JPS60202767A - Formation of recessed pattern on surface of vinyl chloride film - Google Patents

Abstract

PURPOSE:To form recessed patterns having excellent appearance by coating a paint curable by ultraviolet rays on a printed layer wherein recessed patterns are formed with curable ink contg. a liquid-repellent agent, and irradiating ultraviolet rays. CONSTITUTION:A printed layer 2 is formed on the surface of a vinyl chloride film 1 with common ink, and then a printed layer 3 corresponding to recessed patterns is formed by using a curable ink composition contg. a liquid-repellent agent. Subsequently, an ultraviolet-ray curable paint having 100-5,000cps viscosity is coated on the whole surface of the part printed in several colors in 3-50mu cured film thickness. Thereafter, an ultraviolet-ray curable paint layer 4 is formed by irradiating ultraviolet rays. Sharp patterns can be obtained in this way, and recessed patterns which are flat except for the recessed parts and have excellent appearance can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a concave pattern on the surface of a vinyl chloride film (or sheet).

A variety of decorative sheets have been developed as decorative materials for buildings, vehicles, ships, furniture, musical instruments, cabinets, etc. Among these, decorative sheets have been developed that enhance the decorative effect by forming arbitrary uneven patterns on the sheet surface. Seats are known. By the way, as a method for forming an uneven pattern on a sheet surface, various physicochemical unevenness forming methods using a liquid repellent have recently been proposed in place of expensive mechanical unevenness imparting methods such as embossing. That is, for example, Japanese Patent Publication No. 47-7154 discloses that an ink composition containing a liquid repellent such as silicone and a polymerization inhibitor such as hydroquinone in a normal printing ink composition is used in the area where a concave pattern is to be formed. Then, a polymerizable top resin paint is applied,
A method is disclosed in which a concave pattern is formed by drying using the liquid repellent effect of the liquid repellent and the polymerization inhibiting effect of the polymerization inhibitor. However, since this method utilizes the shrinkage effect of the resin film based on the polymerization inhibiting effect of the polymerization inhibitor in addition to the liquid repellent effect of the liquid repellent, variations in the liquid repellent state are likely to occur depending on the curing conditions. Therefore, it is not possible to obtain a fully satisfactory product. In addition, Japanese Patent Publication No. 52-2641 discloses that a liquid repellent is contained in both the printing of the part where the concave pattern is to be formed and the top coat of the entire surface including the printing layer using a normal ink composition to form the concave pattern. A formed decorative sheet is disclosed. However, since this method only utilizes the liquid repellent effect of a liquid repellent such as silicone, the surface condition of the area printed using an ink composition containing this may vary depending on the type of substrate, printing conditions, etc. It is difficult to obtain a uniform surface condition because it is easy to change, and there is virtually no surface protective layer in the areas where the top coat is repelled by the action of the liquid repellent, that is, in the concave areas. Solvent resistance, water resistance, and abrasion resistance are poor, making it difficult to obtain a product with satisfactory practicality. Furthermore, as another method using a liquid repellent, Japanese Patent Application Laid-Open No. 57-31573 discloses that a curable ink composition containing a liquid repellent is applied to the ink used for printing the area where the concave pattern is to be formed, and then heat cured. After applying the mold paint, heating is performed at a temperature equal to or higher than the melting temperature of the top coat, thereby repelling the top coat of the area coated with the curable ink composition to form concave portions. A method is disclosed. However, when this method is applied to a vinyl chloride film to form concave portions, the melting temperature or higher temperature of the top coat is generally higher than the softening temperature of the vinyl chloride film.
The vinyl chloride film shrinks, causing unevenness on the film surface, the so-called ``sagging phenomenon,'' making it impossible to obtain a practical product.

In view of the above-mentioned drawbacks of the conventional method when forming a concave pattern on the film surface using a liquid repellent, the inventors of the present invention have found that even when a vinyl chloride film is used as the bare side, the surface of the film is sharp. It is possible to form a concave pattern, and the surface other than the concave part is smooth, and the concave pattern is excellent in appearance.Furthermore, the entire surface of the film, including the concave part, has solvent resistance, water resistance, abrasion resistance, etc. The present invention was developed as a result of intensive research aimed at providing a method for forming a concave pattern with excellent surface characteristics.

That is, in the present invention, after forming a printed pattern on the surface of a vinyl chloride film, a curable ink composition containing a liquid repellent is used to form a printed layer corresponding to a desired concave pattern, and then printed. Viscosity j00 on the entire surface of the film
This is a method for forming a concave pattern on the surface of a vinyl chloride film, which consists of applying an ultraviolet curable paint adjusted to ~5000 cps to a cured film thickness of 3 to 50μ, and then irradiating it with ultraviolet rays. This is done by making the ultraviolet curable paint coated on the printing layer made of a curable ink composition containing a liquid repellent agent to be liquid repellent.

The method of the present invention will be explained in detail below with reference to the drawings. In other words, as shown in FIG. 1, on the surface of the vinyl chloride film 1,
The printing layer 2 is formed using a conventional ink composition.

Next, a printing layer 3 corresponding to a desired concave pattern is formed using a curable ink composition containing a liquid repellent. Next, an ultraviolet curable paint layer 4 is formed on the entire surface of the area printed in multiple colors using the above method. Next, preferably for 5 seconds or more, the ultraviolet curing paint layer 4 of the printed layer 3 is repelled, and a concave pattern 5 is formed on the printed layer 3 as shown in FIG. Next, the paint layer 4 is cured by irradiation with ultraviolet rays, thereby producing a film having a concave pattern formed on the surface of the vinyl chloride film according to the present invention.

First, the base material for producing the vinyl chloride film 1 provided in the present invention may be either polyvinyl chloride or a copolymer mainly composed of vinyl chloride, and the monomer to be copolymerized may be vinyl chloride. Ester, vinyl ether, acrylic acid or methacrylic acid and its esters, maleic acid or fumaric acid or their esters, maleic anhydride, aromatic vinyl compounds, vinylidene halides, acrylonitrile or methacrylonitrile, etc. History includes ethylene, propylene, etc. Examples include olefins.

Moreover, various plasticizers and additives are added to these vinyl chloride resins as necessary.

Plasticizers are used to adjust the flexibility, hardness, etc. of molded products. Fatty acid esters, phosphoric acid esters such as 1-licresyl phosphate and triphenyl bosphate, epoxy esters such as epoxidized soybean oil and epoxidized linseed oil, citric acid esters such as acetyl tributyl citrate and acetyl tributyl citrate, Various other examples include polyester. Additionally, as additives, carboxylic acids such as calcium stearate, zinc stearate, lead stearate, pallium stearate, and cadmium stearate are used to improve properties such as lubricity and stability. Metal salts, tribasic lead sulfate, dibasic lead phosphite, organotin compounds such as cibdeltin dilaurate, octyltin malate, octyltin mercaptite, ester compounds such as butyl stearate, ethylene. Examples include fatty acid amide I-1 higher fatty acids and their esters such as bis-stearamide, and polyethylene wax.

In addition, various additives used in the molding of vinyl chloride resins include well-known fillers, reinforcing agents, heat resistance improvers,
Examples include antioxidants, ultraviolet absorbers, antistatic IL agents, foaming agents, dropless agents, pigments, dyes, and crosslinking aids.

Furthermore, as a method for forming the vinyl chloride film, methods conventionally used for forming vinyl chloride films, such as calendar molding, extrusion molding, inflation molding, and gear-sting molding, can be used. . Furthermore, a composite material obtained by forming a vinyl chloride film with another vinyl chloride film or a material such as metal, wood, paper, or synthetic resin may also be used.

Next, as the ink composition for forming the printing layer 2, acrylic, vinyl chloride, EVA, 'J (D
A conventional printing ink composition in which pigments and dyes are dispersed in a vehicle with good adhesion to a hinyl chloride resin and dissolved in a solvent can be used.

Next, the curable ink composition containing a liquid repellent for forming the printing layer 3 is one in which a liquid repellent is added to a vehicle that is curable at a temperature below the softening temperature of the hinyl chloride film. A composition is used in which the ink layer itself is stable and can form a film with good surface properties such as solvent resistance, abrasion resistance, weatherability, and heat resistance.

Such ink compositions include vehicles for various curable inks, such as two-component curable inks that are cured by reaction of polyester polyols or polyether polyols with isocyanate to form polyurethane resins, and epoxy. Epoxy-based curable ink that is cured by the reaction between resin and polyamide 1-, polyamine, or acid anhydride; a polymerization initiator such as peroxide and a polymerization catalyst such as cobalt naphthenate are added to a mixture of unsaturated polyester and styrene monomer. thermosetting ink made of melamine resin or urea resin and alkyd resin with para-toluene sulfonic acid added, or epoxy acrylic 1- or urethane acrylic 1-
An electron-beam or UV-curable ink vehicle containing photosensitizers such as benzophenone and hengeine ether is used, and these are combined with plasticizers, stabilizers, dispersants,
A composition obtained by adding known additives such as fillers and coloring agents such as dyes and pigments, and further adding a solvent and a diluent and kneading the mixture may be used. These curable ink compositions are usually used in a two-component form, and therefore a method is adopted in which a reaction catalyst and a reaction accelerator are added to the ink composition immediately before use.

Further, as the liquid repellent added to the above-mentioned curable ink composition, conventionally known materials such as silicone, wax, fluororesin, etc. can be used. Such a liquid repellent may be added to the ink composition in advance, or may be added immediately before use.

The amount added is 5 to 30% based on the dry weight of the ink composition.
Preferably, it is % by weight.

The curable ink composition containing the liquid repellent described above is printed on a vinyl chloride film by a known method, such as the Gravity 4 printing method, offset printing method, letterpress printing method, or screen printing method, in the same way as ordinary printing inks. do.

However, when the liquid repellent-containing ink is an electron beam curing type or ultraviolet curing type ink as described above, after applying the above ink, the printing layer is cured by irradiation with an electron beam or ultraviolet rays. Apply the top coat described above.

Furthermore, when using a single-liquid ink other than the above, after coating, the solvent is evaporated and the ink is dried to such an extent that blocking does not occur, and then a top coat is applied.

Next, in the present invention, an ultraviolet curing type paint that forms a transparent surface protective layer is used as the top coat. Such UV-curable paints include epoxy acrylate, acrylic urethane, polyester prepolymers, etc., with liquid monomers as diluents, crosslinking agents, sensitizers, and dyes and matting agents added to an extent that does not impair transparency. be done.

These UV-curable paints generally have a high viscosity, and when the viscosity is high, liquid repellency occurs on the printed layer of the curable ink containing a liquid repellent, but as shown in FIG.
The vicinity of the boundary 6 between the top coat layer 4 and the convex portion swells, and a concave portion that is sharp and good in appearance is not formed. The viscosity of the ultraviolet curing paint that forms sharp and good concave portions 5 is 100 to 5000 cps, preferably 200 cps.
It was found to be ~2000 cps. In addition, as a method of adjusting the viscosity within the above range, the usual method of adding a low molecular weight polymer may not provide the desired performance of the cured film, so a solvent that is compatible with the ultraviolet curable paint is used. Sharper concave portions are formed by adding .

Furthermore, since UV-curable paints generally have poor affinity for the vinyl chloride film that is the base material, it is desirable to use a solvent in order to improve the affinity with the base material.

Such a solvent may be any commonly used solvent as long as it has an affinity for UV-curable paints and vinyl chloride films; In order to achieve this, it is desirable to use ethyl acetate or a solvent containing ethyl acetate as a main component.

The amount of the solvent added can be adjusted to the above-mentioned viscosity range within the range of 5 to 50% by weight.

The use of a solvent causes the solvent to penetrate into the vinyl chloride film and the curable ink layer, activating the surface, and also has the effect of strengthening the adhesion of the ultraviolet curable paint to these layers.

Next, the coating amount of the top coat made of ultraviolet curable paint is 3 to 50 μm, preferably 5 to 20 μm in thickness after curing.
μ, and can be adjusted as appropriate depending on the sharpness and depth of the recess and the required surface characteristics.

If the coating amount is less than 3μ, the same phenomenon as when the viscosity is low occurs, that is, liquid repellency does not occur or liquid repellency is insufficient, and if the coating amount exceeds 50μ, the viscosity is high. This is not desirable because a phenomenon similar to that described above, that is, a bulge may occur at the boundary between the concave portion and the two convex portions, or liquid repellency may not occur.

If the base material is a permeable material such as paper, the coating amount will have little effect because the top coat will permeate. If not, applying the coating within the above range is an important factor in forming sharp recesses.

The above-mentioned top coat paint can be applied using normal coating methods such as roll coating,
It can be applied by methods such as gravure coating, barcode coating, air knife coating, flow coating, and spray coating.

Next, after applying the top coat, it is cured by irradiating it with ultraviolet rays, but it is desirable that this irradiation be carried out after 5 seconds or more have elapsed after application. If it takes less than 5 seconds, the appearance quality tends to be poor because the recesses are insufficiently formed, the edges of the recesses are raised, and the coated surface other than the recesses is not smooth.

Further, in the present invention, when a solvent is added to the ultraviolet curable paint, the temperature is 100°C or less, for example 40 to 60°C.
The coating layer is heated to a temperature of 100 to completely volatilize the solvent. Due to this addition i'J+A, the top coat paint is kept at a relatively low viscosity, and the formation of sharp concave portions and the smoothing of the coated surface other than the concave portions further proceed. By being irradiated with ultraviolet rays in this state, the coating material hardens and a concave printing pattern with sharp concave areas is formed. Furthermore, due to the coating surface other than the concave areas, a product with excellent appearance quality is obtained. It will be done.

As explained in detail above, according to the present invention, a printed layer corresponding to a desired concave pattern is formed on the surface of a vinyl chloride film on which a normal printed pattern is applied using a curable ink composition containing a liquid repellent. was formed, and then an ultraviolet curable paint with a viscosity adjusted to 100 to 5 o o cps was applied to the entire surface of these printed layers to a cured film thickness of 3 to 50 μm, and ultraviolet rays were irradiated. The surface properties of the product are extremely excellent because the concave areas are coated with curable ink and the other areas are coated with ultraviolet curable paint. A product that is formed smoothly and has an extremely good appearance quality can be obtained. By adding a solvent, especially ethyl acetate, to the UV-curable paint and adjusting its viscosity within the above range, there are advantages such as a product with good adhesion (X=I) to the vinyl chloride film of the paint. be. Therefore, by bonding the vinyl chloride film obtained by the process of the present invention to various base materials using adhesives, etc., it can be used as a decorative material for buildings, vehicles, ships, furniture, gear vignettes, etc., and has a robustness with extremely high design effects. A decorative board having the following properties is obtained.

Example 100 parts by weight of vinyl chloride resin, 20 parts by weight of dioquidyl phthalate 1 (DOP) as a plasticizer, 5 parts by weight of epoxidized soybean oil, Cd-Ba stabilizer (mixture of cadmium stearate and barium stearate) A polyvinyl chloride film having a thickness of 0.2 parts was prepared by calendering a mixture of 3 parts by weight and 5 parts by weight of a brown pigment.

Gravure printing was performed on this film using vinyl ink (manufactured by Inu Nichiseika Kogyo Co., Ltd.) using a wood grain blurring pattern plate, and then the wood grain pattern was gravure printed using a curable ink containing a liquid repellent with the following composition. A printed vinyl chloride film was obtained by printing.

Acrylic polyol 20 parts by weight Handle 15 "Acetate ester 60 Silicone 5 Isocyanate prepolymer 10 110 l/A UV curable paint having the following composition was applied to the above printed vinyl chloride film under the conditions shown in Table 1. and ultraviolet rays (
After curing by irradiating with 80 w/cm x 1 lamp), the liquid repellency, appearance and adhesion of the ultraviolet curable paint were evaluated by cellophane tape test.

The results are shown in Table 1 and Figure 4.

Composition of ultraviolet curable paint Urethane acrylate 64 parts by weight Hensiphenon 2 〃 Benzoin ether 3 〃 Silica-based quenching agent 5 ~ Ethyl acetate 25 liters Silicone 1 〃 100〃 In other words, in Figure 4 (al ~ (fl are respectively The surface conditions after coating and curing corresponding to the upper column divisions of Table 1 are shown, and the surface conditions of FIG. 4 (al) corresponding to Examples of the present invention are shown in FIG. It is clear that the surface condition is much better than that of ff).

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view showing the state before ultraviolet irradiation in which a regular printing layer, a printing layer using a liquid repellent-containing curable ink, and an ultraviolet curable paint layer are formed on a vinyl chloride film by the method of the present invention. , Fig. 2 is a schematic cross-sectional view after irradiation with the same ultraviolet rays, Fig. 3 is a schematic cross-sectional view showing the finished surface state when the viscosity of the ultraviolet curable paint is high, and Fig. 4 is a schematic cross-sectional view showing the finished surface state of the ultraviolet curable paint in the case of an example of the present invention and a comparative example. A schematic cross-sectional view showing the corresponding finished surface condition is shown. 1... Vinyl chloride film, 2...
Printing layer made of a conventional ink composition, 3... Printing layer made of a curable ink composition containing a liquid repellent, 4...
.....Ultraviolet curable paint layer, 5 ..... recessed part,
6... Swelling part - Figure 1 Figure 2 Figure 3-), Ro 1 Figure 4 (o) (b) (c) 1 ■ (d) (e) (f) r l l

Claims (2)

[Claims] (1) After forming a printed pattern on the surface of a vinyl chloride film, a curable ink composition containing a liquid repellent is used to form a printed layer corresponding to the desired concave pattern, and then the printed film Viscosity 100-5000 on the entire surface
Cured film thickness of UV curable paint adjusted to cps is 3~
A method for forming a concave pattern on the surface of a vinyl chloride film, the method comprising applying ultraviolet rays after coating the film to a thickness of 50 μm. (2) Claim 1, characterized in that the viscosity of the ultraviolet curable paint is adjusted by adjusting the amount of ethyl acetate added.
The method described in section. (3) The method according to claim 1 or 2, wherein the ultraviolet irradiation is carried out after 5 seconds or more have elapsed after application of the ultraviolet curable paint.