JPS6333430A - Production of embossed sheet - Google Patents

Abstract

PURPOSE:To obtain the titled sheet having a printed pattern coinciding with relief pattern and suitable as a flooring material, by applying a foamable resin layer to a substrate, printing a pattern with a printing ink containing a foam- suppressing agent, applying a transparent layer to the printed substrate, foaming the foamable resin layer with heat and embossing the product. CONSTITUTION:A layer of a foamable synthetic resin composition having an average polymerization degree of >=1,200 is applied to a substrate and an arbitrary pattern is printed on the layer with a printing ink containing a foam- suppressing agent. The surface of the printed substrate is covered with a transparent or translucent synthetic resin layer having an average polymerization degree of higher than that of the synthetic resin in the foamable synthetic resin composition by >=100 and having an average expansion ratio of <=4. The foamable layer is foamed with heat to develop a rugged surface pattern. The objective embossed sheet having a printed pattern coinciding with relief surface pattern can be produced by embossing the above laminate with an embossing roll having arbitray embossing pattern on the surface.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention is applicable to building materials such as flooring materials and wall materials, vehicle seats, bags,
This invention relates to a method for manufacturing an embossed sheet with excellent decorative properties, which has a concavo-convex pattern that matches a printed pattern used for bags, furniture, etc., and has a delicate and sharp squeeze pattern on its surface.

(Prior art) As a method for manufacturing an embossed sheet with a matching printed pattern and uneven pattern as described above, printing ink containing a foaming suppressor and/or foaming accelerator is printed on the surface of a foamable synthetic resin layer, There is a chemical embossing method in which this is foamed to create an uneven pattern, and a synchronized embossing method in which an embossing roll is used to emboss according to the printed pattern, but in the chemical embossing method, the printed pattern and the uneven pattern match. However, it is impossible to express delicate and sharp unevenness.
In addition, in the case of synchronized embossing, it is possible to express delicate and sharp unevenness depending on the shape of the embossing roll used, but in order to mechanically match the printed pattern and the uneven pattern, it is necessary to create a variety of patterns depending on the expansion and contraction of the sheet, machine conditions, etc. There were problems in that it was difficult to match, the workability was very poor, and there were many defects.

(Means for solving the problems) The present invention forms a layer of a foamable synthetic resin composition on a base material,
An arbitrary pattern is printed on the surface using printing ink containing a foaming inhibitor, a transparent or translucent synthetic resin layer is formed on the surface, and then heated and foamed to reveal an uneven pattern. In the method for producing a synchronized embossed sheet in which the printed pattern and the concave-convex pattern match using an embossing roll subjected to the process, the average degree of polymerization of the synthetic resin used in the foamable synthetic resin composition is 1200 or more. Ashi,
The average degree of polymerization of the synthetic resin used for the transparent or translucent synthetic resin layer is 9100 or more higher than the average degree of polymerization of the synthetic resin used for the foamable synthetic resin composition, and the expansion ratio is 4 times or less. A method for easily producing an embossed sheet with excellent decorative properties, in which the printed pattern matches the uneven pattern, and furthermore, the surface thereof has a delicate and sharp drawing pattern formed by the drawing pattern of the embossing roll. It is something.

The base materials used in the present invention include one or more types of inorganic or organic fibers such as natural animal or vegetable fibers, asbestos, glass fibers, rock wool, pulp, and synthetic fibers, and if necessary, calcium carbonate, clay, Other layered carriers such as woven fabrics, knitted fabrics, non-woven fabrics, and paper mixed with fillers such as aluminum hydroxide and resin binders can be used, and these can be used freely depending on the intended use of the product. It is. In addition to the above, a foamed or non-foamed synthetic resin sheet may be laminated on the back surface of the woven fabric, knitted fabric, nonwoven fabric, paper, etc. (the surface opposite to the surface on which the layer of the foamable synthetic resin composition is formed). can also be used as a base material for the tuned embossed sheet of the present invention.

The layer of the foamable synthetic resin composition is composed of a thermoplastic synthetic resin, a chemical blowing agent that decomposes (by heating) to generate gas, and a blowing aid that accelerates the decomposition of the blowing agent, and may contain other ingredients as necessary. Commonly used additives such as plasticizers, stabilizers, fillers, fungicides, viscosity reducers, and colorants are used.

Thermoplastic synthetic resins include vinyl chloride resin, acrylic resin, vinyl acetate resin, polyethylene, polypropylene,
Ethylene-vinyl acetate copolymer resin, urethane resin ring Any commonly used synthetic resin may be used, but vinyl chloride resin is particularly preferred. The vinyl chloride resin mentioned here refers to polyvinyl chloride resin, copolymers of vinyl chloride and other monomers such as ethylene, vinyl acetate, vinyl ether, maleic acid ester, acrylic, urethane, etc., as well as polyvinyl chloride resin and others. The synthetic resin used must have an average degree of polymerization of 1200 or more. If the average degree of polymerization of the synthetic resin is less than 1200, the melt viscosity of the foam layer will be low during heat embossing, and the compression of the embossing roll will cause surface roughness due to destruction of foam cells, making embossing difficult.

As the blowing agent, commonly used ones can be used, but azodicarbonamide is particularly preferred. The amount added is preferably 0.5 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin.

The foaming aid that accelerates the decomposition of the foaming agent can be one that is normally used depending on the type of foaming agent, but when using azodicarbonamide as the foaming agent, zinc-based or lead-based foaming agents such as zinc acetate can be used. A foaming aid that also serves as a stabilizer is preferred.

Plasticizers include dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, didodecyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, dioctyl phthalate, didodecyl phthalate, diisononyl phthalate, dioctyl adipate, diindecyl adipate, dibutyl sepacate, dioctyl sebacate, and tributyl. In addition to phosphate, tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate, trioctyl phosphate, diphenyl cresyl phosphate, etc., epoxy plasticizers such as trimellitic acid ester plasticizers, epoxidized soybean oil and various epoxy resins, Common plasticizers such as polyester polymer plasticizers can be used.

In addition, when using a vinyl chloride resin paste as a foamable synthetic resin composition, gasoline, octane, benzene, toluene, naphtha,
Commonly used diluents such as dodecylbenzene derivatives, secondary plasticizers, viscosity reducing agents, etc. are used in combination with the plasticizer.

The amount of plasticizer added is 20 to 100 parts by weight per 100 parts by weight of vinyl chloride resin, and the amount of diluent and secondary plasticizer is 1 to 100 parts by weight.
20 parts by weight, and the viscosity reducing agent preferably ranges from 0.1 to 5 parts by weight.

As the stabilizer, commonly used stabilizers can be used, but when azodicarbonamide is used as a foaming agent, it is preferable to use zinc-based or lead-based materials such as zinc oxide, which have the effect of acting as a foaming aid and stabilizer. . The amount of the stabilizer added is preferably in the range of 0.5 to 7 parts by weight per 100 parts by weight of the vinyl chloride resin.

Any filler can be used as long as it does not undergo physical or chemical changes such as melting or decomposition at the processing temperature.
Calcium carbonate, magnesium carbonate, clay, talc,
Silica, diatomaceous earth, silica sand, pumice powder, flake powder, mica powder, asbestos, aluminum hydroxide, aluminum oxide, aluminum sulfate, barium sulfate, calcium sulfate, glass bulb, foam glass bulb, fly ash bulb, volcanic glass hollow Inorganic fillers such as powdered fibers (shirasu balloons), organic fillers such as powdered cellulose (cellulose powder), polyvinyl alcohol fibers, cork powder, wood flour, thermosetting resin powder, thermosetting resin hollow spheres, etc. can be used. . The amount of filler added is 5 to 400 parts by weight per 100 parts by weight of vinyl chloride resin.
Parts by weight ranges are preferred.

Commonly used antifungal agents can be used, but
Among them, there are 10 types that sometimes discolor vinyl chloride resin, and those that inhibit the foaming suppressing effect of foaming inhibitors.
Organic compounds such as 10'-oxybisphenoxyarsine, N(fluorodichloromethylthiothyphthalimide, N-trichloromethylmercapto-4-cyclohexene-1,2-dicarboximide, 2,4,5,6-teto2chloroiso7talonitrile) Vinyl chloride resin 100% anti-fungal agent
When 0.1 to 5 parts by weight is required to maintain the effect, it is preferable to use 1 to 30 parts by weight of an inorganic antifungal agent such as barium metaborate.

Of course, the above antifungal agents can be used alone or in combination of two or more.

The printing ink used in the present invention can be any commonly used printing ink. However, at least one color of the printing ink used to print the pattern must contain a commonly used foaming inhibitor such as trimellitic anhydride or dithiocyanuric acid derivatives, which suppress foaming of the foamable synthetic resin layer and form recesses. It is necessary to. The amount of the foaming inhibitor added is appropriately adjusted depending on the desired depth of the recess, but is preferably in the range of 1 to 30% by weight relative to the printing ink.

As the transparent or translucent synthetic resin layer of the present invention, any commonly used thermoplastic synthetic resin composition can be used. In terms of the reproducibility of the embossed pattern by the embossing roll (emboss suitability) and the foaming suppressing effect of the foaming inhibitor, it is preferable that the average degree of polymerization of the synthetic resin used is low.
On the other hand, if the average polymerization degree of the synthetic resin in the foamable synthetic resin composition is lower, the interface between the transparent or translucent synthetic resin layer and the foamed synthetic resin layer (
In other words, due to the significant generation of air bubbles on the printed surface, a clear printed pattern cannot be obtained and the surface smoothness deteriorates.
The average degree of polymerization of the synthetic resin used for the transparent or translucent synthetic resin layer is preferably 100 to 4,000 higher than the average degree of polymerization of the synthetic resin of the foamable synthetic resin composition. If the average degree of polymerization of the synthetic resin used for the transparent or translucent synthetic resin layer is equal to or lower than the average degree of polymerization of the synthetic resin of the foamable synthetic resin composition, the desired product cannot be obtained for the above reasons. Moreover, if it exceeds 4oOO, it is not only undesirable that the embossing suitability is deteriorated, but also that the foaming suppressing effect is extremely poor. Other commonly used additives such as plasticizers, stabilizers, fillers or matting agents, fungicides, viscosity reducers, colorants, etc. may be used as necessary.

The thermoplastic synthetic resin and various additives used as necessary can be used in the same amounts as those used in the above-mentioned foamable synthetic resin composition. However, the filler or matting agent used in the above-mentioned foamable synthetic resin composition can be used in an amount of 0.5 to 20 parts by weight per 100 parts by weight of the synthetic resin.

If the blending amount exceeds 20 parts by weight, the synthetic resin layer becomes opaque and the desired product cannot be obtained, which is undesirable.

The synchronized embossed sheet of the present invention is produced by applying a layer of a foamable synthetic resin composition to the above-mentioned sheet-like base material by a calendering method, an extrusion method, or an extrusion method.
It is formed by a conventional method such as a laminating method or a paste coating method, and contains a foaming inhibitor in at least one color on its surface by a conventional method such as a gravure printing method, a flexo printing method, a rotary screen printing method, a silk screen printing method, etc. After printing an arbitrary pattern using printing ink and forming a transparent or translucent 0 synthetic resin layer on the surface by a normal method such as calendaring, extrusion, laminating, paste coating, etc., the foamable synthetic resin is The composition is heated and foamed at a temperature higher than the decomposition temperature of the blowing agent contained in the composition to obtain a sheet-like material with a printed pattern and a concave-convex pattern that match, and then an embossing roll with an arbitrary drawing pattern is formed using an ordinary embossing machine. It can be obtained by heat embossing.

Embossing methods include heating and foaming in an off-line process where a foaming furnace and embossing machine are installed separately, and then reheating and embossing, and another method that performs foaming immediately after foaming using an in-line machine with an embossing device installed immediately after the foaming furnace. There are two methods of heat embossing, and either method is applicable.

When embossing is performed offline, the foam layer once formed has been completely cooled, so the pressure of the embossing roll will not destroy the foam cells and cause surface roughness, but the unrefined material remaining on the foam layer will not be destroyed. It is necessary to apply heating conditions that will not cause the decomposition foaming agent to decompose and cause secondary foaming, causing foam cell roughness.If embossing is performed in-line immediately after heating and foaming, the foam layer may be in a softened state. Therefore, cool only the back side (the side opposite the embossed side) as much as possible.
It is necessary to perform embossing by heating the surface under conditions that do not cause secondary foaming of the undecomposed foaming agent remaining in the foam layer. Furthermore, performing so-called clearance embossing, in which a gap is provided between the embossing roll and the rubber roll (backup roll) during embossing, is effective in preventing foam cell destruction in the foam layer. In this case, the clearance (gap) varies somewhat depending on the foaming ratio of the foam layer and the average degree of polymerization of the synthetic resin forming the foam layer, so it is necessary to set it after checking each. In this case, the expansion ratio must be 4 times or less.

The foaming ratio of the foam layer is 2.5 times or less, the average degree of polymerization of the synthetic resin forming the foam layer is 1200 or more, and the foam layer is 2.5 times or less.
By heating under heating conditions that do not cause subsequent foaming and embossing with an embossing roll pressure of 2 to 3 Kt/m (gauge pressure), there is no problem such as destruction of foam cells even without providing a clearance as described above. The desired synchronized embossed sheet can be easily obtained. The foaming ratio of the foam layer is 2
．． When it exceeds 5 times, it is preferable to provide a clearance as the expansion ratio increases.

Also, heating during embossing is done using a commonly used electric heater.
Infrared or extended infrared heaters, ceramic heaters, etc. are preferred.

Also, the embossing rolls used here include those with a squeezed pattern formed by mill pressing, those with a squeezed pattern formed by corrosion (etching), those with a squeezed pattern formed by electroforming, silicone resin, etc. Any type of heat-resistant synthetic resin with drawn patterns can be used, but in particular, electroforming embossing rolls that can produce the same surface shape from natural materials, and rolls made of synthetic resins such as silicone. is preferable, and electroforming embossing rolls are more preferable from the viewpoint of durability, shape retention (less changes in size and shape due to temperature changes), and coolability.

(Operation and Effect) The present invention forms a layer of a foamable synthetic resin composition on the surface of a base material, prints an arbitrary pattern on the surface with a printing ink containing a foaming inhibitor, and then prints a transparent or semi-transparent pattern on the surface. After forming a transparent synthetic resin layer, it is heated and foamed to reveal an uneven pattern that matches the printed pattern, and an embossing roll with a desired design on its surface is used to form a shibori pattern using a heated embossing method. By doing so, it is possible to easily and economically produce a harmonized embossed sheet with a rich design, in which the printed pattern and the uneven pattern match, and a delicate and sharp drawing pattern is formed on the surface.

In addition, if the average degree of polymerization of the synthetic resin used in the foamable synthetic resin composition is 1200 or more, the average polymerization degree of the synthetic resin used in the transparent or translucent synthetic resin layer formed on the surface of the foamable synthetic resin composition through the printed pattern is The degree of polymerization must be 100 or more higher than the average degree of polymerization of the synthetic resin used in the foamable synthetic resin composition, and the expansion ratio must be 4 times or less, so that embossing using an embossing roll is possible. The desired synchronous embossed sheet can be easily produced without problems such as foam cell destruction and surface roughening due to suppression of the embossing roll of the foam layer which is softened or melted by heating.

Furthermore, the present invention adds design expression by a squeeze pattern made on an embossing roll to the design expression that perfectly matches the printed pattern and the uneven pattern by multicolor printing using printing ink that partially contains a foaming inhibitor. Finally, a sheet-like product with unprecedented complexity and delicate decoration was obtained, which is suitable for use in building materials such as flooring and wall materials, vehicle seats, bags, furniture, etc. It is something.

Next, examples will be given to explain the present invention in more detail, but the present invention is not limited thereto.

(Example) Examples 1 to 2, Comparative Example 1 Using a test coater with an effective machine width of 450z, the surface of 0.95% thick inorganic filler paper whose main components are glass fiber, pulp, inorganic filler, and binder was coated. Apply the expandable vinyl chloride resin pastes (n) to (IV) listed in Table 1 to the surface using a doctor knife to a thickness of 0.45X, and
The foamable vinyl chloride resin base) (II) to (IV) was passed through a heating furnace set at 'i'oC at a speed of 2 m and 7 minutes.
was heated to gel. A multicolor gravure print with a wood grain pattern is applied to this surface, and the joints corresponding to the seams between the wooden boards are printed with printing ink containing an inhibitor).
The transparent vinyl chloride resin base described in 1) (1) was applied with a doctor knife to a thickness of 0.3%, and 17
The transparent vinyl chloride resin paste (■) was heated and gelled by passing through a heating furnace set at 0° C. at a speed of 2 m and 7 minutes. After that, the heating furnace set at 190°C was heated to L1 to L4.
The total thickness immediately after foaming is 2.2 to 2.5 m at a speed of 7 minutes.
z, and an embossing device installed in-line immediately after the heating furnace uses an electroforming embossing roll with a grain design similar to that of natural wood, and heats it with an electric heater (the foam layer undergoes secondary foaming). Embossing was performed (the clearance (gap) between the embossing roll and the backup roll was set to L9~&1%, the pressing force of the embossing roll was sl/aj (gauge pressure)).

The results are shown in Table-2.

As is clear from Table 2, the average degree of polymerization of the vinyl chloride resin used in the foamable vinyl chloride resin paste composition is 12.
With the formulation of 10.1455, embossing can be performed without any problems by setting appropriate embossing conditions.The resulting matched embossed sheet has a delicate wood grain design similar to natural wood, and is suitable as a flooring material. there were.

Table 2 Examples 3 to 4, Comparative Examples 2 to 3 Using a test coater with an effective machine width of 450
, 68X thick inorganic filler paper was coated with foamable vinyl chloride resin pastes (D) to (odors) listed in Table 3 using a doctor knife so as to have a thickness of 0.63%, and heated at 165°C.
The foamable vinyl chloride resin pastes (D) to (6) were heated and gelled by passing through a heating furnace set at a rate of 2 noodles/minute. Multicolor gravure printing with a wood grain pattern is applied to this surface, and the joints corresponding to the joints between the wooden boards are printed with printing ink containing an inhibitor), and the transparency described in Shikarukoga-3 is applied. PVC resin pastes (4) to (C) were applied to a thickness of 1 s% using a doctor knife in the combinations shown in Table 4, and passed through a heating furnace set at 165°C at a speed of 2 W. The transparent vinyl chloride resin paste (4) to (C)
was heated to gel. After that, it was passed through a heating furnace set at 195°C at a speed of 4 m for 7 minutes, with a total thickness of L9 to 2.1X immediately after foaming (immediately after exiting the foaming furnace), and installed in-line immediately after the heating furnace. Heat embossing was performed using an electric heater using an electroforming embossing roll with a wood grain design similar to that of natural wood. (Heating conditions are such that the electric heater second foam layer does not undergo secondary foaming, clearance between the embossing roll and backup roll is 20 (nashi), pressure of the embossing roll: 2 noodles/
- (gauge pressure)).

The results are shown in Table 4.

Hata 1 Viscosity reducer manufactured by Bic Chemie As is clear from Table 4, the average degree of polymerization of the vinyl chloride resin used in the foamable vinyl chloride resin paste composition is 1.
The average degree of polymerization of the vinyl chloride resin used in the transparent vinyl chloride resin layer formed through printing in 455 is the average degree of polymerization of the vinyl chloride resin used in the foamable vinyl chloride resin paste composition! 7100 or higher, air bubbles will be generated at the interface between the foam layer and the transparent layer, and the transparency and surface smoothness will not deteriorate, and by setting the foaming ratio to about 2 times or less, it can be used as an embossing roll. Even if the clearance with the backup roll is 0 (without creating a gap), the embossing work can be carried out without any problems without destroying the foam cells due to the suppression of the embossing roll, and the resulting synchronous embossed sheet resembles natural wood. It has a delicate and sharp grain pattern, making it suitable for flooring.

Claims (1)

[Claims] A layer of a foamable synthetic resin composition is formed on a base material, and an arbitrary pattern is printed on the surface with a printing ink containing a foaming inhibitor.
After forming a transparent or semi-transparent synthetic resin layer on top of the resin layer, it is heated and foamed to reveal an uneven pattern, and then an embossing roll with an arbitrary design on the surface is used to form a squeeze pattern. In the method for producing a synchronized embossed sheet with a matching uneven pattern, the average degree of polymerization of the synthetic resin used in the foamable synthetic resin composition is 1200 or more, and the average polymerization degree of the synthetic resin used in the transparent or translucent synthetic resin layer is A method for producing a tuned embossed sheet, characterized in that the degree of polymerization is 100 or more higher than the average degree of polymerization of the synthetic resin used in the foamable synthetic resin composition, and the expansion ratio is 4 times or less.