JPS605476B2 - How to form three-dimensional patterns - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a three-dimensional pattern, and more particularly, to a method for forming a three-dimensional pattern having an uneven three-dimensional effect on the surface.

Conventionally, various methods have been developed and proposed to create three-dimensional patterns using unsaturated polyester resin. There are two methods: a method of etching the surface partially, a method of partially etching the surface, and a method of imparting irregularities to the surface.

However, in such a method, for example, a mold having irregularities is expensive and is disadvantageous for mass production, or etching causes stains and damage on the surface, and furthermore, it is difficult to operate using a wet method. There are some drawbacks. On the other hand, recently, as a method of chemically embossing, a curing retardant of an unsaturated polyester resin is included in the ink, and the ink is used to suppress the curing of the printed area, thereby delaying the curing of the printed area. There is a way to create a recess.

The current situation is that the diffusion of inhibitors and retarders from the printed area into the unsaturated polyester resin is slow, and there are many unstable factors due to changes over time after printing, making it impossible to obtain a satisfactory uneven pattern. be. As a result of various studies in order to form a three-dimensional pattern using the above-mentioned unsaturated polyester resin, the present inventor added two or more types of initiators with different polymerization initiation energies to the initial condensate of the unsaturated polyester resin, and The present invention was completed by discovering that by selectively curing each condensate, it is possible to form a three-dimensional pattern rich in uneven realism and three-dimensionality by utilizing the volume change of the resin during curing. It is something.

That is, in the present invention, two or more types of initiators having different polymerization initiation energies are added to an initial condensate of an unsaturated polyester resin, and each of the initial condensates is selectively cured,
This is a method for forming a three-dimensional pattern, characterized in that unevenness is created by changing the type of cured resin due to the selective curing reaction. The above-mentioned present invention will be explained in more detail below.

First, in the above-mentioned present invention, the initial condensate of the unsaturated polyester resin is an unsaturated polyester resin produced by a polycondensation reaction of an unsaturated dicarboxylic acid such as maleic acid or fumaric acid and a glycol such as ethylene glycol or diethylene glycol. It is a mixture of saturated polyester and a vinyl compound such as styrene, and can be used in an uncured state.

In the above, as the unsaturated dicarboxylic acid, maleic anhydride, fumaric acid, itaconic acid, etc. can be used, and as the glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 3-butylene glycol, etc. can be used, and as the vinyl compound, styrene, vinyl acetate, methyl methacrylate, vinyltoluene, etc. can be used.

In the present invention, in the initial condensate of the unsaturated polyester resin, as a part of the unsaturated dicarboxylic acid, for example, saturated dicarboxylic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, adivic acid, and others are added. can be used.

Next, in the present invention, initiators having different polymerization initiation energies may be used when the initial condensate of an unsaturated polyester resin is cured by causing crosslinking through a polymerization reaction. Any initiator that can be used can be used as long as it can be
Specifically, for example, initiators that generate radicals by thermal decomposition such as penzoyl peroxide, lauroyl peroxide, 2,2-azobisisobutyronitrile, methyl ethyl ketone peroxide, diphenyl sulfite, penzoyl peroxide, etc. Two or more types of polymerization catalysts such as initiators that generate radicals by photolysis such as methyl ether can be used in combination. Accordingly, in the present invention, the initiator may be used in combination with one or more of the above initiators that generate radicals by thermal decomposition and one or more initiators that generate radicals by photolysis. The polymerization initiation energy source is different, and the difference in polymerization energy is significant, which is the most desirable one.

In addition, in the present invention, in addition to the above-mentioned initiator, a promoter such as cobalt naphthenate may be used in combination with the initial condensate of the unsaturated polyester resin. Next, in the above-mentioned present invention, the method of selectively curing the initial condensate of unsaturated polyester resin will be explained. One or more initiators that generate radicals and one initiator that generates radicals by photolysis.
To explain the case of using a combination of two or more species, first, an initiator that generates radicals through thermal decomposition and an initiator that generates radicals through photolysis are added to the initial condensate of unsaturated polyester resin, and other co-catalysts are added. etc. to produce an uncured resin composition.

On the other hand, in the present invention, for example, vinylon film,
Heat-resistant and transparent resin films such as polyvinyl chloride film, polystyrene film, polycarbonate film, polyester film, and polyamide film, or glass plates, etc., are coated with materials that do not transmit light but absorb heat, such as black ink. A pattern document is manufactured by forming a desired image using a conventional printing or drawing method using a suitable ink or coating composition.

In the present invention, when a glass plate is used, it is effective to use a vapor deposited film of Sn02 or the like as a thermal pattern. In the present invention, as shown in FIG. 1, the uncured resin composition obtained above is coated on the substrate 1 by, for example, roll coating, gravure coating, bar coating, dip coating, flow coating, etc. A coating layer 2 is formed by coating by brushing or other methods, and then the pattern original 3 obtained above is superimposed on the coating layer 2. Next, in the present invention, as shown in FIG. 2, after the pattern originals 3 are superimposed as described above, thermal energy 4 such as heat rays and light energy 4 such as ultraviolet rays are applied from above the pattern originals 3.
′ and irradiate alternately. Therefore, in the present invention, when the thermal energy and light energy are irradiated as described above, first,
When thermal energy is irradiated, the black part of the image area of the pattern document selectively absorbs heat, and the temperature rises in this part.The thermal energy due to this temperature rise acts as a Korean radiation, and the coating layer is heated. This acts on the initiator that generates radicals through thermal decomposition, and as a result, the initiator decomposes and generates radicals, and the radicals act on the initial condensate of unsaturated polyester, resulting in a crosslinking reaction due to its polymerization reaction. occurs, hardening the initial condensation product of the unsaturated polyester, and on the other hand, in the transparent non-image area of the pattern original, heat is transmitted and the temperature rises.
Therefore, in this part, thermal energy does not act selectively on the initiator in the coating layer.
This means that the curing reaction of the initial condensate of unsaturated polyester does not occur. Next, when light energy is irradiated, a phenomenon completely opposite to that of thermal energy described above occurs, and the black part of the image area of the pattern original does not transmit light, so the light energy does not act on the initiator. On the other hand, the transparent part of the non-image area of the pattern document transmits light, and the transmitted light energy acts on the initiator to decompose it to generate radicals and to decompose the unsaturated polyester resin. This results in selective curing of the initial condensate.

Accordingly, in the present invention, as shown in FIG. 3, two or more initiators having different polymerization initiation energies are added to the initial condensate of unsaturated polyester resin as described above, and the curing of the initial condensate is effected. When each of these is selectively performed, the volume change of the cured resin due to the selective curing reaction causes unevenness 5 to appear on the surface, thereby forming the three-dimensional pattern of the present invention.

In the above, when using a pattern original in which a Sn02 pattern film is provided on a glass plate as a pattern original, when heat rays are irradiated, the Sn02 film reflects the heat rays, and on the other hand, parts other than the Sn02 film Then, the heat rays pass through and act on the initiator. In the above, the pattern manuscript includes, in addition to those listed above, for example:
Of course, photographic images such as negative film or positive film can also be used.

Next, as the substrate in the above, any substrate can be used as long as it can retain the coating layer of the uncured resin composition, such as wood, plywood, particle board, etc. Board; Paper; Films or sheets of various resins; Plates or foils of various metals such as iron, copper, aluminum, stainless steel, zinc; Glass;
Ceramics; Fiber board for hard boats; Gypsum board,
Composite base materials of organic polymer compounds and inorganic substances, such as pulp cement boards, rock wool boards, and wood wool cement boards;
Calcium silicate board; asbestos slate board, etc. can be mentioned.

In the present invention, when forming a coating layer of an uncured resin composition on the above-mentioned substrate, the surface of the substrate may be optionally subjected to a known pretreatment, if necessary. can.

Next, in the above, as the irradiation source or irradiation method of thermal energy, light energy, etc., for example, infrared rays are most preferable as thermal energy, and such infrared rays include filament lamps, discharge lamps, arc light,
There are flashing light bulbs, etc., and the radiation heat from these light sources is transmitted to the shading pattern.

On the other hand, as light energy, ultraviolet rays are most preferable;
Examples of such ultraviolet light sources include low-pressure mercury pumps (Kaniko chemical lamps), high-pressure mercury lamps, and ultra-high-pressure mercury lamps. Therefore, in the present invention, light from a light source of each energy is irradiated, but it is important to note that as much as possible, the thermal energy wavelength range is used as thermal energy, and the ultraviolet energy wavelength range is used as thermal energy. must be irradiated as ultraviolet energy.

For example, when using a high-pressure mercury lamp for ultraviolet irradiation,
Naturally, the wavelength of the infrared light (Kan radiation) also comes out, but this wavelength light must be cut off in advance so that it only irradiates less than 40 ribs of the wavelength light, which is the ultraviolet light. The same thing must be done when irradiating infrared rays. In the present invention, there is no restriction on the order of irradiation of thermal energy and light energy, and either one may be performed first or the other may be performed later.

Next, in the above, the blending ratio of the initiator to the initial condensate of the unsaturated polyester resin is, for example, 0.5%M to 4M% of the thermal energy initiator to the resin;
Light energy initiator is 0.5% to 0.4% based on resin
Good wt, 1% to 4% wt of both together based on resin
is the best.

In addition, the blending ratio varies depending on the order of energy irradiation, and the more energy initiator is irradiated first, the better.
A ratio of 3 to 8:2 is best. Therefore, the unevenness that appears above can be generated in correspondence with the image of the pattern original. For example, if thermal energy is first irradiated,
Convex portions are formed in the unsaturated polyester resin that is first cured by the action of the thermal energy, and concave portions are formed in the portions of the unsaturated polyester resin that are subsequently cured by the action of the irradiated light energy. , This allows unevenness to be formed according to the image of the pattern original.

Conversely, if light energy is irradiated first, the unsaturated polyester resin will form a convex portion in the part of the unsaturated polyester resin that is first cured by the action of the light energy, and then the unsaturated polyester resin will be cured by the action of the thermal energy applied later. A concave portion is formed in the resin portion, and unevenness can be formed corresponding to the pattern document. In the present invention, the reason why the unevenness appears as described above is not clear, but it is thought to be as follows.

First, the initiator selectively acts on the hardening of the unsaturated polyester resin depending on the pattern, and in the hardened area, the resin in the hardened area moves due to changes in the resin type, and the formation of unevenness has already begun from this point. Next, when starting energy is applied to the uncured portion, the uncured portion is cured, and the resin similarly undergoes a volume change, and the difference in unevenness becomes even larger, which is thought to cause the appearance of unevenness.

From these reasons, it is thought that unevenness occurs due to the movement and volume change of the resin, so the faster the curing rate, that is, the faster the crosslinking rate, the unsaturated polyester resin, the more likely it is that unevenness will occur. Differences in unevenness occur in systems where the rate of radical reaction is fast. In the present invention, the ability to form an uneven surface of unsaturated polyester resin corresponding to the image of a pattern original as described above has various advantages and can be applied to various applications at the same time. be.

For example, as shown in FIG. 4, a wood grain pattern or the like can be formed directly on the substrate 1 after performing known pretreatment if necessary, or by pasting decorative paper or the like. A desired image 6 is formed, and then the above-mentioned hardening resin composition is applied to the entire surface including the image 6 to form a coating layer 2 of the composition, and then, on the coating layer 2, For example, in the case of a wood grain pattern, pattern originals 3 having an image 7 of a portion where a recess is to be formed in the desired image 6, such as a wood grain conduit groove, are superimposed. Next, in the present invention, as shown in FIG. 5, after the pattern originals 3 are superimposed as described above, ultraviolet rays 4 are first irradiated from above the pattern originals 3 as polymerization initiation energy. The initial condensate of the unsaturated polyester resin corresponding to the non-image area 8 is cured, and the initial condensate of the unsaturated polyester resin corresponding to the image part 7 is not cured. When irradiated from above 3, the initial condensate of uncured unsaturated polyester resin corresponding to the image area 7 of the pattern original 3 is cured,
On the other hand, the initial condensate of unsaturated polyester resin corresponding to the non-image area 8 has already been cured by the ultraviolet rays 4', and as shown in FIG. By selectively curing the resin, a volume change is caused in the cured resin, and the unevenness 5 that corresponds to the image of the pattern document described above is revealed, and the unevenness 5 that is aligned with the desired image 6 is formed on the substrate 1. It is possible to obtain a decorative material rich in three-dimensional effect, realism, etc. The substrate having a three-dimensional pattern obtained in the present invention described above is suitable for various uses, for example, as a decorative material or a printing plate, i.e., as a letterpress printing plate when using convex portions, and as a gravure plate when using concave portions. It is also used as a Braille pattern.

Next, the present invention will be described in more detail with reference to Examples.

<Example 1> After laminating 80mm titanium paper with a wood grain pattern printed on a 27mm thick plywood board using a vinyl acetate emulsion-urea resin adhesive, an unsaturated polyester resin having the following composition was applied. I coated it for 200 evenings/day.

Unsaturated polyester resin composition ■ Commercially available unsaturated polyester resin ■ Initiator 1 Methyl ethyl ketone peroxide
・%Wt〃 2 Diphenyl sulfide 1%wt On top of this, a Tetron film with a conduit part whose pattern matched that of the decorative paper was printed in advance with ink containing carbon black was placed so as to match the pattern of the decorative paper, and then , smooth and remove any air bubbles, then apply a chemical lamp (
The entire surface was irradiated for 5 minutes with a 40W (manufactured by Tokyo Shibaura Electric Co., Ltd.).

The irradiation conditions were chemical lamps arranged at 10 feet intervals at a height of 10 skins. After irradiation, the entire surface was irradiated with heat rays for 3 minutes. The irradiation was performed using infrared heaters (IKW/1 heater) arranged at 20-meter intervals at a height of 30 arcs. After irradiation, the Tetron film was removed, and a stereotonic polyester decorative board was obtained in which only the conduit portions were concave. <
Example 2 After pasting 50 mm of black titanium paper onto plywood with a skin thickness of >27 using a vinyl acetate emulsion-urea resin adhesive, 40 mm of unsaturated polyester resin having the following composition was attached.
Coated with 0 evening/.

Unsaturated polyester resin composition ■ Commercially available unsaturated polyester resin ■ Initiator 1 Methyl ethyl ketone peroxide
1.5wt%2 Pesozoin methyl ether 0.5wt% ■ Accelerator Cobalt naphthenate 0.5wt%
On top of this, a floral pattern is printed in advance on vinylon film with ink containing carbon black, this film is placed on it, and
It was smoothed to remove air bubbles, and then first irradiated with light for 7 minutes using the same device as in Example 1.

Next, heat rays were irradiated for 5 minutes. When the vinylon film was removed after irradiation, a three-dimensional polyester decorative board with only the floral pattern as a recess was obtained. Example 3> A commercially available calcium silicate board with a phase pattern printed on it.
After bonding the titanium paper together with a melamine adhesive, it was coated with 300 coats of unsaturated polyester resin having the following composition.

Unsaturated polyester resin composition ■ Commercially available unsaturated polyester resin ■ Initiator 1 Penzoyl peroxide 1.5 wt% 2 Penzoin methyl ether 0.5 wt% Here, prepare a conduit part whose pattern matches the decorative paper in advance. A polyester film made by photolithography is prepared. First, a vinylon film is placed on the resin surface. After the above film is placed on top of it, it is first irradiated with light for 7 minutes using the apparatus of Example 1, and then The photographic film was then removed and heat rays were irradiated for 5 minutes.

When the vinylon film was removed after irradiation, a stereotonic polyester decorative board with recesses only in the conduit portion was obtained. <Example 4> The method of Example 2 was repeated, except that the order of irradiation was changed.

However, white titanium paper was used. That is, first, a heat ray was irradiated for 3 minutes, and then a chemical lamp was irradiated for 5 minutes. When the Tetoron film was removed after the carp was dried, the unevenness was reversed from that in Example 2. In other words, a three-dimensional polyester leveling board was obtained in which the portion other than the floral pattern had a concave portion. In this case, since heat rays were irradiated together, mirror (radiation) of thermal energy was generated in areas other than the black areas, and the unevenness was gentle. <Example
5> A vinylon sheet with a thickness of 2 tsubo was laminated on a steel slope, and an unsaturated polyester resin having the following composition was coated thereon for 500 m2/m.

Unsaturated polyester resin composition ■ Commercially available unsaturated polyester resin ■ Initiator 1 Methyl ethyl ketone peroxide
○-5Wt%2 Penzoin methyl ether 1.5wt% A photographic pattern with halftone dots that will become the printing manuscript is placed on top of this, smoothed further to remove air bubbles, and then a chemical lamp (manufactured by Matsushita Electric Industry Co., Ltd.) is applied. The entire surface was irradiated at 120 W for 1 minute.

The irradiation conditions were chemical lamps placed at a height of 10 feet and spaced apart by 10 skins. After irradiation, the entire surface was irradiated with heat rays for 3 minutes. The irradiation was performed using infrared heaters (IKW/1 heater) arranged at 20-degree intervals at a height of 30 arcs. When the photographic film was removed after irradiation, an unsaturated polyester plate with depressions only in the blackened areas (silk dots) of the photograph was completed. Printing was performed using this uneven printing plate, and good printing was achieved. Example 6 A commercially available calcium silicate plate was sanded and polished to make it printable.

A phase pattern was printed on this Kical board using a rotary screen printing machine. On top of this, the same unsaturated polyester resin as in Example 1 was placed for 300 minutes, and then a polyester film in which a conduit portion corresponding to the phase pattern was made by photolithography was placed, and then the same unsaturated polyester resin as in Example 1 was placed. A similar irradiation method was performed with the device. When the polyester film was removed after irradiation, a stereotonic polyester decorative board with recesses only in the conduit portion was obtained. <Example 7> An Sn02 film was previously created on a glass plate as an energy cut pattern by vapor deposition or chemical conversion, and a desired pattern (flower pattern) was created by etching.

This etched area was screen printed with black ink to form an energy cut pattern. A lined glass slope was coated with 500 g of an unsaturated polyester resin having the following composition, and the above glass pattern was placed on it and irradiated with ultraviolet rays and heat rays in the same manner as in Example 1, and an uneven floral pattern was formed. Unsaturated polyester composition ■ Commercially available unsaturated polyester resin ■ Methyl ethyl ketone peroxide 1.0 Wt% ■
Penzoin ethyl ether 1.0 wt% In the above, the order of irradiation with ultraviolet rays and heat rays could be in any order.

[Brief explanation of the drawing]

1 to 3 are schematic cross-sectional views showing the configuration of each step of the three-dimensional pattern forming method of the present invention, and FIGS. 4 to 6 are schematic cross-sectional views showing the configuration of each step of the three-dimensional pattern forming method of the present invention. FIG. 3 is a schematic cross-sectional view showing the configuration of each step of manufacturing a decorative material. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Coating layer, 3... Pattern original, 4, 4'... Thermal energy and light energy,
5...Unevenness. Figure 2 Figure 3 Figure 4 Figure 5 Figure 6

Claims (1)

[Claims] 1. One or more types of initiators that generate radicals by thermal decomposition and one or more types of initiators that generate radicals by photolysis are added to an initial condensate of an unsaturated polyester resin, and the initial condensate is cured by light energy and A method for forming a three-dimensional pattern, characterized in that the method is selectively performed using thermal energy, and unevenness is caused by a change in the volume of a cured resin due to the selective curing reaction.