JP3473813B2 - Functional retroreflective sheet and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to road signs, guide signs,
The present invention relates to a functional retroreflective sheet useful for signs such as construction signs, license plates for vehicles such as automobiles and motorcycles, safety materials such as clothes, shoes, life-saving equipment, and marking materials for signs and vehicles.

More specifically, a support containing a functional resin layer containing a functional pigment as an essential component, a microsphere-embedded layer partially formed in an arbitrary shape and area on the surface of the functional resin layer, And a base sheet comprising a retroreflective microsphere lens embedded and supported in the microsphere embedding layer, a transparent protective film provided above the surface of the base sheet on the side of the microsphere lens, and the base sheet and The present invention relates to a functional retroreflective sheet composed of a retroreflective region and a visual functional development region, which is composed of a joint part that partially joins a transparent protective film.

[0003]

2. Description of the Related Art Conventionally, a retroreflective sheet that retroreflects light in the direction of a light source is well known. In the wide field as described above, it is possible to utilize the excellent nighttime visibility based on its retroreflective performance. It is used. For example, road signs and construction signs using retroreflective sheets are
Light from a light source such as a headlight of a vehicle such as a moving automobile is reflected in the direction of the light source, that is, toward the traveling vehicle, to provide excellent visibility to the driver of the vehicle who is the sign viewer. , Has the excellent property of enabling clear information transmission.

However, since the retroreflective sheet generally retroreflects light from the light source toward the light source, it provides excellent visibility in the direction of the light source, but the viewer can see it in a direction different from the direction of the light source. If there is, the visibility will be extremely poor. Further, the retroreflective sheet, by its nature, has a larger deviation between the incident angle of light from the light source to the retroreflective sheet and the observation angle of the driver of the vehicle as the light source of the vehicle such as an automobile approaches. Remarkably reduces visibility. In recent years, with the development of the road network and the diversification of the information provided, the amount of information described in one sign has increased. Considering the speed of the vehicle, It has become extremely difficult to read the necessary information in a very short time.

Therefore, in the case where more accurate information is provided and an excellent advertising effect is required, the conventional retroreflective sheet having only retroreflective performance has a limited visibility. In particular, even when the viewer is positioned in a direction different from the light source direction at night, there is a strong demand for an excellent retroreflective sheet that can always provide the viewer with excellent visibility. It was

[0006] Various attempts have been made to improve the visibility of the retroreflective sheet for the purpose of responding to such demands. For example, Japanese Patent Laid-Open No. 5-173008 discloses retroreflective microspheres. A transparent resin layer is used as a support body for embedding and supporting a lens (that is, a microsphere lens having a retroreflective property, whose semispherical surface is covered with a metal vapor deposition film (5)), and the rear surface (light incidence) of the support body is used. (The surface opposite to the side)
Discloses a capsule lens type retroreflective sheet having a layer containing a phosphorescent luminescent substance and having a retroluminescent property and a luminescent property. However, in this proposal, due to the structure of the obtained retroreflective sheet, the light emitted from the light-emitting substance is blocked by the embedded retroreflective microsphere lens, and the amount of emitted light becomes extremely poor, which improves the visibility. In terms of points, it was absolutely inadequate.

Further, in International Patent Application Publication No. WO93 / 14422, a phosphorescent pigment (phosphrescent pigmen) is attached to a connecting portion connecting a surface of a cube corner forming side and a support.
A photoluminescent capsule cube-corner retroreflective sheet containing t) is disclosed. This publication also suggests a method for imparting fluorescence to the capsule lens type retroreflective sheet. However, also in the second proposal, the light emission amount of the phosphorescent pigment is not so large as the phosphorescent pigment of the first proposal, and even if the phosphorescent pigment is used as a marker or the like, the description content is confirmed from a position apart to some extent. It couldn't be as visible as it could be.

Further, in International Patent Application Publication No. WO96 / 18920, a capsule lens type retroreflective sheet is described.
Printing with a protective film or a UV-light-emitting resin composition on the base sheet, a bonding portion for partially connecting the base sheet and the protective film in which the retroreflective microsphere lens is embedded and supported on the support, and printed. There is disclosed an ultraviolet light emitting retroreflective sheet which is formed as an ultraviolet light emitting layer by means and is then fused to a base sheet or a protective film by heating or is adhered with an appropriate adhesive. Further, in the same publication, the support is formed of an ultraviolet light emitting resin composition, or at least the side where the microsphere lens is embedded in the support is set as an ultraviolet light emitting layer formed of the ultraviolet light emitting resin composition, and these ultraviolet light emitting layers are formed. There is also suggested an ultraviolet light-emitting retroreflective sheet in which a support having a layer is partially heated and melt-molded by an embossing roll or the like to serve as a bonding portion that partially connects the protective film and the base sheet.

However, in the above-mentioned third proposal, the ultraviolet light emitting layer is substantially only the connecting portion which connects the protective film and the base sheet, and the ratio of the ultraviolet light emitting layer to the surface of the retroreflective sheet is extremely small, and the connecting portion is also formed. There is a problem that the amount of the luminescent substance to be contained cannot be increased too much. Therefore, the amount of light emitted by the luminescent substance tends to be insufficient,
It has also been found that there are problems such as poor adhesion between the ultraviolet light emitting layer and the coating layer and difficulty in forming an adhesive layer on the formed ultraviolet light emitting layer.

[0010]

In view of these drawbacks of the prior art, the present invention has a retroreflective area and a visual functional expression area by a very simple and inexpensive method and is excellent even at night. It is intended to provide a lens-type functional retroreflective sheet having visibility.

[0011]

According to the present invention, however, a support having a functional resin layer containing a functional pigment exhibiting visual functionality and a resin component as an essential constituent, A microsphere embedding layer partially formed in an arbitrary shape and area on the surface of the resin layer, and in the microsphere embedding layer, substantially covered with the metal vapor deposition film so as to be substantially lined up in one layer. A base sheet comprising a microsphere lens in which a semispherical surface is embedded and supported, and a substantially hemisphere surface not covered with the metal vapor deposition film is exposed on the microsphere embedding layer, and the microsphere lens of the base sheet is exposed. The transparent protective film provided above the surface on the side of the base sheet and the transparent protective film which are partially covered with each other so as to retain an air layer between the layer of the microsphere lens and the transparent protective film. It consists of a joining part to join, At least the microspheres are embedded in the retroreflective area of the area where the bonding portion is not formed in the area where the small ball lens is embedded, and at least the surface of the functional resin layer on the side where the transparent protective film is provided. Provided is a functional retroreflective sheet characterized by being constituted by a visual functional expression region consisting of a non-exposed portion.

The present invention will be described in detail below with reference to FIGS.

FIG. 1 is a plan view of a capsule lens type functional retroreflective sheet which is a typical functional retroreflective sheet of the present invention, and FIG. 2 is a sectional view taken along line AA.

In FIGS. 1 and 2, (1) is a visual functional expression region, and (2) is a retroreflective region. (3) is a continuous linear joining portion for joining the base sheet (13) and the transparent protective film (6), whereby the joining portion (3), the transparent protective film (6) and the base sheet (13) A sealed small compartment (capsule) (9) having an air layer (10) formed therein is formed, and the joint part (3) itself has a visual functional expression region (1). Form part of. Base sheet (13)
Is a support (1 that has the functional resin layer (7) as an essential component.
2), a microsphere embedding layer (8) partially formed with an arbitrary shape and area on the light incident side surface thereof and the microsphere embedding layer
It consists of a layer of microsphere lenses (4) embedded in (8). Support
(12) is a reinforcing layer on the back surface of the functional resin layer (7) if necessary.
(11) may be laminated. In the microsphere embedding layer (8), a substantially hemispherical surface of the microsphere lens (4) on the side where the metal vapor deposition film (5) is formed is densely and substantially embedded in one layer. Of the layers of this microsphere lens (4),
The part where the coupling part (3) is formed loses its retroreflective property, but the part enclosed in the sealed small compartment (9) excluding that part constitutes the retroreflective region (2). The remaining part of the sealed small compartment vacancy (9) and the connecting part (3) form a visual functional expression region (1).

The support (12) is a functional resin layer as described above.
(7) is an essential component. Functional resin layer (7)
Are those containing a functional pigment exhibiting visual functionality and a resin component. As the functional pigment, for example, a phosphorescent pigment, an ultraviolet light emitting fluorescent pigment, etc. are preferably used.

The above-mentioned phosphorescent pigment is one which stores daylight of sunlight, light of illumination at night such as a fluorescent lamp, an automobile headlight and the like and gradually emits light even in the dark, and is not particularly limited. It is possible to use any of the organic phosphorescent pigments and the inorganic phosphorescent pigments, but from the viewpoint of good phosphorescent performance, the inorganic phosphorescent pigments, particularly the oxide phosphorescent pigments are preferably used, particularly the general formula MAl2O4 ( In the formula, M represents at least one kind of alkaline earth metal) as a mother crystal, and a rare earth metal atom of 1 × 10 −6 as an activator.
It is preferable that the phosphorescent pigment is contained in a proportion of 0.2 (provided that the total number of metal M atoms and rare earth metal atoms is 1).

Examples of the alkaline earth metal include Ca and Ba.
And at least one metal selected from the group consisting of Sr, and the rare earth metal is Sc,
Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy,
It is preferable that at least one metal selected from the group consisting of Ho, Er, Tm, Yb and Lu. Further, such a phosphorescent pigment may further contain Mn, Sn as a co-activator, if necessary.
And at least one metal selected from the group consisting of Bi at a ratio of 1 × 10 ^{-6 to} 0.2 (provided that the total number of metal M atoms, rare earth metal atoms and coactivator metal is 1). It is preferable that

As such a phosphorescent pigment, for example, S
rAl ₂ O ₄ : Eu, SrAl ₂ O ₄ : Eu, Dy, SrAl ₂ O ₄ : Eu,
Nd, SrAl ₂ O ₄ : Eu, Pr, SrAl ₂ O ₄ : Eu, Sm, SrA
l ₂ O ₄ : Eu, Tb, SrAl ₂ O ₄ : Eu, Ho, SrAl ₂ O ₄ : Eu,
Mn, SrAl ₂ O ₄ : Eu, Sn, SrAl ₂ O ₄ : Eu, Bi, CaA
l ₂ O ₄ : Eu, Nd, CaAl ₂ O ₄ : Eu, Sm, CaAl ₂ O ₄ : Eu,
Tm, CaAl ₂ O ₄ : Eu, Nd, La, CaAl ₂ O ₄ : Eu, Nd, C
e, CaAl ₂ O ₄ : Eu, Nd, Pr, CaAl ₂ O ₄ : Eu, Nd, S
m, CaAl ₂ O ₄ : Eu, Nd, Gd, CaAl ₂ O ₄ : Eu, Nd, T
b, CaAl ₂ O ₄ : Eu, Nd, Dy, CaAl ₂ O ₄ : Eu, Nd, H
o, CaAl ₂ O ₄ : Eu, Nd, Er, CaAl ₂ O ₄ : Eu, Nd, T
m, CaAl ₂ O ₄ : Eu, Nd, Yb, CaAl ₂ O ₄ : Eu, Nd, L
u, CaAl ₂ O ₄ : Eu, Nd, Mn, CaAl ₂ O ₄ : Eu, Nd, S
n, CaAl ₂ O ₄ : Eu, Nd, Bi, Ca _0.9 Sr _0.1 Al ₂ O ₄ : E
u, Nd, La, Ca _0.9 Sr _0.1 Al ₂ O ₄ : Eu, Nd, Dy, Ca _0.7
Sr _0.3 Al ₂ O ₄ : Eu, Nd, Dy, Ca _0.9 Sr _0.1 Al ₂ O ₄ : E
u, Nd, Ho, Ca _0.7 Sr _0.3 Al ₂ O ₄ : Eu, Nd, Ho and the like can be mentioned. These can be used alone or as a mixture of two or more.

As these phosphorescent pigments, those having afterglow characteristics measured according to the following method are generally 150 mcd / m ² or more, preferably 200 mcd / m ² or more, and more preferably 250 mcd / m ² or more. .

Measurement of afterglow characteristics: Sample phosphorescent pigment powder 0.05
Weigh g in an aluminum sample dish with an inner diameter of 8 mm, and weigh about 12
After storing in the dark for a long time to eliminate the afterglow, irradiate for 30 minutes at a light receiving intensity of 1000 Lx using a D65 regular light source, and then in the dark
After leaving for a minute, the amount of luminescence of the sample is measured from a distance of about 30 cm from the sample using a luminance meter [“LS-100” manufactured by Minolta Camera Co., Ltd.) to obtain the afterglow characteristic.

The ultraviolet-emitting fluorescent pigment that can be used as a functional pigment in the present invention is not particularly limited as long as it is a fluorescent pigment that emits light upon receiving ultraviolet rays, and generally, an organic material having a relatively high light-transmitting property. -Based fluorescent pigments such as naphthotriazole-based and benzoxazole-based pigments;
Generally, it can be arbitrarily selected from various non-transparent inorganic fluorescent pigments, for example, inorganic metal salt-based, halide-based, and sulfide-based fluorescent pigments. In addition, it is preferable that such an ultraviolet-emitting fluorescent pigment emits light when irradiated with ultraviolet rays having a wavelength of 250 to 400 nm.

Examples of the organic fluorescent pigments include diaminostilbenzene, uranin, thioflavin T, eosin, rhodamine B, acridine orange, and diphenylmethane-based, triphenylmethane-based, xanthene-based, thiazine-based and thiazole-based dyes. Examples include organic pigments as a base material. These can be used alone or as a mixture of two or more.

Examples of the inorganic fluorescent pigment include Y
₂ O ₃ : Eu, Y (P, V) O ₄ : Eu, Y ₂ O ₃ S: Eu, 0.5 Mg
F ₂ · 3.5MgO · GeO ₂ : Mn, YVO ₄ : Eu and (Y, Gd) B
O ₃ : Eu and other red-emitting inorganic fluorescent pigments; for example, Zn ₂ Ge
O ₄ : Mn, ZnO: Zn, ZnS: Cu, ZnS: (Cu, Al),
(Zn, Cd) S: (Cu, Al), ZnS: (Cu, Au, Al), Zn ₂ S
iO ₄ : Mn, ZnS: (Cu, Ag), (Zn, Cd) S: Cu, Gd ₂ O
₂ S: Tb, La ₂ O ₂ S: Tb, Y ₂ SiO ₅ : (Ce, Tb), CeM
gAl ₁₁ O ₁₉ : Tb, ZnS: (Cu, Co), LaOBr: (Tb, T
m), La ₂ O ₂ S: Tb, BaMg ₂ Al ₁₆ O ₂₇ : (Eu, Mu) and other green-emitting inorganic fluorescent pigments; for example, Sr ₅ (PO ₄ ) ₃ Cl: E
u, BaMg ₂ Al ₁₆ O ₂₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Zn
S: Ag, CaWO ₄ , Y ₂ SiO ₅ : Ce, ZnS: (Ag, Ga, C
l), blue emitting inorganic fluorescent pigments such as Sr ₂ P ₂ O ₇ : Eu, CaS: Bi, and CaSrS: Bi; and the like. These inorganic fluorescent pigments can be used alone or as a mixture of two or more kinds having the same color emission, or as a mixture of two or more kinds of different color emission in order to emit light in a desired color tone.

Inorganic fluorescent pigments are generally superior to organic fluorescent pigments in light resistance, heat resistance, solvent resistance, etc., so that the obtained ultraviolet light-emitting retroreflective sheet should be used mainly outdoors. In such cases, it is preferable to use an inorganic fluorescent pigment. In addition, among the inorganic fluorescent pigments, the green light emitting inorganic fluorescent pigments and the red light emitting inorganic fluorescent pigments described above are particularly advantageous because they have a large emission intensity during ultraviolet light emission and give excellent visibility to the viewer at night. It is preferable to use a blue light emitting inorganic fluorescent pigment.

The particle size distribution of the above-mentioned inorganic fluorescent pigment is from the viewpoint of good dispersibility of the pigment in the resin component, smoothness of the functional resin layer to be formed, and few defective points such as pinholes. 80% by weight of particles with a particle size of 25 μm or less
It is preferable that the distribution is such that it is contained.

In the present invention, when a luminous pigment is used as the functional pigment, the functional resin layer (7) becomes a luminous luminous resin layer and the visual functional expression region becomes a luminous luminous region. Such a phosphorescent resin layer is one containing a phosphorescent pigment and a resin component, the amount of the phosphorescent pigment is preferably 100 to 900 parts by weight with respect to 100 parts by weight of the resin component.
The amount is preferably 150 parts by weight, more preferably 150 to 800 parts by weight, still more preferably 200 to 700 parts by weight. It is preferable if the blending amount of the phosphorescent pigment is equal to or more than the lower limit value because a sufficient luminous effect can be obtained and excellent visibility can be obtained, and if it is equal to or less than the upper limit value, the formed luminous area becomes too hard. It is preferable because it does not cause inconvenience such as brittleness and does not impair properties such as mechanical strength and flexibility.

In the present invention, when an ultraviolet luminescent pigment is used as the functional pigment, the functional resin layer (7)
Becomes an ultraviolet light emitting resin layer, and the visual functional expression region becomes an ultraviolet light emitting region. Such an ultraviolet light emitting resin layer contains an ultraviolet light emitting fluorescent pigment and a resin component, and the compounding amount of the ultraviolet light emitting fluorescent pigment is the resin component 10
The amount is preferably 10 to 600 parts by weight, more preferably 50 to 400 parts by weight, and further preferably 100 to 300 parts by weight, relative to 0 parts by weight. It is preferable that the addition amount of the ultraviolet light emitting fluorescent pigment is at least the lower limit value because sufficient ultraviolet light emitting function can be obtained and excellent visibility can be obtained, and if it is at most the upper limit value, the formed ultraviolet light emitting region is hard. It is preferable because it does not cause inconveniences such as becoming too brittle and the properties such as mechanical strength and flexibility are not impaired.

Examples of the resin component used in the functional resin layer (7) in the present invention include acrylic resin, urethane resin, polyester resin, vinyl chloride resin,
Vinyl acetate resin, polyolefin resin, fluorine resin, polyamide resin and the like, weather resistance,
It is preferable to use an acrylic resin from the viewpoint of heat moldability.

Further, the functional resin layer (7) may contain a cross-linking agent such as an isocyanate cross-linking agent, a melamine-based cross-linking agent, a metal-based cross-linking agent, etc., if necessary, together with the functional pigment and the resin component. This makes it possible to crosslink the resin component. However, the functional resin layer (7) is partially thermally deformed by heating and pressurization at least when the bonding portion (3) is formed, so that the base sheet (13) and the transparent protective film.
It is preferable that the joint portion (3) that partially joins (6) can be formed, and it is preferable that the fluidity is maintained to such an extent that such thermal deformation can be performed.

In addition to these, the functional resin layer (7) may further contain various fillers such as a cellulose derivative, an internally crosslinked microsphere resin, various colorants, and heat stabilizers, if necessary. The thickness of the functional resin layer (7) is such that the functional manifestation such as the magnitude of the emission intensity when acting as the functional manifestation region is remarkable, and the good thermal deformability in the bonding portion forming step described later. Therefore, usually 20 to 200 μm, preferably 30 to 15
It is preferably about 0 μm.

The support (12) used in the present invention does not necessarily have to be only the functional resin layer (7), and the support shown in FIG.
As shown in, a reinforcing layer (11) may be laminated on the back surface of the functional resin layer (7) if necessary.

The reinforcing layer (11) is usually composed of a cross-linked resin layer, and the resin component used is appropriately selected from those usable in the functional resin layer (7). can do. As the cross-linking agent for cross-linking, the same one as that which can be used in the functional resin layer (7) can be used. Further, the reinforcing layer (11) contains, if necessary, a white pigment such as titanium dioxide, an extender pigment such as calcium carbonate or clay, and various fillers similar to those used for the functional resin layer (7). You can leave.

The thickness of the reinforcing layer (11) is usually 10 to 80 μm, particularly 20 to 60 μm from the viewpoint of weather resistance, mechanical strength, shape stability of the heat-deformed portion of the obtained functional retroreflective sheet. It is convenient to set within the range of.

Further, the support (12) used in the present invention is
If necessary, an intermediate layer may be provided between the functional resin layer (7) and the reinforcing layer (11) to further enhance the adhesiveness between the layers. Thus, the total thickness of the support (12) used in the present invention is usually 30 to 250 μm, preferably about 60 to 200 μm.

In the present invention, a retroreflective microsphere lens, that is, a microsphere lens (4) having a retroreflective property in which a semi-spherical surface thereof is covered with a metal vapor deposition film (5) is a functional resin layer of a support. On the surface of (7), in a microsphere embedding layer (8) partially formed with an arbitrary shape and area, a substantially hemispherical surface covered with the metal vapor-deposited film so as to be substantially lined up in one layer. Is embedded and supported, and a substantially hemispherical surface not covered with the metal vapor deposition film is exposed on the microsphere embedding layer.

The microsphere embedding layer (8) is usually formed by screen printing or gravure printing. When the functional retroreflective sheet to be obtained is a sheet, it is convenient to use a flat screen printing method capable of thick film printing by printing once, and the functional retroreflective sheet is a roll-shaped continuous body. At times, it is convenient to use continuous printing methods such as rotary screen printing or gravure printing. The formation area of the microsphere embedding layer (8) is
From the viewpoint of a good balance between the retroreflective performance of the resulting functional retroreflective sheet and the strength of visual functional expression, the light incident on the functional resin layer (7) in which the microsphere embedding layer (8) is formed. 15-75%, preferably 20-60, relative to 100% of side area
It should be%.

The microsphere embedding layer (8) is a layer mainly composed of a resin component and may have a light-transmitting property, but if necessary, it is the same as that used for the functional resin layer (7). The functional pigment and other additives may be contained, and the resin component may be crosslinked with various crosslinking agents as in the case of the functional resin layer (7). However, the microsphere embedding layer (8) also has a functional resin layer at least when forming the bonding portion (3).
In addition to (7), it is preferable that the fluidity is maintained such that it can be partially thermally deformed by heating and pressurization to form a joint. The thickness of the microsphere embedding layer (8) is usually in the range of 10 to 50 μm, particularly 15 to 40 μm from the viewpoint of good retention of the microsphere lens, good thermal deformability in the bonding portion forming step, and the like. It is convenient to set.

The microsphere lens (4) to be embedded and supported is not particularly limited, and the average particle size is preferably 10 to 100 μm, preferably 30 to 80 μm, and more preferably 40 to 70 μm. . The refractive index of the microsphere lens is preferably around 1.9, and glass beads are usually used.

In the present invention, the transparent protective film (6) provided above the surface of the substrate sheet (13) on the side where the microsphere lenses (4) are exposed is at least 20% or more, preferably 40% or more. The material is not particularly limited as long as it has the above-mentioned total light transmittance and has some flexibility, for example, an acrylic resin film, a fluorine resin film, a polyurethane resin film, a vinyl chloride resin. Examples thereof include films, polycarbonate resin films, polyester resin films, polyolefin resin films and the like.

The transparent protective film (6) is preferably unstretched. This is because the uniaxially or polyaxially stretched film has a high mechanical strength, but distortion may remain in the film, impairing the durability of the obtained retroreflective sheet. The thickness of the transparent protective film (6) can be varied over a wide range depending on the application of the resulting functional retroreflective sheet, etc., but is usually 20-200.
μm, preferably 40-150 μm, particularly preferably 50-100 μm
It is better to set it within the range of m.

In the present invention, the base sheet (13) and the transparent protective film (6) are arranged so that an air layer (10) is retained between the layer of the retroreflective microsphere lens and the transparent protective film (6). The method of forming the joint part (3) to be partially joined is not particularly limited, and for example, the microsphere embedding layer (8)
Similarly to the above, the resin composition for forming a bonding portion can be formed by a printing means such as screen printing or gravure printing.

In this case, the resin composition for forming a bonding portion may be mainly composed of a resin component and have a light-transmitting property, but if necessary, the same function as that used for the functional resin layer (7) is obtained. A functional pigment and other additives can be contained, and the resin component can be crosslinked with various crosslinking agents as in the functional resin layer (7). The thickness of the obtained bonding portion (3) is not particularly limited as long as it can completely bury the microsphere lens (4), and is generally 10 to 100 μm, preferably 30 to 80 μm, and further Preferably, it is within the range of 40 to 70 μm.

The connecting part (3) is composed of the functional resin layer (7),
Alternatively, the functional resin layer (7) and the microsphere-embedded layer (8) on the functional resin layer may be partially thermally deformed to be formed. In order to form the joint portion (3) as described above, heating is performed from the back side of the base sheet (13) using a convex mold, for example, an embossing roll, and the convex mold and the transparent protective film.
An example is a method of applying pressure between a pressing means opposed to the side of (6), for example, a rubber roll.

Among these methods for forming the joint portion (3), stable adhesive strength can be obtained at the time of joining the transparent coating film (6) and the base sheet (13), the equipment is simple and the operating conditions can be controlled. It is preferable to adopt the method by thermal deformation because it is easy.

A transparent protective film for the formed joint.
The width of the portion to be joined with (6) is not particularly limited as long as the adhesiveness between the transparent coating film (6) and the base sheet (13) or a retroreflective region of a predetermined ratio can be secured, but from the light incident side. Looking, generally 200-1000 μm, preferably 250-900 μm,
Particularly preferably, it is in the range of about 300 to 800 μm.

When the connecting portion (3) is formed in a continuous line as shown in FIG. 1, the connecting portion (3) and the transparent protective film are formed.
Surrounded by (6) and the base sheet (13), an air layer (1
A sealed small compartment (capsule) (9) having 0) is formed. In this way, even when the obtained functional retroreflective sheet is used outdoors for a long time, the retroreflective property due to the intrusion of rainwater into the capsule and the visual functional properties such as the luminous luminous property and the ultraviolet luminous property can be achieved. It is preferable because the deterioration of the function is extremely small.

The size of the above-mentioned capsule is such that the deformation of the protective film itself, which is likely to occur with the formation of the capsule, is suppressed as much as possible to maintain the surface smoothness as a functional retroreflective sheet, and the desired shape. When it is cut into pieces and used outdoors, it is generally viewed from the light incident side for the reason of minimizing the amount of dust, dust, rainwater, etc. that enter the capsules destroyed from the cut part of the end. 5-140 mm2,
The range is preferably 10 to 120 mm 2, and particularly preferably 15 to 100 mm 2.

The connecting part (3) can also be formed in a dot shape or a discontinuous line shape. However, in this case, in order to prevent rainwater and the like from entering the gap between the transparent protective film (6) and the support during outdoor use, the functional retroreflective sheet obtained is desired in accordance with the intended use. After cutting into shape,
It is necessary to seal the peripheral portion by an appropriate means. In such a case, it is preferable that the functional resin layer (7) and the microsphere embedding layer (8) are formed of a thermoplastic resin layer, and the peripheral portion is heated and melt-sealed at the time of use.

The functional retroreflective sheet of the present invention thus obtained is a portion of the microsphere lens-embedded region in which the layer of the retroreflective microsphere lens is embedded, in which no coupling portion is formed, and light is incident. A retroreflective area (2) whose side is covered with a transparent protective film (6) through an air layer (10), and a visual functional expression area (a joint portion (3) and a microsphere lens non-embedded area ( 1) -a luminous light emitting region or an ultraviolet light emitting region. In the case of a capsule lens type functional retroreflective sheet in which the coupling portion (3) is formed in a continuous line shape as shown in FIG. 1, the layer of the microsphere lens (4) is enclosed in the capsule (9). The part that constitutes the retroreflective region (2) constitutes the region (1) in which the remaining portion of the capsule (9) and the coupling part (3) appear.

In the functional retroreflective sheeting of the present invention,
The ratio of the area of the retroreflective area (2) to the area of the visual functional expression area (1) must be defined as the same depending on the function to be expressed, that is, the difference in functionality such as accumulated light emission or ultraviolet light emission. However, in general, from the viewpoint of a good balance of retroreflective performance and functional expression (for example, emission intensity), the area of the light incident side surface of the retroreflective sheet is 100%, and the retroreflective region (2) is Area is usually 10
~ 70%, preferably 15 to 50%, the area of the visual functional expression region (1) is usually 30 to 90%, preferably 50 to 85%.
It should be%.

When the visual functional expression region (1) is a luminous light emitting region, the ratio of the area of the retroreflective area to 100% of the area of the light incident side surface of the retroreflective sheet is: Generally, it is in the range of 10 to 50%, preferably 15 to 40%, and the ratio of the area of the light storing and emitting region is in the range of 90 to 50%, preferably 85 to 60%. When the visual functional expression region (1) is an ultraviolet light emitting region, the area ratio of the retroreflective region is 10 to 70%, further 15 to 60%, and particularly 30.
Within the range of ~ 50%, the area ratio of the ultraviolet light emitting region is
It is preferably in the range of 10 to 90%, further 30 to 85%, and especially 40 to 70%.

FIG. 3 is a schematic cross-sectional view showing the flow of the method for manufacturing a functional retroreflective sheeting of the present invention.

FIG. 3A shows a step (a) in the method of the present invention,
That is, it represents a step of forming a microsphere lens temporary support sheet by embedding the microsphere lens in the temporary support (16).
The temporary support (16) used in this step is a microsphere lens (4).
It is composed of a microsphere lens temporary embedding layer (14) for embedding and supporting and a back layer (15) for supporting this layer, and is not particularly limited as long as it has a function of embedding and supporting the microsphere lens. However, a conventionally known microsphere lens temporary embedding layer (14)
Polyethylene laminated paper using a polyethylene film as the back surface and paper as the back layer (15) is most preferably used.

Specifically, for example, glass beads (4), which are microsphere lenses, are densely and substantially sprinkled on a polyethylene laminated paper (16) heated to about 110 ° C. so as to form a single layer. The glass beads (4) are pushed into the polyethylene film (14) using a nip roll or the like so that about 1/3 to 1/2 of the diameter thereof is embedded. Thus, the glass bead (microsphere lens) temporary support sheet (17) is obtained.

FIG. 3 (b) shows a step (b) in the method of the present invention,
That is, it represents a metal vapor deposition process. In this process,
A metal vapor deposition film (5) is formed by vapor-depositing a metal such as aluminum as a light-reflecting element using a vacuum vapor deposition method or the like on the microsphere lens (4) attachment surface side of the microsphere lens temporary support sheet (17). . The metal used in this step is not particularly limited as long as it is a metal capable of being vacuum-deposited, but it is most preferable to use aluminum, which has been conventionally used for a retroreflective sheet and is inexpensive and easily available.

FIG. 3 (c) shows a step (c) in the method of the present invention,
That is, this is a step of forming the support (12) and then forming the microsphere-embedded layer (8) thereon.

More specifically, the support (12)
Is, for example, on a process film (18) such as a polyethylene terephthalate film whose surface has been release-treated with a release agent for silicone resin, and a crosslinkable resin component such as a hydroxyl group-containing acrylic resin and a crosslinkable agent such as an isocyanate crosslinking agent. A reinforcing layer-forming resin composition containing an agent is applied and dried to form a reinforcing layer (11), and directly on the reinforcing layer (11), a functional pigment such as a phosphorescent pigment or an ultraviolet light emitting fluorescent pigment. And coating a functional resin layer forming composition containing a resin component such as an acrylic resin and drying, or coating and drying the functional resin layer forming composition on another process film The functional resin layer (7) thus obtained is laminated on the reinforcing layer (11) to form a support (12) in which the functional resin layer (7) and the reinforcing layer (11) are laminated. To do.

Then, a resin composition for forming a microsphere-embedded layer containing a resin component such as an acrylic resin as a main component is printed in a desired shape on the support (12) using, for example, a gravure roll (19), The microsphere embedding layer (8) is formed by drying. Thus, the support (12) used in the present invention having the microsphere embedding layer (8) is formed.

FIG. 3 (d) shows step (d) in the method of the present invention,
That is, it is a step of embedding a microsphere lens. The microsphere embedding layer (8) of the support (12) having the microsphere embedding layer (8) obtained in step (c) is on the microsphere lens temporary support sheet (17) created in step (a). The support (12) and the microsphere lens temporary support sheet (17) are superposed so as to be in contact with the surface of the microsphere lens (4) on the side having the metal vapor deposition film (5) protruding on the surface, and if necessary. While heating and softening the microsphere embedding layer (8), pressure laminating is performed using a nip roll or the like, and the substantially hemispherical surface of the microsphere lens (4) on the side having the metal vapor deposition film (5), that is, its diameter. Approximately 1/6 to 1/2 of the above is pressed so that it is embedded in the microsphere embedding layer (8). At this time,
The metal vapor deposition film between the microsphere lenses (4) on the microsphere lens temporary support sheet (17) is in direct contact with the surface of the microsphere embedding layer (8), and the metal vapor deposition film forms a microsphere embedding layer ( 8) It is better not to transfer to the surface.

Specifically, in the above-mentioned lamination, a method of laminating the microsphere lens temporary support sheet (17) and the microsphere embedding layer (8) with a gap therebetween; On the surface of the supporting sheet (17) on which the microspheres are embedded, prior to the lamination with the microspheres embedding layer (8), the metal vapor deposition film between the microspheres (4) has a microspheres embedding layer (8).
Examples thereof include a method of forming a thin film that prevents transfer onto the surface, for example, a method of forming a resin thin layer such as an acrylic resin containing a silane coupling agent and the like;

FIG. 3 (e) shows a step (e) in the method of the present invention,
That is, this is a temporary support peeling step. In this step, the temporary support (16) is peeled off from the laminate obtained in step (d) by a method known in the art, and the side having the metal vapor deposition film (5) of the microsphere lens (4). Almost hemisphere part is the functional resin layer (7)
A microsphere lens-embedded region that is embedded only in the microsphere embedding layer (8) formed above, and a substantially hemispherical surface on the side of the microsphere lens (4) that does not have the metal vapor deposition film (5) is projected, A base sheet (13) having a microsphere lens non-embedded region in which the microsphere lens is not embedded is formed.

FIG. 3 (f) shows a step (f) in the method of the present invention,
That is, it is a bonding portion forming step. A transparent protective film (6) is placed on the side of the base sheet (13) obtained in step (e) in which the microsphere lenses are embedded, and the back surface of the base sheet (13), that is, in FIG. A convex die from the side of the reinforcing layer (11) of the sheet (13), for example, an embossing roll (20) is used to heat the convex die and the transparent protective film (6). , The functional resin layer (7) on the base sheet (13) or the functional resin layer (7) and the microsphere-embedded layer on the functional resin layer, for example, by pressing between the rubber roll (21)
Part (8) is thermally deformed to form a joint part (3) for partly joining the base sheet (13) and the transparent protective film (6).

[0063]

【Example】

Hereinafter, the present invention will be described more specifically with reference to Examples. The following methods were used for measurement and evaluation of the retroreflective performance, the afterglow brightness and visibility evaluation of the luminous luminous retroreflective sheet, and the ultraviolet light emission brightness and visibility evaluation of the ultraviolet emissive retroreflective sheet.

(1) Retroreflective performance As a retroreflective performance measuring instrument, “Model (MODEL) 920” manufactured by Advanced Retro Technology, INC. Is used, and a 100 mm × 100 mm luminous retroreflective sheet is used. According to JIS Z 9117, the amount of retroreflected light of each sample was measured at appropriate 5 points with an observation angle of 0.2 ° and an incident angle of 5 °, and the average value was used as the value of the retroreflective performance.

(2) Afterglow of the phosphorescent retroreflective sheet Afterglow of a sample of the phosphorescent retroreflective sheet of 100 mm × 100 mm for 12 hours in the dark, received light intensity 10 using a D65 regular light source
Irradiate with 00Lx for 30 minutes, then leave it in the dark for 10 minutes, and then measure the brightness from a distance of about 30 cm from the sample [Minolta Camera Co.
[LS-100]] was used to measure the afterglow amount of about 5 mmφ at 5 points on the surface of the light-storing luminescent area, and the afterglow brightness of the luminescent retroreflective sheet was determined according to the following formula. Afterglow brightness (mcd / m ² ) = Average amount of afterglow light-emission area afterglow × area occupancy rate of light-emission area (%) ÷ 100

(3) Visibility evaluation of the luminous luminous retroreflective sheet On a 300 mm × 300 mm aluminum plate, the cut letter “N” of the luminous luminous retroreflective sheet was used as the display portion, and the capsule lens type retroreflective material was used as the background portion. Sheet ["Nikkalite
ULS F806 "(blue), manufactured by Nikka Polymer Co., Ltd.] was used to prepare a test piece, and the test piece was left in the dark for 12 hours.
Irradiate for 30 minutes with a light receiving intensity of 1000 Lx using a D65 regular light source,
Then, after standing in the dark for 8 hours, the visibility was evaluated by 20 men and women aged 18 to 50 years in the dark at a point about 30 m away from the test piece. The evaluation was performed according to the following criteria, and the average value was used as the value of the visibility evaluation.

[0068] 5: Very clearly visible 4: Can be seen normally 3: You can barely see the characters 2: Vaguely visible (most characters are invisible) 1: invisible at all

(4) Four ultraviolet light-emitting fluorescent lamps of ultraviolet light-emitting retroreflective sheet having an ultraviolet light emission brightness of 10 W were incorporated, and a visible light cut filter was attached to the front surface, and the main wavelength was around 360 nm and the wavelength range was 300 to 420 nm. Using a UV light emitting device that emits near-UV light from above, irradiate from above a 100 mm × 100 mm sample so that the received light intensity on the surface of the UV light emitting region is 0.88 mW / cm ^2, and from a distance of about 30 cm directly above the sample. Using a luminance meter ["LS-100" manufactured by Minolta Camera Co., Ltd.], the emission luminance of about 5 mmφ was measured at 5 appropriate points on the surface of the ultraviolet emission region, and the average of the ultraviolet light emitting retroreflective sheet was measured as follows. The UV emission brightness was determined.

Average ultraviolet emission luminance of the ultraviolet light-emitting retroreflective sheet (cd / m ² ) = average ultraviolet emission luminance of ultraviolet emission region × area ratio of ultraviolet emission region (%) ÷ 100

(5) Visibility Evaluation of Ultraviolet Light Emitting Retroreflective Sheet On an aluminum plate of 2200 mm × 2700 mm, the cut letters of the ultraviolet light emitting retroreflective sheet were used as the display portion, and the capsule lens type retroreflective sheet [[ Nikka Light U
LS F806 "(blue), manufactured by Nikka Polymer Co., Ltd.] is used to create a guide plate, and the distance from the ground to the bottom of the guide plate is about 4 m.
It was installed so that the plate surface was almost vertical. From the point right below the center of the guide plate in the width direction,
A projection type 400W high pressure mercury lamp was installed at a position 5 m away in the direction of ° and adjusted so that the entire surface of the guide plate was irradiated with ultraviolet rays.

From the position right below the center of the width direction of the guide plate to the guide plate at a position approximately 50 m away in the direction perpendicular to the guide plate surface from the position of 5 m on the right side, 20 men and women aged 18 to 50 years A nighttime visibility evaluation was carried out. The evaluation was performed according to the following criteria, and the average value was used as the value of the visibility evaluation.

[0073] 5: Very clearly visible 4: Can be seen normally 3: You can barely see the characters 2: Vaguely visible (most characters are invisible) 1: invisible at all

Example 1 A temporary support prepared by laminating a polyethylene (PE) layer having a thickness of about 20 μm on paper was heated to about 105 ° C., and glass beads having an average particle size of about 65 μm and a refractive index of about 1.91 were uniformly applied thereon. And densely dispersed in a single layer, and then pressured by a nip roll to embed glass beads in PE by about 1/3 of its diameter,
A glass bead temporary support sheet was formed. Next, aluminum was vacuum-deposited on the surface of the glass bead temporary support sheet on which the glass beads were exposed to form a vacuum vapor-deposited film having a thickness of about 0.1 μm on the substantially hemispherical surface of the glass beads.

Next, polyethylene terephthalate (PET) having a thickness of about 20 μm, which has been subjected to a release treatment with a silicone resin.
Acrylic resin solution [methylmethacrylate (MMA) 20% by weight, ethylmethacrylate (E
A) 65% by weight, 2-hydroxyethyl methacrylate (HEM
A) 100 parts by weight of a methyl isobutyl ketone (MIBK) / toluene (1/1) solution of acrylic resin having a solid content of 50% by weight, which is obtained by copolymerizing 15% by weight, 100 parts by weight, rutile titanium dioxide 21.
Hexamethylene diisocyanate (HMDI) cross-linking agent [1-methoxypropyl acetate-2 / xylene (1/1) solution] containing 5 parts by weight and solid content of 75% by weight 14.2 parts by weight of a mixed solution is applied and dried to a thickness. A reinforcing layer having a thickness of about 30 μm was formed.

Further, on the reinforcing layer, an acrylic resin solution different from the above one (MMA 40% by weight, EA 55% by weight, H
100 parts by weight of a MIBK / toluene (1/1) solution of acrylic resin having a solid content of 50% by weight, which is obtained by copolymerizing 5% by weight of EMA, and an inorganic oxide type phosphorescent pigment [“N-Yoko”, Nemoto Special Chemical Co., Ltd.
Co., Ltd.] 120 parts by weight of a phosphorescent resin composition obtained by coating, and dried to form a phosphorescent resin layer having a thickness of about 250 μm to form a reinforcing layer / phosphorescent resin. A layer-stacked support was obtained.

On the surface of this support on the side of the phosphorescent resin layer,
Acrylic resin solution [34% by weight MMA, 66% by weight EA copolymerized acrylic resin with a solid content of 50% by weight] is printed in a polka dot pattern using a rotary screen, and the dry thickness is approx.
A 30 μm glass bead embedding layer was created. The glass bead embedding layer of the obtained support was about 35% with respect to 100% of the area of the light-incident side surface of the light-storing resin layer.

Next, the glass bead embedding layer side of the above support and the metal bead-deposited glass bead side on the previously prepared glass bead temporary support sheet were superposed so as to face each other, and heated to 75 ° C. About 1/3 of the diameter of the glass beads was embedded under pressure into the glass bead embedding layer of the support. Next, this glass bead temporary support sheet /
A glass bead-embedded region in which a substantially hemispherical surface of a glass bead having no metal vapor deposition film is exposed on the surface by peeling off the temporary support from the support laminate, and glass in which glass beads are not embedded A substrate sheet was obtained in which the bead-non-embedded region had a polka dot appearance.

The base sheet was aged at 35 ° C. for 14 days,
After substantially completing the cross-linking of the reinforcing layer, an acrylic resin film having a thickness of about 50 μm as a transparent protective film (“Acryprene”, Mitsubishi Rayon ( Co., Ltd.), and a surface temperature of about 190 with a mesh-shaped convex engraving with a line width of 1.3 mm
While passing the transparent protective film between the metal embossing roll at 60 ° C and the rubber roll at surface temperature of about 60 ° C so that the transparent protective film contacts the rubber roll side, the metal embossing roll is pressed from the PET process film side to partially cover the base sheet. The base sheet and the transparent protective film were adhesively fixed by heat-melt deformation to complete a photoluminescent retroreflective sheet having a capsule lens structure having a retroreflective region and a photoluminescent region.

The obtained luminous luminous retroreflective sheet has an appearance as shown in FIG. 1, and the area of the retroreflective region is 100% of the area of the light incident side surface of the retroreflective sheet. About 29%, the area of the luminous area is about 71%, the retroreflection performance is 107 cd / Lx.m ² , the afterglow brightness is 64 mcd / m ² , and the visibility evaluation as a luminous luminous retroreflective sheet is 4. There was excellent visibility at night.

Example 2 In Example 1, the acrylic resin solution [MMA / EA / HEM
A = 40/55/5 (wt%) copolymer; solid content 50 wt%]
100 parts by weight and phosphorescent pigment ["N-Yoko", Nemoto Special Chemical Co., Ltd.
Manufactured) coating a phosphorescent resin composition obtained by mixing with 120 parts by weight, instead of forming a phosphorescent resin layer having a thickness of about 250μm by drying, 100 parts by weight of the same acrylic resin solution UV-emitting inorganic oxide fluorescent pigment [“Aurora Rainbow A-160” (green), manufactured by Nemoto Special Chemical Co., Ltd.) A reinforcing layer / ultraviolet emitting resin layer laminated type support was obtained in substantially the same manner as in Example 1 except that an ultraviolet emitting resin layer having a thickness of about 100 μm was formed, and the same resin composition as in Example 1 was gravure-coated. A polka dot pattern was printed using a roll and dried to form a glass bead embedding layer having a dry thickness of about 10 μm. The glass bead embedding layer of the obtained support was about 42% with respect to 100% of the area of the light-incident side surface of the light-storing resin layer.

In the same manner as in Example 1, the glass bead embedding region in which the substantially hemispherical surface of the glass beads on the side not having the metal vapor deposition film is exposed on the surface, and the glass bead in which the glass beads are not embedded are shown. A base sheet was obtained in which the non-embedded region had a polka dot appearance. This base sheet was aged at room temperature for 20 days to substantially complete the cross-linking of the reinforcing layer, and then, in substantially the same manner as in Example 1, the ultraviolet rays of the capsule lens type structure composed of the retroreflective area and the ultraviolet light emitting area were obtained. A luminescent retroreflective sheet was completed.

The obtained ultraviolet light-emitting retroreflective sheet is
The area of the retroreflective area is about 35% and the area of the ultraviolet light emitting area is about 65% with respect to 100% of the area of the light-incident side surface of the retroreflective sheet. It had a nature.

Example 3 In Example 2, the ultraviolet-emitting inorganic fluorescent pigment [“Aurora Rainbow A-160” (green), Nemoto Special Chemical Co., Ltd.
Made in the same manner as in Example 2, except that 120 parts by weight of a red-light-emitting inorganic fluorescent pigment [“A-120”, manufactured by Nemoto Special Chemical Co., Ltd.] was used instead of 120 parts by weight. A luminescent resin layer-laminated support was obtained, and the same resin composition as in Example 1 was printed with a polka dot pattern using a gravure roll and dried to form a glass bead-embedded layer having a dry thickness of about 10 μm. The glass bead-embedded layer of the obtained support was approximately 4% with respect to 100% of the area of the light-incident side surface of the phosphorescent resin layer.
It was 0%.

In the same manner as in Example 2, the glass bead embedding region in which the substantially hemispherical surface of the glass bead on the side not having the metal vapor deposition film is exposed on the surface, and the glass bead in which the glass bead is not embedded are exposed. A base sheet was obtained in which the non-embedded region had a polka dot appearance. This base sheet was aged at room temperature for 20 days to substantially complete the crosslinking of the reinforcing layer, and then, in substantially the same manner as in Example 2, the ultraviolet rays of the capsule lens type structure including the retroreflective area and the ultraviolet ray emitting area were obtained. A luminescent retroreflective sheet was completed.

The obtained ultraviolet light-emitting retroreflective sheet is
The area of the retroreflective area is about 33% and the area of the ultraviolet light emitting area is about 67% with respect to 100% of the area of the light incident side surface of the retroreflective sheet. It had a nature.

Example 4 Instead of using 120 parts by weight of the green light emitting inorganic fluorescent pigment in Example 2, the blue light emitting inorganic fluorescent pigment ["A-18
0 ", manufactured by Nemoto Special Chemical Co., Ltd.] A reinforcing layer / ultraviolet light emitting resin layer laminated type support was obtained in the same manner as in Example 2 except that 120 parts by weight was used. A polka dot pattern was printed on the composition using a gravure roll and dried to form a glass bead-embedded layer having a dry thickness of about 10 μm. The glass bead embedding layer of the obtained support was about 42% with respect to 100% of the area of the light-incident side surface of the light-storing resin layer.

Thereafter, in the same manner as in Example 2, a glass bead embedding region in which a substantially hemispherical surface of the glass bead on the side having no metal vapor deposition film is exposed on the surface, and a glass bead in which the glass bead is not embedded. A base sheet was obtained in which the non-embedded region had a polka dot appearance. This base sheet was aged at room temperature for 20 days to substantially complete the crosslinking of the reinforcing layer, and then, in substantially the same manner as in Example 2, the ultraviolet rays of the capsule lens type structure including the retroreflective area and the ultraviolet ray emitting area were obtained. A luminescent retroreflective sheet was completed.

The obtained ultraviolet light-emitting retroreflective sheet is
The area of the retroreflective area is about 35% and the area of the ultraviolet light emitting area is about 65% with respect to 100% of the area of the light-incident side surface of the retroreflective sheet. It had a nature.

[0090]

[Table 1]

[0091]

The functional retroreflective sheet of the present invention comprises a support containing a functional resin layer containing a functional pigment as an essential component, and a functional resin layer whose surface is partially formed in an arbitrary shape and area. A microsphere-embedded layer formed on the substrate, a retroreflective microsphere lens embedded and supported in the microsphere-embedded layer, and a transparent sheet provided above the surface of the base sheet on the microsphere lens side. A functional retroreflective sheet having a retroreflective region and a visual functional development region, which is characterized by comprising a protective film and a bonding portion for partially joining the base sheet and the transparent protective film.

With such a constitution, the functional retroreflective sheet of the present invention reflects light such as sunlight in the daytime and exhibits excellent visibility, and the retroreflective region has, for example, even at night. Light from a light source such as an automobile headlight is retroreflected in the direction of the light source, and functions to provide excellent visibility to a viewer in the light source direction such as an automobile driver. When the visual functional expression area is a luminous area, it stores sunlight in the daytime, fluorescent light at night, and illumination light such as automobile headlights, even in the darkness where the light source is completely gone. Emits light gradually and provides excellent luminosity and night visibility for drivers and pedestrians.

Further, in the case where the visual functional expression region is an ultraviolet light emitting region, this region emits light by receiving ultraviolet light, which is excellent for a viewer positioned in a direction different from the light source direction at night. Visibility can be exhibited.

[Brief description of drawings]

FIG. 1 is an example of a schematic plan view of a capsule lens type functional retroreflective sheet according to a preferred embodiment of the present invention as seen from a light incident side.

FIG. 2 is a schematic cross-sectional view taken along the line AA of FIG.

FIG. 3 is a schematic cross-sectional view showing the flow of a method for producing a functional retroreflective sheeting of the present invention.

[Explanation of symbols]

1 ・ ・ ・ ・ Visual functional expression region 2 ... Retroreflective area 3 ・ ・ ・ ・ ・ ・ Coupling part 4 ... Microsphere lens 5 ··· Metal deposition film 6 ... Transparent protective film 7: Functional resin layer 8 ・ ・ ・ ・ Microsphere embedding layer 9: Sealed small compartment vacancy (capsule) 10 ・ ・ ・ ・ ・ ・ Air layer 11 ... Reinforcing layer 12 ... Support 13 ... Base sheet 14 --- Microsphere lens 15- ・ Back layer 16 ... Temporary support 17 --- Microsphere lens temporary support sheet 18 ・ ・ ・ ・ ・ ・ Process film 19 ・ ・ ・ ・ ・ ・ Gravure roll 20 ... Embossing roll 21 .. · Rubber roll

Continuation of the front page (56) Reference JP-A-6-160615 (JP, A) JP-A-5-173008 (JP, A) JP-A-7-261008 (JP, A) JP-A-2-196653 (JP , A) JP 8-129351 (JP, A) JP 7-35911 (JP, A) JP 5-113502 (JP, A) JP 7-218708 (JP, A) JP 2-115890 (JP, A) JP 62-121043 (JP, A) JP 57-189839 (JP, A) JP 60-194405 (JP, A) JP 60-67902 (JP, A) JP 62-121047 (JP, A) JP 60-205501 (JP, A) Actual development Sho 53-23303 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) ) G02B 5/128

Claims (23)

(57) [Claims] 1. A support comprising, as an essential constituent, a functional resin layer containing a functional pigment exhibiting visual functionality and a resin component, and screen-printing or graphing on the surface of the functional resin layer.
15-75% of the area of the functional resin layer by via printing
And a microsphere embedding layer partially formed in an arbitrary shape, and a substantially hemispherical surface covered with a metal vapor deposition film is embedded and supported in the microsphere embedding layer so as to be substantially lined up in one layer. A base sheet comprising a microsphere lens exposing a substantially hemispherical surface not covered with the metal vapor deposition film on the microsphere embedding layer, and a surface of the base sheet on the side where the microsphere lens is exposed. A transparent protective film provided above the base sheet and the transparent protective film, and a joint portion for partially joining the base sheet and the transparent protective film so as to hold an air layer between the layer of the microsphere lens and the transparent protective film. , The retroreflective area of the area in which the bonding portion is not formed in the area where the microsphere lens is embedded, and at least the microsphere is embedded in the surface of the functional resin layer on the side where the transparent protective film is provided. A functional retroreflective sheet characterized by being constituted by a visual functional expression region consisting of a portion not provided. 2. The functional retroreflective sheet according to claim 1, wherein the connecting portion is formed in a continuous line shape, and forms a large number of sealed small compartments with the base sheet and the transparent protective film. 3. The bonding portion is formed by partially thermally deforming the functional resin layer or the functional resin layer and the microsphere-embedded layer on the functional resin layer. The functional retroreflective sheet described. 4. The ratio of the area of the retroreflective area to the area of the visual function manifesting area is 10 to 60% and 40 to 100% of the area of the light incident side surface of the retroreflective sheet, respectively.
The functional retroreflective sheet according to claim 1, wherein the functional retroreflective sheet has a content of ˜90%. 5. The functional retroreflective sheet according to claim 1, wherein the functional pigment is a luminescent pigment, the functional resin layer is a luminescent resin layer, and the visual functional expression region is a luminescent region. . 6. The functional retroreflective sheet according to claim 5, wherein the phosphorescent pigment is an oxide phosphorescent pigment. 7. A phosphorescent pigment having the general formula MAl2O4 (wherein M is
Represents at least one kind of alkaline earth metal) as a mother crystal, and a rare earth metal atom as an activator in a ratio of 1 × 10 −6 to 0.2 (provided that the metal M atom and the rare earth metal atom are present). And the total number of atoms is 1), and the functional retroreflective sheet according to claim 6, which is an oxide-based phosphorescent pigment. 8. The functional retroreflective sheet according to claim 7, wherein the alkaline earth metal is at least one metal selected from the group consisting of Ca, Ba and Sr. 9. The rare earth metal is Sc, Y, La, Ce or P.
r, Nd, Sm, Eu, Gd, Tb, Dy, Ho, E
The functional retroreflective sheet according to claim 7, which is at least one metal selected from the group consisting of r, Tm, Yb, and Lu. 10. The phosphorescent pigment further contains, if necessary, at least one metal selected from the group consisting of Mn, Sn and Bi as a co-activator in a proportion of 1 × 10 −6 to 0.2 (provided that the metal M atom is a metal atom). The total number of atoms of the rare earth metal atom and the coactivator metal is 1), and the functional retroreflective sheet according to claim 7, which is an oxide-based phosphorescent pigment. 11. The functional retroreflective sheet according to claim 5, wherein the phosphorescent resin layer contains 100 to 900 parts by weight of a phosphorescent pigment with respect to 100 parts by weight of the resin component. 12. The functional recursion according to claim 1, wherein the functional pigment is an ultraviolet light emitting fluorescent pigment, the functional resin layer is an ultraviolet light emitting resin layer, and the visual functional expression region is an ultraviolet light emitting region. Reflective sheet. 13. The functional retroreflective sheet according to claim 12, wherein the ultraviolet-emitting fluorescent pigment is an inorganic fluorescent pigment. 14. The inorganic fluorescent pigment, wherein the ultraviolet emitting fluorescent pigment contains at least one selected from a red emitting inorganic fluorescent pigment, a green emitting inorganic fluorescent pigment and a blue emitting inorganic fluorescent pigment. The functional retroreflective sheet described in. 15. A red light emitting inorganic fluorescent pigment is Y ₂ O ₃ : E.
u, Y (P, V) O ₄ : Eu, Y ₂ O ₃ S: Eu, 0.
5MgF ₂ · 3.5MgO · GeO ₂ : Mn, YV
The functional retroreflective sheet according to claim 14, which is at least one selected from the group consisting of O ₄ : Eu and (Y, Gd) BO ₃ : Eu. 16. A green light emitting inorganic fluorescent pigment is Zn ₂ GeO.
₄ : Mn, ZnO: Zn, ZnS: Cu, ZnS: (C
u, Al), (Zn, Cd) S: (Cu, Al), Zn
S: (Cu, Au, Al), Zn ₂ SiO ₄ : Mn, Z
nS: (Cu, Ag), (Zn, Cd) S: Cu, Gd
₂ O ₂ S: Tb, La ₂ O ₂ S: Tb, Y ₂ SiO ₅ :
(Ce, Tb), CeMgAl ₁₁ O ₁₉ : Tb, Zn
S: (Cu, Co), LaOBr: (Tb, Tm), L
a ₂ O ₂ S: Tb and BaMg ₂ Al ₁₆ O ₂₇ : (E
15. The functional retroreflective sheet according to claim 14, which is at least one selected from the group consisting of u and Mu). 17. A blue light emitting inorganic fluorescent pigment is Sr ₅ (PO
4) ₃ Cl: Eu, BaMg ₂ Al ₁₆ O ₂₇ : Eu,
BaMgAl ₁₀ O ₁₇ : Eu, ZnS: Ag, CaW
O ₄ , Y ₂ SiO ₅ : Ce, ZnS: (Ag, Ga, C
l), Sr ₂ P ₂ O ₇ : Eu, CaS: Bi and CaS
15. The functional retroreflective sheet according to claim 14, which is at least one selected from the group consisting of rS: Bi. 18. The functional retroreflective sheet according to claim 13, wherein the inorganic fluorescent pigment has a particle size distribution containing 80% by weight or more of particles having a particle size of 25 μm or less. 19. The ultraviolet light-emitting fluorescent pigment has a wavelength of 250 to 40.
The functional retroreflective sheet according to claim 12, which emits light when irradiated with ultraviolet rays within a range of 0 nm. 20. The ultraviolet-emitting resin layer comprises a resin component 100.
The functional retroreflective sheet according to claim 12, which contains 10 to 600 parts by weight of the ultraviolet-emitting fluorescent pigment with respect to parts by weight. 21. A resin component containing as a main component at least one resin selected from the group consisting of acrylic resins, urethane resins, polyester resins, vinyl chloride resins and fluorine resins. Claim 1, 1
The functional retroreflective sheet according to 1 or 20. 22. The following steps (a) to (f) and (a): A large number of microsphere lenses are densely packed in a temporary support having a resin layer capable of temporarily embedding and supporting the microsphere lenses.
Further, by embedding and supporting the substantially hemispherical surface so as to be substantially one layer, a microsphere lens temporary support sheet is prepared, and (b) on the side of the microsphere lens temporary support sheet on which the microsphere lenses are embedded. Metal deposition is performed on the surface to form a metal deposition film on a substantially hemispherical surface protruding above the temporary support of the microsphere lens, and (c) a functional resin layer containing a functional pigment and a resin component separately. On the functional resin layer .
Of the functional resin layer by clean printing or gravure printing
A microsphere embedding layer having an area of 15 to 75% is partially formed in an arbitrary shape, and (d) a metal vapor deposition in which the microsphere embedding layer on the functional resin layer is projected on the temporary support. The support and the microsphere lens temporary support sheet are superposed and pressure-laminated so as to come into contact with the surface of the microsphere lens on the side having the film, and the metal deposition film of the microsphere lens is almost formed in the microsphere embedding layer. (E) The microsphere lens is transferred to the microsphere embedding layer on the functional resin layer by embedding the hemisphere, and then (e) peeling the temporary support from the laminate, and (f) the obtained microsphere lens. Microspheres of a base sheet having both a microsphere lens-embedded region in which a semi-spherical surface on the side not having the metal vapor deposition film is projected and a microsphere lens-non-embedded region in which the microsphere lens is not embedded. Keep transparent on the side where the lens is buried The films are placed one on top of the other, and the functional resin layer on the base sheet or the microspheres on the functional resin layer and the functional resin layer under heat and pressure using a convex mold from the back surface of the base sheet. The embedded layer is partially thermally deformed to form a joint portion that partially joins the base sheet and the transparent protective film, and the portion where the joint portion is not formed in the microsphere lens embedded region is formed. , A retroreflective region whose light-incident side is covered with a transparent protective film through an air layer, and a visual functional region having a joint portion and a microsphere lens non-embedded region are formed. And a method for producing a functional retroreflective sheet. 23. The manufacturing method according to claim 22, wherein the connecting portion is formed in a continuous line shape to form a large number of sealed small compartment cavities together with the base sheet and the transparent protective film.