JPH11165370A - Manufacturing method of porous ceramic decorative panel - Google Patents

Abstract

(57) [Abstract] (with correction) [PROBLEMS] To provide a method for producing a porous ceramic decorative panel excellent in water resistance and design. SOLUTION: A mixture of an acrylic resin or a polyester resin and a polyisocyanate compound is applied on a porous ceramic substrate 1, and an OH group is reacted with an NCO group, or a polyisocyanate compound is applied, and the NCO group is converted into air. A polyurethane layer 2 'is formed by reacting the moisture therein or an OH group of the substrate 1, and an ultraviolet curable resin layer 3 is formed thereon, and then an extender pigment and an acrylic resin or polyester and a polyisocyanate compound are formed thereon. Is applied to form the urethane resin layer 4. Further, after the ink layer 5 is formed thereon by a transfer method, a mixture of an acrylic resin or a polyester resin and a polyisocyanate compound is applied thereon to form the urethane resin layer 6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a decorative board suitable for construction materials used indoors or outdoors.

[0002]

2. Description of the Related Art Porous ceramic materials are suitable for construction materials because they are nonflammable. In many cases, two or more resin film layers are formed on the surface for imparting design properties or for protection. For example, in Japanese Unexamined Patent Publication No. Hei 6-321655, in order to complete the water resistance of the surface and to impart a natural appearance, a ceramic coating is impregnated with a sealer and then coated with a clear paint.

However, since many inorganic ceramic materials are porous and exhibit alkalinity, various methods have been proposed for forming a resin film layer on the surface thereof. JP 6
In JP-A 1-286281, a moisture-curable urethane sealer layer is formed on an inorganic ceramic substrate such as calcium silicate, and an unsaturated polyester-type ultraviolet-curable resin is cured on the surface thereof to form a cured layer as a sealing layer. A method for forming an acrylic urethane resin layer thereon is disclosed. However, the purpose of this method is to impart antistatic properties, and is different from the purpose of imparting design properties by transfer in the present invention.

[0004] Also, Japanese Patent Application Laid-Open No. Hei 3-96355 discloses that
A method is disclosed in which a sealer layer and an acrylic urethane resin layer having a hiding property are formed on an inorganic ceramic substrate, and then an ink layer is formed by transfer and a clear layer is formed for surface protection. The sealer layer used here is for improving the adhesion of the paint layer, but has no effect on improving the water resistance. Further, since the glass transition point of the acrylic urethane resin layer having a hiding property used here is 0 ° C. or less,
Even if the resin layer is applied softly to the substrate, it cannot cover the holes in the substrate and make it smooth (hereinafter referred to as a seal),
Only a decorative board with poor design was obtained.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to obtain a porous ceramic decorative panel excellent in water resistance and design.

[0006]

According to the present invention, an acrylic resin (a) having an OH group or
A mixture (d) obtained by mixing a polyester resin (b) having an H group and a polyisocyanate compound (c) having an NCO group is applied, and the OH group and the NCO group are reacted, or the NCO group-containing polyisocyanate compound is reacted. (C)
To form a polyurethane layer 2 ′ by reacting the NCO group with the moisture in the air or the OH group of the porous ceramic substrate 1, and to cure the polyurethane layer 2 ′ on the urethane resin layer 2 or the polyurethane layer 2 ′. Mold resin composition (e)
Is applied, and ultraviolet rays are irradiated to cure the ultraviolet-curable resin composition (e) to form an ultraviolet-curable resin layer 3. Then, the extender pigment (f) and O
A mixture (g) of a mixture of an acrylic resin (a) having an H group or a polyester resin (b) having an OH group and a polyisocyanate compound (c) having an NCO group is applied, and the OH group is reacted with the NCO group. After forming a urethane resin layer 4 having a concealing property and further forming an ink layer 5 on the urethane resin layer 4 by a transfer method, an acrylic resin (a) having an OH group is formed on the ink layer 5. Or OH
A mixture (h) obtained by mixing a polyester resin (b) having a group and a polyisocyanate compound (c) having an NCO group is applied, and the OH group and the NCO group are reacted to form a urethane resin layer 6. This is a method for producing an inorganic ceramic decorative panel.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As the porous ceramic substrate 1 used in the present invention, a cement plate, a slate plate, a calcium silicate plate, a mortar plate reinforced by mixing asbestos fiber, glass fiber or the like as necessary. And plaster boards.

In the present invention, the mixture (d) used to form the urethane resin layer 2 comprises an acrylic resin (a) having an OH group or a polyester resin (b) having an OH group and a polyisocyanate having an NCO group. It is a mixture of the compound (c). Further, an extender can be added to the mixture (d) as necessary. Furthermore, in the present invention, it is possible to form the polyurethane layer 2 'by applying the polyisocyanate compound (c) having an NCO group alone.

As the acrylic resin (a) having an OH group, Olester Q-186 (a product of Mitsui Toatsu Chemicals, Inc.) and Dianal LR-257 (a product of Mitsubishi Rayon Co., Ltd.)
Products), Hitaloid 3008 (product of Hitachi Chemical Co., Ltd.), Desmophen A160 (product of Sumitomo Bayer Urethane Co., Ltd.), etc., and have sufficient strength by reacting with a polyisocyanate compound (c) having an NCO group described below. In order to form a resin layer having the following, it is preferable that the resin has a hydroxyl value of 10 to 300 and a number average molecular weight of 2,000 to 20,000.

Examples of the polyester resin (b) having an OH group include phthalkid 806-70 (a product of Hitachi Chemical Co., Ltd.), Desmophen 651 (a product of Sumitomo Bayer Urethane Co., Ltd.), and Takerak U-25 (a product of Takeda Pharmaceutical Co., Ltd.) Co., Ltd.) having a hydroxyl value of 10 to 300 and a number average of from 10 to 300 in order to form a resin layer having sufficient strength by reacting with a polyisocyanate compound (c) having an NCO group described below. It is preferable that the molecular weight is from 2,000 to 20,000.

Among the polyisocyanate compounds having an NCO group (c), xylene is preferred when used in combination with an acrylic resin having an OH group (a) or a polyester resin having an OH group (b). -Di-isocyanate (XDI), tolylene-di-isocyanate (TDI), 4,4'-diphenylmethane-di-isocyanate (MDI), hexamethylene-di-isocyanate (HMDI), or a modified product thereof;
Specific examples include Duranate 24A-100 (a product of Asahi Kasei Corporation), Sumidur N-75 (a product of Sumitomo Bayer Urethane Co., Ltd.), and Takenate D-110N (a product of Takeda Pharmaceutical Co., Ltd.). The polyisocyanate compound (c) having an NCO group is reacted with an acrylic resin (a) having an OH group or a polyester resin (b) having an OH group to form a resin layer having sufficient strength. It is preferable that the compound has 2 to 6 NCO groups in the molecule and has a low molecular weight of 100 to 1000.

Among the polyisocyanate compounds (c) having an NCO group, those which are suitable when used alone to form the polyurethane layer 2 'include Desmodur E22 (a product of Sumitomo Bayer Urethane Co., Ltd.),
Olester M87-60CX (manufactured by Mitsui Toatsu Chemicals, Inc.) and the like. In order to form a resin layer having sufficient strength by curing alone, the number average molecular weight is 1000-2.
0000 is preferred.

As described above, the mixture (d) is a mixture of the acrylic resin (a) having an OH group or the polyester resin (b) having an OH group and the polyisocyanate compound (c) having an NCO group. , OH group and NCO
It is preferable to mix the groups so that the ratio of the groups is 4: 6 to 6: 4. If either one of the groups is extremely large, unreacted OH groups or NCO groups tend to remain, and the film strength, water resistance, and alkali resistance of the urethane resin layer 2 tend to decrease.

Urethane resin layer 2 or polyurethane layer 2 '
Is obtained by applying the mixture (d) or the polyisocyanate compound having an NCO group (c) alone on the porous ceramic substrate 1 and leaving it or drying it by heating to 40 to 100 ° C. It may be obtained by reacting with a group. The thickness of the dried coating film is preferably 0.5 to 20 μm, and the coating method is a roll coating method,
Curtain flow method, spray coating method and the like can be mentioned.

In the present invention, the ultraviolet-curable resin composition (e) is applied onto the urethane resin layer 2 or the polyurethane layer 2 'obtained as described above, and the ultraviolet-curable resin composition is irradiated with ultraviolet rays. The composition (e) is cured to form an ultraviolet curable resin layer 3. The ultraviolet-curable resin composition (e) generates a radical or a cation by absorbing ultraviolet light with a compound having at least one double bond in a molecule, for example, urethane acrylate, polyester acrylate, or epoxy acrylate. It is a mixture with a photoinitiator. If necessary, a resin containing no double bond or a solvent may be added to the ultraviolet-curable resin composition (e). The UV-curable resin layer 3 preferably has a cured coating thickness of 5 to 50 μm, and examples of a coating method include a roll coating method and a curtain flow method.

Next, the extender pigment (f) and the acrylic resin (a) having an OH group or the polyester resin (b) having an OH group and N
A mixture (g) obtained by mixing a polyisocyanate compound (c) having a CO group is applied, and an OH group and an NCO group are reacted to form a urethane resin layer 4 having a hiding property.
The urethane resin layer 4 having a hiding property is required to conceal the surface state of the porous ceramic substrate 1 and to maintain a sufficient adhesive force with the ink layer 5 to be formed next.

The extender pigment (f) used in the present invention
Examples thereof include titanium oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, silicon dioxide, barium sulfate, zinc stearate, zinc sulfide, and talc. Titanium oxide is particularly preferred in that it has excellent concealing properties. Examples of the acrylic resin (a) having an OH group, the polyester resin (b) having an OH group, and the polyisocyanate compound (c) having an NCO group used for forming the urethane resin layer 4 having a hiding property include: Those described above can be used similarly. The method for applying the mixture (g) is the same as that for forming the urethane resin layer 2, and the drying and curing conditions are preferably left to stand or 40 to 150 ° C, and the dry coating thickness is preferably 10 to 50 µm.

Next, the urethane resin layer 4 having a hiding property
The ink layer 5 is formed on the substrate by a transfer method. The ink layer 5 is formed by transferring the ink layer 5 previously formed on a plastic film by pressing the ink layer 5 on the urethane resin layer 4 having a concealing property. When transferring,
In order to further increase the adhesive strength between the urethane resin layer 4 having the concealing property and the ink layer 5, the porous ceramic substrate formed up to the urethane resin layer 4 having the concealing property, or the transfer roll to be pressed to 70 to 200 ° C. It is desirable to heat.

Finally, on the ink layer 5, a mixture (h) in which an acrylic resin (a) having an OH group or a polyester resin (b) having an OH group and a polyisocyanate compound (c) having an NCO group are mixed. OH group and N
The urethane resin layer 6 is formed by reacting with a CO group.

Acrylic resin having an OH group (a), OH
As the polyester resin (b) having a group and the polyisocyanate compound (c) having an NCO group, those described above can be similarly used. The urethane resin layer 6 can be made translucent by blending an appropriate extender into the mixture (h) as necessary.

The method for applying the mixture (h) is the same as that for forming the urethane resin layer 2; the drying and curing conditions are preferably left to stand or 40 to 100 ° C .;
It is preferably about 60 μm.

[0022]

The present invention will be described in more detail with reference to the following examples. In the examples, parts mean parts by weight unless otherwise specified. [Example 1] A 3 mm-thick J as a porous ceramic substrate 1
ISA5403 (F) A slate plate whose surface is polished with sandpaper is used, and on the surface, an acrylic resin having an OH value of 50 and a polyisocyanate compound are used.
The mixture mixed so that the ratio of the groups became 1: 1 was roll-coated so as to have a dry coating film thickness of 10 μm, and dried at 80 ° C. for 5 minutes to form a urethane resin layer 2.

Next, on the acrylic urethane resin layer 2, 97 parts of a urethane acrylate resin containing at least one double bond in its molecule and Irgacure 18
4 (Nihon Ciba Geigy Co., Ltd., photopolymerization initiator) and 3 parts of an ultraviolet curable resin composition were cured to a thickness of 30 μm.
m, and cured by irradiating ultraviolet rays, and the cured layer was polished to form an ultraviolet-curable resin layer 3.

Next, on the ultraviolet curable resin layer 3, OH
A mixture obtained by mixing a polyisocyanate compound with a mixture of 40 parts of an acrylic resin having a valency of 50 and 60 parts of titanium oxide so that the ratio of OH groups to NCO groups is 1: 1 is adjusted so that the dry coating thickness becomes 40 μm. Flow coated, 8
The resultant was dried at 0 ° C. for 10 minutes to form a urethane resin layer 4 having a hiding property.

Next, the ink film 5 was transferred and formed by pressing the transfer film having the ink layer 5 on the urethane resin layer 4 having a hiding property at 160 ° C.

Finally, an acrylic resin having an OH value of 50 and a polyisocyanate compound are placed on the ink layer 5,
The mixture mixed so that the ratio of CO groups was 1: 1 was spray-coated so as to have a dry coating film thickness of 40 μm.
After drying at 0 ° C. for 5 minutes, a urethane resin layer 6 was formed to obtain a porous ceramic decorative panel.

Example 2 A porous ceramic decorative panel was prepared in the same manner as in Example 1 except that a polyisocyanate compound containing 5% of NCO groups was applied and dried to form a polyurethane layer 2 '. Obtained.

Comparative Example 1 A porous ceramic decorative panel was obtained in the same manner as in Example 1 except that the urethane resin layer 2 was not formed.

Comparative Example 2 A porous ceramic decorative panel was obtained in the same manner as in Example 1 except that the ultraviolet-curable resin layer 3 was not formed.

Comparative Example 3 A porous ceramic decorative panel was obtained in the same manner as in Example 2 except that the ultraviolet-curable resin layer 3 was not formed.

Table 1 shows the results of water resistance tests performed on the porous ceramic decorative panels obtained in Examples 1 and 2 and Comparative Examples 1 to 3. In the water resistance test, a 100 mm × 100 mm test piece was immersed in warm water at 50 ° C. for 7 days, and the appearance of the test piece after immersion and the adhesion (peeling rate) by a cross-cut adhesion test were evaluated.

As is apparent from Table 1, the porous ceramic decorative board formed with both the urethane resin layer 2 or the polyurethane layer 2 'and the ultraviolet curable resin layer 3 has the appearance and adhesion even after the water resistance test. It was good. On the other hand, when the urethane resin layer 2 was not formed, both the appearance and the adhesion after the water resistance test were inferior. In addition, the appearance after the water resistance test was inferior unless the ultraviolet curable resin layer 3 was formed.

[0033]

[Table 1]

[0034]

According to the present invention, it has become possible to provide a porous ceramic decorative panel which is excellent in water resistance and excellent in design, suitable for construction materials for indoor or outdoor use.

[Brief description of the drawings]

FIG. 1 is a sectional view of a decorative board according to the present invention.

[Explanation of symbols]

 1: porous ceramic substrate 2: urethane resin layer 2 ': polyurethane layer 3: ultraviolet curable resin layer 4: urethane resin layer having concealment 5: ink layer 6: urethane resin layer

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 31/28 B32B 31/28 33/00 33/00 C04B 41/71 C04B 41/71 E04F 13/14 103 E04F 13/14 103A

Claims (2)

[Claims] 1. A mixture obtained by mixing an acrylic resin (a) having an OH group or a polyester resin (b) having an OH group and a polyisocyanate compound (c) having an NCO group on a porous ceramic substrate 1. d) is applied, an OH group and an NCO group are reacted to form a urethane resin layer 2, an ultraviolet-curable resin composition (e) is applied on the urethane resin layer 2, and ultraviolet light is applied to the urethane resin layer 2. The ultraviolet-curable resin composition (e) is cured to form an ultraviolet-curable resin layer 3, and then, on the ultraviolet-curable resin layer 3, an extender pigment (f) and an acrylic resin (a) having an OH group or an OH group (G), which is a mixture of a polyester resin (b) having the formula (I) and a polyisocyanate compound (c) having an NCO group, is reacted with the OH group and the NCO group to form a urethane resin layer 4 having a masking property. And, further, on the urethane resin layer 4, after the formation of the ink layer 5 by a transfer method, onto the ink layer 5, an acrylic resin having an OH group (a)
Alternatively, a mixture (h) obtained by mixing a polyester resin (b) having an OH group and a polyisocyanate compound (c) having an NCO group is applied, and the OH group and the NCO group are reacted to form a urethane resin layer 6. A method for producing an inorganic ceramic decorative panel characterized by the following. 2. An NCO group-containing polyisocyanate compound (c) is applied on a porous ceramic substrate 1 to obtain an NCO
The group is reacted with the moisture in the air or the OH group of the porous ceramic substrate 1 to form a polyurethane layer 2 ′, and an ultraviolet-curable resin composition (e) is applied on the polyurethane layer 2 ′. To cure the ultraviolet-curable resin composition (e) to form an ultraviolet-curable resin layer 3, and then, on the ultraviolet-curable resin layer 3, an extender pigment (f) and an acrylic resin having an OH group ( a) or a mixture of a polyester resin (b) having an OH group (b) and a polyisocyanate compound (c) having an NCO group (g) is applied, and the OH group and the NCO group are reacted with each other to form a urethane resin having a masking property. After forming an ink layer 5 on the urethane resin layer 4 by a transfer method, an acrylic resin (a) having an OH group is formed on the ink layer 5.
Alternatively, a mixture (h) obtained by mixing a polyester resin (b) having an OH group and a polyisocyanate compound (c) having an NCO group is applied, and the OH group and the NCO group are reacted to form a urethane resin layer 6. A method for producing an inorganic ceramic decorative panel characterized by the following.