JP2001262523A - Retroreflection sheet for road marking and execution method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a retroreflection sheet for road marking with excellent durability. SOLUTION: This retroreflection sheet for road marking is three- dimensionally visible a flat part by head lights of a car by disposing the graphics of different hues in a specified pattern.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel retroreflective sheet for road marking and a construction method thereof.

[0002]

2. Description of the Related Art Conventionally, in order to ensure safety on a road, conventionally, as a means for securing visibility in a dark place, light is surely retroreflected in the direction of a light source such as a vehicle headlight. Retroreflective materials that ensure visibility have been used.

[0003] However, the conventional retroreflective material exhibits good visibility when it is newly installed, but the surface is gradually contaminated by exhaust gas of a car or soot from a factory or the like, and the retroreflective property is reduced over time. It was very time-consuming to clean and replace them regularly.

[0004] Conventionally, road markings such as zebra markers and chevron markers have been used for the purpose of promoting deceleration and danger prediction in order to prevent a traffic accident due to excessive speed at a sharp curve portion or a tunnel entrance portion of a road. Has been adopted.

[0005] However, such road markings have a problem that visibility is inferior because they are viewed two-dimensionally and, as described above, the surface is contaminated during long-term use and visibility is reduced. there were.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the conventional retroreflective sheet for a specific road sign and the specific construction method have caused problems. The inventors have found that all the points can be solved, and have completed the present invention.

That is, the present invention provides: 1. A recursive road marking which is characterized by arranging figures having different hues in a predetermined shape so that a plane portion can be three-dimensionally viewed by a headlight of an automobile or the like. 2, a reflective sheet comprising an adhesive layer (A), a base sheet layer (a) if necessary, an adhesive layer (b) if necessary, a retroreflective sheet layer (B), 2. The retroreflective sheet for road marking as described in 1 above, wherein the pressure-sensitive adhesive layer (c) and the hydrophilic non-stainable sheet layer (C) are sequentially laminated according to The road according to the above 1 or 2, wherein the layer (B) is a high-luminance retroreflective sheet of an exposed lens type retroreflective sheet, an encapsulated lens type retroreflective sheet or a capsule lens type retroreflective sheet. Retroreflective sheet for marking, 4, hue Is a retroreflective sheet for road marking as described in 1 above, characterized by high lightness and low lightness, high saturation and low saturation, or a combination thereof, 5. red / white color, yellow color 5. The recursion for road marking as described in 1 or 4 above, which is a combination of black / black, red / yellow, red / white / yellow or red / white / yellow / black. 3. The reflex for road marking as described in (2) above, wherein the hydrophilic reflection sheet, and 6, the hydrophilic non-soiling type sheet layer (C) is a cured coating layer composed of a modified polysiloxane resin having a ladder structure. Adhesive sheet (7), adhesive layer (A), base sheet layer (a), adhesive layer (b), retroreflective sheet layer (B), adhesive layer (A) c), a road mark formed by sequentially laminating a hydrophilic non-staining type sheet layer (C) A retroreflective sheet (I) for use in which the pressure-sensitive adhesive layer (A) of the sheet (I) and the base material for road marking are pressure-bonded and joined to each other, 8, An adhesive layer (A), a retroreflective sheet layer (B), an adhesive layer (c), and a hydrophilic non-stainable sheet layer (C) are sequentially laminated to form a retroreflective sheet for road marking (II). 9. The method according to claim 8, wherein after attaching to the immobilization substrate, the immobilization substrate is bonded to a road marking substrate such as concrete. The construction according to the above item 8, characterized in that the part and a part of the road marking base material surface are partially joined by an adhesive so that a gap is provided between the two to remove invading rainwater and the like. 10. In the above paragraph 8, the fixed base material surface and the road marking base material surface are anchor bolts or the like. According to construction methods described above 8, characterized in that to more physically joined.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, components of the present invention will be described.

The retroreflective sheet for road marking according to the present invention is characterized in that, by arranging figures having different hues in a predetermined shape, a flat portion can be visually recognized three-dimensionally by a headlight of an automobile or the like. It is.

The different hues are not limited to the hues combining two or more colors, but in particular, red / white, yellow / black, red / yellow, red / white / yellow or The combination of red / white / yellow / black is particularly preferable because the combination is excellent in human visibility.

[0011] In addition, by using colors of different hues of high lightness and low lightness, and high chroma and low chroma, the visibility to humans is further improved.

As for figures, figures (pictures, characters, lines, arrows, etc.) commonly used on roads, such as road signs,
Conventionally used figures such as guide signs, signs for safety guidance, direction instructions and the like, and new figures for displaying these can be used. Further, these figures can be appropriately arranged in a predetermined shape in order to achieve the above-mentioned object.

[0013] Sheets that allow three-dimensional viewing of a plane include: (1) an exposed lens type retroreflective sheet;
A retroreflective sheet such as (2) an encapsulated lens type retroreflective sheet and (3) a capsule lens type retroreflective sheet, particularly a high-luminance sheet is preferable.

The seat is developed so that when a headlight of an automobile or the like is irradiated, the light beam is retroreflected in the direction of the light source so that the driver can visually recognize the figure. Such a sheet is conventionally known, for example, a sheet in which light-reflecting particles such as quartz glass or acrylic are embedded in a flexible synthetic resin sheet, or a coating containing light-reflecting particles is applied to the surface of the synthetic resin sheet. What you did,
A material in which light reflector particles are fixed on the surface of a synthetic resin sheet with an adhesive can be used without any particular limitation.

(1) As an exposed lens type retroreflective sheet, for example, a reflecting mirror is formed by a metal such as aluminum on the lower hemisphere of a glass sphere, and the glass sphere is embedded in a so-called glass sphere binder layer. In particular, a structure that shines brightest among retroreflective materials to which glass spheres are applied is particularly preferable.

(2) The enclosed lens type retroreflective sheet is a sheet in which glass spheres are encapsulated in a resin film so that the relative refractive index of the glass spheres is always kept constant to maintain the retroreflective performance. Here, the refractive index of the resin is about 1.5
Because of the front and rear, in order to focus inside the encapsulated glass sphere and efficiently perform retroreflection, about 2.8 to
It is preferable to use a glass sphere having a refractive index of 2.9.

(3) The capsule lens type retroreflective sheet is also referred to as a retroreflective high-brightness reflective sheet. The retroreflective performance is ensured while the front surface of the glass bulb is always in contact with air, and the exposed lens is exposed. This is a retroreflective material in which a film is arranged on the front surface of a mold retroreflective sheet. Examples of the capsule lens type retroreflective sheet include, for example,
-122509, JP-A-8-62410,
JP-A-9-302632, JP-A-10-1116
No. 60, JP-A-10-333616, JP-A-8-122509 and the like can be used.

The sheet of the present invention comprises an adhesive layer (A), an optional base sheet layer (a), an optional adhesive layer (b), a retroreflective sheet layer (B), and an optional adhesive layer. A layer obtained by sequentially laminating the pressure-sensitive adhesive layer (c) and the hydrophilic non-staining type sheet layer (C) is preferably used.

The pressure-sensitive adhesive layer (A) is preferably a pressure-sensitive pressure-sensitive adhesive layer, and is adhered by strongly pressing the sheet against a target substrate. Examples of the type of the adhesive include natural rubber, acrylic resin, ethylene / vinyl acetate copolymer, polyurethane, polyester, silicone rubber,
It is a layer formed of a conventionally known pressure-sensitive adhesive such as fluorine rubber and polyvinyl butyral. The adhesive includes, for example, a tackifier, an adhesion regulator, an antioxidant, a stabilizer,
A coloring agent and the like can be included. Also, on one side of the pressure-sensitive adhesive layer (the side other than the polyvinyl chloride film layer), for example, a release of paper, a film or a film exhibiting releasability itself treated with a release agent such as silicon, wax, or fluororesin. Sex sheets can be laminated. The thickness of the adhesive layer ranges from about 10 to 1000 microns, preferably from about 20 to 500 microns.

As the base sheet layer (a), a colored or transparent sheet can be used. The sheet is not particularly limited as long as it is generally used in the field, and a conventionally known sheet can be used. Examples of the type of the sheet layer include polyethylene, polypropylene, polyisobutylene, polybutadiene, polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride (PVF), polyethylene terephthalate (PET), and ethylene / tetrafluoroethylene copolymer ( ETFE), polytetrafluoroethylene / perfluoropropoxyvinyl ether copolymer (PFA), nylon, polystyrene, polyurethane, polycarbonate (PC), polyvinyl alcohol (PVA), ethylene / vinyl alcohol Copolymer (E
VOH), polycarbonate, polyacetal, AS resin, ABS resin, melamine resin, acrylic resin, epoxy resin, silicone resin, polyester resin, and other thermoplastic or crosslinked plastic films. . Further, these plastic films may contain an ultraviolet absorber, a filler, a heat stabilizer, a colorant, and the like. Among them, polyvinyl chloride resin and polyethylene terephthalate resin are particularly preferable. The sheet includes, for example, a plasticizer, a heat (light) stabilizer,
Pigments and the like can also be included. The thickness of the sheet is about 20
It is in the range of ~ 500 microns, preferably about 30-100 microns.

As the pressure-sensitive adhesive layers (b) and (c), those similar to the above-mentioned pressure-sensitive adhesive layer (A) can be used.

As the retroreflective sheeting layer (B), those described above can be used. The thickness of the sheet ranges from about 20 to 500 microns, preferably about 30 to 100 microns.

The hydrophilic hardly contaminating type sheet layer (C) is located on the sheet surface, and is washed away by water such as rain due to the hydrophilic effect of the sheet when contaminants adhere, that is, self-cleaning. Since it has a function, it can be supplied to the retroreflective film without reducing the amount of incident light from the headlight, and furthermore, the retroreflected light is not reduced, so that the visibility is excellent.

As the hardly contaminated type sheet layer (C), conventionally known ones can be used without any limitation, and a cured coating layer of the following modified polysiloxane resin is particularly preferable. Further, the sheet layer may be a cured layer of the modified polysiloxane resin described below or a layer in which a cured layer of the modified polysiloxane resin is formed on the surface of a base film (for example, a urethane film).

The modified polysiloxane resin is a tetrafunctional organosilicon compound such as tetramethoxysilane and tetraethoxysilane and / or a trifunctional organosilicon compound such as methyltrimethoxysilane, methyltriethoxysilane and phenyltrimethoxysilane. Is a highly condensed product of an organosilicon having a ladder structure obtained by condensing a compound represented by the following general formula (1)

[0026]

Embedded image

(Wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n is an integer of 30 to 80).

Further, other than the above, a compound represented by the general formula (2)

[0029]

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(In the formula, R ₁ represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and R ₂ , R ₃ and R ₄ represent an alkoxyl group having 1 to ₄ carbon atoms or a hydroxyl group.) 70 to 99.999 mol% of the compound (A) represented by the general formula (3)

[0031]

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(Wherein, R ₅ represents a hydrogen atom or a methyl group, and R ₆ , R ₇ and R ₈ represent a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms or an aliphatic hydrocarbon group having 1 to 8 carbon atoms) However,
R ₆ , R ₇ and R ₈ are not all aliphatic hydrocarbon groups having 1 to 8 carbon atoms. n shows the integer of 1-6. ) Of the compound (B) represented by the formula (1), which has at least two free functional groups selected from a hydroxyl group and an alkoxyl group and has a number average molecular weight of 400 ~ 1
A polysiloxane-based macromonomer of 00000 and a copolymer containing an oxirane group-containing vinyl monomer as a monomer component, and a 6-coordinate organic aluminum chelate compound and / or an 8-coordinate organic zirconium chelate compound. It is preferable to use a curable resin composition characterized by the above. The composition is described in JP-A-63-22.
Since it is described in Japanese Patent Publication No. 1123, the detailed description is replaced with the description in the claims.

The modified polysiloxane resin can be coated with a solution dissolved in an organic solvent by ordinary coating, for example, by brush coating, spray coating, roller coating, dip coating, and the like. No, but generally 10μm
１100 μm. The coated modified polysiloxane-based resin is subjected to a curing treatment.
7 days, preferably in the range of about 1 hour to 5 days. If necessary, the modified polysiloxane resin may be, for example, an acidic catalyst such as sulfuric acid, phosphoric acid, paratoluenesulfonic acid, trichloroacetic acid, trifluoromethanesulfonic acid, monobutyl phosphate, dibutyl phosphate, and boron trifluoride. ,
For example, monoethanolamine, diethanolamine,
Contains basic catalysts such as tributylamine, for example, metal catalysts such as dibutyltin oxide, monobutyltin hydroxide, tetrabutylzirconate, tetrabutyltitanate, stannous chloride, zinc oleate, tin oleate, and zinc acetate can do.

Further, Si (OR ₁₀ ) 4 (R
₁₀ are the same or different and represent a methyl group, an ethyl group, a propyl group, a butyl group) and / or a low condensate thereof (2-
It is preferable to add a tetraalkoxysilicate having a condensation degree of 20, preferably 3 to 10). Examples of the tetraalkoxysilicate include commercially available products such as methyl silicate 51, ethyl silicate 40, and ethyl silicate 48 (all trade names, manufactured by Colcoat Co., Ltd.).
The compounding amount of the tetraalkoxysilicate is preferably in the range of 1 to 30 parts by weight, particularly preferably 2 to 20 parts by weight based on 100 parts by weight of the modified polysiloxane resin. In particular, it is preferable to add a tetraalkoxy silicate, since the compound exhibits an excellent effect on hydrophilic stain resistance.

[0035]

The sheet of the present invention has excellent long-term stain resistance, excellent adhesion between layers, excellent weather resistance of the sheet surface, simple construction, and durability of the sheet after construction. It has the effect of being excellent and having excellent visibility.

[0036]

EXAMPLES The present invention will be described in more detail with reference to examples.

Example 1 Pressure-sensitive adhesive layer (A) (butyl rubber, 1000 μm), base sheet layer (a) (polyethylene terephthalate, 12
0 μm), pressure-sensitive adhesive layer (b) (acrylic pressure-sensitive adhesive, 30 μm)
m), retroreflective sheet layer (B) (high-brightness film (manufactured by Kiwa Chemical Co., Ltd.), 30 μm), pressure-sensitive adhesive layer (c) (acrylic pressure-sensitive adhesive, 30 μm), hydrophilic non-staining sheet layer (C) A retroreflective sheet for road marking (I) obtained by sequentially laminating (the following sheet layer, 80 μm) a pressure-sensitive adhesive layer (A) surface of the sheet (I) and a road marking substrate surface such as concrete. Were bonded by pressing so that they were in contact with each other.

Example 2 Adhesive layer (A) (same as above), retroreflective sheet layer (B) (same as above), adhesive layer (c) (same as above), A retroreflective sheet for road marking (II), which is formed by sequentially laminating a hydrophilic non-stainable sheet layer (C) (same as above), is adhered to an immobilization substrate (polyethylene terephthalate, 1 mm thick). After that, a part of the obtained surface of the immobilized substrate and a part of the surface of the road marking substrate (concrete) were partially bonded with an adhesive to form a gap therebetween.

Example 3 The immobilized substrate obtained in Example 2 was joined to a road marking substrate (concrete) by an anchor bolt.

Example 4 The procedure of Example 1 was repeated, except that the retroreflective sheet layer (B-1) (manufactured by Sumitomo Suriem Co., 130 μm) was used instead of the retroreflective sheet layer (B). The sheets were bonded in the same manner as in Example 1 by using a bonding method.

Example 5 The procedure of Example 1 was repeated except that the hydrophilic stain resistant sheet layer (C-1) (the following composition) was used instead of the hydrophilic stain resistant sheet layer (C). Bonding was performed using the same sheet and bonding method.

Comparative Example 1 A sheet was bonded in the same manner as in Example 1 except that the hydrophilic hardly stainable sheet layer (C) was formed.

In the above Examples 1 to 5 and Comparative Example 1, the retroreflective sheet layer (B) uses a sheet of two colors (two colors of white and red) as shown in FIG. I placed the shape.

Hydrophilic non-stainable sheet layer (C): A urethane film (50 μm) was coated with the following composition and left at 20 ° C. for 5 days to cure the resin (30 μm).
m) The layer that was applied.

Composition: 187 parts by weight of methyltriethoxyquinane and 187 parts by weight of ethyl alcohol were added, and heated to 8 parts.
After the temperature reached 0 ° C, 30 parts by weight of 0.2N-hydrochloric acid was added and reacted at 80 ° C for 10 hours. Then add 30 parts by weight of triethylamine
A product obtained by raising the pH to 7 or more and conducting a condensation reaction at 80 ° C for 2 hours.

Hydrophilic non-stainable sheet layer (C-1): The following composition was applied to the surface of a urethane film (50 μm) at 50 ° C.
(30 μm).

Preparation of macromonomer: A mixture of 2720 parts by weight of methylmethoxysilane, 230 parts by weight of γ-methacryloxypropyltrimethoxysilane, 1130 parts by weight of deionized water, 2 parts by weight of 1% formic acid, and 1 part by weight of hydroquinone was mixed with 80 parts by weight. The mixture was reacted at a temperature of 5 ° C. for 5 hours to obtain a polysiloxane macromonomer having a number average molecular weight of 2,000.

Production Example of Organosilicon Copolymer A monomer mixture comprising 35 parts by weight of styrene, 20 parts by weight of glycidyl methacrylate, 20 parts by weight of 2-hydroxyethyl acrylate, and 25 parts by weight of the above macromonomer was prepared. The reaction was carried out at 100 ° C. for 8 hours in the presence of a xylene solvent to obtain an organosilicon copolymer having a number average molecular weight of about 18,000.

Next, the above-mentioned organosilicon copolymer (solid content)
100 parts by weight, 2 parts by weight of aluminum tris (ethyl acetoacetate), and 10 parts by weight of ethyl silicate 48 were added and dispersed.

The following tests were performed on the sheets of the examples and comparative examples.

Table 1 shows the results.

The performance in Table 1 was evaluated according to the following criteria.

Sheet appearance: The sheet surface was visually observed. ○ indicates good, Δ indicates inferior, and × indicates extremely poor.

Adhesion: Cross-cut the coating film from the sheet surface with a sharp blade, and apply an adhesive cellophane to the coating film.
After the tape was adhered and peeled off rapidly, the surface condition was evaluated. ○ indicates good, Δ indicates inferior, and × indicates extremely poor.

Stain resistance (1): After applying the soot paste adhering to the muffler of the car to the surface of the sheet, 7
After standing for one day, the smoke paste was lightly wiped off, washed with water, and then stained on the sheet surface by visual observation. ◎ means no stain at all, ○ means a little stain but no practical problem, △ means noticeable stain, and × means notable stain.

Stain resistance (2): (Initial retroreflectivity /
(Retroreflectance after testing for stain resistance (1)) x 100
Was measured.

Table 1

[0058]

[Table 1]

[0059]

[Brief description of the drawings]

FIG. 1 Figures used in Examples and Comparative Examples

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yasushi Maekawa 4-7-6 Doshomachi, Chuo-ku, Osaka-shi, Osaka F-term in Kansai Paint Co., Ltd. 2D064 AA12 AA22 BA01 CA03 CA05 CA09 DA05 DA06 EA02 EA03 EB22 JA02 2H042 EA04 EA13 EA17

Claims (10)

[Claims] 1. A retroreflective sheet for road marking, wherein a flat portion can be visually recognized three-dimensionally by a headlight of an automobile or the like by arranging figures having different hues in a predetermined shape. 2. The reflection sheet comprises an adhesive layer (A), an optional base sheet layer (a), an optional adhesive layer (b), a retroreflective sheet layer (B), if necessary. The retroreflective sheet for road marking according to claim 1, wherein the pressure-sensitive adhesive layer (c) and the hydrophilic non-stainable sheet layer (C) are sequentially laminated according to the order. 3. The retroreflective sheet layer (B) is a high brightness retroreflective sheet of an exposed lens type retroreflective sheet, an encapsulated lens type retroreflective sheet or a capsule lens type retroreflective sheet. The retroreflective sheet for road marking according to claim 1 or 2, wherein: 4. The method according to claim 1, wherein the hue is high brightness and low brightness, high saturation and low saturation, or a combination thereof.
The retroreflective sheet for road marking according to the above. 5. The hue is red / white, yellow / black, red / yellow, red / white / yellow or a combination of red / white / yellow / black. The retroreflective sheet for road marking according to claim 1 or 4, wherein: 6. The road marking recursion according to claim 2, wherein the hydrophilic non-staining type sheet layer (C) is a cured coating layer composed of a modified polysiloxane resin having a ladder structure. Reflective sheet. 7. An adhesive layer (A), a base sheet layer (a), an adhesive layer (b), and a road marking substrate such as concrete.
A retroreflective sheet for road marking (I), which is obtained by sequentially laminating a retroreflective sheet layer (B), an adhesive layer (c), and a hydrophilic non-contamination type sheet layer (C), is adhered to the sheet (I). A construction method characterized in that the agent layer (A) surface and the road marking substrate surface are pressure-bonded and joined so as to be in contact with each other. 8. A retroreflective road marking comprising a pressure-sensitive adhesive layer (A), a retroreflective sheet layer (B), a pressure-sensitive adhesive layer (c), and a hydrophilically soil-resistant sheet layer (C) sequentially laminated. After sticking the sheet (II) to an immobilization substrate, the immobilization substrate is bonded to a road marking substrate such as concrete. 9. The method according to claim 8, wherein a part of the surface of the immobilized base material and a part of the surface of the road marking base material are partially joined by an adhesive so that a gap is provided between the two to allow rainwater or the like to enter. The method according to claim 8, wherein the material can be removed. 10. The method according to claim 8, wherein the surface of the fixed base material and the surface of the road marking base material are physically joined by anchor bolts or the like.