JP2011231241A - Resin film, decoration film consisting of it, and decorative molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin film which can provide a decoration film which excels in hydrolysis resistance and also considers environment under the good work environment, the decoration film which has the resin film with a decoration layer, a decorative molding which carries out laminate unification of the decoration film and a molding, and its manufacturing method.SOLUTION: The resin film includes an aliphatic polyester, wherein the aliphatic polyester includes a compound (C component) which has at least a cyclic structure which has one carbodiimide group and in which the first nitrogen and the second nitrogen are combined by a bonding group, the film elongation at break in an MD direction or a TD direction is 100-1,000%, and the stress (100°C measured value) at the time of 100% elongation is in the range of 0.1-25 MPa. In addition, the resin film which is in a substantially non-crystalline state is used as a substrate of the decoration film.

Description

  The present invention relates to a resin film that can be usefully used as a substrate for a decorative film, a decorative film comprising the resin film, and a decorative molded product.

A molded body such as a resin molded body or a metal molded body by injection molding or the like is used for an exterior of an electric product such as a mobile phone, a personal computer, or a television, or an interior of an automobile. In order to decorate the surface of such a molded body, various techniques are used.
In particular, the method of obtaining a decorative molded product by decorating the outermost surface of a molded body with a decorative film having a substrate as a support and a design layer for applying a design on the substrate is directly applied to the surface of the molded body. Compared to a method of printing on the surface using ink or the like, there is an advantage that the degree of freedom of design is higher and, for example, it is possible to easily decorate a molded article surface having three-dimensional irregularities.

Two typical methods are demonstrated among the methods of decorating a molded object using a decorating film.
One is a technique called an injection molding simultaneous bonding method that is used only when the molded body is a resin molded body. This injection molding simultaneous bonding method is further divided into two. One is to insert a decorative film between male and female molds for injection molding, and to inject molten resin from one side of the mold to form an injection molded body. At the same time, the above film is applied to the molded body. This is a method of bonding, which is sometimes called an in-mold method. Another method is a method in which a decorative film is pre-shaped by vacuum forming, pressure forming, or the like, and then inserted into an injection mold, and a molten resin is injected into the decorative film so as to be integrally formed with the decorative film. It is. This is sometimes called the insert mold method. Such injection molding simultaneous bonding methods include, for example, JP-A-59-31130 (Patent Document 1), JP-A-62-196113 (Patent Document 2), JP-A-7-9484 (Patent Document). 3) etc.

The other is a vacuum bonding method. A decorative film is coated and bonded to a previously formed molded body in a vacuum. For example, in Japanese Patent No. 3733564 (Patent Document 4), Japanese Patent Application Laid-Open No. 2006-224459 (Patent Document 5), etc. Proposed.
Moreover, it is also proposed by Unexamined-Japanese-Patent No. 2005-15783 (patent document 6) to use a polylactic acid-type film as a board | substrate of a decoration film from the heightening of environmental consciousness.
However, a decorative film using a polylactic acid-based film has a technical problem that the decorative molded product has poor hydrolysis resistance and the like.

  In general, aliphatic polyester typified by polylactic acid is a resin that is susceptible to hydrolysis, and the durability time required varies depending on the application. When used as a decorative film in the field, appearance problems such as an increase in haze and occurrence of cracks may occur. When used in such an environment, it is necessary to improve hydrolysis resistance by some means.

Addition of a carbodiimide compound as a technique for improving the hydrolysis resistance of an aliphatic polyester is disclosed in Japanese Patent Laid-Open No. 2003-003052 (Patent Document 7).
The carbodiimide compound used in Patent Document 7 is a carbodiimide compound having a linear structure. When this linear carbodiimide compound is used as a terminal blocker of a polymer compound, the carbodiimide compound is bonded to the terminal of the polymer compound. As a result of this reaction, the compound having an isocyanate group is liberated, generating a unique odor of the isocyanate compound, and deteriorating the working environment.

JP 59-31130 A JP 62-196113 A Japanese Patent Laid-Open No. 7-9484 Japanese Patent No. 3733564 JP 2006-224459 A JP 2005-15783 A JP 2003-003052 A

  An object of the present invention is to solve the above-described problems of the prior art, and can provide a decorative film that is excellent in hydrolysis resistance and environmentally friendly under a good working environment. The object is to provide a film, a decorative film provided with a design layer on the resin film, a decorative molded product obtained by laminating and integrating the decorative film and a molded body, and a manufacturing method thereof.

The present invention has arrived at the present invention as a result of intensive investigations in view of the above-described prior art.
That is, the first object of the present invention is to
1. A resin film containing an aliphatic polyester (component A), the aliphatic polyester having at least a cyclic structure having one carbodiimide group in which the first nitrogen and the second nitrogen are bonded by a bonding group Including the compound (C component), the film breaking elongation (100 ° C. measured value) in the MD direction and TD direction is 100 to 1000%, and the stress at 100% elongation (100 ° C. measured value) is in the range of 0.1 to 25 MPa. Furthermore, it is achieved by a resin film characterized by being in a substantially non-crystalline state.

The above invention also includes the following.
2. 2. The resin film as described in 1 above, wherein the resin film further contains an acrylic resin (component B).
3. 2. The resin film as described in 1 above, wherein the component C 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.)
4). 4. The resin film as described in 3 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.)
5). 4. The resin film as described in 3 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.)
6). Q _a is represented by the following formula (2-1), (2-2) or a resin film of the 5 wherein the divalent linking group represented by (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 above)
7). 4. The resin film as described in 3 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.)
8). Q _b is represented by the following formula (3-1), (3-2) or a resin film of claim 7 wherein the trivalent linking 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.)
9. 9. The resin film as described in 7 or 8 above, wherein Y is a single bond, a double bond, an atom, an atomic group or a polymer.
10. 4. The resin film as described in 3 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.)
11. 11. The resin film as described in 10 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.)
12 12. The resin film as described in 10 or 11 above, wherein Z ¹ and Z ² are each independently a single bond, a double bond, an atom, an atomic group or a polymer.

The second object of the present invention is to
13. The resin film according to any one of claims 1 to 12 is used as a substrate, and the decorative film is provided with a design layer on the substrate.
The above invention includes the following.
14 14. The decorative film as described in 13 above, wherein the substrate is in a substantially non-crystalline state.

The third object of the present invention is to
15. This can be achieved by a decorative molded product in which the decorative film described in 13 above is laminated and integrated on the surface of the molded body.
The above invention includes the following.
16. 16. The decorative molded product according to 15, wherein the molded product is a resin molded product.
17. 17. The decorative molded product according to 16 above, wherein the resin molded product contains stereocomplex polylactic acid.

Finally, the fourth object of the present invention is to
18. In the method for producing a decorative molded product according to 15 or 16, wherein the decorative film and the molded body are bonded together, the substrate of the decorative film is used in a substantially non-crystalline state. Production method of decorative molded products,
19. The method for producing a decorative molded product according to 15 or 16, wherein the decorative film and the molded body are bonded together by heating the decorative film and contacting the surface of the molded body under vacuum, And the manufacturing method of the decorative molded product characterized by using the thing of the substantially amorphous state of the board | substrate of the decorative film before a heating.
20. 16. The method for producing a decorative molded product according to 16 above, wherein when the decorative film and the molded body are bonded together, the bonding is inserted into a mold for injection molding after preliminarily shaping the decorative film. Next, the decoration is performed by an insert molding method in which a resin as a molding material is injected into a mold, and the decorative film substrate before pre-shaped is used in a substantially non-crystalline state. Manufacturing method of molded products,
21. 15. The method for producing a decorative molded product according to 15 or 16 above, wherein the decorative film and the molded body are bonded together, wherein the decorative film substrate is not in a substantially non-crystalline state. , Manufacturing method of decorative molded products,
22. The method for producing a decorative molded product according to any one of 18 to 20 above, wherein the substrate of the decorative film used for bonding is bonded in a substantially non-crystalline state when the decorative film and the molded body are bonded. It can be achieved by a method for producing a decorative molded product, characterized in that the substrate is brought into a substantially crystalline state after bonding.

  ADVANTAGE OF THE INVENTION According to this invention, the resin film which can provide the decoration film which was excellent in hydrolysis resistance and considered the environment under a favorable work environment, This resin film is used as a board | substrate, and a design layer is provided. It is possible to provide a decorative film, a decorative molded product obtained by laminating and integrating the decorative film and a molded body, and a method for manufacturing the decorative molded product.

It is a schematic diagram which shows the one aspect | mode of the decorative molded product in this invention. It is a schematic diagram which shows the one aspect | mode of the decorative molded product in this invention. It is a schematic diagram showing the shape of the resin molding in an Example, a reference example, and a comparative example. It is a schematic diagram showing the shape of the resin molding in an Example.

Hereinafter, the present invention will be described in detail.
<Resin film>
In the present invention, the resin film is a resin film containing an aliphatic polyester (component A), and the aliphatic polyester has one carbodiimide group, and the first nitrogen and the second nitrogen are bonded by a bonding group. And a compound having at least a cyclic structure (C component), and a film elongation at break (100 ° C. measured value) in the MD direction and TD direction of 100 to 1000%, and a stress at 100% elongation (100 ° C. measured value). It is in the range of 0.1 to 25 MPa, and is further substantially in an amorphous state.

  Here, it is necessary that the film breaking elongation (100 ° C. measured value) in the MD direction and the TD direction is 100 to 1000%, and the stress at 100% elongation (100 ° C. measured value) is in the range of 0.1 to 25 MPa. However, when it is in this range, when used as a substrate for a decorative film, the resulting decorative film can be bonded to the surface of the target molded product with good quality, wrinkles, etc. There is no breakage of the film.

  Considering the case of bonding to a molded body deep-drawn into a shape having a sharp bend, the film breaking elongation (measured at 100 ° C.) in the MD and TD directions is 200 to 700% and 100% when stretched The stress (measured at 100 ° C.) is preferably in the range of 0.5 to 20 MPa, more preferably the film breaking elongation (measured at 100 ° C.) in the MD and TD directions is 250 to 600% and 100% stretched. The stress (measured at 100 ° C.) is preferably in the range of 1 to 15 MPa, and most preferably, the film breaking elongation (measured at 100 ° C.) in the MD direction and TD direction is 300 to 500% and the stress at 100% elongation ( (Measured value at 100 ° C.) is preferably in the range of 2 to 10 MPa.

In the present invention, the film breaking elongation (measured value at 100 ° C.) and the stress at 100% elongation (measured value at 100 ° C.) in the MD direction and TD direction were measured as tensile testers in which the chuck portion was covered with a heating chamber. Using a precision universal testing machine Autograph AG-X manufactured by Shimadzu Corporation, the sample film was cut into a width of 10 mm and a length of 100 mm, a sample was mounted at a distance of 50 mm between chucks, and a tensile speed of 50 mm / min according to JIS-C2151. The tensile test was performed under the conditions. The sample cutting direction is the MD direction which is the film flow direction, and the width direction perpendicular to the MD direction is the TD direction, the MD direction and the direction parallel to the TD direction are respectively sampled as the length direction, and the MD direction and the TD direction are sampled. The tensile measurement value of was evaluated.
At this time, the heating chamber installed in the chuck portion of the tensile tester was kept at 100 ° C. in the atmosphere in which the sample was present, and the measurement was performed five times to obtain the average value.

The film elongation at break (measured value at 100 ° C.) was calculated as% of the value obtained by subtracting the sample length before tension from the length at break and dividing by the sample length before tension. The stress at 100% elongation (measured value at 100 ° C.) was calculated (MPa) by dividing the load at 100% elongation of the load elongation curve by the cross-sectional area of the sample before tension.
Here, as a resin film, it is essential to contain the aliphatic polyester (A component) mentioned later, but also about the C component mentioned later. Furthermore, what contains the A component, B component, and C component which are mentioned later is also used suitably.

  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.

  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.

<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.

The polylactic acid may be one having L-lactic acid and / or D-lactic acid as the main repeating unit, and particularly preferably has a melting point of 150 ° C. or higher (here, the main is Means that the component occupies 50% or more). When the melting point is lower than 150 ° C., the dimensional stability, high temperature mechanical properties, etc. of the film cannot be improved.

Preferably, the melting point of polylactic acid is 170 ° C. or higher, more preferably 200 ° C. or higher. Here, the melting point means the peak temperature of the melting peak obtained by DSC measurement. In particular, in order to impart heat resistance, it is preferable that polylactic acid forms a stereocomplex phase crystal.
Here, the stereocomplex polylactic acid contains a eutectic formed by a poly L lactic acid segment and a poly D lactic acid segment.

  Stereocomplex phase crystals usually have a higher melting point than homophase crystals formed solely by poly L lactic acid or poly D lactic acid, so that even if they are contained in a slight amount, the effect of increasing heat resistance can be expected. This is remarkably exhibited when the amount of stereocomplex phase crystals is large relative to the amount of crystals. The stereocomplex crystallinity (S) according to the following formula is preferably 90% or more, and more preferably 100%.

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 ).
[Equation 1]
(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 a resin film having a stereocomplex crystallinity (S) of 90% or more is used, the surface transparency can be kept high in a decorative film and a decorative molded product obtained from this resin film. Moreover, the heat resistance of the decorative molded product surface is also high.

The resin film of the present invention is further characterized by being in a substantially non-crystalline state.
Here, “substantially non-crystalline state” means DSC measurement (differential scanning calorimeter) and the rate of temperature rise determined at 20 ° C./min, the peak calorific value of the stereocomplex polylactic acid crystal during the first temperature rise ( ΔHc _sc ) satisfies the following expression (30). In the present specification, unless otherwise specified, the peak heat amount of the polymer crystal is expressed as ΔHc, and ΔHc _sc is assumed to be ΔHc in the case of stereocomplex polylactic acid.
[Equation 2]
ΔHc _sc > 1 J / g (30)

When the above formula is not satisfied, when a molded article having a large three-dimensional unevenness is bonded to a decorative film obtained from a resin film, for example, it is deep-drawn into a shape having a sharp bend. When bonding to a molded object, a decorative film may fracture | rupture or a shaping | molding defect may arise. Preferably,
[Equation 3]
ΔHc _sc > 3 J / g (31)
More preferably,
[Equation 4]
ΔHc _sc > 5 J / g (32)
Most preferably,
[Equation 5]
ΔHc _sc > 10 J / g (33)
It is.

The “substantially crystalline state” means DSC measurement (differential scanning calorimeter), and the rate of temperature rise was 20 ° C./min. The peak calorific value (ΔHc _sc ) of the stereocomplex polylactic acid crystal at the first temperature rise. Does not satisfy the above equation (30). In the present specification, unless otherwise specified, the peak heat amount of the polymer crystal is expressed as ΔHc, and ΔHc _sc is assumed to be ΔHc in the case of stereocomplex polylactic acid.

In order to satisfy the above-mentioned stereocomplex crystallinity suitably, in polylactic acid, the weight ratio of poly D-lactic acid component to 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.

  In addition, the weight average molecular weights of the poly L-lactic acid component and the poly D-lactic acid component in the present invention are preferably 100,000 to 500,000, more preferably 110,000 to 350,000 in order to achieve both the mechanical properties and moldability of the film. More preferably, a range of 12 to 250,000 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 (such as a rotary kiln) 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) 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.

  Poly L-D-lactic acid and / or poly D-lactic acid immediately after melt ring-opening polymerization usually contains 1 to 5% by weight of lactide, but poly L-D-lactic acid and / or poly D-lactic acid polymerization is completed. At any stage from the point of time to the polylactic acid molding, a conventionally known lactide weight loss method, that is, a vacuum devolatilization method in a single-screw or multi-screw extruder, or a high vacuum treatment in a polymerization apparatus is used alone. Alternatively, the lactide can be reduced to a suitable range when combined.

  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 resin film of the present invention, and the advantage that the film can be efficiently manufactured and the heat-and-moisture stability 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 resulting composition. 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. When melt molding such as injection molding is performed, the molding temperature is set to the heat resistant temperature of polylactic acid so that the resin viscosity is 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 resin film 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.

When stereocomplex polylactic acid is used as the aliphatic polyester used in the resin film of the present invention, the poly L-lactic acid component and the poly D-lactic acid component have a weight ratio of 10/90 to 90/10 as described above. It can be obtained by contacting in a range, 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.

  In the polylactic acid used in the present invention, a method of blending a specific additive in order to stably and highly advance the formation of a stereocomplex polylactic acid crystal is preferably applied without 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 the present invention, the carboxyl end group concentration of the aliphatic polyester 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 the aliphatic polyester to 10 (equivalent / ton) or less, the C component described later is used.

<C component>
In the present invention, at least a cyclic structure in which a polylactic acid component (component A), a component C that may be preferably included in a resin film, and a carbodiimide group and the first nitrogen and the second nitrogen are bonded by a bonding group The compound containing is demonstrated. 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 preferably 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 resin film 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. If the amount of component C is within this range, the stability to moisture and the hydrolysis resistance can be suitably increased.

  From such a viewpoint, the content ratio of the cyclic carbodiimide compound (component C) is more preferably 0.01 to 5 parts by weight, more preferably 0.1 to 4 parts by weight per 100 parts by weight of the aliphatic polyester (component A). Selected. 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 resin film contains an acrylic resin (component B) described later, the ratio of the cyclic carbodiimide compound (component C) in the resin film is 100 weights of the above “aliphatic polyester (component A)”. "Part" may be read as "100 parts by weight of the total amount of aliphatic polyester 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 a conventionally known method. 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.

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.

<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 resin film, and preferably 200,000 or less from the viewpoint of moldability and fluidity. A more preferable range is 70,000-150,000. In the present invention, isotactic polymethacrylate and syndiotactic polymethacrylate can be used simultaneously.

  As a method for producing the acrylic resin (component B), generally used polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, and anionic polymerization can be used. In forming the sheet, it is preferable to avoid mixing of fine 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.

<Other than A, B, and C components>
The resin film of the present invention includes thermoplastic resins other than components A, B, and C, stabilizers, ultraviolet absorbers, crystallization accelerators, fillers, mold release agents, antistatic agents, plasticizers, and impact resistance stability. At least one selected from the group consisting of agents can be contained. 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 polylactic acid 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-t ert-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 Etc. 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. In addition, from the viewpoint of preventing deterioration of the polarizing film and the liquid crystal, those having excellent absorption ability of ultraviolet rays having a wavelength of 370 nm or less and less visible light absorption having a wavelength of 400 nm or more are preferable from the viewpoint of liquid crystal display performance.

  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 the pamphlet of 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 resin film in the present invention can contain an organic or inorganic crystallization accelerator. By containing a crystallization accelerator, a decorative molded product having excellent heat resistance 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 resin film 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 the aliphatic polyester.

  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 polylactic acid film of the present invention, the antistatic agent may be used alone or in combination of two or more. 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 the aliphatic polyester.

  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 further preferably 0.1 to 10 parts by weight per 100 parts by weight of the resin film. In the present invention, each of the crystal nucleating agent and the plasticizer may be used alone, or more preferably used in combination.

<Manufacture of resin film>
In order to obtain the resin 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.

  When a resin film is obtained by extrusion molding, a material in which an aliphatic polyester (component A) and other components are previously melt-kneaded can be used, or can be molded through melt-kneading during extrusion molding. The resin film can be produced by extruding a molten film onto a cooling drum and then bringing the film into close contact with a rotating cooling drum and cooling it. At this time, the molten film is blended with an electrostatic adhesion agent such as quaternary phosphonium salt of sulfonic acid, and an electric charge is easily applied from the electrode to the film melting surface in a non-contact manner, whereby the film is adhered to the rotating cooling drum. By making it, you may obtain a resin film with few surface defects. At that time, the ratio (draft ratio) between the lip opening of the extrusion die and the thickness of the sheet extruded on the cooling drum is preferably 2 or more and 80 or less. If the draft ratio is less than 2, the take-off speed from the extrusion die lip becomes too slow, and the speed of separation of the polymer from the die lip becomes slow, which may increase the number of defects such as die lip stripe defects, which may be undesirable. From this viewpoint, the draft ratio is preferably 3 or more, more preferably 5 or more, still more preferably 9 or more, and particularly preferably 15 or more. On the other hand, if the draft ratio is greater than 80, the deformation when the polymer leaves the die lip may be too large, or the flow may become unstable, resulting in poor thickness variation (thickness unevenness), which may be undesirable. From this viewpoint, the draft ratio is preferably 60 or less, more preferably 40 or less, and particularly preferably 30 or less.

  As described above, it is preferable that the resin film serving as the substrate in the decorative film is crystallized after the completion of the target decorative molded product. However, when the decorative film is bonded to a molded body having a complicated three-dimensional shape, such as deep drawing, according to the shape, the resin film is preferably in a substantially non-crystalline state as described above.

  Here, in order to obtain a substantially non-crystalline resin film, it is preferable that the resin in a molten state discharged from the die is rapidly cooled. Therefore, the temperature of the cooling drum is preferably a glass transition temperature (Tg) of the resin of −50 ° C. or higher, more preferably Tg−40 ° C. or higher, and further preferably Tg−30 ° C. or higher. Further, the upper limit temperature of the cooling drum temperature is preferably Tg + 20 ° C. or less, more preferably Tg + 10 or less, and further preferably Tg ° C. or less. Therefore, in the case of polylactic acid, since the Tg is about 60 ° C., the temperature of the cooling drum is preferably set to 10 ° C. to 80 ° C., more preferably 20 ° C. to 70 ° C., most preferably 30 ° C. to 60 ° C. When the temperature of the cooling drum is lower than Tg-50 ° C, the adhesion to the cooling drum may be deteriorated. When the temperature is higher than Tg + 20 ° C, it may be difficult to obtain a substantially non-crystalline state.

  In addition, as long as the substantially non-crystalline state is maintained, a resin film stretching process or a heat setting process performed thereafter may be performed. Such a technique may be adopted when bonding to a three-dimensional molded body that is not complicated.

  The stretching of the resin film can be performed by known longitudinal uniaxial stretching, lateral uniaxial stretching, simultaneous biaxial stretching, etc., and the film is stretched for enhancing crystallinity and for suppressing heat shrinkability, etc. A heat setting process may be performed. In the present invention, a resin film in a substantially non-crystalline state after stretching may be used. From the viewpoint of pastability, unstretched is preferable.

  The draw ratio is appropriately determined depending on the purpose. The resin film has an area stretch ratio (longitudinal magnification x lateral magnification) of preferably 3.0 times or less, more preferably 2.0 times or less, and even more preferably 1.7 times or less. In the case of crystallization in the step, the range is preferably 1.02 times or more, more preferably 1.05 times or more. When the area stretch ratio is 3.0 times or more, stretchability may be deteriorated and it may be difficult to obtain a paste composite shape.

The stretching temperature is preferably selected from the range of the glass transition temperature (Tg) to the crystallization temperature (Tc) of the resin constituting the resin film. Further, a temperature range higher than Tg and as close to Tc as possible but where crystallization does not proceed is more preferably employed.
Since the molecular chain is fixed at a temperature lower than Tg, it is difficult to suitably proceed the stretching operation, and crystallization proceeds at Tc or higher, and also in this case, it is difficult to proceed the stretching process well. Become.
Accordingly, the stretching temperature is more preferably Tg-10 ° C or higher, further preferably Tg-5 ° C or higher, more preferably Tc + 10 ° C or lower, and further preferably Tc + 5 ° C or lower.

<Decorative film>
In the present invention, the decorative film means a resin film as a substrate and a design layer provided on the substrate.
Further, in the present invention, the “design layer” may be a layer that can give a so-called design to the molded product as a target of the decorative film. For example, a printed layer, a colored layer, a metal thin film layer, an inorganic layer A thin film layer, a shaping layer having surface irregularities, a multilayer structure thereof, and the like can be given. If the substrate itself can serve as a design layer, a single-layer structure may be used.

  In addition to these design layers on the outermost surface of the decorative film, a hard coat layer for preventing damage, an antistatic layer, an antifouling layer, an antireflection layer, an adhesive layer, an adhesive layer, an antistatic layer, an antifouling layer A layer, an antireflection layer, or the like may be provided. The design layer may be formed directly on the surface of the substrate, or may be formed via another layer.

  For the formation of the printed layer on the substrate, a known printing method such as gravure printing, flat printing, flexographic printing, dry offset printing, pad printing, or screen printing can be used depending on the product shape and printing application. In particular, offset printing and gravure printing are suitable for multicolor printing and gradation expression. In addition, when the decorative film is molded into a complicated shape, it is preferable to use a printing ink with excellent spreadability, and the binder resin is mainly composed of a flexible resin such as polyurethane resin, acrylic resin, or vinyl chloride resin. Ink is preferred.

  The design layer may be not only a printed layer but also a colored layer, a metal or metal oxide thin film layer, or a combination of a printed layer and a metal (oxide) thin film layer. If a thin film layer of metal or metal oxide is formed, the permeation of water vapor and oxygen to the molded body inside the decorative molded product is suppressed, so that the durability of the molded body can be improved.

  Examples of the method for forming a metal (oxide) thin film layer include vapor deposition, thermal spraying, and plating. As the vapor deposition method, either physical vapor deposition or chemical vapor deposition can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method. Examples of the thermal spraying method include an atmospheric pressure plasma spraying method and a low pressure plasma spraying method. Examples of the plating method include an electroless plating (chemical plating) method, a hot dipping method, and an electroplating method. In the electroplating method, a laser plating method or the like can also be used. Among these, the vapor deposition method and the plating method are preferable for forming the metal layer, and the vapor deposition method is preferable for forming the metal oxide layer. The vapor deposition method and the plating method can be used in combination.

The decorative film of the present invention may have an adhesive layer or a pressure-sensitive adhesive layer in order to improve the adhesion to the molded body. The adhesive layer and the pressure-sensitive adhesive layer are not particularly limited, but polyester-based, urethane-based, acrylic-based, polypropylene chloride-based, and the like are preferably used.
In addition, as long as it exists in the range with the effect of this invention, the material used for a design layer, an adhesive layer, an adhesion layer etc., and the formation method can employ | adopt all the well-known things used for a decorating sheet.

  The decorative film of the present invention preferably has a substantially non-crystalline substrate. If the non-crystalline state is present, a molded article having large three-dimensional irregularities is pasted to a decorative film obtained from a resin film. In the case of matching, for example, in the case of bonding to a molded body having a shape with a sharp bend, the decorative film does not break or a molding defect does not occur.

<Decorated molded product and manufacturing method thereof>
There is no particular limitation on the method for producing a decorative molded product, and an injection molding simultaneous bonding method, a vacuum bonding method, and the like are preferably used. In particular, an insert molding method and a vacuum bonding method, which are a kind of the injection molding simultaneous bonding method, are more preferable. Used.
Depending on the shape of the target molded product, the substrate of the decorative film can be used in a substantially non-crystalline state or not in a non-crystalline state before bonding, for example, deep drawing processing In the case of covering a molded product having a complicated three-dimensional structure, the substrate state of the molded product and the decorative film before bonding is substantially non-crystalline from the viewpoint of improving the stretchability of the decorative film. It is preferable to crystallize (approx. Crystallized state) by applying heat during or after bonding of the decorative film and the molded body.

  When stereocomplex polylactic acid is used as the substrate material, the degree of crystallization is determined by the stereocomplex crystallization rate defined by the formula (II) according to the intensity ratio of diffraction peaks by wide-angle X-ray diffraction (XRD) measurement ( More preferably, Sc) has a value of 50% or more, preferably 50 to 100%, more preferably 70 to 100%, particularly preferably 90 to 100%.

That is, when the polylactic acid has the 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 remarkably reduce haze as compared with polylactic acid having no stereocomplex crystal, and it is more suitable as a decorative film.
[Equation 6]
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.

  In the insert molding method, preliminary shaping is performed by vacuum forming, pressure forming, or the like, and then inserted into an injection mold. The molten resin is injected therein and integrally molded with the decorative film. In the case of this method, it is preferable that at least the state of the substrate of the decorative film before preliminary shaping is a substantially non-crystalline state.

  The lower limit of the film heating temperature during this pre-shaping is preferably Tg-20 ° C or higher, more preferably Tg-10 ° C or higher, and further preferably Tg-5 ° C or higher. The upper limit of the heating temperature is preferably Tg + 20 ° C. or less, more preferably Tg + 10 ° C. or less, and further preferably Tg + 5 ° C. or less. The glass transition temperature of polylactic acid is approximately 55 to 65 ° C., which is the same for polylactic acid having a stereocomplex crystal.

  The pre-shaped resin film is inserted into an injection mold, injected with a molten resin to be a molded body (resin), and integrally molded with the decorative film. The temperature of this injection molding is appropriately set depending on the type of resin. Further, the temperature of the mold is set in consideration of the physical properties and process of the decorative film. When it is desired that the decorative film substrate is not substantially amorphous in the injection mold, the lower limit of the mold temperature is preferably Tg-5 ° C or higher, more preferably Tg + 5 ° C or higher, and Tg + 10 ° C or higher. Further preferred. The upper limit of the mold temperature is preferably Tc + 30 ° C. or less, more preferably Tc + 20 ° C. or less, and further preferably Tc + 15 ° C. or less.

  On the other hand, when the decorative molded product is taken out after the injection molding step so that the substrate of the decorative film is not in a substantially non-crystalline state, the lower limit of the mold temperature is preferably Tg-10 ° C or higher, and Tg-5 ° C or higher. Is more preferable. The upper limit of the mold temperature is preferably Tg + 30 ° C. or less, more preferably Tg + 20 ° C. or less, and further preferably Tg + 10 ° C. or less.

  In the vacuum bonding method, a molded body is prepared separately by injection molding or the like, and a decorative film is coated and bonded in vacuum. This molding decoration method is a three-dimensional surface decoration technique (“TOM”) described in the above-mentioned Patent Document 4 (Patent No. 373356) and the literature (Journal of Imaging Society of Japan, Vol. 48, No. 4, p277 to p284 (2009)). It is preferable to use the method “)”. In the case of this method, it is preferable that the state of the substrate of the decorative film before bonding is a substantially non-crystalline state.

  A decorative film and a molded body provided with an adhesive layer or an adhesive layer are placed in a vacuum device, and then the decorative film is heated by infrared rays and bonded to the molded body. Tg + 70 ° C. or lower is preferable, Tg + 70 ° C. or lower is more preferable, and Tg + 50 ° C. or lower is further preferable.

  The lower limit is preferably Tg-10 ° C or higher, more preferably Tg + 10 ° C or higher, and further preferably Tg + 20 ° C or higher. At Tg + 70 ° C. or higher, the decorative film may be too soft and may break during standing before bonding in a vacuum apparatus, and at temperatures lower than Tg−10 ° C., it may be successfully bonded to the molded body. It can be difficult.

Next, the decorative molded product of the present invention will be specifically described with reference to the drawings. 1 and 2 are schematic views showing one embodiment of the present invention.
In FIG. 1, 1 is a substrate (resin film), 2 is a decorative film, 3 is a design layer, 4 is an adhesive layer or adhesive layer, 5 is a molded product, 6 is a decorative molded product, and 7 is a decorative molded product. It is the outermost surface. Although the design layer 3 in FIG. 1 is between 1 and 4, it may be on one or both of the surfaces of 1.
In FIG. 2, 11 is a substrate (resin film), 12 is a design layer, 13 is a decorative film, 14 is a decorative molded product, 15 is a molded body, and 7 is the outermost surface of the decorative molded product. In FIG. 2, twelve design layers are on the outermost surface of thirteen decorative films, but may be between eleven substrates (resin films) and fifteen molded bodies.

<Molded body>
In the present invention, any of a metal molded body and a resin molded body can be adopted as a target molded body to which a decorative film is bonded to form a decorative molded product. The resin used as the resin molded body is not particularly limited, and examples thereof include polyester resins, polyamide resins, polyacetal resins, polyolefin resins such as polyethylene resins and polypropylene resins, polystyrene resins, acrylic resins, polyurethane resins, chlorinated polyethylene resins, Chlorinated polypropylene resin, aromatic and aliphatic polyketone resin, fluorine resin, polyphenylene sulfide resin, polyetherketone 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 oxa De resins, poly-4-methylpentene-1, polyetherimide resin, and thermoplastic resins such as polyvinyl alcohol resins.

  In particular, from the viewpoint of the environment and adhesion to the decorative sheet of the present invention, polylactic acid, more preferably, stereocomplex polylactic acid having a high crystallization speed and excellent moldability is used more favorably than polylactic acid having only homocrystals. It is done. In particular, the material of the resin molding is preferably the same as the material used for the decorative film from the viewpoint of material reuse.

  There is no particular limitation on the method for producing the resin molded body, and compression molding, injection molding, rotational molding, injection molding, reaction injection molding, etc. are selected according to the purpose, but from the viewpoint of moldability and productivity. The injection molding method is preferable. In the injection molding of the resin molding, in-mold molding, insert molding, or the like, which is a method of integrating with the decorative film, may be used.

  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 detector; differential refractometer (manufactured by Shimadzu Corporation) RID-6A column; Toso-Co., Ltd. TSKgel G3000HXL, TSKgel G4000HXL, TSKgel G5000HXL and TSKguardcocumHXL-L TSKgel G2000HXL, TSKgelG3000HXL, and TSKguardcocumHXL-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) Thickness measurement:
Measurement was performed with an electronic micro manufactured by Anritsu.

(3) Identification of cyclic carbodiimide structure by nuclear magnetic resonance (NMR) and determination of cyclic carbodiimide in the 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.

(4) 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.

(5) Film breaking elongation (100 ° C. measured value) in MD direction and TD direction, stress at 100% elongation (100 ° C. measured value):
Using a tensile testing machine (manufactured by Shimadzu Corporation, Precision Universal Testing Machine Autograph AG-X) with the chuck part covered with a heating chamber as a measuring device, cut the sample film into a width of 10 mm and a length of 100 mm, and a sample between the chucks of 50 mm And a tensile test was performed according to JIS-C2151 under the condition of a tensile speed of 50 mm / min. The sample cutting direction is the MD direction which is the film flow direction, and the width direction perpendicular to the MD direction is the TD direction, the MD direction and the direction parallel to the TD direction are respectively sampled as the length direction, and the MD direction and the TD direction are sampled. The tensile measurement value of was evaluated.
At this time, the heating chamber installed in the chuck portion of the tensile tester was kept at 100 ° C. in the atmosphere in which the sample was present, and the measurement was performed five times to obtain the average value.
The film elongation at break (measured value at 100 ° C.) was calculated as% of the value obtained by subtracting the sample length before tension from the length at break and dividing by the sample length before tension. The stress at 100% elongation (measured value at 100 ° C.) was calculated (MPa) by dividing the load at 100% elongation of the load elongation curve by the cross-sectional area of the sample before tension.

(6) Judgment of whether or not it is in “substantially amorphous state”:
The measurement using a DSC (differential scanning calorimeter), the rate of temperature rise was determined at 20 ° C./min, and the peak calorific value (ΔHc _sc ) of the stereocomplex crystal at the first temperature rise satisfies the following equation (30). In some cases, it was judged to be in a substantially non-crystalline state. Further, when not satisfied, it was judged to be in a substantially crystalline state.
[Equation 7]
ΔHc _sc > 1 J / g (30)

(7) Carboxyl end group amount of aliphatic polyester:
The amount of carboxyl end groups was determined by dissolving a weighed sample in o-cresol adjusted to a water content of 5%, adding an appropriate amount of dichloromethane to this solution, and then titrating with 0.02 N potassium hydroxide methanol solution. . If the carboxyl end group amount is 10 equivalent / ton or less, the hydrolysis resistance is good.

<Manufacture of aliphatic polyester (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. and the melting point was 216 ° C.

<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>
o- nitrophenol (0.11 mol) and pentaerythrityl tetra bromide (0.025 mol), potassium carbonate _{(0.33mol), N, N- N} 2 dimethylformamide 200ml in reactor installed with a stirrer and a heating device After charging in an atmosphere and reacting at 130 ° C. for 12 hours, DMF was removed under reduced pressure, and the resulting solid was dissolved in 200 ml of dichloromethane and separated 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 B component (abbreviated as TX1) and (molecular weight: 516) having the structure shown below. The structure of TX1 was confirmed by NMR and IR.

<Manufacture of resin film materials>
(1) C1: polylactic acid;
It is the same as PLLA1 obtained by the above operation.

(2) C2: a composition comprising polylactic acid and polymethyl methacrylate;
Mixing 80 parts by weight of PLLA obtained by the above operation and the product name “Acrypet VH001”, which is polymethyl methacrylate (PMMA) manufactured by Mitsubishi Rayon Co., Ltd., and 20 parts by weight with a blender, 110 ° C., 5 hours vacuum After drying, from the first supply port of the kneader, 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, chipping with a chip cutter, and making PLLA and PMMA A composition (C2) was obtained. The glass transition point (Tg) was 59 ° C. and the melting point was 215 ° C.

(3) C3: polylactic acid (containing TX1);
PLLA, 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 (C3). The glass transition point (Tg) was 56 ° C. and the melting point was 214 ° C.

(4) C4: a composition containing polylactic acid and PMMA (containing TX1);
PLLA obtained by the above operation, 80 parts by weight, 20 parts by weight of “Acrypet VH001”, which is polymethyl methacrylate manufactured by Mitsubishi Rayon Co., Ltd., TX1, 1 part by weight is mixed with a blender, 110 ° C., 5 hours After vacuum drying, the composition is supplied from the first supply port of the kneader, melted and kneaded while evacuating at a cylinder temperature of 230 ° C. and a vent pressure of 13.3 Pa, extruded into a water tank, and chipped with a chip cutter. (C4) was obtained. The glass transition point (Tg) was 59 ° C. and the melting point was 215 ° C.

(5) C5: polylactic acid (containing linear polycarbodiimide);
PLLA, 100 parts by weight, Nisshinbo Chemical Co., Ltd. “Carbodilite” LA-1, 1.0 part by weight are mixed in 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. and the melting point was 214 ° C.

(6) C6: Stereocomplex polylactic acid 100 parts by weight and 1.0 part by weight of SPLLA1 and TX1 were mixed with a blender, vacuum dried at 110 ° for 5 hours, and then supplied from the first supply port of the kneader. The mixture was melt-kneaded while evacuating at a 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 blend composition (C6). The glass transition point (Tg) was 56 ° C. and the melting point was 215 ° C.

[Example 1]
After the resin film material C3 is dried at 100 ° C. for 5 hours, it is melt-kneaded with an extruder at 195 ° C., melt-extruded in a film form from a T-die at a die temperature of 195 ° C., and adhered to the surface of a cooling drum at 40 ° C. Solidified to obtain an unstretched film (F1-1). The film thickness was 100 μm. The evaluation results of the obtained resin film are shown in Table 1. In addition, generation | occurrence | production of the isocyanate odor was not recognized at the time of film forming of the said film, and film-forming was possible under favorable working environment. The carboxyl end group concentration was 0.05 equivalent / ton.

[Example 2]
After the resin film material C4 is dried at 100 ° C. for 5 hours, it is melt-kneaded by an extruder at 215 ° C., melt-extruded in a film form from a T-die at a die temperature of 215 ° C., and closely adhered to the surface of a cooling drum at 40 ° C. Solidified to obtain an unstretched film (F2-1). The film thickness was 100 μm. The evaluation results of the obtained resin film are shown in Table 1. In addition, generation | occurrence | production of the isocyanate odor was not recognized at the time of film forming of the said film, and film-forming was possible under favorable working environment. The carboxyl end group concentration was 0.04 equivalent / ton.

[Example 3]
After the resin film material C6 is dried at 100 ° C. for 5 hours, it is melt-kneaded with an extruder at 230 ° C., melt-extruded in a film form from a T-die at a die temperature of 230 ° C., and is in close contact with the surface of a cooling drum at 40 ° C. Solidified to obtain an unstretched film (F3-1). The film thickness was 120 μm. The evaluation results of the obtained resin film are shown in Table 1. In addition, generation | occurrence | production of the isocyanate odor was not recognized at the time of film forming of the said film, and film-forming was possible under favorable working environment. The carboxyl end group concentration was 0.03 equivalent / ton.

[Comparative Example 1]
The resin film obtained by the operation of Example 1 was stretched at a stretching temperature of 75 ° C. and a magnification of 2 times by a longitudinal and transverse biaxial stretching machine successively at a stretching temperature of 80 ° C. and a magnification of 2 times. The film (F1-2) having a thickness of 40 μm was obtained by carrying out heat setting at 145 ° C. with equipment. The evaluation results of the obtained resin film are shown in Table 1. The carboxyl end group concentration was 0.03 equivalent / ton.

[Comparative Example 2]
The resin film obtained by the operation of Example 2 was stretched at a stretching temperature of 75 ° C. and a magnification of 2 times by a continuous longitudinal and biaxial stretching machine at a stretching temperature of 80 ° C. and a magnification of 2 times. A film (F2-2) having a thickness of 41 μm was obtained by carrying out heat setting at 145 ° C. with equipment. The evaluation results of the obtained resin film are shown in Table 1. The carboxyl end group concentration was 0.05 equivalent / ton.

[Comparative Example 3]
After the resin film material C1 is dried at 100 ° C. for 5 hours, it is melt-kneaded in an extruder at 195 ° C., melt-extruded in a film form from a T-die at a die temperature of 195 ° C., and closely adhered to the surface of a cooling drum at 40 ° C. Solidified to obtain an unstretched film (F3-2). The film thickness was 120 μm. The evaluation results of the obtained resin film are shown in Table 1. Further, the carboxyl end group concentration was 0.3 equivalent / ton.

[Comparative Example 4]
The resin film obtained by the operation of Comparative Example 3 was stretched at a stretching temperature of 75 ° C. and a magnification of 2 times by a sequential longitudinal and transverse biaxial stretching machine at a stretching temperature of 80 ° C. and a magnification of 2.5 times. A 50 μm-thick film (F4-2) was obtained by carrying out heat setting at 148 ° C. with the same equipment. The evaluation results of the obtained resin film are shown in Table 1. The carboxyl end group concentration was 0.2 equivalent / ton.

[Comparative Example 5]
After the resin film material C5 is dried at 100 ° C. for 5 hours, it is melt-kneaded with an extruder at 195 ° C., melt-extruded in a film form from a T-die at a die temperature of 195 ° C., and closely adhered to the surface of the cooling drum at 40 ° C. Solidified to obtain an unstretched film (F5-2). The film thickness was 100 μm. The evaluation results of the obtained resin film are shown in Table 1.
However, when the film was formed, an isocyanate odor was generated, and film formation under a good working environment was impossible. For this reason, with respect to the resin film obtained in Comparative Example 5, the subsequent operation was not performed. The carboxyl end group concentration was 0.11 equivalent / ton.

<Manufacture of decorative film>
A design layer and a printing layer were formed by screen printing using white ink on the films obtained by the operations of Examples 1 to 3 and Comparative Examples 1 to 4. In addition, for the decorative film for vacuum forming (corresponding to the manufacturing 1 and 2 of the decorative molded product described later), the adhesive layer is all on one side of the decorative film substrate (the opposite side on which the printed layer is formed). It was installed at a layer thickness of about 25 μm (the layer structure of this decorative film was a design layer (printing layer) // substrate (resin film) // adhesive layer). This adhesive layer was formed by transferring the adhesive layer using a highly transparent adhesive sheet sandwiched between commercially available release polyester films.

<Manufacture of resin molding for vacuum bonding>
The product name “Panlite AD5503”, which is a polycarbonate (PC) manufactured by Teijin Chemicals Ltd., is dried at 120 ° C. for 6 hours and then shaped as shown in FIG. 3 at an injection molding machine with a cylinder temperature of 280 ° C. and a mold temperature of 100 ° C. A resin molded body PC-A having the following was produced. Further, a resin molded body PC-B having the shape of FIG. 4 was manufactured under the same conditions. In either case, the long side of the schematic plan view is 15 cm, the short side is 10 cm, and the thickness is about 2 mm.
Furthermore, after scPLA1 obtained by the above operation was dried at 110 ° C. for 5 hours, a resin molded product scPLA-A having the shape of FIG. 3 was formed at a cylinder temperature of 280 ° C. and a mold temperature of 110 ° C. with an injection molding machine. Manufactured.

<Manufacture of decorative molded products 1>
Addition with adhesion layer using resin film obtained by operation of Examples 1-3 and Comparative Examples 1-4 obtained by operation as described in Resin Molded Body PC-A and <Manufacture of Decorated Film> The decorative film was placed in a vacuum chamber under the trade name “NGF-0709”, which is a vacuum bonding apparatus manufactured by Fuzoku Vacuum Co., Ltd., with the adhesive layer side as the resin molding side. After the vacuum chamber was closed and the vacuum was applied, the decorative film was heated to 100 ° C. with infrared rays, and then the decorative film was bonded to the resin molded body. After pasting, the atmospheric pressure in the vacuum chamber was returned to atmospheric pressure, and this was taken out to obtain a decorative molded product. Then, it put into a thermostat for 3 minutes at 140 degreeC, the crystallization of the board | substrate of a decoration film was accelerated | stimulated, and operation which makes this board | substrate a substantially crystalline state was also performed.
All the decorative molded articles obtained by using the resin film obtained by the operation of the examples as a substrate of the decorative film were excellent in aesthetics. On the other hand, the decorative molded product using the resin film obtained by the operations of Comparative Examples 1, 2, and 4 as a substrate of the decorative film has a problem in aesthetics such as generation of wrinkles and cracks on the surface.
Next, in order to examine these heat-and-moisture resistance, the decorative molded article was preserve | saved for 100 hours in 80 degreeC85% RH environment. Since the decorative molded product using the resin film obtained by the operation of Comparative Examples 3 and 4 as a decorative film substrate has a low hydrolysis resistance, cracks and the like are generated. It was found that there was a problem with durability. On the other hand, it was confirmed that the decorative molded article using the resin film obtained by the operations of Examples 1 to 3 as a decorative film substrate did not have any problems in appearance even after the end of the moisture and heat resistance test.

<Manufacture of decorative molded products 2>
In the production 1 of the decorative molded product, the same operation was performed except that scPLA1 was used as the resin molded body. The decorative molded product obtained by using the resin film obtained by the operation of the example as the substrate of the decorative film was excellent in aesthetic appearance. Moreover, although the moisture-and-heat test similar to the manufacture 1 of the said decorative molded product was implemented, the change was not looked at by the external appearance.

<Manufacture of decorative molded products 3>
The shape of the decorative film is pre-shaped with a vacuum molding machine in the same shape so that the resin molded body of FIG. 4 can be coated in advance, and this is inserted into an injection molding machine, and the molten resin is inserted and integrated. A resin molded body was produced by a molding method.
The resin to be injection-molded was a product name “Acrypet VH” which is polymethyl methacrylate (PMMA), dried at 80 ° C. for 6 hours, and then injected with an injection molding machine at a cylinder temperature of 240 ° C. and a mold temperature of 70 ° C. The decorative molded product in which the decorative film having the shape of FIG. 4 and the resin molded body were laminated and integrated was manufactured.
The decorative molded product obtained by using the resin film obtained by the operation of Example 1 as a substrate of the decorative film was excellent in aesthetic appearance. Moreover, although the moisture-and-heat test similar to the manufacture 1 of the said decorative molded product was implemented, the change was not looked at by the external appearance.

1 Substrate (resin film)
2 Decorative film 3 Design layer 4 Adhesive layer or adhesive layer 5 Molded body 6 Decorative molded product 7 Uppermost surface 11 of Decorative molded product Substrate (resin film)
12 Design layer 13 Decorative film 14 Decorative molded product 15 Molded body 31 Resin molded body PC-A
32 Haze measurement point 33 Sharp bent part 41 Resin molded body PC-B
42 Haze measurement points

Claims (22)

  A resin film containing an aliphatic polyester (component A), the aliphatic polyester having at least a cyclic structure having one carbodiimide group in which the first nitrogen and the second nitrogen are bonded by a bonding group Including the compound (C component), the film breaking elongation (100 ° C. measured value) in the MD direction and TD direction is 100 to 1000%, and the stress at 100% elongation (100 ° C. measured value) is in the range of 0.1 to 25 MPa. A resin film characterized by being in a substantially non-crystalline state.   The resin film according to claim 1, wherein the resin film further contains an acrylic resin (component B). The resin film of Claim 1 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 resin film according to claim 3, 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 resin film of Claim 3 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.) Q _a is represented by the following formula (2-1), (2-2) or a resin film according to claim 5 wherein the divalent linking group represented by (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 above) The resin film of Claim 3 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 resin film according to claim 7, 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 resin film according to claim 7 or 8, wherein Y is a single bond, a double bond, an atom, an atomic group or a polymer. The resin film of Claim 3 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 resin film according to claim 10, 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 resin film according to claim 10 or 11, wherein Z ¹ and Z ² are each independently a single bond, a double bond, an atom, an atomic group or a polymer.   The decoration film which uses the resin film in any one of Claims 1-12 as a board | substrate, and equips this board | substrate with a design layer.   The decorative film according to claim 13, wherein the substrate is in a substantially non-crystalline state.   A decorative molded product, wherein the decorative film according to claim 13 is laminated and integrated on the surface of the molded body.   The decorative molded product according to claim 15, wherein the molded product is a resin molded product.   The decorative molded product according to claim 16, wherein the resin molded product contains stereocomplex polylactic acid.   It is a manufacturing method of the decorative molded product of Claim 15 or 16, Comprising: When bonding a decorative film and a molded object, the board | substrate of a decorative film uses the thing of a substantially non-crystalline state, It is characterized by the above-mentioned. The manufacturing method of a decorative molded product.   It is a manufacturing method of the decorative molded product of Claim 15 or 16, Comprising: By making the decorative film and the molded object contact the molded object surface under vacuum in the state which heated the decorative film. And the board | substrate of the decoration film before a heating uses the thing of a substantially non-crystalline state, The manufacturing method of the decorative molded product characterized by the above-mentioned.   It is a manufacturing method of the decorative molded product of Claim 16, Comprising: In pasting a decorating film and a molded object, after pasting a decorating film, it inserts in the metal mold | die of injection molding Next, the process is performed by an insert molding method in which a resin as a molding material is injected into a mold, and the substrate of the decorative film before pre-shaping is used in a substantially non-crystalline state. A method for producing a decorative molded product.   It is a manufacturing method of the decorative molded product of Claim 15 or 16, Comprising: When bonding a decorative film and a molded object, the board | substrate of a decorative film uses the thing of a substantially crystalline state, It is characterized by the above-mentioned. A method for producing a decorative molded product.   It is a manufacturing method of the decorative molded product in any one of Claims 18-20, Comprising: When bonding a decorative film and a molded object, the board | substrate of the decorative film used for bonding is a thing of a substantially non-crystalline state. A method for producing a decorative molded product, wherein the substrate is brought into a substantially crystalline state after bonding.