JPS6123317B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a decorative sheet having a gloss difference in synchronization with a pattern, and more specifically, the present invention relates to a method for producing a decorative sheet having a gloss difference that is in sync with a pattern. The present invention relates to a method for manufacturing a decorative sheet having a gloss difference that is in sync with the above, using a simple process.

It is desirable to enhance the visual three-dimensionality of the pattern by providing interior or exterior materials for furniture, wall materials, floor materials, etc., or decorative materials used as surface materials thereof, with a gloss difference that is in sync with the pattern.

Conventionally, there are the following methods for producing decorative sheets with different gloss.

(1) A method of providing a uniform gloss layer on the entire surface of the base sheet, and then providing a pattern layer with a different gloss from the gloss layer. (2) A method of providing a pattern layer on the base sheet with ink containing pigments and extender pigments, and A method of creating a gloss difference in the transparent resin layer provided on the pattern layer by changing the particle size, shape, amount mixed, and porosity of the extender pigment (3) Adding foamed ink to the base sheet After forming a pattern layer with , then applying a transparent resin layer, or after forming a transparent resin layer and applying a pattern layer with foamed ink, by foaming the foamed ink, the foamed surface roughness of the foamed ink can be improved. (4) After forming a pattern layer on the base sheet using ink that foams when it reacts with the transparent resin layer applied later, the transparent resin layer is applied. A method of creating a gloss difference that is in sync with the pattern layer by rubbing (5) A pattern layer is provided on the base sheet using a printing ink containing a substance that has the property of repelling the resin applied to the sheet, and then the printing ink is A method of providing transparent resin layers with different gloss to provide a gloss difference that is synchronized with the pattern layer.

However, method (1) described above lacks surface properties because the printing ink layer is present on the surface, and method (2) has drawbacks such as the short life of the printing ink containing a large amount of extender pigment. (3) lacks the drying properties of the foamed ink, (4) lacks the stability of the chemical reaction, and (5) lacks the sharpness of the pattern. Also,
With these methods, it is difficult to provide gradation in the gloss difference, and it may be difficult if the pattern area in which the gloss difference is to be provided is large.

As a result of various studies in view of these drawbacks, the inventors of the present invention have developed a method for easily producing a decorative sheet having a pattern of consistent quality and a gloss difference. That is, in the present invention, a thermoplastic film having a certain gloss is embossed at a temperature lower than the film forming temperature to provide a gloss different in degree from the above-mentioned gloss, and then the film is partially embossed to improve its fastness. The gist of the present invention is to provide a method for manufacturing a decorative sheet, which is characterized in that, after forming parts with different gloss, the film is heated to produce parts with different gloss. Here, "emboss fastness" generally refers to glossy embossing applied to a thermoplastic film using a heated roll such as a calendar roll or an embossing roll, which becomes thermodynamically the most stable glossy state due to the distortion of the polymer resin being resolved by heating. It shows the degree of change.

Hereinafter, the present invention will be explained in detail based on its basic aspects with reference to the drawings.

First, as shown in FIG. 1, a thermoplastic film 1 having a certain gloss A is prepared. Next, embossing is performed at a temperature (T _B ) lower than the film forming temperature (T _A ) of the film 1 to provide a gloss B which is different in degree from the gloss A as shown in FIG. A portion 1a having a high emboss fastness and a portion 1b having a low emboss fastness are selectively formed. In this state, portions 1a and 1b form gloss B. In this state, when heated at temperature (T), (T _A
>T>T _B ), the portion 1b has low emboss fastness, so it changes to gloss A, and the portion 1a has high emboss fastness, so it remains as gloss B. In this way, a difference in gloss is formed. Such a phenomenon similarly occurs when the above-mentioned thermoplastic film is laminated, and in this case, the same phenomenon occurs even if a printed layer is provided in the middle and/or on the surface of the laminated film. Furthermore, it is possible to form a difference in gloss in the same manner in various laminated states as long as the requirements of the present invention are met.

In the above, the temperature T was set as T _A > T > T _B , but
This shows a general relationship,
Even when the temperature T is the same as the temperature T _B or slightly lower than the temperature T _B , a difference in gloss can occur in the same way as described above. This means that the return of the embossing from Gloss B to Gloss A is between the total amount of heat during film formation (W _A ), the total amount of heat required to impart Gloss B (W _B )2, and the total amount of heat for heating (W). This is because a difference in gloss occurs when the relationship W _A > W > W _B is satisfied. Therefore, emboss return does not necessarily occur due to temperature alone. The thermoplastic film used here is mainly composed of polyolefin resins such as polyvinyl chloride resin, acrylic resin, polystyrene resin, ABS resin, polycarbonate resin, polyethylene resin, and polypropylene resin, either alone or in the form of a mixture or copolymer. A single-layer film or a composite film with a thickness of 10 μm to 5 mm formed by a calendering method, a casting method, an extrusion method, or the like can be used.

As a method of providing the above-mentioned thermoplastic film with parts having different emboss fastnesses, there is a simple method in which embossing is carried out using embossing rolls at different temperatures, or in some cases, in synchronization with the pattern layer formed by printing ink. There is also. A method that can be used for mass production is to polymerize or crosslink a reactive plasticizer provided on an ultraviolet curable resin film containing a thermoplastic resin, a reactive plasticizer, a photosensitizer, and a thermal polymerization inhibitor. Can efficiency be changed?
There is a method of forming a patterned layer that can change the irradiation efficiency of ultraviolet rays, and then irradiating the layer with ultraviolet rays to selectively provide portions with different emboss fastnesses. In this case, the uncured part of the film becomes a part with low emboss fastness, and the cured part becomes a part with high emboss fastness.

In the above, the thermoplastic film containing a reactive plasticizer is, for example, unsaturated polyester resin, spirane resin, urethane resin, based on 100 parts by weight of thermoplastic resin such as polyvinyl chloride resin, acrylic resin, thermoplastic urethane resin, etc. , curable resins such as acrylic resins, epoxy resins, epoxy-acrylate resins, diallyl phthalate resins, or reactive plasticizers such as their polyfunctional monomers.
10 to 50 parts by weight: Non-reactive plasticizers such as acrylic esters such as allyl acrylate and allyl methacrylate, and phthalate esters such as dioctyl phthalate and dibutyl phthalate, as necessary 0 to 30 parts by weight: Small amount as necessary A reaction initiator such as benzoyl peroxide or azobisisobutyronitrile: 0.5 to 5 parts by weight of a photosensitizer such as benzoin alkyl ether or benzophenone: Other small amounts of a catalyst such as a tertiary amine organometallic compound or stearic acid An ultraviolet curable resin film having a thickness of 20 to 500 microns, for example, is used by adding a stabilizer such as a metal salt to form a film by a calendering method, a casting method, or the like.

Regarding the pattern layer provided on the above-mentioned ultraviolet curable resin film, there are cases where the polymerization or crosslinking efficiency of the reactive plasticizer is changed, and there are cases where the ultraviolet irradiation efficiency is changed, and in the former case, a polymerization inhibitor and/or polymerization accelerator is used. According to research conducted by the present inventors, when a pattern layer is formed using only a polymerization accelerator, the effect is not significant, and rather, it is more effective when used in combination with a polymerization inhibitor.

Polymerization inhibitors contained in the ink of the pattern layer that change the crosslinking efficiency or polymerization efficiency of the ultraviolet polymer composition that crosslinks or polymerizes within the ultraviolet curable resin film include 2-ethylanthraquinone, β-methylanthraquinone, α- Naphthoquinone, cetylamine, laurylamine, triethylenetetramine, N-phenyldiethanolamine, dicyclohexylamine, magnesium, N
-Nitroso-P-tolylhydroxylamine, aluminum-N-nitrosophenylamine, N-
Methyl diphenylamine, stearylamine, tri-n-butylamine, N-N-di-n-butylethanolamine, trimethylhydroquinone, methylhydroquinone, hydroquinone 4-t-butylcatechol, phenylhydrazine, methoxyhydroquinone, N-methyl diethanolamine, 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 may be colored or transparent, but a synergistic effect can be obtained if it is made of black ink that acts to block ultraviolet rays or a relatively dark pigment with hiding power.

Examples of the polymerization accelerator used include sensitizers such as benzoin acetophenone, benzyl, and benzoin alkyl ether.

In the latter case, which changes the irradiation efficiency of ultraviolet rays,
For example, UV-shielding substances include pigments with relatively deep hiding power such as carbon black and titanium white; UV-absorbing substances include benzophenones and benzotriazoles that have absorption wavelengths in the ultraviolet region. Examples of UV absorbers include metals such as aluminum, zinc, copper, brass, stainless steel, etc.
Alternatively, alloys or optical brighteners may be used.

A pattern is formed so that the printing ink containing each of these reagents comes into contact with the ultraviolet curable film. Note that there is no need for contact when changing the irradiation efficiency. This method may include printing directly on the film, using a transfer method, or printing in advance on a film that will be laminated later.
When irradiating a laminate containing the ultraviolet curable film with ultraviolet rays, it may be irradiated from either the patterned layer side or the non-patterned layer side, except when an ultraviolet blocking substance is used, but it is preferable to irradiate from the patterned layer side. This is expected to be more effective. Further, as a step, the layers may be laminated after being irradiated with ultraviolet rays. As the printing method, any printing method such as silk screen, letterpress, offset, gravure, etc. can be adopted. The film after irradiation with ultraviolet rays has a hardened part and an unhardened part in synchronization with the pattern, and since the unhardened part has low embossing fastness, the gloss does not change as described above at the embossing return temperature T. arise. Generally, the heating temperature is preferably about 150°C to 200°C. Further, according to these methods, unevenness may occur due to the difference in shrinkage between the uncured portion and the cured portion of the film.

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

<Example 1> A glossy ultraviolet curable resin film (manufactured by Band Kagaku Co., Ltd., Ultra Film, film formation temperature 220°C) with a thickness of 100μ was coated with PVC-based ink (manufactured by Moroboshi Ink Co., Ltd., VTP) except for winter. After printing the pine pattern with Fuyume's ink containing a polymerization inhibitor (manufactured by the same company, FEX), a 100μ thick ocher colored PVC film (100μ thick, manufactured by Band Kagaku Co., Ltd.,
HZL56105) was laminated with heat and pressure (160℃, 10Kg/cm) and matted at the same time. After irradiating ultraviolet rays from the non-printing side, the cured film laminate was heated to 200℃ with an infrared irradiation lamp. A decorative sheet with glossy eyes only was obtained.

<Example 2> A walnut-patterned conduit was attached to a 100-μ thick ultraviolet curable film (Band - Ultra Film manufactured by Kagaku Co., Ltd.) made at 250°C with no luster and ink with PVC ink containing carbon black (VTR manufactured by Moroboshi Ink Co., Ltd.).
Gravure printing was carried out with black), and then the printed film was laminated with a 100μ brown colored PVC film (BR12225, manufactured by Kagaku Co., Ltd.) so that the printed side of the printed film became the front surface, and at the same time a glossy embossing was applied at 170℃. did. After that, the curable resin film, which has been irradiated with ultraviolet rays from the printed surface, is heated at 230°C using an infrared irradiation lamp.
When heated to ℃, a decorative sheet was obtained in which only the conduit portion lost its luster.

[Brief explanation of the drawing]

FIGS. 1 to 3 are schematic cross-sectional views for explaining each step of the manufacturing method of the present invention. 1: Thermoplastic film, 1a: High emboss fastness, 1b: Low emboss fastness, A, B: Gloss.

Claims (1)

[Claims] 1. A thermoplastic film having a certain gloss is embossed at a temperature lower than the film forming temperature to provide a gloss different in degree from the above-mentioned gloss, and then the film is partially embossed. 1. A method for producing a decorative sheet, which comprises forming parts with different fastnesses and then heating the film to produce parts with different glosses. 2. The thermoplastic film is an ultraviolet curable resin film containing a thermoplastic resin, a reactive plastic, a photosensitizer, and a thermal polymerization inhibitor, and on the film, the polymerization or crosslinking efficiency of the reactive plastic is changed. Claim 1, characterized in that by forming a patterned layer that changes the irradiation efficiency of ultraviolet rays, and further irradiating the film with ultraviolet rays, portions having different emboss fastnesses are provided in the film.
The method for manufacturing the decorative sheet described in Section 1.