JPH08222016A - Cone type safety sign with high retroreflective ability - Google Patents

Abstract

PURPOSE: To provide a cone type safety sign with high shock resistance, high visibility even in a dark place, high recycling capability, high economical efficiency, and hardly decreasing reflecting performance even when stacked. CONSTITUTION: A cone molding is made of polyolefin resin or vinyl chloride resin. A retroreflective surface 4 comprising many reflecting elements is integrally formed in at least part of the inner wall of the cone molding. A cone type safety sign with high retroreflective ability can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used for indicating a route detouring instruction or off-limits indication in the vicinity of a site such as road construction or a traffic accident. The cone type safety sign is provided.

[0002]

2. Description of the Related Art Regarding road signs such as cone type safety signs and barricade type signs, in order to improve visibility in a dark place, a method of installing an electric light in the vicinity or inside is widely used. The cost is extremely high because of problems with the power source and the need for large-scale electric auxiliary equipment. For this reason, a retroreflective element composed of a large number of prism type projections and having various shapes and dimensions (for example, Japanese Patent Publication No. 44-1511, Japanese Patent Publication No. 44-10617, Japanese Patent Publication No. 45-12101, Japanese Patent Publication No. 45-16745, JP-A-51-55691, JP-A-51-60195,
JP-A-51-64896, JP-A-51-64897
No. 5, JP-A-51-82592, and JP-A-54-1037.
Visibility is improved by utilizing each of Japanese Patent No. 78).

For example, generally, it is widely practiced to attach and use a tape having such a highly visible retroreflective element. However, attaching such a tape to a cone or the like is troublesome and costly,
Further, peeling during use is mentioned as a drawback. Also, since the tape material and the marking material are different, if these different resins or adhesives are mixed into the marking material, they will become foreign matter.When reusing a used marking, remove the tape beforehand. It is necessary to leave. for that reason,
At present, there is no active reuse of unnecessary signs.

It is also practiced to mold these signs with a material having excellent transparency such as acrylic resin such as methyl methacrylate resin or polycarbonate resin.
Since it is brittle and fragile and its price is relatively high, it is not used as a cone-shaped safety sign for detouring when road construction or accidents occur. In addition, as a cone-shaped sign or the like, one having a large number of retroreflective elements on the inner surface using a transparent synthetic resin has been devised (for example, Japanese Utility Model Publication No. 62-45).
No. 68) is not practical because the transparency is not always sufficient. In addition, there is a product in which aluminum is vacuum-deposited on the inner surface in order to improve the reflectivity (for example, the actual development 6
No. 2-35016), such a device has a high cost. For the above reasons, there has been a demand for a cone-type safety sign that uses a material that is excellent in transparency, is relatively inexpensive, has good moldability, and has high impact resistance.

[0005]

An object of the present invention is to provide a cone having high visibility even in a dark place by forming a retroreflective surface on at least a part of an inner wall surface of the cone using a resin having good transparency. It provides a type safety sign. The cone of the present invention does not damage the surface of the reflective element even in a stacked state and causes a decrease in reflectivity, and is excellent in recyclability and impact resistance.

[0006]

Means for Solving the Problems As a result of intensive studies in view of the above objects, the present inventors have found that a cone-type safety sign having a retroreflective surface formed on at least a part of the inner wall surface of a cone is a polyolefin resin or a chloride resin. The present invention has been completed by finding that the object is achieved by molding with a vinyl resin. That is, the invention of claim 1 is characterized in that a retroreflective surface composed of a large number of reflective elements is integrally formed on at least a part of an inner wall surface of a cone molded product composed of a polyolefin resin or a vinyl chloride resin. It relates to a cone type safety sign with excellent properties. The invention of claim 2 is characterized in that the polyolefin resin is a resin containing at least one selected from polypropylene resin and 50% by weight or less of the following ethylene (co) polymers (A) and (B). The cone type safety sign having excellent retroreflective property. [Ethylene (co) polymer] (A) Density 0.88 to 0.94
g / cm ³ and ethylene / α-olefin copolymer having a maximum peak temperature of 50 ° C. or more by differential scanning calorimetry (DSC) (B) low-density polyethylene, ethylene / vinyl ester copolymer, and ethylene by high-pressure radical polymerization And α,
Copolymer with β-unsaturated carboxylic acid or its derivative. The invention according to claim 3 is the cone-type safety sign having excellent retroreflective properties, characterized in that a pigment having good transparency is added to the resin. The invention according to claim 4 is the cone-type safety sign having excellent retroreflective properties, characterized in that the cone has a retroreflective surface integrally formed by injection molding. The invention of claim 5 is characterized in that the apex of the reflective element of the retroreflective surface does not protrude from the surface of the portion of the inner wall surface of the cone where the retroreflective surface is not formed. It is a cone type safety sign. The invention of claim 6 is the cone-type safety sign having excellent retroreflective properties, characterized in that the retroreflective surface displays characters and / or patterns.

The present invention will be described in more detail below. A polyolefin resin or a polyvinyl chloride resin is used as the resin constituting the cone type safety sign of the present invention. The polyolefin resin in the present invention is a polypropylene resin or a polypropylene resin mixed with an ethylene (co) polymer or a low crystalline ethylene / α-olefin copolymer.

As the polypropylene resin, a propylene homopolymer which is polymerized by using a Ziegler-Natta type catalyst, a block or random copolymer of propylene and α-olefin, or a mixture thereof is used. As the α-olefin, one type or two or more types having 2 to 8 carbon atoms (excluding 3 carbon atoms) can be used. Specific examples of the resin include homopolypropylene, propylene / ethylene block copolymer, propylene / ethylene random copolymer, propylene / ethylene / 1-butene random copolymer, propylene / 1-butene random copolymer and the like. To be Among these, the propylene / ethylene random copolymer is excellent in transparency, impact resistance and moldability, and is the most preferable. The content of ethylene or 1-butene in these propylene random copolymers is preferably 1 to 10% by weight.

As the vinyl chloride resin in the present invention,
Polyvinyl chloride homopolymer, vinyl chloride / vinyl acetate copolymer, vinyl chloride / vinyl ether copolymer, ethylene / vinyl chloride copolymer, propylene / vinyl chloride copolymer, polyvinyl chloride / styrene graft polymer, polyvinyl chloride -Methyl methacrylate graft polymer,
Polyvinyl chloride / styrene / butadiene graft polymer, polyvinyl chloride / butadiene graft polymer and the like are used, and additives, reinforcing agents, processing aids, plasticizers and the like can be added to these as required.

Ethylene having a density (A) of 0.88 to 0.94 g / cm ³ and a maximum peak temperature of 50 ° C. or higher by differential scanning calorimetry (DSC), which is used as the first ethylene (co) polymer in the present invention. The α-olefin copolymer is a polymer obtained by using a solid catalyst component containing magnesium and titanium and a catalyst composed of an organoaluminum compound and has a density of 0.91 to 0.94 g / cm ^{3 and} a medium density and Low density polyethylene, or density 0.88 to 0.9
It includes what is called 1 g / cm ³ ultra-low density linear polyethylene and low crystalline ethylene / α-olefins polymerized using a catalyst containing vanadium.

The α-olefin of the medium-density and low-density polyethylene or the ultra-low-density linear polyethylene has 3 to 8 carbon atoms, that is, propylene, 1-
Butene, 1-pentene, 4-methyl-1-pentene, 1
-Heptene, 1-hexene, 1-octene and the like are used, and 1-butene and 1-hexene are particularly preferable. Further, the α-olefin of the low crystalline ethylene / α-olefin preferably has 4 or more carbon atoms.

The density of the ethylene copolymer (A) used in the present invention is 0.88 to 0.94 g / cm ³ , as described above,
It is preferably 0.89 to 0.92 g / cm ³ . 0.88g / cm
^If it is less than ³ , the cone type safety sign becomes too soft, and if it exceeds 0.94 g / cm ³ , the impact strength becomes insufficient.

Regarding the ethylene copolymer (A),
It is necessary that the maximum peak temperature by DSC is 50 ° C. or higher, and among them, the crystalline ethylene / α-olefin copolymer having a maximum peak temperature of 100 ° C. or higher and boiling n-hexane insoluble content of 10% by weight or more also has rigidity. Excellent and most preferable. In addition, transparency is insufficient when the maximum peak temperature by DSC is 50 ° C. or less.

In the present invention, the second ethylene (co) is used.
As the polymer, (B) low-density polyethylene by high-pressure radical polymerization, an ethylene / vinyl ester copolymer, and a copolymer of ethylene and an α, β-unsaturated carboxylic acid or its derivative are used. Low-density polyethylene produced by high-pressure radical polymerization means branched low-density polyethylene (L
DPE), generally using a tank reactor or a tubular reactor, in the presence of a radical initiator at a pressure of 500-30.
It is obtained by polymerizing ethylene under the conditions of 00 kg / cm ² and temperature of 150 to 330 ° C. Its density is 0.9
The MFR is 1 to 0.94 g / cm ³ , and the MFR is 0.1 to 60 g / 10 minutes.

Among the ethylene copolymers (B), the ethylene / vinyl ester copolymers are vinyl propionate, vinyl acetate, vinyl caproate containing ethylene as a main component, which are produced by a high pressure radical polymerization method. It is a copolymer with vinyl ester monomers such as vinyl caprylate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate. Among these vinyl ester monomers, vinyl acetate can be mentioned as a particularly preferable one. That is, a copolymer composed of 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a vinyl ester, and 0 to 49.5% by weight of another copolymerizable unsaturated monomer is preferable. Particularly, the vinyl ester content is 3 to 20.
% Is preferable, and more preferably 5 to 15% by weight. The MFR of these copolymers is 0.1-60 g / 10
It is in the range of minutes.

Among the ethylene copolymerizations (B), a typical example of a copolymer of ethylene with an α, β-unsaturated carboxylic acid or its derivative is ethylene with acrylic acid or methacrylic acid or their copolymers. Examples thereof include copolymers with alkyl esters. Specific comonomers include, in addition to acrylic acid and methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylic acid. n-butyl, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate,
Examples thereof include glycidyl acrylate and glycidyl methacrylate. Of these, particularly preferred are methyl ester or ethyl ester of acrylic acid or methacrylic acid. Content of acrylic acid ester or methacrylic acid ester is 3 to 2
It is in the range of 0% by weight, preferably 5 to 15% by weight. The MFR of these copolymers is in the range of 0.1 to 60 g / 10 minutes.

50% by weight of the ethylene (co) polymer component (A) and / or (B) is added to a polypropylene resin.
Blending within the following range is preferable because the impact strength becomes high. If the mixing ratio exceeds 50% by weight, the transparency decreases and the reflection performance becomes insufficient.

In the present invention, it is more preferable to add a nucleating agent to improve transparency. Examples of the nucleating agent used include alkali metal salts of aromatic phosphates, sorbitol derivatives, metal salts of carboxylic acids, and the like. Alkali metal salts of aromatic phosphates include, for example, phosphoric acid 2,2'-methylenebis (4,6-di-te).
rt-butylphenyl) sodium, 2,2'-methylenebis (4,6-di-tert-butylphenyl) lithium phosphate or bis (4-tert-butylphenyl) sodium phosphate,
Examples include lithium bis (4-tert-butylphenyl) phosphate. The sorbitol derivative is, for example, dibenzylidene sorbitol, 1,3,2,4-di (methylbenzylidene).
Sorbitol, 1,3,2,4-di (ethylbenzylidene)
Sorbitol, 1,3,2,4-di (methoxybenzylidene) sorbitol, 1,3,2,4-di (ethoxybenzylidene) sorbitol and the like. The metal salts of carboxylic acids include, for example, sodium adipate, potassium adipate, aluminum adipate, sodium sebacate, potassium sebacate, aluminum sebacate, sodium benzoate, aluminum benzoate, di-p-te.
rt-Butyl aluminum benzoate, hydroxy-di-te
Examples include rt-butyl aluminum benzoate, titanium di-p-tert-butyl benzoate, and chromium di-p-tert-butyl benzoate. All of these are known as nucleating agents for polypropylene (for example, JP-A-53-105550, JP-A-53-1736, JP-A-5-43746, and JP-A-50-139150). , JP-A-56-30449, JP-A-50-6650, etc.). The above nucleating agent is 0.05 with respect to the resin component.
It is mixed at a ratio of 1 part by weight.

Further, the cone type safety sign can be made more visible by coloring it with a transparent pigment having excellent transparency, for example, red. The transparent pigment is a pigment having a particle size of 0.5 μm or less and capable of being colored without impairing transparency, and specifically, N, N ′-(2,5
-Dichloro-1,4-phenylene) bis [4- [2-chloro-5- (trifluoromethyl) -phenyl] azo] -3-
Hydroxy-2-naphthalenecarboxamide (trade name: Pigment Red 242, manufactured by Sand Co.) and N, N '
-(2,5-Dichloro-1,4-phenylene) bis [4-
(2,5-Dichlorophenyl) azo] -3-hydroxy-
Examples thereof include 2-naphthalenecarboxamide (trade name: Pigment Red 214, manufactured by Sand Co.). The amount of transparent pigment added is 0.0005 to 1% by weight. If the added amount is too small, it is not colored, and if the added amount is too large, the reflection performance is lowered and the cost is increased.

In the present invention, an antistatic agent, an antioxidant, a lubricant, an antifogging agent, an ultraviolet absorber, a dispersant or a transparent pigment other than the above-mentioned transparent pigments is used, if necessary, within a range that does not impair the characteristics of the present invention. Known additives such as organic or inorganic pigments can be added.

The retroreflective surface is obtained by closely and regularly arranging a large number of reflective elements, but in the present invention, it is integrally formed on at least a part of the inner wall surface of the molded product. The retroreflective surface can be formed by attaching a tape provided with the retroreflective element to the surface of the molded product as described above, but in the present invention, for example, a metal for integrally molding the reflective element is used. Using the mold
It is formed directly on a part of the cone by injection molding the cone or by engraving the inner surface of the cone. The most suitable molding method for the cone of the present invention is the injection molding method, and it is preferable to integrally form the retroreflective surface at the time of cone molding by carving the prism type protrusions in the mold. Typical examples of the shape of the reflecting element include a triangular pyramid or a quadrangular pyramid whose apex angle is a right angle, or a ridge having a sawtooth cross section or a humpback ridge.
Any shape can be adopted as long as it has excellent retroreflectivity. The dimension is the height from the bottom of the protrusion to the apex, and the length of one side of the pyramid bottom is 0.5 to 5 m.
It is preferably m. If it is less than 0.5 mm, it is difficult to manufacture a mold, and if it exceeds 5 mm, the reflection performance becomes insufficient.

Embodiments of the present invention will be described below with reference to the accompanying drawings. 1 (a), (b) and (c) are perspective views of an example of a typical cone type safety sign. The cone-shaped safety sign 1 is composed of a conical sign part 2 and a pedestal 3 supporting the sign part 2. The shape of the marker portion 2 is not limited to a conical shape, and may be, for example, a pyramid shape such as a triangular pyramid or a quadrangular pyramid shape, or a truncated cone shape, and is not particularly limited. The retroreflective surface 4 is formed on at least a part of the inner wall surface of the marking portion 2, but it is preferable to leave a portion where the retroreflective surface is not formed. In that case, it is possible to display various shapes such as a headband shape, a spiral shape, a checkered pattern, or a specific character or pattern by appropriately combining a part with a retroreflective surface and a part with no retroreflective surface. it can. 1A, 1B, and 1C show examples in which the retroreflective surface 4 displays a spiral shape, a checkered pattern, and characters, respectively. This way,
Not only is the design freely possible and the design is improved, but the area for forming the retroreflective surface is reduced, so that the die manufacturing cost is reduced. In addition to the above-mentioned transparent pigment, for example, the effect as a marker can be further improved by using, for example, coloring black and yellow stripes after molding.

FIG. 2 is a vertical sectional view and a partially enlarged view of the cone-shaped safety signs in a stacked state. As shown in the figure, in the retroreflective surface 4, the apex of the reflecting element 4a is formed so as not to protrude from the surface of the inner wall surface of the cone where the retroreflective surface is not formed. The apex of the reflecting element 4a on the inner wall surface does not come into contact with the outer surface of the lower cone to be damaged, and the performance can be maintained for a long period of time.

Further, in an internally illuminated safety sign in which an electric lamp is attached to the cavity inside the cone to illuminate the interior, a portion without a reflecting element does not refract light emitted from the inside to the outside. Produces a bright-looking effect. FIG. 3 is a schematic vertical cross-sectional view of a general internal lighting cone type safety sign. A bottom plate 7 having a light bulb 5 fixed thereto via a column 6 is attached to the internally illuminated cone type safety sign 1a from the lower side of the pedestal 3a. Here, usually, a metal bolt is attached to the lower surface of the pedestal 3a downward and fixed with a nut through a bolt hole opened in the bottom plate 7. In the present invention, if the bolt 8 is integrally formed at the time of molding the cone and is tightened with the nut 9 made of metal or resin, it is not necessary to remove the bolt when the cone is reused, and the process is facilitated. .

[0025]

[Physical property test method]

(A) Polypropylene and composition (1) MFR JIS K 6758 (2) Flexural modulus ASTM D 790 (3) Izod impact value JIS K 6758 (4) DuPont impact value Thickness 2 mm, diameter 50 mm Is injection-molded and measured with a DuPont impact tester (manufactured by Toyo Seiki Co., Ltd.). (5) Haze A 2 mm x 200 mm x 100 mm sample plate is prepared by injection molding, and the haze measured by a direct reading haze computer (trade name: HGH-2DP, manufactured by Suga Test Instruments Co., Ltd.) according to JISK 7105 is shown. . (6) Retroreflective performance The surface of a metal mold used to form a retroreflective surface in which square pyramids each having a side length of 2 mm and a vertex height of 2 mm from the bottom surface is arranged vertically and horizontally. Chrome plated, thickness 2.3mm, length 20mm x width 20mm
Injection-mold the test piece. This test piece is irradiated with a headlight of an automobile from a distance of 10 m, and visually judged from the driver's seat. The criteria for judgment are as follows. ○: Good retroreflective performance △: Fairly good retroreflective performance ×: Poor retroreflective performance (b) Ethylene / α-olefin copolymer (1) Density according to JIS K 6760 (2) MFR JIS K 6760 ( 3) Measurement by DSC A sheet with a thickness of 0.2 mm was formed by using a heat press, a sample of about 5 mg was punched out, held at 230 ° C for 10 minutes, cooled to 0 ° C at a rate of 10 ° C / min, and then again. 10 ° C /
The temperature at the apex of the maximum peak that appeared while heating to 170 ° C at the speed of min was defined as the maximum peak temperature. (4) n-Hexane insoluble matter A sheet with a thickness of 0.2 mm was formed using a heat press, and 2
Three 0 mm x 30 mm sheets are cut out and extracted with boiling n-hexane for 5 hours using a double-tube Soxhlet extractor. Remove the insoluble matter and vacuum dry (for about 7 hours, 5
(0 ° C.) and then weighed, and the weight ratio of the insoluble matter to the weight before extraction is expressed as a percentage.

[Molding Conditions by Injection Molding Machine] Injection molding machine (1) Mold clamping force 90 ton; Product name: IS-90B (Toshiba Machine
(Made in Japan) (however, used only for making haze and retroreflective performance test pieces) (2) Mold clamping force 100 ton; Product name: JSW100 (manufactured by Japan Steel Works, Ltd.) Molding resin temperature: 220 ° C Cushion molding ・ Mold temperature: 50 ℃

The resin components used are as follows. (A) Polypropylene (RPP) propylene / ethylene random copolymer MFR: 20 g / 10 min, ethylene content: 4.3 wt% propylene / ethylene random copolymer (Nippon Petrochemical Co., Ltd.
(Manufactured by Co., Ltd.), the peroxide 2,5-dimethyl-2,5-
Di (tert-butylperoxy) hexane (0.0175% by weight) was added and pyrolyzed to prepare an MFR of 32 g / 10 min. (B-1) Ethylene / α-olefin copolymer (VLDPE) ultra-low density linear polyethylene polymer MFR: 1.0 g / 10 min, density: 0.900 g / cm ³ , maximum peak temperature: 120 ° C, n- Hexane insoluble matter: 87.0% by weight, comonomer: 1-butene (manufactured by Nippon Petrochemical Co., Ltd.) (EBR) ethylene / 1-butene copolymer Product name: Tufmer A4085 (Mitsui Petrochemical Industry Co., Ltd.)
MFR: 8.5 g / 10 min, density: 0.88 g / cm ³ , maximum peak temperature: 70 ° C., n-hexane insoluble content: 1.5 wt% (EPR) ethylene / propylene copolymer rubber, trade name: EP07P (Nippon Synthetic Rubber Co., Ltd.) MFR: 0.7 g / 10 min., Density: 0.86 g / cm ³ , maximum peak temperature: 33 ° C., n-hexane insoluble matter: 0 (HDPE) high density polyethylene MFR: 5 0.3 g / 10 min, density: 0.963 g / cm ³ , maximum peak temperature: 132 ° C., n-hexane insoluble matter: 97.0 wt% (manufactured by Nippon Petrochemical Co., Ltd.) (b-2) high pressure radical polymer (LDPE) Low density polyethylene Product name: Nisseki Lexron J79 (Nippon Petrochemical Co., Ltd.)
MFR: 45 g / 10 min, density: 0.915 g / cm ³ (EVA) ethylene-vinyl acetate copolymer Product name: Nisseki Lexron V360 (Nippon Petrochemical Co., Ltd.)
Made) MFR: 2.0 g / 10 min, density: 0.930 g / cm ³ , vinyl acetate (VA) concentration: 10 wt% (EEA) ethylene-ethyl acrylate copolymer Product name: Nisseki Lexron EEA A3100 (Japan Petrochemical Co., Ltd.) MFR: 3.0 g / 10 min, density: 0.930 g / cm ³ , ethyl acrylate (EA) concentration: 10 wt%

The nucleating agents used are as follows. (1) Sorbitol compound (C-1) Trade name: Gelol MD (manufactured by Shin Nippon Rika Co., Ltd.) (2) Aromatic phosphate ester compound (C-2) Trade name: MARK NA-11 (Asahi Denka Co., Ltd. Industry Co., Ltd.
(C-3) Product name: MARK NA-10 (Asahi Denka Kogyo Co., Ltd.)
(C-4) Product name: MARK NA-21 (Asahi Denka Kogyo Co., Ltd.)
Made)

Example 1 In addition to the resin components shown in Table 1, antioxidant Irgafos 168 (manufactured by Ciba Geigy)
0.05% by weight, acid absorber calcium stearate.
08% by weight, and Sanol L as an ultraviolet absorber
S770 (manufactured by Sankyo Co., Ltd.) 0.05% by weight and tinuvin
326 (manufactured by Ciba Geigy) was added in an amount of 0.05% by weight, and the mixture was mixed with a Henschel mixer so as to be uniform for about 2 minutes. Then, injection molding was carried out under the above conditions. A test piece for the reflection performance test was also produced by injection molding. A block in which pins having the same dimensions as the reflective element were arranged was embedded in the reflective element portion of the mold, and the surface was plated with chrome. The test results of physical properties are shown in Table 1. Good flexural modulus, Izod impact strength, transparency and retroreflectivity.

Example 2 Using the resin components and the nucleating agent shown in Table 1 and the same various additives as in Example 1, the same operation as in Example 1 was performed. Table 1 shows the test results.
Good Izod impact strength and DuPont impact strength.

Example 3 The same operation as in Example 1 was carried out using the resin components and nucleating agent shown in Table 1 and the same various additives as in Example 1. Table 1 shows the test results.
Good flexural modulus, Izod impact strength and DuPont impact strength.

<Example 4> Vinyl chloride resin (trade name: T
N9063, manufactured by Riken Vinyl Industry Co., Ltd., was used for injection molding. Table 1 shows the test results. Good Izod impact strength, DuPont impact strength, transparency and retroreflectivity.

Example 5 The same operation as in Example 1 was performed using the resin components shown in Table 1 and the same various additives as in Example 1. Table 1 shows the test results. Good flexural modulus, Izod impact strength and DuPont impact strength.

[0034]

[Table 1]

<Examples 6 to 9> The same operation as in Example 1 was performed using the resin components and nucleating agents shown in Table 2 and the same various additives as in Example 1. The test results are shown in Table 2. Flexural modulus, Izod impact strength, DuPont impact strength, transparency and retroreflectivity are all good.

<Example 10> (EBR) Tuffmer A4085 was used as the ethylene-based polymer, and other than that, Example 6 was used.
I went the same way. The test results are shown in Table 2. Good Izod impact strength, DuPont impact strength, transparency and retroreflectivity.

[0037]

[Table 2]

<Examples 11 to 13> Polymers shown in Table 3 were used as the ethylene-based polymer, and the other processes were performed in the same manner as in Example 6. The test results are shown in Table 3. Good flexural modulus, Izod impact strength, transparency and retroreflectivity.

<Example 14> The same composition as in Example 6 was used.
Furthermore, N, N '-(2,5-dichloro-1,4-phenylene) bis [4- (2,5-dichlorophenyl) azo] -3-hydroxy-2-naphthalenecarboxamide (which is a red transparent pigment) A particle size of 0.14 μm; trade name: Pigment Red 214, manufactured by Sand Co., Ltd.) was added in an amount of 0.01% by weight, and the same operation as in Example 1 was performed. The test results are shown in Table 3.
It is colored red and has good flexural modulus, Izod impact strength, DuPont impact strength, transparency and retroreflectivity.

[0040]

[Table 3]

<Comparative Example 1> Using the same composition as in Example 6, a molded product having no retroreflective surface was molded under the same conditions as in Example 6. The retroreflectivity was poor.

[0042]

INDUSTRIAL APPLICABILITY The present invention can provide a cone type safety sign having high visibility even in a dark place by forming a retroreflective surface on the inner wall surface of a cone using a resin having good transparency. Further, the cone of the present invention does not damage the surface of the reflective element even in a stacked state, and is excellent in recyclability and impact resistance.

[Brief description of drawings]

FIG. 1 is a perspective view of an example of a cone-shaped safety sign. An example in which the retroreflective surface displays (a) spiral shape, (b) checkerboard pattern, and (c) characters is shown.

FIG. 2 is a schematic longitudinal cross-sectional view and a partially enlarged view of a state in which cone-type safety signs are stacked.

FIG. 3 is a schematic vertical sectional view of an internally illuminated cone type safety sign.

[Explanation of symbols]

 1, 1a Safety sign 2 Sign part 3, 3a Pedestal 4 Retro-reflective surface 4a Reflective element 5 Light bulb 6 Column 7 Bottom plate 8 Bolt 9 Nut

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[Procedure amendment]

[Submission date] July 5, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The (A) density used as the first ethylene (co) polymer in the present invention is 0.88 to 0.94 g / c.
m ³ and an ethylene / α-olefin copolymer having a maximum peak temperature of 50 ° C. or higher measured by differential scanning calorimetry (DSC) is a polymerization using a solid catalyst component containing magnesium and titanium and a catalyst composed of an organoaluminum compound. The density was 0.91 to 0.94 g / cm ^3.
Medium density and low density polyethylene, or a density of 0.
Objects or called ultra low density linear polyethylene 88~0.91g / cm ^3, including low crystalline ethylene · alpha-olefin copolymer polymerized using a catalyst containing vanadium.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

The α-olefin of the medium-density and low-density polyethylene or the ultra-low-density linear polyethylene has 3 to 8 carbon atoms, that is, propylene, 1-
Butene, 1-pentene, 4-methyl-1-pentene, 1
-Heptene, 1-hexene, 1-octene and the like are used, and 1-butene and 1-hexene are particularly preferable. The α-olefin of the low crystalline ethylene / α-olefin copolymer preferably has 4 or more carbon atoms.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

In the present invention, it is more preferable to add a nucleating agent to improve transparency. Examples of the nucleating agent used include alkali metal salts of aromatic phosphates, sorbitol derivatives, metal salts of carboxylic acids, and the like. Alkali metal salts of aromatic phosphoric acid esters include, for example, sodium 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, phosphoric acid 2,
2′-methylenebis (4,6-di-tert-butylphenyl) lithium, sodium bis (4-tert-butylphenyl) phosphate, lithium bis (4-tert-butylphenyl) phosphate, and the like. The sorbitol derivative is, for example, dibenzylidene sorbitol, 1.3,
2.4-Di (methylbenzylidene) sorbitol, 1.
3,2.4-di (ethylbenzylidene) sorbitol,
Examples include 1,3,2,4-di (methoxybenzylidene) sorbitol, 1,3,2,4-di (ethoxybenzylidene) sorbitol, and the like. The metal salt of carboxylic acid is
For example, sodium adipate, potassium adipate, aluminum adipate, sodium sebacate, potassium sebacate, aluminum sebacate, sodium benzoate, aluminum benzoate, aluminum di-p-tert-butylbenzoate, hydroxy-di-tert.
-Aluminum butyl benzoate, titanium di-p-tert-butyl benzoate, and chromium di-p-tert-butyl benzoate. All of these are known as nucleating agents mainly for polypropylene (for example,
JP-A-53-105550, JP-A-58-1736
JP-A-5-43746, JP-A-50-13915
No. 0, JP-A-56-30449, JP-A-50-665.
No. 0 gazette etc.). The above nucleating agent is added in a proportion of 0.05 to 1 part by weight with respect to the resin component.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

The resin components used are as follows. (A) Polypropylene (RPP) propylene / ethylene random copolymer MFR: 20 g / 10 min, ethylene content: 4.3
0.015 wt% of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, which is a peroxide, in propylene / ethylene random copolymer (manufactured by Nippon Petrochemical Co., Ltd.) of wt% And pyrolyzed, MFR: 32
The thing of g / 10min was prepared. (B-1) Ethylene / α-olefin copolymer (VLDPE) ultra-low density linear polyethylene polymer MFR: 1.0 g / 10 min, density: 0.900 g /
cm ³ , maximum peak temperature: 120 ° C., n-hexane insoluble matter: 87.0% by weight, comonomer: 1-butene (manufactured by Nippon Petrochemical Co., Ltd.) (EBR) ethylene / 1-butene copolymer Product name: Tuffmer A4085 (manufactured by Mitsui Petrochemical Industry Co., Ltd.) MFR: 8.5 g / 10 min, density: 0.88 g / c
m ³ , maximum peak temperature: 70 ° C., n-hexane insoluble matter:
1.5% by weight (EPR) ethylene / propylene copolymer rubber Trade name: EP07P (manufactured by Nippon Synthetic Rubber Co., Ltd.) MFR: 0.7 g / 10 min, density: 0.86 g / c
m ³ , maximum peak temperature: 33 ° C., n-hexane insoluble matter:
0 (HDPE) high density polyethylene MFR: 5.3 g / 10 min, density: 0.963 g /
cm ³ , maximum peak temperature: 132 ° C., n-hexane insoluble matter: 97.0 wt% (manufactured by Nippon Petrochemical Co., Ltd.) (b-2) High-pressure radical polymer (LDPE) low-density polyethylene Product name: Nisseki Lexron J79 (Nippon Petrochemical Co., Ltd.)
Made) MFR: 45 g / 10 min, density: 0.915 g / c
m ³ (EVA) ethylene / vinyl acetate copolymer Product name: Nisseki Lexron V360 (manufactured by Nippon Petrochemical Co., Ltd.) MFR: 2.0 g / 10 min, density: 0.930 g /
cm ³ , vinyl acetate (VA) concentration: 10 wt% (EEA) ethylene-ethyl acrylate copolymer Product name: Nisseki Lexron EEA A3100 (Nippon Petrochemical Co., Ltd.) MFR: 3.0 g / 10 min, density : 0.930 g /
cm ³ , ethyl acrylate (EA) concentration: 10% by weight (EMA) ethylene-methyl acrylate copolymer Brand name: Nisseki Lexpearl RB5120 (Nippon Petroleum Chemical Co., Ltd.)
Gaku Co., Ltd.) MFR: 10 g / 10 min, density: 0.933 g / c
m ³ , concentration of methyl acrylate (MA): 7.5% by weight

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

<Examples 11 to 14 > Polymers shown in Table 3 were used as the ethylene-based polymer, and other operations were performed in the same manner as in Example 6. The test results are shown in Table 3. Examples 11-13
The flexural modulus, Izod impact strength, transparency and retroreflective good. EMA as an ethylene polymer
Example 14 using is the Izod impact strength, DuPont
Good impact strength, transparency and retroreflectivity.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

<Example 15 > The same composition as in Example 6 was used.
Furthermore, N, N '-(2,5-dichloro-1,4-phenyl) bis [4- (2,5-dichlorophenyl) azo] -3-hydroxy-2-naphthalenecarboxamide (which is a red transparent pigment ( Particle diameter 0.14 μm; trade name: Pigment Red 214, manufactured by Sand Co., Ltd.) was added by 0.01% by weight, and the same operation as in Example 1 was performed. The test results are shown in Table 3. It is colored red and has good flexural modulus, Izod impact strength, DuPont impact strength, transparency and retroreflectivity.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

[0040]

[Table 3]

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Claims (6)

[Claims] 1. At least a part of an inner wall surface of a cone molded product made of a polyolefin resin or a vinyl chloride resin,
A cone-shaped safety sign with excellent retroreflectivity, which is characterized by integrally forming a retroreflective surface composed of many reflective elements. 2. The polyolefin resin contains a polypropylene resin and 50% by weight or less of at least one selected from the following ethylene (co) polymers (A) and (B). A cone-type safety sign having excellent retroreflective properties as described above, [ethylene (co) polymer] (A) density of 0.88 to 0.94 g / cm ³ and maximum peak temperature of 50 ° C. by differential scanning calorimetry (DSC). The above ethylene / α-olefin copolymer (B) low-density polyethylene by high-pressure radical polymerization, ethylene / vinyl ester copolymer, and ethylene and α,
Copolymer with β-unsaturated carboxylic acid or its derivative. 3. The cone-type safety sign having excellent retroreflectivity according to claim 1, wherein a pigment having good transparency is added to the resin. 4. The cone type safety sign having excellent retroreflectivity according to claim 1, wherein the cone has a retroreflective surface integrally formed by injection molding. . 5. The apex of the reflective element of the retroreflective surface does not protrude from the surface of the inner wall surface of the cone where the retroreflective surface is not formed, according to any one of claims 1 to 4. A cone-shaped safety sign with excellent retroreflective properties. 6. The cone-type safety sign having excellent retroreflective properties according to claim 1, wherein the retroreflective surface displays characters and / or patterns.