JP2003300288A - Resin laminate containing ultraviolet absorber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an article of a resin laminate excellent in weather resistance. <P>SOLUTION: The resin laminate contains a specific triazine compound as an ultraviolet absorber. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin laminate having excellent weather resistance, and more particularly to a laminate film or a retroreflective sheet.

More specifically, the present invention relates to signs such as road signs and construction signs, license plates for vehicles such as automobiles and motorcycles, safety materials such as clothing and life preservers, marking of signs and the like, visible light, laser light. Alternatively, a retroreflective sheet useful as a reflection plate for infrared light reflection type sensors, and the like,
The present invention relates to a laminated film useful as a marking for signs, marking for vehicles, various protective films, adhesive films and the like.

[0003]

2. Description of the Related Art Various laminated films are well known in the prior art and include, for example, two-wheeled vehicles, four-wheeled vehicles and various other types of vehicles, various land and sea containers, yachts, boats and other various types of ships and other vessels.・ Striped stickers for decoration or display of containers; Advertising stickers used to display advertising letters, figures, patterns on signs and billboards; road signs, guide boards, product marks, etc. It is used in a wide range of applications such as marking films for various types of markings, etc., and protective films for undercoat protection.

Such a laminated film is disclosed in Japanese Patent Laid-Open No. 60-4543 and Japanese Patent Laid-Open No. 60-1951 by Yoshida et al.
No. 47, etc., and is commercially available.

Further, conventionally, a retroreflective sheet which reflects incident light toward a light source is well known, and the sheet utilizing its retroreflectivity is widely used in the above-mentioned fields of use. Among them, the cube-corner retroreflective sheet that uses the retroreflective principle of the cube-corner retroreflective element such as the triangular-pyramidal reflective element has a significantly higher retroreflective efficiency of light than the conventional retroreflective sheet using micro glass balls. It is excellent and its applications are expanding year by year due to its excellent retroreflective performance.

Such a retroreflective sheet and its manufacturing method are described in Stam's Japanese Patent Application Laid-Open No. 49-106839, etc., and are commercially available. .

A capsule lens type retroreflective sheet and a method for producing the same are described in, for example, Japanese Unexamined Patent Publication No. 60-194405 (US Pat. No. 4,653,854), and are commercially available. .

The encapsulating type retroreflective sheet and its manufacturing method are described in Yamanaka, JP-A-51-128293 and Ochi, et al., JP-A-8-101304.
It is also commercially available.

Further, conventionally, benzotriazole-based, cyanoacrylate-based, piperidinyl-based, benzophenone-based hydroquinone-based, salicylic acid-based compounds and the like have been known as ultraviolet absorbers used for laminate films and retroreflective sheets.

The use of the triazine compound of the formula (1) in a retroreflective sheet is disclosed in Pavelka et al., US Pat.
No. 312,132, etc.

However, the weather resistance of a resin laminate using an ultraviolet absorber such as a benzotriazole type, cyanoacrylate type, piperidinyl type, benzophenone type, hydroquinone type, salicylic acid type compound is insufficient,
In order to improve the weather resistance of a resin laminate having a long service life, a large amount of ultraviolet absorber must be added.

When a large amount of an ultraviolet absorber is added to a resin laminate in which hue and reflection performance are important, coloring is observed, which affects the hue of the resin laminate or cracks occur on the surface of the resin laminate. There is a problem in that it is easy to do so that it affects the reflection performance.

Further, since ultraviolet absorbers such as benzotriazole-based, cyanoacrylate-based, piperidinyl-based, benzophenone-based, hydroquinone-based, salicylic acid-based compounds and the like are not so well compatible with resins, heat in actual use, There is a problem that it is likely to be eluted from the sheet due to light or rainwater, and weather resistance cannot be maintained for a long time.

Further, the resin laminate using the ultraviolet absorbent of the formula (1) had insufficient weather resistance, and yellowing was recognized.

[0015]

Therefore, the present inventors have
As a result of intensive research to solve the above problems, it was found that, by using a special triazine-based compound in a resin laminate, the compound is retained in a sheet, and the weather resistance can be maintained for a long period of time. It came to completion.

That is, the present invention is: 1. A resin laminate containing a triazine compound (excluding compounds represented by the following formula (1)): 2. The resin laminate according to 1, wherein the triazine compound is a compound represented by the following formula (2). 3. The resin laminate according to 1 or 2, wherein the resin laminate is a laminate film or a retroreflective sheet. 4. The resin laminated body according to any one of 1 to 3, wherein the resin laminated body is a retroreflective sheet containing at least a triazine compound in a surface layer or a retroreflective element layer of the retroreflective sheet. 5. The resin laminated body according to any one of 1 to 4, wherein the resin laminated body is a triangular-pyramidal cube-corner retroreflective sheet. 6. V-shaped grooves whose cross sections are substantially symmetrical intersect each other, so that three side surfaces (a
₁ face, b ₁ face, c ₁ face or a ₂ face, b ₂ face, c ₂ face), on one bottom face (S-S ') common to a pair of triangular-pyramidal cube-corner retroreflective elements separated by Are arranged in a close-packed state so as to project to one side, the pair of triangular pyramid retroreflective elements, the side surfaces (c ₁ surface, c ₂ surface) facing each other are one base (x) To form a pair, and the bottom surface (S-
S ') is one side surface (a) of the pair of triangular-pyramidal retroreflective elements.
Bottom (z, z) of the _1st and a _2nd surfaces and the other side (b _1st , b _2nd )
Is a common plane that includes both the bases (y, y) of
The side surfaces (a ₁ surface, b ₁ surface) formed by the grooves (y, z) of the triangular-pyramidal retroreflective element are parallel to the common bottom side (x) and have substantially the same cross-sectional shape. Other V-shaped grooves (w, w, ...)
However, by crossing the apex (H ₁ , H ₂ ) of the triangular-pyramidal retroreflective element without cutting it, the side surface (a ₁ surface, b ₁ surface)
Are multiple side surfaces (a ₁₁ side, b ₁₁ side, a ₁₂ side, b ₁₂ side, and a side)
₁₃ planes, b plane ₁₃ ...), so that the three side planes (a plane ₁₁ , b plane ₁₁ , a plane ₁₂ , b) intersecting each other at substantially right angles.
₁₂ planes, a ₁₃ planes, b ₁₃ planes ...) and two or more cube corner element pairs are formed, and the optical axes of these cube corner element pairs are oriented in directions with respect to a common base (x). 6. The resin laminate according to 5, which includes a retroreflective element pair made up of a cube-corner element pair having 180 ° different optical axis inclinations (θ). 7. The resin laminated body according to any one of 1 to 4, wherein the resin laminated body is a capsule lens type retroreflective sheet. 8. The resin laminated body according to any one of 1 to 4, wherein the resin laminated body is an enclosed retroreflective sheet. 9. The resin laminate according to any one of 1 to 3, wherein the resin laminate is a laminate film and at least the surface layer contains a triazine compound represented by the following formula (2). 10, further containing a hindered amine light stabilizer 1
The resin laminate according to any one of 1 to 9. 11. The resin laminate is a retroreflective sheet containing a hindered amine light stabilizer in at least the surface layer or retroreflective element layer of the retroreflective sheet.
The resin laminate according to 0. Regarding [Detailed Description of the Invention]

[0017]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below.

The resin laminate used in the present invention and the method for producing the same are as follows:
The triazine compound of the formula (2) is contained.

The triazine-based compound blocks ultraviolet light in a wavelength range wider than that of conventionally used benzophenone-based ultraviolet absorbers. Further, since the sublimation property is small, it is practically excellent because it can be contained in an amount that does not substantially affect the film strength.

Among the triazine-based compounds, the compounds of the formula (2) are preferable as compared with the compounds of the formula (1), because excellent weather resistance can be obtained. The mechanism of action is not clear, but it is assumed as follows. Tinuvin P (molecular weight 2
In 25.3), since the temperature is applied during pellet molding or sheet molding, the UV absorber added is partially reduced by sublimation. It also has a similar skeleton (2)
Formula Tinuvin 1577 (molecular weight 425) and Formula (1) CYA
Regarding the difference in SORB UV-1164 (molecular weight 510), in the latter case, the reactivity of the —OH group due to steric hindrance due to the methyl group contained in the skeleton in the latter, or the difference in compatibility with polycarbonate resin or acrylic resin I presume.

The compounding amount of the triazine-based compound of the above formula (2) is not strictly limited, and can be varied over a wide range depending on the application of the resin laminate of the present invention and the desired degree of weather resistance. However, in general, 0.0
1 to 10.0 parts by weight, more preferably 0.01 to 3.
It is preferably 0 part by weight, particularly preferably in the range of 0.02 to 2.0 parts by weight.

In the resin laminate according to the present invention,
The triazine-based compound of the formula (2) can be used alone or in combination with other ultraviolet absorbers and / or light stabilizers.

Examples of such an ultraviolet absorber include the following. Hydroquinone series: Hydroquinone, hydroquinone disalicylate, etc. Salicylic acid type: phenyl salicylate, paraoctyl phenyl salicylate, etc. Benzophenone type: 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4-hydroxybenzophenone, 2,
2'-hydroxy 4,4'-dimethoxybenzophenone,
2-hydroxy-4-benzoyloxybenzophenone,
2,2'-hydroxy-4-methoxybenzophenone, 2-
Hydroxy-4-methoxy-5-sulfonebenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone,
2,2'-hydroxy-4,4'-dimethoxy-5-sodium sulfobenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone and the like. Benzotriazole type: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-carboxylic acid butyl ester benzotriazole, 2- (2 '-Hydroxy-5'-
Methylphenyl) -5,6-dichlorobenzotriazole,
2- (2'-hydroxy-5'-methylphenyl) -5-ethylsulfone benzotriazole, 2- (2'-hydroxy
-5'-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-
Amylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-dimethylphenyl) -5-methoxybenzotriazole, 2- (2'-methyl-4'-hydroxyphenyl) benzotriazole,
2- (2'-stearyloxy-3 ', 5'-dimethylphenyl) -5-methylbenzotriazole, 2- (2'-hydroxy-5-carboxylic acid phenyl) benzotriazole ethyl ester, 2- (2'- Hydroxy-3'-methyl-
5'-tert-butylphenyl) benzotriazole, 2-
(2'-Hydroxy-3 ', 5'-ditertiarybutylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-5-methoxyphenyl) benzotriazole, 2
-(2-Hydroxy-5'-phenylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-cyclohexylphenyl) benzotriazole, 2- (2'-
Hydroxy-4 ′, 5′-dimethylphenyl-5-carboxylic acid benzotriazole butyl ester, 2- (2′-hydroxy-3 ′, 5′-dichlorophenyl) benzotriazole, 2- (2′-hydroxy-4) ′, 5′-Dichloro) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-
Dimethylphenyl) -5-ethylsulfone benzotriazole, 2- (2'-hydroxy-5'-phenylphenyl)
Benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) -5-methylbenzotriazole, 2- (2'-hydroxy- 5'-methylphenyl) -5-carboxylic acid ester benzotriazole, 2-
(2'-acetoxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditertiarybutylphenyl) -5-chlorobenzotriazole, 2-2'
-Methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] and the like. Cyanoacrylate-based: ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.

Among these UV absorbers, benzophenone-based and benzotriazole-based ones are preferable. Among them, benzophenone-based ones are 2,3′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′. -Dihydroxy-4-methoxybenzophenone and 2,2 ', 4,
4'-tetrahydroxybenzophenone; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5- in the benzotriazole system
Methylphenyl) -5,6-dichlorobenzotriazole, 2- (2-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl
-5'-tert-butylphenyl) benzotriazole, 2-
(2'-Hydroxy-3 ', 5'-ditertiarybutylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-5'-phenylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-5'-octoxyphenyl) benzotriazole and the like are effective.

Further, in a commercially available product, a benzotriazole-based or benzophenone-based UV absorber can be used as the UV absorber, and as an example of the benzotriazole-based UV absorber, Seesorb 701, 702 manufactured by Cipro Kasei Co., Ltd. , 703, 704, 706, 70
9: Asahi Denka Co., Ltd. ADEKA STAB LA31, LA3
2; Sumitomo Chemical 250 manufactured by Sumitomo Chemical Co., Ltd .; Biosorb 590 manufactured by Kyodo Pharmaceutical Co., Ltd., and the like.
Examples of the benzophenone-based ultraviolet absorber include ADEKA STAB 1413 and LA51 manufactured by Asahi Denka Co., Ltd., Seesorb 1001 and 103 manufactured by Cipro Kasei Co., Ltd., and Sumisorb 110S manufactured by Sumitomo Chemical Co., Ltd.

The addition amount of these ultraviolet absorbers is usually
It is preferably in the range of 0.01 to 10.0 parts by weight, particularly 0.01 to 3.0 parts by weight, and particularly 0.02 to 2.0 parts by weight.

If necessary, a light stabilizer may be added to the resin laminate of the present invention for the purpose of improving weather resistance, and among them, it is preferable to add a hindered amine light stabilizer. As the light stabilizer that can be used in that case, a piperidine-type hindered amine light stabilizer having a tertiary amine structure with a molecular weight of 600 or more is particularly preferable because it can maintain weather resistance.

Examples of hindered amine light stabilizers that can be used are listed in Table 1 below.

[Table 1] Those having structural formulas such as

Commercially available products include, for example, TINUVIN 622LD, 765, 144, manufactured by Ciba-Geigy Co., Ltd. of Japan.
KIMASORB 119FL; ADEKA STAB LA52 and LA62 manufactured by Asahi Denka Kogyo Co., Ltd., Sanol LS2626 manufactured by Sankyo Co., Ltd., and the like.

These light stabilizers may be used alone or in combination of two or more kinds, usually in the range of 0 to 3 parts by weight, preferably 0.1 to 1 part by weight, particularly preferably 0.2 to 0.8 part by weight. Can be blended in an amount within.

Furthermore, the above-mentioned light stabilizer can be introduced into the skeleton of the resin in the form of, for example, an ester with (meth) acrylic acid. Examples of such a reactive light stabilizer include 1,2,2,6,6-pentamethylpiperidyl methacrylate and 2,2,6,6-tetramethylpiperidyl methacrylate, which constitute a resin. The light stabilizer group can be introduced into the resin skeleton by copolymerization with other reactive monomers such as (meth) acrylic acid esters, vinyl acetate, vinyl chloride and the like.

When a fluorescent colorant is used in the resin laminate used in the present invention, it is preferable to add a light stabilizer to the layer containing the fluorescent colorant because the weather resistance is improved.

Further, the layer containing the fluorescent dye may be blended with a benzoate light stabilizer for the purpose of imparting weather resistance. The benzoate-based light stabilizer that can be used is a benzoate-type quencher, for example, Tinuvin 1 manufactured by Ciba-Geigy Co., Ltd. of Japan.
20 (brand name) can be illustrated.

Hereinafter, the resin laminate of the present invention will be described in more detail with reference to the drawings. The retroreflective sheet of the present invention will be described first with reference to FIG. 1, which is a sectional view, of one mode of a preferred structure of a cube-corner type retroreflective sheet.

In FIG. 1, (3) is a retroreflective element layer in which triangular pyramidal cube-corner reflective elements are arranged in the closest packing state, and a retroreflective sheet is used for this retroreflective element layer (3). Depending on the purpose and usage environment, moisture penetrates into the back surface of the surface protective layer (1), the printed layer (2) for transmitting information to the observer or coloring the sheet, and the retroreflective element layer (3). A binder layer (6) for achieving an encapsulating structure for preventing the occurrence of sticking, a support layer (7) supporting the binder layer (6), and the retroreflective sheet are attached to another structure. For this purpose, an adhesive layer (8) and a release material layer (9) can be provided (for details, see, for example, PCT International Publication WO98 / 18028).

The printing layer (2) is usually the surface protective layer (1).
Between the reflection element layer (3) and the surface protection layer (1)
Or on the reflective side surface of the reflective element layer (3), and usually by means of gravure printing, screen printing, inkjet printing or the like. It is also possible to suppress fading by using the present invention or the above-mentioned ultraviolet absorbers alone or in combination with these printing layers, and further by using a light stabilizer alone or in combination.

Cube corner type retroreflective element layer (3)
Can be made of a polycarbonate resin, an acrylic resin, a vinyl chloride resin, or a urethane resin. Additives such as an ultraviolet absorber, a light stabilizer and an antioxidant may be added to the retroreflective element layer individually or in combination for the purpose of improving weather resistance. Further, as a colorant, various organic pigments, inorganic pigments, fluorescent pigments, non-fluorescent dyes, etc. can be contained.

The same resin as that used for the retroreflective element layer (3) can be used for the surface protective layer (1), and for the purpose of improving weather resistance, an ultraviolet absorber, a light stabilizer and an oxidation agent are used. Additives such as inhibitors can be blended alone or in combination. Further, various organic pigments, inorganic pigments, fluorescent pigments, fluorescent dyes, non-fluorescent dyes, etc. can be contained as colorants. Further, the surface protective layer (1) may be divided into two or more layers, and each layer may contain the above-mentioned various additives and colorants individually or in combination.

The material forming the retroreflective element layer (3) is not particularly limited as long as it satisfies the flexibility which is one of the objects of the present invention, but generally,
Those having optical transparency and uniformity are preferable. Examples of materials that can be used to form the retroreflective element layer (3) in the present invention include polycarbonate resin, vinyl chloride resin, (meth) acrylic resin, epoxy resin, styrene resin, polyester resin, fluororesin, and polyethylene. Olefin resins such as resins and polypropylene resins, cellulosic resins, urethane resins and the like, among them, among others,
Polycarbonate resin, (meth) acrylic resin, vinyl chloride resin and urethane resin are suitable.

The retroreflective element layer (3) is generally provided with an air layer (5) on the back surface of the cube-corner retroreflective element in order to satisfy the conditions for total internal reflection. It is preferable that the retroreflective element layer (3) and the binder layer (6) are hermetically sealed by a mesh-shaped joint portion (4) in order to prevent a decrease in the critical angle due to the penetration of water under the use conditions.

As the method of hermetically sealing, for example, US Pat. Nos. 3,190,178 and 4,025,15 are cited.
The method disclosed in Japanese Utility Model Publication No. 9 and Japanese Utility Model Publication No. 50-28,669 can be used. Examples of the resin used for the binder layer (6) include (meth) acrylic resin, polyester resin, alkyd resin, and epoxy resin, and the bonding portion (4) can be formed by an embossing method. At that time, the retroreflective element layer (3) and the binder layer (6)
As a method for bonding with, a known heat-fusible resin bonding method, a thermosetting resin bonding method, an ultraviolet curable resin bonding method, an electron beam curable resin bonding method or the like can be appropriately adopted.

The binder layer (6) used in the present invention can be formed on the entire surface of the support layer (7), or printed on the joint portion with the retroreflective element layer (3), that is, the joint portion (4). It is also possible to selectively install by a method such as a method.

Examples of the material constituting the support layer (7) include a film or plate made of the same resin as the resin constituting the retroreflective element layer (3) or a general film moldable resin, fiber, cloth, Metal foils or plates made of stainless steel or aluminum can be used alone or in combination.

The adhesive layer (8) used for sticking the resin laminate of the present invention to a metal plate, a wooden plate, a glass plate, a plastic plate and the like and a release layer (9) for covering the adhesive layer are Those known per se can be appropriately selected and used. The adhesive for the adhesive layer (8) can be appropriately selected from pressure-sensitive adhesives, heat-sensitive adhesives, cross-linking adhesives and the like. The ultraviolet absorber of the present invention can be added to these adhesives. As the pressure-sensitive adhesive, for example, polyacrylic acid ester adhesive obtained by copolymerizing acrylic acid ester such as butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, nonyl acrylate with acrylic acid, vinyl acetate, etc., silicone. A resin-based adhesive, a rubber-based adhesive, or the like can be used, and as the heat-sensitive adhesive, for example, an acrylic-based, polyester-based, or epoxy-based resin can be used.

According to the present invention, in the cube-corner type retroreflective sheet having the above-mentioned structure, the incident light side (arrow 10 in FIG. 1) with respect to the enclosed air layer (5).
At least one layer close to
In FIG. 1, at least one layer of the surface protective layer (1), the printing layer (2) and the retroreflective element layer (3), preferably the retroreflective element layer (3), is provided with the triazine compound represented by the above formula (2). Is optionally blended with other UV absorbers and / or light stabilizers as described above, whereby
A cube-corner retroreflective sheet having excellent weather resistance can be obtained.

The retroreflective element layer is compounded by, for example, a method of kneading and melting with a resin, a method of dispersing and dissolving in a resin compounding solution, a method of dissolving with a solvent and then mixing with a resin compounding solution, and the like. You can

Further, in the present invention, a specular reflection layer made of a metal such as aluminum, copper, silver or nickel can be provided on the surface of the retroreflective element. In the present invention, the thickness of the specular reflection layer is not particularly limited, but 800 to 1
500 angstroms is preferred. If the thickness of the specular reflection layer is 800 angstroms or more, the reflection efficiency at the specular reflection layer is sufficient, and the amount of light passing through the specular reflection layer is extremely small, which is preferable, and if it is 1500 angstroms or less, the retroreflection efficiency decreases. It is preferable because it does not darken the appearance. In the case where the specular reflection layer is provided, the critical angle for reflection is improved, and the incident angle is 30
It is preferable because the retroreflective performance is excellent at an angle of not less than 40 °, preferably not less than 40 °.

The specular reflection layer can be provided by means such as vacuum deposition, chemical plating and sputtering. Among the methods for providing the specular reflection layer, the vacuum vapor deposition method using aluminum can reduce the vapor deposition temperature, so that the thermal deformation of the retroreflective element in the vapor deposition step can be suppressed to the minimum, and the resulting specular reflective layer The color tone is also brightest, which is preferable.

The continuous vapor deposition treatment apparatus for the aluminum specular reflection layer is laminated on a vacuum container capable of maintaining a vacuum degree of about 7 to 9 × 10 −4 mmHg, a substrate sheet installed therein, and the light incident side surface thereof. The unwinding device that unwinds the prismatic raw sheet consisting of two layers of the surface protection layer, the winding device that winds up the vapor-deposited prismatic raw sheet, and the aluminum heater between them in the graphite crucible with the electric heater. It consists of a heating device capable of melting. In a graphite crucible, pure aluminum pellets having a purity of 99.99% by weight or more and granular metal titanium are charged so that the weight ratio is 100: 1. For example, AC voltage 350 to 360V, current 115 to 120A. At a processing rate of 30 to 70 m / min, vapor deposition can be performed as a specular reflection layer on the reflection side surface by the molten and vaporized aluminum atoms.

Further, in the present invention, the retroreflective element of the triangular-pyramidal cube-corner retroreflective sheet of the present invention has three V-shaped grooves having substantially symmetrical cross-sections intersecting each other, so that three substantially right angles are formed. Side faces (a1 face, b1 face, c1
Surface or a2 surface, b2 surface, c2 surface), a pair of triangular-pyramidal cube-corner retroreflective elements separated by a pair of close-packed so as to project to one side on one common surface (S-S ') The pair of triangular-pyramidal retroreflective elements are arranged in a
Sides facing each other (c1 surface, c2 surface) have one base (x)
To form a pair, the bottom surface (S-S '), one side surface (a1 surface, a2 surface) of the pair of triangular pyramid retroreflective elements (z, z) and the other side. The side surface (a1, b2 surface) is a common plane that includes both the bottom sides (y, y) of the triangular pyramid retroreflective element and is formed by the grooves (y, z). Face, b
1) is parallel to the common base (x) and has another V-shaped groove (w, w, ...) Of substantially the same sectional shape as the apex of the triangular-pyramidal retroreflective element. By crossing without cutting (H1, H2), the side surfaces (a1 surface, b1 surface) have a plurality of sub-side surfaces.
(A11 plane, b11 plane, a12 plane, b12 plane, and a13 plane, b13 plane ...
...), so that the three sub-side surfaces (a11 plane, b11 plane, a12 plane, b12 plane, and a13 plane) intersect at substantially right angles to each other.
Surface, b13 surface ...), two or more cube corner element pairs are formed, and the optical axes of these cube corner element pairs are different from each other by 180 ° with respect to the common base (x), It is preferable to include a retroreflective element pair composed of a cube corner element pair having the same optical axis inclination (θ).

The triangular-pyramidal cube-corner type retroreflective sheet having the above-mentioned sub-side surface is different from the retroreflective coefficient of the conventional triangular-pyramidal cube-corner type retroreflective sheet in comparison with the retroreflective coefficient in the front direction of the sheet and the incidence. It is preferable because excellent retroreflective properties in the direction of a large angle can be obtained.

Next, a capsule lens type retroreflective sheet which is another preferred embodiment of the present invention will be described with reference to FIG. 2 which is a sectional view thereof.

In FIG. 2, (3) is a retroreflective element layer in which micro glass sphere type reflective elements in which a part of the glass spheres of the present invention are mirror-finished are arranged in the closest packing state. The layer (3) includes a surface protective layer (1), a printing layer (2) for transmitting information to an observer or coloring the sheet, and a retroreflective layer, depending on the purpose of use and environment of use of the retroreflective sheet. A binder layer (6) for achieving an enclosed and sealed structure for preventing moisture from entering the back surface of the element layer (3), a support layer (7) supporting the binder layer, and the retroreflective sheet. Can be provided with an adhesive layer (8) and a release material layer (9) for attaching the same to other structures (for details, see, for example, JP-A-8-86910 (US Pat. 824,390; European Patent No. 693,697.
No.))).

As the material forming each layer of the capsule lens type retroreflective sheet, the same materials as those described above for each corresponding layer of the cube-corner type retroreflective sheet can be used.

According to the present invention, in the capsule lens type retroreflective sheet shown in FIG. 2, at least one layer closer to the incident light side (the side indicated by the arrow 10 in FIG. 2) than the enclosed air layer (5). That is, the surface protection layer (1) and / or the printing layer (2) in FIG.
The triazine-based compound of the formula is optionally blended with other UV absorbers and / or light stabilizers,
Thereby, the capsule lens type retroreflective sheet having excellent weather resistance can be obtained.

Next, an encapsulated retroreflective sheet, which is another aspect of the preferred structure of the present invention, will be described with reference to FIG. 3 which is a sectional view thereof.

As shown in FIG. 3, a surface layer (1) made of a transparent resin which supports a large number of high refractive index transparent microspheres (3) such as transparent micro glass spheres so as to be embedded in the surface layer (1). Is formed along the curved surface of the layer of the transparent microspheres (3), which is installed so as to embed approximately 1/2 of the diameter, and the layer of the transparent microspheres (3) protruding from the surface layer, and is formed on the surface thereof. The specular reflection layer (11) is formed of an aluminum vapor-deposited film having a constant thickness so that the specular reflection layer (11) is located substantially at the optical focus position of the transparent microspheres (3).
The high refractive index transparent microspheres (3), the focal layer (10), and the specular reflection layer (11) are substantially arranged in a positional relationship that optically satisfies the retroreflection condition of light, and the lens type retroreflection element is used. Is forming. The surface layer may have a two-layer structure of a surface protective layer which is the outermost layer of the encapsulation type retroreflective sheet and a transparent microsphere binding layer which is embedded adjacently and supports the transparent microspheres. (For details, see JP-A-8-101304.
reference)

As a material for forming each layer of the encapsulated retroreflective sheet, the same materials as those described above for the corresponding layers of the cube-corner retroreflective sheet can be used.

According to the present invention, in the encapsulated retroreflective sheet shown in FIG. 3, the surface layer and the reflective layer have the same triazine-based compound of the formula (2) as in the case of the cube-corner retroreflective sheet. As described above, if necessary, it is blended with other UV absorbers and / or light stabilizers, whereby an encapsulated retroreflective sheet having excellent weather resistance can be obtained.

Similarly, the laminate film is also blended with the triazine compound of the formula (2), if necessary, together with other UV absorbers and / or light stabilizers, whereby the weather resistance is improved. An excellent laminate film can be obtained.

Also, when the laminate film is a protective film for protecting the underlayer, the triazine compound represented by the formula (2) may be added to the other UV absorber and / or the light stabilizer as necessary as described above. A film having excellent weather resistance capable of protecting the underlayer for a long period of time can be obtained by blending with the agent.

In these laminated films, the triazine-based compound of the above formula (2) is blended in the film base material and / or the pressure-sensitive adhesive layer together with other ultraviolet absorbers and / or light stabilizers as necessary, as described above. As a result, a laminated film having excellent weather resistance can be obtained.

3 parts by weight of a stabilizer (Adeka Stab AC-111, manufactured by Asahi Denka), an epoxidized soybean oil (O-130P, manufactured by Asahi Denka), an acrylic resin (AF
R-075A, manufactured by Nippon Carbide Industry Co., Ltd.) and 10 parts by weight of triazine compound TINUVIN 1 manufactured by Nippon Ciba Geigy Co., Ltd.
2.57 parts by weight of 577 was dissolved in 50 parts by weight of trimethylbenzene (Solvesso 100) to prepare a uniform solution. Add polyester plasticizer (Adeka Sizer
(PN-1430, Asahi Denka Co., Ltd.) 35 parts by weight and stirred to form a uniform solution, then 100 parts by weight of vinyl chloride resin (PSH-10, Kanebuchi Kagaku Co., Ltd.) is added, stirred, mixed and homogenized. A paste sol was obtained. PET paste (SG
Z, made by Teijin DuPont Film) and dried at 120 ° C for 2 minutes and then at 200 ° C for 1 minute to a thickness of about 5
A 0 μm transparent resin layer was formed. This transparent resin layer was peeled off from the PET film to obtain a transparent film. Mold manufacturing

A diamond plate having a tip angle of 71.52 ° was used on a brass plate of 100 mm square whose surface was cut flat, and the V-shaped groove had a repeating pitch of 210.88 μm in the y and z directions. The depth of the V-shaped groove is 100 μm, and the intersection angle of the V-shaped groove in the y direction and the z direction is 58.76.
A large number of V-shaped parallel groove groups having symmetrical y-direction and z-direction cross-sectional shapes were cut by a fly-cutting method in a repeating pattern so that the cross-section became 0 °.

Thereafter, the V-shaped groove in the x direction was formed by using a diamond bite having a tip angle of 68.53 °, the repeating pitch of the V-shaped groove was 214.92 μm, and the depth of the V-shaped groove was 115 μm. And a V-shaped parallel groove which is parallel to a straight line connecting two intersections of the y-direction groove and the z-direction groove, and has a symmetrical cross-sectional shape in the x-direction so that the offset amount from the straight line is 11 μm. The group was cut in a repeating pattern to form a mother board in which a large number of convex triangular pyramidal cube corner element groups were arranged in a close-packed shape on a brass plate.

The height (hx1) from the vertex (H1) to the bottom surface (Sx-Sx ') of the pair of triangular pyramidal retroreflective elements thus formed is 115 μm, and the height from the vertex (H2) to the bottom surface (Sx-Sx-) is 115 μm. The height (hx2) from Sx ′) is 100 μm, and the height (hyz1) from the apex (H1) to the bottom surface (SS ′) is 100 μm, and the height (H2) from the apex (H2) to the bottom surface (S
The height (hyz2) up to −S ′) was 85 μm. The triangular pyramidal retroreflective element had an optical axis tilt angle (θ) of + 1 °, and the apex angles of the side surfaces forming the reflective element were 90 °. (Mold 1) (For this mold, see Japanese Patent Application No. 2001-280575)

Using a diamond bite with a tip angle of 83.11 ° on a brass plate of 100 mm square whose surface was cut flat
Repeating pitch of V-shaped groove in y direction and z direction is 201.4
5 μm, the depth of the V-shaped groove is 100.00 μm, and y
Fly-cutting with a repeating pattern of multiple V-shaped parallel groove groups with symmetrical y-direction and z-direction cross-sections so that the crossing angle of the V-shaped grooves in the z-direction is 38.207 ° It was cut by the method.

Further, a V-shaped groove in the x direction was formed by using a diamond bite having a symmetric cross-sectional shape and a tip angle of 40.53 °, and the V-shaped groove had a repeating pitch of 307.77 μm and a V-shaped groove. The depth is 100.00 μm, and V-shaped parallel groove groups are cut in a repeating pattern so as to pass through the two intersections of the y-direction groove and the z-direction groove, and a large number of convex shapes are formed on the brass plate. The triangular pyramid-shaped cube corner element group of was arranged in the closest packing state.

Thereafter, the V-shaped groove in the w direction was formed by using a diamond bite having a similar cross-sectional shape and a tip angle of 40.53 °, and the repeating pitch of the V-shaped groove was 307.77 μ.
The depth of the m-shaped and V-shaped grooves is 100.00 μm.
A V-shaped parallel groove group is cut in a repeating pattern so as to pass through the middle point of the V-shaped groove group, and a large number of convex CC element groups according to the present invention are arranged on a brass plate in a close-packed state. Formed a master mold. In this matrix, the number of V-shaped grooves in the w direction between the two V-shaped grooves in the x direction was one.

The height (h) from the apex (H11 or H21) to the bottom surface (S-S ') of the CC element pair thus formed
Was 100 μm. Also, the optical axis tilt angle of this CC element
(θ) was + 15 °, and the apex angles of the three side faces constituting the reflective element were all 90 °.

The cutting parameters used to create this master block are summarized below. V-groove depth in x, y, z and w directions 100.00 μm y and z-direction V-groove angle 83.11 ° V-groove angle in x and w-direction 40.53 ° y- and z-direction V-groove pitch 201.46 μm x and w-direction V-groove pitch 307.77 μm y-direction and z-direction V-groove crossing angle 38.21 ° y, z-direction and x-direction V-groove crossing angle 70.90 ° Optical axis tilt angle 15 °

Using this brass mother die, a concave cube-corner mold whose material was nickel and whose shape was inverted was obtained by electroforming using a nickel sulfamate solution having a concentration of 55%. It was created. (Mold 2) (For this mold, see Japanese Patent Application No. 2001-241964)

Hereinafter, the present invention will be described more specifically with reference to Examples.

Example 1 Bisphenol-type polycarbonate resin "Iupilon H300" manufactured by Mitsubishi Engineering Plastics Co., Ltd.
0 ”100 parts by weight of an ultraviolet absorber represented by the chemical formula (2) (trade name: TINUVIN 15 manufactured by Nippon Ciba-Geigy Co., Ltd.)
77) of 0.2 parts by weight, and a rotation speed of 100 using a high-speed rotary mixer and Henschel mixer manufactured by Mitsui Mining Co., Ltd.
Mix for 15 minutes at rpm. This mixed resin is extruded at a temperature of 240 using a short-axis extruder equipped with a screw having a screw length to diameter ratio of 30: 1 and a compression ratio of 3.0.
Pellets were obtained by extruding from a nozzle having a diameter of 4 mm under the conditions of ° C and a rotation speed of 35 rpm, followed by water cooling and cutting.

The pellets were dried at 80 ° C. for 12 hours and then extruded at a temperature of 240 ° C. using a short-axis extruder equipped with a screw having a screw length / diameter ratio of 30: 1 and a compression ratio of 3.0. Extrusion was carried out under the conditions of a rotation speed of 50 rpm to obtain a polycarbonate resin film having a thickness of 200 μm.

The surface layer of this polycarbonate resin film contained 1.8 parts by weight of the triazine-based compound TINUVIN 1577 manufactured by Ciba-Geigy Co., Ltd. in a thickness of 50.
Acrylic resin film (Sanduren 014NST manufactured by Kanegafuchi Chemical Industry Co., Ltd.) having a thickness of μm was laminated by a thermal bonding method using a pair of heat rolls at 200 ° C., and then a polycarbonate resin film was applied to the mold surface using a mold 1. Supply so as to contact,
Compression molding was performed under the conditions of molding temperature of 200 ° C and molding pressure of 50 kg / cm2, the resin sheet was taken out after cooling to 30 ° C under pressure, and a large number of triangular pyramidal retroreflective elements were arranged in a close-packed triangular shape. A pyramidal cube-corner retroreflective sheet intermediate was obtained.

On the other hand, a 38 μm thick white polyethylene terephthalate film manufactured by Mitsubishi Kagaku Polyester Film Co., Ltd. was coated and laminated with a polyester resin hot melt adhesive Byron RN9300 manufactured by Toyobo Co., Ltd. in a thickness of 35 μm by an extrusion method. A binder laminated support film was prepared.

The triangular pyramidal cube-corner retroreflective sheet intermediate and binder laminated support film were passed between a mold roll having mesh-like projections and a backup roll, and then an acrylic adhesive having a thickness of about 70 μm was used. The agent (KP-997 manufactured by Nippon Carbide Industry Co., Ltd.) was laminated to obtain a hermetically sealed cube corner retroreflective sheet.

Example 2 A process in which a polyethylene resin having a thickness of about 20 μm is laminated on paper is heated to about 105 ° C., and an average particle diameter of about 65 is applied on the paper.
Glass beads having a diameter of μm and a refractive index of about 1.91 were uniformly and densely dispersed and pressed by a nip roll to embed the glass beads in polyethylene resin to about 1/3 of the diameter.

Thereafter, aluminum is applied to the surface of the process paper in which the glass beads are embedded by using a vacuum vapor deposition machine to about 0.1 μm of aluminum.
It was vacuum-deposited to a thickness of m.

Next, methyl methacrylate (MMA) -was applied onto the silicon-treated polyethylene terephthalate film.
Methyl isobutyl ketone / toluene (1/1) solution of ethyl acrylate (EA) -2-hydroxyethyl methacrylate (2-HEMA) copolymer (weight composition ratio: MMA / E
A / 2-HEMA = 20/65/15, solid content = 50%) 100 parts by weight and 1-methoxypropylacetate-2 / xylene (1/1) solution of hexamethylene diisocyanate cross-linking agent (solid content = 75% ) Apply 14.2 parts by weight of the mixed solution and dry to a thickness of 40
A reinforcing layer of μm was formed.

Further, on the reinforcing layer, methyl methacrylate (MMA) -ethyl acrylate (EA) -2-
Methyl isobutyl ketone / toluene (1/1) solution of hydroxyethyl methacrylate (2-HEMA) copolymer (weight composition ratio: MMA / EA / 2-HEMA = 40/55/5, solid content = 40%) 100 weight Parts of the acrylic resin solution A obtained by mixing 30 parts by weight of titanium oxide with methyl methacrylate (MMA) -butyl acrylate (BA) -styrene (St) copolymer methyl isobutyl ketone solution B (solid content = 20). %; Multi-stage polymerization type internally crosslinked resin) and 13 parts by weight of a solution of cellosolve acetate butyrate resin in methyl isobutyl ketone (solid content = 15%). A reinforcing layer-binder layer laminate was obtained by forming a binder layer having a thickness of about 80 μm.

Next, glass beads were embedded in the binder layer of the above laminate on the aluminum deposition side of the paper by about 1/3. Then, it was aged at 35 ° C. for 14 days to substantially complete the crosslinking of the reinforcing layer, and the shear stress S of the reinforcing layer and the binder layer was measured. As a result, the bending stress S of the reinforcing layer was 9.48 × 10 6 dyne / cm 2, and the bending stress S of the binder layer was 4.78 × 10 5 dyne / cm 2.

Next, the polyethylene resin laminating process paper was peeled off from this laminate, and 0.2% of the UV absorber represented by the chemical formula (2) (Tinubin 1577 manufactured by Nippon Ciba-Geigy Co., Ltd.) was exposed on the exposed glass beads.
Partial thickness of about 75 μm and total light transmittance of about 93% of non-stretched acrylic film (Sanduren 014NST manufactured by Kanebuchi Chemical Co., Ltd.) are placed on top of each other, and the surface temperature is 0.3 mm with a net-like convex engraving. Thermal deformation molding was carried out by passing the acrylic film side between the metal roll at about 190 ° C. and the rubber roll at surface temperature of about 60 ° C. while pressurizing so that the acrylic film side was in contact with the rubber roll. Here, the shear stress S of the reinforcing layer and the binder layer was measured again, but both the reinforcing layer and the binder layer showed no significant difference from the shear stress before the heat deformation molding.

A silicone-treated polyethylene terephthalate film was removed from this heat-deformed molded product to obtain a thickness of about 40 μm.
A m-acrylic adhesive (KP-997 manufactured by Nippon Carbide Industry Co., Ltd.) was laminated on the reinforcing layer to prepare a retroreflective sheet.

Example 3 A hermetically sealed cube-corner retroreflective sheet was obtained in the same manner as in Example 1 except that the ultraviolet absorber was not added to the polycarbonate resin film.

Example 4 Implementation was carried out except that "Sunduren XT-527" manufactured by Kanegafuchi Chemical Co., Ltd. containing no ultraviolet absorber was used in place of "Sunduren 014NST" manufactured by Kanegafuchi Chemical Co., Ltd. as an acrylic film. A sealed-enclosed cube-corner retroreflective sheet was obtained in the same manner as in Example 1.

Example 5 As a UV absorber to be added to a polycarbonate resin film, TINUVIN 1577 and a benzotriazole-based UV absorber manufactured by Nippon Ciba Geigy Co., Ltd.
Examples except that P was used in an amount of 0.1 parts by weight each and "Sanduren XT-527" was used as the acrylic film instead of "Sanduren 014NST" manufactured by Kanegafuchi Chemical Industry Co., Ltd.
A sealed enclosed cube corner retroreflective sheet was obtained in the same manner as in 1.

Example 6 A hermetically sealed cube-corner retroreflective sheet was obtained in the same manner as in Example 1 except that the mold 2 was used.

Comparative Example 1 A polycarbonate resin film was obtained by using 0.2 parts by weight of benzotriazole type UV absorber TINUVIN P manufactured by Ciba-Geigy Co., Ltd. in place of TINUVIN 1577 as the UV absorber added to the polycarbonate resin film, As an acrylic film, instead of "Sunduren 014NST" manufactured by Kanegafuchi Chemical Industry Co., Ltd., "Sunduren XT-52" manufactured by Kanegafuchi Chemical Industry Co., Ltd., which does not contain an ultraviolet absorber.
A hermetically sealed cube-corner retroreflective sheet was obtained in the same manner as in Example 1 except that "7" was used.

Comparative Example 2 Instead of TINUVIN 1577 as an ultraviolet absorber added to a polycarbonate resin film, a triazine-based ultraviolet absorber "CYASORB UV-116" manufactured by Mitsui Cytec Co., Ltd.
4 ”(Chemical formula 1) is used to obtain a polycarbonate resin film, and“ Sanduren 014NST ”manufactured by Kanegafuchi Chemical Industry Co., Ltd. is used as an acrylic film instead of“ Sanduren ”.
A hermetically sealed type cube-corner retroreflective sheet was obtained in the same manner as in Example 1 except that "XT-527" was used.

Comparative Example 3 A UV absorbent was not used in the polycarbonate resin film, and an acrylic film "Sunduren XT NST" manufactured by Kaneka Corporation was used instead of "Sunduren XT."
A hermetically sealed cube-corner retroreflective sheet was obtained in the same manner as in Example 1 except that "-527" was used.

Comparative Example 4 A capsule lens type retroreflective sheet was obtained in the same manner as in Example 2 except that “Sanduren XT-527” was used as the acrylic film instead of “Sanduren 014NST” manufactured by Kanegafuchi Chemical Industry Co., Ltd. It was

Comparative Example 5 A UV absorber was not used for the polycarbonate resin film, and an acrylic film was used instead of "Sanduren 014NST" manufactured by Kaneka Kagaku Kogyo Co., Ltd. A benzotriazole type UV absorber manufactured by Nippon Ciba Geigy Co., Ltd. A hermetically sealed cube-corner retroreflective sheet was obtained in the same manner as in Example 1 except that 1.8 parts by weight of 234 was added and "Sanduren 007HBT" manufactured by Kanegafuchi Chemical Industry Co., Ltd. was used.

The weather resistance was compared by the following method. Using Atlas Weatherometer Ci65A type manufactured by Toyo Seiki Co., Ltd. equipped with a 6.5KW xenon lamp, the evaluation data was exposed for 2000 hours and 5000 hours, and the color measurement before and after the experiment was visually and spectroscopically measured. YI value measurement based on all JIS K7105 was performed. Table 1 shows the above-mentioned Examples 1, 2, 3,
The weather resistance evaluation results of the cube-corner type and capsule lens type reflecting sheets of 4, 5, 6 and Comparative Examples 1, 2, 3, 4, 5 are shown.

[0096]

[Table 2]

The evaluation criteria are as follows. AA: Particularly excellent. A: Yellowing is observed, but there is no problem in practical use. C: Judge that there is a problem in long-term outdoor use.

As described above, the resin laminate using the ultraviolet absorbent of the present invention showed less yellowing after the weather resistance test and had an excellent appearance.

[Brief description of drawings]

FIG. 1 is a cube-corner retroreflective sheet in which a retroreflective element layer according to one embodiment of the present invention is a cube-corner retroreflective element.

FIG. 2 is a capsule lens type retroreflective sheet in which the retroreflective element layer according to one embodiment of the present invention is made of microglass.

FIG. 3 is an enclosed lens type retroreflective sheet in which the retroreflective element layer according to one embodiment of the present invention is made of microglass.

[Explanation of symbols]

1 Surface protection layer 2 printing layers 3 Retroreflective element layer 4 connection 5 air layer 6 Binder layer 7 Support layer 8 Adhesive layer 9 Release agent layer 10 focal layers 11 Specular reflection layer 12 light incident directions

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 5/124 G02B 5/124 5/128 5/128 5/13 5/13 F term (reference) 2H042 EA04 EA07 EA08 EA12 EA16 EA20 4F100 AH03A AH03B AH03H AK01A AK01B AK25 AK42 AK45 BA02 CA07 CB03 EC03 EC032 EH17 EH172 EJ17 EJ172 EUEJ42 EJ0 EU02 BD01 BD01 CB77BD01 BB1 BB1 BB1 CB1B02B031

Claims (11)

[Claims] 1. A resin laminate containing a triazine compound (excluding compounds represented by the following formula (1)). Formula (1) 2. The resin laminate according to claim 1, wherein the triazine-based compound is a compound represented by the following formula (2). Formula (2) 3. The resin laminate according to claim 1 or 2, wherein the resin laminate is a retroreflective sheet or a laminate film. 4. The retroreflective sheet according to claim 1, wherein the resin laminate is a retroreflective sheet containing a triazine compound in at least a surface layer of the retroreflective sheet or a retroreflective element layer. Resin laminate. 5. The resin laminate according to claim 1, wherein the resin laminate is a triangular-pyramidal cube-corner retroreflective sheet. 6. V-shaped grooves of substantially symmetrical cross-section are provided with each other.
Crossing each other at approximately right angles to each other
Side (a₁Face, b₁Face, c₁Face or a₂Face, b₂Face, c₂Surface)
A pair of triangular pyramidal cube corners recursive
Projection to one side on one bottom surface (S-S ') where the projection element is common
Are arranged in a close-packed manner so that the pair of triangular pyramids
The type retroreflective element has side faces (c₁Face, c₂
(Faces) share one base (x) and form a pair, and the bottom face
(S-S ') is one side of the pair of triangular-pyramidal retroreflective elements
Surface (a₁Face, a₂Base) (z, z) and the other side (b₁Face, b
₂Is a common plane that includes both the bases (y, y) of
Formed by the grooves (y, z) of the triangular-pyramidal retroreflective element.
Above side (a₁Face, b₁Plane) parallel to the common base (x)
Other V-shaped grooves (w, w, ...) With substantially the same cross-sectional shape
…) Are the vertices (H₁, H₂)
By crossing it without taking it, ₁Face, b
₁Surface) has multiple sub-sides (a₁₁Face, b₁₁Face, a₁₂Face, b₁₂Face
And a₁₃Face, b₁₃Faces ...), and thus three
Sub-sides (a₁₁Face, b₁₁Face, a
₁₂Face, b₁₂Face, and a₁₃Face, b₁₃Formed by faces ...)
Two or more pairs of cube corner elements are formed.
The optical axis of the cube corner element pair is paired with the shared base (x).
And the directions are different from each other by 180 °, but the optics are substantially the same.
From a cube-corner element pair that has an axis tilt (θ)
Claims including a pair of retroreflective elements
Item 5. A resin laminate according to item 5. 7. The resin laminate according to claim 1, wherein the resin laminate is a capsule lens type retroreflective sheet. 8. The resin laminate according to any one of claims 1 to 4, wherein the resin laminate is an enclosed retroreflective sheet. 9. The resin laminate is a laminate film,
The resin laminate according to any one of claims 1 to 3, wherein at least the surface layer contains a triazine compound represented by the following formula (2). 10. The resin laminate according to claim 1, further comprising a hindered amine light stabilizer. 11. The resin laminate according to claim 10, wherein the resin laminate is a retroreflective sheet containing a hindered amine light stabilizer in at least the surface layer of the retroreflective sheet or the retroreflective element layer. body.