JPS63193830A - Hydrated cured article decorative body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hydrated cured cosmetic body. More specifically, a high-strength and dense hydrated cured product obtained using hydraulic cement, an organic polymer, or a copolymer has a decorative layer on the surface of which at least the top coat layer is an active energy-curable resin coating. This invention relates to a hydrated and cured cosmetic body that is smooth, has an excellent appearance, has high strength, and is resistant to scratches and impressions.

[Prior art and problems to be solved by the invention] In recent years,
It has a smooth and hard surface and is used for architectural interiors and decorations.
There is a remarkable movement toward cosmetic bodies that are resistant to scratches and have beautiful surface properties, and there are cosmetic bodies that have various types of makeup applied to various base materials.

For example, alpha hemihydrate cow slurry containing glass fiber as a bending strength improving material is poured into a mold and cured, then an electron beam curable resin composition is applied and the coating film is cured by irradiating it with an electron beam. , a method for manufacturing a masonry base tile having a hard surface decorative layer with a pencil hardness of 4H to 6H is known (Japanese Patent Publication No. 29910/1983).

The flexural strength of the masonry wax base material manufactured by this method is as low as 80 to 100 K'j/crA, so the thickness must be increased especially when large-sized products are to be obtained. Generally speaking, the thickness of the plaster base material is 9~
A 20m long one is used, and the weight per 1T/i is 16~
It has the disadvantage that it is heavy, weighing approximately 301g (approximately 301g).Also, due to the low water resistance of stone wax itself, there is also a disadvantage that the places where it can be used are limited.

In order to improve the weak water resistance of this stone wax base tile, cement slurry was injected into an elastomer form, and after curing, an electron beam curable resin was applied to the base material. A hardened cement decorative tile (Japanese Unexamined Patent Publication No. 61-53140) is also being considered. However, even with this method, the bending strength of the hardened cement is 60 to 7.
However, it still has the drawback that it is only 0 Ky/cm, requires a thickness of, for example, about 10 m, and is heavy.

In addition, since cement-based or calcium silicate-based substrates have better water resistance than stone wax, it is possible to use type boards such as silica boards, asbestos slates, and slag plaster boards that have increased bending strength through fiber reinforcement. There are also decorative boards coated with various resin paints, but because of the pinholes caused by the fibers they contain and the papermaking method, they require many steps such as sanding and sealer treatment, and even after these steps, they are not fully coated. It has the disadvantage that it is difficult to obtain a smooth decorative surface.

On the other hand, a water-soluble or water-dispersible organic polymer or copolymer is added to a cement-based raw material, and the mixture is kneaded and formed by adding less water than the water mother conventionally used for hydration hardening of cement. It is known, for example, from Japanese Patent Publication No. 59-43431 and Japanese Unexamined Patent Application Publication No. 57-129853 that a high-strength hydrated cured product having a bending strength of 350 and 3 f/ctit or more can be obtained by curing.

The inventors focused on the fact that this high-strength hydrated cured product has much higher bending strength than conventional products, and conducted various studies on its application to thin, light, and smooth cosmetic bodies that were impossible with conventional technology. I did it. As a result, it is possible to make a cosmetic body in which at least a top coat layer is formed with a coating film cured with active energy rays such as ultraviolet rays, which is thin and lightweight because the hydrated and cured product has high strength. In addition to being less likely to be scratched due to the high hardness of the top coat layer,
The present invention was achieved by newly discovering the following two important advantages.

That is, ■ bending strength of 350 made without coarse particles and thick fibers in the raw material for hydrated cured product, 3/ci or more, 2
A hydrated cured product with a 4-hour water absorption rate of less than 10% has excellent surface smoothness and has no irregularities or pinholes on the base material. For this reason, even if the thickness of the decorative layer is reduced, it is possible to create a beautiful decorative body with a much smoother decorative surface compared to conventional silica boards, asbestos slates, gypsum slag boards, etc. be obtained. ■Indentations created when a sharp object is pressed against the surface of a decorative body are affected not by the hardness of the decorative layer but rather by the properties of the base material when the decorative layer is thin. Bending strength of 350KI/cti or more, water absorption rate 1
The hydration cured product of the present invention is provided with a decorative layer having a hard coating film in which at least the top coat layer is made of active energy ray curable resin paint on the surface of the hydration cured product which is less than 0% dense and has excellent indentation resistance. The present invention was developed based on the discovery that the cosmetic body exhibits extremely superior indentation resistance compared to conventional products.

In particular, the feature (■) is remarkable, and the indentation resistance of the hydrated cured product of the present invention is significantly superior to that of conventional silica boards, asbestos slates, gypsum slag boards, glass fiber-reinforced gypsum boards, etc. It is thought that this contributes to the indentation resistance of the hydrated cured cosmetic body.

Due to its characteristics, the hydrated cured cosmetic body of the present invention is easy to apply when used for the interior of a building, for example, because it is lightweight, and it is smooth and has an excellent appearance, and is resistant to scratches and dents, so it can be used for a long time. It has the advantage of being able to maintain its beauty for a long time. Needless to say, such advantages are also effective for table tops, counters, and other uses that require aesthetics and durability. In general, the hydrated cured product cosmetic body of the present invention can obtain high bending strength even if it does not contain asbestos at all, so there is no problem at all with regard to the effects of asbestos on health, which has been viewed as a problem in recent years.

[Means for solving problems]

The present invention provides at least one hydraulic cement, a water-soluble or water-dispersible organic polymer or copolymer, manufactured from raw materials free of coarse particles and thick fibers with a flexural strength of 35
oKyt/cti or more, a 24-hour water absorption rate of less than 10%, a hydrated cured product having excellent indentation resistance and a decorative layer on the surface of which at least the top coat layer is an active energy ray-curable resin coating. Regarding cosmetics.

The method for producing the hydrated cured product of the present invention will be described below.

Water-soluble or water-dispersible organic polymer or copolymer in an amount of 0.5 to 10% by weight (hereinafter simply referred to as %) based on hydraulic cement such as ordinary Portland cement, 8 to 15% of water, and as necessary. Add appropriate additives and knead using a roll mill or the like, and then form into a sheet using a calendar roll. Further, it is pressed at a pressure of 10 to 50 to 3/ci at room temperature to 150°C and then cured to obtain a sheet of hydrated cured product.

It is also possible to form various shapes by using, for example, an Otsu-wing mixer under vacuum instead of a roll mill, or by using an extrusion molding machine instead of a calender roll. If it is extruded into a shape other than a sheet, it is cured without pressing. In particular, those pressed using a combination of roll mill and calendar roll have fewer pores in the hydrated and cured product, so
It has a low 4-hour water absorption rate, high strength, and excellent indentation resistance.

It goes without saying that by selecting a mold during pressing, it is possible to mold into a three-dimensional shape other than a sheet shape.

In order to obtain especially high strength, it is desirable to perform heat curing after heat pressing.

Hydraulic cements include ordinary portland cement,
Portland cement such as white Portland cement and early-strength Portland cement, mixed cement containing blast furnace slag, fly ash, silica hume, etc., alumina cement, cement containing calcium sulfoaluminate and large amounts of stone wax, etc., or mixtures thereof. be.

As water-soluble or water-dispersible organic polymers or copolymers, amide-substituted polymers such as acrylamide (co)polymers, cellulose ethers such as hydroxypropyl methylcellulose, polyvinylpyrrolidone, polyethylene oxide, etc. can be used. Particularly preferred is partially hydrolyzed polyvinyl acetate. These have the effect of aiding kneading and moldability during the production of a hydrated cured product, and are essential for obtaining a dense, smooth, and high-strength hydrated cured product.

The amount of water required for kneading and hardening is 25% or less, preferably 15% or less based on the weight of the hydraulic cement.

By adding a small amount of high-boiling point polyols such as glycerin, alkylene glycol, and polyalkylene glycol, especially glycerin, crosstalk and moldability are further improved.
It is effective in obtaining a good hydrated cured product.

A water reducing agent or retardant such as a lignin sulfonate or a sulfonate of a formalin condensate of naphthalene, which are commonly used in the production of cement products, may be used in combination.

In addition, fillers that do not contain coarse particles, such as calcium carbonate, silica hneem, silicon carbide, carbon, alumina, metal powder, hard balloons, etc., may be added as necessary. Furthermore, a pigment may be used to color the hydrated cured product.

If necessary, it is possible to add a small amount of fibrous filler not for the purpose of improving bending strength.

If the particle size of these fillers is large, the smoothness of the surface of the hydrated cured product will be impaired, so it is desirable that the filler does not substantially contain particles of 100 μm or more.

Furthermore, it is necessary to avoid impairing the surface smoothness by using a fibrous filler with a large wire diameter, or by using a large amount even if the wire diameter is small.

The hydrated cured product (for example, a sheet) produced in this way has excellent bending strength of 350 kgf/crA or more, and has a 24-hour water absorption of 10% or less, which is dense and excellent in smoothness. Because of its high bending strength of 350 to 3f/cri, it can be used as an interior material for buildings, such as 600#X6.
When used as a sheet with a size of 00m, the thickness is 3
About mm is sufficient, and the weight per tail is about 7 to 7.5 Ky, which is lightweight.

Using partially hydrolyzed polyvinyl acetate as a water-soluble or water-dispersible acidic polymer, the ratio of this to hydraulic cement is 2% or more, and the bending strength is increased by heating pressing and heating curing. It is possible to obtain a dense hydrated cured product with particularly high bending strength and a 24-hour water absorption rate of 500 to 3 f/cti or more and a 24-hour water absorption rate of less than 5%. In this case, it is possible to make the thickness 2m or less, and the weight per piece is 5m.
It is lightweight, weighing less than 1 kg, and is extremely effective when used for ceiling materials, etc.

The hydrated cured product of the present invention has excellent indentation resistance as shown in the Examples. In particular, when alumina cement is used as the hydraulic cement, it is denser and exhibits higher indentation resistance than when Portland cement is used, and is particularly preferable as a substrate for the hydrated hardened cosmetic body of the present invention.

The indentation resistance here is determined by pressing a 2 m diameter steel ball against the hydrated material for 5 seconds at various pressures using a Honya type hardness tester 160Q-E and measuring the diameter of the indentation. Therefore, the smaller the indentation diameter, the better the resistance. The indentation resistance of the hydrated cured cosmetic body is also determined in a similar manner.

Next, a resin layer is formed on the surface of the hydrated cured product.

The top coat layer uses active energy ray-curable resin paint. As the resin, various unsaturated acrylate resins such as unsaturated polyester resin, urethane acrylate, epoxy acrylate, polyester acrylate, spiran acrylate, polyether acrylate, and melamine acrylate are used. Needless to say, initiators, photosensitizers, colorants, etc. are added as necessary.

The reason why an active energy ray-curable resin paint is used for the top coat layer is that the hardness of the cured film is high and scratches are difficult to maintain. Select curing conditions.

Active energy rays include ultraviolet rays, sunlight, electron beams, and radiation, but it is most preferable to use ultraviolet rays because of their low equipment cost and high processing capacity.

In the present invention, the top coat resin layer plays the role of a hard, scratch-resistant, smooth, and aesthetically pleasing decorative layer, but it is roughly influenced by the base material that has the excellent properties of the present invention, and has a high quality finish. A hydrated cured cosmetic body is obtained which has the valuable ability of being strong and difficult to leave impressions on.

Unless the characteristics and functions of such hydrated cured product cosmetics are prohibited, for example, a primer layer that improves the adhesion between the base material and the resin layer of the hydrated cured product, an undercoat layer colored with any pigment, hydration A white paint layer for hiding the color of the base material of the cured product, a layer to which arbitrary patterns, designs, or colors such as marble are transferred can be freely formed between the base material and the top coat layer.

Next, the present invention will be explained based on Examples, but the present invention is not limited by the Examples.

[Example] Example] Alumina cement (manufactured by Asahi Glass! 1, trade name Asagami Alumina Cement No. 1 > 100fflffi parts (hereinafter referred to as parts), partially hydrolyzed polyvinyl acetate (Nippon Gosei Chemical Co., Ltd.)
(trade name: Gohsenol), 2 parts of glycerin, 0.3 parts of glycerin,
and 11 parts of water were mixed gently using a planetary mixer.

Next, after kneading for 3 minutes under high shear conditions using a twin roll mill, the resulting kneaded product was mixed with a calender roll.
It was molded into the shape of ~. Temperature 80″C1 Pressure 30KIf/cr
Hot press for 10 minutes under the conditions of i, then press at a temperature of 20'C for 2
After curing for 4 hours, curing (drying) was performed for 10 hours at 80'C to obtain a sheet of hydrated cured material measuring 3# (thickness) x 600 x 600 m.

The bending strength of the sheet is 530Kfff/c waste, the 24-hour water absorption rate is 3.4%, and the weight per sheet is 2.6kg (7.2K).
y/TIt>, a lightweight and smooth surface was obtained. Furthermore, as shown in Table 1, the indentation resistance was □□□.

A urethane acrylate resin paint containing titanium oxide was applied to a thickness of 70 μm on a sheet of this hydrated cured product and cured, and then an ultraviolet curable spirane acrylate resin clear paint was roughly applied on top of it to a thickness of 70 μm. , and was cured by irradiation with ultraviolet rays.

The surface hardness of the obtained hydrated cured cosmetic body was found to be extremely smooth and glossy in 4 days, and a beautiful white cosmetic body was obtained.

As shown in Table 1, the dent resistance of the hydrated and cured cosmetic body was very excellent.

The indentation resistance here is determined by pressing a 2# diameter steel ball against the hydrated material for 5 seconds at various pressures using a Mizuya hardness tester 1600-E and measuring the diameter of the indentation. Therefore, the smaller the indentation diameter, the better the resistance. The indentation resistance of the hydrated cured cosmetic body is also determined in a similar manner.

Example 2 100 parts of ordinary Portland cement, 7 parts of partially hydrolyzed polyvinyl acetate, 0.7 parts of glycerin, 0.5% of sodium gluconate and 11 parts of water were used as raw materials and cured (dried) at 80'C for 15 hours. A sheet of hydrated cured product was produced in the same manner as in Example 1 except for the following steps.
600M, weight per sheetff12.6Kff (7,3K
A sheet with a bending strength of 660 KIf/cm and a 24-hour water absorption rate of 9.7% was obtained.

As shown in Table 1, the dent resistance of this hydrated cured product sheet was inferior to that of Example 1, but it had considerable resistance.

A decorative layer was formed on the surface of the sheet of this hydrated cured product in the same manner as in Example 1, and a smooth, glossy white hydrated cured cosmetic with a surface pencil hardness of 4 days was obtained. As shown in Table 1, the indentation resistance of the hydrated cured cosmetic body was slightly inferior to that of Example 1, but had considerable resistance.

Example 3 A sheet of hydrated cured product was produced in the same manner as in Example 1 using 100 parts of alumina cement, 7 parts of partially hydrolyzed polyvinyl acetate, 0.7 parts of glycerin and 10.8 parts of water as raw materials,
3% (thickness) x 600 x 600#, bending strength 1750K
If /cti, 24-hour water absorption 1.5%, weight per sheet 2.8 Hg (7.9 Kg/l), a sheet with a very smooth surface was obtained. This sheet had very good indentation resistance as shown in Table 1.

A decorative layer was formed on the surface of this hydrated cured product sheet in the same manner as in Example 1, and a beautiful white decorative body with a surface pencil hardness of 4H and very smooth and glossy was obtained. The indentation resistance of the hydrated cured cosmetic body was very excellent as shown in Table 1.

Comparative Examples 1 to 3 Decorative layers similar to those in Example 1 were formed on the surfaces of commercially available asbestos slate boards (flexible boards), slag plaster boards, and glass fiber reinforced plaster boards, respectively. The pencil strength of the surface was 4H, but the smoothness was inferior to Examples 1 to 3. In addition, as shown in Table 1, the indentation resistance of these substrates is inferior compared to Examples 1 to 3. By forming a decorative layer with high surface hardness, the indentation resistance of the decorative body is better than that of the substrate itself. Examples 1 to 3 with some improvement
Compared to the above, the cosmetic body had inferior indentation resistance and was more likely to be indented.

Table 1 (Effects of the invention) The present invention provides substantially 10%
It has a bending strength of 350 KSf/ci+ or more and a 24-hour water absorption rate of less than 10%, which is produced without using coarse particles or thick fibers exceeding 0 μm, and is dense and has excellent indentation resistance. By forming a hard decorative layer in which the top coat layer is made of active energy ray-curable resin paint, it has high bending strength and can be made thinner and lighter, making it suitable for construction as a building material. The present invention provides a hydrated cured cosmetic that is easy to handle, has a high surface hardness, is resistant to scratches, has excellent indentation resistance, is smooth, and has a high design quality.

Claims (2)

[Claims] (1) Bending strength of 350K manufactured from raw materials containing at least one hydraulic cement, water-soluble or water-dispersible organic polymer or copolymer, and free of coarse particles and thick fibers.
Hydration cured product having a decorative layer on the surface of the hydration cured product with excellent indentation resistance, gf/cm^2 or more, 24-hour water absorption rate of less than 10%, and at least the top coat layer is an active energy ray-curable resin coating. Cosmetic body. (2) The hydrated hardened cosmetic body according to claim (1), wherein the hydraulic cement is an alumina cement.