JPS5855362A - Manufacture of transfer printed dressing board - 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 The present invention provides a method for producing a transfer decorative board by casting a hydration curable slurry onto a transfer sheet, and the present invention provides a transfer decorative board that has quick hardening, transfer stability, weather resistance, and water resistance. The present invention relates to a manufacturing method.

The present inventors have been studying for a long time the structure of the transfer sheet and the composition of the slurry that serves as the base material for a method of creating a transfer decorative board for use in interior and exterior materials, furniture, etc. using a hydration curable slurry. However, conventionally known slurry compositions include the following, each of which has the following problems.

(1) Using hemihydrate gypsum In this method, a slurry is created using σ or β hemihydrate gypsum, such as natural gypsum, removed gypsum, or chemical gypsum, as the main ingredient. Any material can be used as long as it can be transferred, and a transfer sheet base such as plastic film, paper, metal foil, etc., on which a pattern for transfer is printed is used. Specifically, there are the following three methods.

■Method of printing a pattern with water-soluble ink on the transfer sheet base (Special Publication No. 53-1OA11.s) ■Coat a water-soluble release varnish on the transfer sheet base, and then print the pattern with water-permeable ink. Method (Patent Application 1987-1)
44647) ■Coat release varnish as necessary on the transfer sheet base, print the pattern with normal ink,
Furthermore, a method of coating adhesive varnish that adheres to plaster on top of it (Japanese Patent Application No. 54-149718) Although it is possible to use a transfer sheet in any of the three methods above, there are the following problems when using hemihydrate plaster. . In other words, in terms of the strength and specific gravity of the cured product, it is possible to make it sufficiently durable for use as ordinary decorative boards, interior materials, etc. by selecting the main gypsum raw material, the amount of water mixed, water reducing agents, fibrous materials, additive resins, etc. However, it has the drawback of not being completely water resistant.

(2) Those using white cement.

In this method, white cement or ordinary Portland cement is used as a slurry as the main raw material, and fillers such as sand, perlite, and shirasu are mixed in as needed. As for the structure of the transfer sheet, all three types mentioned above are possible, and since cement is the main raw material, it is possible to create a transfer decorative board that is more water resistant than the one in (1). has the same problems as 'U'. That is, since cement exhibits strong alkalinity, it is extremely difficult to select the pigment and binder for the ink used in the transfer sheet. For reference, Table 1 shows the results of a weather resistance test conducted by the present inventors on the structure of the transfer sheet described in (1) above. The sample structure used in this test was to provide a water-soluble release layer made of polypyrrolid/resin on a polypropylene film, and then add 100 parts by weight of each of various pigments or dyes using a salt-vinyl acetate copolymer resin as a binder. An ink was prepared by mixing 2 to 4 parts by weight and further 20 parts by weight of an extender pigment of barium sulfate, and a transfer sheet was prepared by printing the ink in a light color. Then, on the transfer sheet, white cement/perlite aggregate/glass fiber/water/melami water reducing agent-100/201
A slurry prepared at a weight ratio of 0.5150/30 was poured, heated at 40°C and 90% for 24 hours, then removed from the mold and transferred.The test method used was a Long Life Sunshine Weather Meter (Suga Test 200 at machine made)
After time weathering test, JISL-08
Table 1 shows the evaluation of discoloration and fading using the 04 gray scale.
It is.

Table 1: Weather resistance test results As mentioned above, the pigments phthalocyanine, iron oxide, and titanium white yarn show relatively good results, but other organic pigments and dyes cannot withstand use at all. However, even when a top coat or the like is applied as a protective layer on the transferred decorative board, the problem of efflorescence, which is a problem inherent to cement, is unavoidable.

Another problem is that the hardening and setting speed of the cement itself is slow, about 24 hours, so in the transfer method, it takes time to remove the mold, and if the cement is not left stationary after filling until it hardens, the design may bleed or transfer defects. occurs and is extremely unstable. Also, it lacks dimensional stability due to curing shrinkage of the cement itself.

(3) Using a composite of hemihydrate gypsum and Portland cement.

In order to improve the strong alkali and slow hardening properties of cement in (2), we investigated a composite of hemihydrous gypsum and Portland cement, which is a known technology, but the slow hardening property can be improved by an appropriate mixing ratio. Water plaster 1
When adding 10 parts by weight or less of cement to 00 parts by weight, no water resistance was obtained at all, and when adding 20 parts by weight or more of cement, the weather resistance results were almost the same as those shown in Table 1. I couldn't get it. Moreover, this cured product expanded and broke after being left indoors for one month.

(4) Using a composite of dihydrate gypsum and slag.

This is a method for improving the above-mentioned (1) water resistance when using gypsum and (2) alkali resistance when using cement, and is a method disclosed in Japanese Patent Publication No. 55-13629. Specifically, the main raw materials are a mixture of gypsum dihydrate and slag at a weight ratio of 3 to 7.:6, and 0.0.
1 to 5% by weight and 05 to 5% by weight of an aluminum sulfate-containing substance are added as a compounding raw material.Water within a range that maintains plasticity is added to the compounded raw material, kneaded and formed, and then natural curing or moist heat at 90°C or less. It is a method of curing. In this method, the hardened material obtained is ettringite (3CaOAg203 * 3
CaSO4,51-32H20), slag hydrate, and unreacted surplus dihydrate gypsum. It indicates strength and water resistance. If a decorative board is made by a transfer method based on this formulation, a water-resistant base material can be obtained as shown in Japanese Patent Publication No. 56-13629, and since it does not exhibit strong alkalinity like cement, There are no problems with weather resistance.

However, when used as a material slurry for a transfer method in which a transfer material is created by pouring the slurry onto a transfer sheet, it has the following serious drawbacks.

The curing and setting time of the slurry according to this formulation is approximately 24 hours at 25℃ room temperature, 10 hours in a 4D'C atmosphere, and 8 hours in a 60℃ atmosphere. Requires setting time. Regarding this setting time, there is no particular problem when making a board or the like, but in the method of the present invention in which a slurry is poured onto a transfer sheet and removed from the mold after hardening, the following problems occur. That is, 1al-1, in the method of printing a pattern with water-soluble ink described above, which takes time to remove from the mold because the slurry hardens slowly, or in the method of printing a pattern with water-permeable ink on water-soluble release varnish. It is difficult to produce a stable product because the pattern bleeds or transfer defects occur due to movement or vibration when the slurry is cast onto the transfer sheet.

[al-2, When a transfer sheet is set in a frame of a desired shape to create a transfer decorative board, the curing of the slurry is slow and the rotation rate for repeated use of the frame is poor, resulting in poor work efficiency.

(The product warps because a transfer sheet such as a film base is in contact with one side of the BL base material for a long time.The results of tests conducted by the present inventors are shown in Table 2.The test conditions were 2.
Water gypsum/slag/slaked lime/aluminum sulfate 14-1
Slurry consisting of octahydrate salt/water = 50150/15/1.5/40 parts by weight 200% x 200% x 10%
The slurry was filled into a transfer sheet formed into a tray shape, and the warpage of the product was measured. A 0.2X thick unplasticized vinyl chloride film was used as the transfer sheet base of this transfer sheet, and the ink composition was based on the water-soluble release varnish/porous water-permeable ink formulation described above.

Table 2 Warpage test results As mentioned above, warping occurred and the painted object was heated to 40°C after being heated.
The warping did not disappear even after curing was completed after 96 hours of moist heat curing.

(Cl filling suitability is poor. When trying to cast onto a transfer sheet with this formulation, 50 parts by weight or more of water is required for normal filling and 50 parts by weight or more of water for 100 parts by weight of mixed raw materials such as gypsum or slag, and vibration filling is required.) If it is less than 40 parts by weight, it will interfere with the removal of air bubbles on the surface of the transfer surface and the smoothness of the back surface, which is not desirable.Since the amount of water mixed in normal filling is large, the bending strength of the product will be 5.
There is a problem in that the mixed water t is about ok/ffl, and a special vibrating filling device is required when the mixed water t is lowered.

The present invention improves the materials of the conventional methods (1) to (4), and provides a method for manufacturing a transfer decorative board by casting a water-curing slurry onto a transfer sheet, which has improved fast hardening, transfer stability, The present invention provides a method for manufacturing a transfer decorative board having weather resistance and water resistance. That is, the present invention involves forming a transfer sheet into a desired shape to create a mold so that the pattern side of the transfer sheet is the upper surface.
Alternatively, the transfer sheet is set in a formwork of a desired shape, and then, on the transfer sheet, a mixture of hemihydrate gypsum and slag as the main raw materials at a weight ratio of 7:5 to 4:6,
An alkali salt inorganic substance and aluminum sulfate are added to prepare the raw material, and 30 to 6 parts of water is added per 100 parts by weight of the raw material.
Filled with a slurry of hydration hardening material containing 0 parts by weight,
This is a method for manufacturing a transfer decorative board, which is characterized in that it is removed from the mold after being cured.

That is, the feature of the present invention is that dihydrate gypsum is used in normal gypsum slag plates, but hemihydrate gypsum is used.

The structure of the present invention will be explained in more detail below. As described above, the transfer sheet used in the present invention uses a plastic film, paper, metal foil, etc. as a transfer sheet base, and can be transferred onto a hydration hardening material. It is optional as long as the pattern is printed using a suitable method.

Next, the materials for the slurry used in the present invention include natural gypsum as hemihydrate gypsum, flue gas desulfurization gypsum phosphate gypsum,
Other materials such as raw gypsum are optional, but preferably those with high white discoloration will give a good design effect to the transferred material. Moreover, if the specific surface area is 100 ocrl/g or more, there will be no particular adverse effect on filling suitability and product quality.

The slag may be of any type, such as blast furnace slag or electric open hearth slag, and generally any material having a specific surface area of 5 o 0 crll 8 or more may be used. The additives used are alkali salt substances and aluminum sulfate-containing substances to promote the formation of nitrium and njaide, and alkali salt substances include alkali metal salts and alkaline earth metal salts, such as slaked lime and caustic soda. etc., and the amount added is 0.5 to 5%. Products containing aluminum sulfate include light bread,
Sodium light bread, potash light bread, etc. may be used, but light bread and sodium sulfate, sodium sulfate, potassium sulfate, etc. may be added separately in an amount of 0.1 to 5 parts by weight.

Although the aluminum sulfate-containing material may be added to the raw materials in advance, it is preferable to dissolve the material in advance in the mixed water that is added later to obtain a product of more stable quality. In addition, other additives include fibrous substances such as glass fiber, polyolefin fiber, carbon fiber, and asbestos, as well as reducing the amount of mixed water, in order to improve strength and impact resistance as necessary. Water reducers such as melamine, lignin, oxycarboxylate, naphthalene sulfonic acid, and polyalkyl sulfonic acid are used to improve fluidity, and nonionic agents are used to prevent air bubbles in the cod. Antifoaming agents such as antifoaming agents, cationic, silicone, and fluorine-based, and methylcellulose to prevent the paint from penetrating if the surface of the transfer is coated in the subsequent process to protect the surface of the transfer. It is possible to add resins, vinyl acetate emulsions, acrylic emulsions, epoxy emulsions, etc.

Furthermore, in the present invention, the hydration hardening of hemihydrate gypsum is accelerated by the use of aluminum sulfate-containing substances, so the initial hardening time of the slurry is fast (this may result in a short workable time during filling). , borax, sodium citrate, sodium chloride, malic acid, sodium tartrate and their potassium salts, some amino acid-based retarders, starch, gum arabic and other known hemihydrate gypsum setting retarders. It is good to add ℃・.

In the present invention, the ratio of hemihydrate gypsum and slag, which are the main raw materials, is preferably 7:6 to 4:6 by weight. If the amount of hemihydrate gypsum increases beyond this ratio, the formation of ettringite during post-curing will be slow, and no improvement in water resistance can be expected. The initial hardening strength decreases, causing problems in mold removal of the transferred material.Also, water resistance (・
But I can't expect much.

In addition, the amount of water mixed in the slurry in the present invention varies depending on the ratio of semi-aqueous slag to slag described above or the amount of additives such as fibrous substances and water reducing agents, but it is 60 to 60 parts by weight based on 100 parts by weight of the raw material. Desirably 35 to 50 parts by weight are possible.

If the amount of water is 30 parts by weight or less, the viscosity of the slurry is too high, which impedes filling suitability and makes filling difficult even if a vibrating filling device or the like is used. Moreover, if it exceeds 60 parts by weight, the strength and water resistance of the cured product will be impaired. Further, as will be described later in the Examples, the semi-aqueous gypsum and slag system according to the present invention is superior to the known dihydrate gypsum and slag system in terms of filling suitability at the same amount of mixed water. Also, the strength of the cured product with the same amount of water mixed is considerably superior to that of the product of the present invention. This is thought to be due to the improvement in strength due to hardening of the semi-aqueous surface layer.

To create a transfer decorative board using the recipe according to the present invention, mix a slurry based on the above recipe, pour the slurry onto the transfer sheet, and after the semi-water surface hardens, remove the transfer plate from the transfer sheet, and then Natural curing or 80℃
The following step of moist heat curing to generate ettringite is required.The curing time is 7 days or more for natural curing.
In heat curing at 80°C, it is desirable that the time be 2 days or more. Furthermore, sulfide color may occur on the surface after curing, but in this case, the sulfide color on the surface can be removed by performing a heating drying process at a temperature below which does not cause dehydration of the gypsum, preferably at 50° C. or below. Since the present invention has the above-mentioned configuration, it has the following advantages: 1) Since semi-aqueous plaster is used instead of dihydrate gypsum, the initial hardening is caused by the hydration hardening reaction of semi-aqueous plaster (CaSO4-
jH2o+÷H2O4C'aSO4@2H20) When using a normal half-water surface layer, the same hardening and setting time (
5 minutes to 2 hours). Therefore, since the setting time can be selected arbitrarily, the design bleed that occurs due to the slow setting time can be avoided.
Problems such as poor transfer can be avoided.

2> After semi-water surface hardening, ettringite is produced by dihydrate gypsum and calcium oxide and aluminum oxide of the slag through natural curing or moist heat curing, and the hydraulic reaction of the slag also proceeds, resulting in gypsum slag produced from dihydrate gypsum and slag. It has the same water resistance as a board.

5) Due to its fast curing properties, the transfer sheet can be peeled off from the base material at an early stage, so that during curing in the subsequent process, the front and back of the base material are symmetrical, so no warpage occurs.

<4> Due to its fast curing properties, when using a formwork, the repeating rotation of the formwork is efficient and the workability is extremely high. <5> Since it is used on a semi-water surface, it has good filling suitability, i.e. (4) dihydrate gypsum and Although a composite of slag is used (as described in C1, in the case of a mixture of dihydrate gypsum and slag, in normal filling, 50 parts by weight or more of water per 100 parts by weight of the blended raw material, or vibration filling) In addition, water reducing agents such as melamine, lignin, oxycarboxylate, naphthalene sulfonic acid, and polyalkyl sulfo/acid have no significant effect, and the amount of water mixed must be reduced. However, in the formulation according to the present invention, semi-aqueous slag and slag are the main raw materials, so the effect of the water reducing agent as described above is clearly recognized.
Specifically, when D-type hemihydrate gypsum is used in the mixed raw material for semi-aqueous surface gypsum/SLAG 50750 by using a water reducing agent, the amount of water mixed is 30 parts by weight, and when L-type hemihydrate gypsum is used, the amount of water mixed is 40 parts by weight. Normal filling is possible even by weight part, and the amount of mixed water can be kept lower than that of products using dihydrate gypsum, so for slurries with the same filling suitability (same viscosity), the product of the present invention has a lower amount of mixed water than products using dihydrate gypsum. Increases strength.

Since the present invention has the above-mentioned characteristics, not only can a hydration-cured transfer decorative board be produced very effectively, but also the product has water resistance, weather resistance, and high strength, and therefore has extremely high industrial value as an interior and exterior material.

EXAMPLES Next, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the examples shown below unless it exceeds the gist thereof.

(Example 1) A transfer paper was prepared by printing a pattern on a 200μ polypropylene/film using the ink composition shown in Table 3.

Table-5 Transfer paper composition
It was molded into a tray shape of 00% x 200% x 10%. Place the transfer paper on the desk with the pattern side facing up.
A slurry consisting of recipe 4 was poured.

Table 4 Slurry Recipe After injecting the slurry, the hemihydrate gypsum began to harden in about 10 minutes and could be released from the transfer paper in about 20 minutes. 30
After a few minutes, the transfer paper was peeled off, and then the sample was placed at 40° C. and 90% RH and cured for 5 days in an atmosphere.

Table 5 shows the physical property test results of the transcript.

(*Regarding the water-resistant sagging strength and water-resistant compressive strength in the table, the same applies to the results measured after 72 hours of immersion in tap water.) As a comparative example, a slurry made of the formulation shown in Table 6 was poured onto the same tray-shaped transfer paper as shown below. .

Table 6 Comparative Example Slurry Prescription Regarding slurry filling suitability and fluidity, the Comparative Example was inferior to the Example.

(Example-2) Surface-? Transfer paper was created by printing a pattern using the ink composition shown below.

Table 1 Composition of transfer paper The transfer paper was set in a 300 x 300 λ x 10 x mold with the pattern side facing up, and a comparison was made between the slurry formulation according to the present invention consisting of the formulation shown in Table 4 and the formulation shown in Table 6. Table 1 shows the results of a comparative study using the slurry formulation of Example 1 under the same conditions as Example 1.

Table 7 Comparative Study Results As for the water resistance and bending strength, the test was conducted after top coating with acrylic urethane paint, since the use of water-soluble ink causes the pattern to run when immersed in tap water.

The bleeding of the pattern in this comparative example is thought to be due to the slow hardening of the slurry, which causes the water-soluble ink to move and flow due to the water in the slurry when it is left standing or moved.

patent applicant Toppan Printing Co., Ltd.

Claims (1)

[Claims] (1) Create a mold by molding the transfer sheet into a desired shape so that the pattern side of the transfer sheet on which an arbitrary pattern is formed is the top surface, or mold the transfer sheet into a desired shape. Set in a mold, and then on the transfer sheet, an alkali salt inorganic substance and aluminum sulfate are added to a mixture of hemihydrate gypsum and slag as main raw materials at a weight ratio of 7:6 to 4:6. A method for manufacturing a transfer decorative board, characterized in that a slurry of a water-curable material is filled with a slurry of water-curing material made by adding 30 to 60 parts by weight of water per 100 parts by weight of the blended raw material, and then removed from the mold after curing. .