JPH11349701A - Opaque colored soft resin sheet and method for producing the same - Google Patents

Abstract

(57) [Problem] To provide an opaque colored soft resin sheet which is environmentally safe and has excellent optical and mechanical properties, and an opaque colored soft resin sheet which can be produced without lowering surface gloss. A manufacturing method is provided. SOLUTION: This composition includes at least one layer made of a soft polyolefin resin, and (a) has a tensile modulus of 20 to 1000 MPa,
(B) At least one surface has a characteristic that the surface roughness Ra is less than 0.05 μm. The equipment used in the manufacturing method is the first
A metal endless belt 15 wound between the cooling roll 13 and the second cooling roll 14 is provided, and an outer peripheral surface of the first cooling roll 13 is coated with an elastic material 18.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an opaque colored soft resin sheet and a method for producing the same. The obtained sheet is used for stationery (multicolor pen case, zipper case with zipper).
Products), portable bags (fashion bags, travel goods), cosmetics cases, car interior materials, motorcycle seat cover materials, product bags (clothing, sundries), cosmetic sheets (building materials, furniture), clothes covers, It can be used for tablecloths, desk mats, partitions, door curtains, greenhouse covers for agriculture, etc.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a colored flexible polyvinyl chloride sheet (film) has a gloss,
It has excellent secondary workability (printing, embossing, high frequency fusion, etc.) and can be supplied at low cost, so it is used in various applications. However, such polyvinyl chloride (PV)
C) The sheet has environmental problems because toxic plasticizers and monomers bleed out during use, and hydrogen chloride and toxic dioxins were generated when incinerated.

[0003] In order to solve such problems, for example, polyethylene sheets (films) have been proposed (JP-A-5-30979, JP-A-5-29082, etc.).
In addition, as a polypropylene-based sheet (film),
Polypropylene film based on low stereoregularity polypropylene (Japanese Patent Application Laid-Open No. Hei 7-117949), laminated polypropylene film of polypropylene layer / polypropylene-ethylene-butene-1 copolymer layer / polypropylene layer (Japanese Patent Application Laid-Open No. 6-218892) Has been proposed.

However, polyethylene sheets are not as good as polyvinyl chloride sheets in terms of surface gloss, heat resistance, and stiffness. A polypropylene-based sheet is excellent in low-temperature heat sealability and embrittlement temperature, and has mechanical properties such as rigidity and strength close to PVC, but is comparable to PVC in terms of surface gloss (gloss). Things have not yet been obtained.

Accordingly, the present invention provides an opaque colored soft resin sheet which is environmentally safe and has excellent optical and mechanical properties, and an opaque colored soft resin sheet which can be produced without reducing the surface gloss. It is intended to provide a manufacturing method.

[0006]

The opaque colored soft resin sheet according to the first invention of the present invention includes at least one layer made of a soft polyolefin resin and has the following characteristics (a) and (b). Features. That is, the present invention uses a soft polyolefin-based resin instead of PVC, and limits the tensile modulus and surface roughness Ra of the sheet to specific ranges, so that the sheet is environmentally safe and has a good surface gloss. It has been found that an opaque colored soft resin sheet having the following formula can be obtained.

(A) Tensile elastic modulus of 20 to 100 MPa When the tensile elastic modulus is less than 20 MPa, the stiffness of the sheet is too weak, and its practical value is low. Also,
If it is larger than 1000MPa, the sheet becomes hard,
Poor handling properties make it unsuitable for the intended use. Preferably, it is 50 to 800 MPa.

(B) At least one surface has a surface roughness Ra
Less than 0.05 μm If the sheet surface has irregularities, the incident angle and the reflection angle of light will be different, which will have a great effect on the quality of gloss.
When the surface roughness is quantitatively expressed by the center line average roughness Ra, by setting the surface roughness to less than 0.05 μm, it is possible to prevent a decrease in gloss.

The surface roughness can be controlled by a method such as polishing, coating and scribing the sheet surface. In the present invention, a single layer or a multilayer may be used as long as the layer includes the layer made of the soft polyolefin resin. In the case of a multi-layer, the specific number of layers is arbitrary, but is, for example, 2 to 8 layers. This multilayer structure is obtained by, for example, coextrusion.

In this multilayer structure, the layer made of the soft polyolefin resin may be either a surface layer or an intermediate layer. The resin species constituting the layers other than the soft polyolefin-based resin layer in the multilayer may be other than PVC, such as ordinary homopolypropylene, ethylene-propylene random copolymer, and ethylene-propylene-butene-1 random. Copolymer, ethylene-α-olefin copolymer, styrene-α-olefin-styrene copolymer,
Etc. can be used alone or in combination. Further, a blend of a thermoplastic elastomer such as a hydrogenated product thereof may be used.

As a colorant for coloring the present flexible resin sheet, organic pigments, inorganic pigments, dyes, carbon black and the like can be used. The specific color is arbitrary, and can be, for example, white, ivory, black, red, blue, yellow, green, and the like. In the case of a multilayer structure, the coloring agent may be added to all the layers, or the coloring agent may be added to only some of the layers. The sheet of the present invention may be a so-called relatively thin film.

An opaque colored soft tree according to the second invention of the present invention
The fat sheet according to the first invention, wherein the soft polyolefin
Homopolypropylene
Stay ¹³The pentad fraction measured using C-NMR
And low stereoscopic rules with a mmmm ratio (PI value) of 50-90%
It is characterized by using a conductive polypropylene resin.

The mmmm (00000) or (11111) is an isotactic pentad. m indicates the isotactic yard, 0,1 indicates the configuration of individual monomer units along the polymer chain, and 0 indicates 1
One configuration and one represents the opposite configuration. PI (Pentad Isotactici
The ty) value is the isotactic fraction in pentad units in the polypropylene molecular chain. The method for measuring this isotactic fraction is described in Macromolecules (Macr.
omolecules) 6925 (1973). If the PI value is less than 50%, the heat resistance will deteriorate and the strength will also decrease. If it exceeds 90%, the resin becomes hard, and it becomes difficult to use it as a soft sheet. The low stereoregularity polypropylene resin according to the present invention can be produced by a gas-phase one-stage polymerization method or a slurry one-stage polymerization method (Japanese Patent Laid-Open No. 3-48551).
No., JP-A-6-263934).

An opaque colored soft resin sheet according to a third aspect of the present invention is the opaque colored soft resin sheet according to the second aspect, wherein the value of rrrr / (1-mmmm) of the low stereoregularity polypropylene resin is 15 to 50%. Features. The rrrr indicates the degree of so-called syndiotacticity. When rrrr / (1-mmmm) is less than 15%, the resin becomes hard, and it becomes difficult to use it as a soft sheet. If it exceeds 50%, heat resistance deteriorates and strength also decreases.

An opaque colored soft resin sheet according to a fourth invention of the present invention is the opaque colored soft resin sheet according to the third invention, wherein the low stereoregularity polypropylene resin is a boiling heptane having an intrinsic viscosity [η] of 0.5 to 9.0 dl / g. Insoluble polypropylene resin (50-95wt
%) And a boiling heptane-soluble polypropylene resin (5 to 50 wt%) having an intrinsic viscosity [η] of 1.2 dl / g or more.

If the boiling point of the heptane-insoluble polypropylene resin is less than 0.5 dl / g, the impact resistance becomes extremely poor. If it exceeds 9.0 dl / g, molding becomes difficult.
Boiling heptane-soluble polypropylene resin [η]
If it is less than 1.2 dl / g, the breaking stress is low, and the rubber elasticity may be impaired. Note that the intrinsic viscosity [η] is set at a temperature of 135.
It is a value measured in a decalin solution at ° C.

An opaque colored soft resin sheet according to a fifth aspect of the present invention is the opaque colored soft resin sheet according to the first aspect, wherein an ethylene-propylene random copolymer (ethylene content: 5 to 30% by weight) is used as the soft polyolefin resin. Features.

The opaque colored soft resin sheet according to the sixth invention of the present invention is the opaque colored soft resin sheet according to the fifth invention, wherein four continuous units of ethylene (E) and propylene (P) are formed in a racemic form relative to a continuous portion of PP. The ratio of the ethylene-propylene random copolymer having the configuration is extremely small. The specific ratio is preferably less than 1%. When the content is less than 1%, flexibility, tensile strength, heat resistance and workability are excellent. The measurement of this ratio is performed, for example, in "POLYMER" Vol. 29, No. 22,
08 (1988) and "POLYMER" Vol. 29, p. 138 (1988
Year).

The opaque colored soft resin sheet according to the seventh invention of the present invention is characterized in that, in the first invention, an amorphous butene-1-propylene copolymer is used as the soft polyolefin resin.

An opaque colored soft resin sheet according to an eighth aspect of the present invention is the opaque colored soft resin sheet according to the first aspect, wherein a mixture of amorphous butene-1-propylene copolymer and polypropylene is used as the soft polyolefin resin. It is characterized by.

An opaque colored soft resin sheet according to a ninth invention of the present invention is characterized in that, in the first invention, a propylene-ethylene-butene-1 copolymer is used as the soft polyolefin resin.

The opaque colored soft resin sheet according to the tenth invention of the present invention is characterized in that, in the first invention, a mixture of a propylene-ethylene-butene-1 copolymer and polypropylene is used as the soft polyolefin resin. And

The opaque colored soft resin sheet according to the eleventh invention of the present invention is characterized in that, in the first invention, the soft polyolefin resin contains a reactor blend type ethylene-propylene copolymer elastomer.

An opaque colored soft resin sheet according to a twelfth aspect of the present invention is the opaque colored soft resin sheet according to the first aspect, wherein the soft polyolefin resin contains a reactor blend type ethylene-propylene-butene-1 copolymer. And

The opaque colored soft resin sheet according to the thirteenth invention of the present invention is the opaque colored soft resin sheet according to the first invention, wherein the soft polyolefin resin is an ethylene homopolymer or ethylene-
It is characterized by using at least one selected from α-olefin copolymers.

In the opaque colored soft resin sheet according to a fourteenth aspect of the present invention, in the thirteenth aspect, the ethylene homopolymer is at least one selected from a high-pressure low-density polyethylene and a low-pressure low-density polyethylene. It is characterized by the following.

The opaque colored soft resin sheet according to the fifteenth aspect of the present invention is the opaque colored soft resin sheet according to the thirteenth aspect, wherein the ethylene-α
-An olefin copolymer having a long chain branch in the main chain polymerized using a Ziegler-Natta catalyst linear low density polyethylene, a metallocene catalyst linear low density polyethylene, or a metallocene geometrically constrained catalyst; It is characterized by being at least one of octene copolymers.

An opaque colored soft resin sheet according to a sixteenth aspect of the present invention is characterized in that, in the first aspect, the soft polyolefin-based resin is a copolymer of ethylene and a polar group-substituted ethylene. The opaque colored soft resin sheet according to a seventeenth aspect of the present invention is the opaque colored soft resin sheet according to the sixteenth aspect,
Examples of the copolymer of ethylene and ethylene substituted with a polar group include ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-acrylic acid copolymer (EAA), and ethylene-methacrylic. Acid copolymer (EMMA), ethylene-methyl acrylate copolymer (EMA), ethylene-methacrylic acid copolymer (E
MAA) and at least one metal ion cross-linked ethylene-acrylic acid copolymer (EAA). Among the resin types, the type and number of specific resin types to be selected, the mixing ratio of the resin types, and the like are arbitrary.

The opaque colored soft resin sheet according to the eighteenth aspect of the present invention is characterized by being made of a soft polypropylene resin. The softness means that the tensile modulus of the sheet is
It means less than 1000MPa. Preferably 800MPa
Or less, more preferably 600 MPa or less. Specific examples of the soft polypropylene-based resin include ethylene-propylene copolymer resin, ethylene-propylene-diene copolymer resin, and propylene-hexene copolymer resin (JP-A-49-53983).
JP-A-63-243106), elastic polypropylene (JP-A-61-179247), atactic polypropylene (JP-A-63-243106)
Japanese Patent Application Laid-open No.
3-14851, JP-A-6-263934) and the like.

The layer structure of the opaque colored soft resin sheet is arbitrary, and may be, for example, a single layer structure or a multilayer structure by co-extrusion. The sheet of the present invention also includes a relatively thin film. According to the opaque colored soft resin sheet of the present invention, since there is no polyvinyl chloride, there is no risk of generating harmful gas, and the sheet is safe for the environment. In addition, because it is made of a soft polypropylene resin, transparency, haze, optical characteristics such as gloss are improved,
Heat resistance, mechanical strength, and stiffness are also good.

An opaque colored soft resin sheet according to a nineteenth aspect of the present invention is characterized in that, in the eighteenth aspect, hydrogenated styrene / butadiene rubber is blended in an amount of 2 to 30% by weight. If the amount of the hydrogenated SBR is less than 2% by weight, the effect of reforming (softening) is lost. 30% by weight
If it exceeds, stickiness occurs and the appearance becomes poor, and the neck-in becomes large during molding, so that stable ejection becomes impossible. Preferably, it is 5 to 20% by weight.

The opaque colored soft resin sheet according to the twentieth aspect of the present invention is characterized in that, in the eighteenth aspect, 2 to 30% by weight of an ethylene-α-olefin copolymer is blended. Examples of the α-olefin include C 3
~ 8 alpha olefins can be used. When the amount of the ethylene-α-olefin copolymer is less than 2% by weight, the effect of reforming (softening) is reduced. If it exceeds 30% by weight,
Stickiness occurs, resulting in poor appearance. In molding, neck-in becomes large, and stable ejection cannot be performed. Preferably, it is 5 to 20% by weight.

The opaque colored soft resin sheet according to the twenty-first invention of the present invention is characterized in that, in the eighteenth invention, 2 to 15% by weight of an ethylene / octene copolymer is blended. When the amount of the ethylene / octene copolymer is less than 2% by weight, the effect of the modification (softening) is reduced.
If it exceeds 30% by weight, stickiness occurs and the appearance becomes poor, and the neck-in becomes large during molding, so that stable ejection becomes impossible. Preferably, it is 5 to 20% by weight.

The opaque colored soft resin sheets of the first to twenty-first inventions are provided with an antioxidant, an antiblocking agent, a lubricant, a nucleating agent, an antistatic agent within a range not to impair the properties.
UV absorbers, weathering agents, antibacterial agents, petroleum resins, and the like may be added.

According to a twenty-second aspect of the present invention, there is provided a cooling roll, and a metal endless member abutting on the cooling roll via a resin sheet, wherein a resin sheet is provided between the cooling roll and the metal endless member. A method for manufacturing an opaque colored soft resin sheet using a manufacturing apparatus provided with an elastic material on the back side of the metal endless member at a portion where the resin sheet is introduced and cooled, wherein The opaque colored soft resin sheet according to any one of the first to twenty-first aspects is contacted with the cooling end and the metal endless member almost simultaneously at the same time. The opaque colored soft resin sheet is brought into contact with a sheet while being elastically deformed while being introduced between the member and the elastic material, and is cooled.

The resin sheet in the molten state is, for example, a resin sheet immediately after being extruded from a die of an extruder. As the material of the elastic material, fluorine-based rubber, silicone-based rubber, EPDM, or the like can be used. Further, the thickness of the elastic material is preferably 3 mm or more in order to obtain a good surface pressure by elastic deformation. The surfaces of the metal endless member and the roll that come into contact with the resin sheet are preferably mirror surfaces, for example, have a surface roughness of 0.5 S or less. As the material of the endless member, stainless steel, carbon steel, titanium alloy, or the like can be used. Although the thickness of the endless member is optional,
The strength is preferably 0.3 mm or more.

In the present invention, since the resin sheet is cooled by being pressed in a planar manner with the elastic deformation of the elastic material, the efficiency of cooling and mirror transfer is enhanced. Further, the resin sheet,
The metal endless member that is in contact with the cooling roll and the cooling roll and the metal endless member are brought into contact with the cooling roll at substantially the same time, thereby pressing and cooling the resin sheet. Can be performed simultaneously, and the transparency of the resin sheet can be increased. If the resin sheet is brought into contact with the metal endless member or the cooling roll first, the cooling and solidification of the resin sheet will proceed before the mirror surface transfer is performed on both surfaces of the sheet.

According to a twenty-third aspect of the present invention, in the method for manufacturing an opaque colored soft resin sheet according to the twenty-second aspect, the metal endless member is wound around at least two rolls, and the elastic material is It is characterized in that it is formed on the outer peripheral surface of the roll on the cooling roll side.
That is, in the present invention, the metal endless belt is a metal endless belt wound around at least two rolls. Note that a cooling roll or a tension adjusting roll may be provided in the metal endless belt as a roll other than the two rolls.

The method for manufacturing an opaque colored soft resin sheet according to the twenty-fourth aspect of the present invention is the method according to the eighteenth aspect, wherein the cooling roll is included so as to run in parallel with one of the metal endless members. An endless member is wound and the opaque colored soft resin sheet of any of the first to seventeenth inventions in a molten state is brought into contact with the one and the other metal endless members almost simultaneously, so that the two endless members are made of metal. The soft transparent resin sheet is pressed in a planar manner and cooled while elastically deforming the elastic material. That is, in the case of the present invention, cooling is performed by sandwiching an opaque colored soft resin sheet between two metal endless members.

According to a twenty-fifth aspect of the present invention, in the method for manufacturing an opaque colored soft resin sheet according to the twenty-second aspect, the elastic material is formed on an outer peripheral surface of a roll, and the metal endless member is provided on an outer periphery of the elastic material. The surface is formed in a cylindrical shape. That is, in the present invention, the metal endless member is formed as an outer layer of a roll.

The method for producing an opaque colored soft resin sheet according to the twenty-sixth aspect of the present invention is the method according to any of the twenty-second to twenty-fifth aspects, wherein the metal endless member and the cooling roll are in direct contact with the resin sheet. Dew point ~
The temperature is set to 50 ° C. When the temperature of the metal endless member and the roll for cooling the resin sheet is lower than the dew point, water droplets are generated on the sheet. Also,
If it exceeds 50 ° C., good transparency cannot be obtained. Preferably, it is 30 ° C. or lower.

The method for manufacturing an opaque colored soft resin sheet according to the twenty-seventh aspect of the present invention is the method according to any one of the twenty-second to twenty-sixth aspects, wherein the resin sheet is brought into planar contact with the elastic material by elastic deformation. Is characterized in that the surface pressure is 0.1 MPa to 20.0 MPa. If the surface pressure is lower than 0.1 MPa,
If the efficiency of mirror surface transfer and cooling is reduced, and if the surface pressure is higher than 20.0 MPa, the tension is increased in the case of an endless belt, which is not preferable in terms of life.

The method for producing an opaque colored soft resin sheet according to the twenty-eighth aspect of the present invention is the method according to any of the twenty-second to twenty-seventh aspects, wherein the elastic material has a hardness (based on JIS K6301 A type) of 95 degrees. It is characterized by the following. When the hardness is greater than 95 degrees, the elastic force is weakened, and a resin bank is likely to be formed when the resin sheet is brought into contact with the cooling roll and the metal endless member substantially simultaneously.

The method for producing an opaque colored soft resin sheet according to the twenty-ninth aspect of the present invention comprises a water basin having a slit through which cooling water flows, a water tank disposed below the water basin, and a water tank provided in the water tank. A method for manufacturing an opaque colored soft resin sheet using a manufacturing apparatus provided with a pair of rollers for pinching arranged at least partially submerged in water, wherein any one of the first to twenty-first inventions in a molten state The opaque colored soft resin sheet is cooled with cooling water while being passed through the slit, and then the resin sheet is introduced into the water of the water tank through the pair of rolls for pinching. The temperature of the cooling water is preferably 10 ° C. or less. Calcium chloride may be added to this water as needed.

The method for producing an opaque colored soft resin sheet according to the thirtieth invention of the present invention is characterized in that in any one of the twenty-second to twenty-ninth inventions, the obtained resin sheet is subjected to an annealing treatment. . The annealing treatment is performed, for example, at 80 to 130 ° C, preferably at 110 to 130 ° C. By this annealing treatment, the hardness of the sheet surface can be increased.

[0046]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [First Embodiment] An opaque colored soft resin sheet 11 according to the present embodiment and a method for manufacturing the same will be described with reference to FIG. First, the configuration of a manufacturing apparatus used in the manufacturing method of the present embodiment will be described. This manufacturing apparatus includes a T-die 12 of an extruder (not shown), a metal endless belt 15 wound between a first cooling roll 13 and a second cooling roll 14, a resin sheet 11, The third cooling roll 16 is in contact with the first cooling roll 13 via the metal endless belt 15, and the fourth cooling roll 17 is provided near the second cooling roll 14. .

The first cooling roll 13 has an outer peripheral surface coated with an elastic material 18 such as fluoro rubber. This elastic material
18, the hardness (according to JIS K6301 A type) is 95 degrees or less,
Thickness is 3 mm or more. The metal endless belt 15 is made of stainless steel or the like and has a mirror surface having a surface roughness of 0.5 S or less. First and second cooling rolls 13, 14
The rotation shaft 19 is connected to rotation driving means (not shown).

The third cooling roll 16 also has a surface roughness of 0.
It has a mirror surface of 5S or less. And this cooling roll 1
6 is provided so as to be in contact with the first cooling roll 13 via the resin sheet 11 and the metal endless belt 15 and to embrace the resin sheet 11 pressed by the endless belt 15 toward the cooling roll 16. . That is, the metal endless belt 15 and the resin sheet 11 in contact with the endless belt 15 meander so as to wind around a part of the outer peripheral surface of the third cooling roll 16. The fourth roll
17 is a case where the resin sheet 11 is the second through the endless belt 15.
This guides the resin sheet 11 so as to be pressed against the cooling roll 14.

Of the cooling rolls, the first and third cooling rolls 13 and 16 are provided with a temperature adjusting means (not shown) of a water-cooling type or the like which can adjust the surface temperature. The other cooling roll 14 is not particularly provided with a temperature adjusting means, but may be provided. As shown by a dashed line in FIG. 1, a cooling roll 31 is further provided before the first cooling roll 13 in the endless belt 15, and an upstream portion of the endless belt 15 reaching the first cooling roll 13 is provided. You may make it cool beforehand. The cooling roll 31 also functions for adjusting the tension of the endless belt 15.

Next, a method of manufacturing the opaque colored soft resin sheet 11 of this embodiment using the above-described manufacturing apparatus will be described.
First, the surface temperature of the metal endless belt 15 and the third cooling roll 16 which are in direct contact with the resin sheet 11 is 50 ° C. or less,
The temperature of each of the cooling rolls 13, 14, and 16 is controlled so as to maintain the temperature above the dew point.

After the raw material pellets containing the colorant are charged into the extruder and melt-kneaded, the molten resin sheet 11 extruded from the T-die 12 is transferred to the endless end contacting the first cooling roll 13. Belt 15 and third cooling roll 16
And between the first and third cooling rolls 13 and 16 so that the resin sheet 11 is pressed into contact with the first and third cooling rolls 13 and 16 at 50 ° C. or less. Cool. At this time, the elastic member 18 is provided with the first and third cooling rolls 13,1.
The elastic sheet 18 is elastically deformed so as to be compressed by the pressing force, and the resin sheet 11 is elastically deformed at the angle θ1 from the center of the rolls 13 and 16 where the elastic material 18 is elastically deformed.
6 is a planar pressure welding. The surface pressure at this time is 0.1MP
a to 20.0 MPa.

Subsequently, the resin sheet 11 is pressed against the third cooling roll 16 with the endless belt 15 having the mirror surface and cooled to 50 ° C. or less. The resin sheet 11 pressed by the endless belt 15 toward the cooling roll 16 is
Embraced by the cooling roll 16 at an angle θ2 from the center of 16
The resin sheet 11 is pressed in a planar manner by the endless belt 15 and the third cooling roll 16 at the holding angle θ2. The surface pressure at this time is 0.01 MPa to 0.5 MPa.

Next, the resin sheet 11 is transferred to the endless belt 15
When the endless belt 15 is rotated, the resin sheet 11 is moved to the second cooling roll 14 side together with the endless belt 15 so that the resin sheet 11 is moved through the endless belt 15 to the second cooling roll.
The opaque colored soft resin sheet 11 of the present embodiment is manufactured by pressing against 14 and cooling to 50 ° C. or less. When the resin sheet 11 is pressed toward the cooling roll 14 by the guide of the fourth roll 17, the resin sheet 11 is pressed in a plane at an angle θ3 from the center of the cooling roll 14 via the endless belt 15. ing. The surface pressure at this time is 0.01 MPa to 0.
5MPa. As shown by a two-dot chain line in FIG. 1, the resin sheet 11 may be cooled by the first and third cooling rolls 13 and 16 and then immediately peeled off from the endless belt 15 and taken off.

According to the present embodiment, the first and third rolls 13 in which the elastic material 18 is elastically deformed with respect to the molten resin sheet 11 extruded from the T-die 12 using the colored soft polyolefin resin as a raw material. The sheet 11 is pressed and cooled by the two rolls 13 and 16 at the angle θ1 of the angle θ and the metal endless belt 15 at the angle θ2.
After the sheet 11 is pressed and cooled by the third cooling roll 16 and the sheet 11 is pressed by the endless belt 15 and the second cooling roll 14 at the angle θ3 of the second cooling roll 14. To perform cooling, the obtained sheet 11 has the following characteristics (a to c).

(A) Tensile elastic modulus is 20 to 100 MPa (b) Surface roughness Ra of at least one surface is less than 0.05 μm

[Second Embodiment] An opaque colored soft resin sheet 11 according to the present embodiment and a method for manufacturing the same will be described with reference to FIG. The manufacturing apparatus used in the manufacturing method of the present embodiment is a metal endless belt according to the first embodiment, which is wound between a first cooling roll 13 and a second cooling roll 14 as a metal endless member. Instead of 15, a metal endless layer 20 is formed on the outer peripheral surface of the elastic member 18 of the first cooling roll 13.

In the manufacturing method using the apparatus of this embodiment, the first and second elastic members 18 are elastically deformed with respect to the molten resin sheet 11 extruded from the T-die 12 using a soft polyolefin resin as a raw material. 3 rolls 13, 16 angle θ1
In the part, the sheet 11 is pressed and cooled by the two rolls 13 and 16 so that the sheet having the characteristics (a, b) is obtained.
11 is obtained.

[Third Embodiment] An opaque colored soft resin sheet 11 according to the present embodiment and a method of manufacturing the same will be described with reference to FIG. First, the configuration of the manufacturing apparatus used in the present embodiment will be described. This manufacturing apparatus includes a T-die 12 of an extruder,
A first metal endless belt 23 wound between a first cooling roll 21 and a second cooling roll 22, and a winding between a third cooling roll 24 and a fourth cooling roll 25; The second
A metal endless belt 26, a fifth roll 27 provided near the fourth cooling roll 25, and an endless belt
Two pairs of rolls 28,2 provided as means for applying pressure to 23,26
9 is provided.

The first cooling roll 21 is coated on its surface with an elastic material 18 such as fluoro rubber. This elastic material 18
Has a hardness (based on JIS K6301 A type) of 95 degrees or less and a thickness of 3 mm or more. The first and second metal endless belts 23 and 26 are sandwiched between the first and second rolls 21 and 22 and between the third and fourth rolls 24 and 25 with the opaque colored soft resin sheet 11 interposed therebetween. It is provided to run side by side. These endless belts 23 and 26 are each made of stainless steel or the like, and have a mirror surface having a surface roughness of 0.5 S or less.

Two pairs of rolls 28 and 29 serving as the pressing means
The two endless belts 23, 26 are provided substantially between the first and second rolls 21, 22 and between the third and fourth rolls 24, 25.
Are provided so as to face each other. There is some space between the upper and lower rolls 28,29. Note that the paired rolls 28 and 29 may be arranged so as to be shifted from each other without facing each other. The fifth roll 27 guides the resin sheet 11 so that the resin sheet 11 is pressed against the fourth cooling roll 25 via the second endless belt 26. Each of the cooling rolls 21, 22, 24, and 25 is provided with a water-cooling type or the like temperature adjusting means (not shown) for adjusting the surface temperature.

Next, a method of manufacturing the opaque colored soft resin sheet 11 of this embodiment using the above-described manufacturing apparatus will be described.
First, the temperature of each of the cooling rolls 21, 22, 24, and 25 is controlled so that the surface temperature of the metal endless belts 23 and 26 that are in direct contact with the resin sheet 11 is maintained at 50 ° C. or less and above the dew point. Keep it.

Then, the molten resin sheet 11 extruded from the T die 12 of the extruder is brought into contact with the first metal endless belt 23 which is in contact with the first cooling roll 21 and the third cooling roll 24. The first and third cooling rolls 21 and 24 are introduced between the first and second metal endless belts 23 and 26 so as to substantially simultaneously contact the second metal endless belt 26 and the first and third cooling rolls 21 and 24. Then, the resin sheet 11 is pressed and cooled to 50 ° C. or less. At this time, the elastic member 18 is elastically deformed by being pressed by the pressing force between the first and third cooling rolls 21 and 24,
The resin sheet 11 is planarly pressed by the two rolls 21 and 24 at the angle θ1 from the center of the two rolls 21 and 24 where the elastic deformation 18 occurs. The surface pressure at this time is 0.1MPa ~
20.0MPa.

Subsequently, in a section where both endless belts 23 and 26 run in parallel, two pairs of rolls 28 and 2 serving as pressing means are provided.
9 Resin sheet 11 sandwiched between both endless belts 23, 26
And cooled to below 50 ° C. The resin sheet 11 sandwiched between the two endless belts 23 and 26 between the upper and lower rolls 28 and 29 is pressed in a planar manner by the pressing force of the pair of rolls 28 and 29. The surface pressure at this time is 0.01 MPa to 0.5 MPa.

Next, the opaque colored soft resin sheet 11 is moved to the second and fourth cooling rolls 22 and 25 together with the rotation of the endless belts 23 and 26, and the resin sheet 11 is moved to the second endless belt 26. To cool it to 50 ° C. or lower by pressing against the fourth cooling roll 25. The polyolefin resin sheet 11 guided by the fifth roll 27 and pressed toward the cooling roll 25 has an angle θ3 from the center of the cooling roll 25.
The portion is pressed against the endless belt 26 in a planar manner. The surface pressure at this time is 0.01 MPa to 0.5 MPa.

According to the present embodiment, the surface of the sheet 11 by the endless belts 23 and 26 and the rolls 21 and 24 and the endless belts 23 and 26 at the angle θ1 of the first and third rolls 21 and 24 where the elastic member 18 is elastically deformed. Two pairs of rolls for pressing and cooling and pressing means
Sheet pressure welding and cooling of sheet 11 between 28 and 29 and angle θ
The second metal endless belt 26 in three parts and the fourth
The sheet 11 having the above-mentioned characteristics (a, b) is obtained by the planar pressing and cooling of the sheet 11 by the cooling roll 25 described above.

[Fourth Embodiment] The configuration of the apparatus used in the manufacturing method according to the present embodiment is the same as that of the first embodiment. The method of manufacturing the opaque colored soft resin sheet 11 using this manufacturing apparatus is the same as in the first embodiment, except that a pellet made of a soft polypropylene-based resin, A pellet in which one of hydrogenated SBR, ethylene-α-olefin copolymer, and ethylene-octene copolymer is blended is prepared.

According to this embodiment, a soft polypropylene-based resin, or hydrogenated SBR, ethylene-α
An elastic material 18 is elastically deformed with respect to a resin sheet 11 extruded from a T-die 12 using a mixture of one of an olefin copolymer and an ethylene-octene copolymer as a raw material. The sheet 11 is pressed and cooled by the two rolls 13 and 16 at the angle θ1 of the third rolls 13 and 16, and then the sheet 11 is formed by the metal endless belt 15 and the third cooling roll 16 at the angle θ2. After the planar pressing and cooling of the second cooling roll 14, the angle θ3
The endless belt 15 and the second cooling roll 14
Thus, the resin sheet 11 can be manufactured at a high speed because the sheet 11 is pressed in a plane and cooled.

[Fifth Embodiment] A method for manufacturing an opaque colored soft resin sheet 11 according to this embodiment will be described with reference to FIG. First, the configuration of the manufacturing apparatus used in the present embodiment will be described. This device comprises an extruder T-die 12, a basin 31,
The water basin 31 is provided with a water tank 32 disposed below the water basin 31 and a pair of rolls 33 for sheet pressing arranged in the water tank 32. Further, guide rolls 34 for guiding the resin sheet 11 are arranged in the water tank 32 and in the vicinity of the water tank 32.

The basin 31 has a slit 35 formed at the center thereof, through which cooling water flows. The length of the slit 35 is slightly larger than the width of the resin sheet 11.
The pair of rolls 33 are arranged such that both rolls 33 are opposed to each other, and a gap between these rolls 33 is located below the slit 35. These rolls 33 are arranged so that about half of them are immersed in water 36 in the water tank 32. Using this apparatus, an opaque colored soft resin sheet 11 is manufactured as follows.

While the molten resin sheet 11 extruded from the T-die 12 of the extruder is passed through the slit 35, water for cooling
Cool at 36. Subsequently, the resin sheet 11 is introduced into the water 36 of the water tank 32 through a pair of rollers 33 for pinching, and is drawn out of the water tank 32 via the guide rolls 34.

The resin sheet 11 obtained in the first to fourth embodiments may be subjected to an annealing treatment. This annealing treatment can be performed via a heating roll or a belt wound between the heating rolls.
The number of these heating rolls or heating rolls is arbitrary. Alternatively, the same processing as in the first embodiment may be performed on the resin sheet 11 in a molten state by heating the resin sheet 11.

[0072]

EXAMPLES Examples 1 to 17 In the first embodiment, the opaque colored soft resin sheet 11 was manufactured by changing the specific examples, the mixing ratios, and the like of the sheet raw materials in each example as follows. The resin sheets 11 of Examples 1 to 8 have a single-layer structure.
Table 1 shows the characteristics (a, b) of the resin sheet 11 of each embodiment. Extruder diameter ... 90mm. T die width… 800mm. Elastic material: Material: silicone rubber, thickness: 10 mm, hardness: 30
Every time.

Sheet take-off speed: 16 m / min. Surface temperature of the endless belt and roll in contact with the sheet: 20 ° C. Soft polyolefin-based resin of Example 1: low stereoregular homopolypropylene (MI: 3.1 g / 10 min, density: 0.90 g / cm)
³ , Tensile modulus: 500MPa, PI: 76%, rrrr / (1-mmm
m): 24.2%, boiling heptane insolubles: 90 wt%). TPO E-2900 (trade name) manufactured by Idemitsu Petrochemical Co., Ltd. Sheet thickness: 0.2mm. Colorant: 5 parts of PEX3203 Green manufactured by Tokyo Ink Co., Ltd. (pigment master batch, the same applies hereinafter).

The soft polyolefin resin of Example 2 was synthesized using a multi-stage polymerization reactor, and an ethylene-propylene copolymer having a form in which about 43 wt% of an ethylene-propylene rubber (EPR) component was uniformly and finely dispersed ( MI: 0.
84 g / 10 min, density: 0.89 g / cm ^3, tensile modulus: 150MP
a). Highmont Cataloy KS-082P (trade name).
Sheet thickness: 0.3mm. Colorant: 5 parts of PEX3161 Blue manufactured by Tokyo Ink Co., Ltd.

The soft polyolefin resin of Example 3 was synthesized using a multi-stage polymerization reactor, and had a EPR of about 50 wt%.
Ethylene-propylene copolymer having a form in which the components are uniformly finely dispersed (MI: 0.60 g / 10 min, density: 0.89 g / cm ³ ,
Tensile modulus: 100 MPa). Cataloy KS-052P (trade name) manufactured by Himont Corporation. Sheet thickness: 0.3mm. Colorant: 5 parts of PEX3022 Red manufactured by Tokyo Ink Co., Ltd. The soft polyolefin resin of Example 4: ethylene 20 wt%
Ethylene-propylene random copolymer (MI: 1.50 g / 10 min, density: 0.88) in which a soft segment and a hard segment are formed in a one-stage reactor from propylene and 80 wt% of propylene
g / cm ³ , tensile modulus: 100 MPa). Tokuyama Corporation
PER T-310E (product name). Sheet thickness: 0.2mm. Colorant: 5 parts of PEX3161 Blue manufactured by Tokyo Ink Co., Ltd.

Soft polyolefin resin of Example 5: An ethylene-propylene random copolymer (M) synthesized from 10% by weight of ethylene and 90% by weight of propylene in the same manner as in Example 4.
I: 1.50 g / 10 min, density: 0.88 g / cm ³ , tensile modulus: 12
0MPa). PER T-310J (trade name) manufactured by Tokuyama Corporation. Sheet thickness: 0.2mm. Colorant: PEX197101 White5 manufactured by Tokyo Ink Co., Ltd.
Department. The soft polyolefin resin of Example 6: 70% by weight of the same low stereoregular homopolypropylene as in Example 1 and 30% by weight of hydrogenated styrene / butadiene rubber (Dynalon 1320P, trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.) were blended. Resin composition. Sheet thickness: 0.3mm. Colorant: PEX197101 White5 manufactured by Tokyo Ink Co., Ltd.
Department.

The soft polyolefin resin of Example 7: 80 wt% of low stereoregular homopolypropylene as in Example 1.
And 20 wt% of ethylene-propylene rubber (EPR) (Tuffmer P0280, trade name, manufactured by Mitsui Petrochemical Co., Ltd.). Sheet thickness: 0.3mm. Colorant: PEX197101 White5 manufactured by Tokyo Ink Co., Ltd.
Department. Soft polyolefin resin of Example 8: 85 wt% of low stereoregular homopolypropylene as in Example 1 and ethylene
A resin composition blended with 15 wt% of an octene copolymer (Engage EG-8200, trade name, manufactured by Dow Chemical Co., Ltd.). Sheet thickness: 0.3mm. Colorant: PEX197101 White5 manufactured by Tokyo Ink Co., Ltd.
Department.

The resin sheets 11 of Examples 9 to 11 have a two-layer structure. Soft polyolefin resin in one layer of Example 9: low-pressure linear low-density polyethylene (L-LDPE, MI: 3)
g / 10 min, density: 0.907 g / cm ³ ). Moretec V-0398CN (trade name) manufactured by Idemitsu Petrochemical Co., Ltd. Thickness ... 120 μm. Resin of the other layer in Example 9: a hard polypropylene resin. F-704NP (trade name) manufactured by Idemitsu Petrochemical Co., Ltd. Thickness… 80μm. Soft polyolefin resin in one layer of Example 10: an ethylene-octene copolymer having a long chain branch in the main chain polymerized using a metallocene geometrically constrained catalyst (MI: 1 g /
10 minutes, density: 0.902 g / cm ³ ). Dow Plastomer Affinity PL1880 (trade name). Thickness: 120 μm. Resin of the other layer of Example 10: Hard polypropylene resin. F-704NP (trade name) manufactured by Idemitsu Petrochemical Co., Ltd. Thickness… 80μm.

Soft polyolefin resin in one layer of Example 11: an ethylene-octene copolymer having a long chain branch in the main chain polymerized using a metallocene-based geometrically constrained catalyst (MI: 1 g / 10 min, Density: 0.902 g / cm ³ ). Dow Plastomer Affinity PL1880 (trade name). thickness…
160 μm. Resin of the other layer of Example 11: Hard polypropylene-based resin. F-704NP (trade name) manufactured by Idemitsu Petrochemical Co., Ltd. Thickness… 40μm. The colorants used in Examples 9 to 11 were the same as the colorants in Example 5, and were included in each layer.

The resin sheets 11 of Examples 12 to 17 have a three-layer structure. Soft polyolefin resin in the middle layer of Examples 12 to 14: an amorphous polyolefin synthesized by random copolymerization of butene-1 (35 wt%) and propylene (65 wt%) (density: 0.1
86 g / cm ³ , melt viscosity at 190 ° C .: 10,000 cps) 50 wt%, crystalline polypropylene (MI: 1.00 g / 10 min, density: 0.90 g /
cm ³ ) 50 wt% and a resin composition (tensile modulus: 100 MPa). CAP-355Y (trade name) manufactured by Ube Lexen Co., Ltd. The thickness of the middle layer ... 0.16mm. Resin of both surface layers of Examples 12 to 14: Hard polypropylene resin. F-704NP (trade name) manufactured by Idemitsu Petrochemical Co., Ltd. Thickness of each surface layer ... 0.02mm. The same colorant as in Example 5 was added to both surface layers (PP layers) of Examples 12 to 14 by 10 parts.

Soft polyolefin resin for the intermediate layer of Example 15: high-pressure low-density polyethylene (LDPE, MI: 4)
g / 10 min, density: 0.921 g / cm ³ ). Petrocene 190 (trade name) manufactured by Tosoh Corporation. The thickness of the middle layer ... 0.16mm. As the colorant, 10 parts of the same colorant as in Example 1 were added only to the intermediate layer. Resin of both surface layers of Example 15: random polypropylene (ethylene-propylene random copolymer, ethylene content: 4 wt%, MI: 11 g / 10 min). Grand Polypro S235 (trade name) manufactured by Grand Polymer Co., Ltd. Thickness of each surface layer ... 0.02mm. The same coloring agent as in Example 2 was used for the intermediate layer and both surface layers.
I put it in.

Soft polyolefin resin for the intermediate layer of Example 16: low-pressure linear low-density polyethylene (L-LDP)
E, MI: 3 g / 10 min, density: 0.907 g / cm ³ ). Moretec V-0398CN (trade name) manufactured by Idemitsu Petrochemical Co., Ltd. The thickness of the middle layer ... 0.16mm. Resin for both surface layers of Example 16: random polypropylene (ethylene-propylene random copolymer, ethylene content: 4 wt%, MI: 11 g / 10 min). Grand Polypro S235 (trade name) manufactured by Grand Polymer Co., Ltd. Thickness of each surface layer ... 0.02mm. As the coloring agent, 10 parts of the same colorant as in Example 5 were put only in the intermediate layer.

Soft polyolefin resin in the intermediate layer of Example 17: an ethylene-octene copolymer having a long chain branch in the main chain polymerized using a metallocene-based geometrically constrained catalyst (MI: 1 g / 10 min, density: : 0.902 g / cm ³ ). Dow Plastomer Affinity PL1880 (trade name). The thickness of the middle layer ... 0.16mm. Resin of both surface layers of Example 17: random polypropylene (ethylene-propylene random copolymer, ethylene content: 4 wt%, MI: 7 g / 10 min). F-744NP (trade name) manufactured by Idemitsu Petrochemical Co., Ltd. Thickness of each surface layer ... 0.02mm. As the coloring agent, 10 parts of the same colorant as in Example 5 were put only in the intermediate layer.

[Comparative Examples 1 and 2] A resin sheet was manufactured by a conventional touch roll type sheet forming method using a cooling roll. The temperature of the chill roll is 40 ° C. In the case of Comparative Example 1, the raw material resin is the same as in Example 1. In the case of Comparative Example 2, it has the same three-layer structure as in Example 15, and the same raw material resin. The same coloring agent as in Example 5 was used in Comparative Example 1, and 10
In Comparative Example 2, 10 parts were put in the intermediate layer.

[Evaluation of Characteristics] With respect to the resin sheets obtained in Examples 1 to 17 and Comparative Examples 1 and 2, the tensile modulus, surface roughness and gloss were measured. The results are shown in Tables 1 and 2.

The tensile modulus was measured according to JIS K-7113. The surface roughness was measured according to JIS B 0610-1982. As the measuring device, an electron beam three-dimensional roughness analyzer (ERA-4000) manufactured by Elionix, Inc. was used.
The image was observed at a magnification of × 00, and fine irregularities on the sample surface were measured with an electron probe to calculate the center plane average roughness Ra.
This measurement was performed on the inner surface side and the outer surface side of the rolled sheet.

The gloss was measured by irradiating the sheet with light at an incident angle of 60 degrees using an automatic colorimeter (for example, AUD-CH-2 type-45, 60, manufactured by Suga Test Instruments Co., Ltd.). Similarly, when the reflected light is received at 60 degrees, the reflected light flux ψs is measured, and the refractive index is 1.
The ratio of the reflected light flux ψos from the glass surface of 567 to
It was determined as follows. Gross (Gs) = (ψs / ψos) × 100

[0088]

[Table 1]

[0089]

[Table 2]

As shown in Table 1, the opaque colored soft resin sheet 11 according to Examples 1 to 8 is made of a soft polyolefin resin having the above-mentioned characteristics (a, b), so that the gloss is high and the gloss is good. You can see that. In addition, Examples 9 to
According to the opaque colored soft resin sheet 11 according to 17, it can be seen that similar good characteristics can be obtained even when at least one of the surface layers has a multilayer structure made of a hard polypropylene resin. Further, the opaque colored soft resin sheet 11 having the properties (a, b) can be manufactured by the manufacturing method according to the present invention.

On the other hand, from Table 2, according to Comparative Examples 1 and 2,
It can be seen that the obtained resin sheet has low gloss and poor gloss. Comparative Example 1 has a high tensile modulus and is inferior in flexibility.

[Examples 18 to 21] In the second embodiment, the resin sheet 11 was manufactured by changing the specific examples, the mixing ratios and the like of the sheet raw materials of the respective examples as follows. Examples 18 to 21
The resin sheet 11 has a three-layer structure. Table 3 shows the characteristics (a, b) of the resin sheet 11 of each embodiment. The specific conditions for the manufacture are the same as in Example 1. The resin of the intermediate layer and both surface layers of Example 18 is the same as that of Example 12.
The resin of the intermediate layer and both surface layers of Example 19 is the same as that of Example 15. The resin of the intermediate layer and both surface layers of Example 20 is the same as that of Example 16 described above. The resin of the intermediate layer and both surface layers of Example 21 is the same as that of Example 17 described above. The coloring agent and the compounding amount thereof in each embodiment are the same as those of the corresponding embodiment.

Comparative Examples 3 and 4 Resin sheets were produced in the same manner as in Comparative Example 1. The configuration of the resin sheet and the resin composition according to Comparative Examples 3 and 4 are the same as those in Comparative Examples 1 and 2. Further, the coloring agents and the amounts of the coloring agents of each comparative example are the same as those of the corresponding comparative example.

[Evaluation of Characteristics] With respect to the resin sheets obtained in Examples 18 to 21 and Comparative Examples 3 and 4, the tensile modulus, surface roughness and gloss were measured. The results are shown in Tables 3 and 4.

[0095]

[Table 3]

[0096]

[Table 4]

According to Table 3, according to the opaque colored soft resin sheet 11 having a three-layer structure according to Examples 18 to 21, the characteristics (a,
b) is made of a soft polyolefin resin having
It can be seen that the gloss is high and the gloss is good. Also,
The opaque colored soft resin sheet 11 having the above characteristics (a, b) can be manufactured by the manufacturing method according to the present invention.

On the other hand, from Table 4, according to Comparative Example 3, the raw materials were the same as in Example 18, but a resin sheet was manufactured by a touch-roll-type sheet molding method, and the obtained resin sheet had a gloss. It can be seen that the gloss was low and the gloss was poor. Further, it has a high tensile modulus and is inferior in flexibility. According to Comparative Example 4, since the resin sheet was manufactured by the touch-roll-type sheet forming method, the obtained resin sheet had low gloss and poor gloss.

[Examples 22 to 25] In the third embodiment, the resin sheet 11 was manufactured by changing the specific examples, the mixing ratios, and the like of the sheet raw materials of the respective examples as follows. Examples 22 to 25
The resin sheet 11 has a three-layer structure. Table 5 shows the characteristics (a, b) of the resin sheet 11 of each embodiment. The specific conditions for the manufacture are the same as in Example 1. The resin of the intermediate layer and both surface layers of Example 22 is the same as that of Example 12.
The resin for the intermediate layer and both surface layers in Example 23 is the same as that in Example 15 described above. The resin of the intermediate layer and both surface layers of Example 24 is the same as that of Example 16 described above. The resin for the intermediate layer and both surface layers in Example 25 is the same as that in Example 17 described above. The coloring agent and the compounding amount thereof in each embodiment are the same as those of the corresponding embodiment.

Comparative Examples 5 and 6 Resin sheets were produced in the same manner as in Comparative Example 1. The configurations of the resin sheets and the compositions of the resins according to Comparative Examples 5 and 6 are the same as Comparative Examples 1 and 2. Further, the coloring agents and the amounts of the coloring agents of each comparative example are the same as those of the corresponding comparative example.

[Evaluation of Properties] The tensile modulus, surface roughness and gloss of the resin sheets obtained in Examples 22 to 25 and Comparative Examples 5 and 6 were measured. The results are shown in Tables 5 and 6.

[0102]

[Table 5]

[0103]

[Table 6]

According to Table 5, according to the opaque colored soft resin sheet 11 having a three-layer structure according to Examples 22 to 25, the characteristics (a,
b) is made of a soft polyolefin resin having
It can be seen that the gloss is high and the gloss is good. Also,
It can be seen that the tensile modulus is low and the flexibility is high. Further, by the manufacturing method according to the present invention, the characteristics (a,
The opaque colored soft resin sheet 11 having b) can be manufactured. On the other hand, from Table 6, according to Comparative Examples 5 and 6,
The obtained resin sheet has low gloss and poor gloss. Comparative Example 5 has a high tensile modulus and is inferior in flexibility.

[Examples 26 to 34] In the fourth embodiment, the resin sheet 11 was manufactured by changing the specific examples, the mixing ratios and the like of the sheet raw materials of the respective examples as follows. Table 7 shows the characteristics (a, b) of the resin sheet 11 of each embodiment.
The specific conditions for the manufacture are the same as in Example 1. Further, the added colorant and the compounding amount thereof are also the same as in Example 1.

The resin sheets 11 of Examples 26 to 33 have a single-layer structure. Soft polypropylene resin of Example 26: low stereoregularity homopolypropylene (MI: 3.1 g / 10 min, density: 0.90 g / c)
m ³ , Tensile modulus: 500 MPa, boiling heptane insolubles: 90 wt
%). TPO E-2900 (trade name) manufactured by Idemitsu Petrochemical Co., Ltd.
Resin sheet thickness: 0.2mm. Soft polypropylene resin of Example 27: an ethylene-propylene copolymer (MI: 0.84) synthesized using a multi-stage polymerization reactor and having a form in which about 43 wt% of an ethylene-propylene rubber (EPR) component is uniformly finely dispersed. g / 10 min, density: 0.89 g / cm ³ , tensile modulus: 150 MPa). Highmont Cataloy KS-082P (trade name).

The soft polypropylene-based resin of Example 28 was synthesized using a multi-stage polymerization reactor and had an EPR of about 50 wt%.
Ethylene-propylene copolymer having a form in which the components are uniformly finely dispersed (MI: 0.60 g / 10 min, density: 0.89 g / cm ³ ,
Tensile modulus: 100 MPa). Cataloy KS-052P (trade name) manufactured by Himont Corporation. Soft polypropylene resin of Example 29: ethylene 20 wt%
Ethylene-propylene random copolymer (MI: 1.50 g / 10 min, density: 0.1) in which a soft segment and a hard segment are formed in a single-stage reactor from propylene and 80 wt% of propylene.
88 g / cm ³ , tensile modulus: 100 MPa). PER T-310E (trade name) manufactured by Tokuyama Corporation.

Soft polypropylene resin of Example 30: An ethylene-propylene random copolymer (M) synthesized in the same manner as in Example 18 from 10 wt% of ethylene and 90 wt% of propylene
I: 1.50 g / 10 min, density: 0.88 g / cm ³ , tensile modulus: 12
0MPa). PER T-310J (trade name) manufactured by Tokuyama Corporation. Soft polypropylene resin of Example 31: 70 wt% of low stereoregular homopolypropylene as in Example 1 and 30 wt% of hydrogenated styrene / butadiene rubber (Dynalon 1320P, trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.) were blended. Resin composition.

The soft polypropylene resin of Example 32: 80% by weight of low stereoregular homopolypropylene as in Example 26
And 20 wt% of ethylene-propylene rubber (EPR) (Tuffmer P0280, trade name, manufactured by Mitsui Petrochemical Co., Ltd.). The soft polypropylene-based resin of Example 33: 85% by weight of the same low stereoregular homopolypropylene as in Example 15,
A resin composition blended with 15% by weight of an octene copolymer (Engage EG-8200, trade name, manufactured by Dow Chemical Co., Ltd.).

The resin sheet 11 of Example 34 has a three-layer structure. Soft polypropylene resin in the middle layer of Example 34: an amorphous polyolefin synthesized by random copolymerization of butene-1 (35 wt%) and propylene (65 wt%) (density: 0.86 g /
cm ³ , melt viscosity at 190 ° C .: 10000 cps) 50 wt%, crystalline polypropylene (MI: 1.00 g / 10 min, density: 0.90 g / cm)
³ ) A resin composition blended with 50% by weight (tensile modulus: 100 MPa). Ube Lexen CAP-355 (trade name). Thickness: 160 μm. Resin for both surface layers of Example 34: Hard polypropylene resin. F-704NP (trade name) manufactured by Idemitsu Petrochemical Co., Ltd. Thickness of each surface layer: 20 μm.

Comparative Examples 7 and 8 Resin sheets were produced in the same manner as in Comparative Example 1. The configuration of the resin sheet and the resin composition according to Comparative Examples 7 and 8 are the same as those in Comparative Examples 1 and 2.

[Evaluation of Characteristics] With respect to the resin sheets obtained in Examples 26 to 34 and Comparative Examples 7 and 8, the tensile modulus, surface roughness and gloss were measured. The results are shown in Tables 7 and 8.

[0113]

[Table 7]

[0114]

[Table 8]

According to Table 7, according to Examples 26 to 30, the resin sheet 11 extruded from the extruder using the soft polypropylene resin as a raw material was cooled by the above-mentioned manufacturing apparatus. 11 indicates that the gloss is high and the gloss is good. In addition, the tensile modulus is low,
It turns out that it is rich in flexibility.

According to Example 31, since a resin composition comprising a soft polypropylene-based resin and hydrogenated SBR was similarly produced as a raw material, the obtained resin sheet 11 has a low haze and a high gloss. According to Example 32, a resin composition composed of a soft polypropylene-based resin and an ethylene-α-olefin copolymer was similarly used as a raw material, and thus it was found that the obtained resin sheet 11 had a high gloss. In addition, it has a low tensile modulus and a high flexibility.

According to Example 33, a resin composition comprising a soft polypropylene-based resin and an ethylene / octene copolymer was similarly used as a raw material, and thus the obtained resin sheet was obtained.
11 indicates that the gloss is high. In addition, it has a low tensile modulus and a high flexibility. According to Example 34, even in the case of a three-layer structure in which both surface layers are made of a hard polypropylene resin, the gloss and the tensile modulus are good.

On the other hand, from Table 8, according to Comparative Example 7, the raw materials were the same as in Example 1, but the resin sheet was manufactured by a touch-roll type sheet forming method. Low and poor gloss. According to Comparative Example 8, since the resin sheet was manufactured by the touch-roll-type sheet forming method, the obtained resin sheet had low gloss and poor gloss.

[Examples 35 to 37] In the above-described fourth embodiment, a resin sheet 11 was manufactured by changing the specific examples, the mixing ratios, and the like of the sheet raw materials in each example as follows. Table 9 shows the characteristics (a, b) of the resin sheet 11 of each embodiment.
The specific conditions for the manufacture are the same as in Example 1. Cooling water 36
Is 6 ° C.

The soft polypropylene resin of Example 35 was
This is the same as Example 17. The same applies to the coloring agent and the amount thereof. In Example 36, the endless belt 15 of the first embodiment was used.
Was heated to 100 ° C., and the resin sheet 11 obtained in Example 35 was annealed with the endless belt 15. In Example 37, the endless belt of the third embodiment was used.
23, 26 were heated to 100 ° C., and the resin sheet 11 obtained in Example 35 was annealed by these endless belts 23, 26.

[Examples 38 and 39] In Example 38, the endless belt 15 of the first embodiment was heated to 80 ° C., and the endless belt 15 of the resin sheet 11 obtained in Example 17 was heated.
Was subjected to an annealing treatment. In Example 39, the endless belts 23, 26 of the third embodiment were heated to 100 ° C., and the resin sheet 11 obtained in Example 17 was annealed by these endless belts 23, 26.

[Evaluation of Characteristics] With respect to the resin sheets 11 obtained in Examples 35 to 39, the tensile elastic modulus, the surface roughness, and the gloss were measured. Table 9 shows the results.

[0123]

[Table 9]

From Table 9, it can be seen that the opaque colored soft resin sheets obtained in Examples 35 to 39 are made of a soft polyolefin resin having the above-mentioned properties (a, b), and therefore have high gloss and good gloss. I understand. Further, it can be seen that the tensile modulus is low and the flexibility is high. Further, the opaque colored soft resin sheet 11 having the above characteristics (a, b) can be manufactured by the manufacturing method according to the present invention.

[0125]

According to the opaque colored soft resin sheet of the present invention, it is safe for the environment and has excellent optical and mechanical properties. Further, according to the production method of the present invention, the opaque colored soft resin sheet can be produced without reducing gloss.

[Brief description of the drawings]

FIG. 1 is a schematic view of a manufacturing apparatus used in a method for manufacturing an opaque colored soft resin sheet according to a first embodiment of the present invention.

FIG. 2 is a schematic view of a manufacturing apparatus used in a method for manufacturing an opaque colored soft resin sheet according to a second embodiment of the present invention.

FIG. 3 is a schematic view of a manufacturing apparatus used in a method of manufacturing an opaque colored soft resin sheet according to a third embodiment of the present invention.

FIG. 4 is a schematic view of a manufacturing apparatus used in a method for manufacturing an opaque colored soft resin sheet according to a fourth embodiment of the present invention.

[Explanation of symbols]

 11 resin sheet 13 first cooling roll 14 second cooling roll 15 metal endless belt 16 third cooling roll 17 fourth cooling roll 18 elastic material 22 metal endless layer 31 basin 32 water tank

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23/16 C08L 23/16 // B29K 23:00 B29L 7:00 9:00

Claims (30)

[Claims] 1. An opaque colored soft resin sheet comprising at least one layer made of a soft polyolefin-based resin and having the following properties (a) and (b). (A) Tensile modulus of elasticity is 20 to 100 MPa (b) Surface roughness Ra of at least one surface is less than 0.05 μm 2. The opaque colored soft resin sheet according to claim 1, wherein, as the soft polyolefin-based resin, a ratio of mmmm in a pentad fraction (PI) measured for stereoregularity of homopolypropylene using 13C-NMR. Value) is 50
An opaque colored soft resin sheet characterized by using a low stereoregularity polypropylene resin having a content of up to 90%. 3. The opaque colored soft resin sheet according to claim 2, wherein rrrr / (1-mmm) of the low stereoregularity polypropylene resin.
An opaque colored soft resin sheet, wherein the value of m) is 15 to 50%. 4. The opaque colored soft resin sheet according to claim 3, wherein the low stereoregularity polypropylene resin is a boiling heptane-insoluble polypropylene resin having an intrinsic viscosity [η] of 0.5 to 9.0 dl / g. (50-95wt%) and intrinsic viscosity [η] 1.2dl /
An opaque colored soft resin sheet, characterized by comprising a boiling heptane-soluble polypropylene resin (5 to 50% by weight) of at least g. 5. The opaque colored soft resin sheet according to claim 1, wherein the soft polyolefin resin is an ethylene-propylene random copolymer (ethylene content: 5 to 30% by weight).
An opaque colored soft resin sheet characterized by using: 6. The opaque colored soft resin sheet according to claim 5, wherein four continuous units of ethylene (E) and propylene (P) are provided.
An opaque colored soft resin sheet in which PPEP has an extremely small proportion of an ethylene-propylene random copolymer having a racemic configuration with respect to a continuous portion of PP. 7. The opaque colored soft resin sheet according to claim 1, wherein the soft polyolefin resin is amorphous butene.
An opaque colored soft resin sheet characterized by using a 1-propylene copolymer. 8. The opaque colored soft resin sheet according to claim 1, wherein the soft polyolefin resin is amorphous butene.
An opaque colored soft resin sheet characterized by using a mixture of 1-propylene copolymer and polypropylene. 9. The opaque colored soft resin sheet according to claim 1, wherein a propylene-ethylene-butene-1 copolymer is used as the soft polyolefin-based resin. 10. The opaque colored soft resin sheet according to claim 1, wherein a mixture of a propylene-ethylene-butene-1 copolymer and polypropylene is used as the soft polyolefin-based resin. Resin sheet. 11. The opaque colored soft resin sheet according to claim 1, wherein the soft polyolefin-based resin is a polypropylene-based resin containing a reactor blend type ethylene-propylene copolymer elastomer. Colored soft resin sheet. 12. The opaque colored soft resin sheet according to claim 1, wherein the soft polyolefin resin is a polypropylene resin containing a reactor blend type ethylene-propylene-butene-1 copolymer. Colored soft resin sheet. 13. The opaque colored soft resin sheet according to claim 1, wherein as the soft polyolefin resin, at least one selected from ethylene homopolymer and ethylene-α-olefin copolymer is used. Colored soft resin sheet. 14. The opaque colored soft resin sheet according to claim 13, wherein the ethylene homopolymer is at least one selected from a high-pressure low-density polyethylene and a low-pressure low-density polyethylene. Opaque colored soft resin sheet. 15. The opaque colored soft resin sheet according to claim 13, wherein the ethylene-α-olefin copolymer is a Ziegler-Natta catalyst linear low density polyethylene, a metallocene catalyst linear low density polyethylene, An opaque colored soft resin sheet, which is at least one of ethylene-octene copolymers having a long-chain branch in a main chain polymerized by using a metallocene-based geometrically constrained catalyst. 16. The opaque colored soft resin sheet according to claim 1, wherein the flexible polyolefin resin is a copolymer of ethylene and a polar group-substituted ethylene. 17. The opaque colored soft resin sheet according to claim 16, wherein the copolymer of ethylene and the polar group-substituted ethylene is ethylene-vinyl acetate copolymer (EVA) or ethylene-ethyl acrylate copolymer. (EEA), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMMA), ethylene-methyl acrylate copolymer (EMA), ethylene-methacrylic acid copolymer (E
An opaque colored soft resin sheet, which is at least one selected from a metal ion crosslinked product of MAA) and a metal ion crosslinked product of ethylene-acrylic acid copolymer (EAA). 18. An opaque colored soft resin sheet comprising a soft polypropylene resin. 19. The opaque colored soft resin sheet according to claim 18, wherein 2-30% by weight of hydrogenated styrene / butadiene rubber is blended. 20. The opaque colored soft resin sheet according to claim 18, wherein the ethylene-α-olefin copolymer is blended in an amount of 2 to 30% by weight. 21. The opaque colored soft resin sheet according to claim 18, wherein an ethylene / octene copolymer is blended in an amount of 2 to 15% by weight. 22. A cooling roll, and a metal endless member abutting on the cooling roll via a resin sheet, wherein the resin sheet is introduced between the cooling roll and the metal endless member, and 22. A method of manufacturing an opaque colored soft resin sheet using a manufacturing apparatus provided with an elastic material on a back side of the metal endless member at a portion where the metal is cooled, wherein the sheet is in a molten state. The opaque colored soft resin sheet according to any one of the above, the metal endless member in contact with the cooling roll, and between the cooling roll and the metal endless member so as to contact the cooling roll almost simultaneously. Introducing, the opaque colored soft resin sheet characterized in that the elastic material is elastically deformed and the opaque colored soft resin sheet is pressed in a planar shape and cooled. Production method. 23. The method for producing an opaque colored soft resin sheet according to claim 22, wherein the metal endless member is wound between at least two rolls, and the elastic material is one of the rolls. A method for producing an opaque colored soft resin sheet, which is formed on an outer peripheral surface on a cooling roll side. 24. The method for manufacturing an opaque colored soft resin sheet according to claim 22, wherein the other metal endless member including the cooling roll is wound so as to run in parallel with one of the metal endless members. The opaque colored soft resin sheet according to any one of claims 1 to 21, which is in a molten state, is introduced between the two metal endless members so as to contact the one and other metal endless members substantially simultaneously. A method of manufacturing an opaque colored soft resin sheet, wherein the opaque colored soft resin sheet is cooled while being pressed in a planar manner while elastically deforming the elastic material. 25. The method for manufacturing an opaque colored soft resin sheet according to claim 21, wherein the elastic material is formed on an outer peripheral surface of a roll, and the metal endless member is formed in a cylindrical shape on the outer peripheral surface of the elastic material. A method for producing an opaque colored soft resin sheet, characterized by being formed. 26. The method for manufacturing an opaque colored soft resin sheet according to claim 22, wherein the temperature of the metal endless member and the temperature of the cooling roll that are in direct contact with the resin sheet are set to a dew point of 50 to 50. C., a method for producing an opaque colored soft resin sheet. 27. The method for producing an opaque colored soft resin sheet according to claim 22, wherein the surface pressure at the time of pressing the resin sheet in a planar manner with the elastic deformation of the elastic material is 0.1 MPa. To 20.0 MPa. 28. The method for producing an opaque colored soft resin sheet according to claim 22, wherein the elastic material has a hardness (based on JIS K6301A type) of 95.
The method for producing an opaque colored soft resin sheet, wherein the temperature is not more than the degree. 29. A water basin having a slit through which cooling water flows, a water tub disposed below the water basin, and a pair of pressure-pressing rolls at least partially disposed in the water basin. 22. A method of manufacturing an opaque colored soft resin sheet using a manufacturing apparatus provided with: an opaque colored soft resin sheet according to any one of claims 1 to 21 in a molten state for cooling while passing through the slit. And then introducing the resin sheet into the water of the water tank through the pair of rolls for pinching. 30. The method for manufacturing an opaque colored soft resin sheet according to claim 22, wherein the obtained resin sheet is subjected to an annealing treatment. Production method.