JPH03266642A - Sheet for molding use - Google Patents

Abstract

PURPOSE:To obtain a sheet for molding with a wide molding temp. range and excellent steam barrier properties, gas barrier properties, transparency, heat resistance and n-heptane resistance by laminating a polyester film layer on at least one face of a composite sheet wherein a polypropylene resin layer is placed on one face of a layer prepd. by blending a polypropylene with a specified petroleum resin having no polar group and a specified hydrogenation rate, through a polyurethane resin layer. CONSTITUTION:A sheet for molding is prepd. by laminating a layer (layer D) consisting of a polyester film on at least one layer of a layer B consisting of a polypropylene resin of a composite sheet having the layer B of at least one face on a layer (layer A) prepd. by blending 100 pts.wt. polypropylene with 10-100 pts.wt. petroleum resin having at least no polar group and a hydro genation rate of 95 % or higher, through a layer (layer C) consisting of a polyu rethane resin. The petroleum resin having at least no polar group incorporated in the layer A is a cyclopentadiene resin using directly a petroleum unsatd. hydrocarbon as a raw material or a resin using a higher olefinic hydrocarbon as a raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a moldable sheet having excellent water vapor barrier properties, gas barrier properties, transparency, heat resistance, and moldability.

[Prior art] Conventional molding sheets are mostly made of polypropylene, polyvinyl chloride, polystyrene, and polyester.
In order to add properties to these materials, materials laminated with polyvinylidene chloride, ethylene vinyl alcohol copolymer, paper, etc. are known.

Also, an example in which a polyolefin film is arranged between polyester films (Japanese Patent Application Laid-Open No. 1979-11-1979)
There is.

Recently, it has been disclosed that a petroleum resin is added to polypropylene to improve transparency and water vapor barrier properties (for example, Japanese Patent Laid-Open No. 163949/1983).

[Problems to be Solved by the Invention] The various types of molding sheets described above each have advantages and disadvantages, so food and pharmaceutical manufacturers currently use them depending on the contents.

Polypropylene has good water vapor barrier properties and transparency, but
Poor moldability, heat resistance and gas barrier properties. Polyvinyl chloride and polystyrene have good moldability, gas barrier properties, and transparency, but are poor in water vapor barrier properties and heat resistance. Although polyester has good moldability, transparency, gas barrier properties, and heat resistance, it has poor water vapor barrier properties, and is expensive and uneconomical compared to other materials.

In addition, a film in which a polyolefin film (especially a polyethylene film) is placed between polyester films (
JP-A No. 52-111979) cannot obtain sufficient moldability due to the polyolefin film of the intermediate layer.
Moreover, the water vapor barrier property was also not sufficient.

In addition, a film made of polypropylene with petroleum resin added (
In JP-A-60-163949), the molding temperature range of the molding machine was narrow, and the petroleum resin bleed out from the film surface during molding, resulting in surface stickiness, poor transparency, and poor appearance, which was not desirable. .

In addition, when used for oil-based foods, if extraction is performed with n-hebutane in the food hygiene test (Ministry of Health and Welfare No. 20), all of the added petroleum resin will be extracted, which is not hygienic. . (Hereinafter referred to as petroleum resin or n-
The resistance to extraction by hebutane is abbreviated as n-hebutane resistance. ) The present invention aims to solve the above-mentioned problems and provide a molding sheet that has a sufficiently wide molding temperature range and has excellent water vapor barrier properties, gas barrier properties, transparency, heat resistance, and n-heptane resistance. It is something to do.

[Means for Solving the Problems] The present invention provides 100 parts by weight of polypropylene with 1 part petroleum resin containing no polar groups and a hydrogenation rate of 95% or more.
A layer made of a polyurethane resin (layer C) on at least one B layer side of a composite sheet having a layer made of a polypropylene resin (layer B) on at least one side of a layer made of a mixture of 0 to 100 parts by weight (layer A). The present invention relates to a molding sheet characterized by laminating a layer (D layer) made of polyester film with a polyester film interposed therebetween.

The polypropylene applied to the A layer and B layer in the present invention is not particularly limited, and has an intrinsic viscosity (η) of
is 1.0-3.6di, 7g, especially 1°3-2. 4d
1. ,．． It is desirable that the weight is in the range of 7g, and the isotactic index (IT) is preferably 95W1% or more.

A second component other than polypropylene, such as ethylene or butene, may be copolymerized within a range that does not significantly impede crystallinity. Of course, the polypropylene has additives such as crystal nucleating agents, antioxidants, heat stabilizers, slip agents, antistatic agents, anti-blocking agents, fillers, deodorizing agents, antibacterial agents, etc.
A viscosity modifier, color inhibitor, etc. may be added.

In addition, the petroleum resin that does not contain at least polar groups to be added to the A layer refers to hydroxyl groups (-OH), carboxyl groups (-CO
OH), halogen group (-X), sulfonic acid group (-
8o, YXY=H, Na, Mg, etc.) and modified products thereof, petroleum resins without polar groups, i.e., cyclopentadiene-based or higher olefins made directly from petroleum-based unsaturated hydrocarbons. It is a resin whose main raw material is hydrocarbon. Glass transition temperature T of the petroleum resin
g is preferably 50°C or higher, more preferably 76°C or higher for the moldable sheet of the present invention.

The hydrogenation rate (hereinafter sometimes abbreviated as hydrogenation rate) of the petroleum resin needs to be 95% or more, and it is particularly preferable when the hydrogenated petroleum resin is 98% or more for the laminate of the present invention. Typical examples of the resin include hydrogenated alicyclic petroleum resins (for example, the trade name "Escolettes" (manufactured by Tonex ■, etc.).

In addition, petroleum resins that do not contain polar groups include terpene resins that do not have polar groups such as hydroxyl groups, aldehyde groups, ketone groups, carboxyl groups, halogen groups, sulfonic acid groups, and modified products thereof, i.e. (C5Ha
) n (where n is an integer of 2 to 15) and modified compounds derived therefrom. Terpene resins are also sometimes called terpenoids. Typical chemical compounds include pinene, carene, myrcene, ocimene, limonene, terpinolene, terpinene, sapinene, tricyclene, pisapolene, gingiperene, santarene, camphorene, mylene, and totalene, and in the case of the laminate of the present invention, hydrogen add
The hydrogenation rate needs to be 95% or more, preferably 98% or more, and hydrogenated β-pinene, hydrogenated dipentene, etc. are particularly preferred.

In addition, petroleum resin with polar groups or hydrogenation rate of 95%
If the petroleum resin is less than 100%, the water vapor barrier property will deteriorate, so it is not suitable as the layer A of the present invention.

Layer A needs to contain 10 to 100 parts by weight of the petroleum resin based on 100 parts by weight of the polypropylene resin. If the amount added is less than 10 parts by weight, water vapor barrier properties and moldability will deteriorate, and if it exceeds 100 parts by weight, moldability, heat resistance and transparency will deteriorate, which is not preferred.

The thickness of layer A is Press-Through for pharmaceutical packaging.
100~ when used for h-Pack (FTP) molding
The range is preferably 500 μm, and when used for container molding such as food packaging, the range is preferably 100 to 1000 μm.
00 to 700 μm is more preferable. If it is thinner than the above range, the shape retention after molding is poor, and on the other hand, if it is thicker than the above range, the shape retention after molding is good, but the transparency deteriorates and it is not economical.

In the present invention, a polypropylene resin layer (B layer) needs to be laminated on at least one side of the A layer.

Without layer B, the petroleum resin added to layer A would bleed out to the surface layer, resulting in poor extrusion castability and weak adhesive strength with layer C. Furthermore, petroleum resin migrates to layer B when layer A is laminated thereon, but in order to layer layer C, it is preferable to limit the amount of the transfer to 5% or less.

The thickness of layer B is not particularly limited, but is 10 to 1
00 μm is preferable, and 20 to 50 μm is more preferable.

If it is thinner than 10 μm, bleed-out of the petroleum resin cannot be suppressed, and if it exceeds 100 μm, the molding temperature range becomes narrow.

Furthermore, in the present invention, when the A layer has the B layer on only one side, it is applied to the 8 layer surface, and when the A layer has the B layer on both sides, at least one of the 8 layer surfaces is provided with the C layer described later. It is necessary to stack the D layer. Without the C layer, not only the D layer cannot be laminated, but also the n-hebutane resistance is poor.

The C layer is made of polyurethane resin and has a thickness (after solvent removal) of 0. 2-20 μm is preferable, 0°5-15 μm
is more preferable. C layer thickness is 0. If it is less than 2 μm, not only will lamination be difficult, but the n-hebutane resistance will be poor. Moreover, if it exceeds 20 μm, not only will unevenness occur during molding, but the line speed in the drying process will be slow, resulting in poor productivity, high price, uneconomical, and the molding temperature range will be narrow.

The polyurethane resin used for the C layer is a polyurethane adhesive having urethane bonds in the repeating unit of the main chain, and is made by reacting isocyanate and polyol at room temperature or under heating.

Specific examples of isocyanates include 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and molecules obtained from these derivatives. Some compounds have more than one isocyanate group.

Polyols include polyether type ones such as polyoxypropylene glycol and polyoxypropylene-polyoxyethylene glycol, terephthalic acid,
There are polyester types that are mainly made by condensing dicarboxylic acid components such as isophthalic acid, adipic acid, and sebacic acid with ethylene glycol, 1,4-butanediol, diethylene glycol, polyethylene glycol, and neopentyl glycol.

The former is called polyether polyurethane, and the latter is called polyester polyurethane. There are also acrylic and epoxy resins.

The polyurethane adhesive used in the present invention is
- Polyester polyurethane adhesives are particularly preferred from the viewpoint of hebutane properties, adhesive properties, etc.

The mixing ratio of polyol and polyisocyanate is hydroxyl group,
Equivalent proportion of isocyanate groups [NGO]/[0)(
] is 1-9, preferably 1,5-7. If the value is less than 1, lamination will not be performed sufficiently, and if the value exceeds 9, cracks will occur in the C layer during molding, resulting in improved moldability, transparency, water vapor barrier properties, gas barrier properties, and n-hebutane resistance. The characteristics of the moldable sheet of the present invention may deteriorate.

Further, in the present invention, it is necessary that the D layer is laminated on at least one B layer surface with the C layer interposed therebetween. Without the D layer, not only is the heat resistance inferior, but the molding temperature range is narrowed, the gas barrier properties are inferior, and the curling resistance after bonding with aluminum foil etc. is inferior.

Layer D is composed of polyester film.

As the polyester applied to the D layer, polyethylene terephthalate obtained by polycondensing terephthalic acid and ethylene glycol can be exemplified as a representative example, but it is not limited thereto, and polyethylene terephthalate units are 70 to 70. Other dicarboxylic acids, diol components, etc. may be copolymerized within a range of 97 mol %, but copolymerization is preferable since the molding temperature range is wider.

Copolymerization components include dicarboxylic acids such as adipic acid, sebacic acid, and isophthalic acid, polyfunctional carboxylic acids such as trimellitic acid and pyromellitic acid, diethylene glycol, neopentyl glycol, P-xylene glycol, and 1,4-cyclohexane. Dimetator, average molecular weight 150-20. 000 polyalkylene glycol,
Examples include diol components such as butanediol. Further, the polyester may contain antioxidants, heat stabilizers, lubricants, pigments, ultraviolet absorbers, etc. within a range that does not impede the object of the present invention.

The melting temperature Tm of the polyester is 210°C to 265°C
, preferably 215 to 250°C, provides good moldability. Further, when the crystallinity Xc is 30 to 50%, preferably 35 to 45%, shape retention after molding is good.

When the film made of polyester is biaxially oriented, it will have good moldability after being laminated with the polypropylene sheet, and will have good gas barrier properties and heat resistance. The birefringence of the biaxially oriented polyester film is 0.
02 to 0.20, more preferably 0.05 to 0.0.
The range is 15. If it is less than 0.02, gas barrier properties are poor, heat resistance is poor, and shape retention is poor. On the other hand, 0.20
If it exceeds this value, the moldability will deteriorate, such as the film breaking during molding.

One of the characteristics required for sheets for containers and PTP is that the sheet be easy to mold (a wide range of molding temperatures). Generally, the temperature range at which polypropylene can be molded is said to be 1 to 2°C, and polypropylene alone is difficult to mold. Therefore, the addition of petroleum resin made it possible to improve the water vapor barrier properties of polypropylene and widen the molding temperature range. In addition, by using the molding sheet of the present invention, the molding temperature range can be further widened, and the temperature range can be sufficiently molded even with a molding machine for molding PVC (polyvinyl chloride resin). resistance, n resistance
- It was also possible to impart hebutane properties.

Next, a method for producing a molding sheet according to the present invention will be described, but the method is not limited thereto.

A resin made by adding and mixing a specific petroleum resin to polypropylene (raw material for layer A), and polypropylene resin (raw material for layer B)
are fed to separate extruders, the molten polymers are laminated in the die, extrusion cast onto a casting drum kept at 20 to 70°C, cooled and solidified to form A layer/B layer or B layer/A layer. A polypropylene composite sheet having the structure of /B layer is obtained.

On the other hand, thoroughly dried intrinsic viscosity 0.50~0°80,
Preferably, polyester pellets of 0.55 to 0.70 are fed to an extruder heated to 270 to 290°C to
It is extruded into a sheet form from a die die, cooled and solidified on a casting drum maintained at 25 to 50°C to obtain a sheet, and then longitudinally stretched to 3 to 5 times at 70 to 120°C. Cool on a cooling roll at °C. Subsequently, both ends of the film are held with clips, introduced into a stenter, stretched 3 to 5 times in an atmosphere at 60 to 130°C, and immediately heat treated at 170 to 230°C for several seconds.

If heat treatment is performed while allowing several percent relaxation at this time, dimensional stability will be improved.

Polyester film obtained as above (D layer)
The surface of the substrate is subjected to corona discharge treatment or plasma treatment in an atmosphere of oxygen, carbon dioxide, nitrogen gas, etc. as necessary. In addition, coating with printing ink, polyvinylidene chloride, etc. that imparts gas barrier properties, or coating of other ultraviolet absorbing agents may be applied, and a transparent vapor deposited layer with gas barrier properties may be provided by sputtering a metal oxide. Also good.

Next, after applying a polyol/isocyanate mixture to a certain thickness on the surface of the polyester film (layer D),
The solvent is removed through an oven kept at 50°C to 90°C to obtain a polyester composite film consisting of C layer/D layer. Subsequently, at the oven exit, the polypropylene composite sheet (layer A/layer B or layer B/layer A/layer B)
Layer B layer and C layer/D layer so that the 0 layer matches, and then add A layer/
B layer/C layer/D layer, B layer 7/A layer, /73 layer/C layer/D
At the same time as laminating layers D, C, B, A, B, C, and D, they are press-bonded with a roll heated to 60 to 100°C, cooled with a cooling roll, and then rolled up. , a molded sheet of the present invention is obtained.

[Effects of the Invention] The present invention provides a molding sheet in which a polyester film is laminated via a polyurethane resin layer on a sheet in which a polypropylene resin is laminated on at least one side of a layer made of polypropylene and a specific petroleum resin. , which produces the following excellent effects.

(1) It has excellent water vapor barrier properties and gas barrier properties, and can be applied to a wide range of applications such as food and pharmaceutical packaging.

(2) Compared to a sheet in which a polypropylene homopolymer layer is laminated with a polyester layer, it has excellent moldability and good shape retention after molding.

(3) It has better heat resistance than polypropylene sheets, and can be used not only for water-based foods but also for food packaging containers for oily foods, has a wider operating temperature range than before, and can be used in microwave ovens and retorts.

(4) Good transparency makes it easy to visually check the contents of the container.

(5) There is almost no extraction of additives and petroleum resins by n-hebutane.

[Measurement method and evaluation criteria for characteristic values] (1) Water vapor transmission rate A value measured at 40° C. and 90% RH according to JIS Z-0208, expressed in g/%·day/sheet. The water vapor barrier properties of the sheet for molding include a water vapor transmission rate of 0.
80 or less is required.

(2) Oxygen permeability The value was measured according to ASTM D-1434 and expressed in units of cc/day/sheet. The gas barrier property as a sheet for molding requires an oxygen permeability of 100 or less.

(3) Resistance to n-hebutane After soaking the D layer side of the polypropylene laminate in a petri dish filled with n-hebutane at room temperature for 1 hour and taking it out,
Observe the state of the core after the hebutane has evaporated; if there is no change: O (good), if the surface is sticky or if the additive bleeds out and shines: × (bad).
And so.

(4) Intrinsic viscosity [η] Measured in tetralin according to ASTM D-1601, expressed in di/g.

(5) Isotactic index (II) It is expressed as the extraction residual amount (w1%) of boiling n-hebutane.

(6) Birefringence (Δn) Using an Abbe refractometer with methylene iodide as the mounting liquid, measure the refractive index nX in the longitudinal direction and the refractive index ny in the width direction of the film, and find it by the difference between nx and ny. Ta.

(2) Melting temperature (Tm) - Melt crystallization temperature (T me
) Sample 5 was measured using a scanning calorimeter DSC-II model (Perki
n (manufactured by EImer) and measured from room temperature under a nitrogen stream at a heating rate of 20° C./min, and the endothermic peak temperature accompanying melting is defined as the melting temperature Tm.

Similarly, after keeping the sample at 280°C for 5 minutes, the temperature was lowered to room temperature at a cooling rate of 20°C/min.
Let it be mc.

(8) Glass transition temperature Tg The glass transition temperature was measured using a scanning calorimeter DS.
Set in a C-It type (manufactured by Perkin Elmer) and heated to 120°C at a heating rate of 40°C/min under a nitrogen stream.
A thermograph is drawn starting from ℃, and the arithmetic mean value of the temperature at which the endothermic peak deviates from the baseline and the temperature at which it returns is determined as temperature Tg.

(9) Crystallinity (Xc) A mixture of n-hebutane and carbon tetrachloride is poured into a glass cylinder to obtain a linear density gradient, and a sample is placed in this to determine the equilibrium position at 25°C. Read the density (d) and calculate the crystallinity of the sample using the following formula.

Xc: crystallinity dC: density of crystalline regions.

da: Density of amorphous area (g) Transparency When the contents are packed in an FTP or container and viewed from the outside, the text, color, and shape of the contents are clearly visible. FTP molding machine (FTP molding machine)
The moldability was evaluated by visually observing the moldable temperature range, surface stickiness (appearance), and curl state after sealing with aluminum foil (curl resistance) as follows.

○: The moldable temperature range is 4°C or higher, the surface is sticky, and the curl is small.

×: The moldable temperature range is 28C or less, the surface is sticky, and the curl is large.

△ Something between ○ and ×.

In addition, molding tests on food packaging containers are conducted by Mitsubishi Heavy Industries, Ltd.
When the polyester film (layer D) was preheated to 120° C. to 140° C. and formed on the inside of the container using a MOP-504 molding machine produced by MOP-504, the appearance of the molded product was evaluated as follows.

○: Shaped sharply down to the bottom corner.

△: The bottom corners are somewhat lacking in sharpness.

×: The molded product cannot be molded according to the mold or cracks occur in the molded product.

Heat Resistance (Shape Retention) The molded product (container) was placed in a hot air oven, and the shape retention was visually observed and evaluated as follows.

○: Items that do not lose their shape even after 2 minutes at 150°C.

At 62150℃ for 2 minutes, the edges are slightly deformed, but 14
Items that do not lose their shape after 2 minutes at 0℃.

X: Items that lose their shape after 2 minutes at 140°C.

Note that deformation refers to distortion of the edges of a molded container, rounding of the bottom corner, or unevenness of the entire or partial container.

[Example code] Next, embodiments of the present invention will be described based on Examples.

Example I The polypropylene of the A layer had an intrinsic viscosity [η co=1. ．．
90 dl/g, isotactic index (II
) = 98w1% Mitsui "Noblen" (manufactured by Mitsui Toatsu Chemical ■) was used as a petroleum resin, and a non-polar polydicyclopentadiene resin "Escolettes" 53 with a hydrogenation rate of 99% was used.
20 (manufactured by Tonex ■) was used. A raw material obtained by uniformly blending 100 parts by weight of the polypropylene resin and 30 parts by weight of the petroleum resin was supplied to a 90-cylinder diameter main extruder heated to 240°C. For the 35-hole sub-extruder heated to 240°C, [η] = 1.40 dl/g, I T = 98
wt% polypropylene (Mitsui “Noblen”) was supplied. The molten raw materials were made into a three-layer structure (B/A/B) of 5 polypropylene/10 petroleum resin/polypropylene using the pinol method, and then extruded into a sheet from a T-shaped die to form a metal with a surface temperature of 63°C. Wrap it around a drum, cool and solidify it to a thickness of 25/350. /25μm
An unstretched sheet was obtained. Corona discharge treatment (in air) was performed on the surface layer of layer B.

For the D layer, pellets made by copolymerizing polyethylene terephthalate with 15 mol% of isophthalic acid were thoroughly dried in vacuum, and then fed into an extruder heated to 290°C and extruded into a sheet form from a T-shaped die, and then heated to a surface temperature of 30°C. It was wound around a metal drum, cooled and solidified to obtain an unstretched sheet. This unstretched sheet was introduced into a group of preheated rolls with a surface temperature of 75° C., stretched 3.3 times in the machine direction, and then preheated in an atmosphere of 90° C. and stretched 3.3 times in the transverse direction. Subsequently, tension heat treatment was performed in an atmosphere at 220°C to obtain a biaxially stretched film with a thickness of 12 μm. Corona discharge treatment (in air) on the surface of the film
I did this.

A polyester/polyurethane adhesive was used as the zero layer. For the polyester, resins of terephthalic acid/sebacic acid (molar ratio 60./40) and ethylene glycol/neopentyl glycol (molar ratio 35/65) are used.
25% solution of copolymerized polyester (toluene/MEK=
8/2) For 100 parts by weight, as isocyanate “
12 parts by weight of Coronate HL (manufactured by Nippon Polyurethane) were mixed and used.

On the corona discharge treated surface of the polyester film (Layer D), use a reverse coater to coat the 0 layer with 5
Coat the film to a thickness of 9 μm and dry in a drying oven.
Layer B, which was dried at 0°C and subjected to corona discharge treatment on the C layer surface at the oven exit, was stacked and pressed with a press roll heated to 80°C to obtain a laminated sheet (B/A/B/C/D). Ta.

The results of evaluating this sheet are shown in Table 1.
It has excellent water vapor barrier properties, gas (oxygen) barrier properties, and n-heptane resistance, has a sufficiently wide molding temperature range in PTP molding, and has good curl resistance after laminating with aluminum foil, making it excellent as an FTP packaging material. It was something. In addition, this sheet was put through a vacuum forming machine, and the length was 150 mm, the width was 100 mm,
A container with a depth of 30 mm was molded. The moldability was good, the transparency was also good, and the heat resistance (shape retention) was also good.

Example 2 In Example 1, a non-polar petroleum resin with a hydrogenation rate of 96% was used, and 80 parts by weight of the petroleum resin was uniformly blended with 100 parts by weight of polypropylene. Example 1- (D/C/B) (Lamination sheet) in the same manner as in Example 1, except that 128 layers of polypropy were laminated, and 0 layers of polyester were further laminated on both sides via the 0 layer of polyester polyurethane adhesive of Example 1. /A/B/C/D) were obtained. The evaluation results of this sheet are shown in Table 1. As can be seen from the table, all the properties required for a moldable sheet were satisfied.

Example 3 Example 1 except that a non-polar polyterpene resin "Clearon" (manufactured by Cheap Crude Oil) with a hydrogenation rate of 99% was used instead of the polydicyclopentadiene resin "Escolette" 5320. A molding sheet was obtained in the same manner as above. As shown in Table 1, the evaluation results satisfied all the properties required for a sheet for molding.

Comparative Example 1 In Example 1, the petroleum resin polydicyclopentadiene resin "Escolettes" 5320 was replaced with a polar group -C
Example 1 except that non-hydrogenated gum rosin “Ester Gum H” (manufactured by Arayo Kagaku ■) having OOH was used.
A molding sheet was obtained in the same manner as above.

As shown in Table 1, this evaluation result shows that there are polar groups,
Non-hydrogenated resins had poor compatibility with polypropylene and were poor in water vapor barrier properties, transparency, and moldability.

Comparative Example 2.3 Molding sheets were obtained in the same manner as in Example 1, except that the amount of petroleum resin added was 5 parts by weight and 120 parts by weight based on 100 parts by weight of polypropylene.

As shown in Table 1, the evaluation results show that if the amount of petroleum resin added is less than 10 parts by weight, water vapor barrier properties and moldability will be poor, and if it exceeds 100 parts by weight, moldability, heat resistance, and transparency will deteriorate. It got worse.

Comparative Example 4.5.6 In Comparative Example 4, Layer B was not laminated in Example 1, but Layer D was laminated on the surface of Layer A with Layer 0 interposed therebetween. In addition, Comparative Example 5 is
Layer B was only laminated on both sides of layer A, and layer 0 and layer D were not laminated.

In Comparative Example 6, one side of the B layer in Example 1 was subjected to a known anchor treatment, and then the treated side was coated with polyvinylidene chloride (PVDC) to a thickness of 5 μm as a zero layer, and then P
Polyethylene (PE) was extrusion laminated as a D layer on the VDC surface to a thickness of 30 μm to obtain a sheet for molding.

The thus obtained laminate was evaluated.

If Layer B in Comparative Example 4 was not laminated, the petroleum resin added to Layer A would bleed out during extrusion casting, resulting in 0.
When laminating layers, the interfacial adhesion with layer A is weak, causing peeling during molding, resulting in poor moldability and heat resistance (shape retention), and petroleum resin remains at the interface between layer A and layer 0. Transparency has deteriorated.

In Comparative Example 5, if the 0 layer and the D layer were not laminated, the n-
Hebutanability and heat resistance (shape retention) deteriorated. 0 again
In Comparative Example 6, in which PVDC was laminated as the layer and PE was laminated as the D layer, the PVDC layer cracked during molding, resulting in poor n-hebutane resistance, and PE adhered to the mold during molding, resulting in poor molding. , heat resistance also deteriorated.

Claims (1)

[Claims] (1) 10 to 100 parts by weight of polypropylene contain at least 10 to 10 parts of petroleum resin containing no polar groups and a hydrogenation rate of 95% or more.
100 parts by weight of a layer (A layer) mixed with a polypropylene resin layer (B layer) on at least one side of the composite sheet, a layer made of polyurethane resin (C layer) on at least one side of the B layer. A molding sheet characterized by being formed by laminating a layer (D layer) made of polyester film.