JP6689715B2 - Polypropylene-based laminate, molded article containing the same, and method for producing the same - Google Patents

Description

  The present invention relates to a polypropylene-based laminate, a molded product including the same, and a method for producing the same.

  Presently, in home appliances, OA, automobiles, industrial materials, construction fields, etc., polycarbonate sheets having good transparency and flame retardant performance satisfying VTM-0 are used. However, since the solvent resistance of polycarbonate itself is low, it cannot be used in applications requiring solvent resistance. Therefore, a laminate including a sheet made of polypropylene having good solvent resistance and having high transparency and satisfying the flame retardancy VTM-0 (0.2 mm in thickness) is desired.

  Patent Document 1 discloses that a small amount of a NOR type hindered amine, which is a weathering agent, is added to a polymeric material to exhibit flame retardancy in fibers, sheets and films, but it is transparent and VTM-0. There is no description of polypropylene sheet / film.

  Patent Document 2 describes that flame retardancy of a film is improved by adding a phosphoric acid ester (1% by mass) to polypropylene / NOR hindered amine (1 to 1.5% by mass). (Examples 1 to 4). However, the flame retardance is JIS No. No polypropylene film has been obtained which has a degree of passing the vertical combustion test method of the L-1091A4 method and which satisfies a higher level of VTM-0. Further, since 1% of phosphoric acid ester is added, there is a problem that the phosphoric acid ester bleeds out on the film surface.

  Patent Document 3 discloses a flame-retardant sheet having a three-layer structure of A layer (surface layer) / B layer (intermediate layer) / C layer (surface layer), in which A layer is polyethylene / random polypropylene and B layer is homopolypropylene / random polypropylene. / NOR type hindered amine (3% by mass) / phosphate ester (10% by mass), a flame retardant sheet using block polypropylene for the C layer is disclosed (Example 3), but the flame retardancy is VTM-2. However, a polypropylene sheet which is transparent and satisfies VTM-0 of a higher degree has not been obtained. In particular, since the compatibility of the phosphate ester and polypropylene is very poor, if the phosphate ester is blended in an amount of 10% by mass, there is a problem that the phosphate ester bleeds out on the surface of the sheet, or the phosphate ester is phase-separated and becomes cloudy. , There is a problem that it is not transparent.

  With respect to such a problem, in Patent Document 4, a polyolefin resin (63 to 70% by mass) and a phosphoric acid compound (10 to 15% by mass) such as a phosphoric acid ester are added to a cyclic olefin compound (10 to 18%). It is disclosed that bleeding of the phosphoric acid-based compound is suppressed, the transparency of the composition is good, and the flame retardancy is good in the VTM test (Examples 1 to 6). ). However, the processing temperature of the cycloolefin-based resin is much higher than the processing temperature of the polyolefin-based resin, so that thermal decomposition of polypropylene is a concern, which is not realistic. Further, the cost of cycloolefin resin is very high, and it is not practical as a blend material with a polyolefin material which requires low cost.

Patent Document 5 discloses, as a method for suppressing bleed-out of a phosphoric acid derivative flame retardant, a polymer containing an OH group such as ethylene vinyl alcohol (EVOH) and a phosphoric acid derivative such as phosphoric acid or a phosphate compound. A method for suppressing the bleed-out of a phosphoric acid derivative flame retardant by carrying out a dehydration reaction of the flame retardant and binding it with a covalent bond is disclosed.
However, in Example 1, the high-density polyethylene / EVOH / primary ammonium phosphate salt mixture is produced by melt-kneading accompanied by reaction, but bleed-out of unreacted components is a concern. There is also a method in which a polymer containing an OH group and a phosphoric acid derivative flame retardant are chemically reacted in advance to produce a flame-retardant resin component and then melt-kneading with a polyolefin resin, but the number of steps is increased and the cost is increased. Further, no material having high flame retardancy of VTM-0 is disclosed.

  In Patent Document 6, by blending polypropylene with an amine phosphate piperazine pyrophosphate and a nitrogen compound melamine cyanurate, flame retardant VTM-0 is achieved with a sheet of 0.1 to 0.3 mm. However, since the flame retardant has no melting point and exists as a powder during melt-kneading, a transparent sheet cannot be obtained.

  That is, a sheet made of polypropylene having high transparency and satisfying the flame retardant performance VTM-0 (thickness: 0.2 mm) and suppressing the bleed-out of a phosphorus-based flame retardant such as a phosphoric acid ester, and a laminate using the same are still available. Not reported.

Special table 2002-507238 gazette JP 2004-83913 A JP, 2014-139001, A JP, 2011-241368, A JP, 2004-83788, A JP, 2013-124340, A

  An object of the present invention is to provide a laminate having excellent transparency and flame retardancy, suppressing the bleed-out of the phosphorus-based flame retardant, and having an excellent appearance, and a molded product using the same.

  In a sheet made of a resin composition containing a polypropylene resin, a phosphorus flame retardant and a NOR type hindered amine, if a large amount of the phosphorus flame retardant is blended in order to obtain VTM-0 having high flame retardancy, the phosphorus flame retardant Since the compatibility of the resin with polypropylene resin is low, the phosphorus flame retardant phase-separates and bleeds out on the surface of the sheet, resulting in poor appearance.

The cause of bleeding out of the phosphorus-based flame retardant is considered as follows.
Among the phosphorus-based flame retardants, amine phosphates and the like having no melting point are present as powder during melt-kneading, and even when subsequently molded into a sheet, they are present as powder, so a large amount should be added. It is also difficult to bleed out. However, as in Patent Document 6, flame retardant performance VTM-0 (thickness 0.2 mm) cannot be obtained unless it is blended in an extremely large amount, and since it exists as a powder in the sheet molded body, it is transparent. I can't get a seat.

  On the other hand, among the phosphorus-based flame retardants, the phosphorus-based flame retardant having a melting point in the melt-kneading temperature range (150 to 300 ° C.) of the polypropylene-based resin exists as a liquid during the melt-kneading. Therefore, when molded into a sheet, there are more components dissolved (compatibility or miscibility) in the amorphous or resin than in the powder in the sheet molded body, and there are less components present as powder, The transparency of the sheet molded product is good. However, since such a phosphorus-based flame retardant has a high polarity, it has a low compatibility with a non-polar polypropylene resin, and phase separation occurs over time, and bleed-out occurs on the sheet surface.

  As a method for suppressing the bleed-out of the phosphorus-based flame retardant, the addition of a compatibilizer component of the polypropylene-based resin and the phosphorus-based flame retardant in the compounding, and the sandwich structure in the sheet are generally studied.

  In Patent Document 4, a cycloolefin resin is described as a compatibilizing agent for a polypropylene resin and a phosphoric acid ester, but since the melting point of the cycloolefin resin is high, the kneading / processing temperature becomes high, so that the polypropylene resin is used. Due to the thermal decomposition of the resin, the molecular weight was lowered and the NOR-type hindered amine was thermally decomposed, and a uniform sheet having high flame retardancy and a good surface appearance could not be obtained.

  Patent Document 5 describes a polymer containing an OH group as a compatibilizing agent for a phosphate ester, but the phosphate ester did not react with the OH group of ethylene vinyl alcohol. Further, since the compatibility between ethylene vinyl alcohol and the phosphoric acid ester is low, the phosphoric acid ester bleeds out, and a uniform sheet having transparency and high flame retardancy and having a good surface appearance cannot be obtained.

  Patent Document 3 describes a laminate in which a layer (B layer) of a resin composition containing a polyolefin resin, a phosphoric acid ester, and a NOR-type hindered amine is sandwiched between polyolefin resin layers (A and C layers). After the sheet was formed, the phosphate ester bleeded out from the surface of the sheet, and a uniform sheet having transparency and high flame retardancy and a good surface appearance could not be obtained.

  As a result of diligent studies by the present inventors, a specific amount of an ethylene vinyl acetate copolymer was used as a compatibilizing agent for a polypropylene resin and a phosphorus flame retardant in a composition consisting of a polypropylene resin, a phosphorus flame retardant and a NOR hindered amine. A layered product in which a layer ((C) layer) of the compounded composition is sandwiched by a layer ((B) layer) of a composition comprising a polypropylene resin, a NOR type hindered amine and a specific ethylene vinyl acetate copolymer. As a result, it was found that the bleed-out of the phosphorus-based flame retardant on the sheet surface can be reduced, and the present invention has been completed.

According to the present invention, the following laminated body etc. are provided.
1. At least a (B) layer, a (C) layer, and a (B) layer are included in this order,
The (B) layer contains the following components (a), (b1) and (c), and the two (B) layers may be the same or different,
The layer (C) is a laminate containing the following components (a), (b2), (c) and (d).
Layer (B):
(A) Polypropylene resin 67-96.8 mass%
(B1) Ethylene vinyl acetate copolymer having a content of structural units derived from vinyl acetate of 25% by mass or more 3.0 to 30% by mass
(C) NOR type hindered amine compound 0.2 to 3.0 mass%
(C) layer:
(A) Polypropylene resin 16-95.8 mass%
(B2) Ethylene vinyl acetate copolymer 1-40% by mass
(C) NOR type hindered amine compound 0.2 to 4.0 mass%
(D) Phosphorus flame retardant having a melting point of 300 ° C. or less 3.0 to 40% by mass
2. Further, (a) two (A) layers which may be the same or different and which contain a polypropylene resin,
2. The laminate according to 1, which includes at least a layer (A), a layer (B), a layer (C), a layer (B), and a layer (A) in this order.
3. 3. The laminate according to 2, wherein the polypropylene resin as the component (a) of one or more layers selected from the (A) layer, the (B) layer and the (C) layer contains a smectic crystal.
4. The laminate according to any one of 1 to 3, which satisfies the following formula (1).
X ≦ 3.7225 × Y + 3 (1)
(In the formula, X is the content (mass%) of the (d) component of the (C) layer, and Y is the (b2) component with respect to the total of the (a) to (d) components of the (C) layer. The content (% by mass) of the structural unit derived from vinyl acetate in the product.)
5. The laminate according to any one of 1 to 4, wherein the content of the structural unit derived from vinyl acetate in the component (b2) of the layer (C) is 10 to 90% by mass.
6. The laminate according to any one of 1 to 5, wherein the content of the structural unit derived from vinyl acetate in the component (b2) of the layer (C) is 30 to 90% by mass.
7. The laminate according to any one of 1 to 6, wherein the mass ratio ((b2) / (d)) of the contents of the (b2) component and the (d) component of the (C) layer is 1 or more.
8. The laminate according to any one of 1 to 7, wherein the phosphorus content in the component (d) of the layer (C) is 8% by mass or more.
9. The laminate according to any one of 1 to 8, wherein the component (d) of the layer (C) is at least one selected from a phosphoric acid ester compound, a phosphazene compound and a phosphonic acid ester compound.
10. The laminate according to any one of 1 to 9, wherein the crystallization rate of the polypropylene resin (a) at 130 ° C is 2.5 min ^-1 or less.
A molded product including the laminate according to any of 11.1 to 10.
12. 12. The molded body according to 11, wherein the crystallization rate of the polypropylene resin (a) at 130 ° C. is 2.5 min ⁻¹ or less.
13. The method for producing a molded body according to 11 or 12, wherein the laminate according to any one of 1 to 10 is mounted on the inner surface of a molding die, and a molding resin is supplied to be integrated.
14. The laminated body according to any one of 1 to 10 is shaped so as to match the inner surface of the molding die, and the obtained shaped product is attached to the surface of the molding die to form a molding resin. 13. The method for producing a molded body according to 11 or 12, which comprises supplying and integrating.
15. The inside of the chamber box in which the core material to be covered is arranged is decompressed, the laminate according to any one of 1 to 10 is heated and softened, the inside of the chamber box is pressurized, and the laminate is heated and softened. 13. The method for producing a molded body according to 11 or 12, wherein the core material is pressed to cover the core material and integrated.
16. A method for manufacturing a laminated body in which a laminated body is provided on at least a part of a base body, comprising a mirror-like endless belt wound around a plurality of cooling rolls and a mirror-like cooling roll, and the mirror-like cooling roll and the mirror-like endless belt. In the meantime, by a T-die extruder, a molten resin composed of a composition for layer (B) containing the following components (a), (b1) and (c) and the following components (a), (b2) and (c): And a molten resin comprising the composition for layer (C) containing (d) is extruded and introduced, pressed into a sheet shape, and rapidly cooled at a rate of 80 ° C. or more per second to form a transparent layer (B). The method of manufacturing the laminated body containing a (C) layer.
(B) Layer composition:
(A) Polypropylene resin 67-96.8 mass%
(B1) Ethylene vinyl acetate copolymer having a content of structural units derived from vinyl acetate of 25% by mass or more 3.0 to 30% by mass
(C) NOR type hindered amine compound 0.2 to 3.0 mass%
(C) Layer composition:
(A) Polypropylene resin 16-95.8 mass%
(B2) Ethylene vinyl acetate copolymer 1-40% by mass
(C) NOR type hindered amine compound 0.2 to 4.0 mass%
(D) Phosphorus flame retardant having a melting point of 300 ° C. or less 3.0 to 40% by mass

  According to the present invention, it is possible to provide a laminate having excellent transparency and flame retardancy, suppressing the bleed-out of a phosphorus-based flame retardant, and having an excellent appearance, and a molded product using the same.

It is a schematic structure figure of an example of a manufacturing device for manufacturing a layered product of the present invention.

[Laminate]
The layered product of the present invention contains at least (B) layer, (C) layer, and (B) layer in this order.
The two (B) layers may be the same or different. The layer (B) contains the following components (a), (b1) and (c).
(A) Polypropylene resin 67-96.8 mass%
(B1) Ethylene vinyl acetate copolymer having a content of structural units derived from vinyl acetate of 25% by mass or more 3.0 to 30% by mass
(C) NOR type hindered amine compound 0.2 to 3.0 mass%

The (C) layer contains the following components (a), (b2), (c) and (d).
(A) Polypropylene resin 16-95.8 mass%
(B2) Ethylene vinyl acetate copolymer 1-40% by mass
(C) NOR type hindered amine compound 0.2 to 4.0 mass%
(D) Phosphorus flame retardant having a melting point of 300 ° C. or less 3.0 to 40% by mass

  The layers may be laminated in the order of (B) layer / (C) layer / (B) layer. Even if another layer is inserted between the layers, another layer is formed on the (B) layer. May be further laminated.

  With the above layer structure, the bleed-out of the phosphorus-based flame retardant from the (C) layer to the layer surface can be suppressed by the (B) layer.

Furthermore, it is preferable to stack the (A) layer on both sides of the (B) layer / (C) layer / (B) layer. The two (A) layers may be the same or different. The (A) layer preferably contains a polypropylene resin.
In this case, the layer structure is such that (A) layer / (B) layer / (C) layer / (B) layer / (A) layer are laminated in this order, and another layer is inserted between each layer. Also, another layer may be further laminated on the (A) layer. The layer (A) is preferably the outermost layer.

  In a laminate comprising (A) layer / (B) layer / (C) layer / (B) layer / (A) layer, the ethylene vinyl acetate copolymer of the component (b2) of the (C) layer gives (d) ) The bleed-out of the phosphorus-based flame retardant of component (b) is suppressed to some extent, and the ethylene-vinyl acetate copolymer of the component (b1) of layer (B) migrates from the layer (C) of the phosphorus-based flame retardant of component (d). Bleed-out is further suppressed, and the polypropylene resin in the (A) layer further suppresses the bleed-out of the phosphorus-based flame retardant of the component (d) that has migrated from the (B) layer, and the bleed-out is almost eliminated, and the appearance is A good and transparent laminate is obtained.

  Further, the reduction of flame retardancy due to lamination is suppressed by the NOR-type hindered amine-based stabilizer of the component (c) of the layer (B), and the laminate has a high level of flame retardancy (VTM-0 at 0.2 mm) which has never been obtained. ) Is given.

  Further, the hardness of the laminate can be adjusted by the polypropylene resin of the layer (A). When the layer (B) is the outermost layer, the surface of the laminate has low hardness and a soft sheet is obtained. Further, when the layer (A) is laminated to form the outermost layer, the hardness of the surface of the laminated body is increased and a hard sheet is obtained. Thus, the hardness can be adjusted by changing the layer structure.

  With the above-mentioned structure, a laminate having excellent flame retardancy and transparency, and suppressing the bleed-out of the phosphorus-based flame retardant and having an excellent appearance can be obtained.

  The components forming each layer will be described below. The component (b1) and the component (b2) may be collectively referred to as the component (b).

(Component (a))
The layer (A), the layer (B) and the layer (C) contain the component (a). The component (a) of each layer may be the same or different.
Examples of the polypropylene resin as the component (a) include homopolypropylene, block polypropylene, and random polypropylene. Solvent resistance can be imparted by blending the polypropylene resin as the component (a).
Homopolypropylene is a homopolymer of propylene. Examples of the block polypropylene include a copolymer of α-olefin other than propylene or ethylene and propylene, and the like, for example, a block copolymer of ethylene and propylene. Examples of the random polypropylene include α-olefins other than propylene or ethylene, and copolymers of propylene, and the like. For example, those that are random copolymers of ethylene and propylene are those obtained by a conventionally known method. it can. In addition, one kind may be used alone, or two or more kinds may be used in combination.
The stereoregularity expressed by the isotactic pentad fraction, the melting characteristics such as the melt tension and the swell ratio, and the like are not particularly limited. Further, in order to improve transparency, an additive such as a crystal nucleating agent may be added.

  The MFR (230 ° C., 2.16 kg load) of the polypropylene resin as the component (a) is preferably 0.5 to 30 g / 10 minutes, more preferably 1 to 20 g / 10 minutes, and further preferably 2 It is -10 g / 10 minutes. You may mix and use the polypropylene type resin from which MFR differs. MFR is measured at 230 ° C. under a load of 2.16 kg according to the method of JIS K7210.

  If the MFR of the component (a) used in the layers (B) and (C) is 0.5 g / 10 minutes or more, heat generation by melt shear during melt kneading can be prevented, and the components (c) and (d) can be prevented. Since the thermal decomposition of the can be suppressed, excellent flame retardancy can be secured. Further, since there is no large difference in melt viscosity from the component (b) (for example, a combination of a polypropylene resin having an MFR of less than 0.5 and an ethylene vinyl acetate copolymer having a high MFR), there is a decrease in compatibility. Phase separation during melt-kneading is suppressed, and excellent transparency, flame retardancy, and solvent resistance can be secured.

  If the MFR is 30 g / 10 minutes or less, sheet formation can be performed without problems. Further, since the fluidity is appropriate, there is no ignition of the molten drip cotton during the flame retardancy test, and excellent flame retardancy can be secured. In addition, there is no large difference in melt viscosity between the component (b) and the ethylene-vinyl acetate copolymer (for example, a combination of an ethylene-vinyl acetate copolymer having a low MFR and a polypropylene resin having a high MFR), so that the compatibility is high. Deterioration and phase separation during melt-kneading are suppressed, and excellent transparency, flame retardancy, and solvent resistance can be secured.

When the component (a) is used in the layer (A), if it has almost the same MFR as that of the composition of the layer (B), it imparts and secures excellent transparency, flame retardancy, solvent resistance, and surface hardness. it can.
The content (mass%) of the component (a) in the (C) layer is 16.0 to 95.8 mass%, preferably 46.0 to 91.8 mass%, and more preferably 61.0 to. It is 89.8 mass%.
The content (mass%) of the component (a) in the layer (B) is 67.0 to 96.8 mass%, preferably 70.0 to 90.0 mass%, more preferably 75.0 to. It is 87.0 mass%.

  When homopolypropylene is used, the molded product has excellent strength and rigidity. Moreover, when homopolypropylene or random polypropylene is used, the transparency when formed into a sheet (layer) is excellent.

Homopolypropylene is preferably used as the component (a) of the layer (A).
As the homopolypropylene, polypropylene having an isotactic pendat fraction of 85 mol% to 99 mol% is preferable from the viewpoint of scratch resistance. The isotactic pentad fraction is an isotactic fraction of pentad units (five propylene monomers continuously isotactically bonded) in the molecular chain of the resin composition.

  The isotactic pendat fraction of polypropylene is preferably 85 mol% to 99 mol%, more preferably 90 mol% or more. When the isotactic pendat fraction is less than 85 mol%, the surface hardness is poor, and the surface of the laminate may be scratched and the appearance may be impaired.

The isotactic pendat fraction of polypropylene can be measured by the following method.
The isotactic pendat fraction is measured by evaluating the 13 C-NMR spectrum of polypropylene. Specifically, the measurement of the isotactic pendat fraction is carried out according to the following apparatus and conditions according to the attribution of the peak proposed in “Macromolecules, 8, 687 (1975)” by A. Zambelli and others. And the calculation formula.

[Device / Condition]
Device: JNM-EX400 type 13C-NMR device manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10000 times [calculation formula]
Isotactic pendat fraction [mmmm] = m / S × 100
S: Signal intensity of side chain methyl carbon atoms of all propylene units m: Mesopentad chain: 21.7 to 22.5 ppm

The polypropylene resin preferably has a crystallization rate of 2.5 min ⁻¹ or less at 130 ° C. from the viewpoint of moldability. It is more preferably 2.0 min ^-1 or less. When the crystallization rate exceeds 2.5 min ⁻¹ , the laminated body which is heated and softened during shaping is rapidly hardened at the portion that first contacts the mold, and the elongation becomes poor. There is a risk of whitening and deterioration of the design.

The crystallization rate can be measured by the following method.
The crystallization rate of polypropylene is measured using a differential scanning calorimeter (DSC) (product name "Diamond DSC", manufactured by Perkin Elmer). Specifically, polypropylene is heated from 50 ° C to 230 ° C at 10 ° C / min, held at 230 ° C for 5 minutes, cooled from 230 ° C to 130 ° C at 80 ° C / min, and then heated to 130 ° C. Hold and crystallize. The measurement of the change in the amount of heat is started from the time when the temperature reaches 130 ° C., and a DSC curve is obtained. From the obtained DSC curve, the crystallization rate is determined by the following procedures (i) to (iv).
(I) A baseline is obtained by approximating the change in the amount of heat from the time 10 times the time from the start of measurement to the peak top to the time 20 times the time by a straight line.
(Ii) The intersection point of the tangent line having the slope at the inflection point of the peak and the baseline is obtained, and the crystallization start and end times are obtained.
(Iii) The time from the obtained crystallization start time to the peak top is measured as the crystallization time.
(Iv) Obtain the crystallization rate from the reciprocal of the obtained crystallization time.

The polypropylene resin preferably does not contain a nucleating agent.
In order to make the polypropylene resin, which is a crystalline resin, transparent, for example, a method of forming a smectic crystal by cooling at a temperature of 80 ° C./sec or more when manufacturing a layer containing the polypropylene resin, and adding a nucleating agent and forcing it There is a method of generating fine crystals. The nucleating agent improves the crystallization rate of polypropylene to a rate exceeding 2.5 min ⁻¹ and generates and fills a large number of crystals to eliminate the physically growing space and reduce the size of the crystals. There is. However, since the nucleating agent has a substance serving as a core, the nucleating agent is slightly whitish even if it becomes transparent, so that the designability may be deteriorated.
Therefore, the crystallization rate of the polypropylene-based resin is set to 2.5 min ⁻¹ or less without adding a nucleating agent, and cooling is performed at 80 ° C./second or more to form a Smetica crystal, thereby forming a laminate excellent in design. can get. Furthermore, when the laminated body is heated by an infrared heater to be shaped, the polypropylene-based resin is transformed into α crystal while maintaining the fine structure derived from the Smetica crystal. Due to this transition, the surface hardness and transparency can be further improved as compared with the case where a nucleating agent is used.

The polypropylene resin preferably contains smectic crystals.
The polypropylene resin is a crystalline resin and can take a crystal form such as α crystal, β crystal, γ crystal, and smectic crystal. Among these crystal forms, the Smetica crystal can be produced as an amorphous and crystalline intermediate by cooling the polypropylene resin from the molten state at a rate of 80 ° C. or more per second. The Smetica crystal is not a stable structure having a regular structure like a crystal, but a metastable structure in which fine structures are gathered together. Therefore, the interaction between the molecular chains is weak, and it has a property that it is easily softened when heated, as compared with A crystal or the like which has a stable structure.

  Since the polypropylene-based resin of the laminate of the present invention is made of a polypropylene-based resin containing smectic crystals, the stress at the time of shaping the laminate can be reduced and whitening can be prevented. Therefore, even if the laminate of the present invention is formed into a complicated three-dimensional shape, the design is not damaged. The proportion of smectic crystals in polypropylene is more preferably 30% or more, 50% or more, 70% or more, or 90% or more.

The fact that the polypropylene resin contains smectic crystals can be confirmed by the following crystal form measurement method.
The crystalline form of polypropylene is described by T. Confirmation is performed by wide-angle X-ray diffraction (WAXD: Wide-Angle X-ray Diffraction) with reference to the method used by Konishi et al. (Macromolecules, 38, 8749, 2005).
In the analysis, the X-ray diffraction profile is subjected to peak separation for each of the amorphous phase, the intermediate phase, and the crystalline phase, and the abundance ratio is determined from the peak area attributed to each phase.

  For example, when the polypropylene-based resin does not include Smetica crystals and is made of a polypropylene-based resin that includes α crystals having a stable structure, when the laminate is formed into a three-dimensional shape by vacuum molding, the molecules in the polypropylene-based resin are The interaction between chains becomes greater than that in the case of Smetica. Therefore, in a portion with a large aperture such as the R portion or the boss, the polypropylene resin may be forcibly stretched and the polypropylene resin may be whitened, and the brightness and the depth of design may be lost. The polypropylene-based resin containing α crystal in a stable state occurs when a nucleating agent is used for transparency in addition to the heating temperature.

(Other resin and processing aid components)
The layer (A), the layer (B), and the layer (C) are, if necessary, within the range not impairing the effects of the present invention, and if necessary, a conventionally known resin (in the case of (A), a resin other than the component (a) component, In the case of the layers (B) and (C), it is possible to contain components (a resin other than the components (a) and (b)) and a processing aid component.

  For the purpose of imparting impact resistance, if necessary, low density polyethylene, linear low density polyethylene, high density polyethylene, polyolefin thermoplastic elastomer (TPO) or styrene thermoplastic elastomer may be used for transparency and flame retardancy. Can be used in an appropriate amount within a range (about 5% by mass or less) in which does not decrease.

  Examples of these resins include SBR [polystyrene-polybutadiene rubber], SBS [polystyrene-polybutadiene block-polystyrene], SEBS [polystyrene-poly (ethylene / butylene) block-polystyrene], SIR [polystyrene-polyisoprene rubber], SIS. [Polystyrene-polyisoprene block-polystyrene], SEEPS [polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene], SEP [polystyrene-poly (ethylene / propylene) block], SEPS [polystyrene-poly (ethylene / propylene)] Block-polystyrene] and the like. Among them, hydrogenated butadiene block copolymer, block TPO, SEBS, SEPS, etc. are particularly preferably used.

  Examples of commercially available products include Dynaron 6200 manufactured by JSR Corporation, R-110MP manufactured by Prime Polymer Co., Ltd., Kraton series such as Kraton G1651 manufactured by Shell Chemical Co., and Septon series such as Septon 2104 manufactured by Kuraray Co., Ltd. , Tough Tech H series manufactured by Asahi Kasei Chemicals Corporation, and the like.

  In addition, for the purpose of increasing strength and rigidity, polypropylene resin, polyethylene resin, polybutene resin, polypentene resin, thermoplastic elastomer, etc., which have been modified with maleic anhydride, etc., if necessary, have transparency and An appropriate amount can be used within the range where flame retardancy does not decrease (about 5% by mass or less).

Further, for the purpose of improving the flame retardancy, an appropriate amount of flame retardant resin can be added, if necessary.
Examples of the flame-retardant resin include polyphenylene ether manufactured by SABIC, Noryl PPO640, and nylon 6, manufactured by Unitika Ltd., A1020LP.
The amount of the flame-retardant resin added is preferably within the range (about 10% by mass or less) in which the transparency is not lowered.

In addition, for the purpose of improving processability and impact resistance, if necessary, a mineral oil-based softening agent is added in an appropriate amount within a range (about 5% by mass or less) in which flame retardancy and transparency are not deteriorated. You can
Mineral oil-based softeners are high boiling petroleum fractions, paraffinic ones having a paraffin chain carbon number of 50% or more of the total carbon number, and naphthenic ones having a naphthene ring carbon number of 30-40%, aroma. Those having a group carbon number of 30% or more are called aromatic mineral oil softeners.
As the mineral oil-based softening agent, a mineral oil-based softening agent for rubber used for rubber is preferable. The mineral oil-based softening agent for rubber is a mixture in which an aromatic ring, a naphthene ring and a paraffin chain are combined. This mineral oil-based softening agent for rubber has a stronger pollutant when the amount of aromatic components increases, and also reduces weather resistance. Therefore, a paraffin-based or naphthene-based mineral oil-based softening agent for rubber, which is a non-aromatic type, Particularly, the paraffin-based mineral oil-based softening agent is preferred because it is colorless and transparent. Further, a liquid or low molecular weight synthetic softening agent may be used together with the mineral oil softening agent. Examples of commercially available products include process oils PW90, PW100 and PW380 manufactured by Idemitsu Kosan Co., Ltd.

(Component (b))
The layer (B) and the layer (C) contain the component (b1) and the component (b2), respectively. The component (b1) and the component (b2) may be the same or different. Preferably, the component (b1) and the component (b2) are the same.
The ethylene vinyl acetate copolymers of the components (b1) and (b2) are copolymers obtained from ethylene and vinyl acetate, and include a polypropylene resin as the component (a) and a phosphorus flame retardant as the component (d). Acts as a compatibilizer for. Since the component (b2) uniformly disperses the phosphorus-based flame retardant of the component (d) in the composition, it is possible to melt-knead the resin composition (the composition containing the resin constituting the layer is referred to as "resin composition"). Therefore, excellent flame retardancy can be obtained. Further, the bleed-out of the phosphorus-based flame retardant as the component (d) in the layer (C) is suppressed, and the transparency can be improved.

The MFR of the ethylene-vinyl acetate copolymer as the component (b) is preferably 0.5 to 30 g / 10 minutes, more preferably 1 to 20 g / 10 minutes, and further preferably 3 to 10 g / 10 minutes. is there. The MFR of the component (b) is measured at 190 ° C. under a load of 2.16 kg according to the method of JIS K 6924-1.
When the MFR is 0.5 g / 10 min or more, shearing heat generation during melt kneading can be prevented, and thermal decomposition of the components (c) and (d) can be suppressed, so that excellent flame retardancy can be secured. Further, there is no large difference in melt viscosity from the polypropylene resin as the component (a) (for example, a combination of an ethylene vinyl acetate copolymer having a low MFR and a polypropylene resin having a high MFR), and the compatibility is reduced or the melting is reduced. Phase separation during kneading is suppressed, and excellent transparency, flame retardancy, and solvent resistance can be secured.
If the MFR is 30 g / 10 minutes or less, the strand can be drawn without any problem and extrusion molding can be performed. Further, since there is no large difference in the melt viscosity from the polypropylene resin as the component (a) (for example, a combination of an ethylene vinyl acetate copolymer having a high MFR and a polypropylene resin having a low MFR), the compatibility is excellent, Excellent transparency, flame retardancy and solvent resistance.

The content (mass%) of the component (b) ethylene vinyl acetate copolymer in the resin composition in the case of the (C) layer is 1 to 40 mass%, preferably 3 to 30 mass%, and more preferably Is 5 to 20 mass%. When it is 1% by mass or more, the amount of the component of the vinyl acetate structural unit having a high polarity is appropriate for the compatibility of the phosphorus-based flame retardant of the component (d) having a high polarity, and melt kneading becomes possible. Further, when the content is 40% by mass or less, since the vinyl acetate structural unit having high polarity is not excessive and is in an appropriate amount, compatibility with the polypropylene resin as the component (a) having low polarity is appropriately increased, and melt kneading is performed. It will be possible.
In the case of the (B) layer, the amount is 3.0 to 30% by mass, preferably 5 to 25% by mass, and more preferably 7 to 20% by mass. When the amount is 3.0% by mass or more, the phosphorus-based flame retardant of the component (d) having a high polarity, which is transferred from the layer (C), can be taken in from the sheet surface. Bleed out of the phosphorus-based flame retardant as the component (d) can be suppressed. Further, when the content is 30% by mass or less, similarly, since the vinyl acetate structural unit having high polarity is not an excess but an appropriate amount, the phosphorus-based flame retardant of the component (d) having high polarity transferred from the (C) layer is incorporated. It is possible to suppress bleeding out of the phosphorus-based flame retardant of the component (d) from the surface of the sheet, and it is possible to suppress deterioration of flame retardancy.

The content of the structural unit derived from vinyl acetate in the ethylene-vinyl acetate copolymer of the component (b) is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass in the case of the (C) layer. And more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass. Hereinafter, the “content of the structural unit derived from vinyl acetate” may be simply referred to as the “vinyl acetate content”. When the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 10% by mass or more, the component amount of the vinyl acetate structural unit having high polarity is suitable for the compatibility of the phosphorus-based flame retardant of component (d) having high polarity. Therefore, melt-kneading becomes easy. When the content of vinyl acetate is 90% by mass or less, the ethylene-vinyl acetate copolymer is not a lump, and therefore the production is easy with a continuous melt extruder.
In the case of the (B) layer, the content of the structural unit derived from vinyl acetate is 25% by mass or more, preferably 25 to 90% by mass, more preferably 40 to 80% by mass, and more preferably 45. ˜70% by mass, more preferably 50 to 60% by mass. When the content of vinyl acetate is 25% by mass or more, the component amount of the vinyl acetate structural unit having high polarity can incorporate the phosphorus-based flame retardant of component (d) having high polarity transferred from the layer (C). Bleeding out of the phosphorus flame retardant of the component (d) from the surface of the sheet can be suppressed. When the content of vinyl acetate is 90% by mass or less, similarly, since the vinyl acetate structural unit having a high polarity is an appropriate amount rather than an excess, the phosphorus-based component (d) having a high polarity transferred from the (C) layer is used. The flame retardant can be incorporated, and the bleed-out of the phosphorus-based flame retardant as the component (d) from the sheet surface can be suppressed.

The content of the structural unit derived from vinyl acetate in the component (b) is measured according to JIS K6924-1.
In the case of the layer (C), if the vinyl acetate content of the ethylene vinyl acetate copolymer of the component (b2) and the content of the phosphorus-based flame retardant of the component (d) satisfy the relationship of the formula (1). preferable.
X ≦ 3.7225 × Y + 3 (1)
(In the formula, X is the content ratio (mass%) of the component (d) in the (C) layer, and Y is vinyl acetate in the component (b2) in the total amount of the components (a) to (d). The content (% by mass) of the structural unit derived from
When the formula (1) is satisfied, the vinyl acetate structural unit having a high polarity is relatively large, so that the compatibility with the phosphorus-based flame retardant of the component (d) having a high polarity is high, and as a result, the polarity (d) is high. Since the phosphorus-based flame retardant as a component and the polypropylene resin as the component (a) having low polarity are excellent in compatibility, they are excellent in kneadability.

  In the case of the layer (C), the content of the component (b2), the content of vinyl acetate in the component (b2), the ratio of the component (b2) / the component (d), etc. are limited as shown below. As a result, the compatibility of the component (d) is further increased, the bleed-out of the component (d) is suppressed, and the compatibility of the component (a) is further increased, whereby the transparency of the sheet can be improved.

  Specifically, the content (mass%) of the ethylene-vinyl acetate copolymer as the component (b2) is preferably 5 to 30 mass%, more preferably 7 to 25 mass%, further preferably 10 It is 20% by mass. When it is 5% by mass or more, since the vinyl acetate structural unit having high polarity is relatively large, the phase separation of the phosphorus-based flame retardant as the component (d) and the bleed-out of the phosphorus-based flame retardant as the component (d) are reduced. That is, since the phosphorus-based flame retardant as the component (d) is mixed more uniformly, the transparency of the sheet is excellent. Further, when the content is 30% by mass or less, since the vinyl acetate structural unit having a high polarity is a proper amount, it has excellent compatibility with the polypropylene resin of the component (a) having a low polarity, and is uniformly kneaded without phase separation. The sheet has excellent flame retardancy, transparency and solvent resistance.

Further, the content of the structural unit derived from vinyl acetate is preferably 30 to 70% by mass, more preferably 35 to 65% by mass, and further preferably 40 to 60% by mass. When the content of vinyl acetate is 30% by mass or more, since the vinyl acetate structural unit having high polarity is relatively large, phase separation of the phosphorus-based flame retardant having high polarity and bleed-out of the phosphorus-based flame retardant are reduced. That is, since the phosphorus-based flame retardant is mixed more uniformly, the transparency of the sheet is excellent.
If it is 70% by mass or less, the vinyl acetate structural unit having a high polarity is not excessive and is in an appropriate amount, so that it has excellent compatibility with the polypropylene resin as the component (a) having a low polarity and is uniformly kneaded without phase separation. can do. That is, the molded product is excellent in flame retardancy, transparency and solvent resistance.
Further, when the content is 70% by mass or less, free acetic acid is not generated at the time of heat molding, and it is possible to prevent corrosion of the metal part of the apparatus and health damage to workers. Further, the crosslinking reaction and gelation due to the elimination of acetic acid can be suppressed, and the quality of the product is not adversely affected.

  Further, the ratio (b2) / (d) of the content (mass) of the ethylene vinyl acetate copolymer of the component (b2) and the content (mass) of the phosphorus-based flame retardant of the component (d) is 1 or more. Preferably there is. When it is 1 or more, since the vinyl acetate structural unit having a high polarity is relatively large, phase separation of the phosphorus-based flame retardant as the component (d) and bleed-out of the phosphorus-based flame retardant as the component (d) are reduced. That is, since the phosphorus-based flame retardant as the component (d) is mixed more uniformly, the transparency of the sheet is excellent. (B2) / (d) is preferably 1.2 or more, more preferably 1.5 or more.

As the ethylene-vinyl acetate copolymer (b), one obtained by a conventionally known method can be used. Examples of commercially available products of the component (b) include Soablene manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Evaflex manufactured by Mitsui DuPont Polychemical Co., Ltd., and Levaprene manufactured by LANXESS.
As for (b), one type may be used alone, or two or more types may be used in combination.

(Component (c))
The layers (B) and (C) contain the component (c). The component (c) of each layer may be the same or different.
The component (c) is a NOR (alkoxyimino group) type hindered amine compound.
The NOR type hindered amine compound (stabilizer) not only functions as a light stabilizer, but also as a flame retardant. The alkoxyimino group of the NOR-type hindered amine-based stabilizer refers to an N-alkoxyl group (>) for an NH-type in which a portion of the imino group of the piperidine ring remains NH and an NCH ₃ type in which H is replaced by a methyl group. It has a structure of N-OR) and traps an alkyl peroxy radical (RO _2. ) To easily become a radical and exhibits a flame retardant effect. In the case of the N-methyl type hindered amine stabilizer or the N—H type hindered amine stabilizer, not the NOR type hindered amine stabilizer, the flame retardancy is lowered.
The above alkoxyl group (OR) is not limited to an alkoxyl group in which oxygen is bonded to an alkyl group, and R includes a cycloalkyl group, an aralkyl group, and an aryl group in addition to the alkyl group. As specific examples of these alkoxyl groups, a methoxy group, a propoxy group, a cyclohexyloxy group, an octyloxy group are preferable, and a propoxy group, a cyclohexyloxy group, an octyloxy group, etc. are particularly preferable because the molecular weight of the alkoxyl group increases. It is preferable in that it can suppress the bleed-out.

  The NOR type hindered amine stabilizer used in the present invention is not particularly limited as long as it is a compound having a structure of N-alkoxyl group (> N-OR). Specific examples thereof include NOR-type hindered amine stabilizers described in Japanese Patent Publication No. 2002-507238, International Publication No. 2005/082852, International Publication No. 2008/003605 and the like.

  The component (c) is preferably a compound containing a carbonate bond. When the carbonate bond is contained, it is excellent in flame retardancy and bleed resistance.

Moreover, the following compounds are mentioned as an example of a specific compound.
(A) 1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine (B) Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) Sebacate (C) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -S-triazine ( D) Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate (E) 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethyl Piperidine) and 2,4-dichloro-6-[(1-octyloxy-2,2,2] end-capped with 2-chloro-4,6-bis (dibutylamino) -S-triazine. Oligomeric compound (F) 4,4'-hexamethylenebis (amino-2,2,6,6), which is a condensation product with 6,6-tetramethylpiperidin-4-yl) butylamino] -S-triazine -Tetramethylpiperidine) and 2-chloro-4,6-bis (dibutylamino) -S-triazine endcapped 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6). Oligomeric compound (G) 2,4-bis [(1-cyclohexyloxy-2,2,6,6), which is a condensable product with 6-tetramethylpiperidin-4-yl) butylamino] -S-triazine -Piperidin-4-yl) -6-chloro-S-triazine (H) Peroxidized 4-butylamino-2,2,6,6-tetramethylpiperidine and 2,4,6-trichloro-S -The reaction product of triazine, cyclohexane, and N, N'-ethane-1,2-diylbis (1,3-propanediamine) (N, N ', N "'-tris {2,4-bis [(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) N-butylamino] -S-triazin-6-yl} -3,3'-ethylenediiminodipropylamine)
(I) Bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (J) 1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-one (K) Bis (1-stearyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate

  Examples of commercially available products include FLAMESTA BNOR116FF, TINUVIN NOR371, TINUVIN 123S, TINUVIN XT850FF, TINUVIN XT855FF manufactured by BASF and LA-81 manufactured by ADEKA Corporation. The NOR-type hindered amine-based stabilizer as the component (c) may be used alone or in combination of two or more.

  In the case of the (C) layer, the content (mass%) of the NOR type hindered amine-based stabilizer of the component (c) is 0.2 to 4 mass%, preferably 0.5 to 3 mass%, and Preferably it is 1-2 mass%. If it is 0.2% by mass or more, highly flame-retardant VTM-0 can be obtained. Further, when the content is 4% by mass or less, there is no problem such as fusion of the pellets and sheets at the time of melt kneading and molding by the component (d) acting as a plasticizer, coloring, etc., and high quality pellets and sheets are obtained, Further, it is possible to avoid the cost increase due to the addition of a large amount of expensive NOR type hindered amine stabilizer.

  In the case of the layer (B), the content (mass%) of the NOR type hindered amine-based stabilizer of the component (c) is 0.2 to 3 mass%, preferably 0.3 to 2 mass%, and It is preferably 0.5 to 1.5% by mass. If it is 0.2% by mass or more, highly flame-retardant VTM-0 can be obtained. Further, when the content is 3% by mass or less, there is no problem of bleed-out of the phosphorus-based flame retardant of the component (d) which acts as a plasticizer and migrates from the layer (C) to the sheet surface, A sheet with a good appearance can be obtained.

(Component (d))
The layer (C) contains the component (d).
The phosphorus-based flame retardant as the component (d) has a melting point of 300 ° C. or lower, that is, it is a liquid flame retardant when melt-kneaded with the polypropylene resin. Usually, the polypropylene resin and the flame retardant are melt-kneaded at 150 ° C to 300 ° C. When a solid flame retardant (for example, a flame retardant that does not have a melting point) is used during melt-kneading, the flame-retardant is not in a liquid state during melt-kneading, so that it cannot be uniformly dispersed in the component (a) or the component (b2). However, there is a possibility that physical properties may be deteriorated or flame retardancy may be deteriorated. In addition, the transparency decreases.

  The phosphorus-based flame retardant as the component (d) is not particularly limited as long as it satisfies the above conditions, and those obtained by a conventionally known method or commercially available products can be used. A phosphoric acid ester compound, a phosphazene compound, or a phosphonic acid ester compound is preferable, and among them, a phosphoric acid ester having excellent transparency is most preferable.

  Examples of the phosphate compound include trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl. Monomeric phosphate ester compounds such as diphenyl phosphate (CDP), resorcinol bis-dixylenyl phosphate, resorcinol bis-diphenyl phosphate, bisphenol A bis-diphenyl phosphate (BADP), bisphenol A bis-dicresyl phosphate Phosphorus oxychloride and divalent phenolic compounds such as phosphates, biphenol bis-diphenyl phosphate, and biphenol bis-dixylenyl phosphate, and phenol (or alkyl phosphite). Aromatic condensed phosphoric acid ester compounds such as a reaction product of Knoll) and the like.

  Of these, triphenyl phosphate (TPP), tricresyl phosphate (TCP), resorcinol bis-dixylenyl phosphate, resorcinol bis-diphenyl phosphate, bisphenol A bis-diphenyl phosphate (BADP) are preferable. , Biphenol bis-diphenyl phosphate, biphenol bis-dixylenyl phosphate, more preferably triphenyl phosphate (TPP), resorcinol bis-dixylenyl phosphate, resorcinol bis-diphenyl phosphate, and Preferred is resorcinol bis-dixylenyl phosphate.

  As the phosphazene compound, 1,1,3,3,5,5-hexa (methoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (ethoxy) cyclotriphosphazene, 1,1,3 , 3,5,5-Hexa (N-propoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (iso-propoxy) cyclotriphosphazene, 1,1,3,3,5,5 -Hexa (N-butoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (iso-butoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (phenoxy) cyclo Triphosphazene, 1,1,3,3,5,5-hexa (P-tolyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (M-tolyloxy) cyclotriphosphazene, 1 1,3,3,5,5-hexa (O-tolyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-ethylphenoxy) cyclotriphosphazene, 1,1,3,3 , 5,5-Hexa (4-N-propylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-iso-propylphenoxy) cyclotriphosphazene, 1,1,3,3 , 5,5-Hexa (4-T-butylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-T-octylphenoxy) cyclotriphosphazene, 1,1,3,3 , 5,5-Hexa (2,3-dimethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (2,4-dimethylphenoxy) cyclotriphosphazene, 1,1,3,3 , 5,5-Hexa (2,5-dimethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (2,6-dimethylphenoxy) cyclotriphosphazene, 1,3,5-tris (Methoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (N-propoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (iso-propoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3 , 5-Tris (N-butoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (iso-butoxy) -1,3,5-tri Sus (phenoxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (P-tolyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3 5-tris (M-tolyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (O-tolyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy)- 1,3,5-Tris (P-tolyloxy) cyclotriphosphazene, 1,3,5-Tris (ethoxy) -1,3,5-tris (M-tolyloxy) cyclotriphosphazene, 1,3,5-Tris (Ethoxy) -1,3,5-tris (O-tolyloxy) cyclotriphosphazene, 1,3,5-tris (N-propoxy) -1,3,5-tris (P- Ryloxy) cyclotriphosphazene, 1,3,5-tris (N-propoxy) -1,3,5-tris (M-tolyloxy) cyclotriphosphazene, 1,3,5-tris (N-propoxy) -1, 3,5-Tris (O-tolyloxy) cyclotriphosphazene, 1,3,5-Tris (iso-propoxy) -1,3,5-tris (P-tolyloxy) cyclotriphosphazene, 1,3,5-Tris (N-butoxy) -1,3,5-tris (P-tolyloxy) cyclotriphosphazene, 1,3,5-tris (iso-butoxy) -1,3,5-tris (P-tolyloxy) cyclotriphosphazene , 1,3,5-Tris (methoxy) -1,3,5-tris (4-T-butylphenoxy) cyclotriphosphazene, 1,3,5-tris (meth) ) -1,3,5-Tris (4-T-octylphenoxy) cyclotriphosphazene, 1,3,5-tris (N-propoxy) -1,3,5-tris (4-T-butylphenoxy) cyclo Examples thereof include triphosphazene and 1,3,5-tris (N-propoxy) -1,3,5-tris (4-T-octylphenoxy) cyclotriphosphazene.

  Among these, preferably 1,1,3,3,5,5-hexa (methoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (ethoxy) cyclotriphosphazene, 1,1, 3,3,5,5-hexa (phenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (P-tolyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1 , 3,5-Tris (phenoxy) cyclotriphosphazene and 1,3,5-tris (ethoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, more preferably 1,1,3. 3,5,5-hexa (ethoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (phenoxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3 - tris (phenoxy) a cyclotriphosphazene, more preferably 1,1,3,3,5,5 hexa (phenoxy) cyclotriphosphazene.

式（１０）中、Ｒ^１〜Ｒ^５は、水素原子、又は置換基を有していてもよい炭化水素基であり、Ｒ^１〜Ｒ^５はそれぞれ同一でも異なっていてもよい。
炭化水素基としては、鎖状（直鎖及び分岐鎖のいずれでもよい）及び環状（単環、縮合多環、架橋環及びスピロ環のいずれでもよい）のいずれであってもよく、例えば、側鎖を有する環状炭化水素基が挙げられる。また、炭化水素基は、飽和及び不飽和のいずれでもよい。
炭化水素基としては、例えばアルキル基、シクロアルキル基、アリル基、アリール基、アルキルアリール基、アリールアルキル基等が挙げられる。 Examples of the phosphonate ester include those represented by the following formula (10).

In formula (10), R ^{1 to} R ⁵ are a hydrogen atom or a hydrocarbon group which may have a substituent, and R ^{1 to} R ⁵ may be the same or different.
The hydrocarbon group may be either linear (which may be a straight chain or branched chain) or cyclic (which may be a monocyclic ring, a condensed polycyclic ring, a bridged ring or a spiro ring), for example, a side group. Examples include cyclic hydrocarbon groups having a chain. The hydrocarbon group may be saturated or unsaturated.
Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an alkylaryl group and an arylalkyl group.

これらのうち、好ましくは式（１０）−１〜（１０）−６であり、より好ましくは式（１０）−１〜（１０）−３であり、さらに好ましくは式（１０）−１である。 Specific examples of the phosphonate ester represented by the above formula include compounds represented by the following formulas (10) -1 to (10) -8.

Of these, the formulas (10) -1 to (10) -6 are preferable, the formulas (10) -1 to (10) -3 are more preferable, and the formula (10) -1 is more preferable. .

The content (mass%) of the phosphorus-based flame retardant of the component (d) is 3 to 40 mass%, and may be 5 mass% or more, 15 mass% or more, 20 mass% or less, or 10 mass% or less. The content (mass%) of the component (d) is preferably 5 to 35 mass%, more preferably 15 to 30 mass%.
If it is 3% by mass or more, the high flame retardancy of VTM-0 can be obtained. When the content is 40% by mass or less, the content of the phosphorus-based flame retardant of the component (d), which has a low compatibility with the polypropylene resin of the component (a), is an appropriate amount, so that the ethylene vinyl acetate copolymer of the component (b2) Is contained in a specific amount, there is no phase separation of the phosphorus-based flame retardant of the component (d) and uniform melt kneading is possible.

式（２０）中、Ｒ_１〜Ｒ_５は水素原子、炭素数１〜１０のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数１〜１０のアルコキシ基又はハロゲン原子であり、Ｒ_１〜Ｒ_５は同一でも異なっていてもよい。Ｎは０〜３０の整数であり、好ましくは０〜１０の整数である。
アルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、第２ブチル、第３ブチル、アミル、第３アミル、ヘキシル、２−エチルヘキシル、Ｎ−オクチル、ノニル、デシル等が挙げられる。シクロアルキル基としてはシクロヘキシル等が挙げられる。アリール基としては、フェニル、クレジル、キシリル、２，６−キシリル、２，４，６−トリメチルフェニル、ブチルフェニル、ノニルフェニル等が挙げられる。アルコキシ基としては、メトキシ、エトキシ、プロポキシ、ブトキシ等が挙げられる。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子等が挙げられる。 The phosphorus content of the phosphorus flame retardant as the component (d) is preferably 8% by mass or more, and more preferably 9% by mass or more, or 10% by mass or more. When the phosphorus content is 8% by mass or more, the phosphorus atom having flame retardant performance is sufficiently contained, so that the flame retardancy is excellent.
The phosphorus content is measured by absorptiometry.
The phosphorus-based flame retardant as the component (d) is preferably represented by the following formula (20). When this compound is used, the transparency and bleeding resistance of the sheet are excellent.

In formula (20), R _{1 to} R ₅ are hydrogen atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. It is a group or a halogen atom, and R _{1 to} R ₅ may be the same or different. N is an integer of 0 to 30, preferably 0 to 10.
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, sec-butyl, amyl, sec-amyl, hexyl, 2-ethylhexyl, N-octyl, nonyl and decyl. Cyclohexyl etc. are mentioned as a cycloalkyl group. Examples of the aryl group include phenyl, cresyl, xylyl, 2,6-xylyl, 2,4,6-trimethylphenyl, butylphenyl, nonylphenyl and the like. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

  From the viewpoint of achieving both flame retardancy and transparency, the phosphorus-based flame retardant of component (d) is the compound No. Compound No. 1, 2 or 3 is preferable. 2 or 3 is more preferable, and Compound No. 2 is more preferred.

式（２０）のリン酸エステル化合物を使用すると、難燃性ＶＴＭ−０と透明性を両立できる。
式（２０）のリン酸エステル化合物の含有量（質量％）は、好ましくは３〜２０質量％であり、より好ましくは４〜１５質量％、さらに好ましくは５〜１０質量％である。３質量％以上であれば、高度な難燃性のＶＴＭ−０が得られ、透明性も良好である。また、２０質量％以下であれば、（ａ）成分のポリプロピレン系樹脂と相溶性が低い（ｄ）成分のリン酸エステル化合物の含有量が適量であるため、（ｄ）成分のリン酸エステル化合物の相分離及びブリードアウトが少なく、その結果、透明で高度な難燃性ＶＴＭ−０が得られる。
（ｄ）成分は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Compound No. 1 (triphenyl phosphate) is, for example, TPP, compound No. 2 (resorcinol bis-dixylenyl phosphate) is, for example, PX-200 manufactured by Daihachi Chemical Industry Co., Ltd., Compound No. As 3 (resorcinol bis-diphenyl phosphate), for example, CR-733S manufactured by Daihachi Chemical Industry Co., Ltd. can be used.

When the phosphoric acid ester compound of formula (20) is used, flame retardancy VTM-0 and transparency can be compatible.
The content (mass%) of the phosphoric acid ester compound of formula (20) is preferably 3 to 20 mass%, more preferably 4 to 15 mass%, and further preferably 5 to 10 mass%. When it is 3% by mass or more, highly flame-retardant VTM-0 is obtained, and the transparency is also good. Further, when the content is 20% by mass or less, the content of the phosphate ester compound of the component (d), which has low compatibility with the polypropylene resin of the component (a), is an appropriate amount, and therefore the phosphate ester compound of the component (d) is Has less phase separation and bleed-out, resulting in a transparent and highly flame-retardant VTM-0.
As the component (d), one type may be used alone, or two or more types may be used in combination.

(Other additive components)
In the layer (A), the layer (B) and the layer (C) of the present invention, in addition to the components (a) to (d), the other resin and the processing aid component, the effect of the present invention is not impaired, Conventionally known additives and the like can be added as necessary. Examples of these additives and the like include antioxidants, weathering agents, lubricants, antistatic agents, nucleating agents, metal deactivators, and fillers.
Examples of the antioxidant include phenol-based compounds, phosphorus-based compounds and thioether-based compounds.

  Examples of the phenolic antioxidant include 2,6-di-tert-butyl-P-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-). Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditertiarybutyl-4-hydroxyphenyl) propionic amide], 4,4′-thiobis (6-tertiarybutyl-M-cresol) 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-) M-cresol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (4-tert-butyl-6-tert-butylpheno) ), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-th) Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-) Hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bi [(3,5-Ditertiary butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-ditertiary butyl-4-hydroxyphenyl) propionate], bis [3,3 -Bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) ) Phenyl] terephthalate, 1,3,5-tris [(3,5-ditertiarybutyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- { (3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] unde Can, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like can be mentioned.

Examples of the phosphorus-based antioxidant include trisnonylphenylphosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite. Fight, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di 3-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite Fight, bis (2,4-dicumylphenyl) pentae Thritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-N-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexylphosphite, 2,2'-methylenebis (4,6-) Tert-Butylphenyl) -octadecyl phosphite, 2,2'-ethylidene bis (4,6-di Butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [D, F] [1,3,2] dioxaphosphepin-6-yl) oxy] Examples thereof include ethyl) amine, 2-ethyl-2-butylpropylene glycol and phosphite of 2,4,6-tri-tert-butylphenol.
Examples of the thioether-based antioxidants include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (Β-alkylmercaptopropionate esters). Is mentioned.

  You may use the said antioxidant in mixture of 2 or more types.

  As the weather resistance agent, an ultraviolet absorber, a hindered amine light stabilizer (a stabilizer other than the component (c) for the (B) and (C) layers) can be used.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditertiarybutylphenyl) -5-chlorobenzo Triazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tertiary octyl Phenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2,2' 2- (2'- such as methylenebis (4-tertiary octyl-6- (benzotriazolyl) phenol), 2- (2'-hydroxy-3'-tertiary butyl-5'-carboxyphenyl) benzotriazole and the like. Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiary butylphenyl-3,5-ditertiary butyl-4-hydroxybenzoate, 2,4-ditertiary amylphenyl-3, Benzoates such as 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4 '. -Substituted oxanilides such as dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate Cyanoacrylates such as methyl-2-cyano-3-methyl-3- (P-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-di) Tert-Butylphenyl) -S-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-S-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl)- Examples include triaryltriazines such as 4,6-bis (2,4-ditertiarybutylphenyl) -S-triazine.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6. , 6-Tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-4-piperidyl) sebacate , Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4- Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6 6-Tetramethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -di (tridecyl) ) -1,2,3,4-Butane tetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl- 4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinole / diethyl succinate polycondensate, 1,6-bis (2,2,2) 6,6-Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-S-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperidylamino) Sun / 2,4-dichloro-6-tertiary octylamino-S-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6 , 6-Tetramethyl-4-piperidyl) amino) -S-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-Butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -S-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-Tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -S-triazin-6-yl] aminoundecane, 1,6 , 11-Tris [2,4-bis (N-butyl-N- (1,2,2,6 And hindered amine compounds such as 6-pentamethyl-4-piperidyl) amino) -S-triazin-6-yl] aminoundecane.

  You may use the said weather-resistant agent in mixture of 2 or more types.

  As the lubricant, fatty acid amide type, fatty acid ester type, fatty acid type, fatty acid metal salt type and the like can be used.

  Examples of the aliphatic amide lubricant include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylenebisstearic acid amide, ethylenebisoleic acid amide, ethylenebiserucic acid amide, and ethylenebislauric acid amide. To be

  Aliphatic ester lubricants include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, palmitic acid. Isopropyl, octyl palmitate, coconut fatty acid octyl ester, octyl stearate, beef tallow fatty acid octyl ester, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, straight chain with 28 to 30 carbon atoms, saturated without branching Monocarboxylic acid (abbreviated as montanic acid) and ethylene glycol ester, montanic acid and glycerin ester, montanic acid and butylene glycol ester, montanic acid and trimethylolethane ester Esters of montanic acid and trimethylolpropane, esters of montanic acid and pentaerythritol, glycerin monostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, Examples thereof include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan trioleate.

  As saturated fatty acids among fatty acid-based lubricants, specifically, lauric acid (dodecanoic acid), isodecanoic acid, tridecylic acid, myristic acid (tetradecanoic acid), pentadecyl acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid) , Stearic acid (octadecanoic acid), isostearic acid, tuberculostearic acid (nonadecanoic acid), 2-hydroxystearic acid, arachidic acid (icosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetradocosanoic acid), serotic acid ( Hexadocosanoic acid), montanic acid (octadocosanoic acid), melissic acid, and the like, and particularly lauric acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, montanic acid, and the like.

  As unsaturated fatty acids among the fatty acid-based lubricants, specifically, myristoleic acid (tetradecenoic acid), palmitoleic acid (hexadecenoic acid), oleic acid (CIS-9-octadecenoic acid), elaidic acid (TRANS-9-octadecenoic acid) ), Ricinoleic acid (octadecadienoic acid), vaccenic acid (CIS-11-octadecenoic acid), linoleic acid (octadecadienoic acid), linolenic acid (9,11,13-octadecatrienoic acid), estearic acid ( Examples thereof include 9,11,13-octadecatrienoic acid), gadoleic acid (icosanoic acid), erucic acid (docosanoic acid), and nervonic acid (tetradocosanoic acid).

  Examples of the fatty acid metal salt-based lubricant include lithium salts, calcium salts, magnesium salts and aluminum salts of the fatty acid of the above fatty acid-based lubricant.

  You may use the said lubricant in mixture of 2 or more types.

As the antistatic agent, cationic type, anionic type, nonionic type, amphoteric type, fatty acid partial esters such as glycerin fatty acid monoester, and the like can be used.
Specifically, alkyltrimethylammonium salt, dialkyldimethylammonium salt, benzalkonium salt, N, N-bis (2-hydroxyethyl) -N- (3-dodecyloxy-2-hydroxypropyl) methylammonium mesosulfate. , (3-laurylamidopropyl) trimethylammonium methyl sulfate, stearoamidopropyldimethyl-2-hydroxyethylammonium nitrate, stearoamidopropyldimethyl-2-hydroxyethylammonium phosphate, cationic polymer, alkylsulfonate , Alkylbenzene sulfonate, sodium alkyl diphenyl ether disulfonate, alkyl nitrate ester salt, phosphoric acid alkyl ester salt, alkyl phosphate amine salt, stearic acid monoglyceride , Pentaerythritol fatty acid ester, sorbitan monopalmitate, sorbitan monostearate, diglycerin fatty acid ester, alkyldiethanolamine, alkyldiethanolamine fatty acid monoester, alkyldiethanolamide, polyoxyethylene dodecyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol Examples thereof include monolaurate, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyether block copolymer, cetyl betaine, hydroxyethyl imidazoline sulfate and the like. You may use these in mixture of 2 or more types.

As the nucleating agent, sorbitols, phosphorus compounds, rosins, petroleum resins and the like can be used.
Examples of the sorbitols include alkyl-substituted benzylidene sorbitol and the like, and examples thereof include 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di- (P-methylbenzylidene) sorbitol and 1,3-O-. Methylbenzylidene 2,4-P-methylbenzylidene sorbitol, 1,3,2,4-di- (P-ethylbenzylidene) sorbitol, 1,3,2,4-di- (2 ', 4'-dimethylbenzylidene) Examples include sorbitol. Examples of phosphorus-based compounds include sodium bis (4-T-butylphenyl) phosphate, sodium 2,2′-ethylidene-bis (4,6-di-T-butylphenyl) phosphate, and organic phosphate-based composite products. Is mentioned. In addition, sodium benzoate, aluminum P-T-butylbenzoate, sodium montanate, calcium montanate, aluminum oxide, kaolin clay, talc, rosins, petroleum resins and the like can be mentioned. You may use these in mixture of 2 or more types.

As the metal deactivator, triazines, phosphones, epoxies, triazoles, hydrazides, oxamides and the like can be used.
Specifically, N, N'-bis [3- (3,5-di-T-butyl-4-hydroxyphenyl) propionyl] hydrazine, bis (2-phenoxypropionylhydrazide) isophthalate, and decanedicarboxylic acid disali Tyroyl benzazide, bisbenzylidene hydrazide oxalate, N, N'-bis {2- [3- (3,5-di-T-butyl-4-hydroxyphenyl) propionyloxyl] ethyl} oxamide, 3- (N -Salicyloyl) amino-1,2,4-triazole, acid amide system, melamine, tris [2-T-butyl-4-thio (2'-methyl-4'-hydroxy-5-T-butyl) phenyl- 5-methyl] phosphite and the like can be mentioned. You may use these in mixture of 2 or more types.

  As the filler, talc, calcium carbonate, barium sulfate, carbon fiber, mica, wollastonite, whiskers and the like can be used.

  In addition, anti-blocking agents, colorants, anti-blooming agents, surface treatment agents, antibacterial agents, and anti-eye candy agents (silicone oils described in JP2009-120717A, monoamide compounds of higher aliphatic carboxylic acids, and higher aliphatic carboxyls). An anti-corrosion agent such as a monoester compound obtained by reacting an acid with a monovalent to trivalent alcohol compound) and the like may be added.

  The amount of the additive and the processing aid added is usually 0.05 to 5% by mass in each of the layers (A), (B) and (C).

The layer (A) may consist essentially of the component (a) and optionally the above-mentioned additional components. The layer (B) may consist essentially of the components (a) to (c) and optionally the above-mentioned additional components. The layer (C) may consist essentially of the components (a) to (d) and optionally the above-mentioned additional components.
“Substantially consisting of” means that the predetermined component occupies 95% by mass or more and 100% by mass or less, 98% by mass or more and 100% by mass or less, or 99% by mass or more and 100% by mass or less of the layer.

(Method for manufacturing laminated body)
When the layer (A), the layer (B), or the layer (C) is composed of a plurality of components, a resin composition (raw material mixture) forming each layer is produced. Specifically, for example, the components constituting the layer are melt-kneaded by an arbitrary method to produce a resin composition. For example, a high-speed stirrer typified by a Henschel mixer, a batch-type kneader typified by a Banbury mixer, a single-screw or twin-screw continuous kneader, a roll mixer and the like are used alone or in combination.

Next, by molding the resin composition, a laminate can be manufactured. First, after manufacturing each layer, these layers may be laminated to form a laminated body, or each layer may be formed and laminated at the same time. The layer (A) may be produced by using a polypropylene resin alone instead of the resin composition.
As a molding method, a conventionally known molding method can be adopted, and examples thereof include injection molding, sheet molding, extrusion molding, profile extrusion molding, and hot press molding. Among these, the method of molding using a melt extruder is preferable from the viewpoint of excellent appearance of the obtained molded article and economical efficiency. The molding conditions are not particularly limited.

When the laminate of the present invention is produced by the co-extrusion method, the materials for the respective layers may be melted and cooled at a cooling rate of 80 ° C./sec or more until the internal temperature of the laminate falls below the crystallization temperature. preferable.
When polypropylene is cooled from a molten state at a rate of 80 ° C./sec or more, a structure in which a majority of Smectic crystals are present is formed. Smectic crystals are metastable mesophases, and each have a small domain size, so they have excellent transparency. Further, since it is in a metastable state, the sheet is softened by a lower heat amount as compared with the α crystal which has been crystallized, so that it has a feature of excellent formability.
In this case, it is preferable to perform the rapid cooling using a cooling roll whose surface temperature is maintained at a dew point or higher and 50 ° C. or lower. By doing so, it is possible to further prevent whitening of the laminate.

Further, the laminate of the present invention comprises a mirror-like endless belt wound around a plurality of cooling rolls and a mirror-like cooling roll, and an apparatus in which the surface temperature of the mirror-like endless belt and the mirror-like cooling roll is kept at a dew point or higher and 50 ° C. or lower. Can be used for the production.
In this case, the material of each layer melted by the T-die extruder is introduced between the mirror-like cooling roll and the mirror-like endless belt and pressed to form a sheet, and the mirror-like endless belt has a temperature lower than the surface temperature of the belt. A laminated body is manufactured by spraying cooling water and quenching.
It is preferable that the obtained laminated body is formed into a non-planar shape and provided on at least a part of the substrate. Whitening of a sheet can be prevented even when molded into a complicated shape, and even a molded product having a complicated shape can be favorably decorative-molded without impairing the appearance.

FIG. 1 shows a schematic configuration of an example of a manufacturing apparatus for manufacturing the laminated body of the present invention.
The manufacturing apparatus shown in FIG. 1 includes a T-die 12, an first cooling roll 13, a second cooling roll 14, a third cooling roll 15, a fourth cooling roll 16, an endless belt 17 made of metal, and a cooling water spray nozzle 18 of an extruder. , A water tank 19, a water absorption roll 20, and a peeling roll 21.

An example of a method for manufacturing the laminated sheet (laminated body) 11 by quenching using the manufacturing apparatus configured as described above will be described below.
First, the resin of each layer melt-kneaded by an extruder is laminated by a feed block, and is directly contacted with the molten resin of a laminated body which is formed into a sheet shape by a T die and extruded, and is cooled by a metal The temperature of each of the cooling rolls 13, 14, 15, 16 is controlled in advance so that the surface temperatures of the endless belt 17 and the fourth cooling roll 16 are maintained at the dew point or higher and 50 ° C. or lower, preferably 30 ° C. or lower.
Here, when the surface temperature of the fourth cooling roll 16 and the metal endless belt 17 is lower than the dew point, dew condensation may occur on the surface, which may make it difficult to form a uniform film. On the other hand, when the surface temperature is higher than 50 ° C., the transparency of the obtained laminated sheet 11 becomes low and α crystals are increased, which may make thermoforming difficult. Therefore, the surface temperature is, for example, 20 ° C.
Next, the molten resin (not containing the nucleating agent) extruded from the T die 12 of the extruder is sandwiched between the metal endless belt 17 and the fourth cooling roll 16 on the first cooling roll 13. In this state, the molten resin is pressed against the first and fourth cooling rolls 13 and 16 and rapidly cooled at 14 ° C.
At this time, the elastic material 22 is compressed and elastically deformed by the pressing force between the first cooling roll 13 and the fourth cooling roll 16.
At the elastically deformed portion of the elastic member 22, that is, the circular arc portion corresponding to the central angle Θ1 of the first cooling roll 13, the rapidly cooled sheet is pressed by the cooling rolls 13 and 16 in a planar manner. The surface pressure at this time is usually 0.1 MPa or more and 20 MPa or less.

The sheet pressed and contacted as described above and sandwiched between the fourth cooling roll 16 and the metallic endless belt 17 is subsequently joined to the metallic endless belt 17 at an arc portion corresponding to substantially the lower half of the fourth cooling roll 16. It is sandwiched between the fourth cooling rolls 16 and pressed in a planar manner, and is further rapidly cooled by the cooling water spraying nozzle 18 spraying the cooling water onto the back surface side of the metallic endless belt 17. The surface pressure at this time is usually 0.01 MPa or more and 0.5 MPa or less, and the temperature of the cooling water is 8 ° C., for example.
The sprayed cooling water is collected in the water tank 19, and the collected water is discharged from the drain port 19A.

After being pressed and cooled by the fourth cooling roll 16 in this manner, the sheet adhered to the metallic endless belt 17 is moved onto the second cooling roll 14 as the metallic endless belt 17 rotates. Here, the sheet guided by the peeling roll 21 and pressed to the side of the second cooling roll 14 is, as described above, planarly pressure-contacted by the metal endless belt 17 in an arc portion corresponding to substantially the upper half circumference of the second cooling roll 14. And cooled again at a temperature below 30 ° C. The surface pressure at this time is usually 0.01 MPa or more and 0.5 MPa or less.
The water adhering to the back surface of the metal endless belt 17 is removed by the water absorbing roll 20 provided during the movement from the fourth cooling roll 16 to the second cooling roll 14.
The laminated sheet cooled on the second cooling roll 14 is wound at a predetermined speed by a winding roll (not shown).

(Uses of laminate)
The laminate of the present invention can have flame retardancy that passes UL94 VTM-0 (thickness: 0.2 mm).
The laminate can be suitably used for applications requiring tracking resistance, electrical insulation, chemical resistance, and the like, which are characteristics of polypropylene. Specifically, among the laminated bodies, a transparent thin-walled laminated body is, for example, a computer part such as a desktop personal computer or a notebook personal computer, a mobile phone part, an electric / electronic device, a portable information terminal, a home electric appliance part, an automobile part, an industrial material. And is preferably used as a building material. In particular, the transparent thin-walled molded product is preferably used as a display film, a decorative film, an insulating sheet, a masking sheet, and a curing sheet. Further, in recent years, a decorative sheet, a battery case, a plastic frame, and the like, for which the demand for a transparent thin-walled laminated body has been increasing, can be cited as suitable applications.

[Molded body]
(Production of molded body)
The molded product of the present invention can be obtained by molding the laminate of the present invention.
In-mold molding, insert molding, or coating molding is preferably used as the molding method.

In-mold molding is a method in which a laminated body is placed in a mold and molded into a desired shape with the pressure of a molding resin supplied into the mold to obtain a molded body.
The in-mold molding is preferably performed by mounting the laminate on a mold and supplying a molding resin to integrate the resin.

In the insert molding, a shaped body to be installed in a mold is preliminarily shaped, and the shape is filled with a molding resin to obtain a shaped body. More complex shapes can be produced.
As insert molding, it is preferable that the laminated body is shaped so as to match the mold, the shaped laminated body is mounted on the mold, and molding resin is supplied and integrated.
The shaping (preliminary shaping) that matches the mold is preferably performed by vacuum molding, pressure molding, vacuum pressure molding, press molding, plug assist molding, or the like.

The molding resin is preferably a moldable thermoplastic resin. Specific examples thereof include polypropylene, polyethylene, polycarbonate, acetylene-styrene-butadiene copolymer, acrylic polymer and the like, but not limited thereto. An inorganic filler such as fiber or talc may be added.
The supply is preferably performed by injection, and the pressure is preferably 5 MPa or more and 120 MPa or less.
The mold temperature is preferably 20 ° C. or higher and 90 ° C. or lower.

As the coating molding, the core material is arranged in the chamber box, the laminate is arranged above the core material, the pressure in the chamber box is reduced, the laminate is heated and softened, and the laminate is formed on the upper surface of the core material. It is preferable to press the laminated body, which is brought into contact with and softened by heating, onto the core material to cover it.
After heating and softening, it is preferable to bring the laminate into contact with the upper surface of the core material.
For the pressing, it is preferable to pressurize the opposite side of the core material of the laminated body while depressurizing the side in contact with the core material of the laminated body in the chamber box.
The core material may be convex or concave, and examples thereof include a resin having a three-dimensional curved surface, a metal, and a ceramic. The resin may be the same as the resin used for the above-mentioned molding.

Specific methods include the following methods. It is preferable to use a chamber box composed of two upper and lower molding chambers that are separable from each other.
First, the core material is placed on the table in the lower molding chamber and set. The laminate, which is the molding target, is fixed to the upper surface of the lower molding chamber with a clamp. At this time, the upper and lower molding chambers are at atmospheric pressure.
Next, the upper molding chamber is lowered, the upper and lower molding chambers are joined, and the inside of the chamber box is closed. Both the upper and lower molding chambers are brought to a vacuum suction state by a vacuum tank from the atmospheric pressure state.
After evacuating the upper and lower molding chambers, the heater is turned on to heat the decorative sheet. Next, the table in the lower molding chamber is raised while the upper and lower molding chambers are in a vacuum state.
Next, the vacuum in the upper molding chamber is released and the atmospheric pressure is applied, so that the laminate to be molded is pressed against the core material and overlaid (molded). By supplying compressed air into the upper molding chamber, it is possible to bring the laminate, which is the molding target, into close contact with the core material with a greater force.
After the overlay is completed, turn off the heater, release the vacuum in the lower molding chamber to return to atmospheric pressure, raise the upper molding chamber, and take out the product with the decorative printed laminate covered as a skin material. .

(Modification)
Not limited to the structure in which the laminate is insert-molded, in-molded, or covered-molded, for example, a transfer molding method in which the laminated body is peeled off after coating to leave only the ink, and the like, in which the laminated body can be provided in a part of the substrate. A method is available. Further, the laminated body is not limited to the configuration in which only one is provided on a part of the surface of the molded article, and a plurality of molded articles may be provided.
The improvement in designability can be obtained by the transparency being obtained. Further, a printing layer or a vapor deposition layer may be provided to form a laminate, and insert molding may be performed as a molded body, or the molded body obtained by forming the laminated body may be provided with the printing layer. The molded product may have the layer structure shown below.
(A) Laminate / Substrate (B) Laminate / Printing Layer / Substrate (C) Printing Layer / Layer / Substrate (D) Laminate / Printing Layer / Polypropylene Layer (Base Layer) / Substrate (E) Printing Layer / Layered body / Printed layer / Substrate (F) Laminated body / Printed layer / Metal thin film layer / Substrate (G) Laminated body / Vaporized layer / Substrate (H) Vapor deposited layer / Laminated body / Substrate (I) Laminated body / Vaporized layer / Polypropylene layer (base material layer) / Substrate (J) Printed layer / Laminate / Printed layer / Substrate (K) Laminate / Easy adhesive layer / Printed layer / Substrate (L) Laminate / Easy adhesive layer / Vaporized layer / Examples of the structure include a substrate.

  Here, in the layer structure of (B) which is the present embodiment, the printing layer is protected by the laminate located on the front surface side, and good designability due to the printing layer can be stably provided for a long period of time. With the configuration (C), even if the print layer is weak against heat during insert molding, for example, a good print layer can be formed without being modified by the heat during insert molding. In the layer configuration of (D), since the base material layer is provided, it is not deformed by heat during insert molding, a good printing layer can be formed, and the laminate can prevent peeling of printing, so that it is a design for decoration or the like. It can be easily improved. In the layer structure of (E), high designability can be provided by providing a plurality of printing layers. In the layer structure of (F), high designability can be provided by providing a metal thin film layer having a reflection characteristic such as an aluminum layer. In the layer structure of (G), the vapor deposition layer is protected by the laminate located on the front surface side, and good designability due to the vapor deposition layer can be stably provided for a long period of time. With the configuration (H), even if the vapor deposition layer is weak against heat during insert molding, for example, a good vapor deposition layer can be formed without being modified by the heat during insert molding. In the layer structure of (I), since the base material layer is provided, it is not deformed by heat during insert molding, a good vapor deposition layer can be formed, and the laminated body can prevent peeling of the vapor deposition layer. It is easy to improve the design. In the layer structure of (J), high designability can be provided by providing a plurality of vapor deposition layers. In the layer structure of (K), since the easy-adhesion layer is provided between the laminate and the printing layer, the ink adhesion of the printing layer can be improved. In the layer structure of (L), since the easy-adhesion layer is provided between the laminate and the vapor deposition layer, the adhesion strength of the metal or metal oxide of the vapor deposition layer can be improved. Further, another layer may be provided in the above layer structure.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

The components used in Examples and Comparative Examples are shown below.
[Polypropylene resin]
Homopolypropylene A [MFR = 3.0 g / 10 minutes (230 ° C., 2.16 kg), F-133A manufactured by Prime Polymer Co., Ltd.]
Homopolypropylene B [MFR = 20 g / 10 minutes (230 ° C., 2.16 kg), Y-2005GP manufactured by Prime Polymer Co., Ltd.]
Homopolypropylene C [MFR = 10 g / 10 min (230 ° C., 2.16 kg), H-700 manufactured by Prime Polymer Co., Ltd.]
Random polypropylene A [MFR = 7.0 g / 10 minutes (230 ° C., 2.16 kg), Prime Polymer Co., Ltd. F-744NP]
Random polypropylene B [MFR = 25 g / 10 minutes (230 ° C., 2.16 kg), F329RA manufactured by Prime Polymer Co., Ltd.]

[Other resins]
-Polyethylene A [MFR = 2.3 g / 10 minutes (190 ° C., 2.16 kg), SP2020 manufactured by Prime Polymer Co., Ltd.]

[Ethylene-vinyl acetate copolymer]
-Ethylene-vinyl acetate copolymer A [MFR = 1 g / 10 minutes (190 ° C, 2.16 kg), vinyl acetate content (VA) 40% by mass, LANPESS 400 Repaprene 400]
-Ethylene vinyl acetate copolymer B [MFR = 1.7 g / 10 minutes (190 ° C., 2.16 kg), vinyl acetate content 50% by mass, LANXESS Repaprene 500]
-Ethylene vinyl acetate copolymer C [MFR = 3.8 g / 10 minutes (190 ° C., 2.16 kg), vinyl acetate content 70% by mass, LANPESS 700 Reppalen 700]
-Ethylene vinyl acetate copolymer D [MFR = 5.0 g / 10 minutes (190 ° C., 2.16 kg), vinyl acetate content 24% by mass, NUC NUC-3195]

[Other compatibilizers]
Cycloolefin polymer [MFR = 10 g / 10 minutes (260 ° C., 2.16 kg), glass transition temperature 123 ° C., ZEONEX 330R manufactured by Zeon Corporation]
-Ethylene-vinyl alcohol copolymer [MFR = 12 g / 10 minutes (210 ° C, 2.16 kg), ethylene content 44 mol%, Soarnol A4412 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.]

・ホスファゼン化合物［株式会社伏見製薬所製 ラビトルＦＰ−１１０、融点１０９℃、リン含有量１３％］
・リン酸アミン塩化合物：ピロリン酸又はポリリン酸とアミン化合物との塩［株式会社ＡＤＥＫＡ製 ＦＰ−２０５０、融点なし、リン含有量１９％］ [Phosphorus flame retardant]
-Phosphoric acid ester A (Compound No. 1): triphenyl phosphate [TPP manufactured by Daihachi Chemical Industry Co., Ltd., melting point 49 ° C, phosphorus content 9.5%]
-Phosphate ester B (Compound No. 2): Resorcinol bis-dixylenyl phosphate [PX-200 manufactured by Daihachi Chemical Industry Co., Ltd., melting point 92 [deg.] C., phosphorus content 9.0%].
-Phosphate ester C (Compound No. 5): Bisphenol A bis-diphenyl phosphate [FP-600 manufactured by ADEKA Corporation, liquid at 23 ° C, phosphorus content 8.8%]

-Phosphazene compound [Ravitor FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd., melting point 109 ° C, phosphorus content 13%]
-Amine phosphate compound: salt of pyrophosphoric acid or polyphosphoric acid and an amine compound [FP-2050 manufactured by ADEKA CORPORATION, no melting point, phosphorus content 19%]

[Nitrogen-containing compound]
-NOR hindered amine stabilizer A [BASF Corporation Flamestab NOR116FF]
-NOR hindered amine stabilizer B [LA-81 manufactured by ADEKA Corporation]
-N-methyl type hindered amine stabilizer [LA-52 manufactured by ADEKA Corporation]
-N-H type hindered amine stabilizer [LA-57 manufactured by ADEKA Corporation]

[Additive]
(Dispersant / lubricant)
Glycerin monostearate [Lion Co., Ltd. GS95P]
(Phenolic antioxidant)
Tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane [ADEKA STAB AO60 manufactured by ADEKA Corporation]
(Phosphorus antioxidant)
Tris (2,4-di-t-butylphenyl) phosphite [ADEKA STAB 2112 manufactured by ADEKA Corporation]

Examples 1-16, Comparative Examples 1-26
[1] Production of pellet resin composition for producing each layer Polypropylene resin as component (a), compatibilizer such as ethylene vinyl acetate copolymer as component (b), NOR type hindered amine as component (c) A component forming each layer selected from a system stabilizer, a phosphorus-based flame retardant as the component (d) and other components was mixed and melt-kneaded with a twin-screw extruder to obtain a pellet-shaped resin composition. Hereinafter, each step will be described in detail.

(1) Preliminary Mixing Each component shown in Tables 1, 3 to 5 was blended for each layer with the composition (% by mass) shown in Tables 1, 3 to 5, and premixed with a Henschel mixer. Regarding the layers (B) and (C) of Examples 1 to 16 and Comparative Examples 1 to 26, components (a), (b), (c), (d) and other flame retardants / fillers, etc. Table 1 , GS95P (0.3 parts by mass), ADEKA STAB AO60 (0.1 parts by mass), and ADEKA STAB 2112 (0.2 parts by mass) were added as additives to 100 parts by mass of the components shown in FIGS.

(2) Melt kneading The obtained preliminary mixture is kneaded at 180 to 230 ° C. using a twin-screw kneader (trade name: TEX30α manufactured by Japan Steel Works, Ltd.) to prepare a composition, and strand cutting is used. Pelletized.

[2] Molding of Each Sheet (Layer) and Production of Laminate A laminate having a constitution of (A) layer / (B layer) / (C) layer / (B layer) / (A) layer using the above composition Manufactured body.
(1) To manufacture the sheets of layers (A), (B) and (C) of Examples 1 to 13 and Comparative Examples 1 to 20, Labo Plastomill 4M150 (full flight screw, manufactured by Toyo Seiki Co., Ltd.) An extruder equipped with T150C (die width 150 mm) manufactured by Toyo Seiki Seisaku-sho, Ltd. as a T die is used for the screw diameter of 25 mm).
The pellets obtained by the melt-kneading are introduced into the hopper of the extruder, and melt-extruded from the T-die under the following extrusion conditions. The extrusion conditions are an extrusion temperature of 200 to 230 ° C., a screw rotation number of 10 to 50 rpm, and a lip opening of 0.1 to 1.0 mm. The resin to be extruded is cooled and solidified by a winding machine equipped with a cooling roll, and wound to obtain an extruded sheet having a desired thickness (0.005 to 0.2 mm). The winding conditions are a roll temperature of 50 to 90 ° C. and a take-up speed of 1 to 2 m / min.
After that, the sheets of each layer are laminated using a press molding machine PY-50 / 50A manufactured by Kodaira Seisakusho Co., Ltd., heated to 200 ° C., and pressed at a pressure of 30 tons for 1 minute. Then, it is pressed with a water-cooling press at a pressure of 30 tons for 3 minutes to obtain a laminate having a thickness of 0.2 mm.
Comparative Examples 1, 2, 4, 7, and 11 have poor kneading properties and cannot be formed into sheets.

(2) For manufacturing the sheets of Examples 14 to 16 and Comparative Examples 21 to 26, a laminate was manufactured under the following conditions using the manufacturing apparatus shown in FIG.
・ Diameter of extruder for layer (A): 50 mm
・ Diameter of extruder for layer (B): 65 mm
・ Diameter of extruder for layer (C): 75 mm
・ Width of T-die: 900mm
・ Laminated sheet take-up speed: 6m / min ・ Cooling roll and metal endless belt surface temperature: 20 ° C
・ Cooling rate: 10,800 ° C / min

[3] Evaluation (1) Kneadability of composition forming layer (C) The kneadability was evaluated as follows. The results are shown in Tables 1, 3 and 4.
A TEX30α kneader was used. When the compatibility of the polypropylene resin and the phosphorus flame retardant was low at the time of melt-kneading, and there was a production failure phenomenon as described below, it was rated as x.
-Polypropylene resin pellets or melts squirt from open vents or vacuum vents.
・ Discharge rate becomes unstable, surging phenomenon occurs, and strand breakage occurs.
・ Phosphorus flame retardant elutes (bleeds out) into the water tank and pollutes the discharged water.
-When a resin having a high melting point such as a cycloolefin polymer is used and kneaded at a high temperature of 280 ° C, the flame retardant and the polypropylene resin are decomposed and intensely colored.
The case where there was no above-mentioned problem was rated as ◯.

(2) Flame-retardant property of laminated body It evaluated by the UL94-VTM test. The results are shown in Tables 2-5.
The obtained laminated body having a thickness of 0.2 mm was cut into a width of 50 mm and a length of 200 mm to prepare a sample. Using a HVUL plastic UL combustion test chamber manufactured by Atlas, the produced sample was subjected to a 20 mm vertical combustion test according to the UL94-VTM test standard. The five samples were ranked according to the UL94-VTM standard based on the first and second burning times and the presence or absence of ignition of cotton. The combustion rank is highest in VTM-0, and the flame retardancy decreases as it becomes VTM-1 and VTM-2. However, those not corresponding to any of the ranks of VTM-0 to VTM-2 are not-VTM.

(3) Transparency of laminate The transparency was evaluated by the internal haze value. The lower the internal haze value, the more transparent it is. The results are shown in Tables 2-5.
The internal haze value was measured according to the test standard JIS K 7136 using a haze meter NDH-200 manufactured by Nippon Denshoku Industries Co., Ltd. Regarding the internal haze, in order to measure the transparency inside the sheet excluding the influence of the surface roughness of the sheet, silicone was applied to the surface of the sheet, and the haze was measured with both surfaces sandwiched by glass plates. The internal haze can be measured by dividing the haze value of the glass only from the haze value.

(4) Evaluation of Bleed Test of Laminated Body Using a constant temperature dryer DO-600FA manufactured by As One Co., Ltd., the laminated body was treated at 40 ° C. and a humidity of 30 to 40% for 7 days, and bleeding was evaluated. The appearance after the treatment is evaluated. If there is no change, the bleed is “absent”, and if there is white powder, the bleed is “present”. The results are shown in Tables 2-5.
Further, the internal haze value before and after the treatment was measured, and the changed value was evaluated. When the change value exceeds 3.5%, the bleeding is large, and when the change value is 3.5% or less, the bleeding is small. The results are shown in Tables 2-5.

(5) Evaluation of Pencil Hardness of Laminated Body The surface hardness of the laminated body was evaluated under a load of 750 g according to the pencil hardness test method of JIS K5600.

The following can be seen from Tables 1-5.
1. Regarding Examples (1) As is clear from Examples 1 to 11, the composition of the (C) layer can be melt-kneaded without any problem, and (A) / (B) / (C) / (B) It can be seen that the laminate of / (A) has high flame retardancy (VTM-0), improved transparency, no bleeding, and good appearance.
(2) As is clear from Examples 12 and 13, it is understood that the arrangement of the layer (A) imparts surface hardness.
(3) As is clear from Examples 14 to 16, the laminate of (A) / (B) / (C) / (B) / (A) of the present invention was processed by an extruder equipped with quench belt cooling. The film-formed laminate had good transparency as compared with a product obtained by stacking sheet-formed films by an extruder equipped with a conventionally known air knife type cooling and press-molding.

2. Comparative Examples (1) In Comparative Examples 1 and 2, since the composition of the ethylene-vinyl acetate copolymer in the (C) layer is small or large, the phosphoric acid ester is not mixed properly and the melt-kneading is impossible.
(2) In Comparative Example 3, since the amount of the phosphoric acid ester in the (C) layer is small, the flame retardancy of the laminate is lowered.
(3) In Comparative Example 4, since the amount of the phosphoric acid ester in the (C) layer is too large, the phosphoric acid ester is not uniformly mixed during melt kneading, and melt kneading is impossible.
(4) Comparative Example 5 is a case in which an amine phosphate salt having no melting point is blended as the phosphorus-based flame retardant for the layer (C), and since the amine phosphate salt is present as a powder in the laminate, There is no bleeding, but the transparency is reduced. Further, the amine phosphate salt forms a carbonized layer on the surface of the molded product at the initial stage of combustion and blocks heat from the outside to exhibit flame retardancy, but in order to exert this flame retardant effect, the melting point is Compared with a phosphorus-based flame retardant such as a phosphoric acid ester having a temperature of 300 ° C. or less, it is necessary to add a large amount of amine phosphate salt, and the flame retardancy is insufficient.
(5) In Comparative Example 6, since the NOR type hindered amine-based stabilizer in the (C) layer is small, the flame retardancy of the laminate is lowered.
(6) In Comparative Example 7, since there are many NOR type hindered amine-based stabilizers in the (C) layer, they act as a plasticizer of polypropylene during melt kneading, resulting in defective pellet cutting and fusing phenomenon, making kneading impossible. is there.
(7) In Comparative Examples 8 and 9, since the N-methyl type and N-H type hindered amine-based stabilizers are used in the (C) layer, the flame retardancy is lowered.
(8) In Comparative Example 10, since polyethylene having a low compatibility with the phosphate ester is used in the (C) layer instead of polypropylene, transparency and bleeding resistance are deteriorated. Further, since the flame retardancy of polyethylene is low, the flame retardancy is lowered.
(9) Comparative Example 11 is in the (C) layer. This is an example of using a cycloolefin polymer instead of an ethylene-vinyl acetate copolymer, but since the cycloolefin polymer has a high melting point and a high melt-kneading temperature, the molecular weight of the polypropylene resin is reduced by thermal decomposition and NOR hindered amine is used. Thermal decomposition occurs, melt kneading is insufficient, and the laminate cannot be processed.
(10) Comparative Example 12 is an example in which an ethylene-vinyl alcohol copolymer (EVOH) is used in the (C) layer instead of the ethylene-vinyl acetate copolymer, but a phase of EVOH and a phosphate ester is used. Since the solubility is low, the phosphate ester bleeds out, and a sheet having transparency and high flame retardancy and having a good surface appearance cannot be obtained.
(11) Comparative Example 13 is a case where the blending amount of the ethylene-vinyl acetate copolymer in the (B) layer is small and the flame retardancy is good, but the ethylene-vinyl acetate copolymer as the compatibilizer is small. However, the phosphate ester transferred from the layer (C) cannot be taken in, and the phosphate ester bleeds.
(12) Comparative Example 14 is a case where the blending amount of the ethylene vinyl acetate copolymer in the (B) layer is large, and since the ethylene vinyl acetate copolymer is large, the phosphate ester transferred from the (C) layer is taken in. However, since the ethylene-vinyl acetate copolymer has low flame retardancy, the flame retardance is lowered.
(13) In Comparative Example 15, since the NOR type hindered amine-based stabilizer in the (B) layer is small, the flame retardancy of the laminate is lowered.
(14) Comparative Example 16 is a case where there are many NOR type hindered amine-based stabilizers in the (B) layer, and although flame retardancy does not decrease, it acts as a plasticizer for polypropylene and thus inhibits crystallization of polypropylene. , The phosphoric acid ester transferred from the (C) layer easily passes through the (B) layer and easily bleeds.
(15) Comparative Example 17 is a case where the vinyl acetate content of the ethylene vinyl acetate copolymer of the (B) layer is small, and the ethylene vinyl acetate copolymer of the compatibilizing agent is small, so The transferred phosphate ester cannot be taken in, and the phosphate ester bleeds.
(16) Comparative Example 18 is a case where polyethylene was used in place of the polypropylene of the (B) layer, and since polyethylene having low compatibility with the phosphate ester was used, the phosphoric acid migrated from the (C) layer The ester easily passes through the layer (B), and the transparency and bleeding resistance are reduced. Further, since the flame retardancy of polyethylene is low, the flame retardancy is lowered.
(17) Comparative Example 19 has a laminated structure of (A) / (C) / (A) without the (B) layer arranged, and since the (A) layer of polypropylene is thick, Although there is little bleeding of the acid ester, the flame retardancy is reduced because the layer (A) containing no flame retardant is laminated.
(18) Comparative Example 20 is the case of only the (C) layer, which has good flame retardancy, but the phosphate ester bleeds because the (B) layer is not present.
(19) Comparative example 21 and subsequent ones are film products manufactured by rapid cooling, and Comparative example 21 is a case where the (B) layer is not arranged and the laminated structure is (A) / (C) / (A), Since the (A) layer of polypropylene is thick, the bleeding of the phosphate ester is small, but the (A) layer containing no flame retardant is laminated, so that the flame retardancy is lowered.
(20) Comparative Example 22 has a laminated structure of (A) / (C) / (A) in which (B) is not arranged, and the thickness of the (A) layer of polypropylene is the same as that of Comparative Example 21. Since it is thin, the phosphoric acid ester bleeds and the (A) layer containing no flame retardant is laminated, so that the flame retardancy decreases.
(21) Comparative Example 23 is a case where the ethylene vinyl acetate copolymer is not contained in the (B) layer, and although the flame retardancy is good, there is no compatibilizer ethylene vinyl acetate copolymer. , The phosphoric acid ester transferred from the (C) layer cannot be taken in, and the phosphoric acid ester bleeds.
(22) In Comparative Examples 24 and 25, since the NOR type hindered amine-based stabilizer is not present in the (B) layer, the flame retardancy of the laminate is lowered.
(23) Comparative Example 26 is a case where the vinyl acetate content of the ethylene vinyl acetate copolymer of the (B) layer is low, and the ethylene vinyl acetate copolymer of the compatibilizing agent is low, so The transferred phosphate ester cannot be taken in, and the phosphate ester bleeds.

  The laminated body and molded body of the present invention are used for computer parts such as desktop personal computers and notebook personal computers, mobile phone parts, electric / electronic devices, personal digital assistants, home appliance parts, automobile parts, industrial materials and construction materials. be able to.

11 Sheet 12 T Die 13 1st Cooling Roll 14 2nd Cooling Roll 15 3rd Cooling Roll 16 4th Cooling Roll 17 Metal Endless Belt 18 Cooling Water Spray Nozzle 19 Water Tank 19A Drain Port 20 Water Absorbing Roll 21 Peeling Roll 22 Elastic Material

Claims (16)

At least a (B) layer, a (C) layer, and a (B) layer are included in this order,
The (B) layer contains the following components (a), (b1) and (c), and the two (B) layers may be the same or different,
The layer (C) is a laminate containing the following components (a), (b2), (c) and (d).
Layer (B):
(A) Polypropylene resin 67-96.8 mass%
(B1) Ethylene vinyl acetate copolymer having a content of structural units derived from vinyl acetate of 25% by mass or more 3.0 to 30% by mass
(C) NOR type hindered amine compound 0.2 to 3.0 mass%
(C) layer:
(A) Polypropylene resin 16-95.8 mass%
(B2) Ethylene vinyl acetate copolymer 1-40% by mass
(C) NOR type hindered amine compound 0.2 to 4.0 mass%
(D) Phosphorus flame retardant having a melting point of 300 ° C. or less 3.0 to 40% by mass Further, (a) two (A) layers which may be the same or different and which contain a polypropylene resin,
The layered product according to claim 1 containing at least (A) layer, (B) layer, (C) layer, (B) layer, and (A) layer in this order.   The laminate according to claim 2, wherein the polypropylene resin as the component (a) of one or more layers selected from the (A) layer, the (B) layer, and the (C) layer contains a smectic crystal. The laminated body according to any one of claims 1 to 3, which satisfies the following formula (1).
X ≦ 3.7225 × Y + 3 (1)
(In the formula, X is the content (mass%) of the (d) component of the (C) layer, and Y is the (b2) component with respect to the total of the (a) to (d) components of the (C) layer. The content (% by mass) of the structural unit derived from vinyl acetate in the product.)   The laminate according to any one of claims 1 to 4, wherein the content of the structural unit derived from vinyl acetate in the component (b2) of the layer (C) is 10 to 90% by mass.   The laminate according to any one of claims 1 to 5, wherein the content of the structural unit derived from vinyl acetate in the component (b2) of the (C) layer is 30 to 90% by mass.   The laminate according to any one of claims 1 to 6, wherein the mass ratio ((b2) / (d)) of the contents of the component (b2) and the component (d) in the (C) layer is 1 or more.   The layered product according to any one of claims 1 to 7, wherein the phosphorus content in component (d) of layer (C) is 8% by mass or more.   The laminate according to claim 1, wherein the component (d) of the layer (C) is at least one selected from a phosphoric acid ester compound, a phosphazene compound and a phosphonic acid ester compound. The laminated body according to any one of claims 1 to 9, wherein a crystallization rate of the polypropylene resin (a) at 130 ° C is 2.5 min ^-1 or less.   A molded product comprising the laminate according to claim 1. The molded product according to claim 11, wherein the crystallization rate of the polypropylene resin (a) at 130 ° C is 2.5 min ^-1 or less.   The method for producing a molded product according to claim 11 or 12, wherein the laminate according to any one of claims 1 to 10 is mounted on an inner surface of a molding die, and a molding resin is supplied to integrate the laminate.   A laminate according to any one of claims 1 to 10 is shaped so as to conform to the inner surface of a molding die, and the obtained shaped product is mounted on the surface of the molding die to form a molding resin. The method for producing a molded body according to claim 11 or 12, wherein the molded body is supplied and integrated.   The inside of the chamber box in which the core material to be coated is arranged is depressurized, the laminated body according to any one of claims 1 to 10 is softened by heating, and the inside of the chamber box is pressurized to soften the heat. The method for producing a molded article according to claim 11 or 12, wherein the laminate is pressed against the core material to cover the core material, and the core material is integrated. A method for manufacturing a laminated body in which a laminated body is provided on at least a part of a base body, comprising a mirror-like endless belt wound around a plurality of cooling rolls and a mirror-like cooling roll, and the mirror-like cooling roll and the mirror-like endless belt. In the meantime, by a T-die extruder, a molten resin composed of a composition for layer (B) containing the following components (a), (b1) and (c) and the following components (a), (b2) and (c): And a molten resin comprising the composition for layer (C) containing (d) is extruded and introduced, pressed into a sheet shape, and rapidly cooled at a rate of 80 ° C. or more per second to form a transparent layer (B). The method of manufacturing the laminated body containing a (C) layer.
(B) Layer composition:
(A) Polypropylene resin 67-96.8 mass%
(B1) Ethylene vinyl acetate copolymer having a content of structural units derived from vinyl acetate of 25% by mass or more 3.0 to 30% by mass
(C) NOR type hindered amine compound 0.2 to 3.0 mass%
(C) Layer composition:
(A) Polypropylene resin 16-95.8 mass%
(B2) Ethylene vinyl acetate copolymer 1-40% by mass
(C) NOR type hindered amine compound 0.2 to 4.0 mass%
(D) Phosphorus flame retardant having a melting point of 300 ° C. or less 3.0 to 40% by mass

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