JPH09220798A - Pattern protecting layer in molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern protecting layer preventing the generation of pinholes in the pattern layer provided to a molding sheet even after the pattern layer receives physical maltreatment such as the stretching deformation caused by heating molding and keeping toughness, durability, abrasion resistance and chemical resistance. SOLUTION: A molded object 10 molded from a sheet has an opening part 35 and at least one surfaces of the outside and inside thereof are formed from a thermoplastic resin layers. The protective layer covering the pattern layer 2 provided on at least one surface of the outside and inside of the surfaces formed of the thermoplastic resin layers is formed into a pattern protecting layer 3 having plastic properties and capable of following stretching even at temp. at a time of the molding of a molding sheet.

Description

Detailed Description of the Invention

[0001] The present invention relates to a pattern protective layer applied to a pattern layer of a sheet of a molded article made of a plastic molding sheet having a pattern layer, more specifically, a method for molding by a method belonging to the so-called thermoforming category. Although the sheet is stretched and deformed to form a molded product having an opening, the pattern layer formed on the side surface of the molded product can maintain the strength without deformation or falling off. Belongs to the protective layer.

Further, the printed matter provided with the pattern protection layer of the present invention can be applied to, for example, drawing of a plastic sheet (hereinafter referred to as sheet molding) which belongs to the category of so-called thermoforming methods, and can be applied to display portions and molded articles. It is not restricted by shape or size. In addition, although the pattern layer formed by sheet molding of the mass-produced printed matter is stretched and deformed, strong adhesion and various resistances are maintained.

[0003]

The pattern protective layer of the present invention is a pattern of a molded product when the pattern layer printed on the molding sheet is further subjected to physical abuse such as heating, drawing and deformation such as drawing. The layer has strong adhesion, moldability that follows molding, and abrasion resistance against dies, etc., and also forms a tough and durable picture layer by preventing erosion of water, organic solvents, chemicals, etc. It is an object to provide a protective layer for the pattern.

[0004]

In order to solve the above-mentioned problems, the pattern protection layer of the present invention is a molded product formed from a sheet and has an opening and at least one of the outside and the inside. Is formed of a thermoplastic resin layer, and,
The protective layer that covers the pattern layer provided on the sheet surface formed by stretching at least one of the outside and the inside of the surface formed of the thermoplastic resin layer has plasticity at the temperature during molding of the molding sheet. A pattern protection layer in a molded product, which is composed of a resin layer which can be deformed following the stretching of the molding sheet. The molding sheet has a multi-layered structure, and is a pattern protection layer of a molded product including a thermoplastic resin layer formed on a pattern layer on at least one of the outside and / or the inside. The pattern protection layer made of the thermoplastic resin has a thickness of 2 to 100 μm and is a pattern protection layer in a molded product that exhibits flexibility at the sheet molding temperature. Further, the pattern protection layer is a polyolefin resin, polystyrene resin, polyester resin,
Of thermoplastic resins such as chlorine-containing resin, fluorine-containing resin, polyamide resin, polyimide resin, polyurethane resin, etc., dry lamination of a film of one type or a mixture of two or more types, or extrusion coating of molten resin Is formed on the pattern layer by using, or in addition to the thermoplastic resin, an acrylic ionizing radiation curable resin
It is a pattern protective layer in a molded product in which one kind or two or more kinds are mixed and dispersed and dissolved and varnish is applied on the pattern layer.

[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 forming by stretching with a pressure reducing means such as vacuum or compressed air 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 article formed by sheet molding, it is usually printed directly on the surface thereof, for example, dry offset printing, gravure offset printing, pad printing, silk screen printing, transfer printing or It is carried out by a method such as sticking a label.
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 of different types or colors] is adopted. 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.

Further, when molding is performed from a molding sheet provided with a pattern layer, thickness unevenness due to stretching unevenness is likely to occur unlike deep drawing of a metal plate. In particular, there is a tendency for uneven drawing to easily occur in a portion corresponding to a side surface portion of a molded body or a portion molded into a complicated shape. Therefore, the pattern layer provided on the forming sheet is significantly stretched and deformed in the sheet forming process, and the pattern protective layer provided on the pattern layer causes pinholes.

As described above, it can be applied to sheet forming,
It is said that a pattern protection layer that does not completely prevent erosion of water, organic solvents and chemicals while maintaining abrasion resistance to withstand abuse during molding, flexibility to follow stretching deformation, adhesive strength is not obtained. The current situation.

The pattern protection layer of the present invention is formed on the pattern layer provided on at least one surface of a molding sheet containing a thermoplastic resin as a main component, and when the molding is completed, the molding sheet is stretched. Even if the pattern layer is stretched and deformed into a desired shape following the deformation, the pattern layer is prevented from falling off, and a tough uniform layer without pinholes is formed.

Further, although the molded article provided with the pattern protection layer of the present invention is manufactured by sheet molding, a portion where stretch unevenness is likely to occur, for example, a side surface portion or a complicated surface shape is complicated. It protects and maintains a tough picture layer even in places, and such a molded product has never been available before.

[0013]

Next, an embodiment of the present invention will be described. FIG. 1 is a perspective view showing an example of a molded body 10 having a pattern protection layer 3 on a pattern layer 2 which is the object of the present invention, and FIG. 2 is a schematic vertical cross section of a multilayer molded body 10. It is the figure shown. FIG. 3A is a perspective view of the molding sheet 1 provided with the pattern layer 2 and the pattern protection layer 3, and FIG. 3B is a perspective view showing a molded body 10 of the sheet.

As shown in FIG. 1, a molded body 10 having a pattern layer according to the present invention has a hollow interior and an opening 35 and a bottom 33.
And a side surface portion 31 and a flange 36, and the outer side surface portion 31
The pattern protection layer 3 is formed on the pattern layer 2 provided on at least one surface of a and the inner side surface portion 31b. Molded body 1
No. 0 is produced by forming a 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.

The shape of the molded body is not limited to the flat-bottomed cylindrical molded body 10 shown in FIG. 1, but may be any of those shown in FIGS.
As shown in (D) and (E), a sheet-moldable shape such as a round-bottomed cylindrical shape 51, a hemispherical shape 52, a shallow convex shape 53, a rectangular parallelepiped shape 54, or a polygonal column shape 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 bottom surface portion 33 is not clear, but the side surface portion of the molded body according to the present invention is not clear. The reference numeral 31 means a region that constitutes the body of the molded product, does not deform at a draw ratio that is simply calculated by the draw ratio of the forming sheet, and is likely to cause draw unevenness. It also includes those that are not.

As the pattern layer of the molded product, as shown in FIG. 3 (A), a molding sheet 1 in which a pattern protective layer 3 is provided on a pattern layer 2 which is printed in anticipation of deformation, is formed by sheet molding. Will be completed. Although the pattern protection layer 3 in the drawing is described so as to partially cover only the pattern layer 2 for emphasis, it is usually applied to the entire surface by dry lamination of the film.

The molding sheet of the present invention 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 a pattern layer is always provided on the thermoplastic resin layer. , And a pattern protective layer formed on the pattern layer. For example, in the case of the molded body 10, a multilayer structure as shown in FIG. 2 is formed, and the thermoplastic resin layer 20 and the pattern layer 2 are provided on the outer surface where the pattern layer 2 is provided.
And the picture protection layer 3 is formed. And the other layers,
That is, the two intermediate layers 22 and 23 and the innermost surface layer 25 are laminated layers arbitrarily selected 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 sheets. Furthermore, the pattern protection layer 3 causes scratches due to contact with a mold during molding, and scratches due to friction, dropping, etc. as a print sheet or a molded product.
And as a printed sheet or molded product, water, organic solvent,
It is possible to provide resistance to dissolution of the pattern layer due to erosion of chemicals.

The pattern protection layer is one or more of polyolefin resin, polystyrene resin, polyester resin, chlorine resin, fluorine resin, polyamide resin, polyimide resin, polyurethane resin and the like. Laminating a film of a mixed system, forming an image on a pattern layer by extrusion coating a molten resin, or one or more acrylic ionizing radiation curable resins other than the thermoplastic resin Can be formed by mixing, dispersing and applying a dissolved varnish. In addition, the thickness of the pattern protection layer, which can follow the sheet molding and prevent cracks during molding, is 2 to 100 μm.

The pattern protective layer imparts slipperiness, abrasion resistance, anti-blocking property, scratch resistance, water resistance and water repellency, and therefore, plant waxes such as carnauba wax and tree wax, animal waxes such as beeswax and anhydrous lanolin, Addition of paraffin wax, microcrystalline wax, mineral wax such as petrolatum, synthetic wax such as polyethylene wax, polytetrafluoroethylene, chlorinated paraffin, and fatty acid amide has the effect of improving physical properties.

Further, nonionic activators such as polyoxyalkylene glycol derivatives and fatty acid esters, alcohols such as octyl alcohol, tridecyl alcohol and oleyl alcohol, defoaming agents such as pine oil, mineral oil and metal soaps, antifoaming agents. , Antifoaming agent, foaming agent such as azodicarbonamide, alkylamine salt of dimer acid or trimer acid, alkylamine salt of oxycarboxylic acid, alkylamine phosphate, silicone oil, eugenol, amphoteric surfactant, nonionic Antistatic agents such as type activators, anion type activators and cationic type activators, flame retardants such as antimony trioxide and paraffin chloride, anti-slip agents such as colloidal silica and synthetic rubber latex can be added.

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, the layer is exemplified by the layers described below as the layers other than the thermoplastic resin layer of the molding sheet, which are formed by interposing an adhesive or an adhesive resin as needed.

The thickness of the molding sheet is usually 50-100.
The thickness of the sheet is 0 μm, and the sheet is formed by the usual melt extrusion molding method of T die or circular die in the case of a single layer, and in the case of a multilayer sheet, a method by coextrusion or a plurality of sheets as necessary. Can be formed by laminating using an adhesive or an adhesive resin.

The thermoplastic resin forming the pattern protection layer is 2
A material capable of forming a film having a thickness of up to 100 μm or a material capable of melt extrusion coating is selected according to the purpose such as the resistance of the film. For example, polyethylene, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ionomer, polypropylene, ionomer and other polyolefin resins, ethylene / vinyl alcohol copolymer, saponified polyvinyl alcohol, polystyrene resin, polyester Examples thereof include system resins, chlorinated resins, polyamides, polyimides, polyurethanes, acrylic resins, crosslinked products of these resins, hydrogenated products, and polymer alloys and polymer blends composed of several kinds of thermoplastic resins.

More specifically, low / medium density polyethylene,
Isotactic polyethylene, ethylene-propylene copolymer, ionomer, polybutene-1, ethylene
Butene-1 copolymer, propylene / butene-1 copolymer, ethylene / propylene copolymer, ethylene / propylene /
Examples thereof include butene-1 copolymer and vinyl chloride / vinyl acetate copolymer.

Examples of polystyrene resins include polystyrene, high-impact polystyrene, styrene / butadiene copolymers, styrene / isoprene copolymers, acrylonitrile / butadiene / styrene copolymers and acrylonitrile / styrene copolymers.

Examples of the polyester resin include polyethylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and polybutylene naphthalate.

Examples of the chlorinated resin include polyvinyl chloride, polyvinylidene chloride and propylene / vinyl chloride copolymer. Examples of the fluorine-containing resin include tetrafluoroethylene, trifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride and the like.

As the polyamide resin, nylon 6,
Examples include nylon 66, nylon 6.66 copolymer, metaxylylene adipamide, nylon 6/10 copolymer, nylon 11, nylon 12, nylon 13 and the like.

Examples of the acrylic resin include polymethylmethacrylate, methylmethacrylate / styrene copolymer, methylmethacrylate / butylmethacrylate copolymer and the like.

As the inner surface resin layer, the following materials can be used in addition to the materials applicable to the above-mentioned pattern protection layer. For example, polyimide-based resins include polyamide-imide and polyether-imide. Examples of the gas barrier resin include polyacrylonitrile and ethylene / vinyl alcohol copolymer. Examples of the hygroscopic resin include polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyvinyl methyl ether, and vinyl alcohol / acrylic acid copolymer. Examples of the adhesive resin include ethylene / acrylic acid copolymer, ionomer, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, acrylic acid grafted polyethylene, ethylene / vinyl acetate copolymer, polyester and polyamide. it can.

Examples of natural polymer resins include regenerated cellulose, ethyl cellulose, cellulose acetate, cellulose propionate, and cellulose nitrate.

Examples of thermoplastic elastomers include polystyrene-based elastomers, vinyl chloride-based elastomers, polyolefin-based elastomers, polyester-based elastomers, polyamide-based elastomers and polyurethane-based elastomers. As a polymer elastomer, which is a kind of thermoplastic elastomer, the hard component is polystyrene, and the soft segment is at least one of polybutadiene, polyisoprene, ethylene / butylene block copolymer, and ethylene / prolene block copolymer. You can exemplify what you have.

Examples of the vinyl chloride elastomer, which is one kind of thermoplastic elastomer, include those having polyvinyl chloride as a hard segment component and at least one of nitrile butadiene rubber, polyurethane and polyester as a soft segment component.

The olefin elastomer has polyethylene as a hard segment component, and ethylene / prolene block copolymer, butyl rubber, ethylene / prolene / diene copolymer rubber, ethylene / vinyl acetate copolymer rubber, ethylene as a soft segment component. Ethyl acrylate copolymer rubber Nitrile butadiene copolymer rubber, acrylic rubber and the like can be exemplified.

The polyester elastomer has polyethylene terephthalate as a hard segment component, an aliphatic polyether (for example, a condensation product of tetramethylene glycol and terephthalic acid) as a soft segment component, and an aliphatic polyester (for example, polycaprolactone). Of the block copolymers)
The thing which has at least 1 type can be illustrated.

The polyamide elastomer has at least one of nylon 6, nylon 66, nylon 6/10, nylon 6/12, nylon 11 and nylon 12 as a hard segment component, and a polyol (eg polyethylene) as a soft segment component. Examples thereof include those containing at least one kind of polyester composed of glycol, polypropylene glycol, polytetramethylene glycol, and the like.

Examples of polyurethane-based elastomers include those having polyurethane as a hard segment component and at least one of polycarbonate-based polyol, ether-based polyol, caprolactone-based polyol, adipate-based polyol carbonate ester-based polyol as a soft segment component. it can.

As the copolymer of ethylene and an acrylic acid derivative or a methacrylic acid derivative, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / ethyl acrylate copolymer, ethylene.
Examples thereof include a methyl methacrylate copolymer and an ethylene / ethyl methacrylate copolymer.

As the amorphous polyolefin, a polyvinyl cyclohexane resin obtained by hydrogenating a benzene nucleus of a styrene resin can be exemplified as one having a cyclic structure in its side chain, and one having a cyclic structure in its main chain. -Opening polymer having dicyclopentadiene as a monomer and its hydrogenated product, copolymer of dicyclopentadiene and ethylene and its hydrogenated product, ring-opening polymer having pentacyclopentadecene as a monomer and its hydrogenated product Products, ring-opening polymers of tetracyclododecenes and norbornenes and hydrogenated products thereof, addition polymers of polycyclonorbornenes of tetracyclododecenes or higher and α-olefins and hydrogenated products thereof, If necessary, pentacyclopentadecane and / or pentacyclopentadecene may be used together with other comonomers. And which may or may not be ring-opening polymerization of ring-opening obtained polymers and hydrogenated products thereof.

As other elastomers, a combination of a hard segment component / a soft segment component is syndiotactic-1,2 polybutadiene / atactic-1,2 polybutadiene, polyethylene / isobutene.
Examples thereof include isopropylene copolymer rubber, ionomer / amorphous polyethylene, trans-polyisoprene / amorphous polyisoprene, fluororesin / fluororubber, polyethylene / natural rubber, polypropylene / natural rubber and the like. In addition, polycarbonate, polyacetal, polyaryl ester, polyether sulfone,
Examples thereof include polyphenylene sulfide, polyether ether ketone, wholly aromatic polyamide, polyester ether, polyparabanic acid, polyoxadiazole, and aramid.

Examples of the adhesive for adhering the respective layers of the molding sheet include polyolefin-based, polyethyleneimine-based, polybutadiene-based, alkyl titanium compounds, isocyanate-based, urethane-based, polyester-based and polyether-based adhesives. . Examples of the adhesive resin include thermoplastic resins having at least one carbonyl group derived from carboxylic acid, carboxylic acid salt, carboxylic acid anhydride, carboxylic acid amide, or carboxylic acid ester in the main chain or side chain. Among them, ethylene / acrylic acid copolymer, ionomer, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, acrylic acid grafted polyethylene, ethylene / vinyl acetate copolymer, polyester and polyamide are preferable. The adhesive layer and the adhesive resin layer can be used by a known laminating method or coating method to form a multilayer molding sheet. The thickness of the adhesive is usually 0.01 to 5 μm.
m, and the thickness of the adhesive resin layer is 3 to 60 μm and is not particularly limited.

Components other than the thermoplastic resin may be added to the thermoplastic resin layer with an upper limit of about 30% by weight. Examples of such materials include plasticizers, fillers, combustion inhibitors, release agents, antistatic agents and the like.

Examples of the plasticizer for improving the plasticity of the picture protection layer include phthalic acid ester, sebacic acid ester, adipic acid ester, phosphoric acid ester, ricinoleic acid ester, esters of aliphatic dihydric alcohol such as ethylene glycol, butadiene-acrylic. Examples thereof include nitrile copolymers, sulfonamides, polyesters, epoxy compounds, chlorine-containing compounds, camphor and ethers.

To prevent decomposition and alteration in the thermoforming process,
Alternatively, as a heat stabilizer for preventing color deterioration due to aging, lead stearate, dibasic lead stearate, tribasic lead sulfate, basic lead carbonate, dibutyltin laurate, dibutyltin malate, tribenzyltin stearate. , Tribenzyl tin laurate, cadmium stearate, cadmium ethylhexylate, cadmium naphthenate, zinc stearate, zinc 2ethylhexylate, barium stearate, barium laurate, barium ricinoleate, strontium stearate, strontium laurate, strontium naphthenate , Magnesium stearate, calcium stearate, calcium ricinoleate, calcium ethyl acetoacetate and the like.

As a filler for improving the physical properties such as strength and appearance of the molded product, calcium carbonate, carbonates such as magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide, oxidation such as zinc oxide and magnesium oxide. Substances, silicates such as aluminum silicate and magnesium silicate, powdered fillers containing silicic acid as a main component, flake fillers such as mica, mineral fibers, potassium titanate, gypsum fibers, fibrous fillers such as magnesium fibers. Agents and the like.

As a flame retardant for making a sheet or a molded product flame-retardant or non-flammable, paraffin chloride, tricresyl phosphate, chlorinated oil, tetrachlorophthalic anhydride,
Tetrabromophthalic anhydride, tetrabromobisphenol A, dibromopropyl phosphate, tri (2,3 dibromopropyl) phosphate, antimony oxide and the like can be mentioned.

Other anti-blocking agents such as methylenebisamide as a release agent for improving the releasability during the molding process, metal stearate, isobutyl stearate, polytetrafluoroethylene as a lubricant having a lubricating effect. Examples thereof include rosin powder and talc fine powder.

The pattern protective layer is formed by applying the above-mentioned resin and additives for the pattern protective layer to the pattern layer with or without an adhesive, an adhesive resin, or an adhesion promoter, or a domination with the resin film. It can be formed by extrusion coating of molten resin. Further, the resin and additive for the pattern protection layer, or the acrylic UV curable or electron beam curable resin are mixed and dispersed, and a varnish dissolved therein is applied to form the pattern protective layer. As a coating method, a roll coating method, an air knife coating method, a spray coating method, or the like can be selected depending on the type of varnish and the coating amount. The varnish is characterized in that it can be formed into a thin film as compared with dry lamination of a film and melt extrusion coating of a resin.

Examples of ionizing radiation curable resins include acrylate monomers, polyester acrylates, epoxy acrylates, urethane acrylates, silicone acrylates and polybutadiene acrylates.

FIGS. 5 to 16 show examples of the molding sheet in which the pattern protection layer 3 having the multilayer structure of the present invention is provided with the pattern protection layer 3 via the adhesive layer 41 as required. (1) A molding sheet 1 shown in FIG. 5, which has a layer structure of a pattern protection layer 3, a pattern layer 2, an outer surface thermoplastic resin layer 20, an adhesive layer 41, and an innermost layer 25S. The innermost surface layer 25S may be formed by adjusting the total thickness of the molding sheet, laminating a thermoplastic resin layer of a material different from the outer surface thermoplastic resin layer 20, or laminating a colored thermoplastic resin layer. it can. (2) The pattern protection layer 3 / the pattern layer 2 / the outer surface thermoplastic resin layer 20 / the adhesive layer 41 / the inner surface thermoplastic resin layer 25 shown in FIG.
A molding sheet 1 in which the pattern layer 2 is provided on the inner surface thermoplastic resin layer 25S of FIG. 5 having a layer structure of S / pattern layer 2 / pattern protection layer 3. (3) Design protection layer 3 / design layer 2 / outer surface thermoplastic resin layer 20 / adhesive resin layer 42 / oxygen-blocking thermoplastic resin layer 11 / adhesive resin layer 42 / inner surface thermoplastic resin layer 25S shown in FIG.
Sheet 1 having a layer structure of (4) Design protection layer 3 / design layer 2 / outer surface thermoplastic resin layer 20 / oxygen absorbing thermoplastic resin layer 12 / oxygen blocking thermoplastic resin layer 11 shown in FIG. / Oxygen absorbing thermoplastic resin layer 1
2 / Molding sheet 1 having a layer structure of the inner surface thermoplastic resin layer 25S. (5) Design protection layer 3 / design layer 2 / outer surface thermoplastic resin layer 20 / moisture absorbing thermoplastic resin layer 13 / oxygen blocking thermoplastic resin layer 11 / moisture absorbing thermoplastic resin layer 1 shown in FIG.
3 / Molding sheet 1 having a layer structure of the inner surface thermoplastic resin layer 25S. (6) Molding having a layer structure of the pattern protection layer 3 / the pattern layer 2 / the outer surface thermoplastic resin layer 20 / the adhesive resin layer 42 / the metal foil 17 / the adhesive resin layer 42 / the inner surface thermoplastic resin layer 25S shown in FIG. Sheet 1. (7) A molding sheet 1 shown in FIG. 11, which has a layer structure of a pattern protection layer 3 / a pattern layer 2 / an outer surface thermoplastic resin layer 20 / paper (or a non-woven fabric) 18 / an inner surface thermoplastic resin layer 25S. (8) A molding sheet 1 shown in FIG. 12, which has a layer structure of a pattern protection layer 3, a pattern layer 2, an outer surface thermoplastic resin layer 20, an adhesive layer 41, and a non-adhesive resin layer 14. (9) A molding sheet 1 shown in FIG. 13, which has a layer structure of a pattern protection layer 3 / a pattern layer 2 / an antibacterial, antifungal material or a biodegradable inner thermoplastic resin layer 15. (10) A molding sheet 1 shown in FIG. 14, which has a layer structure of a pattern protection layer 3, a pattern layer 2, an outer surface thermoplastic resin layer 20, an adhesive layer 41, and a 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.

[0052]

【Example】

(Example 1) Moldability of the pattern protective layer, protection of the printed surface, and transparency of the printed surface were tested by the following methods. Thermoplastic resin component (acrylic / vinyl chloride / vinyl acetate based copolymer = 400 μm thick polyvinyl chloride sheet)
55/45) is provided with a pattern layer 2 with an ink containing 5% by weight of carbon black, and then an acrylic resin varnish is added.
The pattern protection layer 3 was provided so as to have a thickness of 1, 2, 5, and 10 μm (solid content) to prepare the molding sheet 1 of Example 1.

(Example 2) A polyester / isocyanate adhesive was provided on the surface of the picture layer 2 of the polyvinyl chloride sheet prepared in Example 1 to give a thickness of 20, 50, 10
Dry lamination was performed with 0, 150, 200, and 250 μm acrylic resin sheets to prepare a molding sheet 1 of Example 2 in which the acrylic resin sheet was used as a pattern protection layer.

Example 3 A polyvinyl chloride sheet having a thickness of 400 μm was mixed with 100 parts by weight of a thermoplastic resin component (acrylic / vinyl chloride / vinyl acetate copolymer = 55/45) and 20 parts of yellow lead (yellow pigment). The entire surface is printed with an ink containing 1% by weight to provide the pattern layer 2, and then the pattern protection layer 3 of acrylic resin varnish or acrylic resin film shown in Examples 1 and 2 is provided to form the molding sheet 1 of Example 3. Created.

(Example 4) Diethylene glycol diacrylate and hexanediol dimethacrylate were used as main components on the surface of the picture layer 2 of the polyvinyl chloride sheet prepared in Example 1 with 1, 3, 5 and 10 μm of UV reactive resin.
After the coating, the reaction was completed by irradiating with ultraviolet rays so that the thickness of the sheet was 1 to prepare a molding sheet 1 of Example 4.

The molding sheet 1 of Examples 1, 2, 3 and 4 and the printed sheet having no pattern layer are fixed around the periphery with a sheet fixing jig by a pressure molding machine to form a molding sheet. A flat-bottomed cylindrical shaped body 1 having a flange 36 at the opening 35 shown in FIG.
0 was molded.

The degree of pinholes formed in the picture protection layer outside the side surface of the molded body 10 and the effect of the picture protection layer on the color tone were evaluated as follows. -Pinhole: The surface resistivity of the pattern protection layer 3 on the molding side surface portion 31a of the molded bodies of Examples 1, 2 and 4 was measured using a surface resistance meter Hiresta IP (trade name, manufactured by Mitsubishi Chemical Corporation). It was measured. Organic solvent resistance: A solvent prepared by mixing the surface of the pattern protection layer 3 in the molding side surface portion 31a of the molded bodies of Examples 1, 2 and 4 with toluene and ethyl alcohol in a ratio of 1: 1.
A wiper (trade name, manufactured by Jujo Kimberley Co., Ltd.) was rubbed and wiped 100 times at a load of 30 g / cm ² at 25 ° C., and the ink colored on the wiper was visually evaluated. ◯: Good with no change Δ: Very slight bleeding of the picture layer is seen ×: Clearly ink bleeding and flow are observed ・ Effect on color tone of printed surface: For the sample of Example 3, The color difference of the molded side surface portion 31 was measured using a colorimeter color computer SM-5 (trade name, manufactured by Suga Test Instruments Co., Ltd.).

Table 1 shows the evaluation results of the surface resistivities and organic solvent resistances of Examples 1, 2 and 4 and the color tone of the printed surface of Example 3.

[0059]

[Table 1]

As is clear from the results shown in Table 1, when the pattern protection layer is thin, the conductive ink on the lower printing surface is not completely covered with the pattern protection layer and pinholes are formed, and a part of the base material is used. Is exposed on the outermost surface of. On the other hand, when the pattern protection layer is thick, it is difficult to recognize the original color of the printing ink by hindering the see-through of yellow, which is the lower printing surface. When the thickness of the pattern protection layer is thin, no effect can be expected to prevent scratches on the printed surface or erosion of water or solvent from the pattern layer, which is not preferable.

Further, when the thickness of the pattern protection layer was 100 μm or less, sufficient protection was achieved without affecting the color tone of the pattern layer. Those having a thickness of 100 to 200 μm had a slight effect on the color difference, but had no problem in practical use. Further, when the thickness of the pattern protection layer exceeds 100 μm, the protection effect of the pattern layer is excellent, but not only the productivity is lowered and the cost is increased, but also the color of the printed surface becomes thin and the color becomes cloudy. However, it is not preferable in terms of the printing effect of the pattern layer.

[0062]

As described above, according to the formation of the picture protection layer of the sheet molding of the present invention, the scratches caused by the contact with the mold during molding can be achieved without disturbing the change in the color tone of the printed surface and the recognition. It is possible to prevent the occurrence of scratches, scratches due to friction, dropping, etc. when processed as a printing sheet or handled as a molded article, and erosion of the printing surface due to contact with water, solvent, chemicals and the like.

[Brief description of drawings]

FIG. 1 is a perspective view showing 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 perspective view of a molding sheet for explaining the stretching state of the molding sheet provided with a 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 showing a shallow convex molding. (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 pattern layer 3 pattern protection layer 10 molded body 11 to 15 functional resin layer 11 oxygen-blocking 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 Outer thermoplastic resin layer 22, 23 Inner resin layer 25 Innermost resin layer 25S Inner thermoplastic resin layer 31 Side part 31a Side 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 (4)

[Claims] 1. A molded article molded from a sheet,
It has an opening and at least one of the outer side and the inner side is formed of a thermoplastic resin layer, and at least one of the outer side and the inner side of the surface formed of the thermoplastic resin layer is stretched and molded. The protective layer covering the pattern layer provided on the sheet surface to be formed is a molded article characterized by comprising a resin layer which has plasticity at the temperature at the time of molding the molding sheet and is deformed in accordance with the stretching of the molding sheet. A picture protection layer. 2. The molding sheet according to claim 1, wherein the molding sheet has a multi-layered structure, and a thermoplastic resin layer is formed on a picture layer on at least one surface of the outside and / or the inside. A pattern protection layer in the molded product. 3. The thermoplastic resin layer according to claim 2,
A pattern protection layer in a molded article, which has a thickness of 100 μm and exhibits flexibility at a sheet molding temperature. 4. The pattern protection layer in the molded article is made of a heat-resistant material such as polyolefin resin, polystyrene resin, polyester resin, chlorine-containing resin, fluorine-containing resin, polyamide resin, polyimide resin, polyurethane resin and the like. Of the plastic resins, one kind or a mixture of two or more kinds of films is dry-laminated, a molten resin is formed on the pattern layer by extrusion coating, or an acrylic ionization other than the thermoplastic resin is used. A pattern protective layer in a molded article, characterized in that one or more radiation curable resins are mixed and dispersed and a varnish dissolved and applied is applied onto the pattern layer.