JPH1036690A - Weather resistance indicating composition and method for using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a weather resistance indicating composition which can be faded or discolored at an arbitrary time of an outdoor exposure sample, can sensitively coincide with the exposed dosage of ultraviolet rays received by the outdoor exposure sample over a long period of time and can judge e.g. the durability according to the weather resistance of the outdoor exposure sample and to provide a method for using the same. SOLUTION: A composition which indicates weather resistance is prepared by adding a specified amount of a pigment (e.g. organic pigment) which can fade or discolor in response with the absorbed dosage of ultraviolet rays to a transparent plastic having excellent weathering resistance. Alternatively, at least two pigments having different weathering resistance are added to a transparent plastic having excellent weathering resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a weather-resistant display composition and a method of using the same, and more particularly to a composition which discolors or discolors in response to the amount of ultraviolet irradiation for outdoor exposure products. The present invention also relates to a weather-resistant display composition capable of fading or discoloring the outdoor-exposed product at an arbitrary time over time and capable of determining durability and the like based on the weather resistance of the outdoor-exposed product.

In the present invention, the term "weather-resistant display composition" refers to the meaning as a raw material of the weather-resistant display composition, and from the weather-resistant display composition processed into a fixed form such as a film or a rod. Both meanings as so-called weather-resistant display materials are included.

[0003] The determination of the durability based on the weather resistance of an outdoor exposure product includes the fact that the outdoor exposure product is actually deteriorated by ultraviolet rays, and the actual replacement time can be determined. It also means that the degree of deterioration can be estimated by fading or discoloration over time, and it is possible to determine a future replacement time.

[0004]

2. Description of the Related Art In recent years, weather resistance and mechanical properties of outdoor exposure products such as electric wires, signal lines, electric wire covers, signal line covers, traffic signs, outdoor decorative boards, and the like have been improved, and long-term use is possible. However, its durability is generally determined to be 4 to 5 years under outdoor exposure.
That is, the corresponding amount of ultraviolet light is JIS A14
15 and corresponds to 1500 to 2500 hours.

[0005] Here, in order to satisfy such a weather resistance test, as described in JP-B-36-12787, improvement in weather resistance of the basic material itself of an outdoor-exposed product, and the publication of JP-B-36-12 As described in JP-A-15931, antioxidants and ultraviolet inhibitors added to basic materials have been improved, and the weather resistance of outdoor exposure products has been dramatically improved.

[0006] However, it is still the case that the deterioration due to ultraviolet rays is finally caused in the outdoor exposure product, that is, it is necessary to replace the outdoor exposure product, and it is still difficult to determine the time to replace the outdoor exposure product. The problem remained.

In particular, for outdoor exposure products directly connected to social lifelines such as electric wires and signal wires, even if the durability is improved, strict maintenance and inspection before the expiration date are required. In addition, the electric wires and signal lines are generally provided in a fictitious location, and have the particularity that they are in direct contact with each other and cannot be easily inspected. Inspection with a jig has not been established, and its durability management has been practically unavoidable by visual observation from a distance, resulting in a problem that it tends to be inaccurate and insufficient.

On the other hand, conventionally, pigments have been added to plastic materials in view of excellent coloring properties, concealing properties, and optical properties of pigments, and have been widely used as paints and molded products. That is, the coloring property of the pigment is used to improve the commercial value of daily necessities and home appliances, and to provide a decorative effect. Concealment or plastic weather resistance has been improved, and further, a solar heat collecting film for agricultural use, a heat reflective film for controlling temperature rise, and the like have been provided by utilizing the optical properties of pigments. .

[0009] Further, as a special use of the pigment,
As disclosed in JP-A-31022, the pigment has been used as a temperature indicating material or the like by utilizing the property of releasing or decomposing water of crystallization with a change in temperature.

[0010] Therefore, in the technical field of pigments, the focus has only been on improving weather resistance and maintaining excellent coloring properties and temperature-indicating properties, while controlling change deterioration such as fading, No consideration was given to the application to the weather-resistant display composition by actively utilizing it.

Further, as shown in FIG. 1, the present invention has a proportional relationship between the color difference according to the Hunter's color difference formula as an alternative value of the fading or discoloration of the pigment and the outdoor exposure time. As shown in FIG. 3, there is a similar proportional relationship between the color difference and the exposure time of the ultraviolet irradiation test. Further, as shown in FIG. 3, the exposure time of the ultraviolet irradiation test and the tensile strength of the weather resistance indicating composition The inventors have found that there is an inversely proportional relationship between the residual ratio of the elongation and the elongation, and the present invention has been completed by using these.

[0012]

Accordingly, the present invention responds to the long-term exposure to ultraviolet radiation of an outdoor-exposed product by combining a specific plastic and a pigment, and makes the outdoor-exposed product optional over time. It is an object of the present invention to provide a weather-resistant display composition and a method of using the same, which are capable of fading or discoloring at the same time, and capable of judging durability and the like based on the weather resistance of an outdoor-exposed product.

Further, in order to more accurately determine the durability based on the weather resistance of an outdoor exposure product, the type of pigment (dispersant treatment, etc.) Including the difference) and its addition amount,
Pigment mixing type and its addition amount, specific plastic type, antioxidant and ultraviolet absorber added to the plastic type and its addition amount, and further, the weather-resistant display composition is molded into a film, An object of the present invention is to provide a weather-resistant display composition, a method for using the same, and a weather-resistant display material using the same by strictly controlling the thickness and the like in that case.

[0014]

SUMMARY OF THE INVENTION The present invention provides a composition exhibiting weather resistance, characterized in that a pigment which fades or discolors in accordance with the amount of ultraviolet absorption is added to a transparent plastic having excellent weather resistance. It is a weather-resistant display composition.

In another embodiment of the present invention, a display material comprising a weather-resistant display composition obtained by adding a pigment which fades or discolors in accordance with the amount of absorbed ultraviolet light to a transparent plastic having excellent weather resistance is used for outdoor use. This is a method for using a weather-resistant display composition, which is used for an exposed product and which measures durability based on the weather resistance of the outdoor-exposed product. Hereinafter, the present invention will be described in detail by dividing into components and the like.

(Pigment) The pigment used in the present invention is defined as having a function of fading or discoloring according to the amount of ultraviolet absorption. Therefore, as the type of the pigment used in the present invention, if it has the function of fading or discoloring,
There is no particular limitation, and natural pigments, synthetic pigments, inorganic pigments, and organic pigments can be suitably used. Natural pigments are inexpensive, synthetic pigments have uniform coloring properties, inorganic pigments are inexpensive and have excellent heat resistance, and organic pigments have high coloring power with a small amount of addition and have a specific gravity. It is small and has good dispersibility, and further has relatively poor weather resistance.
It is preferable that the discoloration or discoloration of the pigment can be more easily controlled in 0 to 10,000 hours.

Conventionally, it has been pointed out that when an organic pigment is added to a polyolefin-based resin, thermal deterioration of the resin is promoted or migration is liable to occur. However, in the present invention, the type of the polyolefin-based resin and the antioxidation added to the polyolefin-based resin in 1000 to 10000 hours in accordance with JIS A1415, taking into account the deterioration time of the outdoor exposure product. It has been found that the problem can be solved by optimizing the type and amount of the agent or the like, or the dispersion treatment and the amount of the organic pigment, and the pigment is positively used for weather resistance display.

Further, among the organic pigments, the weather resistance is further inferior, and 1000 to 1 according to JIS A1415.
Monoazo, diazo, polyazo and phthalocyanine organic pigments, which can easily control the fading or discoloration of the pigment in 0000 hours, are preferred.

The color of the pigment is not particularly limited. According to the color classification of the Japan Pigment Technical Association, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment, blue pigment, green pigment Fluorescent pigments, black pigments, white pigments, extender pigments and the like can be suitably used.

As a specific example suitable for each pigment color, lead chromate (yellow 10G,
5G, G, R), disazo yellow AA, disazo yellow HR, isoindoline yellow, condensed aloe yellow, zinc chromate, barium chromate, strontium chromate,
Titanium yellow, naphthol yellow S as a nitrona-based yellow pigment, Hansa yellow 10G as an azo-based yellow pigment, Hansa yellow G, Hansa yellow 3G, pigment yellow L, permanent yellow, permanent orange as an orange pigment, molybdate orange, perinone orange, As a brown pigment, permanent brown FG, as a red pigment, lead tetroxide, as an azo red pigment,
Rake red, permanent red 2B, brilliant carmine 6B, naphthol red, pyrazolone red,
Fire Red, Permanent Red 4R, Fast Scarlet, Vulcan Fast Rubin B, Anthosine B, Permanent Red F5R, Helio Bordeaux BL,
Bon Maroon Light, Rhodamine Lake B, Alizarin Lake, Thio Indigot B, Thio Indigo Maroon,
Permanent red FGR, monolite fast red YS as a vat dye red pigment, quinacridone red pigment, fast violet B of a purple pigment, phthalocyanine blue pigment phthalocyanine blue as a blue pigment, vat dye blue pigment Indanthrene blue RS, ultramarine, cobalt green as a green pigment, pigment green B as a nitroso-based green pigment, phthalocyanine green as a phthalocyanine-based green pigment, zinc sulfide as a fluorescent pigment, zinc silicate as a black pigment, carbon as a black pigment Black has a function of fading or discoloring suitably, and according to JIS A1415, 10
It is suitable for use in the present invention in that the weather resistance for 00 to 10000 hours can be displayed.

Particularly, among the above-mentioned pigments, lead chromate (lead 10G, 5G, G, R), disazo yellow A
A, disazo yellow HR, isoindoline yellow, molybdate orange, perinone orange, lake red,
Permanent red 2B, brilliant carmine 6B,
Naphthol red, pyrazolone red, perinone orange, phthalocyanine blue, and phthalocyanine green have relatively poor weather resistance, and in the present invention, the naphthol red is preferably 1000 to 1 according to JIS A1415.
It is optimal in that the weather resistance for 0000 hours can be displayed. That is, in the present invention, rather than pigments that are generally said to have good weather resistance, pigments that are relatively poor in weather resistance, fading, and pigments that are liable to undergo discoloration are easier to display weather resistance. This is preferable in that it can be controlled.

The specific gravity of the pigment used in the present invention is not particularly limited, but is preferably, for example, in the range of 1.0 to 7.0. Specific gravity is 1.
If it is less than 0, handling becomes difficult, so that it may be soared or automatic weighing at the time of addition may be difficult. On the other hand, if the specific gravity exceeds 7.0, the difference in specific gravity with the added plastic becomes large, and This is because there is a possibility that mixing and dispersion of the pigment become non-uniform.
Therefore, more preferably, it is in the range of 1.1 to 2.1,
In order to fall within the range, the use of an organic pigment is generally preferred.

Next, the amount of the pigment added in the present invention will be described. That is, there is no particular limitation as long as the function of fading or discoloring can be exhibited according to the amount of ultraviolet absorption. For example, the amount of the pigment to be added is 0.1 per 100 parts by weight of a transparent plastic having excellent weather resistance. 0
A range of from 0.01 to 10 parts by weight is preferred.

When the amount of the pigment is less than 0.001 part by weight, the coloring property of the plastic is reduced, the resulting color difference is reduced, and it becomes difficult to judge the durability of the outdoor exposed product based on the weather resistance. This is because there is a fear. on the other hand,
When the amount of the pigment exceeds 10 parts by weight, the color difference of the pigment similarly becomes small in relation to the coloring property of the remaining pigment,
It is difficult to judge the durability of outdoor exposure products based on weather resistance, or it is difficult to disperse in transparent plastic excellent in weather resistance, or there is a risk that migration becomes easy, etc. This is because there is a possibility that a problem may occur such that the oxidative deterioration of the transparent plastic having excellent weather resistance is easily promoted.

Therefore, the amount of the pigment to be added is more preferably from 0.01 to 1.5 parts by weight per 100 parts by weight of the transparent plastic having excellent weather resistance, from the viewpoint of better balance. Optimally, it is in the range of 0.03 to 0.7 parts by weight.

Next, in the present invention, a weather-resistant display composition using two or more pigments will be described. That is, it is preferable to use two or more kinds of the above-mentioned pigments.

(1) By mixing and using a pigment having a fast change in color difference and a pigment having a slow change in color difference, it is possible to perform fine color difference control as a whole of the weather-resistant display composition.

(2) For example, by using pigments such as yellow having relatively good weather resistance and red having relatively poor weather resistance, even if the red pigment fades first, the remaining yellow pigment develops color. This is because it is possible to visually recognize the color change of the weather-resistant display composition more clearly than the color difference.

Therefore, for example, in an ultraviolet irradiation test based on JIS A1415, when a single pigment is measured,
Pigment having a color difference of 10.0 or more in less than 500 hours (based on Example 2, an ultraviolet irradiation experiment standard as a weather-resistant display composition, an addition amount of 0.1 part by weight, a film thickness of 2.0 m)
m), similarly, in an ultraviolet irradiation test based on JIS A1415, 1500 hours or more, more preferably 25 hours or more.
Color difference of 1 hour or more, optimally 3000 hours or more
It is preferable to mix and use a pigment having a value of 0.0 or less. In addition, it is preferable to use a mixture of three types and four types of pigments having different weather resistances in that a multi-stage color change can be provided.

When two or more pigments are used, the mixing ratio is preferably determined based on the change in color difference of the weather-resistant display composition, but more specifically,
Based on the pigment having the least weather resistance, the reference pigment 10
It is preferable to mix and use other pigments in the range of 10 to 150 parts by weight with respect to 0 parts by weight. If the other pigment is less than 10 parts by weight, the effect of mixing and adding the pigment is poor, while if it exceeds 150 parts by weight, it may be difficult to control the color difference of the weather-resistant display composition.
Therefore, from the viewpoint of better balance, the other pigment is in the range of 30 to 70 parts by weight with respect to 100 parts by weight of the reference pigment.

Next, a method of adding the pigment used in the present invention will be described. That is, as long as it is uniformly dispersed and mixed in plastic, it is not particularly limited. For example, two-roll, three-roll, high-specialty mixer, Banbury mixer, kneader, ball mill, jet mill, micro mill Fluidizers and the like can be suitably used.

In addition, when the pigment is added, the transparent plastic having excellent weather resistance is softened or liquefied by heating and / or using a solvent for the plastic in order to mix and disperse the pigment more uniformly and in a short time. It is also suitable to put.

For example, when heating and softening or liquefying a transparent plastic having excellent weather resistance, it is preferable to carry out while paying attention to the decomposition of the plastic.
Specifically, it is preferable to carry out at a temperature 0 to 100 ° C higher, more preferably 10 to 70 ° C higher, optimally 20 to 60 ° C higher than the softening point or melting point of the plastic. Therefore, when polyethylene is used as the transparent plastic having excellent weather resistance, the rolls may be 50-1.
50 ° C, more preferably 60-120 ° C, optimally 7
It is preferable to heat to a temperature range of 0 to 110 ° C.

In the case of softening or liquefaction using a transparent plastic solvent having excellent weather resistance, it is necessary to pay attention to the solubility of the pigment, that is, the pigment does not dissolve but only the plastic dissolves. Optimally, a solvent is used.

The viscosity of the transparent plastic having excellent weather resistance when softened or liquefied may be from 1,000 to 1,000, from the viewpoint of easy kneading of the pigment into the plastic and good dispersibility. 000 cps (25
C), more preferably 5000 to 500,000 cps
(25 ° C.) is appropriate.

Further, in the pigment used in the present invention, the handleability of the pigment itself is improved, and the dispersion of the pigment in the plastic is made uniform and shortened, and the control of the weather resistance is further facilitated. In order to prevent the migration of the pigment, it is preferable that the pigment and the wax, the amide-based resin or the plasticizer, the surfactant, and the like are preliminarily mixed and further powdered, flaked, that is, subjected to a so-called dispersion treatment. It is.

The reason is that the pigment is generally a powder and easily flutters, and it is difficult to handle the pigment when mixing.
This problem is solved by surrounding the pigment with wax or the like.Also, by uniformly surrounding the pigment with wax or the like, the dispersibility of the pigment in plastic, particularly at low temperatures, is improved. Or, by a wax layer around the pigment, etc., the weather resistance is further improved, and as a result,
This is because it is easy to control the weather resistance of the pigment.Furthermore, in general, when the pigment is added to a plastic, there is a possibility that the pigment migrates and oozes out to the outside or causes color unevenness. This is because, by uniformly surrounding with such a method, the migration of the pigment can be controlled and such migration can be effectively prevented.

Here, the type of wax is not particularly limited. For example, a low molecular weight petroleum resin is suitable, and more specifically, a paraffin wax or an aromatic wax is used. It is suitable. Especially,
As the paraffin wax, those having a main component of a linear paraffin wax having 20 to 30 carbon atoms have good compatibility with polyethylene and polypropylene as transparent plastics having excellent weather resistance, and are more excellent. This is the most suitable for the present invention in that the effect of preventing the migration of the pigment is obtained.

The type of the amide resin, the plasticizer, the surfactant and the like are not particularly limited.
Fatty acid amide compounds, DOP, DBP, DAP, coupling agents, vegetable oils, polymeric surfactants, etc. are applicable.

Further, the mixing ratio of the pigment and the wax is not particularly limited, but the wax is preferably in the range of 10 to 400 parts by weight based on 100 parts by weight of the pigment. When the mixing ratio of the wax is less than 10 parts by weight,
The mixing effect of the wax may be poor,
If the mixing ratio of the wax exceeds 400 parts by weight, the wax itself may ooze out and the heat resistance and mechanical properties of the resulting weather-resistant display composition may be reduced.

From the viewpoint that the balance is more preferable, the mixing ratio of the wax is 30 to 300 parts by weight, optimally 50 to 200 parts by weight, per 100 parts by weight of the pigment.
It is in the range of parts by weight.

(Transparent Plastic with Excellent Weather Resistance) Since the plastic used in the present invention is used, for example, as a basic material for outdoor exposure products or as an indicator material for indicating weather resistance, it must be excellent in weather resistance. In addition, the excellent weather resistance of the plastic ensures that the pigment has poor weather resistance, thereby achieving the desired control of the weather resistance display of the present invention.

More specifically, the plastic used in the present invention exhibits excellent weather resistance in an ultraviolet irradiation test in accordance with JIS A1415 for at least 1000 hours or more, more preferably between 1000 and 10000 hours. The ones shown are preferred.

If the weather resistance of the plastic is less than 1000 hours based on JIS A1415, there is a possibility that the value of the weather-resistant display composition may be reduced, or the plastic may be deteriorated before discoloration of the pigment. However, if it is deteriorated by ultraviolet rays, cracks will occur in the plastic or the pigments will be directly irradiated with ultraviolet rays. This is because there is a possibility that the amount of the chromium is reduced.

The weather resistance of the plastic is more preferably 1000 to 10 in accordance with JIS A1415.
In order to obtain excellent weather resistance exceeding 10,000 hours, excessive addition of an antioxidant or the like may be required, or use of an expensive resin may be required. This is because it occurs.

Here, the concrete judgment of the weather resistance of the transparent plastic means that no cracks or discoloration of the transparent plastic are generated or almost not. Further, regarding the discoloration of the transparent plastic,
In an ultraviolet irradiation test based on JIS A1415,
The criterion is that the color difference according to the Hunter's color difference equation is less than 10.0, more preferably less than 5.0, and optimally less than 3.0 during 1000 to 10000 hours. This is because, if the color difference is within the range, the weather-resistant display composition does not hinder the external color change from being identified.

Further, the plastic used in the present invention is required to have transparency. This is for the purpose of fading or discoloring the pigment so that the color change can be identified from the outside. This is because the pigment is transmitted and the pigment is uniformly irradiated with ultraviolet rays.

Here, as a concrete judgment of the transparency of the transparent plastic, it suffices to transmit only a small amount of visible light, the discriminability of the color change is better, and the control of the change in the color fading property of the pigment is controlled. From the viewpoint of easier light transmission (thickness 2
The value is 30% or more, and optimally 50% or more.

Specific examples of the transparent plastic having excellent weather resistance used in the present invention include polyethylene resin, polypropylene resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, polybutene resin, and the like. At least one of a polyester resin, an ionomer resin, a polymethylpentene resin, an acrylic resin, a silicone resin, a fluorine resin, a polyvinyl chloride resin, a polyamide resin, a polyacetal resin, a polyurethane resin, a polycarbonate resin, and an epoxy resin. Are selected from the following.

In particular, the polyethylene resin is excellent in weather resistance, electric insulation and lightness, and is inexpensive, and the polypropylene resin is more excellent in weather resistance, electric insulation and lightness. Furthermore, the ethylene-propylene copolymer resin is preferable because it has more heat resistance and also has the characteristics of a polyethylene resin and a polypropylene resin.

As described above, generally, it is said that the polyethylene-based resin promotes thermal deterioration by the pigment or has poor compatibility with the pigment, so that migration of the pigment is likely to occur. Can be suitably used in the present invention from the viewpoint that the migration can be effectively prevented by appropriately selecting the above or by subjecting the pigment to the above-described dispersion treatment.

On the other hand, the ethylene-vinyl acetate copolymer resin is suitable for the present invention in that it is superior in light weight, electric insulation and weather resistance.

Next, an antioxidant and an ultraviolet absorber which are preferably added to the transparent plastic having excellent weather resistance in the present invention will be described. That is, in the present invention, in order to improve the weather resistance of the plastic, it is preferable to add an antioxidant and / or an ultraviolet absorber, but the amount of the antioxidant added is 100 parts by weight of the transparent plastic. Is preferably in the range of 0.01 to 10 parts by weight. If the amount of the antioxidant or the like is less than 0.01 part by weight, the effect of the addition may be poor.
If the amount exceeds 10 parts by weight, dispersion and mixing may be difficult, or the mechanical properties of the transparent plastic may be reduced.

Accordingly, the balance is better from the viewpoints of preventing oxidation and / or UV deterioration and dispersibility and mixing properties. Therefore, an antioxidant and / or an ultraviolet absorber per 100 parts by weight of the transparent plastic is used. To 0.
It is preferable to add 0.5 to 5 parts by weight, optimally 0.1 to 1 part by weight.

It is preferable that the antioxidant and the ultraviolet absorber are used alone or in combination. When the antioxidant and the ultraviolet absorber are used alone, there is an advantage that the time required for mixing and dispersing is reduced, and when the antioxidant and the ultraviolet absorber are used alone, a synergistic effect is expected with respect to the antioxidant, etc. This is because there is an advantage that the amount of use is small.

In the present invention, the method of adding the antioxidant and / or the ultraviolet absorber is not particularly limited, but it is generally preferable to uniformly add the antioxidant and / or the ultraviolet absorber. Kneading,
Alternatively, it is preferable to add the compound by dissolving or dispersing it in a solvent.

Next, the types of the antioxidant and the ultraviolet absorber suitably added to the transparent plastic in the present invention will be described. That is, as an antioxidant,
Commonly used phenol, sulfur, phosphorus,
At least one amine antioxidant can be used, and more specifically, hindered phenol tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4 ′). -Hydroxyphenyl) propionate] methane, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid,
1,1,3-tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4)
-Hydroxybenzyl) benzene, poly [(6-morpholy) -S-triazine-2,4-diyl) (2,2
6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6,6-tetramethyl-4-
Piperidyl) imino)), sulfur tetrakis- [3
-(Dodecylthio) propionyloxymethyl] methane, dilaurylthiodipropionate, dimystylthiodipropionate, distearylthiodipropionate, phosphorus-based triphenyl phosphite, diphenylisodecyl phosphite, phosphorous acid Tris (nonylphenyl) and the like are more excellent in the antioxidant effect and are preferred.

Further, particularly, tetrakis- [methylene-3]
-(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanur Acid, 1,1,3-tris (2-
Methyl-4-hydroxy-5-t-butylphenyl) butane and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene is most suitable for the present invention in that it has a relatively high molecular weight among antioxidants and can provide an antioxidant effect over a long period of time.

When a polyolefin resin, for example, a polyethylene resin is used as a transparent plastic having excellent weather resistance, carbon black is used for the light transmittance of 5%.
It is preferable to add it within a range that does not lower it to within 0%. This is because the weather resistance of the polyolefin resin can be significantly improved. Further, the type of the carbon black is not particularly limited, but the average particle diameter is 2 in terms of being able to impart more excellent weather resistance.
A channel black of 5 mμ or less is optimal.

On the other hand, as the kind of the UV absorber, at least one kind of general UV absorber such as salicylic acid type, benzophenone type, benzotriazole type, cyanoacrylate type and light stabilizer can be used. Specifically, salicylic acid-based phenyl salicylate, benzophenone-based 2-hydroxy-4-methoxybenzophenone, and benzotriazole-based 2- (2′-hydroxy-
5'-methylphenyl) benzotriazole, 2- (2
'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, cyanoacrylate-based ethyl-2-cyano-3,3'-diphenylacrylate, HALS as a light stabilizer There is bis (2,2,6,6-tetramethyl-4-piperidyl)
Sebacate, poly [(6-morpholy) -S-triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [(2,
2,6,6-tetramethyl-4-piperidyl) imino)], nickel bis (octylphenyl) sulfide and the like can be suitably used.

Among these ultraviolet absorbers, HALS as a light stabilizer is excellent in antioxidant effect, and particularly, poly [(6-morpholy) -S-triazine-2,
4-diyl) (2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6
Oligomer or polymer type HA having a high molecular weight such as 6-tetramethyl-4-piperidyl) imino)]
LS is, for example, only 0.5% by weight added to polyethylene resin. In a weather resistance test based on JIS A1415 standard, oxidative deterioration is not observed for 5000 hours or more. The obtained point is optimal for the present invention.

Furthermore, in the present invention, it is preferable to use a mixture of HALS with an ultraviolet absorber other than HALS. This is because it is possible to exhibit the ultraviolet absorbing effect more effectively and to have a synergistic effect in antioxidation and the like. In addition, UV absorbers other than HALS and HAL
The weight ratio of S is preferably in the range of 1: 3 to 5.

HALS has a low molecular weight of 1,000 or less and a high molecular weight of more than 1,000, and both can be suitably used in the present invention. HALS having a low molecular weight is suitable for giving an initial effect as an ultraviolet absorbing effect, and HALS having a high molecular weight is preferable.
LS is suitable for obtaining the continuity of the long-term effect of ultraviolet absorption, or for reducing the mobility of HALS and preventing bleeding as much as possible.

Here, the ultraviolet absorber is defined as a substance having a mechanism of releasing the energy as harmless heat when the plastic is irradiated with ultraviolet rays (wavelength: 300 to 400 nm), and then returning to the original shape. On the other hand,
HALS (hindered amine light stabilizer) is one of ultraviolet absorbers, and is defined as having a function of converting radicals generated by ultraviolet light into a stable form, particularly by ultraviolet light.

In addition, it is preferable that the antioxidant and / or the ultraviolet absorber described herein are added to the wax or the like as the pigment dispersant described above. This is because the wax and the like themselves are effectively prevented from being oxidized, and the amount of ultraviolet light obtained in the vicinity of the pigment is more precisely controlled. As a result, the weather resistance of the pigment can be more easily controlled.

Next, the crosslinkability of the transparent plastic having excellent weather resistance in the present invention will be described. That is, it is preferable to add a cross-linking agent to the plastic material and then heat or introduce the cross-linking structure into the molecule by electron beam irradiation or the like without using the cross-linking agent. This is because the introduction of a crosslinked structure in the molecule of the transparent plastic dramatically improves weather resistance, heat resistance, mechanical properties, and the like.

However, when introducing the cross-linked structure into the transparent plastic, it is preferable to introduce the cross-linked structure before adding the pigment, since it is easy to uniformly introduce the cross-linked structure. In this case, it is preferable that the pigment can be uniformly and easily added.

The crosslinked structure is suitable for improving the weather resistance and the like if introduced into at least a part of the molecule of the plastic. For example, only the surface of the plastic is irradiated with an electron beam or the like, and It is also preferable to introduce a crosslinked structure from the viewpoint that the weather resistance is improved and the production can be performed easily and quickly.

Further, in the weather-resistant display material of the present invention, the above-mentioned transparent plastic having excellent weather resistance is not limited to one kind, and a plurality of layers may be added or a plurality of layers may be added depending on the use of an outdoor exposure product. It is also preferable to provide different transparent plastics having excellent weather resistance.

In particular, the use of a highly weather-resistant resin such as a fluororesin or a silicone resin only in the outer layer of the product of the present invention as a plurality of layers is also advantageous in that the whole transparent plastic excellent in weather resistance becomes inexpensive. It is suitable. For example, FIG.
In or 7, in only the outer layer, a fluorine resin, a silicone resin, or the like is used, and in the other inner layers, a general polyolefin resin, acrylic resin, polyvinyl chloride resin, or the like is used.

In particular, the fact that the polyvinyl chloride resin can be used for the inner layer by adopting the above structure means that the resin has good compatibility with the pigment, and excellent dispersibility and migration characteristics. It is suitable for.

(Weather-Resistant Display) In the present invention, it is sufficient for the weather-resistant display to be able to visually discriminate a change in color due to fading.

Specifically, it is preferable that the color difference ΔE according to the Hunter's color difference formula is 10.0 or more in the fading or discoloration change of the pigment in the weather-resistant display composition. If the color difference is less than 10.0, it may be difficult to identify a change in color of the composition from the outside.

Therefore, more preferably, the color difference is 15.0 or more, further preferably 20.0 or more, and most preferably 30.0 or more.

Here, the color difference according to the Hunter's color difference formula is
It is defined by the following equation. ΔE = [(ΔL) ² + (Δa) ² + (Δb) ² ] ^1/2 (1) ΔE: Color difference between two objects according to Hunter's color difference equation ΔL: 2 in Hunter's color difference equation Δa, Δb: difference between color coordinates a, b of two objects in Hunter's color difference equation

The values of L, a, and b are determined using standard light C and tristimulus values X, Y, and Z specified in JIS Z8722.
Is a value calculated by the following equations (2) and (3). L = 10Y ^1/2 (2) a = 17.5 (1.02X−Y) / Y ^1/2 (3) b = 7.0 (Y−0.847Z) / Y ^1/2 (4)

Next, the so-called weather resistance display time in which the pigment in the weather resistance display composition of the present invention fades or discolors in accordance with the amount of ultraviolet irradiation to display weather resistance will be described.

That is, the weather-resistant display composition of the present invention comprises:
Depending on the durability of the outdoor exposure product, it is preferable to display or display the weather resistance during the ultraviolet irradiation test based on JIS A1415 during the period of 1000 to 10000 hours by fading or discoloration. The reason why the weather resistance display time is preferably 1000 hours or more is to match the durability of the outdoor exposure product, while if it exceeds 10,000 hours, the display time of the weather resistance display composition must be controlled. This is because there is a possibility that the operation becomes difficult.

Therefore, considering the durability of the outdoor exposure product and the ease of controlling the display time of the weather-resistant display composition, more preferably, the weather-resistant display composition is used for 1500 to 7500 hours.
More preferably, it fades or discolors between 2000 and 5000 hours.

It is also preferable to use two or more weather resistant display compositions having the same weather resistant display time. In any case, it is possible to consider variations in the irradiation amount of ultraviolet rays and variations in the display performance of the weather-resistant display composition, and as a result,
This is because it is possible to make a more accurate judgment based on the indication of the weather resistance indicating composition.

Further, it is also preferable to use two or more weather resistant display compositions having different weather resistance display times. This is because deterioration over time of the outdoor exposure product is estimated, and as a result, it is possible to make a more accurate judgment based on the display of the weather resistance indicating composition.

(Regarding the Form Based on the Weather-Resistant Display Composition) The weather-resistant display composition of the present invention can be used in various forms. For example, it is easy to identify the color change of the composition from the outside. As shown in FIG. 5, it is preferable to mold and use a plate as shown in FIG. 5 in that the influence of the thickness on the color difference can be reduced as much as possible.

That is, the composition is molded into a plate to reduce the difference in the amount of ultraviolet light reaching the weather-resistant display composition in the thickness direction, uniformly irradiate the ultraviolet light, and remain in the thickness direction. As a result, the influence of the pigment can be made as small as possible. As a result, the change in the color difference per unit time is larger in the thin plate-shaped weather-resistant display composition than in the thick composition. .

On the other hand, in the case of an extremely thin plate, it is difficult to control the color difference or the mechanical strength may be lacking.

Therefore, specifically, when the composition is molded into a plate, the thickness is 10 μm to 10 μm.
mm is preferred, more preferably 50 microns to 7 m
m, optimally in the range of 100 microns to 5 mm.

Further, as to the embodiment based on the weather-resistant display composition of the present invention, a plurality of layers are provided as described above, and FIG.
As shown in the above, no pigment is added to the exposed parts,
It is preferable to provide a layer made of a transparent plastic having excellent weather resistance. By adopting this configuration, it is not necessary to make a separate weather-resistant display composition according to the type of the outdoor exposure product only by making one reference layer containing a fixed amount of pigment. This is because it becomes possible to provide a weather-resistant display composition that can quickly control weather-resistant display as desired.

Further, as shown in FIG.
On a base material such as metal or glass, a pigment layer that fades or discolors in accordance with the amount of ultraviolet absorption is applied or laminated to a thickness of 1 mm or less, more preferably 500 μm or less, and even more preferably 100 μm or less. In addition, it is also preferable that a transparent plastic layer having excellent weather resistance is provided thereon so as to cover the pigment layer as a form based on the weather-resistant display composition of the present invention.

According to this configuration, the thickness of the pigment layer can be controlled more precisely, and as a result, the color difference can be strictly controlled. In addition, with this configuration, since it can be easily and mass-produced with a knife coater, a roll coater or the like, as a result, there is an advantage that a weather-resistant display composition having stable performance can be provided at a low cost.

In the weather resistant display compositions shown in FIGS. 6 and 7, it goes without saying that the above-mentioned pigments, transparent plastics having excellent weather resistance, antioxidants, ultraviolet absorbers and the like can be used.

It is also preferable that the substrate shown in FIG. 7 has a function of reflecting ultraviolet light or visible light.
For example, when a reflective layer such as a mirror is provided, ultraviolet light transmitted through the weather-resistant display composition is reflected by the reflective layer,
This is because the pigment is introduced again into the weather-resistant display composition, and the pigment absorbs the ultraviolet rays effectively and uniformly from the side opposite to the direction of entry of the ultraviolet rays, so that the pigment can be faded without variation.

[0091]

The present invention will be described more specifically with reference to the following examples.

Example 1 A monoazo red pigment SPEC-048 (manufactured by Sumitomo Color Co., Ltd.) was used as a pigment, and the pigment was mixed with a linear paraffin wax having 20 to 30 carbon atoms. Was pre-mixed so as to be 40%. Then, the pre-mixed pigment is mixed with a low-density polyethylene (oligomer-type HALS agent, 0.5 parts by weight, hindered phenol-based antioxidant, 0.1 parts by weight) using two rolls until the mixture is visually uniform. 1 part by weight) and kneaded for about 15 to 20 minutes to obtain a weather-resistant display composition of the present invention, which was subjected to the following tests.

The amount of the pre-mixed pigment added is 1
The weight of the two rolls was 0.05 ° C., and the temperature of the two rolls was 108 ° C. for the front roll and 95 ° C. for the rear roll.

(Ultraviolet Irradiation Test) The above weather-resistant display composition was molded into a square plate shape (30 mm long,
(Width 30 mm, thickness 2.0 mm), JIS A-1415
An ultraviolet irradiation test was performed in accordance with No. The ultraviolet irradiation conditions were as follows. Table 5 and FIG. 2 show the results of the color difference obtained based on the above-mentioned Hunter equation. In the following, the color difference data in each chart is based on Hunter's equation. Tester: Suga Test Machine Co., Ltd. Sunshine Weatherometer WEL-SUN-HC Irradiation condition: Black panel temperature 63 ± 3 ° C Spray cycle 18 minutes out of 120 minutes

(Tensile strength measurement test) A dumbbell test piece was prepared from the above weather resistance indicating composition in accordance with JIS K-6301, and a tensile strength measurement test was performed. Fig. 3 shows the results.
Shown in Test machine: Autograph AG-500E manufactured by Shimadzu Corporation Measurement conditions: tensile speed 200 mm / min With the number of samples being 3, the average value of the tensile strength of three times was calculated.

(Elongation Rate Measurement Test) A dumbbell test piece was prepared from the above-mentioned weather resistance indicating composition in accordance with JIS K-6301, and an elongation rate measurement test was performed. The results are shown in FIG. Test machine: Automatic extensometer for soft material manufactured by Shimadzu Corporation Measurement conditions: tensile speed 200 mm / min The number of samples was 3, and the average value of the tensile strength of 3 times was calculated.

(Examples 2 to 5) The same conditions as in Example 1 were used except that the amount of the premixed pigment was changed to 0.1, 0.2, 0.3, and 0.5 parts by weight. Then, a weather-resistant display composition of the present invention was prepared and subjected to the same ultraviolet irradiation test. Tables 1 to 4 show the results of the obtained color differences.

(Examples 6 to 9) The kind of the pre-mixed pigment was changed to a polyazo red pigment SPEC-110 (manufactured by Sumitomo Color Co., Ltd.), and the added amount was 0.1, 0.2, 0. .
A weather-resistant display composition of the present invention was prepared under the same conditions as in Example 1 except that it was changed to 3, 0.5 parts by weight, and subjected to the same ultraviolet irradiation test. Tables 1 to 4 show the results of the obtained color differences.
Shown in

(Examples 10 to 13) The same conditions as in Examples 2 to 4 were used except that the kind of the pre-mixed pigment was changed to monoazo red pigment SPEC-056 (manufactured by Sumitomo Color Co., Ltd.). Then, a weather-resistant display composition of the present invention was prepared and subjected to the same test. Tables 1 to 4 show the results of the obtained color differences.

(Examples 14 to 17) The kind of the pre-mixed pigment was SPEC-5, a phthalocyanine molybdenum blue pigment.
Example 2 was changed to 16 (manufactured by Sumitomo Color Co., Ltd.).
Under the same conditions as in Nos. 1 to 4, the weather resistance indicating composition of the present invention was prepared and subjected to the same test. Table 1 shows the obtained color difference results.
Are shown in FIGS.

Examples 18 to 21 The same as Examples 2 to 4 except that the kind of the pre-mixed pigment was changed to a lead chromate yellow pigment PEC-393 (manufactured by Sumitomo Color Co., Ltd.). Under the conditions described above, a weather-resistant display composition of the present invention was prepared and subjected to the same test. Tables 1 to 4 show the results of the obtained color differences.

(Examples 22 to 25) The same conditions as in Examples 2 to 4 were used except that the kind of the pre-mixed pigment was changed to a disazo yellow pigment SPEC-354 (manufactured by Sumitomo Color Co., Ltd.). Then, a weather-resistant display composition of the present invention was prepared and subjected to the same test. Tables 1 to 4 show the results of the obtained color differences.

(Examples 26 to 29) The kind of the pre-mixed pigment was changed to phthalocyanine green pigment SPEC-40.
4 (manufactured by Sumitomo Color Co., Ltd.)
Under the same conditions as in Example 4, a weather-resistant display composition of the present invention was prepared and subjected to the same test. Table 1 shows the obtained color difference results.
Are shown in FIGS.

(Examples 30 to 33) The kind of the pre-mixed pigment was changed to titanium oxide white pigment PEMN-750.
(Manufactured by Sumitomo Color Co., Ltd.)
Under the same conditions as above, to produce a weather-resistant display composition of the present invention,
It was subjected to a similar test. Tables 1 to 4 show the results of the obtained color differences.
Shown in

(Example 34) The types of the pre-mixed pigments were monoazo red pigment SPEC-048 (manufactured by Sumitomo Color Co., Ltd.) and phthalocyanine green pigment SPEC-048.
A weather-resistant display composition of the present invention was prepared under the same conditions as in Example 1 except that the mixture was changed to a mixture of 404 (manufactured by Sumitomo Color Co., Ltd.), and subjected to the same ultraviolet irradiation test. Table 5 shows the results of the obtained color differences. The amount of the pre-mixed pigment is SPEC- of the monoazo red pigment.
048 and SPEC-404, a phthalocyanine green pigment
Was 0.05 parts by weight per 100 parts by weight of the low-density polyethylene resin.

(Example 35) The types of the pre-mixed pigments were monoazo red pigment SPEC-048 (manufactured by Sumitomo Color Co., Ltd.) and phthalocyanine blue pigment SPEC-048.
A weather-resistant display composition of the present invention was prepared under the same conditions as in Example 34 except that the mixture was changed to a mixture of 516 (manufactured by Sumitomo Color Co., Ltd.), and subjected to the same test. Table 5 shows the obtained color difference results.

(Example 36) The types of the pre-mixed pigments were monoazo red pigment SPEC-048 (manufactured by Sumitomo Color Co., Ltd.) and lead chromate yellow pigment PEC-393.
A weather-resistant display composition of the present invention was prepared under the same conditions as in Example 34 except that the mixture was changed to a mixture of (Sumitomo Color Co., Ltd.) and subjected to the same test. Table 5 shows the obtained color difference results.

Examples 37 to 40 The monoazo red pigment SPEC-048 of Example 36 was added in an amount of 0.1,
A weather-resistant display composition of the present invention was prepared under the same conditions as in Example 36 except that the amounts were changed to 0.15, 0.2, and 0.3 parts by weight, and subjected to the same test. Table 5 shows the obtained color difference results.

Example 41 As a pigment, a polyazo red pigment SPEC-110 (manufactured by Sumitomo Color Co., Ltd.) and a phthalocyanine green pigment SPEC-404 (manufactured by Sumitomo Color Co., Ltd.) were used. A linear paraffin wax having 20 to 30 carbon atoms was pre-mixed so that the pigment content was 40%. The pre-mixed pigment is then converted to low density polyethylene (oligomer type HA).
LS agent, 0.5 parts by weight, hindered phenolic antioxidant, 0.1 parts by weight added) 100 parts by weight, using two rolls so that each becomes 0.05 parts by weight, visually Kneaded for about 15-20 minutes until uniform. Then, first, the composition was placed on a plate (length 3).
0 mm, width 30 mm, thickness 2.0 mm) to obtain a plate-shaped weather-resistant display composition of the present invention, and further heat and pressurize the plate using a pressure press to about 50 to 200 μm. A thin-film plate-shaped weather-resistant display composition was obtained. Then, both the plate-shaped weather-resistant display compositions were subjected to the ultraviolet irradiation experiment described in Example 1.
FIG. 4 shows the obtained color difference results.

Reference Examples 1 and 2 0.5 parts by weight of an oligomer type HALS agent and a low molecular weight type HALS were added to the low density polyethylene used in Example 1 without adding a pigment.
After adding 0.35 parts by weight of each agent, each was processed into a plate shape (length 30 mm, width 30 mm, thickness 2.0 m).
m) and subjected to the ultraviolet irradiation experiment described in Example 1. FIG. 8 shows the obtained color difference results.

[0111]

[Table 1]

[0112]

[Table 2]

[0113]

[Table 3]

[0114]

[Table 4]

[0115]

[Table 5]

[0116]

According to the present invention, the outdoor-exposed product can be faded or discolored at an arbitrary time with the elapse of time. It has become possible to provide a weather-resistant display composition and a use method using the same, which can judge durability and the like based on properties.

In a weather-resistant display composition comprising a combination of a specific plastic and a pigment, the type of pigment (including a difference in dispersant treatment, etc.) and the amount added, the type of mixed pigment and the amount added, Plastic type,
The type and amount of the antioxidant or ultraviolet absorber added to the plastic, and furthermore, by molding the weather-resistant display composition into a film and strictly controlling the thickness and the like in that case, more It has become possible to provide a weather-resistant display composition capable of accurately determining the durability based on the weather resistance of an outdoor exposure product and a method of using the same.

Further, by using two or more kinds of the weather resistance indicating compositions, it became possible to judge the durability based on the weather resistance of the outdoor exposure product with high accuracy.

[Brief description of the drawings]

FIG. 1 is a view showing the relationship between the color difference of a weather-resistant display composition (Example 1) and outdoor exposure time in the present invention.

FIG. 2 is a graph showing the relationship between the color difference of the weather-resistant display composition (Example 1) of the present invention and the exposure time in an ultraviolet irradiation test according to JIS A-1415.

FIG. 3 shows the residual tensile strength and residual elongation and the JIS A-141 of the weather resistance indicating composition (Example 1) in the present invention.
FIG. 5 is a diagram showing the relationship between exposure times in an ultraviolet irradiation test according to No. 5;

FIG. 4 is a diagram showing a relationship between a color difference and a film thickness in the present invention.

FIG. 5 is a conceptual diagram showing a film-like weather resistance indicating composition in the present invention.

FIG. 6 is a cross-sectional view showing a film-like weather-resistant display composition having a pigment-free resin layer in the present invention.

FIG. 7 is a cross-sectional view showing a film-like weather-resistant display composition having a pigment layer and a resin layer having excellent weather resistance on a substrate in the present invention.

FIG. 8 is a graph showing the relationship between the color difference and the exposure time of an ultraviolet irradiation test based on JIS A-1415 in a low density polyethylene resin to which a low molecular weight type HALS agent and an oligomer type HALS agent are respectively added. is there.

[Explanation of symbols]

 1: Pigment 2: Transparent plastic excellent in weather resistance 3: Transparent plastic excellent in weather resistance not containing pigment 4: Pigment layer 5: Substrate 6: Reflective layer

Claims (14)

[Claims] 1. A weather resistant display composition comprising a transparent plastic having excellent weather resistance, and a pigment which fades or discolors in accordance with the amount of absorbed ultraviolet light. 2. The weather-resistant display composition according to claim 1, wherein the pigment is an organic pigment. 3. The pigment according to claim 1, wherein the pigment is an azo pigment or a phthalocyanine pigment.
3. The weatherability indicating composition according to item 1. 4. The weather-resistant display composition according to claim 1, wherein the pigment is two or more pigments having different weather resistances. 5. The weather-resistant display composition according to claim 4, wherein the pigment is a yellow pigment and a red pigment. 6. The method according to claim 1, wherein at least one of the pigments is JIS.
In an ultraviolet irradiation test based on A1415, 1000
The weather-resistant display composition according to any one of claims 1 to 5, wherein the composition fades or discolors in a period of 1 to 10,000 hours. 7. The transparent plastic 1 having excellent weather resistance.
7. The composition according to claim 1, wherein the pigment is added in an amount of 0.001 to 10 parts by weight per 100 parts by weight.
Item 8. The weather resistance indicating composition according to item 1. 8. The transparent plastic having excellent weather resistance includes polyethylene resin, polypropylene resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, polybutene resin, polyester resin, ionomer resin, and polymethyl resin. Selected from at least one of pentene resin, acrylic resin, silicone resin, fluorine resin, polyvinyl chloride resin, polyamide resin, polyacetal resin, polyurethane resin, polycarbonate resin and epoxy resin. The weather-resistant indicating composition according to any one of claims 1 to 7. 9. The transparent plastic having excellent weather resistance has a color difference of less than 5.0 in a Hunter color difference equation between 1,000 and 10,000 hours in an ultraviolet irradiation test based on JIS A1415. Do
The weather-resistant display composition according to any one of claims 1 to 8. 10. The transparent plastic having excellent weather resistance is characterized by adding 0.01 to 10 parts by weight of an antioxidant and / or an ultraviolet absorber per 100 parts by weight of the transparent plastic. The weather-resistant display composition according to any one of claims 1 to 9. 11. The color difference according to the Hunter's color difference equation in the fading or discoloration of the pigment in the weather-resistant display composition is 10.0 or more.
11. The weather-resistant display composition according to any one of items 10 to 10. 12. A composition exhibiting weather resistance, wherein a pigment which fades or discolors in accordance with the amount of ultraviolet light absorbed is laminated on a substrate, and a transparent material having excellent weather resistance is provided so as to cover at least the surface of the pigment. A weather-resistant display composition obtained by laminating plastics. 13. A weather-resistant display composition according to claim 1, which is used for an outdoor-exposed product, and the durability of the outdoor-exposed product is measured based on the weather resistance. How to use the weather resistance indicating composition. 14. The method for using the weather-resistant display composition according to claim 12, wherein the weather-resistant display composition is at least two types having different weather resistance display times.