JPS6056102B2 - Method for manufacturing decorative material having a synchronized embossing pattern - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a decorative material having a synchronized embossed pattern, and in particular to a method for changing the curability of the film when irradiated with ultraviolet rays by combining an ultraviolet curable resin film and a pattern layer in contact with the same. The present invention aims to produce a decorative material having a synchronized embossed pattern through a simple process.

Interior or exterior materials such as furniture, wall materials, floor materials, etc., or decorative materials used as surface materials for these materials, may have a harmonious embossed pattern, that is, a relief or uneven pattern that is in harmony with the pattern, either as a decoration or as a practical matter. It is especially preferred because it enhances the feeling.

Conventionally, the following methods are known as methods for applying a coordinated emboss pattern to decorative materials using ultraviolet curable resins. (1) A pattern is provided on the base material using a substance containing a photopolymerization initiator, and then an ultraviolet curable resin is applied,
A method of irradiating ultraviolet rays (2) A method of applying an ultraviolet curable resin on a substrate with a pattern containing a photocuring inhibitor and then irradiating it with ultraviolet rays (3) A method of applying ultraviolet rays to the substrate A method in which a film coated with a resin and pre-patterned with a photopolymerization initiator is brought into contact with the surface, and then ultraviolet rays are irradiated to adhere or peel the film (4).
) A method in which an ultraviolet curable resin is applied to a base material, a film on which a patterned photocuring inhibitor has been applied in advance is brought into contact with the surface, and then ultraviolet rays are irradiated to adhere or peel the film (5) as described above. (1) A method in which a photopolymerization initiator or a photocuring inhibitor is applied to the entire surface in the methods of (2), (3), and (4), and a substance that inhibits the action of these agents is provided in a pattern (6) Substrate (7) A method of applying ultraviolet curable resin to the substrate and irradiating the ultraviolet rays through a film patterned with a substance that blocks or absorbs ultraviolet rays, and (7) the above (1) and (2). (3)(
4) A method in which the patterned film in methods of (5) and (6) is made into an impregnated film such as non-woven fabric and embedded between layers of an ultraviolet curable resin. These methods can be roughly divided into the following based on the principle of forming unevenness: It is classified as follows.

(a) A method in which the ultraviolet curable resin on the base material contracts during curing to form a recessed portion in the delayed cured portion. (b) A method in which the uncured portion of the ultraviolet curable resin on the substrate is resolvated with a solvent to form a recessed portion. and (c) a method of removing the uncured portion of the ultraviolet curable resin on the base material by a physical method such as brushing to form a concave portion. However, none of the above methods (1) to (7) This method includes a step of applying an ultraviolet curable resin to the material, which has the disadvantage that the entire process becomes extremely complicated.

In addition, the cured ultraviolet curable resin becomes extremely rigid, so it can be bent by making a V cut from the base material side (i.e. cutting a ■-shaped groove) and making use of the flexibility of the cured resin film. It also has the disadvantage that it cannot be used to form corners. In addition, the following drawbacks are recognized for each method. That is, in methods (1) to (4), which are considered to be the prototype of methods (1) to (7) above, (
Methods 1 and 2 have the disadvantage that the pattern becomes unclear when using the ultraviolet curable resin and that a sufficient embossing effect cannot always be obtained. In addition, an improved embossing effect can be obtained by using the auxiliary pattern film (8) and (4), but in this case, the pattern layer is on the surface, so the pattern has to be synchronized with the uneven pattern. In order to do this, the pattern layer must adhere to both the cured resin (cured ultraviolet curable resin; the same applies hereinafter) and the auxiliary film, or it must be peeled off from the film and transferred to the cured resin. must have the characteristics of For this reason, there is a drawback that the vehicle for the printing ink constituting the pattern layer is restricted. In addition, since both of the above methods are coating type,
If a thermoplastic resin such as polyvinyl chloride is used as a base material, there is a drawback that the base material deteriorates due to the solvent mixed therein.

This drawback is particularly noticeable when the unevenness forming method is one of the above-mentioned methods (a) and (b). In addition, in the case of method (c), solvent deterioration of the base material is not so much of a problem, but unless the hardness of the cured and uncured areas is precisely controlled, the surface will be scratched, and generally the glossy surface will be I can't get it. The drawback of the above-mentioned conventional method is that the behavior or characteristics of the ultraviolet curable resin coated on the base material are basically used to form the uneven pattern.

However, according to the research of the present inventors, the above-mentioned (a
) The characteristics of the ultraviolet curable resin used in the method, namely:
The property of preferential shrinkage of delayed curing portions to form concave portions is not unique to coating-type ultraviolet curable resins. That is, an ultraviolet curable resin film obtained by forming an uncured ultraviolet curable resin into a film having a hardness enough to have self-shape maintaining properties also has similar shrinkage characteristics upon curing. ) In the past, the present inventors have developed a method using an ultraviolet absorber, a method of blocking ultraviolet rays, a method of reflecting ultraviolet rays, etc. as methods for applying a synchronized emboss pattern to the ultraviolet curable resin film. All of these methods are methods in which the irradiation efficiency of the ultraviolet rays irradiated onto the ultraviolet curable resin film is varied.

If a pattern layer that has the effect of changing the efficiency of UV ray irradiation is formed on the UV curable resin film by printing, etc., and then irradiated with UV rays, the above-mentioned drawbacks of using a coated UV curable resin can be avoided. A decorative material that can easily form a synchronized embossed pattern and that includes a cured film (which means a cured ultraviolet curable resin film; the same shall apply hereinafter) that has this synchronized embossed pattern can be It can be used as a covering material on the base material. As a result of further intensive research on these methods, the present inventors have found that a UV-curable resin film can be prepared by infiltrating a polymerization inhibitor and/or a polymerization accelerator into the UV-curable resin film by printing or the like, and then polymerizing it by UV irradiation. By partially changing the crosslinking efficiency or polymerization efficiency to obtain a cured film with different degrees of curing between the printed pattern layer and the other parts, a cured film having a clear embossed pattern with even larger irregularities and a synchronization effect can be obtained. This is what I discovered.

To describe the present invention in more detail, a laminate having an ultraviolet curable resin film and a pattern layer formed of an ink containing a polymerization inhibitor and/or a polymerization accelerator on at least one surface of the ultraviolet curable resin film is irradiated with ultraviolet rays, and the ultraviolet curable resin film is cured by ultraviolet rays. By changing the crosslinking efficiency or polymerization efficiency of the ultraviolet polymerization composition that crosslinks or polymerizes within the plastic film with the polymerization inhibitor and/or polymerization accelerator contained in the ink, it is possible to This method is characterized in that the UV-curable resin film is made of an ultraviolet-curable resin film with different degrees of curing in different parts, and an uneven pattern that is synchronized with the pattern layer is imparted to the ultraviolet-curable resin film.

The following mechanism is considered for unevenness formation. available. As an example, a case where a polymerization inhibitor is used will be described. Incidentally, when a polymerization accelerator is used, the opposite is true. However, according to the research conducted by the present inventors, the effect is not significant when a pattern layer is formed using only a polymerization accelerator; rather, it is more effective to use it in combination with a polymerization inhibitor pattern as described below. be. First, by irradiating ultraviolet rays, a relatively soft part with a low crosslinking rate or polymerization rate in contact with the pattern layer and a relatively hard part with a high crosslinking rate or polymerization rate without the pattern layer are generated.

This hardness difference corresponds to the softening temperature difference within the cured film. In addition, due to volume shrinkage due to crosslinking or polymerization reactions, reaction heat accumulated during the formation of the ultraviolet curable resin film, internal stress, and heat radiated from the ultraviolet irradiator, relatively soft It is thought that tension is concentrated in the part, and as a result, a concave part is created compared to a relatively hard part without the pattern layer, and an uneven pattern that is in sync with the pattern layer is generated. Hereinafter, basic aspects of the present invention will be explained in more detail with reference to the drawings.

According to the present invention, in its most basic aspect, the first
As shown in the figure, ultraviolet rays are applied from one side of a laminate A consisting of an ultraviolet curable resin film 1 and a polymerization inhibitor-containing pattern layer 2 that changes the crosslinking efficiency or polymerization efficiency of the polymer composition in the ultraviolet curable resin film. Decorative materials are manufactured by irradiation.

The ultraviolet curable resin constituting the ultraviolet curable resin film 1 is based on 100 parts by weight of a thermoplastic resin such as vinyl chloride resin, acrylic resin, thermoplastic urethane resin, etc.
As the ultraviolet polymerization composition, monomers, oligomers, or prepolymers such as unsaturated polyester resins, spiran resins, unsaturated urethane resins, modified alkyd resins, polyamide resins, acrylic resins, epoxy resins, epoxy-acrylate resins, and diallyl phthalate resins are used. 10
~(4) Parts by weight: O to 3 parts of plasticizers such as acrylic esters such as allyl acrylate and allyl methacrylate, phthalate esters such as dioctyl phthalate and dibutyl phthalate; A small amount of benzoyl as necessary Reaction initiators such as peroxide and azobisisobutyronitrile; 0.5 to 5 parts by weight of photosensitizers such as benzoin alkyl ether and benzophenone; other small amounts of catalysts such as tertiary amines and organometallic compounds, or stearin. A stabilizer such as an acid metal salt is added. Such an ultraviolet curable resin is formed into a film by a calendering method, a casting method, or the like to obtain an ultraviolet curable resin film having a thickness of, for example, 20 to 500 microns. The ultraviolet curable resin film thus obtained maintains a certain degree of flexibility even after curing, and also has the advantage of being able to be V-cut from the substrate side when cured on a substrate. It is preferable that the film be a colorless or colored transparent material for uniform curing in the thickness direction. In addition, the polymerization inhibitors contained in the ink of the pattern layer 2 that change the crosslinking efficiency or polymerization efficiency of the ultraviolet polymerization composition that crosslinks or polymerizes within the ultraviolet curable resin film include 2-ethylanthraquinone, β-
Methylanthraquinone, α-naphthoquinone, cetylamine, laurylamine, triethylenelatramine, N-phenyldiethanolamine, dicyclohexylamine,
Magnesium, N-nitrolyp-tolylhydroxylamine, aluminum N-nitrophenylamine, N-
Memethyldiphenylamine, stearylamine, tri-n-butylamine, N-N-di-n-butylethanolamine, trimethylhydroquinone, )2●5-di-t-
Butylhydroquinone, methylhydroquinone, hydroquinone 4-t-butylcatechol, phenylhydrazine, methoxyhydroquinone, N-methyldiethanolamine,
N*N-dimethylbenzylamine, 4-t-butylcatechol, P-nitroacetophenone, homocatechol, 1,2,4-trihydroxybenzene and the like have good solubility in the ink.

Further, the pattern layer 2 may be colored or transparent, but a synergistic effect can be obtained if it is a black or relatively dark pigment that has the effect of blocking ultraviolet rays and has a hiding power. Similarly, a synergistic effect can be obtained using ultraviolet absorbing substances and ultraviolet reflecting substances. Benzophenones as ultraviolet absorbing substances,
Examples include ultraviolet absorbers that have an absorption wavelength in the ultraviolet region, such as benzotriazoles and acrylates that can form conjugated double bonds. Examples of the ultraviolet reflective material include metals and alloys such as aluminum, zinc, copper, brass, and stainless steel. In any case, the main ingredient that provides the ultraviolet curable resin film 1 with an embossing effect in good synchronization with the pattern layer 2 regardless of the shade of color, from colored to transparent, is a polymerization inhibitor. A laminate A is obtained by printing ink containing each of the reagents on the film 1.

For printing, any printing method such as silk screen, letterpress, offset, gravure, etc. can be adopted. The pattern layer 2 can have a thickness of, for example, 0.1 to 5p. In addition, even if other inks are present between the pattern layer 2 and the film 1, those inks do not have a significant effect on the amount of ultraviolet light transmitted (for example, pigments with extremely hiding power, inorganic pigments, ultraviolet absorbing (4). 1 to 6 μ), there is no particular problem with the effect of the polymerization inhibitor, and there is no problem in normal gravure printing. This means that there are no limitations on the color of ink containing a polymerization inhibitor or on the printing order, and a direct printing method, a back printing method, and a transfer method in gravure printing are possible. A decorative material is obtained by irradiating ultraviolet rays from one side of such a laminate A. At this time, the shape of the unevenness that is generated differs slightly depending on which direction the ultraviolet rays are irradiated. That is, when the laminate A is irradiated with ultraviolet rays from the pattern layer 2 side (that is, the upper side of Fig. 1a), the reaction of the polymerizable composition in the ultraviolet curable resin film is almost completely inhibited, and as shown in Fig. 1b. As shown in the figure, the pattern layer 2 forming portion becomes a recessed portion. On the other hand, when ultraviolet rays are irradiated from the ultraviolet curable resin film 1 side of the laminate A (the lower side of FIG. 1a), the polymerization reaction or crosslinking reaction proceeds in the portion where the polymerization inhibitor is not present. Therefore, there is almost no difference in the degree of hardening between the portion in contact with the pattern layer 2 and the other portions, and the sharpness of the synchronized embossed feel is somewhat impaired. In such a case, ultraviolet rays are irradiated from the pattern layer 2 side (lower side of Fig. 2 a) of the laminate B, which is made by laminating transparent resin films 3 printed by the back printing method as shown in Fig. 42 a. Emboss can be applied with different degrees of hardening. Furthermore, as shown in FIG. 2b, the embossment becomes even larger when the film is heated and fused to a thermoplastic colored resin film (ultraviolet opaque layer) 4 as another base material and then heated and stretched using the softening temperature difference. Addition of the transparent resin layer 3 to the laminate B has effects such as adjusting the gloss of the product decorative material, increasing weather resistance and surface strength, and especially as shown in FIG. 3 or FIG. 6 covering the pattern layer 2 described later. Effective for various uses. In addition, the transparent resin layer 3 is a thermoplastic resin film that is stretched by a calender-fu method or the like during film formation, and the hardness is equal to or lower than the hardness of the part of the cured film that is in contact with the pattern layer after curing. The unevenness effect caused by stretching during ultraviolet irradiation or subsequent heating stretching is influenced by the difference in hardness that occurs within the cured film and the relaxation of internal stress due to heat in the thermoplastic resin film, resulting in a synergistic unevenness effect. On the other hand, the ultraviolet opaque layer has a design effect or a reinforcing effect. In the cases shown in FIGS. 3 and 6, the transparent resin layer 3 can be formed by coating a transparent resin or laminating a transparent resin film with an adhesive or heat.

On the other hand, the ultraviolet opaque layer 4 can be formed by forming a colored resin layer in the same manner, or by first forming a layer of plywood, particle board, paper, metal plate, colored glass, etc. using an adhesive or the like.
It is obtained by adhering to a laminate A as shown in the figure. According to the present invention, a decorative material with excellent decorative effects and surface properties can be obtained by bonding the surface having the pattern layer 2 or the opposite surface to another base material by heat-sealing or using an adhesive. I can do it.

The most basic aspect of the method for producing a decorative material of the present invention has been described above.

However, the following modifications are possible within the scope of the present invention, and unique effects can be expected in each embodiment. First, a transparent resin layer 3 or an ultraviolet non-transparent layer 4 is additionally added to the laminate A consisting of the above-mentioned ultraviolet curable resin film 1 and pattern layer 2 to form a laminate as shown in FIGS. 3 to 6. The method of the present invention can also be carried out by obtaining B and irradiating it with ultraviolet rays from one side. In this case, in any case, it is not effective to use the UV curable resin film 1 in a direction that completely blocks the irradiation of UV rays, or to use it in a direction that allows the UV rays to pass from the UV curable resin film 1 to the pattern layer 2. . That is, in FIGS. 3 to 6, the ultraviolet rays are irradiated from the upper side of each figure. Furthermore, Figure 2 a1 No. 3
In order to obtain a laminate B as shown in FIGS.
A method of adhering this to the ultraviolet curable resin film 1 with an adhesive or the like can also be used.

In order to further clarify the synchronous embossing effect, it is also possible to further increase the degree of curing by using a polymerization accelerator in a portion other than the pattern layer 2 containing the polymerization 1 inhibitor.

Examples of the polymerization accelerator used include sensitizers such as benzoin, acetophenone, benzyl, and benzoin alkyl ether. The most preferable method is to form the pattern layer 2 with an ink containing a polymerization inhibitor as shown in FIG. There is a method in which the pattern layer 5 is formed using a negative printing plate for the pattern layer 2 using an ink containing a mulch agent (water-soluble but releasable to the ink). As a result, a laminate C is obtained. In addition, there is a method of forming by overprinting as shown in FIGS. 8 and 9. However, in the methods shown in FIGS. 8 and 9, the effect of the polymerization inhibitor may be offset by the effect of the multiplier at the overlapping portion of patterned layer 2 and patterned layer 5 during ultraviolet irradiation. must not. The decorative material thus obtained by irradiating the laminates B or C in FIGS. 2 to 9 with ultraviolet rays is itself a product according to the method of the present invention, but it is also possible to use an arbitrary base material for reinforcement. It can also be used as a decorative material for products by adhering to it. Of course, the ultraviolet opaque layer 4 itself also has the characteristics of a base material. As described above, the method of the present invention is capable of producing a decorative material having a synchronous embossed pattern by combining an ultraviolet curable resin film with a pattern layer containing a polymerization inhibitor and/or a polymerization accelerator that changes the crosslinking efficiency and polymerization efficiency of the film. This method has the advantage that it can be easily obtained with a few steps and decorative materials having various embossed patterns can be obtained.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, both "part" and "%" are based on weight. Example 1 Vinyl chloride/vinyl acetate/acrylic copolymer was added to a 100 μ thick ultraviolet curable resin film (manufactured by Bando Chemical Co., Ltd.; dioctyl phthalate nodule, ultraviolet polymerization composition (a) part, polyvinyl chloride 100 parts) as a vehicle. Ink containing 5% aniline black and 10% hydroquinone (
FEX series manufactured by Morohoshi Ink Co., Ltd.), the conduit part of the wood grain was printed using the gravure method, and as shown in Figure 5, after heat-sealing a 100μ thick colored vinyl chloride film, the four sides of laminate B were fixed and exposed to ultraviolet light. When ultraviolet rays were irradiated from the curable resin film side using an ultraviolet irradiation lamp (120 W' x 2 lamps), a decorative sheet in which the wood grain conduit portions were recessed portions was obtained.

Example 2 One side of the same ultraviolet curable resin film as in Example 1 was coated with a transparent ink using an organic pigment using a vinyl chloride/vinyl acetate copolymer as a vehicle, and then coated with 55% of t-butylcatechol. % containing transparent colored ink (FEX series manufactured by Moroboshi Ink Co., Ltd.) was used for the conduit portion to print a wood grain pattern.

Next, a 100μ thick transparent polyvinyl chloride film (25 parts of plasticizer) was heat-sealed on top of the pattern layer, and a colored vinyl chloride film (17 parts of plasticizer) was heat-sealed under the ultraviolet curable resin film. Emboss was formed by irradiating ultraviolet rays from the surface of the polyvinyl chloride film under tension in the biaxial directions of the laminate, and then passed through a heating oven at about 150° C. for 30 seconds, which amplified the emboss. In this way, a decorative sheet in which the conduit portions were recessed portions was obtained. Example 3 An ink containing 10% methylhydroquinone and a brown organic pigment (FEX series manufactured by Morohoshi Ink Co., Ltd.) was printed on the same ultraviolet curable resin film as in Example 1 as 7 conduit sections, and then vinyl chloride/vinyl acetate was printed. Laminated body B in which a wood grain pattern is back-printed by overprinting with a transparent colored ink using a polymer as a vehicle and an organic pigment.
(having the specifications shown in Figure 2a) was manufactured.

9 Next, apply an ultraviolet irradiation lamp (120W) from the transparent resin layer side.
After forming an embossing by irradiating it several times intermittently for 1 to 2 seconds at 80W (1 lamp), a colored vinyl chloride film (17 parts of plasticizer) was laminated to form a laminate as shown in FIG. 2b.

Thereafter, when the laminate B was passed through a near-infrared heating furnace at a temperature of about 3@ with tension applied in biaxial directions, the embossment was amplified. In this way, a decorative sheet was obtained in which the ultraviolet curable resin film was the top layer and the wood grain conduits were concave portions.

[Brief explanation of the drawing]

Fig. 1 a1 Fig. 2 a and Figs. FIG. b is a cross-sectional view of a laminate (decorative material) showing the outline of the embossed pattern obtained by the present invention. 1... Ultraviolet curable resin film, 2...
...Polymerization inhibitor-containing pattern layer, 3...Transparent resin layer, 4...Ultraviolet opaque layer, 5...
Pattern layer containing polymerization accelerator.

Claims (1)

[Claims] 1. A laminate having an ultraviolet curable resin film and a pattern layer formed of an ink containing a polymerization inhibitor and/or a polymerization accelerator on at least one surface of the ultraviolet curable resin film is irradiated with ultraviolet rays to crosslink within the ultraviolet curable resin film. Alternatively, by changing the crosslinking efficiency or polymerization efficiency of the ultraviolet polymerization composition to be polymerized by using a polymerization inhibitor and/or polymerization accelerator contained in the ink, the degree of curing between the portion in contact with the pattern layer and the other portions may be changed. 1. A method for producing a decorative material having a synchronized embossed pattern, the method comprising providing an ultraviolet curable resin film with a concavo-convex pattern synchronized with the pattern layer by making the patterns different.