JPH09241563A - Printing ink for molding sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing ink which enables a pattern layer provided on a molding sheet to retain good shapeability and adhesion even upon exposure to physically severe conditions, such as heating, drawing, stretching and deformation. SOLUTION: In a molding 10 for stretching a molding sheet using a plug and a means for applying or reducing pressure, the molding has an opening 35, at least one of the external and inner surfaces is made of a thermoplastic resin layer, and a printing ink of a pattern layer 2 provided on the surface of the thermoplastic resin comprises a binder of a thermoplastic resin, which is softened and becomes plastic at 60 deg.C, and an ionizing radiation-curable resin.

Description

Detailed Description of the Invention

[0001] The present invention relates to a printing ink used for printing a sheet of a molded article composed of a plastic molding sheet having a picture layer, and more specifically, a method for forming a molding sheet by a method belonging to the so-called thermoforming category. Despite being stretched and deformed to form a molded product having an opening, the pattern layer formed on the side surface of the molded product belongs to a printing ink for a molding sheet having strength that does not deform or drop. .

A molding sheet printed with the printing ink of the present invention can be applied to, for example, draw molding (hereinafter referred to as sheet molding) which belongs to the category of so-called thermoforming methods.
The pattern layer formed by sheet molding, which is suitable for mass production without being restricted by the portion of the display, the shape or size of the molded body, is stretched and deformed, but strong adhesion and various It maintains the tolerance of.

[0003]

The printing ink of the plastic molded sheet of the present invention can be applied to a molded article in which the pattern layer printed on the molding sheet has been subjected to physical abuse such as heating, drawing and stretching / deformation. Another object of the present invention is to provide a printing ink capable of forming a tough pattern layer having strong adhesion, moldability following molding, and abrasion resistance against dies.

[0004]

In order to solve the above problems, the present invention provides a molded article obtained by stretching a molding sheet using a plug and pressure or pressure reducing means, wherein the molded article is A surface having at least one of an outer side and an inner side formed with a thermoplastic resin layer having an opening, and a surface on the side formed with the thermoplastic resin layer. The pattern layer having at least one of the side surfaces predicts the stretching of the molding sheet at the time of molding, and the printing ink provided with the pattern layer is a thermoplastic resin which softens at a temperature of 60 ° C. and exhibits plasticity. A printing ink for a molding sheet, which comprises an ionizing radiation curable resin as a binder. Further, the molded body has a multi-layer structure, and the laminated structure can be provided on a multi-layer sheet in which at least one of the outer surface and the inner surface is formed of a thermoplastic resin layer, and it is possible to follow the stretching of the molding sheet. It is a printing ink for molding sheets that has flexibility. The ionizing radiation curable resin has a wavelength of 180
Photoinitiator, photopolymerizable monomer or photopolymerizable oligomer that generates free radicals by utilizing ultraviolet rays or visible light of nm or more, or 100 KeV to 10 ⁶ KeV
A printing ink for a molding sheet containing a photopolymerizable monomer or photopolymerizable oligomer that generates a free radical by an electron beam of energy, a polyalkyl acrylate, and a polyalkyl methacrylate as main components.

[0005]

2. Description of the Related Art In a method for producing a molded product made of a synthetic resin, sheet molding is performed by softening or not heating a sheet-shaped thermoplastic resin, and fixing the periphery thereof with a plug or plug. A method of molding by means such as vacuum or pressure is widely used. Such sheet molding is suitable for mass production because the equipment cost of the molding machine is low and the molding speed is high as compared with other molding methods (for example, injection molding).

When a pattern layer such as characters, pattern figures, and images is provided on a molded product formed by sheet molding, it is usually printed directly on the surface of the molded product, for example, dry offset printing, gravure offset printing, pad printing, silk screen printing, Transfer printing or label sticking is used. However, it is difficult for these methods to directly perform printing when the shape of the printing surface is complicated or the size is small.

When it is difficult to form a pattern layer to be printed on a molded body, a method of simultaneously performing molding and printing [injection molding by inserting a label into a mold (in-mold label method), transfer film to mold A method of transferring the pattern layer by heat and pressure during molding, or a method of injection molding using several resins having different kinds or colors]. However, these methods are injection molding methods and thus have good dimensional accuracy of the molded body, but are disadvantageous in terms of production cost because of high mold cost and low productivity. In particular, in the method of inserting a label or a transfer film into a mold, an automatic insertion machine may be required, and there is a problem that equipment costs are high.

The above-mentioned in-mold label method is also applied to sheet molding, but since an automatic insertion machine is required, the scale of equipment becomes large, the equipment cost is high, and the label is inserted at the time of label insertion. Since wrinkles are generated and the position of the label is displaced, there is a problem that production loss increases.

Conventionally, when a printing ink is printed on a molding sheet by an arbitrary method, the printing ink is composed of a pigment displaying a color, and a thermoplastic resin dispersed or dissolved in an organic solvent or water for adhering to the molding sheet. A solvent evaporation drying type printing ink using a resin as a main binder is used.
After printing, these are dried with hot air at 90 to 140 ° C. to form an ink film and a pattern layer is provided. However, when the printing ink is printed on the molding film or sheet and dried with hot air, the molding film or sheet undergoes thermal expansion and contraction due to heat, and the pattern layer part is displaced or distorted, and There is a problem that it is not possible to print a simple pattern layer.

A printing ink, especially a gravure ink, which can be applied to sheet molding, has a abrasion resistance during molding, has abrasion resistance, has flexibility to follow stretching deformation, and can form a pattern layer without lowering adhesive strength, is obtained. That is not the case.

The printing ink of the present invention contains a thermoplastic resin that softens at 60 ° C. and an ionizing radiation-curable resin as main binder components, and does not move beyond the deformation of the sheet during the molding process. When the molding is completed, the desired pattern layer can be formed by following the stretching deformation of the molding sheet. That is, the binder of the printing ink of the present invention is a photoinitiator, a photopolymerizable monomer, or a photopolymerizer that generates a free radical by utilizing a thermoplastic resin such as an alkyl acrylate or an alkyl methacrylate and an ultraviolet ray or a visible ray having a wavelength of 180 nm or more. Oligomer, photocurable printing ink or 100 KeV to 10 ⁶
This is a photopolymerizable monomer or photopolymerizable oligomer electron beam curable printing ink that generates free radicals by an electron beam of KeV energy, which prevents deformation of the pattern layer due to thermal softening of the printing ink in the sheet forming process. It is the lowest.

The printing ink of the present invention has good adhesiveness to a molded article and followability of stretching during molding (hereinafter referred to as moldability), and the pattern layer of the molded article is faint, detached, It is a good product with no tape peeling. Further, the molded product having the pattern layer formed by the ink of the present invention is not limited to the one manufactured by sheet molding, but a site where uneven stretching is likely to occur, for example, a side surface part or a complicated surface shape place, etc. However, it is not in the conventional molded product having a tough picture layer.

[0013]

Embodiments of the present invention will now be described. FIG. 1 shows a molded product 1 having a pattern layer which is the object of the present invention.
2 is a perspective view showing an example of No. 0, and FIG.
It is the figure which showed the vertical cross section of typically. FIG. 3A is a perspective view of the molding sheet 1 provided with the pattern layer 2. FIG. 3B is a perspective view showing the molded body 10 of the sheet. 4 (A), (B), (C), (D) and (E) show other examples 51, 52, 53, 54 of molded articles having a pattern layer using the ink of the present invention. FIG. 55 is a perspective view showing 55.

As shown in the molded body 10 of FIG. 1, the molded body having a pattern layer of the present invention has a hollow interior, has an opening 35, a bottom surface portion 33, a side surface portion 31 and a flange 36, and has an outer side. The pattern layer 2 is provided on at least one surface of the surface portion 31a and the inner side surface body 31b. The molded body 10 is manufactured by sheet-molding the molding sheet 1 provided with the disc-shaped pattern layer 2 shown in FIG. 3 by using a plug and a pressurizing or depressurizing means with its periphery fixed. is there.

The shape of the molded body is not limited to the flat-bottomed cylindrical shape like the molded body 10 shown in FIG. 1, but the round-bottomed cylindrical shape 51, the hemispherical shape 52, the shallow convex surface 53, the rectangular parallelepiped shape 54 shown in FIG. Any shape that can be formed by sheet molding such as a polygonal column 55 can be adopted. When the molded body has a round bottom, a hemisphere, a shallow convex surface, or the like, the boundary between the side surface portion 31 and the flange 36 is not clear, but in the present invention, the side surface portion 31 of the molded body is the molded body. It means a region that constitutes the body part of the above, and is likely to cause uneven drawing, and also includes one that is not apparent in appearance.

The molding sheet to which the printing ink of the present invention is applied is not only a single layer sheet of a thermoplastic resin but also a multi-layer sheet in which at least one thermoplastic resin layer is present and the pattern layer is always a thermoplastic layer. It may be provided on the resin layer. For example, in the case of the molded body 10, a multilayer structure as shown in FIG. 2 is formed, the outer surface on which the pattern layer 2 is provided is formed of the thermoplastic resin layer 20, and the other layer, that is, 2 The intermediate layers 22 and 23 and the inner surface layer 25 of the layers are laminated by arbitrarily selecting layers in consideration of the use of the molded body.
Two or more thermoplastic resin layers may be present in the laminated structure. For example, the other layers 22 and 23 described above may be thermoplastic resin layers or other materials. .
In addition, the pattern protection layer 3 can provide the pattern layer or the surface of the molded article with properties (slip, writing, etc.) and resistance (prevention of contamination, scratch resistance, chemical resistance, etc.).

The pattern layer ink in the present invention can be printed on a molding substrate by a known method. Examples of the printing method include a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, a transfer printing method and a pad printing method. The preferred printing method in the present invention is preferably a gravure printing or a screen printing method in which the plate material can use a metal or the like and the selection range of the solvent is wide.

In the present invention, the printing ink for forming the pattern layer 2 is a vinyl chloride / vinyl acetate copolymer,
Thermoplastic resins such as linear polyester, polystyrene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ionomer, polymethacrylic acid acrylic resin, etc. A photoinitiator that generates free radicals by using ultraviolet rays or visible light of 180 nm or more, a photopolymerizable monomer or photopolymerizable oligomer, a photocurable printing ink containing a coloring pigment as a main component, or 100 KeV to 10 ⁶ KeV energy An electron beam curable printing ink containing a photopolymerizable monomer or photopolymerizable oligomer that generates a free radical by an electron beam and a coloring pigment as main components is preferable.

As a photoinitiator for generating free radicals by utilizing ultraviolet rays or visible rays having a wavelength of 180 nm or more, benzoisobutyl ether, benzyl dimethyl ketal,
Intramolecular bond cleavage type radical polymerization initiators such as diethoxyacetophenone, acyloxime ester, chlorinated acetophenone, hydroxyacetophenone, acylphosphoxide, glyoxyester, and cyclic benzyl,
Benzophenone, Michler's ketone, dibenzosuberone,
Intermolecular hydrogen abstraction type radical polymerization initiators such as 2-ethylanthraquinone, isobutylthioxanthone, benzyl, 3-ketomachrine, camphorquinone,
Anthraquinone, α-naphthyl, acenaphthene, p,
dicarbonyl-based radical polymerization initiators for curing visible light such as p'-dimethoxybenzyl, p, p'-dichlorobenzyl, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, Thioxanthone-based radical polymerization initiators for curing visible light, such as 2,4-diethyloxanson, 2,4,6-trimethylbenzoyldiphenylphosphonoxide (TMDP
O), acylphosphone oxide-based radical polymerization initiators for curing visible light such as 2,6-dimethylbenzoylphosphon oxide, cantercure PDO, Eos
and a radical polymerization initiator for visible light curing such as in Y. Also, a water-soluble photoinitiator such as 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and a copolymerizable polymer such as α-allylbenzoin, α-allylbenzoin aryl ether, and benzophenone derivative. Photoinitiators are mentioned.

In addition to these photoinitiators, photoinitiating aids such as amines, sulfones and phosphines can be used in combination. By using the photoinitiator together,
Radical generation reaction is promoted by using a photoinitiator alone,
The curing reaction can proceed more efficiently. The main photoinitiator aids are triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, aliphatic amines such as diethylaminoethyl methacrylate, Michler's ketone, 4,4′-diethylaminophenone, 4 -Aromatic amines such as ethyl dimethylaminobenzoate, (n-butoxy) ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, phosphines such as tri-n-butylphosphine, and sulfones such as allylthiourea. Can be mentioned.

The photopolymerizable monomer or photopolymerizable oligomer used in the present invention undergoes a polymerization reaction by the free radicals generated from the photoinitiator by ultraviolet rays and visible rays, and reacts from the monomer or oligomer to the polymer. Form the layers. The photopolymerizable oligomer is a polymer in which the number of repeating structural units of the formed polymer is about 2 to 20, and is epoxy acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene acrylate. , Silicon acrylate, polybutadiene acrylate, polystyrylethyl acrylate, polycarbonate diacrylate and the like.

The photopolymerizable monomer has an acryloyl group (C
H ₂ = COCO-) or methacryloyl group (CH ₂ = C (C
There are one having one H ₃ ) CO-) (monofunctional acrylate) or one having two or more (multifunctional acrylate) per molecule. Alternatively, some have a vinyl group (CH ₂ = CH-). As an aliphatic monofunctional acrylate, an alkyl type such as 2-ethylhexyl acrylate and lauryl acrylate, an alkoxyalkylene glycol type such as methoxydiethylene glycol acrylate and methoxy polyethylene glycol methacrylate, a cyclohexyl type such as cyclohexyl acrylate, and a tetrahydrofuryl acrylate such as tetrahydrofurfuryl acrylate. Freele type, isobornyl type such as isobonyl acrylate,
Examples thereof include dicyclopentenyl acrylate and dicyclopentadienyl acrylate, and other dicyclopentenyl acrylates, N-dimethylaminoethyl acrylate and other amine types, and tetrafluoropropyl acrylate and heptadecafluorodecyl acrylate and other fluorine types.

As the aliphatic polyfunctional acrylate, 1,4
Alkyl type such as butanediol diacrylate, neopentyl glycol diacrylate and 1,6 hexanediol diacrylate, alkylene glycol type such as diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol 400 diacrylate and tripropylene glycol diacrylate, Hydroxypivalate ester type such as neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane type such as ethoxylated trimethylolpropane tetraacrylate, pentaerythritol triacrylate,
Examples thereof include pentaerythritol type such as dipentaerythritol hexaacrylate, isocyanurate type such as tris (acryloxyethyl) isocyanurate, and alicyclic type such as dicyclopentanyl diacrylate and ethoxylated hydrogenated bisphenol A diacrylate.

The aromatic monofunctional acrylate includes phenyl type such as phenyl acrylate, benzyl type such as benzyl acrylate, and phenoxy type such as phenoxydiethylene glycol acrylate and nonylphenoxy polyethylene glycol acrylate. Examples of the aromatic polyfunctional acrylate include bisphenol A type such as ethoxylated bisphenol A diacrylate, ethoxylated bisphenol F diacrylate, and ethoxylated bisphenol S diacrylate.

Acrylates containing OH groups include alcohol types such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and hydroxydiethylene glycol methacrylate, butoxyhydroxypropyl acrylate,
Epoxy type such as phenoxyhydroxypropyl acrylate, hydroxypropyl dimethacrylate, diethylene glycol bis (hydroxypropyl acrylate), propoxylated bisphenol A bis (hydroxyfluoropropyl acrylate), trimethylolpropane type such as hydroxypropylated trimethylolpropane triacrylate, mono Pentaerythritol type such as hydroxypentaerythryl triacrylate; Allyl group-containing acrylates include allyl acrylate.

Examples of the glycidyl group-containing acrylate include glycidyl methacrylate. Examples of the acrylate containing a carboxyl group include monoacryloxyethyl phthalate ester and monoacryloxysuccinate ester. In addition, phosphorus-type compounds such as acryloxyethoxydihydroxyphospheon oxide, bis (acrylyloxyethoxy) hydroxyphosphine oxide, and methacryloxyethoxyditoxoxyphosphine oxide,
Examples thereof include metal types such as zinc diacrylate, pyrroliderin types such as N-vinylpyrrolidrin, and vinyl acetate.

The ratio of photoinitiator, photopolymerizable monomer or photopolymerizable oligomer which generates free radicals by utilizing ultraviolet rays or visible rays and the color pigment can be set by the intensity of ultraviolet rays and visible rays, temperature and humidity. Generally, the ratio of the photopolymerizable monomer or oligomer to the photoinitiator is preferably 1 to 20 parts by weight based on 100 parts by weight of the resin component.

Thermoplasticity is given to impart flexibility, abrasion resistance and durability to the cured film and to improve the shapeability of the pattern layer for the stretching process of the molding sheet during thermoforming, that is, the thermoformability. A resin can be added. The ratio of the thermoplastic resin to be added is set depending on the thermoforming conditions, the adhesion between the molding sheet and the ink, and the compatibility with the photopolymerizable monomer or the photopolymerizable oligomer, but in general, the photopolymerizable monomer or the photopolymerizable oligomer is used. The thermoplastic resin is preferably 10 to 120 parts by weight with respect to 100 parts by weight. When the amount of the thermoplastic resin is too large, the solvent becomes a heat-drying type printing ink which requires high-temperature hot-air drying after printing, which causes distortion in the molding sheet and lowers the printing productivity. If the amount of the thermoplastic resin is too small, the effect of adding it will not be recognized.

The printing ink used in the present invention is 100
An electron beam curable printing ink containing a photopolymerizable monomer or photopolymerizable oligomer that generates a free radical by an electron beam having an energy of KeV to 10 ⁶ KeV and an ordinary pigment as a main component may be used.

As the photopolymerizable monomer or photopolymerizable oligomer used in the electron beam curable printing ink, the above-mentioned photopolymerizable monomer or photopolymerizable oligomer which generates a free radical by utilizing ultraviolet rays and visible rays is used.
Further, in order to impart flexibility, abrasion resistance, and durability to the cured film, and to improve the shapeability of the printing ink for the stretching process of the molding film or sheet during thermoforming, that is, the thermoformability. Add thermoplastic.

The thermoplastic resin to be added to the ionizing radiation curable resin is a vinyl chloride / vinyl acetate copolymer, linear polyester, polystyrene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene. Examples include acrylic acid ester copolymers, ionomers, acrylic resins such as polymethacrylic acid ester, and the like. And
The ratio of the thermoplastic resin to be added can be set by thermoforming conditions, adhesion with a molding sheet, compatibility with a coloring pigment and a photopolymerizable monomer or a photopolymerizable oligomer,
Generally, the amount of the photopolymerizable monomer or photopolymerizable oligomer is 20 to 120 parts by weight based on 100 parts by weight. If the amount of thermoplastic resin is too large, not only will the chemical resistance decrease, but a solvent will also become a heat-drying type printing ink that requires printability.After printing, high-temperature hot-air drying or time-consuming drying is required. It will result in poor productivity. If the amount of the thermoplastic resin is too small, the effect of adding it will not be recognized.

The thickness of the molding sheet is usually 50-100.
The thickness is 0 μm, and the sheet is prepared by a method of single layer or co-extrusion by ordinary melt extrusion, or in the case of a multilayer sheet, a plurality of sheets are laminated by using an adhesive or an adhesive resin, if necessary. It can be formed. The thermoplastic resin layer is a polyolefin resin, polystyrene resin, polyester resin, chlorinated resin, polyamide, polyimide, polyurethane, acrylic resin, natural polymer, thermoplastic elastomer, ethylene and acrylic acid derivative or methacrylic acid derivative. Examples thereof include copolymers with, amorphous polyolefins, foams of these resins, crosslinked products, hydrogenated products, and polymer alloys and polymer blends composed of several kinds of thermoplastic resins.

A flexible pattern protection layer is provided on the surface of the pattern layer so as to prevent friction and scratches with the mold at the time of molding, or to prevent the pattern layer from falling off during the distribution process or to prevent damage to chemicals such as contents. It is preferable to provide.

The material forming the protective layer includes, in addition to the above-mentioned thermoplastic resin, ester resin, acrylic resin, olefin resin, urethane resin, vinyl chloride resin, polymer network resin, cellulose derivative and the like. It can be provided by melt extrusion coating or can be provided by coating these solutions or dispersions. In addition, thermosetting varnish such as ionizing radiation curable resin, epoxy ester, and vinylated alkyd, and curable curable resin such as polyester or polyether isocyanate can be applied to the molding sheet and the pattern layer to make it strong and flexible. You can select from excellent materials.

The formation of the protective layer is performed on the molding sheet by
Dry laminating the film of the protective layer material through an adhesive or an adhesion promoter, if necessary,
The resin can be formed by melt extrusion coating, a solution or dispersion of the above materials can be printed on the pattern layer, or can be formed by coating the entire surface. The thickness of the protective layer is 5 to 80 μm, depending on the material and the forming method.

The molding sheet may have a multi-layered structure as well as a single layer. For multi-layer sheets,
Other than the surface provided with the pattern layer being the thermoplastic resin layer, the other layers can be appropriately selected in consideration of the use of the molded product, the processability and the like. Then, as the multilayer, the following layers can be exemplified as the layers other than the thermoplastic resin layer of the molding sheet, which are constituted by interposing an adhesive or an adhesive resin as necessary.

(A) Thermoplastic resin layer as an intermediate layer (b) Oxygen permeation amount at 20 ° C. and relative humidity 65% is 2
Oxygen-blocking resin layer having 0 cc · 20 μm1 / m ² · 24 hr · atm or less (c) Oxygen-absorbing substance-containing layer, oxygen-absorbing thermoplastic resin layer (d) Moisture-absorbing substance-containing layer, moisture-absorbing thermoplastic Resin layer (e) Metal foil (f) Paper (g) Nonwoven fabric (h) Non-adsorbent resin layer (i) Antibacterial / antifungal layer, Antibacterial / antifungal thermoplastic resin layer (j) Biodegradable polymer Layer, biodegradable thermoplastic resin layer (K) expandable polymer layer, expandable resin layer

Further, a single layer may have several functions. For example, one of a plurality of layers or one of a plurality of layers may have an oxygen-absorbing substance and a moisture-absorbing substance. By adding both of these, the oxygen-absorbing substance-containing layer and the water-absorbing substance-containing layer can be made to serve as both layers. 5 to 16 show examples of the molding sheet having the multilayer structure of the present invention. (1) As shown in FIG. 5, the pattern layer 2 / the outer surface thermoplastic resin layer 20 /
A molding sheet 1 having a layer structure of an adhesive layer 41 / innermost surface layer 25S. (2) As shown in FIG. 6, the pattern layer 2 / the outer surface thermoplastic resin layer 20 /
A molding sheet 1 having a layer structure of an adhesive layer 41 / inner surface thermoplastic resin layer 25S / picture layer 2. (3) As shown in FIG. 7, the pattern layer 2 / the outer surface thermoplastic resin layer 20 /
Molding sheet 1 having a layer structure of adhesive resin layer 42 / oxygen-blocking thermoplastic resin layer 11 / adhesive resin layer 42 / inner surface thermoplastic resin layer 25S (4) Design layer 2 / outer surface thermoplastic resin shown in FIG. Layer 20 /
A molding sheet 1 having a layer structure of an oxygen-absorbing thermoplastic resin layer 12, an oxygen-blocking thermoplastic resin layer 11, an oxygen-absorbing thermoplastic resin layer 12, and an inner thermoplastic resin layer 25S. (5) As shown in FIG. 9, the pattern layer 2 / the outer surface thermoplastic resin layer 20 /
A molding sheet 1 having a layer structure of a moisture-absorbing thermoplastic resin layer 13 / an oxygen-blocking thermoplastic resin layer 11 / a moisture-absorbing thermoplastic resin layer 13 / an inner surface thermoplastic resin layer 25S. (6) Design layer 2 / outer surface thermoplastic resin layer 20 shown in FIG.
Molding sheet 1 having a layer structure of / adhesive resin layer 42 / metal foil 17 / adhesive resin layer 42 / inner surface thermoplastic resin layer 25S. (7) Design layer 2 / outer surface thermoplastic resin layer 20 shown in FIG.
Molding sheet 1 having a layer structure of / paper (or non-woven fabric) 18 / inner surface thermoplastic resin layer 25S. (8) Design layer 2 / outer surface thermoplastic resin layer 20 shown in FIG.
Molding sheet 1 having a layer structure of / adhesive layer 41 / non-adhesive resin layer 14. (9) A molding sheet 1 shown in FIG. 13, which has a layer structure of a pattern layer 2 / antibacterial, antifungal material or biodegradable inner thermoplastic resin layer 15. (10) Design layer 2 / outer surface thermoplastic resin layer 20 shown in FIG.
A molding sheet 1 having a layer structure of / adhesive layer 41 / foamed resin layer 16. (11) A molding sheet 1 shown in FIG. 15 having a layer structure of a pattern protection layer 3 / a pattern layer 2 / an inner surface thermoplastic resin layer 25S. (12) As shown in FIG. 16, pattern protection layer 3 / adhesive layer 41 / pattern layer 2 / outer surface thermoplastic resin layer 20 / adhesive layer 41 / oxygen-blocking thermoplastic resin layer 11 / adhesive layer 41 / inner surface heat A molding sheet 1 having a layer structure of a plastic resin layer 25S.

[0039]

EXAMPLES The pattern layer printing ink of the present invention can be printed on a molded sheet by a known method. Examples of the printing method include a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, a transfer printing method and a pad printing method. The preferred printing method in the present invention is gravure printing or screen printing, which can adjust the density of the ink for the pattern layer.

(Example 1) Using a 0.5 mm-thick polypropylene, polystyrene, amorphous polyethylene terephthalate (A-PET), or polycarbonate as a molding sheet, screen printing was performed to print the pattern layer 2 shown in FIG. did. A sample of Example 1 was prepared by curing with ionizing radiation. [Ultraviolet curable ink] ・ Cyanine blue 15 parts by weight ・ Ethyl methacrylate 35 parts by weight ・ Polymethyl acrylate 25 parts by weight ・ 1,6 Hexanediol acrylate 15 parts by weight ・ Tripropylene glycol diacrylate 5 parts by weight ・ 2- Ethylhexyl p- (N, N-dimethylamino) benzoate 2 parts by weight N-vinylpyrrolidone 3 parts by weight α-aminoacetophenone 4 parts by weight It was cured by irradiation with 80 W / cm ultraviolet rays having a main wavelength of 365 nm. [Electron ink] ・ Cyanine blue 15 parts by weight ・ Ethyl methacrylate 35 parts by weight ・ Polymethyl acrylate 25 parts by weight ・ 1,6 Hexanediol acrylate 15 parts by weight ・ Tripropylene glycol diacrylate 5 parts by weight ・ 2-Ethylhexyl -P- (N, N-dimethylamino) benzoate 2 parts by weight N-vinylpyrrolidone 3 parts by weight An electron beam of 200 KeV was applied for 2 seconds for curing.

With respect to the sample of Example 1, a flat-bottomed cylinder shown in FIG. 3 was molded by plug-assisted pressure molding, and the pattern layer 2 on the side surface thereof was evaluated as follows. Mouldability: The appearance of the molded pattern layer is visually evaluated for ink loss and elongation. Adhesiveness: An adhesive tape is pressure-bonded to the pattern layer of the molded product, and the state of the pattern layer after peeling off the tape is visually evaluated. The evaluation results are shown in Table 1.

[0042]

[Table 1]

A printing ink was prepared by mixing 15 parts by weight of phthalocyanine blue with 85 parts by weight of a resin varnish prepared by mixing the oligomer or monomer of the ionizing radiation-curable resin and the thermoplastic resin in the compounding ratio shown in Table 2. , 0.5m
A polyester sheet of m was provided with a pattern layer in the same manner as in Example 1, and the sample was cured with ultraviolet rays by adding an electron beam and α-aminoacetophenone, and the electron beam and ultraviolet ray-cured samples of sample numbers 1 to 14 of Example 2 were obtained. It was created.

[0044]

[Table 2]

A molded body was formed from the sample of Example 2 in the same manner as in Example 1, and the patterning and adhesion results of the pattern layer evaluated in the same manner are shown in Table 3.

[0046]

[Table 3]

[0047]

The molding sheet printed with the printing ink of the present invention comprises the printing ink composed of a binder composed of an ionizing radiation curable resin and a thermoplastic resin.
The cured pattern layer has hardness and is excellent in various resistances. When heated and subjected to pressure-assisted or vacuum forming by plug assist, the thermoplastic resin makes the ink plastic, and as a result, the pattern layer has excellent flexibility, and the pattern layer formed by molding is stretched. Despite being deformed, it maintains strong adhesion and various resistance.

[Brief description of drawings]

FIG. 1 is a perspective view of a molded body of the present invention.

FIG. 2 is a schematic view showing an example of a cross section of a multilayer molded body.

FIG. 3 (A) is a plan view of the molding sheet for explaining the stretching state of the molding sheet provided with the pattern layer. FIG. 3B is a perspective view showing a molded body of the molding sheet.

FIG. 4A is a perspective view showing a round-bottomed cylindrical shaped body. (B) It is a perspective view showing a hemispherical molded body. (C) It is a perspective view which tightens a shallow convex-shaped molded object. (D) is a perspective view showing a rectangular parallelepiped shaped body. (E) is a perspective view showing a polygonal columnar molded body.

FIG. 5 is a schematic sectional view showing an example of the multilayer molding sheet of the present invention.

FIG. 6 is a schematic cross-sectional view showing another example of the multilayer molding sheet of the present invention.

FIG. 7 is a schematic cross-sectional view showing another example of the multilayer molding sheet of the present invention.

FIG. 8 is a schematic cross-sectional view showing another example of the multilayer molding sheet of the present invention.

FIG. 9 is a schematic cross-sectional view showing another example of the multilayer molding sheet of the present invention.

FIG. 10 is a schematic cross-sectional view showing another example of the multilayer molding sheet of the present invention.

FIG. 11 is a schematic sectional view showing another example of the multilayer molding sheet of the present invention.

FIG. 12 is a schematic sectional view showing another example of the multilayer molding sheet of the present invention.

FIG. 13 is a schematic cross-sectional view showing another example of the multilayer molding sheet of the present invention.

FIG. 14 is a schematic cross-sectional view showing another example of the multilayer molding sheet of the present invention.

FIG. 15 is a schematic sectional view showing another example of the multilayer molding sheet of the present invention.

FIG. 16 is a schematic cross-sectional view showing another example of the multilayer molding sheet of the present invention.

[Explanation of symbols]

 1 Molding sheet 2 Design layer 3 Design protection layer 11 to 15 Functional resin layer 11 Oxygen-shielding thermoplastic resin layer 12 Oxygen-absorbing thermoplastic resin layer 13 Moisture-absorbing thermoplastic resin layer 14 Non-adhesive resin layer 15 Antibacterial , Antifungal or biodegradable thermoplastic resin layer 16 Foamed resin layer 17 Metal foil 18 Paper or non-woven fabric 20 External thermoplastic resin layer 22, 22 Inner surface resin layer 25 Innermost surface layer 25S Inner surface thermoplastic resin layer 31 Side surface part 31a Side surface outside 31b Side inside 33 Bottom 33a Bottom outside 33b Bottom inside 35 Opening 36 Flange 41 Adhesive layer 42 Adhesive resin layer 51, 52, 53, 54, 55, molded body with pattern layer

Claims (3)

[Claims] 1. A molded body obtained by stretching a molding sheet using a plug and a pressurizing or depressurizing means, wherein the molded body has an opening, and at least one of the outer surface and the inner surface has a surface. Formed of a thermoplastic resin layer,
And, the surface of the side formed by the thermoplastic resin layer, the pattern layer having at least one side surface of the outer side and the inner side of the molded body, predict the stretching of the molding sheet during molding A printing ink for forming a sheet, wherein the printing ink provided with the pattern layer comprises, as a binder, a thermoplastic resin that is softened at a temperature of 60 ° C. and exhibits plasticity, and an ionizing radiation-curable resin. 2. The molded body has a multi-layer structure, and the laminated structure can be provided with a multi-layer sheet having at least one of the outer surface and the inner surface formed of a thermoplastic resin layer. Printing ink for forming sheets, which has the flexibility to follow. 3. The ionizing radiation curable resin has a wavelength of 18
A photoinitiator, a photopolymerizable monomer or a photopolymerizable oligomer that generates a free radical by utilizing ultraviolet rays or visible rays of 0 nm or more, or 100 KeV to 10 ⁶ Ke
The printing ink for a molding sheet according to claim 1, which comprises a photopolymerizable monomer or photopolymerizable oligomer that generates a free radical by an electron beam of V energy, a polyalkyl acrylate, or a polyalkyl methacrylate as a main component. .