JPS59190848A - makeup sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a decorative sheet having excellent solvent resistance, heat resistance, adhesiveness, etc.

Conventionally, there has been known a decorative sheet in which a pattern layer, a white knee This decorative sheet is applied to the base material to which it is to be laminated by pressure bonding, twisting, or thermocompression bonding. At this time, it is also known to apply an adhesive to the base material or decorative sheet and press it.The adhesive used here is an adhesive using thermoplastic resin-1L or curable resin. The decorative sheet is bonded by thermocompression bonding with an adhesive mainly composed of thermoplastic resin. Examples of this thermoplastic resin include vinyl resin, acrylic resin, polyamide resin, rubber resin, etc. .Decorative sheets are pasted together using an adhesive mainly made of thermoplastic resin.
It is generally inferior in heat resistance and solvent resistance, and its adhesive properties are not necessarily sufficient. Therefore, the reality is that their use in substrates that require these physical properties, such as metal surfaces, is limited.

Arc adhesives using hardening type resins do not have sufficient shelf life as decorative sorting, and the adhesive-coated decorative sheet must be attached to the base material before the adhesive hardens. Therefore, the reality is that they generally do not have a long shelf life. As this curable resin, urethane resin or the like is used.

Note that a transfer painting method disclosed in Japanese Patent Application Laid-Open No. 57-49591 is also known. Although this method has the advantage of being easy to work with, it involves the work of peeling off the base sheet No. 1 (plastic film), and the plastic film that is the base sheet is generally difficult to reuse, so it ends up being discarded. Become. However, the cost of plastic and film is relatively high in m specific gravity in Cosmeton-1, and as a result, this transfer method poses a cost problem.

The present invention does not peel off after laminating the transparent plastic or film to the base material. A decorative sort that uses plastic and film as a protective layer to produce decorative materials that have excellent storage stability as decorative sheets, as well as excellent heat resistance, solvent resistance, and adhesive properties. Regarding.

That is, the present invention is directed to transparent plastic, Kutsudulum (A).
Then, in order, adhesive layer (B), pattern layer (C), concealing layer 0)
and a makeup notebook provided with a radiation-curable adhesive layer. Furthermore, the adhesive layer (B) is a urethane-based curable adhesive, the concealing layer (D) is a white coating layer or a metal vapor deposited film, and the radiation-curable adhesive layer C) is an urethane-based curable adhesive. 10 to 90% by weight of a monomer and or prepolymer having a sexually unsaturated double bond,
and resin 10 having no ethylenically unsaturated double bonds
It is a decorative sheet containing ~90% by weight.

Decorative sheet of the present invention (A) / (B) / (C)
/I) /However, it has the basic composition of /), and has a composition such as a decorative sheet with two layers of pattern layers (0), a decorative sheet with two concealing layers (1)), etc. It's okay.

Transparent plastic film (solvent resistant as Alt,
It is preferable that it has excellent heat resistance, and that the pattern layer C) is transparent enough to be seen through.

For example, various plastics such as polyester film, nylon film, cellophane film, polyethylene film, polypropylene film, polyvinyl butyral film, etc.9. film can be used. Preferred is polyethylene terephthalate film. By using a plastic film with excellent solvent resistance and heat resistance, the obtained decorative material has excellent solvent resistance and heat resistance. Incidentally, pigments and the like can also be added to the plastic film within a range that does not impede transparency.

The adhesive layer (13) may be a thermoplastic resin since it is not the outermost layer as a decorative sort. However, by preferably using a curable resin, it is easier to obtain a decorative sheet that satisfies the physical properties required. It is necessary to use a resin that has excellent adhesiveness to at least (A), (C), and (D).

Examples of curable resins and thermoplastic resins include unsaturated polyester resin, Evoquin resin, urethane resin, urea resin, melamine resin, alkyd resin, acrylic resin, polyamide, urethane-modified epoxy resin, and vinyl chloride 1t.
It is made of T fat, thermoplastic polyester resin, etc., and is coated on transparent plastic or film (A) as a coating composition together with bath additives and various additives. In addition, when a thermosetting resin is used, the thermosetting resin can be completely cured during or after the production of decorative sorting, or after being irradiated with radiation after pasting the decorative sheet.

Furthermore, the adhesive layer (I3) may be a radiation-curable adhesive described later.

As the pattern layer (C), a printed layer formed by various types of printing such as gravure printing, offset printing, flexo printing, and letterpress printing, or a pattern layer formed by partial metal vapor deposition can be used. In the case of the printing layer, various conventional inks can be used as printing inks, and radiation-curable inks may also be used.

The pattern layer is gravure printing, offset, 1 on adhesive 1 (B)
・Pictures can be created using various printing methods such as printing, screen printing, etc.
11r can be formed. In addition, a pattern layer can be provided by a conventionally known metal vapor deposition method,
It may be partially vapor deposited or a combination of printing and vapor deposition.

The hiding layer (1) may be a colored coating layer, a metal thin film layer, etc., or a combination thereof. The colored coating layer is generally white (white coating layer), but coating layers of other hues may be used. Curing type resins are preferred as the type of resin for the coating layer, such as thermosetting or radiation curing type. The coating layer is formed by printing or painting ink or paint on the transparent plastic film (A)/adhesive layer)/picture layer C) IC)-1=. If it contains a solvent, pre-dry it. In the case of thermosetting, the curing may be carried out after the printing layer or coating, or after the decorative sheet is manufactured or the r decorative sheet is bonded to the base material.

Furthermore, when the concealing layer is a radiation-curable resin composition, it is also possible to omit all of 4).

The hiding layer may be a thin film formed by vapor deposition or sputtering of a metal or metal oxide.

The radiation-curable adhesive layer (b) can be made of electron beams, X-rays,
It is an adhesive layer that can be cured by alpha rays, etc., and curing hardly progresses unless it is irradiated with radiation, so it does not have the disadvantages in workability that thermosetting types do. After being folded and attached to a substrate, it is irradiated with radiation, but it can be sufficiently cured even if there is a hiding layer.

Prepolymers and/or monomers having one or more ethylenically unsaturated bonds are used as adhesive layer C). Examples of prepolymers include polyester acrylate, epoxy acrylate, urethane acrylate,
Polyether acrylate, polyol acrylate,
Melamine acrylate, polyester methacrylate,
These include epoxy methacrylate, urethane methacrylate, polyether methacrylate, polyol methacrylate, melamine methacrylate, and unsaturated polyester resin. Examples of monomers include ethylene glycol diacrylate, propylene glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, and ethylene glycol dimethacrylate. They include propylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and the like.

In addition to the prepolymer and/or monomer, an organic solvent, a polymerization inhibitor, a pigment, etc. can be added to the radiation-curable resin composition as needed to make a coating composition suitable for various coating methods. In the present invention, in order to maintain good adhesion to objects to be adhered, such as metal surfaces, we use a prepolymer as the main component and do not use monomers. Alternatively, it is preferable to use a radiation-curable resin composition in a small amount.

Or prepolymer and monomer 10-90
Polymer 10 without weight ratio and ethylenically unsaturated bonds
Compositions having a weight ratio of 90 to 90% by weight are also effective. Polymers without ethylenically unsaturated bonds include acrylic resin, polyamide resin, polyester resin, urethane resin,
These include cellulose resin, evoquino resin, vinyl acetate resin, vinyl chloride resin, butyral resin, poval resin, synthetic rubber, ethylene-vinyl acetate resin, and the like. After coating this adhesive layer, it can be pre-dried if necessary to remove the solvent.

Next, an example of the method for manufacturing a decorative board using the decorative board of the present invention will be described.

Adhesive layer 4) of the decorative sheet is pressed so as to be in contact with the material to be transferred. An example of a pressure-bonding method is a decorative sheet made of transparent plastic, kufirno, etc. (A, J-plane of the decorative sheet is pressure-bonded to the object using a heated press plate or roll if necessary.

After crimping, at least radiation is irradiated.

Examples of radiation include electron beams, X-rays, and gamma rays, but electron beams are the most desirable. Scan type and curtain type devices are known as electron beam accelerators, but low accelerating voltage types may also be used.
Curtain type etc. are preferably used, and the irradiation dose is usually 0.5~
It is about 20M rad. Moreover, irradiation can also be performed in an inert gas atmosphere. The objects to be adhered to include various metal plates such as iron plates, T7-free steel plates, zinc plates, copper plates, and aluminum plates, metal containers such as cans, plastic containers, various plastic molded products such as plastic containers, paper,
These include various types of water systems, plywood, etc.

Next, the present invention will be explained by examples. “Part” in Examples
, "%" indicates parts by weight.

Example] A thermoplastic polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.) was soaked as an adhesive layer on one side of a transparent polyethylene terephthalate film with a thickness of 12 μm in a mixed solvent of methyl ethyl ketone and toluene at a concentration of 30%, and then coated with a bar coater. Film thickness is 5μ (dry film thickness, same below)
The coating was applied to the entire surface to a uniform thickness. 12 after application
Dry at 0°C for 1 minute, remove the solvent, print a picture fjk gravure on it using gravure ink, dry at 80°C for 10 minutes, and apply the electron beam curable resin composition of the following composition to polyester. (Byron 200 manufactured by Toyobo Co., Ltd.)
10 parts titanium white (anatase type) 20 parts methyl ethyl ketone 60 parts A white coating layer was formed by coating the entire surface with a bar coater to a uniform thickness of 10 μm. After application] 2
It was dried at 0° C. for 1 minute to remove the solvent.

Next, the following electron beam curable resin composition was coated with a bar coater to a uniform thickness of 5 μm over the entire surface to form an adhesive layer: 30 parts total methyl ethyl ketone 30 parts toluene. After coating, the coating was dried at 120° C. for 1 minute, and the solvent was removed to prepare a decorative sheet.

Using the obtained decorative sheet, it was laminated on a Tinfree 12-steel plate at 120° C. using a laminator and bonded under heat. Next, under a nitrogen gas atmosphere from the polyester film side, using a curtain type electron beam irradiation device manufactured by Energy Sciences, 1 (iQI (V, 5M at 4rnA)
rad dose,! ! It was cured by irradiating it with an electron beam.

The decorative sheet could be laminated onto a tin-free steel plate with strong adhesive properties.

As for the above test results of the electron beam cured decorative sheet board, lamination property: Good visual judgment Adhesion (after diving): 10 by cellophane tape goblin eye test
0/100, which is good.

Boiling water resistance: As a result of immersion in boiling water at 100°C for 30 minutes,
Good with no change.

Solvent resistance: Good, withstands most solvents.

Refractive properties: Withstands bending to a diameter of 2N.

Pencil hardness = 4H or higher.

Retortability: Good with no change in retort test at 120°C for 30 minutes.

As mentioned above, good results were shown.

Example 2 An adhesive layer and a pattern layer were formed on one side of a 12 μm thick transparent polyethylene terephthalate film in the same manner as in Example 1. Thereon, a two-component curing type urethane having the following composition was applied using a bar coater to a uniform thickness of 10 μm over the entire surface to obtain a white coating layer. After coating] After drying and curing at 20°C for 5 minutes, the coating was cured at 40°C for 2 days.

Next, an electron beam curable resin composition having the same composition was coated using a bar coater in the same manner as described in Example 1, and was coated over the entire surface to a dry film thickness of 5 μm.

Using this decorative sheet, it was pressed onto an aluminum plate using a laminator at 110° C., and the entire decorative sheet was laminated. After lamination, 5 Mrad was applied on the polyester film under conditions similar to Example 1 in a nitrogen gas atmosphere.
It was fully irradiated with electron beam at a dose of . The obtained decorative sheet board was a good decorative sorting board almost similar to that of Example 1.

Example 3 The following composition was coated on one side of a transparent polyethylene terephthalate film with a thickness of 12 μm using a bar coater to give a uniform film thickness of 5 μm over the entire surface. After coating, it was dried and cured at 120°C for 5 minutes. A pattern layer was entirely formed thereon in the same manner as in Example 1. Next, the white coating layer shown in Example 2 was applied to a thickness of 10 μm. Thereafter, it was post-cured at 40°C for 2 days. Next, an electron beam curable resin composition having the composition shown in Example 1 was applied to a film thickness of 5 μm.

Using this decorative sheet, the decorative sheet was laminated onto a tin-free steel plate in the same manner as in Example 1, and as a result of electron beam curing, a good decorative sheet board was obtained.

Example 4 The urethane-based curing type adhesive film shown in Example 3 was formed on a transparent polyethylene terephthalate film having a thickness of 12 μm using the same method to have a film thickness of 5 μm. After forming a pattern layer thereon by the same method as in Example 1, a white coating layer having a thickness of 10 μm consisting of an electron beam curable composition having the same composition as in Example 1 was formed. Electron beam curable resin composition Pylon 200 35 parts Aronix M-6400X 15 parts Methyl ethyl ketone 30 parts Toluene
30 parts were coated to a film thickness of 5 μm and dried at 120° C. for 1 minute.

A decorative sheet was laminated on Tinonly steel under the same conditions as in Example 1 and cured with electron beams. The obtained decorative board showed good properties similar to those of Example 1.

Example 5 As a result of carrying out the same method as in Example 4 using a transparent polypropylene film instead of the transparent polyethylene terephthalate film, good results similar to those in Example 1 were obtained.

Example 6 An adhesive layer and a pattern layer were formed on a transparent polyethylene terephthalate film in the same manner as in Example 1, and an electron beam curable resin composition having the following composition was added thereon by 20 parts of Vylon 200 and Aronix M-6400X5. Part titanium oxide 25 parts Methyl ethyl ketone 50 parts Coating to a film thickness of 10 μm, drying the solvent, laminating on tin-free steel at 120°C, and exposing it to electron beam under the same conditions as in Example 1. As a result of irradiation, a decorative board with good properties was obtained.

Example 7 Adhesives M and I were formed on a transparent polyethylene terephthalate film in the same manner as in Example 1. On top of that, aluminum was applied to a film thickness of 50 OA using a high-vacuum deposition apparatus made by All Japan Vacuum Technology Co., Ltd. Example 1 was deposited on the deposited film.
An electron beam curable adhesive layer having the composition was uniformly applied to the entire surface to a thickness of 5 μm, and dried at 120° C. for 1 minute to prepare a decorative sheet.

The obtained decorative sheet was laminated onto an aluminum plate. Electron beam irradiation 1~ under the same conditions as Example J
, hardened. The resulting aluminum decorative board with metallic luster showed good results.

patent applicant Toyo Ink Manufacturing Co., Ltd. 19-

Claims (1)

[Claims] ■ A transparent plastic film (A) is provided with an adhesive layer (T3), a pattern layer (c), a concealing layer (D), and a radiation-curable adhesive layer opening in this order. A decorative sheet. The decorative sheet according to claim 1, wherein the thread 2 adhesive @ (T3) is a urethane hardening type adhesive. 3. The decorative sheet according to claim 1, wherein the adhesive layer (B) is made of a thermoplastic resin adhesive. Te4. The decorative sheet according to any one of claims 1 to 3, wherein the concealing layer (I) is a white coating layer. 5. The decorative sheet according to claim 4, wherein the hiding layer (1)) is a radiation-curable white coating layer. 6. The decorative sheet according to any one of claims 1 to 3, wherein the concealing layer (I) is a metal thin film. 7. The decorative sheet according to claim 6, wherein the concealing layer (DI is a metal vapor deposited film). 8. The radiation-curable adhesive layer) is made of a heptadium and/or prepolymer having an ethylenically unsaturated double bond. 1
The decorative sheet according to any one of claims 1 to 7, having a weight ratio of 0 to 90i and a weight ratio of 10 to 90i for a resin having no ethylenically unsaturated double bonds.