JPH10291288A - Decorative sheet, decorative laminated sheet, and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent a top coat layer from being broken down and whitened even though post processing such as bending, embossing, etc., is executed by a method wherein a top coat unhardened layer capable of being post processed which contained aqueous active energy rays setting resin, is formed on an embossed sheet. SOLUTION: Ozone gas is at first blown to both surfaces of polyolefin resin sheet 3 extruded with an extruder. Then, the ozone-treated resin sheet 3 is solidified by cooling, and embossing is applied to one side surface of the resin sheet 3. Thereafter, printing is applied to the other side surface to form a printed surface 2. A resin-made base mateal layer 1 is formed on the printed layer 2. lastly, a top coat layer 4 is formed on one side embossed surface of the polyolefin resin sheet 3 containing the active energy setting resin of, for example, ultraviolet rays setting resin or the like, and dried at a specific temperature to obtain a decorative sheet 20. The decorative sheet 20 is bonded onto a board with an adhesive to manufacture a decorative laminated sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet on which, for example, printing and embossing have been performed. The present invention also relates to a decorative plate using such a decorative sheet.

[0002]

2. Description of the Related Art A decorative sheet mainly has an embossed sheet on which printing and embossing have been performed, and a base material such as paper and plastic. The embossed sheet is usually provided with a top coat layer in order to improve the surface chemical resistance, stain resistance, scratch resistance and the like. As the top coat layer, a layer obtained by applying a thermosetting resin by various coating methods such as gravure coating and curing the same is generally used. The decorative sheet manufactured in this way is bonded to, for example, a wooden board with a thermosetting adhesive to be processed into a decorative board. Such a decorative board is used, for example, as a woodwork product by post-processing such as bending and embossing.

[0003] However, there has been a problem that the top coat layer which has already been cured is broken or whitened at the stage of post-processing such as bending, wrapping, and embossing of the decorative board, for example, V-cut.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems.
It is an object of the present invention to provide a decorative sheet and a decorative sheet that do not cause breakage or whitening of the top coat layer even after post-processing such as bending and embossing.

[0005]

Means for Solving the Problems First, the present invention provides a base material layer, a printing layer provided on the base material layer, an embossed sheet provided on the printing layer, and an embossed sheet provided on the embossed sheet. Provided is a decorative sheet having a top coat uncured layer that is formed and can be post-processed and contains a water-based active energy ray-curable resin.

According to the present invention, secondly, there is provided a decorative sheet substrate having a base layer, a printing layer provided on the base layer, and an embossed sheet provided on the printing layer. A decorative sheet, characterized in that a topcoat coating layer obtained by applying a topcoat coating solution containing an aqueous active energy ray-curable resin thereon is dried to form a post-processable topcoat uncured layer. And a method for producing the same.

[0007] Third, the present invention relates to a base material layer, a printing layer provided on the base material layer, an embossed sheet provided on the printing layer, and an aqueous active material formed on the embossed sheet. Provided is a decorative board provided with a decorative sheet having a post-processable top coat uncured layer containing an energy ray-curable resin, and a board adhered on the base layer.

[0008] Fourth, the present invention provides a base material layer, a printing layer provided on the base material layer, an embossed sheet provided on the printing layer, and an aqueous active material formed on the embossed sheet. A decorative sheet having a top coat layer including an energy ray-curable resin, and a decorative sheet including a board formed on the base layer, wherein the top coat layer is obtained by post-processing the decorative sheet. Provided is a decorative board characterized by being hardened.

Fifth, the present invention provides a decorative sheet substrate having a base layer, a printing layer provided on the base layer, and an embossed sheet provided on the printing layer. A step of applying a topcoat coating solution containing an aqueous active energy ray-curable resin on the top, drying the obtained topcoat coating layer to form a topcoat uncured layer, and obtaining a decorative sheet, and the base material Production of a decorative board comprising the steps of: adhering the board to a layer to form a decorative board, performing post-processing of the decorative board, and irradiating the post-processed top coat layer with active energy rays and curing. Provide a way.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have made intensive studies to prevent whitening and destruction of a top coat layer, and have accomplished the present invention. The present invention is roughly classified into the following five aspects.

According to a first aspect of the present invention, there is provided a base layer, a printed layer, an embossed sheet, and a post-processable top coat formed on the embossed sheet and containing an aqueous active energy ray-curable resin. A decorative sheet having a configuration in which cured layers are sequentially laminated is provided.

According to a second aspect of the present invention, there is provided a method of manufacturing a decorative sheet according to the first aspect. In this method, a base material layer, a printing layer, a decorative sheet base material having a configuration in which an embossed sheet is laminated is prepared, and a top coat coating solution containing an aqueous active energy ray-curable resin is applied on the embossed sheet, thereby obtaining The applied top coat layer is dried to form a top coat uncured layer.

According to a third aspect of the present invention, there is provided an embodiment of a decorative board using the decorative sheet according to the first aspect. The decorative board includes a decorative sheet according to the first aspect and a board adhered to the base layer side of the decorative sheet. The top coat of this decorative sheet is an uncured layer and can be post-processed as needed. Further, the post-processed decorative board can be easily cured by irradiating it with active energy rays.

According to a fourth aspect of the present invention, there is provided another embodiment of a decorative board using the decorative sheet according to the first aspect. This decorative board is composed of a decorative sheet according to the first aspect and a board adhered to the base layer side of the decorative sheet, and the top coat of the decorative board is a cured layer, and after post-processing, Has been cured.

According to a fifth aspect of the present invention, there is provided a method of manufacturing a decorative panel according to the fourth aspect using the decorative panel according to the third aspect. In this method, a laminate having a base material layer, a printing layer, and an embossed sheet is prepared, and a top coat coating solution containing an aqueous active energy ray-curable resin is applied on the embossed sheet, and the obtained top coat is applied. A step of drying the layer to form an uncured top coat layer to obtain a decorative sheet, a step of bonding a board to a base layer of the decorative sheet to form a decorative panel, and performing post-processing of the decorative panel; A step of irradiating an active energy ray to a later uncured top coat layer to cure the top coat is included.

In the invention according to the first to fifth aspects, an aqueous active energy ray-curable resin is used in the top coat layer. This top coat layer can be formed using a top coat coating solution containing an active energy ray-curable resin. Apply topcoat coating solution,
By drying, an uncured top coat layer is obtained. The uncured top coat layer is cured by irradiating active energy rays after the post-processing.

The active energy ray-curable resin used in the present invention has an uncured top coat layer obtained by drying.
The Tg and the like are appropriately adjusted so that there is no stickiness at room temperature and sufficient flexibility is provided. Furthermore, the functional group concentration and Tg are adjusted so that the cured layer has sufficient flexibility, and the workability is not problematic.

A conventional thermosetting resin used as a top coat layer of a decorative sheet or a decorative plate has a strong sticky feeling only by drying, and is difficult to handle. However, the uncured top coat layer of the decorative sheet and decorative sheet according to the present invention has no stickiness, is easy to handle, has sufficient flexibility, and has good workability. Further, in the decorative sheet and the decorative plate according to the present invention, since the hardening is performed after the post-processing, the top coat layer is not broken or whitened.

The active energy ray-curable resin used in the present invention includes, for example, an ultraviolet ray-curable resin and an electron beam-curable resin. Specific examples of such resins include mono- or polyfunctional acrylate polymers or oligomers such as polyester acrylate, polyurethane acrylate, polyether acrylate, epoxy acrylate, and silicone acrylate, alone or blended with an acrylic aqueous emulsion resin. Can be

Examples of resins that can be blended with the active energy ray-curable resin include general-purpose aqueous resins such as polyvinyl alcohol, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, polyacrylic acid, casein, gelatin, starch, polyvinylpyrrolidone, polyacrylamide, and the like. Water-soluble resins of these derivatives and at least one or two or more water-dispersible resins such as styrene-butadiene copolymer, polyvinyl acetate and polyacrylate can be used in combination.

In addition to the leveling agent and the titanium pigment, a diluent and the like can be added to the top coat coating solution. In the case of an aqueous emulsion, a dispersant, an antifoaming agent, a wetting agent, an anti-blocking agent, a thickener and the like are used. Can be added.

As the leveling agent, for example, inorganic fillers such as silica, calcium carbonate, aluminum hydroxide and magnesium hydroxide can be used. Mixing of the top coat coating liquid and various additives can be performed using various mixers such as a Henschel mixer, a hyper mixer and a homo mixer.

As a method of applying the topcoat coating solution,
Knife coater, nozzle coater, gravure coater,
Various coating methods such as a microgravure coater, a rotary coater, a reverse roll coater, a comma coater, and a lip coater can be used.

As a method for drying the top coat coating layer,
Hot air or infrared irradiation alone or a combination thereof is preferably used. As the drying temperature, a temperature range that does not affect the softening of the base material or the embossed sheet, etc., that dries the moisture, and that takes into consideration the thickness of the target coat layer and the like is selected.

The method for curing the resin can be appropriately selected from, for example, ultraviolet irradiation, electron beam irradiation, and the like, as necessary. In particular, curing by electron beam irradiation is preferable in some cases because it can be cured even when the top coat layer lacks transparency.

In the case of ultraviolet curing, the presence of a reaction initiator in the top coat resin is required. As a reactive initiator necessary for curing by irradiation with ultraviolet rays, either a self-opening type or a hydrogen abstraction type can be used, but in the case of a hydrogen abstraction type, the presence of a sensitizer is also required. It can be appropriately selected in consideration of the emission wavelength range of the irradiation lamp and the degree of curing due to sensitivity. UV irradiation dose is preferably from ^{10mJ / cm 2 ~5000mJ / cm 2} . As the irradiation method, a method can be appropriately selected according to necessary conditions such as a batch method or a continuous conveyor method.

As an irradiation method of the electron beam irradiation, an electro-curtain method, a scan beam method, or the like can be used. In addition, these methods can be performed using a conveyor system, a batch system, or the like. The electron beam irradiation dose is preferably from 5 to 150 KGy.

Hereinafter, the present invention will be specifically described with reference to the drawings. FIG. 1 is a schematic sectional view illustrating an example of a decorative board according to the present invention. As shown, this decorative board 20 is
For example, a wooden board 10 and a decorative sheet 5 provided on the upper board 10 with an adhesive layer 11 interposed therebetween. The decorative sheet 5 is bonded to the board 10 by the adhesive layer 11. It comprises a printing layer 2, an embossed sheet layer 3, and a top coat layer 4, which are sequentially laminated on the material layer 1 and the base material layer 1.

The decorative sheet 5 is formed, for example, as follows. First, an example of a manufacturing apparatus used will be described. FIG. 2 is a schematic diagram showing an example of a manufacturing apparatus used for manufacturing a decorative sheet according to the present invention.

As shown in the figure, this apparatus contains a molten embossed sheet material, for example, a polyolefin resin 21, and an extruder 22 for extruding the material, an ozone treatment means 23 provided downstream of the extruder 22 and a backup roll 25 in this order. , A cooling embossing roll 24, a peeling roll 26, a solid printing means 27, a pattern printing means 28, a back coat applying means 29, and a top coat applying means 30.

In this apparatus, first, while extruding the polyolefin resin by the extruder 21, ozone gas is blown by the ozone treatment means 23 onto both surfaces of the extruded polyolefin resin sheet 3. Next, the ozone-treated polyolefin-based resin sheet 3 is introduced between the backup roll 25 and the cooling embossing roll 24, where it is cooled and solidified, and one surface of the polyolefin-based resin sheet 3 is embossed and peeled. Roll 2
6 to peel off. The peeled polyolefin-based resin sheet 3 is then subjected to solid printing means 27 and pattern printing means 2.
8, where the other side is printed to form the printed layer 1. The base layer 1 made of resin is formed on the printing layer 1 by, for example, the back coat applying unit 29.
Finally, a polyolefin-based resin sheet 3 containing an active energy ray-curable resin such as an ultraviolet curable resin is introduced into the top coat applying means 30, and a top coat layer 4 is formed on one embossed surface. The decorative sheet 20 is obtained by drying at, for example, about 60 to 80 ° C. by a drying unit (not shown).

The decorative sheet thus obtained is then bonded on a board with an adhesive, and after post-processing,
For example, the decorative board of the present invention can be manufactured by curing with active energy rays such as ultraviolet rays.

The resin used in the embossed sheet of the present invention includes, for example, polyolefin resins and vinyl chloride resins. As the polyolefin resin, particularly, a homopolymer, a random polymerization polymer, a block polymerization polymer, a low-density polyethylene, an α-olefin, or an ethylene-propylene copolymer rubber as a soft component, or a mixture of 5 to 30% by weight of a polypropylene can be used. What consists of resin added by mixing can be used.

As the above-mentioned polypropylene, the homopolymer is used when heat resistance and hardness are required for the obtained sheet, the block polymer is used when impact resistance is required, and the impact resistance and low temperature processing are performed. When the properties and transparency are required, a random polymer can be appropriately selected. However, in order to obtain sufficient low-temperature processability such as a vinyl chloride resin sheet, it is preferable to use a random polymerization type polypropylene.

The amount of the soft component to be added is preferably 5% by weight or more and 30% by weight or less, and if it is less than 5% by weight, there is no effect on low-temperature workability, and if it exceeds 30% by weight, the elasticity of the obtained sheet is reduced. Too big. The soft component to be added may be simply mixed. This not only simplifies the process, but also impairs transparency when cross-linking them, and causes whitening due to the impact on the interface of the soft component that forms a domain structure by cross-linking in polypropylene. This is because the inconvenience may occur.

The vinyl chloride resin sheet is most commonly used as an embossed sheet because it has properties such as moderate flexibility, chemical resistance, stain resistance, and weather resistance. However, vinyl chloride resin generates hydrogen chloride gas during incineration,
Since there is a possibility of generating dioxin, it is preferable to use a polyolefin-based resin from the viewpoint of environmental problems.

Other additives used in the embossed sheet include pigments for obtaining hiding properties in the decorative sheet, and the like.
A hindered amine-based light stabilizer for improving light resistance, a benzotriazole-based ultraviolet absorber, and the like can be used. Pigments and the like can be used in any ratio depending on the desired coloring. The amount of the hindered amine light stabilizer is 0.1 to 100 parts by weight of the embossed sheet material.
The addition amount of 1 part by weight of the benzotriazole-based ultraviolet absorber is preferably 0.2 to 1.5 parts by weight.

In the ozone treatment, for example, an ozone concentration of 20 to
100g / Nm ^3, ozone flow rate 1~10Nm ³ / h (2
In the case of 50 mm), the surface can be oxidized by spraying on both surfaces of the molten polyolefin resin.

As the embossed cooling roll,
It is preferable that the shape of the emboss is a semi-mat because the printability afterwards becomes good. In order to cool and solidify the molten resin, the molten resin can be pressed against the embossed cooling roll by a touch roll. Alternatively, besides this, a casting method such as an air knife or an air chamber method which is conventionally performed by molding of polypropylene can be used. .

With regard to the pattern printing and the structure and material of the coating layer, in addition to the solid printing, pattern printing, top coat and back coat shown in FIG.
Various layer configurations described in JP-A-32951, JP-A-59-10371, JP-A-63-137772 and the like are possible.

As an ink used for an arbitrary pattern,
There is no particular limitation as long as the adhesiveness with the vinyl chloride or polyolefin resin is good, but a urethane-based ink is preferred from the cohesive strength of the ink itself and versatility. In addition, chlorinated olefin-based inks can be used because they adhere to the olefin-based sheet. However, this ink tends to be somewhat difficult to handle because it has a tendency to dislike chlorine.

In order to improve the adhesion to the polyolefin resin, an isocyanate curing agent can be added to the solid ink. The drying temperature of each ink is preferably suppressed to about 100 ° C. in order to prevent the printing of the next step from becoming difficult due to the softening of the polyolefin resin itself.

When the decorative sheet obtained in this manner is used, a decorative sheet having a top coat uncured layer containing an active energy ray-curable resin is stuck on a board to form a decorative plate, and further, such as bending, embossing, etc. By irradiating with active energy rays and hardening after the post-processing, it is possible to suppress the destruction and whitening of the top coat layer in the post-processing.

[0044]

The present invention will be described below in more detail with reference to examples. However, the present invention is not limited by these. The following test method is used for whitening or destruction of the coating film during processing such as bending and embossing of the decorative board.

Using a device specified in ASTM D-1593-81 “Characteristics test concerning polyvinyl chloride”, a bending test was carried out at 5 ° C., and the whitening state of the sheet was determined as follows. Visual evaluation is performed at the stage.

A: No whitening or destruction of the coating film is observed. B: Coating whitening or destruction is slightly observed. C: Coating whitening or destruction is clearly observed.

Using the evaluation methods described above, the following examples and comparative examples were examined. Example 1 A polyolefin resin containing 15% by weight of low-density polyethylene with respect to 100% by weight of polypropylene was used. To this, a phenolic antioxidant was added to 0.1.
2% by weight, 0.3% by weight of hindered amine light stabilizer, 0.5% by weight of benzotriazole type ultraviolet absorber, 0.2% by weight of antiblocking agent, 10% concentration of colorant (pigment) An ozone gas (ozone concentration: 40 g / Nm ³ , ozone flow rate: 4 Nm ³ / h (250 mm)) was blown while extruding the resin mixture to which the master batch was added by 10% by weight with an extruder. next,
The extruded resin sheet is introduced between the cooling roll and the touch roll on which the semi-matte emboss is applied, and the thickness is 90 μm.
m semi-matte sheet was obtained. After solid printing with a two-component curing solid ink by gravure printing, a grain pattern is formed using "Ramister" (manufactured by Toyo Ink Mfg. Co., Ltd.) with a two-component resin-absorbent urethane mat coloring ink (Toyo Ink). A conduit pattern was printed using Ink Manufacturing Co., Ltd.), and a two-component urethane gloss resin was printed on the entire surface to absorb the conduit pattern resin. In the obtained sheet, the applied pipe pattern was faithfully synchronized and reproduced, and an atmosphere close to that of real wood was reproduced. On the sheet, a back coat layer made of a urethane-based resin was applied by a gravure coat method in order to improve the adhesion to the board. Thereafter, a top coat agent having the composition shown in Table 1 below was applied by a comma coat method so as to be about 10 μm after drying. About 60-80
A decorative sheet was prepared by performing sufficient drying in an oven at a temperature of ° C.

[0048]

[Table 1]

Example 2 100 g of a two-component aqueous emulsion adhesive (manufactured by Konishi Co., Ltd .: "CVC36") on a medium fiber board (MDF board).
/ M ² , and the decorative sheet prepared as in Example 1 was bonded. The veneer thus obtained is V-grooved from the MDF substrate side to immediately before the sheet, subjected to post-processing such as bending, so-called bending, embossing, and then to the uncured top coat layer in that state. 120W / c
Using a high-pressure mercury lamp with a wavelength of about 900 mJ / cm ² , irradiate ultraviolet light with an integrated light amount so that there is no unirradiated part.
Irradiation was performed at different angles to completely cure the uncured top coat layer.

A whitening resistance test was performed on the decorative plate processed in this manner. Table 5 shows the results. Example 3 A topcoat agent having the composition shown in Table 2 below was applied to a resin sheet printed in the same manner as in Example 1, and dried in the same manner as in Example 1 to produce a decorative sheet.

[0051]

[Table 2]

Example 4 Using the same decorative sheet as in Example 3, a decorative plate processed in the same manner as in Example 2 was formed. A whitening resistance test was performed on the obtained decorative board in the same manner as in Example 2. Table 5 shows the results.

Example 5 A topcoat agent having the composition shown in Table 3 below was applied to a resin sheet printed in the same manner as in Example 1, and dried in the same manner as in Example 1 to produce a decorative sheet.

[0054]

[Table 3]

Example 6 The same decorative sheet as in Example 5 was used and bonded to an MDF board in the same manner as in Example 2, and after post-processing, an acceleration voltage of 200 kV was applied to the uncured top coat layer. Integrated irradiation amount: An electron beam of 39 KGy was irradiated by a conveyor system, and the uncured top coat layer was cured to form a processed decorative plate. A whitening resistance test was performed on the obtained decorative board in the same manner as in Example 2. Table 5 shows the results.

COMPARATIVE EXAMPLE 1 A decorative sheet prepared in the same manner as in Example 1 was used to form a decorative board in the same manner as in Example 2, and then irradiated with UV to completely cure the coating, and then folded. And post-processing such as embossing. The processed decorative board was subjected to a whitening resistance test. Table 5 shows the results.

Comparative Example 2 A decorative sheet was produced in the same manner as in Example 1. At that time, a thermosetting compound coating liquid shown in Table 2 was used as a top coat agent.

[0058]

[Table 4]

After application, the coating was dried at 60 ° C. for about 96 hours or more to completely cure the coating, and then a decorative plate was prepared in the same manner as in Example 2 and then subjected to post-processing such as bending and embossing. Was done. A whitening resistance test was performed on the obtained decorative plate. Table 5 shows the results.

[0060]

[Table 5]

As is clear from Table 5, the decorative sheets and decorative sheets of Examples 2, 4 and 6 did not show any whitening or destruction of the top coat layer, but the ultraviolet curable type was found in the top coat layer. In both Comparative Example 1 in which the resin was cured before post-processing and Comparative Example 2 in which the thermosetting resin was cured before post-processing, whitening or destruction of the topcoat layer was clearly observed.

[0062]

According to the present invention, it is possible to obtain a decorative sheet and a decorative sheet in which the top coat layer is not broken or whitened even after post-processing such as bending and embossing.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a decorative board according to the present invention.

FIG. 2 is a schematic view showing an example of a manufacturing apparatus used for manufacturing a decorative sheet according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Adhesive layer 3 ... Embossed sheet 4 ... Top coat layer 5 ... Decorative sheet 10 ... Board 11 ... Adhesive layer 20 ... Decorative board 21 ... Polyolefin resin 22 ... Extruder 23 ... Ozone treatment means 24 ... Cooling embossing roll 25 ... Backup roll 26 ... Release roll 27 ... Solid printing means 28 ... Pattern printing means 29 ... Back coat applying means 30 ... Top coat applying means

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Yoshihiro Hino 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd.

Claims (5)

[Claims] 1. A base material layer, a printing layer provided on the base material layer, an embossed sheet provided on the printing layer, and an aqueous active energy ray-curable resin formed on the embossed sheet. A decorative sheet provided with an uncured top coat layer that can be post-processed. 2. A base material layer, a printing layer provided on the base material layer, and a decorative sheet base material having an embossed sheet provided on the printing layer are prepared, and an aqueous active energy is provided on the embossed sheet. A method for producing a decorative sheet, characterized by drying a topcoat coating layer obtained by applying a topcoat coating solution containing a line-curable resin to form an uncured topcoat layer that can be processed later. 3. A base material layer, a printing layer provided on the base material layer, an embossed sheet provided on the printing layer, and a water-based active energy ray-curable resin formed on the embossed sheet. A decorative board comprising: a decorative sheet having a post-processable top coat uncured layer; and a board adhered on the base layer. 4. A base material layer, a print layer provided on the base material layer, an embossed sheet provided on the print layer, and a water-based active energy ray-curable resin formed on the embossed sheet. A decorative sheet having a top coat layer including:
A decorative board comprising: a board formed on the base material layer; wherein the top coat layer is cured after post-processing the decorative board. 5. A base material layer, a printing layer provided on the base material layer, a decorative sheet base material having an embossed sheet provided on the printing layer are prepared, and an aqueous active energy is provided on the embossed sheet. A step of applying a topcoat coating solution containing a line-curable resin, drying the obtained topcoat coating layer to form a topcoat uncured layer, obtaining a decorative sheet, and bonding the board to the base layer And forming a decorative board, and performing post-processing of the decorative board, and irradiating the topcoat layer of the post-processed decorative board with active energy rays to cure the decorative board.