JPS5857986B2 - Method for forming three-dimensional patterns with pine differences - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a three-dimensional pattern having a matte difference, and more specifically, the present invention relates to a method for forming a three-dimensional pattern having a matte difference, and more specifically, by having an uneven three-dimensional effect on the surface and further matting the concave portions, This invention relates to a method of forming a three-dimensional pattern that gives a more three-dimensional effect.

Conventionally, various methods have been developed and proposed for creating three-dimensional patterns using unsaturated polyester resin. There are two methods, such as a method of applying the material, and a method of partially etching the surface to create irregularities.

However, in such methods, for example, the mold having unevenness is expensive and is disadvantageous for mass production, or etching causes surface stains and damage, and furthermore, it is a wet method and is difficult to operate. It has drawbacks such as being difficult.

On the other hand, recently, as a method for chemically embossing, a curing inhibitor and retardant for unsaturated polyester resin is included in ink, and the ink is used to print on the surface of the unsaturated polyester resin layer. There is a method to slow down the curing of the printed area and create recesses.

However, in this method, the diffusion of the inhibitor and retarder 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 difficult to obtain a satisfactory uneven pattern. is the current situation.

As a result of various studies in order to form a three-dimensional pattern using the above-mentioned unsaturated polyester resin, the present inventor also found that by adding two or more types of initiators with different polymerization initiation energy to the initial condensation product of the unsaturated polyester resin, the initial condensation By adding one or more kinds of solvents and selectively curing each of the initial condensates, the volume change of the resin during curing is utilized to create a three-dimensional pattern rich in uneven realism and three-dimensionality. The present invention was completed by discovering that it is possible to form a three-dimensional pattern with a large unevenness effect by forming a matte pattern by evaporating the solvent in the concave portions.

That is, the present invention adds two or more types of initiators having different polymerization initiation energy to an initial condensate of an unsaturated polyester resin, selectively cures each of the initial condensates, and cures the resin by the selective curing reaction. It is a material that forms irregularities due to the change in volume of the material, and evaporates the solvent in the recesses to form a three-dimensional pattern with a matte difference.

The above invention will be explained in more detail below.

First, in the present invention, the initial condensate of the unsaturated polyester resin is, for example, a polycondensation product 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 unsaturated polyester produced by reaction 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, 1- 3-butylene glycol and others can be used, and as vinyl compounds,
Styrene, vinyl acetate, methyl methacrylate, vinyltoluene, and others can be used.

In the present invention, in the initial condensate of the unsaturated polyester resin, for example, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, and other saturated dicarboxylic acids are used as part of the unsaturated dicarboxylic acid. can do.

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 used.Specifically, for example, benzoyl peroxide, lauroyl peroxide, 2,2-azobisisobutyronitrile, methyl ethyl ketone peroxide, etc. It is possible to use a combination of two or more types of polymerization catalysts, such as an initiator that generates radicals by thermal decomposition of , and an initiator that generates radicals by photolysis of diphenyl sulfide, benzoin methyl ether, etc.

Therefore, in the present invention, as an initiator, it is preferable to use a combination of one or more of the above-mentioned initiators that generate radicals by thermal decomposition and one or more initiators that generate radicals by photolysis. It is most desirable because the difference in polymerization energy is remarkable.

In addition, in the present invention, in addition to the above-mentioned initiator, a cocatalyst 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 solvent for forming the unevenness and at the same time matting the depressions by the method described later can be easily dissolved in the initial condensate of the unsaturated polyester resin, and further, Any material can be used as long as it floats on the resin surface during curing.

Examples include alcohols such as evaporated methyl alcohol and ethyl alcohol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate, and aromatic hydrocarbons such as benzene, toluene and xylene.

In the present invention, a mixed solvent of two or more of the above-mentioned solvents may also be used.

The above-mentioned solvent desirably can be easily dissolved in the initial condensate of the unsaturated polyester resin and has a specific gravity lower than the specific gravity of 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. To explain the case of using a combination of one or more initiators that generate radicals and one or more initiators that generate radicals by photolysis, first, an initiator that generates radicals by thermal decomposition of an initial condensate of an unsaturated polyester resin is used. An uncured resin composition is produced by adding an initiator that generates radicals by photolysis, one or more of the above-mentioned solvents, and an exciter and the like.

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 black ink, which does not transmit light but does not transmit heat. A pattern original is manufactured by forming a desired image using an absorbable ink or paint composition using a conventional printing or drawing method.

Further, in the present invention, when a glass plate is used, it is effective to use a vapor deposited film of SnO2 or the like as a heat reflecting pattern.

Hereinafter, the present invention will be explained in detail with reference to the drawings.

1 to 4 are cross-sectional views showing the configuration of each step of the three-dimensional pattern forming method according to the present invention.

Further, FIGS. 5 to 9 are cross-sectional views showing the configuration of each step of manufacturing a decorative material according to the present invention.

First, a desired image is formed on a substrate such as a transparent resin film or a glass plate by ordinary printing or handwriting using an ink or paint composition such as black ink that does not transmit light but can absorb heat, and then the irradiation energy is reduced. A pattern manuscript was created by setting two dissimilar regions with different absorption or transmission abilities.

On the other hand, as shown in FIG. 1, the uncured resin composition is coated on the substrate 1 by, for example, roll coating, gravure coating, barcode coating, dip coating, flow coating, brush coating, or other methods to form a coating layer. form 2,
Next, the pattern original 5 is superimposed on the coating layer 2.

In the figure, reference numeral 3 indicates the substrate of the pattern original, 4a,
4b indicates a heterogeneous region provided on the substrate.

Next, in the present invention, as shown in FIGS. 1A and 1B, energy 6 such as heat rays or light energy 6' such as ultraviolet rays is irradiated onto the top of the pattern document 5, and then light is irradiated as shown in FIGS. 3A and 3B. Energy 6' or thermal energy 6 is irradiated.

When thermal energy is first irradiated as shown in FIG. 2, the black part of the image area 4a of the pattern document 5 selectively absorbs heat, and the temperature rises in this part.
Thermal energy due to this temperature increase acts in the form of radiation on the initiator in the coating layer that generates radicals through thermal decomposition, causing the initiator to decompose and generate radicals, which in turn cause the unsaturated polyester to react with the initiator. Acting on the initial condensate, a crosslinking reaction occurs due to its polymerization reaction,
Curing the initial condensate of the unsaturated polyester, on the other hand,
In the transparent part of the non-image part 4b of the pattern original 5,
The temperature is difficult to rise through heat transmission, and therefore, the thermal energy does not act selectively on the initiator in the coating layer in this area, so the curing reaction of the initial condensate of unsaturated polyester does not occur. It turns out.

Next, when light energy is irradiated as shown in FIG. 2-B, a phenomenon completely opposite to the above-mentioned case of thermal energy occurs, and the black part of the image area 4a of the pattern original 5 does not transmit light, so the light energy does not pass through. , does not act on the initiator, but on the other hand, the transparent portion of the non-image area 4b of the pattern document 5 transmits light, and the transmitted light energy acts on the initiator to decompose it and generate radicals. At the same time, the initial condensate of the unsaturated polyester resin is selectively cured.

Therefore, in the present invention, as shown in FIGS. 3A and 3B,
When two or more types of initiators with different polymerization initiation energies are added to the initial condensate of unsaturated polyester resin and the initial condensates are selectively cured, unevenness corresponding to the image 4a of the pattern original 5 is generated. be able to.

For example, if thermal energy is applied first, the convex portion 7 will be formed in the portion of the unsaturated polyester resin that is first cured in close contact with the pattern document 5 due to the thermal energy acting thereon.

At this point, the four parts 8 are in an uncured state, and the sealed space formed by the pattern original 5 and the recesses 8 is in a vacuum state.

At this time, the solvent 9 in the resin composition moves to the surface of the recess 8 to evaporate, and since that part is in a vacuum state, evaporation starts.

The recesses 8 are cured by the action of the light energy irradiated later, and at that time, the solvent 9 is evaporated and hardened, so that a matte surface 10 can be generated in the recesses 8.
As a result, as shown in FIG. 4A, it is possible to form unevenness according to the image 4a of the pattern original 50, and form an uneven image 11 having a matte surface 10 in the recessed portion 8.

Conversely, if light energy is irradiated first, the light energy will act to form convex portions 7 in the portion of the unsaturated polyester resin that is cured first, and the action of thermal energy applied later will cause the solvent 9 to evaporate. By curing the unsaturated polyester resin, concave portions 8 are formed, and concave and convex portions are formed corresponding to the pattern original 5, and concave and convex portions having a matte surface 10 are formed in the concave portions 8.

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 unsaturated polyester resin according to the pattern, and in the cured area, the resin in the uncured area moves due to the volume change of the resin, and the formation of unevenness has already started from here. On the other hand, the solvent floats on the resin surface and moves to the recess 8 in the uncured portion.

Next, when starting energy is applied to the uncured part, the uncured part hardens with the evaporation of the solvent 9, and a volume change occurs as well.
It is thought that the difference in unevenness becomes even larger, and as a result, unevenness appears, forming a matte surface in the recessed portions.

In the above, it goes without saying that, in addition to those mentioned above, photographic images such as negative film or positive film can also be used as the pattern original.

Next, as the substrate in the above, any material can be used as long as it can retain the coating layer of the uncured resin composition, such as wood, plywood, particle boat, etc. Board; Paper; Films or sheets of various resins; Plates or foils of various metals such as iron, copper, aluminum, stainless steel, and zinc; Glass plates; Ceramics; Fibrous boards such as hardboard; Gypsum board, pulp Examples include composite substrates of organic polymers and inorganic substances such as cement boards, rock wool boards, and wood wool boards; calcium silicate boards; and asbestos slate boards.

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 an irradiation source or irradiation method of thermal energy, light energy, etc., for example, infrared rays are most preferable as thermal energy, and examples of such infrared light sources include filament lamps, discharge lamps, and arc light,
There are flashing light bulbs, etc., and radiant heat transfer from these light sources is transferred 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 (fluorescent 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 care must be taken to treat the thermal energy wavelength range as thermal energy and the ultraviolet energy wavelength range as thermal energy as much as possible. It must be irradiated as ultraviolet energy.

For example, when using a high-pressure mercury lamp for ultraviolet irradiation,
Naturally, wavelengths in the infrared region (radiation) also come out, but this wavelength region is cut in advance and the wavelength region in the ultraviolet region is 4QOm.
It is necessary to irradiate only the area below m.

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 ratio of the initiator and solvent to the initial condensate of the unsaturated polyester resin is, for example, 0.00% of the light energy-initiated polymerization initiator to the resin.
The amount of the thermal energy-initiated polymerization initiator is preferably 0.5% to 4.0% by weight based on the resin, and the best amount is 1% to 4% in total based on the resin.

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.

On the other hand, regarding the solvent, it is best to use 6% to 10% by weight based on the resin, and even when using a mixture of two or more solvents, the best amount is 6% to 10% by weight based on the resin.

In the present invention, the ability to form an uneven surface having a matte surface in the concave portions of the unsaturated polyester resin in accordance with the image of the pattern original as described above has various advantages and is suitable for various applications. It can be applied to

For example, as shown in FIG. 5, a desired wood grain pattern or the like can be formed directly on the substrate 1 after optionally performing known pretreatment if necessary, or by pasting decorative paper or the like. An image 12 is formed, and then the uncured resin composition is applied to the entire surface including the image 12 to form a coating layer 2 of the composition, and then on the drawn coating layer 2,
For example, in the case of a wood grain pattern, an image 4a of a portion of the desired image 12 where a recess is to be formed, such as a wood grain conduit groove, etc.
The pattern originals 5 having the following patterns are superimposed on each other.

Next, in the present invention, as shown in FIG. 6A, after the pattern originals 5 are superimposed as described above, ultraviolet rays 6' are first irradiated from above the pattern originals 5 as polymerization initiation energy. The initial condensate of the unsaturated polyester resin corresponding to the non-image area 4b is cured, and the seventh
As shown in figure A, the initial condensate of the unsaturated polyester resin corresponding to the image area 4a is not cured and the solvent 9 floats on the uncured resin.

At this time, the uncured recess 8 space sealed by the pattern original 5 becomes a vacuum state, and the solvent 9 begins to evaporate.

At that point, heat ray 6 is used as the polymerization initiation energy in Figure 8-
A (7) As shown in FIG. The initial condensate of the unsaturated polyester resin corresponding to part 4b has already been cured by the ultraviolet ray 6', and as shown in FIG. 9A, the initial condensate of the unsaturated polyester resin is selectively cured. By doing so, the volume of the cured resin is changed, and the unevenness corresponding to the image 4a of the pattern original 5 is formed, and the unevenness that is aligned with the desired image 12 is formed on the substrate 1. It is possible to obtain a decorative material 13 having a matte surface 10 in the concave portion 8 and having a rich three-dimensional effect and realism.

On the other hand, as shown in FIG. 6B, when the heat rays 6 are irradiated first, the pattern originals 5 having the image 4a of the part where the convex part is desired to be formed in the desired image 12 are superimposed, and when the heat rays 6 are irradiated, the pattern originals 5 The initial condensation product of the unsaturated polyester resin corresponding to the image area 4a is cured, and the initial condensation product of the unsaturated polyester resin corresponding to the non-image area 4b is not cured, and the solvent 9 is absorbed into the recess 8 as shown in FIG. 7-B. It floats to the top.

Thereafter, when ultraviolet rays 6/ are irradiated from above the pattern original 5 as polymerization initiation energy as shown in FIG. hardens with evaporation,
It is possible to obtain a decorative material 11 having a matte surface 10 in the concave portion 8 as shown in FIG. 9 and having a rich three-dimensional effect and realism.

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

Example 1 80mm wood grain pattern printed on 2.7mm thick plywood.
/m2 After laminating titanium paper with a vinyl acetate emulsion-urea resin adhesive, unsaturated polyester resin having the following composition was applied to the adhesive. /m2 coated.

Unsaturated Polyester Resin Composition On top of this, a polyester film with a summer pattern that matches the pattern of the decorative paper is printed with ink containing carbon black is placed on top of the film to match the pattern of the decorative paper, and then smoothed and air bubbles removed. Then, the entire surface was irradiated for 3 minutes with a chemical lamp (40W manufactured by Tokyo Shibaura Electric Co., Ltd.).

The irradiation conditions were a chemical lamp placed at a height of 10 c/IL and spaced at intervals of 10 cIrL.

After being left for 2 m1n after irradiation, the entire surface was irradiated with heat rays for 10 minutes.

The irradiation was performed using an infrared heater (IKm'/1 unit) installed at 20 cm intervals at a height of 3 ocrIL.

When the polyester film was removed after irradiation with heat rays, it became matte with soot and depressions only in the summer areas, while the winter areas were convex, yielding a three-dimensional polyester decorative board with rich realism.

Example 2 50mm white titanium paper on 2.7mm thick plywood /m'' with a vinyl acetate emulsion-urea resin adhesive, and then 400 g/m of unsaturated polyester resin with the following composition.
Coated with m.

On this unsaturated polyester resin, an abstract pattern was printed in advance on vinylon film using ink containing carbon black, this film was placed on it, and the air bubbles were removed by smoothing, and then light was first applied using the same equipment as in Example 1. It was irradiated for 5 minutes.

Thereafter, heat rays were irradiated for 15 minutes. When the vinylon film was peeled off after irradiation, a three-dimensional polyester decorative board with only the abstract pattern as a recess and a matte surface was obtained.

Example 3 A commercially available calcium silicate board with a stone grain pattern printed on it.
/m'' titanium paper was bonded with melamine adhesive, then unsaturated polyester resin with the following composition 500g/rn
: Coated.

Unsaturated Polyester Resin Composition First, prepare a polyester film with photolithographically created stone-grained areas that match the pattern of the decorative paper. After the above film was placed, it was first irradiated with light for 7 minutes using the apparatus of Example 1, then the photographic film was removed, and heat rays were irradiated for 5 minutes.

When the Vinylon film was removed after irradiation, a three-dimensional decorative board was obtained in which there were depressions in the stone joints, and the depressions became matte, just like when the joints were closed.

Example 4 A vinylon sheet with a thickness of 25μ was laminated on a steel plate,
On top of this, 500% unsaturated polyester resin of the following composition was added.
Coated with g/, l.

Unsaturated polyester resin composition A photographic pattern with halftone dots that will become the printing manuscript is placed on top of this, smoothed further, air bubbles removed, and then the entire surface is irradiated for 1 minute with a chemical lamp (120W manufactured by Matsushita Electric Industry ■). did.

The irradiation conditions were a chemical lamp placed at a height of 10 CIrL and spaced at intervals of 10 CIrL.

After irradiation, the entire surface was irradiated with heat rays for 10 minutes.

The irradiation was carried out using an infrared heater (IKW/1 heater) placed at a height of 30 Cr/L at intervals of 20 CIrL.

When the photographic film was removed after irradiation, an unsaturated polyester plate was completed in which only the blackened areas (internet areas) of the photograph had depressions and were matte.

Example 5 Commercially available calcium silicate plates were sanded and polished to printability.

A wood grain pattern was printed on this Keical board using a rotary screen printing machine.

On top of this, three unsaturated polyester resins similar to those in Example 1 were added.
00 P/m'' was placed thereon, and a polyester film in which a conduit portion matching the wood grain pattern was previously created by photolithography was placed thereon, and then the same irradiation method was performed using the apparatus of Example 1.

When the polyester film was removed after irradiation, a three-dimensionally tuned polyester decorative board with matte conduit portions and recesses was obtained.

Example 6 A SnO2 film was previously formed on a glass plate as an energy cut pattern by vapor deposition or chemical conversion, and a desired pattern (flower pattern) was formed by etching.

This etched area was screen printed with black ink to form an energy cut pattern.

A lined glass plate was coated with an unsaturated polyester resin of the following composition (500 y/rrr), 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, resulting in a floral pattern with unevenness and matte differences. A pattern was formed.

Unsaturated polyester composition - Commercially available unsaturated polyester resin - Methyl ethyl ketone peroxide 1.0 wt% - Benzoin ethyl ether - Methyl ethyl ketone 1.0 wt% 8.0 wt% In the above, the order of irradiation with ultraviolet rays and heat rays could be in any order.

[Brief explanation of the drawing]

FIGS. 1 to 4 are schematic cross-sectional views showing the configuration of each step of the three-dimensional pattern forming method of the present invention, and FIGS. FIG. 3 is a schematic cross-sectional view showing the configuration of each step of manufacturing a decorative material. Explanation of symbols representing main parts of the figure: 1... Substrate of composition layer, 2... Composition layer, 5...
・Pattern original board, 3...Pattern original,
4a... Drawing area of pattern original, 4b...
... Non-printing area of pattern original, 6, 6'... Light energy and thermal energy 7... Convex part, 8.
...Concavity, 9...Solvent, 10...
- Matte surface of concave portion, 11...Three-dimensional pattern molded object.

Claims (1)

[Claims] 1. A layer of a composition obtained by adding two or more types of polymerization initiators having different polymerization initiation energies and one or more types of solvent to an initial condensate of an unsaturated polyester resin is mutually irradiated. Energy selective application means consisting of a plurality of different regions having different energy absorption or transmission abilities are provided in close contact with each other, and energy in different wavelength ranges is sequentially and selectively applied to the plurality of regions of the composition layer via the means. selectively curing the initial condensate in that region by giving a
A method for forming a three-dimensional pattern having a mat difference, characterized in that the surface of the recess is matted by evaporating a solvent into the composition recess space sealed by the energy selection imparting means. 2. A method for forming a three-dimensional pattern having a matte difference according to claim 1, characterized in that a transparent plastic film having a pattern printed with ink having a high heat absorption ability is used as the energy selection imparting means. 3. Claim 1, characterized in that an image with high heat absorption capacity is formed on a transparent plastic film by photolithography on a transparent plastic film as the energy selection imparting means.
A method for forming a three-dimensional pattern having a matte difference as described in Section 1. 4 Sn on a transparent glass plate as an energy selective imparting means
A three-dimensional pattern having a mat difference according to claim 1, characterized in that a pattern of O2 film is provided and the portions not covered by the pattern are covered with an ink film with high heat absorption ability. Formation method. 5. The composition has a matte difference as set forth in claim 1, characterized in that a composition obtained by adding methyl ethyl ketone peroxide, diphenyl sulfide, and methyl ethyl ketone to an initial condensate of an unsaturated polyester resin is used as the composition. How to form three-dimensional patterns. 6. The mat difference according to claim 1, characterized in that the composition is a composition obtained by adding methyl ethyl ketone peroxide, benzoin methyl ether, and acetone to an initial condensate of an unsaturated polyester resin. A method for forming three-dimensional patterns. 7. The matte difference according to claim 1, characterized in that the composition is a composition obtained by adding benzoyl peroxide, benzoin methyl ether, and ethyl acetate to an initial condensate of an unsaturated polyester resin. A method for forming a three-dimensional pattern. 8. A three-dimensional material having a matte difference according to claim 1, characterized in that the composition is a composition obtained by adding methyl ethyl ketone peroxide and benzoin methyl ether to an initial condensate of an unsaturated polyester resin. How to form patterns. 9 Using a transparent plastic film printed with a positive pattern of convex patterns to be formed with black ink as the energy selection imparting means, bringing the energy selection imparting means into close contact with the composition layer, and irradiating the means with heat rays. The matte difference according to claim 1 is characterized in that the means is irradiated with ultraviolet rays to harden the uncured concave portion surfaces and to make them matte. A method for forming three-dimensional patterns. 10 As the energy selection imparting means, a transparent plastic film printed with a negative pattern of convex patterns to be formed with black ink is used, the energy selection imparting means is brought into close contact with the composition layer, and the means is irradiated with ultraviolet rays. The matte difference according to claim 1 is characterized in that, after the convex pattern is revealed, the means is irradiated with heat rays to harden the uncured concave portion surface and make it matte. A method for forming three-dimensional patterns. 11 Claim 1, characterized in that a composition containing 6 to 10% by weight of a solvent is used as the composition.
A method for forming a three-dimensional pattern having a matte difference as described in Section 1. 12 0.5 to 4% by weight of a light energy initiated polymerization initiator, 0.5 to 4% by weight of a thermal energy initiated polymerization initiator, and 6 to 10% of a solvent based on 100% by weight of the initial condensate of unsaturated polyester resin. % by weight, and the total weight % of both initiators is 1 to 4% by weight, and in both initiators, the weight ratio of the initiator to be started first to the initiator to be started later is 7:3. A method for forming a three-dimensional pattern having a mat difference according to claim 1, characterized in that a composition having a ratio of 8:2 to 8:2 is used.