JPS5941852B2 - Manufacturing method for three-dimensional decorative material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyvinyl chloride foam having an uneven pattern, and more specifically to a method for producing a polyvinyl chloride foam having an uneven pattern. The present invention relates to a method for manufacturing a three-dimensional decorative material having a novel uneven pattern for materials such as wood.

As a method for manufacturing decorative materials that usually have uneven patterns, mechanical embossing using an embossing roll has been known, and a technique called valley printing (valley dyeing), in which ink is applied to an embossing roll and embossing is generally used, is also known. It is being done.

However, this method has many drawbacks, such as expensive embossing rolls, difficulty in embossing multiple colors in a synchronous manner, slow production speed, and a tendency to produce defective products. Another method is disclosed in Japanese Patent Publication No. Sho 43-28636, in which an embossing is formed using a foaming inhibitor that changes the foaming temperature in a vinyl chloride resin composition containing a foaming agent. However, since the product obtained by this method is a foam, it cannot withstand the high heat of cigarettes, etc. from the surface and melts and collapses.Also, the pattern is formed by printing ink, so it extends to the ink surface. When the surface protective resin film disappears due to wear, the pattern easily disappears and the original design effect is lost. For this reason, improvements have been made by increasing the thickness of the surface resin layer or providing a resin film layer with high surface hardness. However, it has been difficult to fundamentally solve the above two problems. Furthermore, in addition to this method, Japanese Patent Application Laid-Open No. 48-1784
9. As seen in JP-A-50-66-306, a dry red porous layer is formed and a curable resin ink is applied or a polymerizable monomer is polymerized to the dry red porous layer containing a polymerizable monomer. Apply catalyst ink,
A method of chemically forming an emboss by curing only the ink portion and sintering the unhardened portion without removing or removing it is disclosed.

The product produced by this method has excellent surface heat resistance and abrasion resistance, which are the drawbacks of Japanese Patent Publication No. 43-28636. However, since the ink used in this method is a curable ink or a polymerizable catalyst ink, it has poor stability. In addition, high-temperature heating is required to cause the ink to react with the resin. The present invention was made as a result of intensive research to eliminate the various drawbacks mentioned above, and basically uses a dry blend resin, and a reactive plasticizer and a photosensitizer are added to the dry blend resin in advance. A resin composition that is cured by light is used, and by providing an ultraviolet ray transmitting portion and a blocking portion on the dry blend layer, and irradiating the dry blend layer with ultraviolet rays, the dry blend layer is cured only in the ultraviolet ray transmitting portion.

According to this method, the ink used to block ultraviolet rays does not need to be a special curable ink, and may be any ordinary ink. This is because ordinary colored inks have the effect of blocking ultraviolet rays. In this case, the resin layer can be cured as desired by using transparent ink or opaque ink. Furthermore, since curing of areas other than the ink area is performed by irradiation with ultraviolet rays, it is easier than the high temperature heat treatment used in conventional methods.
In this way, the present invention solves the problems of surface abrasion resistance and high temperature heat resistance, which were impossible with the foaming suppression method, by using a photopolymerizable dry blend resin composition, and also with regard to the embossing method, we have solved the problems of surface abrasion resistance and high temperature heat resistance, which were impossible with the foaming suppression method. The formation can be easily and quickly performed by ultraviolet irradiation.

Further, a major feature of the present invention is that the hardness of the resin film can be arbitrarily obtained by changing the amount of reactive plasticizer, which is one of the great practical values that is superior to the conventional dry blending method. Generally, transparent ink and opaque ink can be used to form UV-transmissive and shielding areas, but in the case of UV-transparent ink, a sensitizer should be used in the ink, and in the case of non-transparent ink, titanium oxide should be used. In addition to adding opaque inorganic substances such as opaque inorganic substances, the effect can be increased by adding ultraviolet absorbers and fluorescent daylight enhancers. Furthermore, in the present invention, in addition to ink, it is also possible to partially use an ultraviolet shielding mask to form these transmitting portions and shielding portions. Furthermore, although these are cases where regular patterns are assumed, for example, if transparent color chips and opaque color chips are placed in the resin composition, random resin cured areas and uncured areas can be formed.

Since these resin hardened portions and unhardened portions are in a flat state as they are, the unhardened portions are scraped off to form recesses relative to the hardened portions.

Generally, a method is used in which only the uncured portion is removed by brushing, but a method in which uncured vinyl chloride is dissolved is also possible. Also, the combination of solvent cleaning and brushing is most effective.

The solvent used may be a ketone type such as methyl ethyl ketone or methyl isobutyl ketone, an aromatic type such as trol xylol, an alcohol type such as methanol or ethanol, or a mixed solution thereof. Also, their cleaning power can be reduced by mixing them with water. After forming an uneven surface by brushing or the like, the entire dry blend resin coating is finally gelled by heating to form a final product. At this time, it is possible to further enhance the design effect of this product by applying a transparent clear resin coat or a color clear resin coat to the surface.In addition to vinyl chloride resin, the resin can also be used such as vinyl chloride acrylic copolymer, acrylic, polyurethane, Polyester, epoxy resin, etc. can be used. These surface coating resins are not limited to thermoplastic resins, but thermosetting resins can also be applied, and furthermore, ultraviolet curable resins can also be applied.

The best method for coating is curtain flow coating, spray coating, or the like, in which the roll or the like does not come into direct contact with the material to be coated. The dry blend resin composition used in the present invention is one in which a part of the plasticizer in a conventional dry blend formulation is replaced with a reactive plasticizer, and a photosensitizer is added at the same time. Basically, depending on the amount of plasticizer added to the polyvinyl chloride paste resin, it will be a hard compound, a semi-hard compound, or a soft compound.
10 parts or less is hard, 10 to 30 parts is semi-hard,
30 to 100 parts results in a soft blend. However, in the present invention, since a reactive plasticizer is used as a part of the plasticizer, when the reactive plasticizer polymerizes, it is affected by the hardness, and the above plasticizer ratio does not necessarily correspond to hard, semi-hard, or soft. However, the higher the proportion of reactive plasticizer, the harder the material becomes. Plasticizers for plasticizing purposes may be dioctyl phthalate, dibutyl phthalate, etc., but heat resistance can be improved by adding a secondary plasticizer for heat resistance such as epoxidized soybean oil. . Next, the reactive plasticizer, which is an important compound of the present invention, will be described. Regarding the ratio of reactive plasticizers to be replaced among the total plasticizers, from the viewpoint of UV curing, the higher the ratio of reactive plasticizers, the more advantageous it is, but from the viewpoint of processing (kneading, coating) of polyvinyl chloride compositions, Less is better, and less is naturally advantageous in terms of cost. Experimental results show that ultraviolet curing is sufficient in the range of 5 to 20 parts, although it depends on the type of reactive plasticizer. Reactive plasticizers are typified by acrylic ester monomers or oligomers and allyl ester monomers or oligomers, but either type can be used in the present invention. Typical examples of the former include ethylene dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1.3 butylene glycol dimethacrylate, 1.4 butylene glycol dimethacrylate, 1 In addition to .6 hexamethylene diglycol dimethacrylate, tripropylene glycol dimethacrylate, and trimethylolpropane trimethacrylate, there are acrylates of the above-mentioned polyhydric alcohols, and any of these can be used as the reactive plasticizer of the present invention. Among these, polyfunctional acrylates basically have a faster ultraviolet curing speed and become harder. Furthermore, when they have the same functional groups, the smaller the molecular weight, the more reactive they are, and the harder they tend to be.

On the other hand, a typical allyl ester type is diallyl phthalate, and its monomer or oligomer can be used as a reactive plasticizer. Both acrylic esters and allyl esters can be cured by ultraviolet light using a photosensitizer. These photosensitizers may be those commonly used as photosensitizers for ultraviolet curing resins, such as benzoin, benzoin methyl ether, benzyl, benzophenone, azobisisobutyronitrile, benzoin ethyl ether, and benzoin isobutyl ether.

The ratio of photosensitizer to reactive plasticizer is 0.5 to 5.00! ) indicates sufficient curing. However, it is of course not limited to this range, and the amount can be selected as appropriate. Next, an embodiment of the present invention will be described in more detail with reference to the drawings.

Although resin dry blending is necessary in the present invention,
This resin dry blend is obtained from a composition containing a resin paste range, a reactive plasticizer, a photosensitizer, and other main components such as a plasticizer, a stabilizer, and a filler.

Generally, the powder, excluding the plasticizer, is first premixed in a pen shell mixer at a jacket temperature of about 80°C, and then the plasticizer is mixed while being gradually added dropwise. The optimum temperature of the dry blend at the time of discharge is around 120°C. In addition to the Pen Shell mixer, the Ridon Friender is also used as a mixing machine. Next, the dry blend resin composition thus prepared is applied to the base material 1 or the base material 1 impregnated with a resin. The powder of the dry blend is sintered in a heating furnace immediately after being regulated with a blade or the like to a constant thickness on the base material. The thickness of the dry blend layer is preferably between 0.5 and 3.0 for flooring. Sintering is 120~1500C1~
It takes 4 minutes. In the dry blend layer, granules contact and fuse to form a porous layer 3. In this case, in order to improve the adhesion between the dry blend layer and the base material, it is also possible to apply an adhesive such as vinyl acetate, vinyl chloride, vinyl chloride acetic acid copolymer, urethane, etc. or vinyl chloride plastisol 2 to the base material 1 in advance. . Any material can be used as the base material 1 of the present invention, such as asbestos, nonwoven fabric, paper, woven fabrics of various fibers, and wood materials.

These substrates may become part of the final product or may be peeled from the product.

Next, in the present invention, in order to form cured portions and uncured portions in the porous layer 3, ultraviolet transmitting portions and ultraviolet blocking portions are provided in a pattern.

In Figures 1 and 2, the ultraviolet transmitting portion and the ultraviolet shielding portion are provided using printing ink, but of course a mask having the ultraviolet transmitting portion and the ultraviolet shielding portion may also be used as described above. Furthermore, an object having an ultraviolet shielding effect, such as a metal foil, may be placed only on the part where it is desired to shield external rays.

Although not shown, the ultraviolet transmitting ink 4 and the ultraviolet shielding ink 5 permeate not only the surface but also the inside of the porous layer 3 formed by dry blending.

Therefore, even if the surface is abraded, the color pattern will not be damaged.
For this reason, it is desirable that the amount of ink deposited be as large as possible, and therefore screen printing or gravure printing using a deep gravure plate is optimal. However, printing is not limited to these printing methods; letterpress printing, offset printing, gravure offset printing, and flexo printing are also possible. In order to improve permeability, it is advantageous to use a fluid ink with a high solid content and low viscosity. The most preferred ink is a vinyl chloride plastisol composition ink. Plastisol ink has good compatibility with rotary screen printing and gravure intaglio printing with a plate depth of 100μ or more because the ink has strong adhesion and the resin in the ink is of the same type as the resin in the dry blend layer. Easy to penetrate inside. Plastisol ink is 1 after printing
Internal penetration and semi-gelation can be achieved at a temperature of 00 to 150°C for 1 to 3 minutes. Printing inks are divided into inks that absorb or block ultraviolet rays and inks that do not absorb or transmit ultraviolet rays. Since the ink that absorbs ultraviolet rays does not allow the ultraviolet rays to reach the dry blend layer, the dry blend layer is not cured. On the other hand, ink that transmits ultraviolet light cures the dry blend layer. In this way, by using the ultraviolet transmitting ink and the shielding ink, it is possible to form hardened portions and non-hardened portions in the porous layer 3 of the dry red layer. Next, regarding ink that transmits ultraviolet rays and ink that does not transmit (shield) ultraviolet rays, generally speaking, it is sufficient to use transparent pigments and opaque pigments, respectively.

However, in the case of dark colors such as black, indigo, and brown, if it is desired to have an ultraviolet transmitting effect, complete transparency cannot be ensured as is, so in that case, a photosensitizer may be added. For example, add 5% benzoin ethyl ether to carbon black pigment. On the other hand, if you use a transparent pigment and do not want to transmit ultraviolet rays, you can mix titanium oxide into the transparent pigment to make it opaque, but the hue will be different, so you will need to use an ultraviolet absorber or fluorescent whitening agent. This can be solved by adding. As the ultraviolet absorber, those having absorption characteristics at 365 mμ are effective, and benzophein-based and benzotriazole-based ultraviolet absorbers are most suitable. Examples of these include 2-hydroxy, 4-octadecyloxybenzophenone, 2,21-dihydroxy-4methoxybenzene, 2(2/-hydroxy 5'methylphenyl)benzotriazole, 2(2'hydroxy 4'otatoxyphenyl) ) benzotriazole, etc. Fluorescent brighteners also have the property of absorbing energy in the ultraviolet region (340-400 mμ) and converting this energy into hues in the visible region (400-500 mμ) from violet to blue. It also shows the property of blocking ultraviolet rays. A typical example of this is 2.5bis(5'tertiarybutylbenzoxazolyl2)thiophene, which is UVlteXO from Chibakaigi Co., Ltd.
B corresponds.

The above ultraviolet absorbers or fluorescent brighteners are contained in the ink at 1%.
By adding ~5%, ultraviolet rays can be absorbed.

Next, a cured portion and an uncured portion are formed in the dry blend layer by UV irradiation after printing.

Ultraviolet rays are irradiated using a high-pressure mercury lamp or other appropriate light source. Normally, a mercury lamp with an output of 80 W/CTn is most often used, but naturally the higher the output, the more effective it is, and the output and number of mercury lamps will vary depending on the processing speed. 80W/C
In the case of one TrL, the standard speed is 5 m/min.

The direction of ultraviolet irradiation is the direction of the arrow indicated by 6 in the figure. Due to such ultraviolet irradiation, the dry blend portion of the ultraviolet-transparent ink portion is cured, but the non-transparent portion is not cured. The hardened and unhardened parts are brittle, and the hardened part is strong. For this purpose, when the entire surface is brushed, the uncured portions of the surface of the dry blend layer are easily removed to form recesses 7. Alternatively, the uncured portion is dissolved or swollen with a diluted solvent and removed. Since the porous layer remaining after removal has poor surface properties, it is finally treated with hot air of 200° C. or higher for 2 to 7 minutes to completely melt the entire resin. The final product is a hardened flooring with an uneven pattern and the pattern ink is colored to the inside. In addition, after brushing the uncured area, a transparent PVC plastisol or colored plastisol of 0.2 to 0.4 is applied to the surface and heated in the same way to melt the plastisol on the surface at the same time as dry blending, to form a surface protective layer. The flooring material has a convex pattern. Both those without a surface protective layer and those with a surface protective layer have cigarette resistance and can be used as flooring materials for heavy walking with excellent wear resistance. In particular, because the pattern is made of ink that penetrates into the interior even when the surface wears down, it has a great advantage in terms of durability compared to conventional chemically embossed flooring made of foamable PVC. The manufacturing method will be specifically described below using Examples.

In the examples, "part" means "part by weight". Example 1: Vinyl chloride plastisol was applied to a thickness of 50μ on 0.6% asbestos paper, and dry blend granules having the following composition were uniformly coated on the gelled sheet to a thickness of 2~ to form.

Dry blend resin is 110% by pen shell mixer.
Processed at °C. This dry blend layer is heated at 130° C. for 2 minutes to form a dry blend porous layer.

The dry blend porous layer and asbestos paper are integrated through a gelled plastisol layer. Next, apply plastisol ink containing transparent and opaque pigments with the following composition to a plate depth of 100 μm.
Gravure printing is performed using a concave engraved plate.

The slow drying temperature for printing was 120°C. The prints were irradiated with two high-pressure mercury lamps with an output of 80 W/CrIL at a speed of 10 m/min.

Next, the surface layer of the opaque ink portion was removed by brushing and heated at 200° C. for 2 minutes to melt the whole. A flooring material with a pattern in which the transparent ink area was depressed compared to the opaque ink area was obtained. Example 2> Dry blend granules processed by a pen shell mixer having the following composition were applied to a base material prepared by applying a vinyl acetate emulsion adhesive to a nonwoven fabric impregnated with latex and drying the mixture using a pen shell mixer having the following composition.
A dry blend porous layer was obtained by applying the mixture uniformly to a thickness of 120° C. and heating at 120° C. for 2 minutes.

Next, rotary screen printing was performed using an 80-line screen plate using an ink having the following composition.

The ink was dried using far infrared rays. At this time, the ink penetrated into the inside of the dry blend porous layer. Ink 1
is an ultraviolet-transparent ink, and ink 2 is an ultraviolet-opaque ink. As in Example 1, ultraviolet rays are irradiated using a high-pressure mercury lamp to harden the ink 1 part and make the insert 2 part uncured.

Next, after scraping off the surface of the uncured area by brushing, 0.3% of transparent plastisol with the following composition was applied at 220°C.
Heat for 3 minutes to completely melt the dry blend porous layer and the surface transparent plastisol. The three-dimensional ornament thus obtained exhibited excellent cigarette resistance and abrasion resistance due to the hardening of the diallyl phthalate monomer on the surface.

Claims (1)

[Claims] 1. A process of forming a resin dry bread layer containing a reactive plasticizer and a photosensitizer and then heating it to form a porous layer that is fused in a state of grain contact, a part that transmits ultraviolet rays and a part that transmits ultraviolet rays. A step in which a pattern is formed to shield parts, a step in which UV light is irradiated to harden only the UV transmitting part, a step in which only the uncured porous part is partially removed to form an uneven surface, and a process in which the uneven surface is formed is heated to form a porous surface. A method for producing a three-dimensional decorative material, including a step of melting a texture layer, and each of the above process steps. 2. The method according to claim 1, wherein a portion that transmits ultraviolet rays and a portion that blocks ultraviolet rays are provided with ink. 3. The method according to claim 1, wherein a part that transmits ultraviolet rays and a part that blocks ultraviolet rays are provided by a mask. 4. The method according to claim 1, wherein the uncured portion of the porous layer is removed by brushing. 5. The method according to claim 1, wherein the uncured portion of the porous layer is removed with a solvent.