JP5266100B2 - Colored substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring base material which is excellent in weatherability, warm water resistance, coating film hardness or the like, excels in long-term durability performance, and does not impede the visibility of a colored base material. <P>SOLUTION: In the coloring base material A, an acrylic resin based clear layer 2, and an organic inorganic composite clear layer 3 are laminated in this order on the colored surface of a base material 1 in which at least one surface is colored. A clear coating material for forming the acrylic resin based clear layer 2 is an acrylic resin coating material in which a light stabilizer is incorporated into a resin structure. The organic inorganic composite clear layer 3 includes an ultraviolet absorber, in which the transmittance of light with a wavelength of 350 nm is 10% or less, and the transmittance of light with a wavelength of 550 nm is 70% or more. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a colored substrate applied to, for example, a building material.

  Conventionally, a colored base material such as an inorganic board having a colored surface is widely used as a building material such as a tile material or a wall material. For example, in recent years, with the prefabrication and cost reduction of houses, the use of cement tiles has increased rapidly in place of conventional Japanese roof tiles and Western roof tiles due to the advantages of workability and manufacturing costs. Expected to grow.

  When producing such a colored base material, generally, a cement-based molding material obtained by mixing cement, reinforcing fibers, aggregates, etc., adding water, mixing, and stirring is placed in a mold having a predetermined shape. It is put into a base material by pressure dehydration molding, and this base material is cured. Examples of the coloring method for the base material include a method of applying a colored paint made of a polymer material to the surface of the cured base material 1. Further, by applying a solvent-type paint or a water-based paint as a sealer and a colored paint on a base material before curing, efflorescence and discoloration during curing may be prevented and durability may be imparted.

  In such a colored base material, a fading phenomenon occurs over time due to the influence of ultraviolet rays, which may cause deterioration of the appearance particularly when used as a building material. Then, in order to improve the weather resistance of the colored substrate, it has been proposed to provide an organic-inorganic composite clear layer in which an organic-inorganic composite resin is a binder (see Patent Document 1).

  However, even when such an organic / inorganic composite clear layer is provided, if the colored substrate is exposed to ultraviolet rays, heat and water for a long period of time, the colored substrate will deteriorate over time. There is a need for further improvement in the weather resistance of the material.

  Therefore, for example, it is conceivable that the organic / inorganic composite clear layer contains an organic ultraviolet absorber such as benzotriazole or benzophenone, but even in this case, when the colored substrate is exposed outdoors, the organic / inorganic composite clear layer The ultraviolet ray cutting function of the colorant deteriorates with time, and the colored base material deteriorates. That is, in the organic-inorganic composite clear layer, the ultraviolet absorber cannot maintain its function for a long time.

  In addition, it is conceivable to cut ultraviolet rays by providing a coating film containing a pigment on the colored base material, but the visible light transmission is also inhibited by the pigment, and the design pattern formed by coloring the colored base material There is a problem of concealing.

JP 2003-238272 A

  The present invention has been made in view of the above points, and is a colored substrate that is excellent in weather resistance, warm water resistance, coating film hardness, etc., excellent in long-term durability performance, and does not impair the visibility of a colored substrate. The purpose is to provide.

  In the colored substrate A according to the present invention, the acrylic resin-based clear layer 2 and the organic-inorganic composite clear layer 3 are laminated in this order on the colored surface of the substrate 1 colored on at least one surface. . The clear paint for forming the acrylic resin-based clear layer 2 is an acrylic resin paint in which a light stabilizer is incorporated in a resin skeleton. The organic-inorganic composite clear layer 3 contains an ultraviolet absorber, and has a light transmittance of 350 nm or less and a light transmittance of 70% or more of a wavelength of 550 nm.

  This colored substrate A has an acrylic resin-based clear layer 2 containing a light stabilizer laminated on the colored surface of the substrate 1, and further has high weather resistance, warm water resistance, and coating film. An organic / inorganic composite clear layer 3 having excellent hardness and low UV transmittance is laminated. In addition, since the light stabilizer in the acrylic resin-based clear layer 2 is incorporated in the resin skeleton, elution of the light stabilizer from the acrylic resin-based clear layer 2 during autoclave curing or outdoor exposure is suppressed. . For this reason, the colored substrate A has very excellent weather resistance, and even when exposed to the outdoors, deterioration such as a fading phenomenon due to the influence of ultraviolet rays, heat, water, etc. is suppressed over a long period of time. Furthermore, since the organic-inorganic composite clear layer 3 has high visible light permeability, it is possible to suppress the visibility from the outside of the colored surface of the substrate 1 from being inhibited.

  In this invention, it is preferable that the said ultraviolet absorber is yellow iron oxide, and the said base material 1 is colored 1 or more in the Munsell color system, and the hue is 10YR-10GY.

  In this case, it is easy to adjust the transmittance of light having a wavelength of 350 nm of the organic-inorganic composite clear layer 3 containing yellow iron oxide to 10% or less and the transmittance of light having a wavelength of 550 nm to 70% or more. Since yellow iron oxide has high stability and is not easily eluted from the organic-inorganic composite clear layer 3, the light transmission characteristics of the organic-inorganic composite clear layer 3 can be maintained over a long period of time. Furthermore, even when a design pattern having a subtle color change such as a gradation pattern due to coloring is formed on the base material 1, the visibility of the design pattern is suppressed from being inhibited by the organic-inorganic composite clear layer 3. Can do.

  In the present invention, it is also preferable that the organic-inorganic composite clear layer 3 is toned by containing a blue pigment and a red pigment.

  In this case, the color of the organic-inorganic composite clear layer 3 can be finely adjusted to further inhibit the visibility of the design pattern from being inhibited by the organic-inorganic composite clear layer 3.

  From the above, according to the present invention, a colored substrate that is excellent in weather resistance, warm water resistance, coating film hardness, etc., excellent in long-term durability performance, and does not hinder the visibility of the colored substrate 1. A can be obtained.

It is a schematic sectional drawing which shows an example of embodiment of this invention. It is a graph which shows the light transmission characteristic of the organic inorganic composite clear layer containing various inorganic particles. It is a graph which shows the weather resistance of the organic inorganic composite clear layer containing various inorganic particles.

  Hereinafter, the form for implementing this invention is demonstrated with reference to FIG.

  Although it does not restrict | limit especially as the base material 1, For example, a kneaded material obtained by mixing cement, a reinforcing fiber, aggregates, etc., adding water, mixing and stirring is put into the mold of a predetermined shape, and it pressurizes. Examples thereof include a hardened cement board obtained by curing and curing an uncured cement board (uncured base material 1) that has been dehydrated and subjected to primary curing.

  At least one surface of the base material 1 is colored. Although the coloring method of the base material 1 is not particularly limited, for example, the colored layer 4 can be formed by applying and forming a colored paint on the surface of the base material 1.

  As the colored paint, for example, an acrylic emulsion resin paint containing a colorant can be used. The acrylic emulsion resin coating contains a matrix resin such as an acrylic emulsion resin or a silyl group-containing acrylic emulsion resin and the colorant, and an organic solvent, a filler, a dye, a curing accelerator, a thickener, if necessary. Contains various additives such as pigment dispersants.

  As the colorant, typical inorganic pigments can be mentioned as typical ones, but depending on the color, organic pigments having alkali resistance and weather resistance may be used. Examples of black pigments include carbon black and iron oxide, red pigments include petals, green pigments include chromium oxide, blue pigments include phthalocyanine blue, and white pigments. Examples thereof include titanium dioxide. The content of the colorant in the colored paint is preferably in the range of 0.1 to 15% by mass.

  The base material 1 is colored by the colored layer 4 in an appropriate color according to the composition of the colorant in the colored paint, the blending amount, etc., the thickness of the colored layer 4, etc. When yellow iron oxide is contained in the layer 3 as an ultraviolet absorber, the substrate 1 is preferably colored in a yellow color, and in particular, the saturation in the Munsell color system is 1 or more and the hue is 10YR to 10GY. It is preferable that the color is colored.

  In forming the colored layer 4, for example, a colored paint is applied to the uncured substrate 1 by an appropriate method such as brush, spray, roll coater, flow coater, shower coater, dipping, and the like, then dried and then uncured. The base material 1 can be steam-cured. In this case, the uncured base material 1 is cured and cured to form the base material 1, and the colored layer 4 is laminated on the base material 1.

  The acrylic resin-based clear layer 2 and the organic-inorganic composite clear layer 3 are laminated in this order on the colored surface of the colored substrate 1.

  An acrylic emulsion paint can be used as a paint for forming the acrylic resin-based clear layer 2 (hereinafter referred to as an undercoat paint). Further, as the undercoat paint, a paint in which a light stabilizer is incorporated in the resin skeleton is used. Examples of the paint in which such a light stabilizer is incorporated in the resin skeleton include a general Hals polymerization type acrylic resin paint, such as Hals Hybrid (registered trademark) sold by Nippon Shokubai Co., Ltd. Is mentioned. Hals polymerization type acrylic resins include, for example, one or more acrylic monomers such as methyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl methacrylate, and a light stabilizer having a polymerizable unsaturated group (light stability). Examples thereof include those having a structure in which a polymerizable monomer having a group; for example, a piperidine-based polymerizable monomer such as 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine) is copolymerized.

By applying this undercoat paint on the colored surface of the substrate 1 according to a normal coating method such as brush, spray, roll coater, flow coater, shower coater, dipping, etc., and baking according to a normal baking method, An acrylic resin-based clear layer 2 can be formed. Coating weight of the acrylic resin-based clear layer 2 is appropriately set, in order to sufficiently improve the weather resistance of the colored base material A is preferably in the range of 100 to 150 g / m ^2.

  After the acrylic resin-based clear layer 2 is formed, the base material 1 provided with the acrylic resin-based clear layer 2 is preferably subjected to autoclave curing before the organic-inorganic composite clear layer 3 is formed. The conditions for the autoclave curing can be, for example, 160 ° C. or more and 5 hours or more. By performing such autoclave curing, it is possible to ensure the strength and durability of the base material 1 while preventing the occurrence of efflorescence on the colored base material 1, and further, as described above, efflorescence. By preventing this, the adhesion durability of the organic-inorganic composite clear layer 3 when the organic-inorganic composite clear layer 3 is formed can be improved. In such an autoclave curing, the acrylic resin-based clear layer 2 is exposed to a high-temperature, high-pressure, high-alkali atmosphere. However, since the light stabilizer in the acrylic resin-based clear layer 2 is incorporated in the resin skeleton, The elution of the light stabilizer from the resin-based clear layer 2 is suppressed.

  The organic / inorganic composite clear layer 3 includes an ultraviolet absorber and a light transmittance of 350 nm or less and a light transmittance of 70% or more of a wavelength of 550 nm. As a paint for forming the organic-inorganic composite clear layer 3 (hereinafter referred to as a top coat), an emulsion paint containing the organic-inorganic composite resin (A) and an ultraviolet absorber can be used.

  As an example of the organic-inorganic composite resin (A), at least one of organoalkoxysilane (a) and its hydrolysis condensate (including a partial hydrolysis condensate) is bonded to a hydrolyzable silyl group or a hydroxyl group. A hydrolysis condensation reaction product with a silyl group-containing vinyl resin (b) having a silyl group having a silicon atom is converted into triethylamine, triethanolamine, dimethylethanolamine, monoethanolamine, N-methyldiethanolamine, N, N-dimethyl. Examples thereof include resins obtained by neutralization with a neutralizing agent such as ethanolamine or morpholine.

Examples of the organoalkoxysilane (a) include a general formula R ¹ _n Si (OR ² ) _4-n (wherein R ¹ is an organic group having 1 to 8 carbon atoms, and R ² is an alkyl group having 1 to 5 carbon atoms). , N is a compound represented by 1 or 2).

  The silyl group-containing vinyl resin (b) is a hydrolyzable silyl group at the terminal or side chain of the vinyl resin, or at least one silyl group having a silicon atom bonded to a hydroxyl group, preferably 2 The acid value is preferably 20 to 150 mgKOH / g, and the molecular weight is, for example, about 1000 to 50000.

This silyl group-containing vinyl-based resin (b) has, for example, the general formula (X) _P (R ³ ) _(3-P) Si—H (where X is an alkoxy group, an acyloxy group, a halogen group, a ketoximate group, a mercapto group, Hydrolyzable group or hydroxyl group such as alkenyloxy group and phenoxy group, R ³ is hydrogen or monovalent hydrocarbon group such as alkyl group having 1 to 10 carbon atoms, aryl group or aralkyl group, P is an integer of 1 to 3 ) And a vinyl resin having a carbon-carbon double bond are reacted according to a conventional method. Typical examples of the hydrosilane compound include methyldichlorohydrosilane, methyldiethoxyhydrosilane, methyldiacetoxyhydrosilane, and the like. The vinyl resin having a carbon-carbon double bond contains, as an essential monomer unit, a carboxylic acid such as (meth) acrylic acid, itaconic acid or fumaric acid, or an acid anhydride such as maleic anhydride. ) Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, cyclohexyl (meth) acrylic acid and other (meth) acrylic acid esters, acrylonitrile, styrene, α-methyl Examples thereof include a copolymer containing a vinyl monomer selected from the group consisting of styrene, vinyl acetate, vinyl propionate and the like as a comonomer unit. The amount of the hydrosilane compound used in producing the silyl group-containing vinyl resin (b) is such that the molar amount is 0.5 to 2 times the number of carbon-carbon double bonds contained in the vinyl resin. Is appropriate. Specific examples of the silyl group-containing vinyl-based resin (b) include Kanekaze Murak manufactured by Kaneka Chemical Industry Co., Ltd., which is a commercially available product.

  By including such component (A), high weather resistance is imparted to the organic-inorganic composite clear layer 3. Further, a compound (C) having an intramolecular epoxy group having reactivity with an alkoxysilane (B) capable of hydrolytic condensation reaction having an amino group as a curing agent and an amino group of the component (B) as a curing agent. ), The weather resistance of the organic-inorganic composite clear layer 3 can be further improved.

As the component (B), for example, the general formula (R ⁶ —NH—R ⁵ —) _n Si (OR ⁴ ) _4-n (R ⁴ is an alkyl group having 1 to ⁵ carbon atoms, R ⁵ is 1 to ⁵ carbon atoms) 5 alkylene group, R ⁶ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, or a substituted or unsubstituted amino group, n is 1 or 2), and specific examples include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N -(Β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-cyclohexyl-γ-aminopropyltrimethoxysilane, N-silane Examples include rohexyl-γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropylmethyldimethoxysilane, and γ-anilinopropyltrimethoxysilane. It is done.

  Examples of the component (C) include epoxy group-containing alkoxysilanes, alkyl glycidyl ethers and esters, cycloepoxy compounds, bisphenol AF low molecular weight epoxy resins, and emulsions thereof. Specific examples include γ-glycids. Xylpropyltrimexisilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropyltriisopropenyloxysilane, gamma -Glycidoxypropyltriiminooxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, γ-isocyanatopropyltriisopropenyloxysilane and glycidol adduct, butyl glycidyl ether, poly Representative examples include reoxyethylene glycidyl ether, Cardura E (trade name, manufactured by Shell), butylphenyl glycidyl ether, Epicoat 815, 828, 834 (trade name, manufactured by Yuka Shell Epoxy), and the like. .

  The ultraviolet absorber is used to adjust the light transmittance of the organic-inorganic composite clear layer 3. The type and content of the UV absorber in the top coat are appropriately set so that the transmittance of light with a wavelength of 350 nm of the organic-inorganic composite clear layer 3 is 10% or less and the transmittance of light with a wavelength of 550 nm is 70% or more. However, the content of the ultraviolet absorber is preferably adjusted so as to be contained in the range of 1 to 5% by mass in the organic-inorganic composite clear layer 3.

  As this ultraviolet absorber, it is particularly preferable to use yellow iron oxide. Yellow iron oxide is contained in the organic-inorganic composite clear layer 3 in a particulate form, for example. Since this yellow iron oxide has a high absorption rate of ultraviolet rays with a wavelength of 350 nm or less and a low absorption rate of visible light, such yellow iron oxide is contained in the organic-inorganic composite clear layer 3 and its content and organic-inorganic composite By adjusting the thickness of the clear layer 3 and the like as appropriate, it is easy to adjust the transmittance of light having a wavelength of 350 nm or less of the organic-inorganic composite clear layer 3 to 10% or less and the transmittance of light having a wavelength of 550 nm to 70%. Become. Moreover, the yellow iron oxide has high stability, can maintain the ultraviolet absorption for a long period of time, and has an advantage that it is difficult to elute from the organic-inorganic composite clear layer 3. The blending amount of the yellow iron oxide in the top coating is preferably adjusted so that the yellow iron oxide is contained in the organic-inorganic composite clear layer 3 in the range of 1 to 3% by mass. A predetermined light transmittance of the composite clear layer 3 can be achieved.

  For reference, FIG. 2 shows the measurement results of light transmittance for a single film of the organic-inorganic composite clear layer 3 containing cerium oxide particles, zinc oxide particles, titanium oxide particles, and yellow iron oxide particles as ultraviolet absorbers. Show. The content of the inorganic particles in the organic / inorganic composite clear layer 3 is in the range of 1 to 5% by mass, and the thickness of the organic / inorganic composite clear layer 3 is 12 μm. In the figure, a is the result when yellow iron oxide particles are used, b is when zinc oxide particles are used, c is when cerium oxide particles are used, and d is the result when titanium oxide particles are used.

  Moreover, about this organic inorganic composite clear layer 3, the test result of the weather resistance by an accelerated weather resistance tester at the time of using various inorganic particles as an ultraviolet absorber is shown in FIG. In the graph of FIG. 3, the horizontal axis represents the test time, and the vertical axis represents the gloss retention. In the figure, ◇ indicates that no UV absorber is used, + indicates that yellow iron oxide particles are used, △ indicates that red iron oxide particles are used, □ indicates that zinc oxide particles are used, and ● indicates cerium oxide particles. ♦ indicates the result when titanium oxide particles are used.

  As shown in these results, for example, when cerium oxide is used, the absorption rate of ultraviolet rays up to a wavelength of 300 nm is high, but the absorption rate starts to decrease at a wavelength of 350 nm. When titanium oxide is used, the absorption rate of ultraviolet rays up to a wavelength of 330 nm is high. However, the absorption rate starts to decrease at a wavelength of 350 nm, and the activity in light is high, so the resin in the organic-inorganic composite clear layer 3 is adversely affected. There is also a risk of affecting. In addition, when zinc oxide is used, zinc oxide is easily dissolved in water, and zinc oxide may flow out from the organic-inorganic composite clear layer 3 and the weather resistance may be lowered. On the other hand, when yellow iron oxide particles are used as the ultraviolet absorber, the organic / inorganic composite clear layer 3 is suppressed in light transmittance in a wide range of the ultraviolet region, and has high light transmittance at a wavelength of 550 nm or more. In addition, the organic / inorganic composite clear layer 3 exhibits high weather resistance.

  Since the organic-inorganic composite clear layer 3 has high visible light permeability, it is possible to suppress the visibility of the colored base material 1 from the outside from being inhibited by the organic-inorganic composite clear layer 3. In addition, when yellow iron oxide is used as an ultraviolet absorber, the organic / inorganic composite clear layer 3 has a yellowish color, so that a design pattern having a subtle color change such as a gradation pattern due to coloring is formed on the substrate 1. In this case, the design pattern of the base material 1 may not be clearly visible due to the organic / inorganic composite clear layer 3, but the base material 1 has a yellow color, particularly the Munsell color system as in this embodiment. When the color saturation is 1 or more and the hue is 10 YR to 10 GY, the design pattern is visually recognized even if a design pattern having a subtle color change is formed on the substrate 1 in such a range. Sex can be prevented from being inhibited.

  Moreover, the visibility of the design pattern which has the subtle color change of the colored base material 1 is inhibited by toning the organic-inorganic composite clear layer 3 by containing a pigment in the organic-inorganic composite clear layer 3. It can also be suppressed. Examples of the pigment include an appropriate pigment used in the above-described colored paint. Toning of the organic-inorganic composite clear layer 3 with a pigment can be appropriately performed so that the design pattern of the colored base material 1 is not obstructed, and not when the base material 1 is colored in a yellowish color. You can do it. As a particularly preferable example of toning with a pigment, when the base material 1 is colored in a yellow color and yellow iron oxide is used as an ultraviolet absorber as in the present embodiment, the organic-inorganic composite clear layer 3 has a blue color. For example, fine adjustment of the color of the organic-inorganic composite clear layer 3 by adjusting the color of the organic-inorganic composite clear layer 3 by adding a pigment and a red pigment. Thereby, inhibition of the visibility of the design pattern can be further suppressed. The blending amount of the pigment in the top coating is preferably adjusted so that the total amount of the pigment is 0.5% by mass or less in the organic-inorganic composite clear layer 3, and the organic-inorganic composite clear layer 3 is dull in this range. The organic-inorganic composite clear layer 3 can be toned while suppressing the occurrence of.

  Further, the top coating material may further contain various additives such as water, an organic solvent and a filler, a curing accelerator, and a thickener as necessary.

This top coat is applied over the acrylic resin-based clear layer 2 in accordance with a normal coating method such as brush, spray, roll coater, flow coater, shower coater, dipping, etc. By baking, the organic-inorganic composite clear layer 3 can be formed. The coating amount of the organic-inorganic composite clear layer 3 is set as appropriate, but the organic-inorganic composite clear layer 3 has a light transmittance at a wavelength of 350 nm of 10% or less and a light transmittance at a wavelength of 550 nm of 70% or more. It is preferable that the basis weight is in the range of 100 to 150 g / m ² or the average film thickness is about 20 μm.

  The colored base material A having the above-described structure has an acrylic resin-based clear layer 2 containing a light stabilizer laminated on the colored surface of the base material 1, and further has high weather resistance thereon, An organic-inorganic composite clear layer 3 having excellent hot water resistance, coating film hardness, etc. and low UV transmittance is laminated. In addition, since the light stabilizer in the acrylic resin-based clear layer 2 is incorporated in the resin skeleton, elution of the light stabilizer from the acrylic resin-based clear layer 2 during autoclave curing or outdoor exposure is suppressed. . For this reason, the colored substrate A has very excellent weather resistance, and even when exposed to the outdoors, deterioration such as a fading phenomenon due to the influence of ultraviolet rays, heat, water, etc. is suppressed over a long period of time. Furthermore, since the organic-inorganic composite clear layer 3 has high visible light permeability, it is possible to suppress the visibility from the outside of the colored surface of the substrate 1 from being inhibited.

  Hereinafter, the present invention will be described in more detail by presenting specific examples of the present invention.

[Formation and Evaluation of Acrylic Resin Clear Layer]
First, an acrylic resin-based clear layer 2 having various compositions was formed on the substrate 1 and its characteristics were evaluated.

(Production Examples 1-7)
An uncured base material 1 was produced by molding a cement-based molding material, and a colored paint was applied to the upper surface thereof, followed by curing and curing, whereby the base material 1 was cured and a colored layer 4 was formed. At this time, the base material 1 was colored with the hue and saturation shown in Table 1 by changing the pigment composition in the colored paint for each of Examples and Comparative Examples.

  An acrylic resin-based clear layer 2 was formed by applying an undercoat paint on the colored surface of the substrate 1 and baking and curing it. As the undercoat paint, an emulsion paint containing an acrylic resin obtained by polymerizing the monomer components shown in Table 1 was used. Of the monomer components in Table 1, MMA represents methyl methacrylate, BA represents butyl acrylate, CHMA represents cyclohexyl methacrylate, and polymerized HALS represents a hindered amine light stabilizer having a polymerizable functional group. In addition, in Production Examples 4 and 5, an additive type HALS (hindered amine type light stabilizer) was blended in the undercoat coating film.

  Next, when “Yes” is written in the column of “Autoclave Curing” in Table 1, the base material 1 provided with the acrylic resin-based clear layer 2 is cured at 160 ° C. for 5 hours. did.

(Evaluation test)
-Adhesion evaluation About each manufacture example, after sticking a cellophane adhesive tape on the surface of the acrylic resin-type clear layer 2 and then peeling it off vigorously, the acrylic resin-type clear layer 2 on the adhesive surface of the tape The degree of adhesion was confirmed. Based on this result, it evaluated as follows.
○: Adhesion of the acrylic resin-based clear layer 2 to the tape is not recognized.
Δ: Adhesion of the acrylic resin-based clear layer 2 is observed on the tape.
X: Adhesion of the acrylic resin-based clear layer 2 is observed on 50% or more of the adhesive surface of the tape.

-Weather resistance evaluation About each manufacture example, after performing the weather resistance test by an accelerated weather resistance tester, the glossiness of the surface of the acrylic resin type clear layer 2 was confirmed. Based on this result, it evaluated as follows.
A: The degree of gloss reduction is slight. ○: The gloss reduction is moderate. X: The degree of gloss reduction is large.

-Base material strength evaluation Bending strength was measured by performing a bending test about each manufacture example. Based on this result, it evaluated as follows.
○: Passed JIS A5423.
X: JIS A5423 failure.

  The above results are shown in Table 1 below.

  According to the results for Production Examples 2 to 7 shown in Table 1, in all cases, no good results were obtained with respect to adhesion, weather resistance, and substrate strength, especially when autoclave curing was applied. As in Production Examples 2, 4 and 6, the weather resistance is remarkably lowered.

  In contrast, Production Example 1 is excellent in adhesion and substrate strength, and has excellent weather resistance while being autoclaved.

[Production and Evaluation of Colored Substrate]
(Examples 1 to 3, Reference Examples 4 and 5, Comparative Examples 1 to 6)
An uncured base material 1 was produced by molding a cement-based molding material, and a colored paint was applied to the upper surface thereof, followed by curing and curing, whereby a colored base material 1 was obtained. At this time, the base material 2 was colored to the hue and saturation shown in Table 1 by changing the pigment composition in the colored paint for each of the examples and comparative examples.

  An acrylic resin-based clear layer 2 was formed on the colored substrate 1 under the same conditions as in Production Example 1.

  Next, an overcoating paint having the composition shown in Table 2 is applied to the acrylic resin-based clear layer 2 so as to be baked and cured, whereby the organic-inorganic composite clear layer 3 having the film thickness and light transmission characteristics shown in Table 1 is obtained. Formed. The light transmission characteristic is a result of separately forming a single film of the organic-inorganic composite clear layer 3 having the film thickness and measuring the light transmittance of this single film.

(Evaluation test)
-Hue evaluation About each Example and a comparative example, it is visually observed whether the hue of the external appearance at the time of formation of the colored layer 4 is maintained when the acrylic resin type clear layer 2 and the organic-inorganic composite clear layer 3 are formed. And evaluated as follows.
A: Hue is maintained.
○: The hue is almost maintained.
(Triangle | delta): Although hue is impaired a little, it exists in an allowable range.
X: Hue is impaired.

Contrast evaluation For each example and comparative example, is the contrast of the gradation pattern appearing in the appearance when the colored layer 4 is formed maintained when the acrylic resin-based clear layer 2 and the organic-inorganic composite clear layer 3 are formed? Whether or not was judged visually, and evaluated as follows.

Based on this result, it evaluated as follows.
A: The contrast is more emphasized.
○: Contrast is maintained.
Δ: The contrast is insufficient.
X: It is difficult to confirm gradation.

-Weather resistance evaluation About each Example and the comparative example, after performing the weather resistance test by an accelerated weather resistance tester, the glossiness of the surface of the acrylic resin type clear layer 2 was confirmed. Based on this result, it evaluated as follows.
A: The degree of gloss reduction is slight. ○: The gloss reduction is moderate. Δ: The degree of gloss reduction is slightly large.
X: The degree of gloss reduction is large.

  The above results are shown in Table 2 below.

As a result, in Examples 1 to 3 and Reference Examples 4 and 5, the colored substrate A exhibited excellent weather resistance. Further, among Examples 1 to 3 and Reference Examples 4 and 5, the appearance is good in Examples 1 to 3 which are colored yellow and have a saturation of 1 or more. In Examples 1 and 2, the appearance was particularly good.

A Colored base material 1 Base material 2 Acrylic resin clear layer 3 Organic / inorganic composite clear layer

Claims (2)

An acrylic resin-based clear layer and an organic-inorganic composite clear layer are laminated in this order on the colored surface of the base material colored on at least one surface,
The paint for forming the acrylic resin-based clear layer is a paint in which a light stabilizer is incorporated in the resin skeleton,
Wherein with the organic-inorganic composite clear layer contains an ultraviolet absorber, 10% transmittance of light having a wavelength of 350nm or less state, and are light transmittance of 70% or more wavelengths 550 nm,
Wherein an ultraviolet absorber is yellow iron oxide, wherein the substrate, the saturation in the Munsell color system is 1 or more, colored substrate hue characterized that you have been colored 5YR～10GY. The colored base material according to claim 1 , wherein the organic-inorganic composite clear layer is toned by containing at least one of a blue pigment and a red pigment.

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