JPH0899454A - Transfer sheet - Google Patents

Abstract

PURPOSE: To obtain a transfer sheet for the production of a decorative board applicable to wide general purposes, especially a transfer sheet suitable for muffle painting of a decorative board for facing by restricting the resin and pigment of ink for a pattern layer to high durability types. CONSTITUTION: A transfer sheet consists of a base sheet 11, delamination layer 12, and a pattern layer 13; printing ink contains a vehicle comprising mainly an acrylic resin or a fluororesin and a pigment of a condensation-type polycylic organic compound, and a printing pattern (pattern layer 13) is provided which is obtained by using printing ink containing at least a red pigment of condensation type polycyclic organic compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer sheet used in the manufacture of painting decorative plates, building materials and the like having a desired pattern on the surface.

[0002]

2. Description of the Related Art Conventionally, a so-called siding board (sid) coated with a ceramic base material has been used as a decorative plate for exterior of a house.
ing boards) are commercially available, but emphasizing embossing as a design expression, they are painted in a single color or about two colors. In addition, some products use a direct printing method to give a more luxurious feel compared to the design expression by painting, but due to manufacturing restrictions, it is not possible to deal with deep embossing and the expression as a pattern is poor. Is. Further, since the pigment used was an iron oxide type, a clear color tone could not be expressed.

[0003]

As a means for solving such a problem, the present inventors have conducted research on a method for producing an embossed decorative board by a roll transfer method, and have variously studied to cope with various embossed shapes. I made a suggestion.

However, the base material for transfer is diversified such as ceramic siding board, GRC, extrusion cement block, metal board, various plastic boards, etc., and the same transfer paper composition is obtained depending on the characteristics of each base material. Even if it is used, there has been a problem that there are remarkable differences in various physical properties. For example, in a base material containing an alkaline component such as a cement block, the pigment used in the ink is decomposed or modified by the alkali,
May cause discoloration.

The present invention has been made in view of the above problems, and by limiting the resin system and the pigment system of the ink used for the pattern layer to those having high durability, more versatile makeup can be obtained. It is to obtain a transfer sheet used for manufacturing a board, particularly a transfer sheet suitable for painting a decorative board for exterior.

[0006]

A first invention of the present invention is a printing ink containing a vehicle mainly composed of an acrylic resin or a fluorine resin and a condensed polycyclic organic pigment,
It is a transfer sheet having a printed pattern obtained by using a printing ink containing at least a red-type condensed polycyclic organic pigment.

Next, a second invention of the present invention is a printing ink containing a vehicle mainly composed of an acrylic resin or a fluororesin and a condensed polycyclic organic pigment, which is at least a red condensed polycyclic resin. It is a transfer sheet having a printed pattern obtained by using a printing ink containing an organic pigment and a printing ink containing a yellow-type condensed polycyclic organic pigment.

The present invention also provides a transfer sheet in which the red condensed polycyclic organic pigment according to the first aspect of the present invention is bromine zanthron scarlet.

The present invention is also a transfer sheet in which the red condensed polycyclic organic pigment in the second invention is bromine zanthron scarlet and the yellow condensed polycyclic organic pigment is isoindolinone yellow.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The transfer sheet of the first invention will be described in detail with reference to an embodiment shown in the structural diagram of FIG.
A printing ink containing a release layer 12, a vehicle mainly composed of an acrylic resin or a fluorine resin, and a condensed polycyclic organic pigment, the printing ink containing at least a red condensed polycyclic organic pigment. The pattern layer 13 is formed by printing.

Further, the transfer sheet of the second invention will be described in detail according to an embodiment shown in the constitutional view of FIG. 1. Mainly, a base sheet 11, a release layer 12 and an acrylic resin or a fluorine resin are mainly used. And a printing ink containing a condensed polycyclic organic pigment, wherein the printing ink contains at least a red condensed polycyclic organic pigment, and a printing ink containing a yellow condensed polycyclic organic pigment. The pattern layer 13 is formed by printing.

The base sheet 11, release layer 12 and pattern layer 13 in the first or second invention have the following constitution. First, the base sheet 11 is a thermoplastic resin film such as a polyvinyl chloride resin film or a polyester resin film. The base sheet 11 is formed by coating or laminating a thermoplastic resin film such as a polyvinyl chloride resin, an acrylic resin, a polystyrene resin, a polyethylene resin, a polypropylene resin, or a thermoplastic resin film on a base material sheet such as paper or synthetic resin. It may be a sheet or a laminated sheet. Alternatively, the base sheet 11 may be a coating sheet obtained by coating a base material sheet such as paper or synthetic resin with a thermosetting resin such as phenol resin, urea resin or unsaturated polyester resin.

The release layer 12 (or release varnish layer) is provided on the surface of the base sheet 11 and has a release function with respect to the pattern layer 13, and the pattern layer 13 (printed pattern) is made of an acrylic resin or a fluorine resin. It is formed by using an ink composed of a vehicle as a main component and a condensed polycyclic organic pigment.

The above-mentioned transfer sheet is such that the surface of a desired transfer-receiving substrate (plywood, particle board, medium-density fiberboard, or concrete board, concrete block, etc.) to be transferred using this has an embossed shape. if there is,
It is appropriate to use a thermoplastic resin film capable of following embossing as the base sheet 11. Specifically, resin films of polyvinyl chloride, polyethylene, polypropylene, nylon, saturated polyester and the like can be used.

The type and thickness of the resin as the base sheet 11 may be appropriately selected in consideration of the degree of embossing (embossing depth) on the surface of the substrate to be transferred, the transfer temperature and the like. According to experiments, 150 ° C to 180 ° C
C. transfer temperature, 6-50 kg / cm transfer pressure (linear pressure;
Pressure per unit length (cm or m) in the axial direction of the pressure roller for pressure transfer, compression (contact) width; 0.3 cm to 1.
Good results have been obtained using a vinyl chloride resin film having a thickness of 100 μm or less, a saturated polyester resin film (polyethylene terephthalate film), an acrylic resin film, etc.

If the surface of the substrate to be transferred to be transferred has a flat shape, in addition to the above-mentioned thermoplastic resin film, a thermoplastic resin or a thermosetting resin can be formed on the surface of the base sheet of paper or thermosetting resin film. It is possible to use the base sheet 11 to which is applied.

The release layer 12 is formed by combining the base sheet 11 and the ink used for forming the pattern layer 13.
It is selected appropriately.

For example, a polyvinyl chloride resin film,
In combination with the ink based on a vehicle mainly composed of an acrylic resin, the polyvinyl butyral resin as the release layer 12 has a good result.

The peeling layer 12 is formed by a gravure printing method, a gravure coating method, a screen printing method,
An offset printing method or the like may be adopted.

Further, in the case of a combination of a saturated polyester resin film (polyethylene terephthalate resin film) and an ink based on a vehicle mainly composed of an acrylic resin, the release layer 12 can be provided if necessary,
Even if it is not provided, there is a good peeling function of the pattern layer 13 from the base sheet 11.

As the printing ink used for forming the pattern layer 13, a vehicle mainly composed of a fluorine resin or an acrylic resin is used in consideration of weather resistance.

There is no problem when the surface of the substrate to be transferred to be transferred is flat, but when the surface of the substrate has an embossed shape, it is necessary to consider the ink elongation of the pattern layer 13.

For example, when an acrylic resin alone is used as a vehicle for printing ink, its elongation is almost zero,
The transfer sheet can be applied only to a flat substrate. However, it has been revealed by the inventors' studies that the elongation of the ink at the time of transfer is improved by blending a resin of vinyl chloride-vinyl acetate copolymer system, for example, 10 to 30%.

When the pattern layer 13 is formed by printing, inks of three primary colors of yellow (yellow), magenta (red) and cyan (indigo) are usually used. Particularly, a yellow pigment used for the yellow ink. It is known that the red pigment used for magenta ink has weak weather resistance.
Further, it is necessary that each pigment used in each color ink is excellent not only in weather resistance but also in water resistance, heat resistance, alkali resistance, and the like, and the pigments of each color have the same performance.

The transfer sheet of the present invention has high weather resistance (such as ultraviolet rays of natural light, rain water, humidity, etc.) as pigments of printing inks of yellow, magenta and cyan, or particularly as pigments of printing inks of magenta and cyan. The weather resistance of the pattern layer 13 is obtained by using a condensed polycyclic organic pigment having resistance to fading and discoloration under climatic conditions.

Yellow, which is used as a printing ink,
Reproduced print image between each color ink of three primary colors of Zenta and Cyan
In consideration of the color balance in
As a red pigment of Bromanthane shown in FIG.
Slon Scarlet Pigment (C _{twenty two}H₈Br₂O₂) Or the
It uses magenta pigments, which are mainly pigments.
As the yellow pigment of the ink, isoindo shown in Fig. 3 (b)
Linon yellow pigment (C_{twenty two}H_FiveCl₈O₂) Or the pigment
Using a yellow pigment mainly composed of
As a blue pigment, a phthalocyanine pigment shown in FIG.
Lou pigment (C₃₂H₁₆Cu₁N₈) Or mainly based on the pigment
The best color balance when using cyan pigments
Good results have been obtained.

A pattern layer 1 using the printing ink having the above constitution
The method of forming 3 may be a gravure printing method, a screen printing method, an offset printing method, or the like.

FIG. 2 is a schematic diagram of a transfer method using the transfer sheet according to the present invention. If necessary, an adhesive is applied by air spray to the surface of a transfer-receiving substrate 21 such as a decorative plate substrate to be painted by transfer, and then the transfer sheet 22 of the present invention shown in FIG. Is superposed on the surface of the pattern layer 13 on which the desired pattern is formed, on the surface of the transferred substrate 21.
The desired pattern is transferred from the back side of the transfer sheet 22 by pressing with a pressing means 23 such as an elastic rubber roll.

The adhesive to be applied to the surface of the substrate 21 to be transferred is appropriately selected depending on the material of the substrate 21 and the material of the ink. Specifically, urethane, polyvinyl alcohol, vinyl acetate emulsion, vinyl chloride-vinyl acetate copolymer resin emulsion and the like are used.

The coating method may be carried out using an air spray, various coaters or the like. When a wood material mainly composed of natural cellulose fibers such as veneer plywood, particle board and medium density fiber board is used for the base material 21,
Precipitation of a sealer (anchor coat / primer coat) or the like is desirable because elution of the resin component (natural resin composition component other than cellulose fiber) contained in the base material 21 is expected.

Regarding the transfer temperature, in the case of transfer to the surface of the substrate 21 to be transferred whose surface is embossed, from the purpose of deforming the transfer sheet along the uneven shape of the surface of the embossed substrate 21. The temperature may be at least the glass transition temperature of the resin of the transfer sheet (the base sheet 11 or the base sheet 11 and the resin such as ink laminated thereon).

If the transfer is to the surface of the decorative plate substrate 21 having a flat surface, it may be below or above the glass transition point of the resin of the base sheet 11,
At least the pattern layer 13 used for the transfer sheet used
The temperature may be higher than the glass transition point of the printing ink vehicle resin.

Whether the surface of the substrate 21 is embossed or flat, the upper limit of the transfer temperature is
From the experiments conducted by the present inventors, the temperature is preferably 200 ° C. or lower. If the pressing means 23 used for transfer is a rubber roll, it is desirable to set the transfer temperature in consideration of its heat resistance.

The transfer pressure is appropriately determined depending on the shape of the decorative plate base material 21. For example, if the surface of the base material 21 is embossed, the transfer pressure of the present invention may be set high in order to follow the embossed shape of the transfer sheet of the present invention. Considering the strength of the pressing means 23 and the output / capacity of a driving source such as a motor for driving the pressing means 23, the transfer pressure (linear pressure) is preferably 50 kg / cm or less.

For example, if the base material 21 is flat, the transfer pressure (linear pressure) may be 6 kg / cm or more.
If it is less than this, although the transfer can be performed on the base material 21, the adhesion between the surface of the base material 21 (or a base coat such as an adhesive appropriately applied on the surface) and the transfer layer (the pattern layer 13) becomes weak. When a top coat (transparent protective coating layer) is applied to the surface of the pattern layer 13 after transfer to the base material 21 using, for example, a transparent resin liquid containing an organic solvent, the transfer is performed by the resin liquid. It has been clarified by experiments by the inventors that a problem such as the dissolution of the picture layer 13 is caused.

As the elastic body of the pressing means 23 used for transfer, a roll-shaped elastic body is suitable because continuous transfer can be performed, and it is also advantageous in terms of transfer efficiency. Although rubber or sponge is suitable as the material of the elastic body, considering heat resistance and durability, specifically, silicone rubber, silicone sponge, nitrile rubber, ethylene propylene rubber, fluorine rubber Etc. can be used.

[0037]

Since the transfer sheet of the present invention is provided with the pattern layer 13 formed of the weather-resistant printing ink, a desired pattern that can endure the exterior use can be transferred by the transfer method to the base material 21 for various decorative sheets. A decorative board that can be applied to the surface and is manufactured by transferring the pattern layer 13 to the surface of the decorative board substrate 21 is a decorative board or a building material that has a weatherproof pattern and can withstand exterior applications. can do.

Specific examples will be shown below. <Example 1> On a polyethylene terephthalate film having a thickness of 25 µm, a pattern layer having a print pattern of granite was printed by a gravure printing method using a printing ink made of the following acrylic resin vehicle. Types of printing inks used for the above gravure printing Magenta ink ... Magenta color pigment; Bromzanzan Suron Scarlet Vehicle; Acrylic resin yellow ink ... Yellow color pigment; Isoindolinone yellow vehicle; Acrylic resin cyan ink ... Cyan color pigment; Phthalocyanine Blue vehicle; acrylic resin

On the other hand, a transparent moisture-curable epoxy resin (one-component curable epoxy resin) was applied as a sealer to a concrete block as a substrate to be transferred at a coating amount of 100 g / m ² using an air spray. 80 this
It was dried in an oven at 0 ° C. for 10 minutes and cured at room temperature for 1 day. Next, a two-component curable urethane resin colored white with titanium oxide (titanium white) as a pigment was applied with an air spray at a coating amount of 50 g / m ² . This was dried in an oven at 80 ° C. for 9 minutes.

Next, the transfer sheet is placed on a concrete block (transferred substrate) so as to face the pattern layer, and from the base sheet of the transfer sheet on the side opposite to the pattern layer,
It was pressed with an elastic silicone pressure rubber roll (surface temperature 150 ° C., hardness 30 ° (Shore hardness), silicone thickness 20 mm, roll diameter 200 mm). The transfer speed (moving speed of the rubber roll moving along the surface of the transferred substrate) is 10 m / min, and the transfer pressure (linear pressure) is 20 kg /
cm.

Then, the base sheet was peeled off, and the pattern layer was transferred to the surface of the concrete block. Subsequently, an acrylic silicone gloss clear top coat was applied to the surface of the concrete block to which the pattern layer was transferred at a coating amount of 80 g / m ² by air spray, and this was dried in an oven at 120 ° C for 15 minutes. Further, by leaving it to stand at room temperature for one day to be sufficiently dried, a concrete block having a granite-like design effect was obtained.

Example 2 The same as Example 1 except that a granite pattern layer was formed on a polyethylene terephthalate film having a thickness of 25 μm by a gravure printing method using a printing ink of the following fluorocarbon resin vehicle. Similarly, transfer the pattern layer to the concrete block,
A concrete block with a granite-like design effect was obtained. Types of printing inks used in the above gravure printing Magenta ink ... Magenta coloring pigment; Bromzanzan Slon Scarlet Vehicle; Fluorine resin yellow ink ... Yellow coloring pigment; Isoindolinone yellow vehicle; Fluorine resin cyan ink ... Cyan coloring pigment; Phthalocyanine Blue vehicle; Fluorine resin

Comparative Example A concrete block was prepared in the same manner as in Example 1 except that a granite-like pattern layer was formed on a polyethylene terephthalate film having a thickness of 25 μm by the gravure printing method using the following printing ink. By transferring the pattern layer to, a concrete block with a granite-like design effect was obtained. Types of printing inks used for the gravure printing Magenta ink ... Magenta coloring pigment; Quinacridone red vehicle; Fluorine resin yellow ink ... Yellow coloring pigment; Condensation azo yellow vehicle; Fluorine resin cyan ink ... Cyan coloring pigment; Phthalocyanine blue vehicle; Fluorine resin

<Comparison result> The above-mentioned first and second embodiments
And the three types of samples obtained by the comparative example and the sunshine weather meter (Suga Test Instruments Co., Ltd.).
The accelerated weather resistance test was conducted. The test conditions were a constant heating temperature of 63 ° C. (black panel temperature control), a shower amount (water injection repeating cycle) of 12 times / hour,
The above-mentioned three types of samples were left in this weather meter environment.

Observing after leaving for 500 hours, the granite pattern of the sample of Comparative Example was
The color balance was lost due to the three primary colors of the printing ink, causing discoloration. When the color difference between the sample of the comparative example in which discoloration occurred and the initial sample of Examples 1 and 2 not tested by a weather meter was measured, ΔEab = 8 to 9, and the hue of the sample of the comparative example was clear. Had changed to. In particular, a showing redness was a = −6 to −7, and it was found that the discoloration of the sample of the comparative example was a discoloration due to the loss of color balance due to the fading of redness.

On the other hand, in the samples of Examples 1 and 2, the color balance and the discoloration due to the three primary colors of the printing ink did not occur even after the irradiation time of 2000 hours, and the samples of Examples 1 and 2 were The color difference was ΔEab≈2. Further, a indicating redness was a≈−1, and almost no reddish discoloration was observed.

According to the above-mentioned test, in the sample of the comparative example, quinacridone red, which is a coloring pigment of magenta ink constituting the reddish component in the pattern layer, exhibits a particularly remarkable fading as compared with other yellow inks and cyan inks. It has been found.

The above-mentioned quinacridone red pigment is known per se as a pigment having weather resistance and resistant to discoloration among various pigments, but printing inks of other colors (yellow, cyan) used together as a printing ink. When used in combination with other pigments, or when it is used for transfer to a strongly alkaline substrate such as a concrete block, which is the substrate to be transferred, the weather resistance is significantly reduced, and other yellow ink or cyan ink It was found by the above-mentioned test that a remarkable difference in the degree of fading occurred between the two, and the color balance of the pattern was lost and the color changed.

[0049]

INDUSTRIAL APPLICABILITY The transfer sheet of the present invention, as a combination of pigments used in a printing ink used for printing a pattern layer, has high temperature, high humidity, and other climatic conditions in which a marked difference between the three primary colors does not occur in the degree of fading. A pattern layer is formed with a printing ink that uses a pigment that has a good discoloration balance due to the fact that such a pattern layer does not cause a noticeable loss of color balance due to climatic conditions such as high temperature and high humidity. Yes, it has the effect of maintaining a beautiful design over a long period of time when it is transferred and painted on a desired base material, including transfer and painting on various decorative boards, building materials, and decorative materials for furniture. In particular, it has a remarkable effect as a transfer sheet for producing transfer painting on a decorative plate for exterior such as outdoors.

[Brief description of drawings]

FIG. 1 is a side sectional view showing an embodiment of a transfer sheet of the first invention or the second invention of the present invention.

FIG. 2 is a schematic side view illustrating a transfer method of transferring to a base material using the transfer sheet of the first invention or the second invention of the present invention.

FIGS. 3 (a) to 3 (c) are pigment molecular structure diagrams of a printing ink used in the pattern layer of the transfer sheet of the first invention or the second invention of the present invention.

[Explanation of sign]

 11 ... Base sheet 12 ... Release layer 13 ... Picture layer 21 ... Transferred substrate 22 ... Transfer sheet 23 ... Pressing means

Claims (4)

[Claims] 1. A printing ink containing a vehicle mainly composed of an acrylic resin or a fluorine resin and a condensed polycyclic organic pigment, wherein the printing ink contains at least a red condensed polycyclic organic pigment. A transfer sheet having the obtained printed pattern. 2. A printing ink containing a vehicle mainly composed of an acrylic resin or a fluorine resin and a condensed polycyclic organic pigment, wherein the printing ink contains at least a red condensed polycyclic organic pigment, and a yellow ink. A transfer sheet, which has a printed pattern obtained by using a printing ink containing a condensed polycyclic organic pigment. 3. The transfer sheet according to claim 1, wherein the red-type condensed polycyclic organic pigment is bromine zanthron scarlet. 4. The transfer sheet according to claim 2, wherein the red-type condensed polycyclic organic pigment is bromzanzanthron scarlet, and the yellow-type condensed polycyclic organic pigment is isoindolinone yellow.