JP5829382B2 - Multilayer film - Google Patents

Description

  The present invention relates to a multilayer film suitably used particularly for packaging material applications.

  Polylactic acid, which has attracted the most attention as an aliphatic polyester, not only has the potential to replace petroleum-based resins as plant-derived materials, but also because it can be formed into a film by a melt extrusion method that does not use a solvent. It is suitable as an environmentally friendly material, and has already been proposed for use in packaging materials (see, for example, Patent Documents 1, 2, and 3).

Films for packaging materials may be multilayered for the purpose of improving water vapor barrier properties, flexibility, strength, etc., depending on the purpose.
However, when polylactic acid is used in a film for packaging materials, it is biodegradable, so the portion using polylactic acid is brittle due to hydrolysis, and this problem is essential even if the film is multilayered. It may not be a solution. For example, depending on the application of the packaging material, it may be necessary to maintain the shape for a long period of time in a high humidity condition. In such a case, the use of polylactic acid is limited.

  Several methods have already been proposed for suppressing the hydrolysis of polylactic acid (for example, Patent Document 3). The carbodiimide compound used in this proposal is a linear carbodiimide compound. When a linear carbodiimide compound is used as an end-capping agent for a polymer compound, a compound having an isocyanate group is liberated as a result of the reaction of the linear carbodiimide compound binding to the end of the polymer compound, generating a unique odor of the isocyanate compound. However, deteriorating the working environment is a problem.

Japanese Patent No. 4122915 Japanese Patent No. 3258302 JP 2001-261797 A

  An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a multilayer film that is particularly suitable for a packaging material that suppresses hydrolysis and is environmentally friendly.

  The present invention has arrived at the present invention as a result of intensive investigations in view of the above-described prior art.

（式中、Ｑは、脂肪族基、脂環族基、芳香族基またはこれらの組み合わせである２〜４価の結合基であり、ヘテロ原子を含有していてもよい。）
６．Ｑは、下記式（１−１）、（１−２）または（１−３）で表される２〜４価の結合基である前記５記載の多層フィルム。

（式中、Ａｒ^１およびＡｒ^２は各々独立に、２〜４価の炭素数５〜１５の芳香族基である。Ｒ^１およびＲ^２は各々独立に、２〜４価の炭素数１〜２０の脂肪族基、２〜４価の炭素数３〜２０の脂環族基またはこれらの組み合わせ、またはこれら脂肪族基、脂環族基と２〜４価の炭素数５〜１５の芳香族基の組み合わせである。Ｘ^１およびＸ^２は各々独立に、２〜４価の炭素数１〜２０の脂肪族基、２〜４価の炭素数３〜２０の脂環族基、２〜４価の炭素数５〜１５の芳香族基、またはこれらの組み合わせである。ｓは０〜１０の整数である。ｋは０〜１０の整数である。なお、ｓまたはｋが２以上であるとき、繰り返し単位としてのＸ^１、あるいはＸ^２が、他のＸ^１、あるいはＸ^２と異なっていてもよい。Ｘ^３は、２〜４価の炭素数１〜２０の脂肪族基、２〜４価の炭素数３〜２０の脂環族基、２〜４価の炭素数５〜１５の芳香族基、またはこれらの組み合わせである。但し、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、Ｘ^１、Ｘ^２およびＸ^３はヘテロ原子を含有していてもよい、また、Ｑが２価の結合基であるときは、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、Ｘ^１、Ｘ^２およびＸ^３は全て２価の基である。Ｑが３価の結合基であるときは、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、Ｘ^１、Ｘ^２およびＸ^３の内の一つが３価の基である。Ｑが４価の結合基であるときは、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、Ｘ^１、Ｘ^２およびＸ^３の内の一つが４価の基であるか、二つが３価の基である。）
７．Ｃ成分が、下記式（２）で表される前記５記載の多層フィルム。

（式中、Ｑ_ａは、脂肪族基、脂環族基、芳香族基またはこれらの組み合わせである２価の結合基であり、ヘテロ原子を含有していてもよい。）
８．Ｑ_ａは、下記式（２−１）、（２−２）または（２−３）で表される２価の結合基である前記７記載の多層フィルム。

（式中、Ａｒ_ａ ^１、Ａｒ_ａ ^２、Ｒ_ａ ^１、Ｒ_ａ ^２、Ｘ_ａ ^１、Ｘ_ａ ^２、Ｘ_ａ ^３、ｓおよびｋは、各々式（１−１）〜（１−３）中のＡｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、Ｘ^１、Ｘ^２、Ｘ^３、ｓおよびｋと同じである。）
９．Ｃ成分が、下記式（３）で表される前記５記載の多層フィルム。

（式中、Ｑ_ｂは、脂肪族基、脂環族基、芳香族基またはこれらの組み合わせである３価の結合基であり、ヘテロ原子を含有していてもよい。Ｙは、環状構造を担持する担体である。）
１０．Ｑ_ｂは、下記式（３−１）、（３−２）または（３−３）で表される３価の結合基である前記９記載の多層フィルム。

（式中、Ａｒ_ｂ ^１、Ａｒ_ｂ ^２、Ｒ_ｂ ^１、Ｒ_ｂ ^２、Ｘ_ｂ ^１、Ｘ_ｂ ^２、Ｘ_ｂ ^３、ｓおよびｋは、各々式（１−１）〜（１−３）のＡｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、Ｘ^１、Ｘ^２、Ｘ^３、ｓおよびｋと同じである。但しこれらの内の一つは３価の基である。）
１１．Ｙは、原子、原子団またはポリマーである前記９または１０記載の多層フィルム。
１２．Ｃ成分が、下記式（４）で表される前記５記載の多層フィルム。

（式中、Ｑ_ｃは、脂肪族基、芳香族基、脂環族基またはこれらの組み合わせである４価の結合基であり、ヘテロ原子を保有していてもよい。Ｚ^１およびＺ^２は、環状構造を担持する担体である。）
１３．Ｑ_ｃは、下記式（４−１）、（４−２）または（４−３）で表される４価の結合基である前記１２記載の多層フィルム。

（式中、Ａｒ_ｃ ^１、Ａｒ_ｃ ^２、Ｒ_ｃ ^１、Ｒ_ｃ ^２、Ｘ_ｃ ^１、Ｘ_ｃ ^２、Ｘ_ｃ ^３、ｓおよびｋは、各々式（１−１）〜（１−３）の、Ａｒ^１、Ａｒ^２、Ｒ^１、Ｒ^２、Ｘ^１、Ｘ^２、Ｘ^３、ｓおよびｋと同じである。但し、これらの内の一つが４価の基であるか、二つが３価の基である。）
１４．Ｚ^１およびＺ^２は各々独立に、原子、原子団またはポリマーである前記１２または１３記載の多層フィルム。
１５．ポリオレフィン（Ｄ成分）がポリエチレンおよび/またはポリプロピレン骨格を含有するものであることを特徴とする前記１〜１４のいずれか記載の多層フィルム。
That is, the first object of the present invention is to
1. An aliphatic polyester (component A), and the aliphatic polyester (component A) includes at least a cyclic structure having one carbodiimide group and a first nitrogen and a second nitrogen bonded by a bonding group ; the layer containing the number of atoms constituting the ring-shaped structure having one carbodiimide group and the first nitrogen and second nitrogen being linked by linking group directly is 8-50 compound (C component) (P Layer) and at least one layer (N layer) made of a resin containing polyolefin (D component).
2. 2. The multilayer film as described in 1 above, wherein the aliphatic polyester (component A) is polylactic acid.
3. 3. The multilayer film according to 2 above, wherein the polylactic acid (component A) is a polylactic acid containing a poly-D-lactic acid component and a poly-L-lactic acid component, and the stereocomplex crystallinity (S) is 90% or more.
{Stereocomplex crystallinity (S) measured by differential scanning calorimetry (DSC), polylactic acid homocrystal melting heat (ΔHm _h ) observed below 190 ° C, polylactic acid stereocomplex observed above 190 ° C It calculates _| requires by following Formula (I) from a crystal melting heat ((DELTA) Hmsc).
(S) = [ΔHm _sc / (ΔHm _h + ΔHm _sc )] × 100 (I)}
4). The multilayer film according to any one of 1 to 3, wherein the P layer further contains an acrylic resin (component B).
5. The multilayer film according to any one of 1 to 4, wherein the C component is represented by the following formula (1).

(In the formula, Q is a divalent to tetravalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom.)
6). 6. The multilayer film as described in 5 above, wherein Q is a divalent to tetravalent linking group represented by the following formula (1-1), (1-2) or (1-3).

(In the formula, Ar ¹ and Ar ² are each independently an aromatic group having 2 to 4 carbon atoms and 5 to 15 carbon atoms. R ¹ and R ² are each independently 1 to 2 carbon atoms having 1 to 4 carbon atoms. 20 aliphatic groups, 2 to 4 valent alicyclic groups having 3 to 20 carbon atoms, or combinations thereof, or these aliphatic groups, alicyclic groups and 2 to 4 valent aromatic carbon atoms having 5 to 15 carbon atoms X ¹ and X ² are each independently a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, a divalent to tetravalent carbon atom having 3 to 20 alicyclic groups, 2 to 4 A valent aromatic group having 5 to 15 carbon atoms, or a combination thereof, s is an integer of 0 to 10. k is an integer of 0 to 10. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ^2. X ³ is a divalent to tetravalent carbon number. An aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 2 to 4 carbon atoms having 3 to 20 carbon atoms, an aromatic group having 2 to 4 carbon atoms having 5 to 15 carbon atoms, or a combination thereof, provided that Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ may contain a hetero atom, and when Q is a divalent linking group, Ar ¹ , Ar ² , R 3 ¹ , R ² , X ¹ , X ² and X ³ are all divalent groups, and when Q is a trivalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ^{One of 2} and X ³ is a trivalent group, and when Q is a tetravalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ One of them is a tetravalent group or two are trivalent groups.)
7). 6. The multilayer film according to 5 above, wherein the component C is represented by the following formula (2).

(Wherein Q _a is a divalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom.)
8). 8. The multilayer film as described in 7 above, wherein Q _a is a divalent linking group represented by the following formula (2-1), (2-2) or (2-3).

(In the formula, Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k are represented by the formulas (1-1) to (1-3), respectively. The same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k in the inside.)
9. 6. The multilayer film according to 5 above, wherein the component C is represented by the following formula (3).

(Wherein Q _b is a trivalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom. Y represents a cyclic structure. It is a carrier to be supported.)
10. Q _b is represented by the following formula (3-1), the multilayer film of the 9 wherein the trivalent linking group represented by (3-2) or (3-3).

(In the formula, Ar _b ¹ , Ar _b ² , R _b ¹ , R _b ² , X _b ¹ , X _b ² , X _b ³ , s and k are represented by the formulas (1-1) to (1-3), respectively. Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s, and k, with one of these being a trivalent group.)
11. 11. The multilayer film as described in 9 or 10 above, wherein Y is an atom, an atomic group or a polymer.
12 6. The multilayer film according to 5 above, wherein the component C is represented by the following formula (4).

(Wherein Q _c is a tetravalent linking group that is an aliphatic group, an aromatic group, an alicyclic group, or a combination thereof, and may have a hetero atom. Z ¹ and Z ² are A carrier carrying a ring structure.)
13. 13. The multilayer film as described in 12 above, wherein Q _c is a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3).

(In the formula, Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s and k are respectively represented by formulas (1-1) to (1-3) Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k, provided that one of them is a tetravalent group or two are 3 Valent group.)
14 14. The multilayer film as described in 12 or 13 above, wherein Z ¹ and Z ² are each independently an atom, an atomic group or a polymer.
15. 15. The multilayer film as described in any one of 1 to 14 above, wherein the polyolefin (component D) contains polyethylene and / or a polypropylene skeleton.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the multilayer film which was excellent in hydrolysis resistance, and was especially suitable for the packaging material which considered the environment.

It is a schematic diagram which shows the one aspect | mode of the multilayer film in this invention. It is a schematic diagram which shows the one aspect | mode of the multilayer film in this invention. It is a schematic diagram which shows the one aspect | mode of the multilayer film in this invention.

Hereinafter, the present invention will be described in detail.
<Multilayer film>
The multilayer film in the present invention contains an aliphatic polyester (component A), and has at least a cyclic structure in which the polylactic acid has one carbodiimide group and the first nitrogen and the second nitrogen are bonded by a bonding group. It includes at least one layer each including a layer (P layer) including a compound (C component) and a layer (N layer) made of a resin including polyolefin (D component).

  The multilayer film of the present invention needs to include at least one layer of P layer and N layer, but another layer (Q layer) is provided between the N layer and P layer, for example, P layer and N layer. It may be provided for improving adhesion between the layers.

  A known material can be used as a material in the layer also serving as the adhesive, but a copolymer resin (a) containing a polar group, or a modified resin (b) modified with a polar group-containing monomer or the like is used. Preferably used. It is sufficient that at least these copolymer resins (a) and / or modified resins (b) are contained, and unmodified resins and other resins may be further contained. Here, as the copolymer resin (a) containing a polar group, an acid group-containing copolymer such as an ethylene-vinyl acetate copolymer resin (EVA), an ethylene-ethyl acrylate copolymer resin, or an ionomer resin is used. Resins can be exemplified. More specifically, as the resin, the brand name sold by Mitsui DuPont Polychemical Co., Ltd. is Evaflex brand P-2807 (EV250), the brand name is EVAFLEX-EEA brand A-707, and the brand name. Can be exemplified by brands 1555 and 1702 of High Milan.

  Another preferable material for the layer also serving as the adhesive is a thermoplastic elastomer and / or a modified resin (b) of an unsaturated carboxylic acid of polyolefin or a derivative thereof. Further, a polyolefin composition obtained by mixing a polyolefin obtained by graphing an unsaturated carboxylic acid or its anhydride or a polyolefin blended with the polyolefin obtained by the graph and a metal powder having a higher ionization tendency than hydrogen and a metal. Preferably used. More specifically, “Admer” is a trade name sold by Mitsui Chemicals, Inc. as the resin.

  When the multilayer film of the present invention is used as a packaging material, the multilayer film may be preferably flexible. The flexibility of the multilayer film is expressed by a tensile elastic modulus, and the elastic modulus of a preferable packaging material varies depending on the use, but is preferably 50 to 2000 MPa, more preferably 100 to 1000 MPa. The value measured at a tensile speed of 100 mm / min by the method described in JIS K7161.

The adhesive peel strength of the multilayer film is preferably 0.2 N / 25 mm or more, more preferably 1 N / 25 mm or more, more preferably 2 N / 25 mm or more, most preferably 3 N / 25 mm in the peel test described in JIS K6854. That's it. If the peel strength is less than 0.2 N / 25 mm, a problem may occur in actual use. In the present invention, unless otherwise specified, the peel rate in the peel strength evaluation was 200 mm / min, and the film width was 25 mm.
Moreover, in a multilayer film, you may laminate | stack a gas barrier layer, a light-shielding layer, a water vapor | steam barrier layer, an oxygen barrier layer, and a gas permeable layer.

<Manufacture of multilayer film>
In order to obtain the multilayer film of the present invention, known molding techniques such as extrusion molding and cast molding can be used. For example, the film can be formed using an extruder equipped with a T die, an I die, a circular die and the like. It is preferable to use multi-layer extrusion using a T-die, I-die, or circular die to which multi-manifold dies, feed blocks, doubling equipment, etc. are connected. The optimum method is selected depending on the number of layers and the physical properties of the resin.

  When a multilayer film is obtained by multilayer extrusion molding, for example, in the case of the P layer, if a material obtained by melt-kneading polylactic acid (component A) and other components in advance can be used, it is molded through melt-kneading at the time of extrusion molding. You can also. The N layer can be formed in the same manner and simultaneously to form a multilayer film. In order to suppress sharkskin and layer thickness variations, which are problematic in multilayer film molding, it is preferable that the melt viscosity of the resin used in each layer is close. Specifically, the difference in melt flow rate between the P layer and N layer resins at the same temperature is preferably 20 (g / 10 min) or less, more preferably 10 or less. This melt flow rate is measured by the method of ISO1133.

  In addition, in order to obtain a multilayer film, the multilayer film may be formed not by multilayer extrusion molding but by separately producing a film of each layer and laminating by lamination. Laminating can be performed by a known method such as heat fusion or a method using an adhesive in between.

  The multilayer film may be stretched. As the stretching method, known longitudinal uniaxial stretching, lateral uniaxial stretching, simultaneous biaxial stretching, and the like can be performed. The film is heat-set after stretching to enhance crystallinity and to suppress heat shrinkability. Processing may be performed.

  The draw ratio is appropriately determined depending on the purpose and the type of resin. The multilayer film has an area stretch ratio (longitudinal magnification x lateral magnification) of preferably 6.0 times or less, more preferably 4.0 times or less, still more preferably 3 times or less, and preferably 1.05 times. More preferably, the range is 1.1 times or more. When the area stretch ratio is 6.0 times or more, the stretchability is deteriorated, and there may be a problem that the frequency of occurrence of breakage during stretching is increased. If the magnification is less than 1.05, the mechanical strength may be insufficient.

The stretching temperature is preferably selected from the range of the glass transition temperature (Tg) of the resin constituting the multilayer film to the crystallization temperature (Tc).
Regarding the heat setting treatment, heat setting treatment is performed in the temperature range from the crystallization temperature (Tc) of the crystalline resin having the highest Tc among the resins constituting the multilayer film to the lowest melting point (Tm) of the resins constituting each layer. It is preferable to do. By performing this heat setting treatment, crystallization of the crystalline polymer of each layer containing stereocomplex polylactic acid can be promoted, and the heat shrinkage rate can be suitably reduced.

  The heat setting treatment is preferably performed in the range of 1 second to 30 minutes. When the heat treatment temperature is high, a relatively short time is required, and when the heat setting temperature is low, a relatively long time is required.

<P layer>
As the resin for the P layer, a compound containing at least a cyclic structure in which an aliphatic polyester (component A) and a carbodiimide group, which will be described later, are bonded to the first nitrogen and the second nitrogen by a bonding group (component C) ) Is essential, but other components may be included.

The content of the aliphatic polyester (component A) component in the resin film is preferably 40% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight or more, particularly preferably 70% by weight or more, Most preferably, it is 75 weight% or more. When the content of the aliphatic polyester (component A) is less than 40% by weight, the significance of using the aliphatic polyester (component A) is reduced. In addition, when containing resin other than aliphatic polyester (A component), it is preferable to use a thermoplastic resin from a viewpoint of resin film moldability.
The aliphatic polyester (component A) is preferably polylactic acid. The polylactic acid will be described later.

  Examples of thermoplastic resins other than aliphatic polyester include aromatic polyester resins, polyamide resins, polyacetal resins, polyolefin resins such as polyethylene resins and polypropylene resins, polystyrene resins, acrylic resins, polyurethane resins, chlorinated polyethylene resins, and chlorinated resins. Polypropylene resin, aromatic polyketone resin, aliphatic polyketone resin, fluorine resin, polyphenylene sulfide resin, polyether ketone resin, polyimide resin, thermoplastic starch resin, AS resin, ABS resin, AES resin, ACS resin, polyvinyl chloride resin , Polyvinylidene chloride resin, vinyl ester resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene Kisaido resin, poly-4-methylpentene-1, polyetherimide resin, and thermoplastic resins such as polyvinyl alcohol resins.

  Particularly preferred are acrylic resins (component B), especially polymethyl methacrylate, from the viewpoints of good compatibility with aliphatic polyester (component A) and close refractive index. The acrylic resin (component B) content in the resin film is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 30% by weight or less. When the acrylic resin is more than 50% by weight, the significance of using the aliphatic polyester is diminished. The acrylic resin will be described later.

In the multilayer film of the present invention, the P layer is preferably in a substantially crystalline state.
Here, the “substantially crystalline state” is DSC measurement (differential scanning calorimeter), and the rate of temperature rise is 20 ° C./min. The peak heat value (ΔHc) of the crystal at the first temperature rise is (30) Satisfy the equation.
ΔHc <1 J / g (30)
When the above formula is satisfied, the multilayer film of the present invention can be more suitably used as a packaging material. Preferably,
ΔHc <0.5 J / g (31)
More preferably,
ΔHc <0.2 J / g (32)
It is.

<N layer>
As the resin for the N layer, it is essential to contain a polyolefin (D component) described later, but it may contain other components.
The content of polyolefin (component D) in the resin film is preferably 10% by weight or more, more preferably 30% by weight or more, more preferably 40% by weight or more, particularly preferably 50% by weight or more, and most preferably 60% by weight or more. When a resin other than polyolefin (component D) is contained, it is preferable to use a thermoplastic resin from the viewpoint of resin film moldability. This preferred weight percent applies whether blended or copolymerized.

Examples of thermoplastic resins other than polyolefin include aromatic polyester resins, polyamide resins, polyacetal resins, polystyrene resins, acrylic resins, polyurethane resins, chlorinated polyethylene resins, chlorinated polypropylene resins, aromatic polyketone resins, aliphatic polyketone resins, Fluoro resin, polyphenylene sulfide resin, polyether ketone resin, polyimide resin, thermoplastic starch resin, AS resin, ABS resin, AES resin, ACS resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl ester resin, MS resin Polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene oxide resin, poly-4-methylpentene-1, polyetherimide resin, It can be exemplified thermoplastic resins such as polyvinyl alcohol resins.
The presence of the N layer can improve the water vapor barrier property as a film.

<Aliphatic polyester (component A)>
In the present invention, the aliphatic polyester (component A) is mainly composed of a polymer mainly composed of an aliphatic hydroxycarboxylic acid, an aliphatic polycarboxylic acid or an ester-forming derivative thereof, and an aliphatic polyhydric alcohol. Examples thereof include polymers formed by polycondensation and copolymers thereof.

  Examples of the polymer having aliphatic hydroxycarboxylic acid as a main constituent component include polycondensates such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, and copolymers. Among them, polyglycolic acid, polylactic acid, poly-3-hydroxycarboxylic butyric acid, poly-4-polyhydroxybutyric acid, poly-3-hydroxyhexanoic acid or polycaprolactone, and copolymers thereof may be mentioned. It can be suitably used for lactic acid, poly-D-lactic acid, stereocomplex polylactic acid forming a stereocomplex crystal, and racemic polylactic acid.

  As polylactic acid (A component), what consists of poly L or D-lactic acid, or the thing containing a poly D-lactic acid component and a poly L-lactic acid component can be used. As long as it contains a poly-D-lactic acid component and a poly-L-lactic acid component, it is preferable to form a stereocomplex crystal and have a stereocomplex crystallinity (S) of 90% or more.

Stereocomplex crystallinity (S) measured by differential scanning calorimetry (DSC), polylactic acid homocrystal melting heat (ΔHm _h ) observed below 190 ° C, polylactic acid stereocomplex crystal melting observed above 190 ° C It is a value obtained by the following formula (I) from heat (ΔHm _sc ).
(S) = [ΔHm _sc / (ΔHm _h + ΔHm _sc )] × 100 (I)
The stereocomplex crystallinity (S) is preferably in the range of 93% to 100%, more preferably 95% to 100%. Particularly preferably, the stereocomplex crystallinity (S) is 100%.

  When polylactic acid having a stereocomplex crystallinity (S) of 90% or more is used as the P layer resin, the transparency of the multilayer film can be kept high. Moreover, heat resistance is also high.

  In order to satisfy the above-mentioned stereocomplex crystallinity suitably, in the polylactic acid (component A), the weight ratio of the poly D-lactic acid component and the poly L-lactic acid component is preferably 90/10 to 10/90. .

  More preferably, it is in the range of 80/20 to 20/80, more preferably 30/70 to 70/30, particularly preferably 40/60 to 60/40, and theoretically preferably as close to 1/1 as possible. Selected.

As the degree of crystallization of polylactic acid (component A) in the multilayer film, the stereocomplex crystallization rate (Sc) defined by the formula (II) is determined by the intensity ratio of diffraction peaks by wide-angle X-ray diffraction (XRD) measurement. It is more preferable to have 50% or more, preferably 50 to 100%, more preferably 70 to 100%, particularly preferably 90 to 100%. That is, when the polylactic acid (component A) has the above (Sc), the transparency, heat resistance, and heat and humidity resistance of the film can be more suitably satisfied. In particular, regarding transparency, it is possible to significantly reduce haze as compared with polylactic acid not having a stereocomplex crystal, and it is more suitable as a film used for applications requiring transparency.
Sc (%) = [ΣI _SCi / (ΣI _SCi + I _HM )] × 100 (II)
[Where ΣI _SCi = I _SC1 + I _SC2 + I _SC3 and I _SCi (i = 1 to 3) are integrated intensities of diffraction peaks around 2θ = 12.0 °, 20.7 °, and 24.0 °, respectively. I _HM represents the integrated intensity I _HM of a diffraction peak derived from a homocrystal appearing in the vicinity of 2θ = 16.5 °. ]

  Further, the melting point of the polylactic acid stereocomplex crystal is suitably selected in the range of 190 to 250 ° C., more preferably 200 to 230 ° C., and the crystal melting enthalpy by DSC measurement is 20 J / g or more, preferably 20 to 80 J / g, More preferably, a range of 30 to 80 J / g is selected.

  The weight average molecular weight of the polylactic acid component in the present invention is preferably 100,000 to 500,000, more preferably 110,000 to 350,000, and still more preferably 120,000 to 250,000 in order to achieve both the mechanical properties and moldability of the film. Range is selected.

The poly L-lactic acid component and the poly D-lactic acid component can be produced by a conventionally known method.
For example, it can be produced by ring-opening polymerization of L-lactide or D-lactide in the presence of a metal-containing catalyst. The low molecular weight polylactic acid containing a metal-containing catalyst is optionally crystallized or without crystallization, under reduced pressure or from normal pressure to increased pressure, in the presence or absence of an inert gas stream. It can also be produced by solid phase polymerization. Furthermore, it can be produced by a direct polymerization method in which lactic acid is subjected to dehydration condensation in the presence or absence of an organic solvent.

  The polymerization reaction can be carried out in a conventionally known reaction vessel. For example, in ring-opening polymerization or direct polymerization method, a vertical reactor or a horizontal reactor equipped with a stirring blade for high viscosity, such as a helical ribbon blade, is used alone, or Can be used in parallel. Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined.

  Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid, such as decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, ethylene glycol, trimethylolpropane, pentaerythritol, etc. Can be suitably used.

  It can be said that the polylactic acid prepolymer used in the solid-phase polymerization method is preferably crystallized in advance from the viewpoint of preventing resin pellet fusion. The prepolymer is polymerized in a solid state in a fixed vertical or horizontal reaction vessel, or in a reaction vessel (rotary kiln, etc.) that rotates itself like a tumbler or kiln, in the temperature range from the glass transition temperature of the prepolymer to less than the melting point. Is done.

  Metal-containing catalysts include alkali metals, alkaline earth metals, rare earths, transition metals, fatty acid salts such as aluminum, germanium, tin, antimony, titanium, carbonates, sulfates, phosphates, oxides, hydroxides , Halides, alcoholates and the like.

  Among them, fatty acid salts, carbonates, sulfates, phosphates, oxides, hydroxides containing at least one metal selected from tin, aluminum, zinc, calcium, titanium, germanium, manganese, magnesium and rare earth elements Products, halides, and alcoholates are preferred.

  Tin compounds due to low catalytic activity and side reactions, specifically stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, tin myristate, tin octylate Tin-containing compounds such as tin stearate and tetraphenyltin are exemplified as preferred catalysts.

  Among these, tin (II) compounds, specifically, diethoxytin, dinonyloxytin, tin (II) myristate, tin (II) octylate, tin (II) stearate, tin (II) chloride and the like are suitable. Illustrated.

The amount of the catalyst used is 0.42 × 10 ⁻⁴ to 100 × 10 ⁻⁴ (mol) per kg of lactide, and is 1.68 × 10 ^{−4 in} consideration of reactivity, color tone and stability of the resulting polylactides. To 42.1 × 10 ⁻⁴ (mol), particularly preferably 2.53 × 10 ⁻⁴ to 16.8 × 10 ⁻⁴ (mol).

The metal-containing catalyst used for polylactic acid polymerization is preferably deactivated with a conventionally known deactivator prior to using polylactic acid.
Examples of such a deactivator include an organic ligand comprising a group of chelate ligands having an imino group and capable of coordinating to a polymerized metal catalyst, dihydridooxoline (I) acid, dihydridotetraoxodilin (II, II ) Acid, hydridotrioxoline (III) acid, dihydridopentaoxodiphosphorus (III) acid, hydridopentaoxodi (II, IV) acid, dodecaoxohexaphosphorus (III) acid, hydridooctaoxotriphosphate (III, IV) , IV) acid, octaoxotriphosphoric acid (IV, III, IV), hydridohexaoxodiphosphoric acid (III, V), hexaoxodiphosphoric acid (IV), decaoxotetralinic acid (IV), hedecaoxotetralinic acid (IV ) acid, Eneaokiso triphosphate (V, IV, IV) acid value 5 or less low oxidation number phosphoric acids such as acid, by the formula xH _{2 O} · _{yP 2} O ₅ Orthophosphoric acid of x / y = 3, 2> x / y> 1, and polyphosphoric acid referred to as diphosphoric acid, triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid and the like based on the degree of condensation, and mixtures thereof, Metaphosphoric acid represented by x / y = 1, especially trimetaphosphoric acid, tetrametaphosphoric acid, ultraphosphoric acid represented by 1> x / y> 0 and having a network structure with a part of the phosphorus pentoxide structure (These may be collectively referred to as metaphosphate compounds), and acid salts of these acids, monovalent and polyhydric alcohols, partial esters of polyalkylene glycols, fully ether, phosphono-substituted lower Examples thereof include aliphatic carboxylic acid derivatives.

From the catalyst deactivation ability, it is represented by the formula xH ₂ O · yP ₂ O ₅ , x / y = 3 orthophosphoric acid, 2> x / y> 1, and based on the degree of condensation, diphosphate, triphosphate, tetra Polyphosphoric acid called phosphoric acid, pentaphosphoric acid and the like and mixtures thereof, metaphosphoric acid represented by x / y = 1, especially trimetaphosphoric acid, tetrametaphosphoric acid, 1> x / y> 0, Ultraphosphoric acid having a network structure in which a part of the phosphorus oxide structure is extended (these may be collectively referred to as metaphosphoric acid compounds), and acid salts of these acids, monovalent and polyhydric alcohols Or partial ester phosphorus oxoacids of polyalkylene glycols or acidic esters thereof, phosphono-substituted lower aliphatic carboxylic acid derivatives and the above-mentioned metaphosphoric acid compounds are preferably used.

  The metaphosphoric acid compound used in the present invention is a cyclic metaphosphoric acid in which about 3 to 200 phosphoric acid units are condensed, an ultra-regional metaphosphoric acid having a three-dimensional network structure, or an alkali metal salt or an alkaline earth metal salt thereof. Onium salts). Among them, cyclic sodium metaphosphate, ultra-region sodium metaphosphate, phosphono-substituted lower aliphatic carboxylic acid derivative dihexylphosphonoethyl acetate (hereinafter sometimes abbreviated as DHPA) and the like are preferably used.

  The polylactic acid used in the present invention preferably has a lactide content of 1 to 5000 ppm. The lactide contained in the polylactic acid deteriorates the resin and deteriorates the color tone at the time of melt processing, and in some cases, it may be disabled as a product.

  The polylactic acid immediately after melt ring-opening polymerization usually contains 1 to 5% by weight of lactide, but at any stage from the end of polylactic acid polymerization to the formation of polylactic acid, a conventionally known lactide weight loss method is used. That is, lactide can be reduced to a suitable range by carrying out vacuum devolatilization in a single-screw or multi-screw extruder, or high vacuum treatment in a polymerization apparatus alone or in combination.

  The smaller the lactide content, the better the melt stability and heat-and-moisture resistance of the resin, but there is also the advantage of lowering the resin melt viscosity, making it reasonable and economical to meet the desired purpose. is there. That is, it is reasonable to set it to 1 to 1000 ppm at which practical melt stability is achieved. More preferably, a range of 1 to 700 ppm, more preferably 2 to 500 ppm, particularly preferably 5 to 100 ppm is selected.

  By having a lactide content in such a range, the polylactic acid component can improve the stability of the resin during the melt-casting of the multilayer film of the present invention, and the advantage that the production of the film can be carried out efficiently and the heat and humidity resistance of the film , Low gas can be improved.

  The weight average molecular weight of the polylactic acid used in the present invention is selected in consideration of the relationship between the molding processability and the mechanical and thermal properties of the obtained molded product. That is, the weight average molecular weight is preferably 80,000 or more, more preferably 100,000 or more, and further preferably 130,000 or more in order to exert mechanical and thermal properties such as strength, elongation and heat resistance of the composition. is there.

However, as the weight average molecular weight increases, the melt viscosity of polylactic acid increases exponentially, and when performing melt molding such as extrusion, the molding temperature is set to the heat resistant temperature of polylactic acid in order to make the resin viscosity within the moldable range. There are cases where it must be set higher than this.
Specifically, when polylactic acid is molded at a temperature exceeding 300 ° C., the film product is colored due to the thermal decomposition of the resin, and there is a high possibility that the value as a product is low.

  Therefore, the weight average molecular weight of the polylactic acid composition is preferably 500,000 or less, more preferably 400,000 or less, and still more preferably 300,000 or less. Therefore, the weight average molecular weight of polylactic acid is preferably 80,000 to 500,000, more preferably 100,000 to 400,000, and still more preferably 130,000 to 300,000.

  The ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is referred to as molecular weight dispersion (Mw / Mn). A large molecular weight dispersion means that there are many ratios of large molecules and small molecules compared to the average molecular weight.

  That is, for example, a polylactic acid having a weight average molecular weight of about 250,000 and a molecular weight dispersion of 3 or more may have a large proportion of molecules having a molecular weight greater than 250,000. In this case, the melt viscosity becomes large, It is not preferable in terms of molding. In addition, in a polylactic acid composition having a relatively small weight average molecular weight of about 80,000 and a large molecular weight dispersion, the proportion of molecules having a molecular weight of less than 80,000 may increase. In this case, the durability of the mechanical properties of the molded product may be increased. Is not preferable in use. From this viewpoint, the range of molecular weight dispersion is preferably 1.5 to 2.4, more preferably 1.6 to 2.4, and still more preferably 1.6 to 2.3.

  As described above, the polylactic acid used in the multilayer film of the present invention is poly L-lactic acid or poly D-lactic acid alone, or the poly L-lactic acid component and the poly D-lactic acid component are 10 by weight. It can be obtained by contacting within the range of / 90 to 90/10, preferably by melt contact, more preferably by melt kneading contact.

  The contact temperature between the poly L-lactic acid component and the poly D-lactic acid component is 220 to 290 ° C., preferably 220 to 280 ° C., more preferably from the viewpoint of improving the stability of the polylactic acid when melted and the stereocomplex crystallinity. A range of 225 to 275 ° C. is selected.

  The melt kneading method is not particularly limited, but a conventionally known batch type or continuous type melt mixing apparatus is preferably used. For example, melt-stirred tanks, single- and twin-screw extruders, kneaders, non-shaft vertical stirrers, "Vibolac" manufactured by Sumitomo Heavy Industries, Ltd., N-SCR manufactured by Mitsubishi Heavy Industries, Ltd., Hitachi, Ltd. You can use glass blades, lattice blades or Kenix type stirrers, or Sulzer type SMLX type static mixer equipped pipe type polymerization equipment, but it is a self-cleaning type polymerization equipment in terms of productivity, quality of polylactic acid, especially color tone. A certain non-shaft vertical stirring tank, N-SCR, twin-screw extruder, etc. are preferably used.

The stereocomplex polylactic acid used in the present invention is preferably applied with a method of blending specific additives in order to stably and highly advance the formation of stereocomplex polylactic acid crystals within the scope not departing from the gist of the present invention. .
That is, for example, a method of adding a metal phosphate represented by the following formula (22) or (23) as a stereocomplex crystallization accelerator can be mentioned.

In formula (22), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹² and R ¹³ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M ₁ represents an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom, p represents 1 or 2, and q represents 0 when M ₁ is an alkali metal atom, an alkaline earth metal atom or a zinc atom. Represents an aluminum atom, 1 or 2.

In the formula (23), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M ₂ represents an alkali metal atom, an alkaline earth metal atom, a zinc atom or aluminum. P represents 1 or 2, q represents 0 when M ₂ is an alkali metal atom, alkaline earth metal atom, or zinc atom, and 1 or 2 when M ₂ is an aluminum atom.

M ₁ and M ₂ of the metal phosphate represented by the formula (22) or (23) are preferably Na, K, Al, Mg, Ca, Li, and in particular, Li, K, Na, Al, and Li. Al can be most preferably used.

  As these metal phosphates, trade names manufactured by ADEKA Corporation, “ADEKA STAB” NA-11, NA-71 and the like are exemplified as suitable agents. The metal phosphate is used in an amount of 0.001 to 2 wt%, preferably 0.005 to 1 wt%, more preferably 0.01 to 0.5 wt%, more preferably 0.02 to 0.3 wt% with respect to polylactic acid. It is preferable. When the amount is too small, the effect of improving the stereocomplex crystallinity (S) is small, and when too large, the stereocomplex crystal melting point is lowered, which is not preferable.

Furthermore, if desired, a known crystallization nucleating agent described below can be used in combination in order to enhance the action of the metal phosphate. Of these, calcium silicate, talc, kaolinite, and montmorillonite are preferably selected.
The amount of crystallization nucleating agent used is selected in the range of 0.05 to 5 wt%, more preferably 0.06 to 2 wt%, and still more preferably 0.06 to 1 wt% with respect to polylactic acid.

  In addition, a functional group selected from the group of stereocomplex crystallization aids [(epoxy group, oxazoline group, oxazine group, isocyanate group, ketene group and carbodiimide group) (hereinafter sometimes abbreviated as a specific functional group) is a molecule. And a method of adding a compound having at least one compound].

  In the present invention, the stereocomplex crystallization aid means that a specific functional group reacts with the molecular end of polylactic acid to partially link a poly L-lactic acid unit and a poly D-lactic acid unit to form a stereocomplex crystal. It is an agent that the present inventors speculate that it is promoted.

  As the stereocomplex crystallization aid, a known agent can be suitably applied as a carboxyl terminal group blocking agent for conventional polyesters described below. Especially, a carbodiimide compound is suitably selected from the stereocomplex crystal formation promotion effect.

  However, stereocomplex crystallization aids, especially nitrogen-containing stereocomplex crystallization aids, have a high risk of causing deterioration of the working environment due to malodor and deterioration of the color tone of polylactic acid due to thermal decomposition of the agent during stereocomplex crystal formation. Therefore, it is preferable not to use it, and when using it, it is limited to a case where emphasis is placed on the high-level formation of stereocomplex crystals, and it is preferable to use it while suppressing it as little as possible.

  The amount of the stereocomplex crystallization aid used is not more than 1 wt%, preferably 0 to 0.5 wt%, more preferably 0 to 0.3 wt%, still more preferably 0 to 0.1 wt% in the same standard as above. Is selected.

  That is, it is preferable to apply the above-described stereocomplex crystallization accelerator technique alone, and it is preferable to apply in combination with the stereocomplex crystallization aid technique when emphasizing stereocomplex crystal formation.

In the present invention, the carboxyl end group concentration of polylactic acid is 0.01 to 10 (equivalent / 10 ⁶ g), and {hereinafter (equivalent / 10 ⁶ g) may be abbreviated as (equivalent / ton). } Is preferred. The range of 0.02 to 2 (equivalent / ton) is more preferable, and the range of 0.02 to 1 (equivalent / ton) is more preferably selected.

  When the carboxyl end group concentration is within this range, the melt stability and wet heat stability can be improved. In order to reduce the carboxyl end group concentration of polylactic acid to 10 (equivalent / ton) or less, a conventionally known method for reducing the carboxyl end group concentration in the polyester composition can be suitably applied. Although amidation can be carried out, it is preferable to use a component C described later.

<Acrylic resin (component B)>
The above acrylic resins (component B) are methacrylic acid esters such as cyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, acrylic acid- One or more monomers selected from acrylic acid esters such as 2-ethylhexyl are polymerized. These monomers can be used alone or in admixture of two or more. Of these, a homopolymer of methyl methacrylate or a copolymer with other monomers is preferable.

  Examples of monomers copolymerizable with methyl methacrylate include other alkyl methallylic esters, alkyl acrylates, aromatic vinyl compounds such as styrene, vinyl toluene and α-methyl styrene, acrylonitrile, methacrylonitrile, etc. Vinyl cyanides, maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, unsaturated carboxylic acid anhydrides such as maleic anhydride, and unsaturated acids such as acrylic acid, methacrylic acid and maleic acid It is done. Among these monomers copolymerizable with methyl methacrylate, acrylic acid alkyl esters are particularly excellent in heat decomposition resistance. A methacrylic resin obtained by copolymerizing alkyl acrylates is preferable because of its high fluidity during molding.

  The amount of alkyl acrylates used when methyl acrylate is copolymerized with methyl methacrylate is preferably 0.1% by weight or more from the viewpoint of thermal decomposition resistance, and 15% from the viewpoint of heat resistance. % Or less is preferable. The content is more preferably 0.2% by weight or more and 14% by weight or less, and particularly preferably 1% by weight or more and 12% by weight or less.

  Among these alkyl acrylates, methyl acrylate and ethyl acrylate are particularly most preferable in terms of the above improvement effect even when they are copolymerized with a small amount of methyl methacrylate. The said monomer which can be copolymerized with methyl methacrylate can also be used 1 type or in combination of 2 or more types.

  The weight average molecular weight of the acrylic resin (component B) is preferably 50,000 to 200,000. The weight average molecular weight is preferably 50,000 or more from the viewpoint of the strength of the molded product, and preferably 200,000 or less from the viewpoint of molding processability and fluidity. A more preferable range is 70,000 to 150,000. In the present invention, isotactic polymethacrylate and syndiotactic polymethacrylate can be used simultaneously.

  As a method for producing the acrylic resin (component B), for example, commonly used polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, and anionic polymerization can be used. In the multilayer film used in the above, it is preferable to avoid the incorporation of minute foreign substances as much as possible. From this viewpoint, bulk polymerization or solution polymerization without using a suspending agent or an emulsifier is desirable. When solution polymerization is performed, a solution prepared by dissolving a mixture of monomers in an aromatic hydrocarbon solvent such as toluene, ethylbenzene, or xylene can be used. In the case of polymerization by bulk polymerization, the polymerization can be started by irradiation with free radicals generated by heating or ionizing radiation as is usually done.

  As the initiator used in the polymerization reaction, any initiator generally used in radical polymerization can be used. For example, azo compounds such as azobisisobutylnitrile, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide An organic peroxide such as -2-ethylhexanoate is used. In particular, when the polymerization is carried out at a high temperature of 90 ° C. or higher, solution polymerization is common, so that the peroxide has a 10-hour half-life temperature of 80 ° C. or higher and is soluble in the organic solvent used, An azobis initiator or the like is preferable. Specifically, 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, cyclohexane peroxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 1,1 -Azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isoptyronitrile, etc. can be mentioned. These initiators are used in the range of 0.005 to 5% by weight.

As the molecular weight regulator used as necessary for the polymerization reaction, any one used in general radical polymerization is used. For example, mercaptan compounds such as butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-ethylhexyl thioglycolate are particularly preferable. These molecular weight regulators are added in a concentration range such that the degree of polymerization is controlled within the above range.
<C component>
In the present invention, the P-layer resin has one carbodiimide group, which is mainly added to suppress hydrolysis of aliphatic polyester, particularly polylactic acid, and the first nitrogen and the second nitrogen are bonded by a bonding group. The compound (C component) containing at least the cyclic structure is described. The C component has a cyclic structure (hereinafter, the C component may be abbreviated as a cyclic carbodiimide compound). The cyclic carbodiimide compound may have a plurality of cyclic structures.

Here, the cyclic structure has one carbodiimide group (—N═C═N—), and the first nitrogen and the second nitrogen are bonded by a bonding group. One cyclic structure has only one carbodiimide group. For example, when there are a plurality of cyclic structures in the molecule, such as a spiro ring, one cyclic structure bonded to a spiro atom is included in each cyclic structure. Needless to say, the compound may have a plurality of carbodiimide groups as long as it has a carbodiimide group. The number of atoms in the cyclic structure is 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and particularly preferably 10 to 15.

  Here, the number of atoms in the cyclic structure means the number of atoms that directly constitute the cyclic structure. For example, it is 8 for an 8-membered ring and 50 for a 50-membered ring. This is because if the number of atoms in the cyclic structure is smaller than 8, the stability of the cyclic carbodiimide compound is lowered, and it may be difficult to store and use. From the viewpoint of reactivity, there is no particular restriction on the upper limit of the number of ring members, but cyclic carbodiimide compounds having more than 50 atoms are difficult to synthesize, and the cost may increase significantly. From this viewpoint, the number of atoms in the cyclic structure is preferably 10-30, more preferably 10-20, and particularly preferably 10-15.

The cyclic structure is preferably a structure represented by the following formula (1).

In the formula, Q is a divalent to tetravalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, each of which may contain a hetero atom and a substituent. A heteroatom in this case refers to O, N, S, P. Two of the valences of this linking group are used to form a cyclic structure. When Q is a trivalent or tetravalent linking group, it is bonded to a polymer or other cyclic structure via a single bond, a double bond, an atom, or an atomic group.
The linking group may include a heteroatom and a substituent, each having a divalent to tetravalent carbon number of 1 to 20 aliphatic group, a divalent to tetravalent carbon number of 3 to 20 alicyclic group, A linking group which is a tetravalent aromatic group having 5 to 15 carbon atoms or a combination thereof and has a necessary number of carbon atoms to form the cyclic structure defined above is selected. Examples of combinations include structures such as an alkylene-arylene group in which an alkylene group and an arylene group are bonded.
The linking group (Q) is preferably a divalent to tetravalent linking group represented by the following formula (1-1), (1-2) or (1-3).

In the formula, Ar ¹ and Ar ² are each independently a 2- to 4-valent aromatic group having 5 to 15 carbon atoms which may contain a hetero atom and a substituent.
As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group (divalent) include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

R ¹ and R ² each independently contain a heteroatom and a substituent, each having 2 to 4 valent aliphatic groups having 1 to 20 carbon atoms and 2 to 4 valent fatty acids having 3 to 20 carbon atoms A cyclic group, and a combination thereof, or a combination of the aliphatic group, the alicyclic group, and a divalent to tetravalent aromatic group having 5 to 15 carbon atoms.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

In the above formulas (1-1) and (1-2), X ¹ and X ² are each independently a divalent to tetravalent C 1-20 aliphatic optionally containing a hetero atom and a substituent. Group, a C2-C20 alicyclic group having 2 to 4 carbon atoms, a C2-C15 aromatic group having 2 to 4 carbon atoms, or a combination thereof.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

In the above formulas (1-1) and (1-2), s and k are integers of 0 to 10, preferably 0 to 3, more preferably 0 to 1. This is because if s and k exceed 10, the cyclic carbodiimide compound is difficult to synthesize, and the cost may increase significantly. From this viewpoint, the integer is preferably selected in the range of 0 to 3. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ² .

In the above formula (1-3), X ³ may contain a heteroatom and a substituent, respectively, a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, and a divalent to tetravalent carbon number of 3 to 20 Are alicyclic groups, divalent to tetravalent aromatic groups having 5 to 15 carbon atoms, or combinations thereof.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, or an ester group. , Ether group, aldehyde group and the like.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, and an ester. Group, ether group, aldehyde group and the like.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ may contain a hetero atom, and when Q is a divalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ are all divalent groups. When Q is a trivalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ is a trivalent group. When Q is a tetravalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ is a tetravalent group or two are trivalent It is a group.

  Examples of the cyclic carbodiimide compound used in the present invention include compounds represented by (a) to (c) below.

<Cyclic carbodiimide compound (a)>
Examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (2) (hereinafter sometimes referred to as “cyclic carbodiimide compound (a)”).

Wherein, Q _a is an aliphatic group, an alicyclic group, an aromatic group or a divalent linking group which is a combination of these, it may contain a heteroatom. The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (2), the aliphatic group, alicyclic group, and aromatic group are all divalent. Q _a is preferably a divalent linking group represented by the following formula (2-1), (2-2) or (2-3).

In the formula, Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k are represented by formulas (1-1) to (1-3), respectively. Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k. However, these are all divalent.
Examples of the cyclic carbodiimide compound (a) include the following compounds.

<Cyclic carbodiimide compound (b)>
Furthermore, examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (3) (hereinafter sometimes referred to as “cyclic carbodiimide compound (b)”).

Wherein, Q _b is an aliphatic group, an alicyclic group, an aromatic group or a trivalent linking group combinations thereof, and may contain a hetero atom. Y is a carrier supporting a cyclic structure. The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (3), the inner one of the group constituting the Q _b is trivalent.
Q _b is preferably a trivalent linking group represented by the following formula (3-1), (3-2) or (3-3).

In the formula, Ar _b ¹ , Ar _b ² , R _b ¹ , R _b ² , X _b ¹ , X _b ² , X _b ³ , s and k are respectively represented by the formulas (1-1) to (1-3). The same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k. However, one of these is a trivalent group.
Y is preferably a single bond, a double bond, an atom, an atomic group or a polymer. Y is a bonding portion, and a plurality of cyclic structures are bonded via Y to form a structure represented by the formula (3).
Examples of the cyclic carbodiimide compound (b) include the following compounds.

<Cyclic carbodiimide compound (c)>
Examples of the cyclic carbodiimide compound used in the present invention include a compound represented by the following formula (4) (hereinafter sometimes referred to as “cyclic carbodiimide compound (c)”).

In the formula, Q _c is a tetravalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may have a hetero atom. Z ¹ and Z ² are carriers that support a cyclic structure. Z ¹ and Z ² may be bonded to each other to form a cyclic structure.
The aliphatic group, alicyclic group, and aromatic group are the same as those described in Formula (1). However, in the compound of formula (4), Q _c is tetravalent. Accordingly, one of these groups is a tetravalent group or two are trivalent groups.
Q _c is preferably a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3).

Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s and k are each Ar ^{1 in} formulas (1-1) to (1-3). , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k are the same. Provided that Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² and X _c ³ are one of which is a tetravalent group or two of which are trivalent It is a group. Z ¹ and Z ² are preferably each independently a single bond, a double bond, an atom, an atomic group or a polymer. Z ¹ and Z ² are bonding portions, and a plurality of cyclic structures are bonded via Z ¹ and Z ² to form a structure represented by the formula (4).
Examples of the cyclic carbodiimide compound (c) include the following compounds.

  In the present invention, the ratio of the cyclic carbodiimide compound (C component) in the multilayer film P layer is 0.001 to 5 parts by weight of the cyclic carbodiimide compound (C component) based on 100 parts by weight of the aliphatic polyester (A component). It is preferable to contain. If the amount of component C is within this range, the stability to moisture and the hydrolysis resistance can be suitably increased.

  From this viewpoint, the content ratio of the cyclic carbodiimide compound (component C) is more preferably selected in the range of 0.01 to 5 parts by weight, more preferably 0.1 to 4 parts by weight per 100 parts by weight of polylactic acid (component A). Is done. If the amount is less than this range, the effect of the cyclic carbodiimide compound (component C) may not be recognized effectively, and even if it is applied in a large amount beyond this range, the hydrolysis stability will be further improved. Not expected.

  As described above, when the P-layer resin contains an acrylic resin (component B), the ratio of the cyclic carbodiimide compound (component C) in the resin is the above-mentioned “polylactic acid (component A) 100 parts by weight”. It may be read as “100 parts by weight of the total amount of polylactic acid (component A) and acrylic resin (component B)”.

  In the present invention, the production method of the cyclic carbodiimide compound is not particularly limited, and can be produced by combining conventionally known methods. For example, a method for producing an amine body via an isocyanate body, a method for producing an amine body via an isothiocyanate body, a method for producing an amine body via a triphenylphosphine body, a urea body from an amine body The method of manufacturing via a thiourea body, the method of manufacturing via a thiourea body, the method of manufacturing from a carboxylic acid body via an isocyanate body, the method of manufacturing a lactam body, etc. are mentioned.

  Moreover, the cyclic carbodiimide compound of this invention can be manufactured by combining the method described in the following literature, or changing or combining suitably according to the target compound.

Tetrahedron Letters, Vol. 34, no. 32, 515-5158, 1993.
Medium- and Large-Membered Rings from Bis (iminophosphoranes): An Efficient Preparation of Cyclic Carbidiimides, Pedro Molina et al.
Journal of Organic Chemistry, Vol. 61, no. 13, 4289-4299, 1996.
New Models for the Study of the Racemization Mechanism of Carbodiimides. Synthesis and Structure (X-ray Crystallography and 1H NMR) of Cyclic Carbodiimides, Pedro Molina et al.
Journal of Organic Chemistry, Vol. 43, No8, 1944-1946, 1978.
Macrocyclic Ureas As Masked Isocynates, Henri Ulrich et al.
Journal of Organic Chemistry, Vol. 48, no. 10, 1694-1700, 1983.
Synthesis and Reactions of Cyclic Carbodiimides, R.A. Richter et al.
Journal of Organic Chemistry, Vol. 59, no. 24, 7306-7315, 1994.
A New and Efficient Preparation of Cyclic Carbodiamids from Bis (iminophosphoranea) and the System Boc ₂ O / DMAP, Pedro Molina et al.

（２）得られたニトロ体を還元して下記式（ｄ）で表わされるアミン体を得る工程、

（３）得られたアミン体とトリフェニルホスフィンジブロミドを反応させ下記式（ｅ）で表されるトリフェニルホスフィン体を得る工程、および

（４）得られたトリフェニルホスフィン体を反応系中でイソシアネート化した後、直接脱炭酸させることによって製造したものは、本願発明に用いる環状カルボジイミド化合物として好適に用いることができる。
（上記式中、Ａｒ^１およびＡｒ^２は各々独立に、炭素数１〜６のアルキル基またはフェニル基で置換されていてもよい芳香族基である。Ｅ^１およびＥ^２は各々独立に、ハロゲン原子、トルエンスルホニルオキシ基およびメタンスルホニルオキシ基、ベンゼンスルホニルオキシ基、ｐ−ブロモベンゼンスルホニルオキシ基からなる群から選ばれる基である。Ａｒ^ａは、フェニル基である。Ｘは、下記式（ｉ−１）から（ｉ−３）の結合基である。） Depending on the compound to be produced, an appropriate production method may be employed. For example, (1) nitrophenols represented by the following formula (a-1), nitrophenols represented by the following formula (a-2) And a compound represented by the following formula (b) to obtain a nitro compound represented by the following formula (c),

(2) A step of reducing the obtained nitro body to obtain an amine body represented by the following formula (d);

(3) a step of reacting the obtained amine body with triphenylphosphine dibromide to obtain a triphenylphosphine body represented by the following formula (e); and

(4) After the obtained triphenylphosphine body is isocyanated in the reaction system and then directly decarboxylated, it can be suitably used as the cyclic carbodiimide compound used in the present invention.
(In the above formula, Ar ¹ and Ar ² are each independently an aromatic group optionally substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group. E ¹ and E ² are each independently a halogen atom. A group selected from the group consisting of an atom, a toluenesulfonyloxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy group, Ar ^a is a phenyl group, X is represented by the following formula (i -1) to (i-3).

  In addition, the cyclic carbodiimide compound can effectively seal the acidic group of the polymer compound. However, as long as it does not contradict the gist of the present invention, for example, a conventionally known polymer carboxyl group sealing agent may be used. Can be used together. Examples of such conventionally known carboxyl group-capping agents include agents described in JP-A-2005-2174, such as epoxy compounds, oxazoline compounds, and oxazine compounds.

<D component>
The polyolefin is preferably polyethylene or polypropylene. Further, it may be copolymerized with other components. The copolymerization may be block, random, or graft polymerization. Although there are various types depending on the degree of polymerization and the like, they can be used according to the purpose and are not particularly limited.

<Other than A, B, C, D components>
The P layer and N layer of the present invention include thermoplastic resins other than the above-described A, B, C, and D components, stabilizers, ultraviolet absorbers, crystallization accelerators, fillers, mold release agents, antistatic agents, It can contain at least one selected from the group consisting of plasticizers and impact stabilizers. The polylactic acid used in the present invention preferably contains a stabilizer. As a stabilizer, what is used for the stabilizer of a normal thermoplastic resin can be used. For example, an antioxidant, a light stabilizer, etc. can be mentioned. By blending these agents, a multilayer film excellent in mechanical properties, moldability, heat resistance and durability can be obtained.

  Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphite compounds, thioether compounds, and the like.

  Examples of hindered phenol compounds include n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5 ′). -Tert-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexanediol- Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) -Propionate], 2,2′-methylene-bis (4-methyl-tert-butylphenol), triethylene glycol-bis 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro ( 5,5) Undecane and the like can be mentioned. As a hindered amine compound, N, N′-bis-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis [3- (3′-Methyl-5′-tert-butyl-4′-hydroxyphenyl) propionyl] diamine, N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionyl ] Hydrazine, N-salicyloyl-N′-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N′-bis [2- {3- (3,5-di) -Tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide and the like. Preferably, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate] and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl) -4-hydroxyphenyl) propionate] methane and the like.

  As the phosphite compound, those in which at least one P—O bond is bonded to an aromatic group are preferable. Specifically, tris (2,6-di-tert-butylphenyl) phosphite, tetrakis ( 2,6-di-tert-butylphenyl) 4,4′-biphenylene phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, tris (mixed mono and di-no Butylphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4'-isopropylidene-bis (phenyl - dialkyl phosphite), and the like.

  Among them, tris (2,6-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,6-di-tert-butyl) -4-Methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,6-di-tert-butylphenyl) 4,4'-biphenylene phosphite and the like can be preferably used.

  Specific examples of thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio) Propionate) and the like.

  Examples of the light stabilizer include oxybenzophenone compounds, cyclic imino ester compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, hindered amine compounds, nickel complex compounds, and the like. I can do it. As a light stabilizer, you may use in combination with the ultraviolet absorber and what capture | acquires the radical produced | generated by photooxidation.

  As the ultraviolet absorber, a cyclic imino ester compound, a benzophenone compound, and a benzotriazole compound are preferable in that absorption in visible light can be minimized.

  Specific examples of useful benzotriazole ultraviolet absorbers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl). ) Benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl)- 5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2, 2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2 ′ Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy Examples include, but are not limited to, a mixture of -5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate. As commercially available products, TINUVIN 109, TINUVIN 171, TINUVIN 326, and TINUVIN 328 (all manufactured by Ciba Specialty Chemicals) can be preferably used.

  Specific examples of the cyclic imino ester compound include 2,2′-bis (3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (3,1-benzoxazin-4-one). ), 2,2′-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one) 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(1,5-naphthalene) bis (3,1-benzoxazine-4-one) ON), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2-nitro-p-phenylene) bis (3,1 -Benzoxazin-4-one) and 2,2 '-(2-chloro-p- Eniren) bis (3,1-benzoxazin-4-one) is illustrated. Among them, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one) And 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) are preferred, especially 2,2′-p-phenylenebis (3,1-benzoxazine-4 -On) is preferred. The cyclic imino ester can be used alone or in combination of two or more.

  The cyclic imino ester can be produced by various methods disclosed in International Publication WO 03/035735. That is, any of a method using isatoic anhydride as a raw material (in particular, a method using recrystallized isatoic anhydride) and a method using anthranilic acid can be used. A cyclic imino ester compound can be obtained by reacting these acid compounds with a carboxylic acid chloride compound. These may be recrystallized after production as disclosed in JP-B-62-31027. Such compounds are commercially available from Takemoto Yushi Co., Ltd. as CEi-P (trade name) and from CYTEC as CYASORB UV-3638 (trade name) and can be easily used.

  Examples of benzophenone compounds include benzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxybenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'- Dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy- 2 ' Carboxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methyl-acryloxyisopropoxy) benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate, 2-hydroxy-4-octyloxy Examples include benzophenone, 4-benzyloxy-2-hydroxybenzophenone, 1,4-bis (4-benzoyl-3-hydroxyphenoxy) -butane, and the like.

  The polylactic acid in the present invention can contain an organic or inorganic crystallization accelerator. By containing the crystallization accelerator, the action of the stereocomplex crystal accelerator can be further enhanced, and a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.

  As the crystallization accelerator used in the present invention, those generally used as crystal nucleating agents for crystalline resins can be used, and both inorganic crystal nucleating agents and organic crystal nucleating agents can be used. .

  As inorganic crystal nucleating agents, talc, kaolin, silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide, boron nitride, Examples thereof include montmorillonite, neodymium oxide, aluminum oxide, and phenylphosphonate metal salt.

  These inorganic crystal nucleating agents are treated with various dispersion aids in order to enhance the dispersibility in the composition and the effect thereof, and the primary particle diameter becomes a highly dispersed state of about 0.01 to 0.5 μm. Some are preferred.

  Organic nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, lauric acid Sodium phosphate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicylate Examples include organic carboxylic acid metal salts such as zinc, aluminum dibenzoate, sodium β-naphthoate, potassium β-naphthoate, and sodium cyclohexanecarboxylate, and organic sulfonic acid metal salts such as sodium p-toluenesulfonate and sodium sulfoisophthalate. It is done.

  Also, organic carboxylic acid amides such as stearic acid amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (tert-butylamide), low density polyethylene, high density polyethylene, polyiso Propylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid copolymer, sodium of styrene-maleic anhydride copolymer Examples thereof include salts (so-called ionomers), benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.

Among these, at least one selected from talc and organic carboxylic acid metal salts is preferably used. Only one type of crystal nucleating agent may be used in the polylactic acid of the present invention, or two or more types may be used in combination.
The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight per 100 parts by weight of polylactic acid.

  Examples of the antistatic agent used in the present invention include (β-lauramidopropionyl) trimethylammonium sulfate, quaternary ammonium salts such as sodium dodecylbenzenesulfonate, sulfonate compounds, and alkyl phosphate compounds. It is done.

  In the multilayer film of the present invention, one type of antistatic agent may be used, or two or more types may be used in combination. The content of the antistatic agent is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of polylactic acid.

  As the plasticizer used in the present invention, generally known plasticizers can be used. Examples include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.

  As a polyester plasticizer, acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, Examples thereof include polyesters composed of diol components such as 1,6-hexanediol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or a monofunctional alcohol.

  Examples of the glycerol plasticizer include glycerol monostearate, glycerol distearate, glycerol monoacetomonolaurate, glycerol monoacetomonostearate, glycerol diacetomonooleate, and glycerol monoacetomonomontanate.

  Polyvalent carboxylic acid plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellitic acid tributyl, trimellitic acid trioctyl, Trimellitic acid esters such as trihexyl meritate, isodecyl adipate, adipic acid esters such as adipate-n-decyl-n-octyl, citrate esters such as tributyl acetylcitrate, and bis (2-ethylhexyl) azelate Examples include sebacic acid esters such as azelaic acid ester, dibutyl sebacate, and bis (2-ethylhexyl) sebacate.

  Examples of the phosphate ester plasticizer include tributyl phosphate, tris phosphate (2-ethylhexyl), trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylhexyl phosphate, and the like.

  Polyalkylene glycol plasticizers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide.propylene oxide) block and / or random copolymers, ethylene oxide addition polymers of bisphenols, tetrahydrofuran addition polymers of bisphenols, etc. And end-capping compounds such as a terminal epoxy-modified compound, a terminal ester-modified compound and a terminal ether-modified compound.

  Examples of the epoxy plasticizer include an epoxy triglyceride composed of alkyl epoxy stearate and soybean oil, and an epoxy resin using bisphenol A and epichlorohydrin as raw materials.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol-bis (2-ethylbutyrate), and fatty acids such as stearamide. Examples thereof include fatty acid esters such as amide and butyl oleate, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.

  As the plasticizer, at least one selected from polyester-type plasticizers and polyalkylene-type plasticizers can be preferably used, and only one type may be used, or two or more types may be used in combination.

  The content of the plasticizer is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, and still more preferably 0.1 to 10 parts by weight per 100 parts by weight of each layer of the multilayer film. In the present invention, each of the crystal nucleating agent and the plasticizer may be used alone, or more preferably used in combination.

Next, the multilayer film of the present invention will be specifically described with reference to the drawings. 1 to 3 are schematic views showing one embodiment of the multilayer film of the present invention.
In FIG. 1, 1 is an N layer, 2 is an adhesive layer, 3 is a P layer, and 4 is a multilayer film of the present invention. In FIG. 2, 5 is an N layer, 6 is a P layer, and 7 is a multilayer film of the present invention. In FIG. 3, 8 and 12 are N layers, 10 is a P layer, 9 and 11 are adhesive layers, and 13 is a multilayer film of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention does not receive any limitation by this.

<Evaluation method>
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer:
The weight average molecular weight and number average molecular weight of the polymer were measured by gel permeation chromatography (GPC) and converted to standard polystyrene. GPC measuring instrument is a detector; differential refractometer (manufactured by Shimadzu Corporation) RID-6A column; Toso-Co., Ltd. TSKgelG3000HXL, TSKgelG4000HXL, TSKgelG5000HXL and TSKguardcolumnHXL-L or Toso- TSKgel G2000HXL, TSKgelG3000HXL, and TSKguardcolumnHXL-L connected in series were used.
Chloroform was used as an eluent, 10 μl of a sample having a concentration of 1 mg / ml (chloroform containing 1% hexafluoroisopropanol) was injected at a temperature of 40 ° C. and a flow rate of 1.0 ml / min.

(2) DSC measurement of stereocomplex crystallinity [S (%)], crystal melting temperature, etc .:
The sample was heated up to 260 ° C. at 20 ° C./min under a nitrogen stream in the first cycle using DSC (TA Instrument Co., Ltd., trade name “Q10”), glass transition temperature (Tg), stereo complex phase polylactic acid crystal melting point (TMSC), stereocomplex phase polylactic acid crystallization temperature _{(Tc sc),} stereocomplex phase polylactic acid crystal melting enthalpy (ΔHm _sc), homo-phase polylactic acid crystal melting enthalpy (.DELTA.Hm _h) and heat of crystallization (ΔHc) was measured.
The stereocomplex crystallinity is a value obtained by the following formula (II) from the stereocomplex phase and homophase polylactic acid crystal melting enthalpy obtained by the above measurement.
S = [ΔHm _sc / (ΔHm _h + ΔHm _sc )] × 100 (II)
(However, ΔHm _sc is the melting enthalpy of stereocomplex phase crystal, ΔHm _h is the melting enthalpy of homophase polylactic acid crystal)

(3) Thickness measurement:
Measurement was performed with an electronic micro manufactured by Anritsu.

(4) Identification of cyclic carbodiimide structure by nuclear magnetic resonance (NMR) and determination of cyclic carbodiimide in polyester composition:
The synthesized cyclic carbodiimide compound was confirmed by ¹ H-NMR and ¹³ C-NMR. For NMR, a trade name “JNR-EX270” manufactured by JEOL Ltd. was used. Deuterated chloroform was used as the solvent.

(5) Identification of carbodiimide skeleton of cyclic carbodiimide by infrared spectroscopy (IR):
The presence or absence of the carbodiimide skeleton of the synthesized cyclic carbodiimide compound was confirmed by FT-IR at 2100-2200 cm ⁻¹ characteristic of carbodiimide. FT-IR used the product name “Magna-750” manufactured by Thermo Nicolet Co., Ltd.

<Manufacture of polylactic acid (component A)>
(1) Production of poly L-lactic acid (PLLA1):
To 100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%), 0.005 part by weight of octylate is added, and 180 ° C. in a reactor equipped with a stirring blade in a nitrogen atmosphere. Then, 1.2 times equivalent of phosphoric acid with respect to tin octylate was added, and then the remaining lactide at 13.3 Pa was removed under reduced pressure to form a chip to obtain poly L-lactic acid (PLLA1). The obtained poly L-lactic acid (PLLA1) had a weight average molecular weight of 152,000, a glass transition point (Tg) of 55 ° C., and a melting point of 175 ° C.

(2) Production of poly-D-lactic acid (PDLA1):
In the production of PLLA1, polymerization was carried out under the same conditions except that L-lactide was changed to D-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%) to obtain poly D-lactic acid (PDLA1). . The obtained poly-D-lactic acid (PDLA1) had a weight average molecular weight (Mw) of 151,000, a glass transition point (Tg) of 55 ° C., and a melting point of 175 ° C.

(3) Production of stereocomplex polylactic acid (SCPLA1):
50 parts by weight of PLLA1 and PDLA1 obtained by the above operation and a metal phosphate (“ADEKA STAB” NA-71: 0.1 part by weight, manufactured by ADEKA Corporation) are supplied to the first supply port of the biaxial kneader. The mixture was melted and kneaded at a cylinder temperature of 250 ° C. to obtain stereocomplex polylactic acid (SCPLA1). The glass transition point (Tg) was 55 ° C., the melting point was 216 ° C., and the stereocomplex crystallinity S = 100%.

<Production of a compound (component C) containing at least a cyclic structure in which one carbodiimide group is included and the first nitrogen and the second nitrogen are bonded to each other through a bonding group>
A reaction apparatus in which 200 ml of o-nitrophenol (0.11 mol), pentaerythrityl tetrabromide (0.025 mol), potassium carbonate (0.33 mol), and N, N-dimethylformamide (DMF) are provided with a stirring device and a heating device. The reaction mixture was charged under N ₂ atmosphere and reacted at 130 ° C. for 12 hours. Then, DMF was removed under reduced pressure, and the resulting solid was dissolved in 200 ml of dichloromethane, followed by separation three times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and dichloromethane was removed under reduced pressure to obtain an intermediate product D (nitro form).

  Next, intermediate product D (0.1 mol), 5% palladium carbon (Pd / C) (2 g), and 400 ml of ethanol / dichloromethane (70/30) were charged into a reactor equipped with a stirrer, and 5 hydrogen substitution was performed. The reaction was performed in a state where hydrogen was constantly supplied at 25 ° C., and the reaction was terminated when there was no decrease in hydrogen. When Pd / C was recovered and the mixed solvent was removed, an intermediate product E (amine body) was obtained.

Next, triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane were charged and stirred in a reactor equipped with a stirring device, a heating device, and a dropping funnel in an N ₂ atmosphere. A solution prepared by dissolving the intermediate product E (0.025 mol) and triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane was gradually added dropwise thereto at 25 ° C. After completion of dropping, the reaction is carried out at 70 ° C. for 5 hours. Thereafter, the reaction solution was filtered, and the filtrate was separated 5 times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and 1,2-dichloroethane was removed under reduced pressure to obtain an intermediate product F (triphenylphosphine compound).

Next, in a reactor equipped with a stirrer and a dropping funnel, di-tert-butyl dicarbonate (0.11 mol), N, N-dimethyl-4-aminopyridine (0.055 mol), dichloromethane under N ₂ atmosphere. 150 ml is charged and stirred. Thereto, 100 ml of dichloromethane in which the intermediate product F (0.025 mol) was dissolved was slowly added dropwise at 25 ° C. After dropping, react for 12 hours. Thereafter, the solid obtained by removing dichloromethane was purified to obtain a component C having the structure shown below (hereinafter sometimes abbreviated as TX1) and (molecular weight: 516). The structure of TX1 was confirmed by NMR and IR.

<Manufacture of multilayer film materials>
(1) C1: Polylactic acid (containing TX1);
PLLA1, 100 parts by weight, TX1, 1.0 part by weight were mixed with a blender, vacuum dried at 110 ° C. for 5 hours, then supplied from the first supply port of the kneader, at a cylinder temperature of 230 ° C. and a vent pressure of 13.3 Pa. The mixture was melt-kneaded while evacuating, extruded into a water tank, and chipped with a chip cutter to obtain a composition (C1). The glass transition point (Tg) was 56 ° C., the crystallization temperature was 135 ° C., and the melting point was 175 ° C.

(2) C2: a composition containing polylactic acid and PMMA (polymethyl methacrylate) (containing TX1);
PLLA1 obtained by the above operation, 70 parts by weight, polymethylmethacrylate manufactured by Mitsubishi Rayon Co., Ltd., 30 parts by weight of “Acripet VH001”, TX1, 1.0 part by weight are mixed with a blender, 110 ° C., 5 After vacuum drying for a period of time, supply from the first supply port of the kneading machine, melt kneading while evacuating at a cylinder temperature of 230 ° C. and a vent pressure of 13.3 Pa, extruding the strand into a water tank, making chips with a chip cutter and blending A composition (C2) was obtained. The glass transition point (Tg) was 61 ° C., the crystallization temperature was 140 ° C., and the melting point was 190 ° C.

(3) C3: stereocomplex polylactic acid (containing TX1);
SPLLA1, 100 parts by weight, TX1, 1.0 part by weight obtained by the above operation were mixed with a blender, vacuum dried at 110 ° C. for 5 hours, then supplied from the first supply port of the kneader, cylinder temperature 230 ° C., The mixture was melt-kneaded while evacuating at a vent pressure of 13.3 Pa, extruded into a water tank, and chipped with a chip cutter to obtain a blend composition (C3). The glass transition point (Tg) was 58 ° C., the crystallization temperature was 114 ° C., and the melting point was 211 ° C.

(4) C4: polylactic acid;
It is the same as PLLA1 obtained by the above operation.

(5) C5: polylactic acid (containing linear polycarbodiimide);
PLLA1, 100 parts by weight, Nisshinbo Chemical Co., Ltd. “Carbodilite” LA-1, 1.0 part by weight are mixed with a blender, vacuum dried at 110 ° C. for 5 hours, and then supplied from the first supply port of the kneader. The mixture was melt kneaded while evacuating at a cylinder temperature of 230 ° C. and a vent pressure of 13.3 Pa, extruded into a water bath, and chipped with a chip cutter to obtain a composition (C5). The glass transition point (Tg) was 56 ° C., the crystallization temperature was 135 ° C., and the melting point was 168 ° C.

(6) C6: soft polypropylene;
The product name “Prime TPO M142E” manufactured by Prime Polymer Co., Ltd. is used.

(7) C7: polyethylene;
The product name “Novatec HD HF313” manufactured by Nippon Polyethylene Co., Ltd. is used.

(8) C8: Adhesive polyolefin The product name “Admer SF600” manufactured by Mitsui Chemicals, Inc. is used.

[Example 1]
Resin C1 was dried at 100 ° C for 5 hours, then put into a hopper of a single screw extruder, melt extruded at 195 ° C, melt extruded from a T die at a die temperature of 190 ° C, and adhered to the surface of a cooling drum at 60 ° C And solidified to obtain an unstretched film. Thereafter, the film was stretched twice in length and twice in width by successive biaxial stretching methods to obtain a film having a thickness of 30 μm. In the melt extrusion process, there was no generation of malodor derived from isocyanate, and the working environment was excellent. Next, the resin C6 was melt-extruded at 170 ° C., melt-extruded in a film form from a T-die at a die temperature of 165 ° C., adhered to the surface of a cooling drum at 30 ° C. and solidified to obtain a film having a thickness of 30 μm. These films were laminated using an acrylic pressure-sensitive adhesive as an adhesive to obtain a laminated film having a thickness of 70 μm.
This film has a three-layer structure in which the resin C1 is a P layer and the resin C6 is an N layer, and an adhesive layer is interposed therebetween. The laminated film was subjected to a durability test at 60 ° C. and 90% RH for 1000 hours to confirm embrittlement. However, the shape was maintained and the mechanical strength was hardly changed from the initial value.
Water was placed in a glass beverage cup to a depth of 1 cm, and the mouth was sealed with this film and left at a temperature of 40 ° C. for 48 hours, but there was almost no water evaporation, and this film has a water vapor barrier property. I found it excellent.

[Example 2]
After the resin C1 was dried at 90 ° C. for 5 hours, the resin C1 was put into the hopper of the extruder A of the three-type three-layer extruder and melt-extruded at 187 ° C. On the other hand, the resin C7 was put into the hopper of the extruder B and melt-extruded at 180 ° C. Further, the resin C8 was put into the hopper of the extruder C and melt-extruded at 180 ° C. These resins are multi-layered in a die, and the multi-layered resin was melt-extruded into a film form from a T-die at a die temperature of 185 ° C., adhered to the surface of a cooling drum at 60 ° C., and solidified to obtain an unstretched film. In the melt extrusion process, there was no generation of malodor derived from isocyanate, and the working environment was excellent. The three-type three-layer extruder is set so that the extruder A is an outer layer, the outer layer of the extruder B is an outer layer, and the extruded wood C is an intermediate layer. The film thickness was 100 μm. The thickness ratio of the three layers was approximately 1: 0.2: 1. Thereafter, this unstretched film was stretched twice at 105 ° C. by a longitudinal uniaxial stretching machine, stretched at a stretching temperature of 107 ° C. and a magnification of 2.5 times by a tenter lateral uniaxial stretching machine, and then 150 ° C. by the same equipment. The film was heat-fixed and the P layer was brought into a substantially crystalline state to obtain a film having a thickness of 30 μm.
The laminated film was subjected to a durability test at 60 ° C. and 90% RH for 1000 hours to confirm embrittlement. However, the shape was maintained and the mechanical strength was hardly changed from the initial value.
Water was placed in a glass beverage cup to a depth of 1 cm, and the mouth was sealed with this film and left at a temperature of 40 ° C. for 48 hours, but there was almost no water evaporation, and this film has a water vapor barrier property. I found it excellent.

[Example 3]
Resin C2 was dried at 95 ° C. for 5 hours, then placed in a hopper of a single screw extruder, melt extruded at 210 ° C., melt extruded from a T die at a die temperature of 209 ° C., and adhered to the surface of a cooling drum at 60 ° C. And solidified to obtain an unstretched film. Thereafter, the film was stretched twice in length and twice in width by successive biaxial stretching methods to obtain a film having a thickness of 30 μm. In the melt extrusion process, there was no generation of malodor derived from isocyanate, and the working environment was excellent. Next, the resin C6 was melt-extruded at 170 ° C., melt-extruded in a film form from a T-die at a die temperature of 165 ° C., adhered to the surface of a cooling drum at 30 ° C. and solidified to obtain a film having a thickness of 30 μm. These films were laminated using an acrylic pressure-sensitive adhesive as an adhesive to obtain a laminated film having a thickness of 70 μm.
This film has a three-layer structure in which the resin C2 is a P layer and the resin C6 is an N layer, and an adhesive layer is interposed therebetween. The laminated film was subjected to a durability test at 60 ° C. and 90% RH for 1000 hours to confirm embrittlement. However, the shape was maintained and the mechanical strength was hardly changed from the initial value.
Water was placed in a glass beverage cup to a depth of 1 cm, and the mouth was sealed with this film and left at a temperature of 40 ° C. for 48 hours, but there was almost no water evaporation, and this film has a water vapor barrier property. I found it excellent.

[Example 4]
Resin C3 was dried at 100 ° C. for 5 hours, then put into a hopper of a single screw extruder, melt extruded at 225 ° C., melt extruded from a T die at a die temperature of 220 ° C., and adhered to the surface of a cooling drum at 60 ° C. And solidified to obtain an unstretched film. Thereafter, the film was stretched twice in length and twice in width by successive biaxial stretching methods to obtain a film having a thickness of 30 μm. In the melt extrusion process, there was no generation of malodor derived from isocyanate, and the working environment was excellent. Next, the resin C6 was melt-extruded at 170 ° C., melt-extruded in a film form from a T-die at a die temperature of 165 ° C., adhered to the surface of a cooling drum at 30 ° C. and solidified to obtain a film having a thickness of 30 μm. These films were laminated using an acrylic pressure-sensitive adhesive as an adhesive to obtain a laminated film having a thickness of 70 μm.
This film has a three-layer structure in which the resin C3 is a P layer and the resin C6 is an N layer, and an adhesive layer is interposed therebetween. The laminated film was subjected to a durability test at 60 ° C. and 90% RH for 1000 hours to confirm embrittlement. However, the shape was maintained and the mechanical strength was hardly changed from the initial value.
Water was placed in a glass beverage cup to a depth of 1 cm, and the mouth was sealed with this film and left at a temperature of 40 ° C. for 48 hours, but there was almost no water evaporation, and this film has a water vapor barrier property. I found it excellent.

[Comparative Example 1]
Resin C4 was dried at 100 ° C. for 5 hours, then put into a hopper of a single screw extruder, melt extruded at 195 ° C., melt extruded from a T die at a die temperature of 190 ° C., and adhered to the surface of a cooling drum at 60 ° C. And solidified to obtain an unstretched film. Thereafter, the film was stretched twice in length and twice in width by successive biaxial stretching methods to obtain a film having a thickness of 30 μm. In the melt extrusion process, there was no generation of malodor derived from isocyanate, and the working environment was excellent. Next, the resin C6 was melt-extruded at 170 ° C., melt-extruded in a film form from a T-die at a die temperature of 165 ° C., adhered to the surface of a cooling drum at 30 ° C. and solidified to obtain a film having a thickness of 30 μm. These films were laminated using an acrylic pressure-sensitive adhesive as an adhesive to obtain a laminated film having a thickness of 70 μm.
This film has a three-layer structure in which the resin C4 is a P layer, the resin C6 is an N layer, and an adhesive layer is interposed therebetween. The laminated film was subjected to an endurance test at 60 ° C. and 90% RH for 1000 hours to confirm embrittlement, but the P layer was cracked and very brittle, and the hydrolysis of the P layer significantly advanced. It was confirmed that

[Comparative Example 2]
Resin C5 was dried at 100 ° C. for 5 hours, then put into a hopper of a single screw extruder, melt extruded at 195 ° C., melt extruded from a T die at a die temperature of 190 ° C., and adhered to the surface of a cooling drum at 60 ° C. And solidified to obtain an unstretched film. In the melt-extrusion process, isocyanate-derived malodor was generated and the working environment deteriorated, so the subsequent tests were stopped.

[Comparative Example 3]
Resin C1 was dried at 100 ° C for 5 hours, then put into a hopper of a single screw extruder, melt extruded at 195 ° C, melt extruded from a T die at a die temperature of 190 ° C, and adhered to the surface of a cooling drum at 60 ° C And solidified to obtain an unstretched film. Thereafter, the film was stretched twice in length and twice in width by successive biaxial stretching methods to obtain a film having a thickness of 30 μm. In the melt extrusion process, there was no generation of malodor derived from isocyanate, and the working environment was excellent.
Water was placed in a glass beverage cup to a depth of 1 cm, the mouth was sealed with this film and left at a temperature of 40 ° C. for 48 hours, but the water was almost gone and this film has excellent water vapor barrier properties. I found out.

1 N layer 2 Adhesive layer 3 P layer 4 Multilayer film 5 N layer 6 P layer 7 Multilayer film 8 N layer 9 Adhesive layer 10 P layer 11 Adhesive layer 12 N layer 13 Multilayer film of the present invention

Claims (15)

An aliphatic polyester (component A), and the aliphatic polyester (component A) includes at least a cyclic structure having one carbodiimide group and a first nitrogen and a second nitrogen bonded by a bonding group ; the layer containing the number of atoms constituting the ring-shaped structure having one carbodiimide group and the first nitrogen and second nitrogen being linked by linking group directly is 8-50 compound (C component) (P Layer) and at least one layer (N layer) made of a resin containing polyolefin (D component).   The multilayer film according to claim 1, wherein the aliphatic polyester (component A) is polylactic acid. The multilayer film according to claim 2, wherein the polylactic acid (component A) is a polylactic acid containing a poly-D-lactic acid component and a poly-L-lactic acid component, and the stereocomplex crystallinity (S) is 90% or more.
{Stereocomplex crystallinity (S) measured by differential scanning calorimetry (DSC), polylactic acid homocrystal melting heat (ΔHm _h ) observed below 190 ° C, polylactic acid stereocomplex observed above 190 ° C It calculates _| requires by following Formula (I) from a crystal melting heat ((DELTA) Hmsc).
(S) = [ΔHm _sc / (ΔHm _h + ΔHm _sc )] × 100 (I)}   The multilayer film in any one of Claims 1-3 in which P layer contains acrylic resin (B component) further. The multilayer film in any one of Claims 1-4 by which C component is represented by following formula (1).

(In the formula, Q is a divalent to tetravalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom.) The multilayer film according to claim 5, wherein Q is a divalent to tetravalent linking group represented by the following formula (1-1), (1-2), or (1-3).

(In the formula, Ar ¹ and Ar ² are each independently an aromatic group having 2 to 4 carbon atoms and 5 to 15 carbon atoms. R ¹ and R ² are each independently 1 to 2 carbon atoms having 1 to 4 carbon atoms. 20 aliphatic groups, 2 to 4 valent alicyclic groups having 3 to 20 carbon atoms, or combinations thereof, or these aliphatic groups, alicyclic groups and 2 to 4 valent aromatic carbon atoms having 5 to 15 carbon atoms X ¹ and X ² are each independently a divalent to tetravalent aliphatic group having 1 to 20 carbon atoms, a divalent to tetravalent carbon atom having 3 to 20 alicyclic groups, 2 to 4 A valent aromatic group having 5 to 15 carbon atoms, or a combination thereof, s is an integer of 0 to 10. k is an integer of 0 to 10. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ^2. X ³ is a divalent to tetravalent carbon number. An aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 2 to 4 carbon atoms having 3 to 20 carbon atoms, an aromatic group having 2 to 4 carbon atoms having 5 to 15 carbon atoms, or a combination thereof, provided that Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ may contain a hetero atom, and when Q is a divalent linking group, Ar ¹ , Ar ² , R 3 ¹ , R ² , X ¹ , X ² and X ³ are all divalent groups, and when Q is a trivalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ^{One of 2} and X ³ is a trivalent group, and when Q is a tetravalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ One of them is a tetravalent group or two are trivalent groups.) The multilayer film of Claim 5 by which C component is represented by following formula (2).

(Wherein Q _a is a divalent linking group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom.) The multilayer film according to claim 7, wherein Q _a is a divalent linking group represented by the following formula (2-1), (2-2), or (2-3).

(In the formula, Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² , X _a ³ , s and k are represented by the formulas (1-1) to (1-3), respectively. The same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k in the inside.) The multilayer film of Claim 5 by which C component is represented by following formula (3).

(Wherein Q _b is a trivalent linking group which is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and may contain a hetero atom. Y represents a cyclic structure. It is a carrier to be supported.) Q _b is represented by the following formula (3-1), (3-2) or a multilayer film according to claim 9, wherein a trivalent bonding group represented by (3-3).

(In the formula, Ar _b ¹ , Ar _b ² , R _b ¹ , R _b ² , X _b ¹ , X _b ² , X _b ³ , s and k are represented by the formulas (1-1) to (1-3), respectively. Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s, and k, with one of these being a trivalent group.)   The multilayer film according to claim 9 or 10, wherein Y is an atom, an atomic group, or a polymer. The multilayer film of Claim 5 by which C component is represented by following formula (4).

(Wherein Q _c is a tetravalent linking group that is an aliphatic group, an aromatic group, an alicyclic group, or a combination thereof, and may have a hetero atom. Z ¹ and Z ² are A carrier carrying a ring structure.) The multilayer film according to claim 12, wherein Q _c is a tetravalent linking group represented by the following formula (4-1), (4-2), or (4-3).

(In the formula, Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s and k are respectively represented by formulas (1-1) to (1-3) Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k, provided that one of them is a tetravalent group or two are 3 Valent group.) The multilayer film according to claim 12 or 13, wherein Z ¹ and Z ² are each independently an atom, an atomic group or a polymer.   The multilayer film according to any one of claims 1 to 14, wherein the polyolefin (component D) contains polyethylene and / or a polypropylene skeleton.

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