (C). While suppressing the deterioration of properties and maintaining the melt viscosity, blending of the lactic acid copolymer (B-2) makes it possible to prevent bleeding out of the plasticizer and changes in mechanical properties during long-term storage.

The plasticizer (C) has a function of lowering and softening the glass transition temperature (Tg) of the resin, but as a plasticizer for the lactic acid-based soft film, from the viewpoint of compatibility and biodegradability, Those composed of one or a combination of two or more selected from the compounds shown in the following (a) to (i) are preferable, and the following (a) and (f) are particularly preferable.
Regardless of the molecular weight of the plasticizer, the composition of the present lactic acid-based flexible film is characterized by being able to suppress bleed-out and changes in mechanical properties during long-term storage.

(A) H ₆ C ₃ (OH) ₃ -n (OOCCH ₃ ) _n (where 0 <n ≦ 3)
This is glycerol monoacetate, diacetate or triacetate, and a mixture thereof may be used, but n is preferably close to 3.
(B) Glycerin alkylate (the alkyl group may have 2 to 20 carbon atoms and a hydroxyl group residue)
Examples thereof include glycerin tripropionate and glycerin tributyrate.
(C) Ethylene glycol alkylate (the alkyl group has 1 to 20 carbon atoms and may have a hydroxyl group residue).
For example, ethylene glycol diacetate can be used.
(D) Polyethylene glycol alkylate having 5 or less ethylene repeating units (the alkyl group may have 1 to 12 carbon atoms and a hydroxyl group residue).
Examples thereof include diethylene glycol monoacetate and diethylene glycol diacetate.
(E) Aliphatic monocarboxylic acid alkyl ester (the alkyl group has 1 to 20 carbon atoms)
Examples thereof include butyl stearate.
(F) Aliphatic dicarboxylic acid alkyl ester The alkyl group may have 1 to 20 carbon atoms and a carboxyl group residue. Among them, those having a number average molecular weight of 100 to 2000 are preferable. Specific examples include di (2-ethylhexyl) adipate and di (2-ethylhexyl) azelate.
(G) Aliphatic tricarboxylic acid alkyl ester The alkyl group may have a residue having 1 to 20 carbon atoms and a carboxyl group. For example, citric acid trimethyl ester can be used.
(H) Natural fats and oils and derivatives thereof Examples include soybean oil, epoxidized soybean oil, castor oil, tung oil, and rapeseed oil.
(I) Polyalkylene ethers Examples include polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol and the like.

Among these, considering food packaging applications, for example, food additives such as glycerin fatty acid ester and polybutene, or indirect food additives such as epoxidized vegetable oil and acetylated citric acid fatty acid ester that are allowed to contact foods. Such additives are more preferred. These may be used alone or in combination of two or more.
Among these, it is preferable to select a glycerin fatty acid ester in consideration of adhesion of the wrap film, drawability, bleed resistance to the wrap film surface, and the like.

  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), R ¹ represents an alkyl group, and R ² and R ³ 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, and is generally preferably 6 to 20.

  In order to obtain good compatibility with the lactic acid polymer (B-1), the molecular weight of the glycerin fatty acid ester is particularly preferably 2000 or less, and particularly preferably 1500 or less.

It is preferable that the compounding quantity of a plasticizer (C) is 1-15 mass parts with respect to a total of 100 mass parts of a lactic acid-type polymer (B-1) and a lactic acid-type copolymer (B-2). With respect to the upper limit, it is more preferably 10 parts by mass or less, particularly 9 parts by mass or less. With respect to the lower limit, it is more preferably 3 parts by mass or more, particularly 5 parts by mass or more.
If the proportion of the plasticizer (C) is increased with respect to the total of the lactic acid polymer (B-1) and the lactic acid copolymer (B-2), flexibility can be imparted without impairing transparency. However, the plasticizer migrates to the surface over time and causes problems such as bleed out that the surface becomes sticky. On the other hand, when the amount of the plasticizer is small, the film becomes poor in flexibility, and the ratio of the lactic acid copolymer (B-2) needs to be increased. Therefore, the blending amount of the plasticizer (C) is preferably within the above range.

(Other ingredients)
The intermediate layer of the present lactic acid-based flexible film can also contain a polyolefin-based polymer (E).

  The polyolefin polymer (E) may be the same polyolefin polymer as the polyolefin polymer (A) constituting the surface layer or may be a different polyolefin polymer, but preferably the same polyolefin polymer. It may be a polymer. If the polyolefin polymer (E) and the polyolefin polymer (A) constituting the surface layer are the same polyolefin polymer, the adhesion between the intermediate layer and the surface layer can be improved, In addition to enhancing the mechanical properties, for example, trimming loss that occurs when the film is trimmed by trimming both ends can be added as a constituent material of the intermediate layer, eliminating the waste of materials and materials Cost can be reduced.

  As the most preferred polyolefin polymer (E), an ethylene-vinyl acetate copolymer having a vinyl acetate content of 10 to 60% by mass can be mentioned. This ethylene-vinyl acetate copolymer can be suitably used as a polyolefin polymer (A) which is a main component of the surface layer, and is transparent when a recycled resin generated from trimming loss is added. There are no practical problems in terms of properties, mechanical properties, and material costs, and they can be stably obtained as industrial materials.

  The blending ratio of the polyolefin polymer (E) is (B-1) + (B) in the ratio to the total mass of the lactic acid polymer (B-1) and the lactic acid copolymer (B-2) in the intermediate layer. -2) :( E) = 99: 1 to 50:50, particularly 95: 5 to 50:50, and particularly preferably 90:10 to 55:45. Within this range, the elastic modulus can be maintained, and “waist” that is one of the wrap characteristics can be maintained, which is preferable.

In addition, the intermediate layer of the lactic acid-based soft film has a heat stabilizer, an antioxidant, a UV absorber, an anti-blocking agent, a light stabilizer, a nucleating agent, and a hydrolysis inhibitor as long as the effects of the main components are not impaired. Additives such as deodorants can be formulated.
For example, in order to maintain the practical properties of the present lactic acid-based soft film, the lactic acid-based mixed resin composition (B) 100 mass comprising the lactic acid-based polymer (B-1) and the lactic acid-based copolymer (B-2). The weight average molecular weight can be increased by adding 0.1 to 3 parts by mass, more preferably 0.5 to 1 part by mass of the carbodiimide compound with respect to parts. Below this range, the effect of increasing the weight average molecular weight is often insignificant, and above this range, fish eyes and gels may be produced during film formation, which is not preferred.

<Adhesive layer>
Next, components of the adhesive layer will be described.

  The adhesive layer has, as a main component, a copolymer of a soft aromatic hydrocarbon and a conjugated diene hydrocarbon or a hydrogenated derivative (F-1) of these copolymers, and a vinyl acetate content of 30 to 80% by mass. Ethylene-vinyl acetate copolymer (F-2), modified polyolefin resin (F-3), lactic acid-based polymer, polymer block mainly composed of acrylate unit and methacrylate unit. What is necessary is just to contain either the lactic acid and the acrylic mixed resin (F-4) which is a mixed resin with the acrylic block copolymer which has a polymer block, and 1 type or 2 types or more of these are included. It may be a mixture (hereinafter, these are collectively referred to as “adhesive layer component F”). Moreover, it can also be used by mixing with other thermoplastic resins, and the type and mixing ratio of the resin to be mixed can be appropriately determined according to the resin constituting both the surface layer and the intermediate layer.

(Adhesive layer component (F-1))
In the adhesive layer component (F-1), styrene is preferably used as the soft aromatic hydrocarbon, and styrene analogs such as α-methylstyrene can also be used.
As the conjugated diene hydrocarbon, 1,3-butadiene, 1,2-isoprene, 1,4-isoprene, 1,3-pentadiene and the like are used, and these may be hydrogenated derivatives. These may be used alone or in admixture of two or more.

  In the copolymer of the soft aromatic hydrocarbon and the conjugated diene hydrocarbon or the hydrogenated derivative (F-1) thereof, the content of the soft aromatic hydrocarbon is based on the mass of the entire copolymer. (100%) is preferably 5 to 40% by mass, more preferably 7 to 35% by mass, and still more preferably 10 to 30% by mass. If the content of the soft aromatic hydrocarbon is 5% by mass or more, good compatibility can be obtained when the regenerated film is regenerated and added to any layer, and clouding of the film can be suppressed. . On the other hand, if the content of the aromatic hydrocarbon is 40% by mass or less, the buffering action against the stress generated between the surface layer and the intermediate layer when stress is applied to the film without reducing flexibility. Works to suppress delamination.

  Copolymers of soft aromatic hydrocarbons and conjugated diene hydrocarbons or their hydrogenated derivatives (F-1) include styrene-conjugated diene random copolymers and styrene-conjugated diene random copolymers The hydrogenated derivative of can be preferably used. Moreover, these copolymers can be used individually or in mixture of 2 or more types. Furthermore, it can also be used by mixing with one or more other thermoplastic resins.

As the copolymer of the soft aromatic hydrocarbon and the conjugated diene hydrocarbon or the hydrogenated derivative (F-1) thereof, a copolymer obtained by introducing a polar group can be selected.
Examples of polar groups to be introduced include acid anhydride groups, carboxylic acid groups, carboxylic acid ester groups, carboxylic acid chloride groups, carboxylic acid amide groups, carboxylic acid groups, sulfonic acid groups, sulfonic acid ester groups, and sulfonic acid chloride groups. Sulfonic acid amide group, sulfonic acid group, epoxy group, amino group, imide group, oxazoline group, hydroxyl group and the like.
Typical examples of the copolymer of a styrene compound having a polar group and a conjugated diene or a hydrogenated derivative thereof include maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, epoxy-modified SEBS, and epoxy-modified SEPS.
These copolymers can be used alone or in admixture of two or more.

  When a copolymer of a soft aromatic hydrocarbon and a conjugated diene hydrocarbon or a hydrogenated derivative thereof (F-1) places importance on both the adhesion between both surface layers and the intermediate layer and extrusion stability For this, it is preferable to select a copolymer with a styrene-conjugated diene hydrocarbon having an MFR (JISK7210, 190 ° C., load 21.18 N) of 0.8 to 30 g / 10 min. If the MFR of the conjugated diene hydrocarbon is 0.8 g / 10 min or more, the extrusion processability is stable, and if it is 30 g / 10 min or less, stable film formation at the time of molding is possible. This is preferable because there is less decrease and variation. From such a viewpoint, those having an MFR of 1 to 20 g / 10 min are more preferable.

(Adhesive layer component (F-2))
In the ethylene-vinyl acetate copolymer (F-2), the vinyl acetate content is preferably 30 to 80%. If the vinyl acetate content is 30% by mass or more, the crystallinity is low, so the elastic modulus at normal temperature is low, self-adhesiveness is easily developed, and the refractive index of the film approaches the components constituting the intermediate layer. This is preferable because the transparency is improved. On the other hand, if it is 80 mass% or less, since blocking of a raw material etc. do not generate | occur | produce and a malfunction does not arise in handling, it is preferable. From these things, 30-80 mass% of vinyl acetate content is preferable, 40-70 mass% is still more preferable, Especially preferably, it is 45-60 mass%.

  In addition, when using an ethylene-vinyl acetate copolymer as the polyolefin polymer (A) which is the main component of both surface layers, rather than the vinyl acetate content of the ethylene-vinyl acetate copolymer of both surface layers, It is preferable to increase the vinyl acetate content of the ethylene-vinyl acetate copolymer of the adhesive layer. For example, the vinyl acetate content of the ethylene-vinyl acetate copolymer of both surface layers is 10% by mass or more and less than 30% by mass, and the vinyl acetate content of the ethylene-vinyl acetate copolymer of the adhesive layer is 30 to 80% by mass. And it is sufficient. By doing in this way, while maintaining the film properties such as heat resistance, film strength, bleed-out suppression, film unwinding property, appearance, etc., the adhesion of each layer (delamination at the time of small rewinding) Transparency can be improved, and in particular, a useful design as a small roll film can be achieved.

  In the case where importance is attached to both the adhesion between the surface layer and the intermediate layer and the extrusion stability, the ethylene-vinyl acetate copolymer (F-2) having a vinyl acetate content of 30 to 80% by mass, It is preferable to select an ethylene-vinyl acetate copolymer having an MFR (JIS K7210, 190 ° C., load 21.18 N) of 0.8 to 30 g / 10 min. If the MFR of the ethylene-vinyl acetate copolymer is 0.8 g / 10 min or more, the extrusion processability is stable, and if it is 30 g / 10 min or less, stable film formation at the time of molding is possible. It is preferable because the mechanical strength is less reduced and uneven. From this, the MFR is preferably 1 to 20 g / 10 min.

  Such an adhesive layer component (F-2) can also be used by mixing with other thermoplastic resins such as other polyolefin copolymers. In that case, the kind of resin to be mixed, the mixing ratio, and the like can be appropriately determined according to the resin constituting both the surface layer and the intermediate layer.

(Adhesive layer component (F-3))
The modified polyolefin resin refers to a resin whose main component is a polyolefin modified with a modified monomer such as an unsaturated carboxylic acid or an anhydride thereof, or a silane coupling agent.

In the modified polyolefin resin (F-3), as the unsaturated carboxylic acid or anhydride thereof, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride, or Examples include ester compounds of monoepoxy compounds of these derivatives and the above acids, reaction products of polymers having acids capable of reacting with these acids in the molecule and acids, or metal salts thereof. Can be used alone, or two or more of these can be mixed and used.
Among the above, as the unsaturated carboxylic acid or anhydride thereof, maleic anhydride is more preferable.

  Examples of the silane coupling agent include vinyltriethoxysilane, methacryloyloxytrimethoxysilane, γ-methacryloyloxypropyltriacetyloxysilane, and the like. These can be used alone or in combination. Two or more of them can be mixed and used.

In order to produce a modified polyolefin resin, for example, these modified monomers can be copolymerized in the stage of polymerizing in advance, or these modified monomers can be graft-copolymerized to the polymer once polymerized. it can. Of these, graft-modified ones are particularly suitable.
In the modification, these modifying monomers can be used alone or in combination. The content of the modified monomer is preferably 0.1 to 5% by mass.

  Among the above modified polyolefin resins, when the extrusion stability is given the highest priority, at least one ethylene resin selected from low density polyethylene, linear low density polyethylene, and linear ultra low density polyethylene, and maleic anhydride, It is preferable to select the graft copolymer.

(Adhesive layer component (F-4))
Lactic acid / acrylic mixed resin (F-4) is an acrylic block copolymer having a lactic acid polymer, a polymer block mainly composed of an acrylate unit and a polymer block mainly composed of a methacrylic ester unit ( G) and mixed resin.

The lactic acid polymer in the lactic acid / acrylic mixed resin (F-4) can be selected from the same type as the lactic acid polymer (B-1) in the intermediate layer.
The lactic acid-based polymer used for the adhesive layer and the lactic acid-based polymer in the intermediate layer may be the same or different, and may have an optimal composition according to the suitability of each layer. A lactic acid polymer should be selected.
The lactic acid-based polymer used for the adhesive layer may contain a copolymer (component) other than lactic acid of any of L-form, D-form, and DL (racemic) -form.
Other copolymer components include ethylene glycol, propylene glycol, butanediol, decanediol, 1,4-cyclohexaneanthyl glycol, neopentyl glycol, glycerin, pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetra Glycol compounds such as methylene glycol, oxalic acid, adipic acid, malonic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, cyclohexanedicarboxylic acid, dodecanedioic acid, naphthalenedicarboxylic acid, bis (P-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutyl Dicarboxylic acids such as phosphonium isophthalic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid and other hydroxycarboxylic acids, and caprolactone, valerolactone, propiolactone, undecalactone, 1 And lactones such as 5-oxepan-2-one.

On the other hand, the acrylic block copolymer (G) includes at least one polymer block (g1) mainly composed of acrylate units and at least one polymer block (g2) mainly composed of methacrylate units. ).
The content of the acrylate unit in the polymer block (g1) and the content of the methacrylic ester unit in the polymer block (g2) are not particularly limited as long as they are the main components. It is preferable that it is the range of 60-100 mass%, respectively, and it is more preferable that it is the range of 80-100 mass%.

  The block (g1) mainly composed of the acrylate unit is a polymer block mainly composed of an acrylate unit, and examples of the acrylate ester for forming the polymer block include methyl acrylate. , Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate Cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, It can include one or a combination of two or more of such acrylic acid 2-methoxyethyl. However, it is not limited to such an example.

  The polymer block (g2) mainly composed of the methacrylic acid ester unit is a polymer block mainly composed of a methacrylic acid ester unit. Examples of the methacrylic acid ester for forming the polymer block include methacrylic ester. Methyl acetate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n methacrylate -Hexyl, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylate Nokishiechiru, 2-hydroxyethyl methacrylate, mention may be made of one or more combinations of methacrylic acid 2-methoxyethyl. However, it is not limited to such an example.

  The acrylic block copolymer (G) includes a polymer block (g1) mainly composed of an acrylate unit and a polymer block (g2) mainly composed of a methacrylic ester unit. Among these, a triblock copolymer in which the polymer block (g2) is bonded to both ends of the polymer block (g1) is preferable in that heat resistance and the like can be improved.

It is also preferable to have a polymer block (g3) derived from a monomer other than the acrylate monomer and the methacrylic acid ester monomer in a block different from these blocks (g1 and g2).
The form of the bond between the polymer block (g3) and the polymer block (g1) or the polymer block (g2) is not particularly limited. For example, (g2)-{(g1)-(g2)} n- ( g3) structure (n is a natural number), (g3)-(g2)-{(g1)-(g2)} n- (g3) structure, and the like.
Examples of monomers constituting the polymer block (g3) include olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene, conjugated diene compounds such as 1,3-butadiene, isoprene and myrcene, styrene, α -Aromatic vinyl compounds such as methylstyrene, p-methylstyrene, m-methylstyrene, vinyl acetate, vinylpyridine, acrylonitrile, methacrylonitrile, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide, ε -Caprolactone, valerolactone and the like.

  In the lactic acid / acrylic mixed resin (F-4), the mass ratio of the lactic acid polymer (L) and the acrylic block copolymer (G) is (L) :( G) = 10: 90 to 70:30. It is preferable that (L) :( G) = 20: 80 to 50:50 is more preferable. If the amount of (G) in the total of (L) and (G) is 30% by mass or more, the function as the adhesive layer can be sufficiently expressed, and if it is 90% by mass or less, the lactic acid series This is preferable because the affinity with the polymer (B-1) and the affinity with the intermediate layer are improved.

  If the melt flow rate (JIS K7210, 190 ° C., load 21.18 N) (hereinafter also referred to as “MFR”) of the lactic acid / acrylic mixed resin (F-4) is 0.2 g / 10 min or more, extrusion processing is performed. However, when used as an adhesive layer, it is preferable that the difference in melt viscosity between the front and back layers or the intermediate layer is small. From such a viewpoint, the MFR of the lactic acid / acrylic mixed resin (F-4) is preferably in the range of 5 to 50 g / 10 minutes, and particularly preferably in the range of 10 to 40 g / 10 minutes.

As long as the effect of the lactic acid / acrylic mixed resin (F-4) is not impaired, in addition to the lactic acid-based polymer and the acrylic block copolymer, other polymers and additives are contained as necessary. You may do it.
Examples of other polymers that can be blended include polyacrylic rubber, polybutene rubber, polyisobutylene rubber, synthetic rubbers such as EPR and EPDM. Examples of additives include mineral oil softeners such as paraffinic oil and naphthenic oil for improving fluidity during molding; carbon dioxide for the purpose of improving heat resistance, weather resistance, etc. Inorganic fillers such as calcium, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate; inorganic fibers or organic fibers such as glass fibers and carbon fibers for reinforcement; heat stabilizers; antioxidants; Light stabilizers; adhesives; tackifiers; plasticizers; antistatic agents; foaming agents. Among these additives, in order to further improve heat resistance and weather resistance, it is practically preferable to add heat stability, an antioxidant, and the like.

The method for preparing the lactic acid / acrylic mixed resin (F-4) is not particularly limited. For example, a lactic acid polymer and an acrylic block copolymer may be mixed together with other polymers and additives as described above as necessary. The mixing operation can be performed using a known mixing or kneading apparatus such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer.
The temperature at the time of mixing or kneading should be appropriately adjusted according to the melting temperature of the lactic acid polymer or acrylic block copolymer, and is usually mixed at a temperature in the range of 110 ° C to 300 ° C. .

(Adhesive layer thickness)
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.

<Surface layer, adhesive layer, intermediate layer>
The surface layer, adhesive layer, and / or intermediate layer of this packaging film are appropriately blended with the following various additives in order to provide performance such as antifogging properties, antistatic properties, slipperiness, and tackiness. can do.
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, glycerin acetyl ricinoleate, polyglycerin stearate, polyglycerin 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.

<Reproduction layer>
The packaging film contains, in addition to the surface layer, the intermediate layer, and the adhesive layer, a regenerated layer, that is, a polyolefin polymer (A), a lactic acid mixed resin composition (B), and an adhesive layer component (F). A reproduction layer can be provided.
This reproduction layer can use trimming loss that occurs when, for example, both ends of a film formed are cut and trimmed, so that waste of material can be eliminated and material cost 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, two surface layers, an intermediate layer, or an adhesive layer are formed, and by adding trimming loss at both ends of the film to one of the layers, 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, depending on whether the layer to which trimming loss is added is the surface layer, the intermediate layer, or the adhesive layer, the surface layer, the intermediate layer, and the adhesive layer in the reproduction layer The mixing ratio of the three components can be adjusted.

<Laminated structure>
The present lactic acid-based soft film may be a laminated film having three layers of both surface layers and an intermediate layer, and other layers (hereinafter referred to as “P layer”) as required, such as improvement of mechanical properties and interlayer adhesion. May be omitted as appropriate. For example, a layer having the same composition as the surface layer (hereinafter sometimes abbreviated as “S layer”) may be interposed as an intermediate layer in addition to both surface layers, and the same composition as the intermediate layer Two or more layers (hereinafter sometimes abbreviated as “M layer”) may be interposed between both surface layers. Specifically, a three-layer configuration consisting of (S layer) / (M layer) / (S layer), a four-layer configuration consisting of (S layer) / (P layer) / (M layer) / (S layer), (S layer) / (P layer) / (M layer) / (P layer) / (S layer), (S layer) / (M layer) / (P layer) / (M layer) / (S layer), etc. A five-layer structure composed of In this case, the resin composition and thickness ratio of each layer may be the same or different.

An adhesive layer can also be provided between the intermediate layer and the surface layer. 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 this lactic acid-based soft 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 each characteristic value (E ′, tan δ) due to dynamic viscoelasticity. For example, when the film is formed by the T-die method, it is stable. Film formation stability can be obtained. Moreover, the mechanical characteristic for expressing the cut property suitable for the wrapping film for food packaging, and the relaxation characteristic for expressing the adhesiveness of a container can also be provided comparatively easily. Furthermore, even when stored in a state where the film is wound, blocking does not occur, antifogging properties and container adhesion are good, and in addition to the fact that molecular weight reduction due to hydrolysis is less likely to occur over time, It can be set as the film for packaging which has favorable adhesiveness between each layer.
Furthermore, when more importance is attached to stable film forming workability and flexibility, the thickness ratio of the intermediate layer to the entire film thickness is preferably 35 to 65%, more preferably 35 to 60%. preferable.
Further, in the case where importance is attached to the cut property and the adhesion to the 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.

  The thickness (whole) of the present lactic acid-based soft film may be a range that can be used as a wrapping film for food packaging, specifically 6 μm to 30 μm, and preferably 10 μm to 20 μm.

<Film characteristic value>
In consideration of the use of the present lactic acid-based soft film as a wrapping film for food packaging, it was measured at a vibration frequency of 10 Hz and a strain of 0.1% by a dynamic viscoelasticity measurement method described in JIS K-7198 A method. The storage elastic modulus (E ′) at ° C. is preferably in the range of 100 MPa to 4 GPa, and in particular, 1 GPa to 4 GPa is preferable for use in a small roll wrap film.
When a film is used as a wrapping film for food packaging, an elastic modulus value near room temperature is an index. Therefore, if the storage elastic modulus (E ′) at 20 ° C. is 100 MPa or more, the films do not adhere to each other or the film and other substances at room temperature due to excessive flexibility, and if it is 4 GPa or less, the film Is suitable for food packaging wrap film applications, since it is not too hard and stretches appropriately.
When the storage elastic modulus (E ′) is less than 1 GPa, since the film is too soft and the stress is too small for deformation, for example, the cutability when pulled out from a paper box and cut may deteriorate. It is preferably 1 GPa or more.

In the same measurement, the value of the loss tangent (tan δ) at 20 ° C. is preferably in the range of 0.1 to 0.8, and more preferably in the range of 0.1 to 0.3.
The peak value of loss tangent (tan δ) is a physical property indicating a delay in deformation when a force is applied, and is one of parameters indicating a stress relaxation behavior. If the value of the loss tangent is small, the relaxation behavior of the film is fast, and conversely if the value is large, the stress relaxation is slow. If the loss tangent (tan δ) value at 20 ° C. is 0.1 or more, the restoring behavior against deformation of the film does not occur instantaneously, and if it is 0.8 or less, the restoring behavior is not too slow. Suitable as a wrapping film for food packaging.

Furthermore, in the same measurement, the loss tangent (tan δ) peak temperature is preferably 20 ° C. to 60 ° C., and the peak value is preferably in the range of 0.1 to 0.8.
When the peak temperature of tan δ is 60 ° C. or lower and the peak value is 0.1 or higher, 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 ′). The loss elastic modulus (E ″) of the material, that is, the contribution ratio of viscosity among viscoelastic properties is increased. By evaluating the tan δ value and the temperature range showing a high value, the adhesion to the container at the time of packaging is improved. It is a big guideline for judging the stress relaxation behavior of the film in the packaging process.

  In order to produce a film satisfying the storage elastic modulus (E ′) and loss tangent (tan δ) as described above, for example, selection of components in the intermediate layer and the surface layer (including an adhesive layer and a reproduction layer in some cases) (Type of resin as the main component, its molecular weight and Tg, type of plasticizer, blending ratio of components, LD ratio of lactic acid polymer and lactic acid copolymer, etc.), thickness ratio of intermediate layer and surface layer (in case Depending on the thickness ratio of the adhesive layer and the reproduction layer), a film forming method, and processing conditions (for example, heat treatment conditions after film formation, etc.) can be appropriately adjusted in a balanced manner.

<Manufacturing method>
Next, the manufacturing method of this lactic acid type soft film is demonstrated.

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, a lactic acid polymer, a lactic acid copolymer, and if necessary, additives are sufficiently dried to remove moisture, and these are melt mixed using a twin screw extruder. The pellets may be produced by extruding into a strand shape while adding a predetermined amount of plasticizer from the vent port.
At this time, it is preferable to appropriately select the melt extrusion temperature in consideration of the viscosity of the mixture changing depending on the mixing ratio of the lactic acid polymer, the lactic acid copolymer and the plasticizer. Actually, it is preferable to select a temperature range of 160 to 230 ° C.

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 that extends 1.2 to 5 times, or a flat stretching method that sequentially biaxially and / or simultaneously biaxially stretches 1.2 to 5 times in both the longitudinal and transverse directions of the film.

  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. Moreover, as a cooling method in that case, any of the method of cooling from the outer surface of a tube and the method of cooling from both the outer side of a tube and an inner surface may be sufficient.

  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.

The stretching temperature is usually preferably 120 ° C. or less, more preferably 100 ° C. or less, usually at the surface temperature at the stretching start point of the film (in the case of inflation, the position where expansion starts as a bubble).
Examples of the stretching method include a roll stretching method, a tenter method, and inflation. Among these, a method of forming a film by simultaneous biaxial stretching is preferable in terms of stretching. When the inflation method is adopted, biaxial simultaneous stretching can be performed, and it can be manufactured relatively inexpensively with high productivity, and the shape can be made into a bag shape (seamless shape). Therefore, it is particularly suitable for the production of bags and bags such as bags and compost bags for preventing water from condensing on the surroundings, such as take-out bags for supermarkets, low-temperature food packs such as frozen foods and meat.
By combining with the coextrusion method, a multilayer film can be produced with high productivity by using a plurality of resin compositions and / or other types of polymers according to the present invention having different properties.

  Moreover, as for the heat processing conditions, it is preferable that temperature is 40 to 120 degreeC, Most preferably, it is 50 to 110 degreeC. If the heat treatment temperature is 40 ° C. or higher, the heat treatment effect can be easily obtained, and if it is 120 ° C. or lower, the elastic modulus does not become too low.

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

<Application>
This lactic acid-based soft film is a shopping bag, garbage bag, compost bag, food / confectionery packaging film, food wrap film, cosmetic / cosmetic wrap film, pharmaceutical wrap film, herbal medicine wrap film, stiff shoulders and sprains, etc. Wrapping films for surgical patches, sanitary materials (paper diapers, sanitary products), agricultural and horticultural films, agricultural chemicals wrapping films, greenhouse films, fertilizer bags, magnetic films such as video and audio Tape cassette product packaging film, floppy disk packaging film, plate-making film, adhesive tape, tape, waterproof sheet, sandbag bag, etc. In particular, it can be suitably used as a food wrap film.

  It should be noted that the upper and lower limits of the numerical range in the present invention are those of the present invention as long as they have the same operational effects as those in the numerical range even if they are slightly outside the numerical range specified by the present invention. It is included in the equivalent range.

  Examples are shown below, but the present invention is not limited by these.

<Example (1-1)>
As the polyolefin polymer (A), an ethylene-vinyl acetate copolymer “LV440” (vinyl acetate content: 15 mass%, MFR: 2.2 g / 10 min, manufactured by Nippon Polyethylene Co., Ltd., hereinafter abbreviated as “a-1”). )
As the lactic acid polymer (B-1), crystalline polylactic acid NatureWorks 4032D manufactured by NatureWorks (L-lactic acid / D-lactic acid = 98.6 / 1.4, weight average molecular weight: 200,000, hereinafter “b-1-1” ”),
As a lactic acid copolymer (B-2), a copolymer of a lactic acid polymer and a diol / dicarboxylic acid (a copolymer of lactic acid and propylene glycol / succinic acid, lactic acid: 48 mol%, propylene glycol: 26 mol%) Succinic acid: 26 mol%, weight average molecular weight: 60,000, Tg: 10 ° C., hereinafter abbreviated as “b-2-1”),
As the plasticizer (C), acetylated monoglyceride (Riken Vitamin Riquemar PL-019, hereinafter abbreviated as “c-1”) was used.

The mixing ratio was b-1-1: b-2-1 = 60: 40 by mass ratio, and c-1 was 10 with respect to 100 parts by mass of the mixed composition of b-1-1 and b-2-1. It was set as the mass part.
The lactic acid copolymer B-2 has one maximum value of loss tangent (tan α) in dynamic viscoelasticity measurement (JIS K-7198 A method; strain 0.1%, vibration frequency 10 Hz). This is a type of copolymer, and the mixture of lactic acid-based polymer b-1-1 and lactic acid-based copolymer b-2-1 was a system having a single glass transition temperature.

  About the resin composition which forms both surface layers, polyolefin polymer (a-1) 100 mass parts, and RIKEN VITAMIN Co., Ltd. diglycerin monooleate "DGO-1" 5.0 mass parts are used as an antifogging agent. Then, it was put into a same-direction twin screw extruder set at an extrusion set temperature of 180 to 200 ° C., melted and kneaded, and extruded into a strand shape to prepare pellets.

  About the resin composition which forms an intermediate | middle layer, after drying a lactic acid type polymer (b-1-1) and a lactic acid type copolymer (b-2-1) fully, respectively, and removing a water | moisture content, mass ratio c-1 was dry blended at a ratio of b-1-1: b-2-1 = 60: 40, and melt-kneaded at a set temperature of 180 ° C. using a 40 mmφ small-sized co-axial twin screw extruder manufactured by Mitsubishi Heavy Industries. It poured from the vent port at a ratio of 10 parts by mass with respect to 100 parts by mass of the total amount of b-1-1 and b-2-1, melted and kneaded at 180 ° C, and extruded into a strand shape to prepare pellets.

  The pellets prepared as described above were put into separate extruders and merged, co-extruded at a three-layer T die temperature of 200 ° C. and a die gap of 2 mm, and rapidly cooled with a cast roll set at a temperature of 30 ° C. A packaging film having a total thickness of 12 μm (surface layer / intermediate layer / surface layer = 3 μm / 6 μm / 3 μm) was obtained. The results of evaluating the obtained film are shown in Table 1.

<Example (1-2)>
In Example (1-1), as the lactic acid-based polymer (B-1), the above b-1-1, NatureWorks 4060D (L-lactic acid / D-lactic acid = 87/13, weight average molecular weight: 190,000 or less) (Abbreviated as “b-1-2”) at a mass ratio of b-1-1: b-1-2 = 30: 70. ), A film having a thickness of 12 μm was obtained.
The obtained film was evaluated for storage elastic modulus (E ′) and loss tangent (tan δ) at 20 ° C., heat resistance, antifogging property, adhesion, and bleeding property. The results are shown in the table.

<Comparative Example (1-1)>
In Example (1-1), pellets pre-compounded in advance so as to have the same composition as the intermediate layer in Example (1-2) were put into an extruder for both surface layers, and substantially a single layer. A food packaging wrap film having a total thickness of 12 μm was obtained in the same manner as in Example (1-1) except that the film was used. The results of evaluating the obtained film are shown in Table 1.

<Comparative Example (1-2)>
In Example (1-1), the same mixed composition as in the front and back layers of Example (1-2) was charged into the extruder for the intermediate layer to make a substantially single layer film. A wrapping film for food packaging having a thickness of 12 μm was obtained. The results of evaluating the obtained film are shown in Table 1.

(Measurement and evaluation method)
The films obtained in Examples (1-1) to (1-2) and Comparative Examples (1-1) to (1-2) were evaluated by the following methods.

(1) Dynamic viscoelastic properties Using a spectro rheometer “VES-F3” manufactured by Iwamoto Seisakusho Co., Ltd. according to the dynamic viscoelasticity measurement method described in JIS K-7198 A method, the lateral direction of the film (TD, film ) At a vibration frequency of 10 Hz, a strain of 0.1%, and a temperature of 20 ° C., and a storage elastic modulus (E ′) and a loss tangent (tan δ) at a temperature of 20 ° C. are obtained. It was.

(2) Wet heat durability The obtained film was placed in a constant temperature and humidity machine LH-112 made by Tabay Espec adjusted to 40 ° C. × 90 mass% for 1 month. The feel of the film after the test was evaluated according to the following criteria.
A: The appearance and feel of the film are almost the same as before the test.
○: The film strength is slightly reduced from before the test, but there is no practical problem.
X: The state in which the film strength is extremely reduced and breakage occurs during rewinding.

(3) Film-forming stability When a film was formed by the T-die forming method, the stability of casting and the degree of sticking to a roll were observed and evaluated according to the following criteria.
A: Extremely stable.
○: Stable.
X: Slightly unstable.

(4) Blocking resistance The obtained roll of film was stored in a temperature-controlled room at 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. did.
A: There is no blocking between films.
○: Peeling is somewhat heavy due to blocking between films.
X: The film cannot be peeled off due to blocking between the films and cannot be reversed.

(5) Container adhesion Water (50 cc) is placed in a bowl-shaped ceramic container having a diameter of 10 cm and a depth of 5 cm, and the entire container is packaged with the obtained film, and stored at 0 ° C. for 15 hours. The degree of adhesion was evaluated.
(Double-circle): The film is in close contact with the container in a state of elasticity.
○: The film and the container are displaced, and some slack is generated.
X: Almost not adhered.

(6) Anti-fogging property Water (50cc) is put into a bowl-shaped ceramic container with a diameter of 10cm and a depth of 5cm, and it is wrapped with a film so that the opening of the bowl is sealed, and stored at 0 ° C for 30 minutes. The cloudiness was evaluated.
A: Transparent and clearly visible inside.
○: A state where fine droplets are visible on the surface.
X: A state of being clouded white.

(Discussion)
As is apparent from Table 1, the films obtained in Examples (1-1) to (1-2) did not cause blocking even when stored in a state in which the formed film was wound, and were anti-fogged. It was confirmed that the film was a polylactic acid-based food packaging film having good properties and container adhesion, and less likely to cause a decrease in molecular weight due to hydrolysis over time.
On the other hand, in the case where there is no front and back layer mainly composed of a polyolefin-based polymer (Comparative Example (1-1)), the container adhesion is good, but the blocking and antifogging properties are insufficient. Thus, it was confirmed that there was a problem, and further, the molecular weight decreased due to hydrolysis over time, and it was confirmed that there was a problem due to insufficient practical characteristics. When there is no intermediate layer mainly composed of a polylactic acid-based polymer composition (Comparative Example (1-2)), blocking and antifogging properties are good, but container adhesion is insufficient. It was confirmed.

<Example (2-1)>
About the resin composition which forms both surface layers, Nippon Unicar Co., Ltd. linear low density polyethylene "NUCG5225" as a polyolefin polymer (A) (density: 0.92 g / cm < ³ >, MFR: 2. 0 g / 10 min) 100 parts by mass and diglycerin monooleate “DGO-1” (5.0 parts by mass) manufactured by Riken Vitamin Co., Ltd. as an antifogging agent were set at an extrusion set temperature of 180 to 200 ° C. The mixture was put into a shaft extruder and melt kneaded.
On the other hand, for the resin composition forming the intermediate layer, “NatureWorks 4060D” (L-form / D-form = 87/13, weight average molecular weight: 200,000) manufactured by NatureWorks is used as the lactic acid polymer (B-1). “Plamate PD-350” (manufactured by Dainippon Ink & Chemicals, Inc.) as a lactic acid copolymer (B-2) (polylactic acid / propylene glycol / succinic acid copolymer / polylactic acid: 48 mol%, propylene glycol: 26 mol%, succinic acid: 26 mol% / weight average molecular weight: 58,000) and mixed at a mass ratio of B-1 / B-2 = 20/80 to make 100 parts by mass. Nisshinbo Co., Ltd. “Carbodilite HMV-8CA” as a carbodiimide compound was added at a ratio of 1 part by mass to the extrusion set temperature of 180 to 200 ° C. As a component (F-1) that is an adhesive resin in an adhesive layer extruder, “Tuftec H1041” (styrene-ethylene-butadiene block copolymer) manufactured by Asahi Kasei Co., Ltd. ) (Hereinafter abbreviated as “f1”).
Then, the resin composition for forming both surface layers melted and kneaded as described above, the resin composition for forming the intermediate layer, and the resin composition for forming both adhesive layers are joined from separate extruders, respectively. , 5 layer T die temperature 200 ° C., co-extrusion at a die gap of 2 mm, and quenching with a cast roll set at a temperature of 30 ° C., resulting in a total thickness of 12 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 2 μm / 1 μm / 6 μm / 1 μm / 2 μm) packaging film was obtained. The results of evaluating the obtained film are shown in Table 2.

<Example (2-2)>
In Example (2-1), the mass ratio of the resin composition forming the intermediate layer is B-1 / B-2 = 40/60 by mass ratio, and the addition amount of the carbodiimide compound is 0.5 parts by mass. A packaging film having a total thickness of 12 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 2 μm / 1 μm / 6 μm / 1 μm / 2 μm) was obtained in the same manner as in Example (2-1) except for changes. Obtained. The results of evaluating the obtained film are shown in Table 2.

<Example (2-3)>
In Example (2-1), the mass ratio of the resin composition forming the intermediate layer is B-1 / B-2 = 60/40 by mass ratio, and the plasticizer (C) is Riken Vitamin Co., Ltd. Example except that the acetylated monoglyceride “Likemar PL019” (molecular weight 420) was melt-kneaded while being injected from the first vent port of the same-direction twin-screw extruder to 5 parts by mass using a metering pump. In the same manner as (2-1), a packaging film having a total thickness of 12 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 2 μm / 1 μm / 6 μm / 1 μm / 2 μm) was obtained. The results of evaluating the obtained film are shown in Table 2.

<Example (2-4)>
In Example (2-2), the component (F-1), which is an adhesive resin, was added to “Primalloy A1800” (a thermoplastic polyester block copolymer and styrene-ethylene-) manufactured by Mitsubishi Chemical Corporation in an extruder for an adhesive layer. A total thickness of 12 μm (surface layer / adhesive layer / intermediate layer / adhesive layer) in the same manner as in Example (2-1) except that the mixture was changed to a mixture with a butadiene block copolymer (hereinafter abbreviated as “f2”). / Surface layer = 2 μm / 1 μm / 6 μm / 1 μm / 2 μm). The results of evaluating the obtained film are shown in Table 2.

<Example (2-5)>
In Example (2-3), the same procedure as in Example (2-1) was conducted except that adipate ester “PX-884” (molecular weight 650) manufactured by Asahi Denka Co., Ltd. was used as the plasticizer (C). A packaging film having a total thickness of 12 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 2 μm / 1 μm / 6 μm / 1 μm / 2 μm) was obtained. The results of evaluating the obtained film are shown in Table 2.

<Example (2-6)>
In Example (2-3), the polyolefin polymer (A) was made from Nippon Polyethylene Co., Ltd. ethylene-vinyl acetate copolymer “LV440” (vinyl acetate content: 15 mass%, density: 0.93 g / cm ^3). , MFR: 2.0 g / 10 min), except that the component (F-1), which is an adhesive resin, is changed to “Hybra 5125” (styrene-vinyl isopropylene block copolymer) manufactured by Kuraray Co., Ltd. In the same manner as in Example (2-1), a packaging film having a total thickness of 12 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 2 μm / 1 μm / 6 μm / 1 μm / 2 μm) was obtained. The results of evaluating the obtained film are shown in Table 2.

<Reference Example (2-1)>
In Example (2-1), the component that is an adhesive resin in the extruder for the adhesive layer was changed to “bond first” (ethylene-ethyl acrylate-glycidyl methacrylate terpolymer) manufactured by Sumitomo Chemical Co., Ltd. The total thickness is 12 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 2 μm / 1 μm / 6 μm) in the same manner as in Example (2-1) except that it is changed to (hereinafter abbreviated as “f3”). / 1 μm / 2 μm) was obtained. The results of evaluating the obtained film are shown in Table 2.

<Reference Example (2-2)>
In Example (2-1), pellets pre-compounded in advance so as to have the same composition as the intermediate layer in Example (2-1) were put into an adhesive layer extruder, and a substantially three-layer film. A packaging film having a total thickness of 12 μm (surface layer / intermediate layer / surface layer = 1.5 μm / 9 μm / 1.5 μm) was obtained in the same manner as in Example (2-1) except that. The results of evaluating the obtained film are shown in Table 2.

(Measurement and evaluation method)
About the film obtained by said Example (2-1)-(2-6) and reference example (2-1)-(2-2), it evaluated by the following method.
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) E ′, tan δ
According to the dynamic viscoelasticity measurement method described in JIS K-7198 A method, a dynamic viscoelasticity measurement device “DVA-200” manufactured by IT Measurement Control Co., Ltd. is used, and the transverse direction (TD) of the film is vibrated. Measured from −50 ° C. to 150 ° C. at a heating rate of 1 ° C./min at a frequency of 10 Hz and a strain of 0.1%. From the obtained data, the storage elastic modulus (E ′) at a temperature of 20 ° C. and loss The tangent (tan δ) peak temperature and its peak value were determined.

(2) Film formation stability When a film was formed by the T-die forming method, the stability of casting and the degree of sticking to a roll were observed and evaluated according to the following criteria.
◎: Extremely stable ○: Stable △: Level that is slightly unstable but possible in actual production ×: Level that is unstable and causes problems in actual production

(3) Blocking resistance The obtained roll of film was stored in a temperature-controlled room at a temperature of 43 ° C. and a relative humidity of 40% for 5 days, and the subsequent surface condition and rewinding property were observed and evaluated according to the following criteria. did.
◎: There is no blocking between films. ○: There is a little blocking between films, but there is no practical problem. △: A level where peeling is somewhat heavy due to blocking between films. Cannot be rolled back

(4) Adhesion of container Adhesion to a container when it was packaged in a bowl made of ceramic bowl having a diameter of 10 cm and a depth of 5 cm was evaluated according to the following criteria.
◎: Level that can be packaged moderately ○: Level that spreads slightly from the shape of the container, but there is no practical problem ×: The film spreads along the container and becomes a practical problem

(5) Anti-fogging property A film is pasted on one side of an opening of a SUS304 cylinder having a diameter of 50 mm and a height of 80 mm, and the film is pasted in an environment with an outside temperature of 0 to 5 ° C. The cylindrical end 30 mm on the open side was immersed in water at a water temperature of 20 ° C., and after 1 hour from the start of immersion, the antifogging property was visually observed and evaluated according to the following criteria.
◎: Water film with uniform moisture and no water droplets ○: Water film with uniform moisture content, but there are fine water droplets in some places △: Water droplets with a diameter of about 1 mm in some places ×: Water droplets with a diameter of about 3 mm

(6) Interlaminar peel strength The strength when the formed film was peeled to TD at a test speed of 200 mm / min by a T-type peel method in an environment of 23 ° C. and 50% RH was evaluated according to the following criteria.
◎: 500 g / 15 mm width or more ○: 200 g / 15 mm width or more and less than 500 g / 15 mm Δ: 50 g / 15 mm width or more and less than 200 g / 15 mm ×: less than 50 g / 15 mm

(7) Small rewinding suitability 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 winding can be performed without any problem even at a winding speed of 600 m / min. ○: Small winding can be performed without a 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.

From Table 2, the films obtained in Examples (2-1) to (2-6) did not block even when stored in a state where the formed film was wound, and further, antifogging properties and containers were obtained. It was confirmed that the adhesion was also good. Moreover, it was confirmed that by providing a specific adhesive layer, the delamination strength was improved, and as a result, a packaging film excellent in small rewindability was obtained.
In contrast, in Reference Example (2-1) and Reference Example (2-2), an ethylene / epoxy / alkyl acrylate copolymer, which is an acrylic-modified polyethylene resin, is used as an adhesive layer between the front and back layers and the intermediate layer. Because of the use of coalescence, the delamination strength becomes insufficient, and delamination occurs during small rewinding (Reference Example (2-1)). The case where the fracture occurred (Reference Example (2-2)) was confirmed.

<Example (3-1)>
About the resin composition which forms both surface layers, Nippon Polyethylene Co., Ltd. ethylene-vinyl acetate copolymer "LV440" as a polyolefin polymer (A) (vinyl acetate content: 15 mass%, MFR: 2. 2 g / 10 min) (hereinafter abbreviated as “A-1”) and 100 parts by mass of diglycerin monooleate “DGO-1” manufactured by Riken Vitamin Co., Ltd. as an antifogging agent were extruded. It put into the same direction twin screw extruder set to preset temperature 180-200 degreeC, and was melt-kneaded.
On the other hand, for the resin composition forming the intermediate layer, “NatureWorks 4060D” (L-form / D-form = 87/13, weight average molecular weight: 200,000) manufactured by NatureWorks is used as the lactic acid polymer (B-1). “Plamate PD-350” (manufactured by Dainippon Ink & Chemicals, Inc.) as a lactic acid copolymer (B-2) (polylactic acid / propylene glycol / succinic acid copolymer / polylactic acid: 48 mol%, propylene glycol: 26 mol%, succinic acid: 26 mol% / weight average molecular weight: 58,000) and mixed at a mass ratio of B-1 / B-2 = 20/80 to make 100 parts by mass. Nisshinbo Co., Ltd. “Carbodilite HMV-8CA” as a carbodiimide compound was added at a ratio of 1 part by mass to the extrusion set temperature of 180 to 200 ° C. It is put into an unloader, melted and kneaded. Further, an ethylene-vinyl acetate copolymer “Evaflex 45LX” manufactured by Mitsui DuPont Polychemical Co., Ltd. is used as an adhesive resin (F-2) component in an adhesive layer extruder. (Vinyl acetate content: 46% by mass, MFR: 2.5 g / 10 min) (hereinafter abbreviated as “f4”) was added. Then, the resin composition for forming both surface layers melted and kneaded as described above, the resin composition for forming the intermediate layer, and the resin composition for forming both adhesive layers are joined from separate extruders, respectively. , 5 layer T die temperature 200 ° C., co-extrusion at a die gap of 2 mm, and quenching with a cast roll set at a temperature of 30 ° C., resulting in a total thickness of 12 μm 2 μm / 1 μm / 6 μm / 1 μm / 2 μm) packaging film was obtained.
The results of evaluating the obtained film are shown in Table 3.

<Example (3-2)>
In Example (3-1), the mass ratio of the resin composition forming the intermediate layer is B-1 / B-2 = 40/60 by mass ratio, and the addition amount of the carbodiimide compound is 0.5 parts by mass. A packaging film having a total thickness of 12 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 2 μm / 1 μm / 6 μm / 1 μm / 2 μm) was obtained in the same manner as in Example (3-1) except for the change. Obtained. The results of evaluating the obtained film are shown in Table 3.

<Example (3-3)>
In Example (3-1), the mass ratio of the resin composition forming the intermediate layer is B-1 / B-2 = 60/40 by mass ratio, and the plasticizer (C) is Riken Vitamin Co., Ltd. Example except that the acetylated monoglyceride “Likemar PL019” (molecular weight 420) was melt-kneaded while being injected from the first vent port of the same-direction twin-screw extruder to 5 parts by mass using a metering pump. In the same manner as (3-1), a packaging film having a total thickness of 12 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 2 μm / 1 μm / 6 μm / 1 μm / 2 μm) was obtained. The results of evaluating the obtained film are shown in Table 3.

<Example (3-4)>
In Example (3-2), the component (F-2), which is an adhesive resin, was added to an extruder for an adhesive layer by using an ethylene-vinyl acetate copolymer “Evaflex 40LX” manufactured by Mitsui DuPont Polychemical Co., Ltd. (Vinyl acetate content: 41% by mass, MFR: 2.0 g / 10 min) (hereinafter abbreviated as “f5”) In the same manner as in Example (3-1), the total thickness was 12 μm (surface layer / Adhesive layer / intermediate layer / adhesive layer / surface layer = 2 μm / 1 μm / 6 μm / 1 μm / 2 μm). The results of evaluating the obtained film are shown in Table 3.

<Example (3-5)>
In Example (3-1), the polyolefin polymer (A) was converted into a linear low density polyethylene “NUCG5225” (density: 0.92 g / cm ³ , MFR: 2.0 g / 10) manufactured by Nippon Unicar Co., Ltd. Packaging with a total thickness of 12 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 2 μm / 1 μm / 6 μm / 1 μm / 2 μm) in the same manner as in Example (3-1) except that A film was obtained. The results of evaluating the obtained film are shown in Table 3.

<Reference Example (3-1)>
In Example (3-1), the polyolefin polymer (A) was converted into a linear low density polyethylene “NUCG5225” (density: 0.92 g / cm ³ , MFR: 2.0 g / 10) manufactured by Nippon Unicar Co., Ltd. And the component that is an adhesive resin in an adhesive layer extruder is “bond first” (ethylene-ethyl acrylate-glycidyl methacrylate terpolymer) manufactured by Sumitomo Chemical Co., Ltd. ( The total thickness is 12 μm (surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer = 2 μm / 1 μm / 6 μm /) in the same manner as in Example (3-1) except that it is changed to “f3” hereinafter. A packaging film of 1 μm / 2 μm) was obtained. The results of evaluating the obtained film are shown in Table 3.

<Reference example (3-2)>
In Example (3-1), pellets pre-compounded in advance so as to have the same composition as the intermediate layer in Example (3-1) were put into an adhesive layer extruder, and a substantially three-layer film. A packaging film having a total thickness of 12 μm (surface layer / intermediate layer / surface layer = 1.5 μm / 9 μm / 1.5 μm) was obtained in the same manner as in Example (3-1) except that. The results of evaluating the obtained film are shown in Table 3.

(Measurement and evaluation method)
About the film obtained by said Example (3-1)-(3-5) and Reference example (3-1)-(3-2), said Example (2-1)-(2- Evaluation was performed in the same manner as in 6).

(Discussion)
From Table 3, the films obtained in Examples (3-1) to (3-5) did not block even when stored in a state where the formed film was wound, and further, antifogging properties and containers were obtained. It was confirmed that the adhesion was also good. Moreover, it was confirmed that by providing a specific adhesive layer, the delamination strength was improved, and as a result, delamination was suppressed and a packaging film excellent in small rewinding suitability was obtained.
On the other hand, in Reference Example (3-1) and Reference Example (3-2), an ethylene / epoxy / alkyl acrylate copolymer which is an acrylic-modified polyethylene resin is used as an adhesive layer between the front and back layers and the intermediate layer. Because of the use of coalescence, the delamination strength becomes insufficient and delamination occurs during small rewinding (Reference Example (3-1)), or because it does not have an adhesive layer, delamination is significantly observed during small rewinding. The case where the fracture occurred (Reference Example (3-2)) was confirmed.
The films obtained in Examples (3-1) to (3-5) were prepared by using an ethylene / epoxy / alkyl acrylate copolymer, which is an acrylic-modified polyethylene resin, as an adhesive layer between the front and back layers and the intermediate layer. Compared with the reference example (3-1) used, it was also excellent in terms of transparency.

Claims (14)

A multilayer lactic acid-based soft film having at least three layers,
Both surface layers contain a polyolefin polymer (A) as a main component,
The intermediate layer contains, as a main component, a lactic acid-based mixed resin composition (B) composed of a lactic acid-based polymer (B-1) and a lactic acid-based copolymer (B-2). Soft film.   According to the dynamic viscoelasticity measurement method described in JIS K-7198 A method, the storage elastic modulus (E ′) at 20 ° C. measured at a vibration frequency of 10 Hz and a strain of 0.1% is in the range of 100 MPa to 4 GPa, and The multilayer lactic acid-based soft film according to claim 1, wherein the value of loss tangent (tan δ) at 20 ° C is in the range of 0.1 to 0.8. 5 or more multilayer lactic acid-based soft films having at least surface layer / adhesive layer / intermediate layer / adhesive layer / surface layer in this order,
Both surface layers contain a polyolefin polymer (A) as a main component,
The intermediate layer contains a lactic acid-based mixed resin composition (B) composed of a lactic acid-based polymer (B-1) and a lactic acid-based copolymer (B-2) as a main component,
Both adhesive layers are composed of a copolymer of a soft aromatic hydrocarbon and a conjugated diene hydrocarbon or a hydrogenated derivative (F-1) of this copolymer, an ethylene-containing vinyl acetate content of 30 to 80% by mass. Vinyl acetate copolymer (F-2), modified polyolefin resin (F-3), lactic acid polymer, polymer block mainly composed of acrylate unit and polymer block mainly composed of acrylate unit It is characterized by containing as a main component an adhesive resin composed of one or a combination of two or more of lactic acid / acrylic mixed resin (F-4) which is a mixed resin with an acrylic block copolymer having The multilayer lactic acid-based soft film according to claim 1.   The storage elastic modulus (E ′) measured at a vibration frequency of 10 Hz and a temperature of 20 ° C. by dynamic viscoelasticity measurement is 1 GPa to 4 GPa, the peak temperature of loss tangent (tan δ) is 20 to 60 ° C., and its peak value Is in the range of 0.1 to 0.8, the multilayer lactic acid-based flexible film according to claim 3.   The polyolefin polymer (A) is low density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, and ethylene-methacrylic acid ester copolymer. 5. The multilayer lactic acid-based soft film according to claim 1, wherein the multilayer lactic acid-based soft film is a mixed resin composed of at least one ethylene polymer selected from a combination or a combination of two or more of these.   The multilayer lactic acid-based soft film according to any one of claims 1 to 5, wherein the lactic acid-based polymer (B-1) is a mixed resin of two or more types of lactic acid-based polymers having different LD ratios.   The lactic acid-based mixed resin composition (B) has a single glass transition temperature measured at a heating rate of 10 ° C / min in differential scanning calorimetry. A multilayer lactic acid-based soft film according to claim 1.   The lactic acid-based mixed resin composition (B) has a maximum loss tangent (tan δ) when measured at a vibration frequency of 10 Hz and a strain of 0.1% by the dynamic viscoelasticity measurement method described in JIS K-7198 A method. The multi-layered lactic acid-based soft film according to any one of claims 1 to 6, characterized in that one exists.   The multi-layered lactic acid-based flexible film according to any one of claims 1 to 8, wherein the lactic acid-based copolymer (B-2) is a copolymer of a lactic acid-based polymer and a diol / dicarboxylic acid.   The lactic acid-based copolymer (B-2) is a copolymer of a lactic acid-based polymer, propylene glycol, and succinic acid, and is a multilayer lactic acid-based soft film according to any one of claims 1 to 9 .   The intermediate layer contains a lactic acid polymer (B-1), a lactic acid copolymer (B-2), and a plasticizer (C) as main components. The multilayer lactic acid-type soft film in any one of.   The intermediate layer contains 1 to 15 parts by mass of a plasticizer (C) having a molecular weight of 2,000 or less with respect to 100 parts by mass of the lactic acid-based mixed resin composition (B). A multilayer lactic acid-based soft film according to claim 1.   The multilayer lactic acid-based soft film according to any one of claims 1 to 12, wherein the intermediate layer further contains a polyolefin-based polymer (E).   Polyolefin-based polymer (A), lactic acid-based mixed resin composition (B), a copolymer of a soft aromatic hydrocarbon and a conjugated diene hydrocarbon, or a hydrogenated derivative of these copolymers (F- 1) An ethylene-vinyl acetate copolymer (F-2) having a vinyl acetate content of 30 to 80% by mass, a modified polyolefin resin (F-3), a heavy polymer mainly composed of a lactic acid polymer and an acrylate unit. From any combination of lactic acid / acrylic mixed resin (F-4), which is a mixed resin with a block copolymer and an acrylic block copolymer having a polymer block mainly composed of methacrylate units. A multilayer lactic acid-based soft film according to any one of claims 1 to 13, further comprising a reproduction layer containing an adhesive resin.