JPH11161174A - Formation of surface hardened label - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide plastic molded goods formed with a label having a design layer of an elaborate photographic tone and tough surface hardness. SOLUTION: An image forming film 1 successively provided with the design layer 2 and an adhesive layer 4 on at least one side is prepd. An adhesive layer 4 of the uncured surface hardened label 15 laminated with a release film 5 via an ionization radiation resin or thermosetting resin which constitutes a surface protective layer 3 and a molded resin 6 are laminated and molded on the other side thereof and thereafter, the surface protective layer 3 is cured by irradiation with the ionization radiation or by heating from the release film 4 side, by which the surface hardened label 10 is formed. The molded goods 20 are obtd. by peeling and removing the release film 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for labeling a surface of a resin molded product, and particularly to a printing effect of the label,
It belongs to a method of forming a surface-hardened label provided on a resin molded product, a metal, a glass product, etc., which forms a beautiful multi-colored print and has a label with excellent surface hardness.

[0002]

2. Description of the Related Art A pattern layer of a molded article of a thermoplastic resin such as polypropylene, polystyrene, polymethyl methacrylate, polycarbonate or the like or a glass product is formed by a so-called curved printing such as a silk screen printing, a gravure plate or a relief offset printing. This has been done by providing a picture and, if necessary, attaching a label provided with a picture layer with a metal foil or a transfer film. However, since silk-screen printing is expensive in order to perform multi-color printing although having a certain density, thermal transfer printing using a transfer film in which a picture layer is printed in advance has been performed. The thermal transfer is performed by a simultaneous painting method provided at the time of molding. In addition, a method of attaching a label created in another step via an adhesive layer has also been performed.

[0003] In these transfer printing and labeling, since the picture layer is the outermost layer, various protective layers have been provided after being attached to a molded article in order to improve abrasion resistance. For example, it has been formed by applying a varnish of a thermoplastic resin or a thermosetting resin to a pattern layer of a molded product. However, in the step of providing a protective layer in a post-process on the pattern layer formed on the molded product, foreign matter adheres to the uncured coating film, or the coating film flows into a low portion of the molded product until it is cured. May cause uneven thickness. In addition, if a method is adopted in which a coated label with a surface protective layer is attached at the same time as molding, the protective performance is maintained by causing cracks in the surface protective layer in the label molding process of forming a hard surface protective layer. On the other hand, if the label is molded and attached (laminated) with the surface protective layer uncured,
There is a problem that the uncured coating film adheres to the mold and is removed.

[0004] The picture layer made of the transfer film has a problem that the printing effect is excellent but the surface properties are inferior. For the purpose of improving it, the release film of the transfer film is provided with a non-adhesive ionizing radiation curable resin at room temperature when it is not cured, and the surface protection layer and the pattern layer are printed and formed in the uncured state. A method of attaching to a molded article at the same time as injection molding, then curing by irradiation with an electron beam, then providing a pattern layer including a protective layer and curing (see Japanese Patent Publication No. 4-19924).
Are also disclosed. However, since the pattern layer is printed on the coating film of the uncured protective layer, there is a problem that it is inferior to precise reproduction of a photographic tone as compared with a pattern layer printed on a plastic film having good smoothness.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a surface-cured label having a fine photographic pattern layer and a tough surface layer made of a curable resin on a plastic molded product or the like. It is.

[0006]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a transparent image forming film provided with a picture layer and an adhesive layer on at least one side in order and a surface protective layer on the other side. After laminating the adhesive layer and the molding resin of the uncured surface-curable label formed by laminating a release film via an ionizing radiation-curable resin or a heat-reaction curable resin, irradiate ionizing radiation from the release film side or This is a method of forming a surface-cured label in which the surface protective layer is reacted and cured by heating, and the release film is peeled off. Further, a pattern layer is formed on one side of the image forming film, and then an uncured uncured radiation-curable resin or a heat-curable resin and a release film which are to be a surface protective layer are sequentially laminated on the pattern layer. After laminating the image forming film of the surface-curable label and the molding resin of the molded product, irradiating or heating with ionizing radiation from the release film side, the surface protective layer reacts and cures, and the release film is peeled off. This is a method for forming a surface-cured label.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION An uncured surface-curable label of the present invention is a transparent image-forming film 1 having a picture layer 2 and an adhesive layer 4 on at least one side as shown in FIG.
An uncured (irrespective of adhesiveness or non-adhesiveness) surface curing in which a release film 5 is laminated on the other side via an ionizing radiation-curable resin serving as the surface protective layer 3 or a heat-reactive resin. The mold label 15 is formed. Then, the adhesive layer 4 of the uncured surface-curable label 15 and the molding resin 6 of the molded product 20
After lamination molding, ionizing radiation is irradiated or heated from the release film 5 side (not shown) to react the surface protective layer 3
Cured to form a surface-cured label 10 and a release film 5
This is a method for forming the surface-cured label 10 on the resin molded product 20 from which the resin is removed. Further, as shown in FIG. 2, an uncured (adhesive film) is formed by laminating a release film 5 on an image forming film 1 via an ionizing radiation-curable resin or a heat-curable resin to be a pattern layer 2 and a surface protective layer 3. , Regardless of non-adhesiveness), after laminating the image forming film 1 of the surface-curable label 15 and the molding resin 6, irradiating or heating ionizing radiation from the release film 5 side to react the surface protective layer 3. This is a method for forming a surface-cured label of the resin molded article 20 that cures and releases and removes the release film 5 times.

[0008] The image forming film provided with a picture layer according to the present invention has elaborate printing excellent in printability and having transparency enough to allow the picture layer on the back side to be seen through the film from the front side of the resin molded article. It can be selected from those having dimensional stability, smoothness and heat resistance that can be obtained. For example, cellulose derivatives such as cellulose triacetate, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon, polypropylene, polymethylpentene, polyolefins such as olefin-based thermoplastic elastomers, polymethyl methacrylate, methyl methacrylate. Use of stretched or unstretched films of acrylic resins such as butyl methacrylate copolymer, thermoplastic resins such as polycarbonate, polyimide, polyurethane, polyvinyl chloride, polyvinyl acetal, saponified ethylene / vinyl acetate copolymer Can be. Of these, moderate moldability,
For those having releasability and strength, olefin-based thermoplastic elastomers are preferred. As the olefin-based thermoplastic elastomer, for example, the following can be selected and used. JP-B-6-23278 discloses (A) a soft segment having a number average molecular weight Mn of 25,000 or more, and a weight average molecular weight Mw and a number average molecular weight Mn.
10 to 90% by weight of atactic polypropylene soluble in boiling heptane with w / Mn ≦ 7 and (B) a hard segment having a melt index of 0.1 to 4 g / 10
A soft polypropylene comprising a mixture of isotactic polypropylene insoluble in boiling heptane in 90 min to 10% by weight. Among such olefin-based thermoplastic elastomers, isotactic polypropylene and atactic polypropylene, which are less likely to cause so-called "necking" and have good suitability for forming into various shapes by heating and pressing, are preferred. And a mixture with
And the weight ratio of atactic polypropylene is 5% by weight or more.
It is 50% by weight. Although the polypropylene-based olefin-based thermoplastic elastomer itself is known,
When used for a conventionally known use such as a packaging container, the weight ratio of atactic polypropylene as a soft segment is less than 5% by weight in order to emphasize strength. However, when this is applied to a novel use such as forming into a three-dimensional shape or a concavo-convex shape as intended by the present invention, the necking described above occurs, and good processing is difficult. Accordingly, the present inventor has conducted various studies and found that, contrary to the conventional composition design, the weight ratio of the atactic polypropylene in the polypropylene-based thermoplastic elastomer is 5% by weight or more, so that the three-dimensional shape, or It has been found that defects such as uneven deformation of a film due to necking when formed into an article having an uneven shape and resulting wrinkles and distortion of a picture can be solved. Particularly, the case where the weight ratio of the atactic polypropylene is 20% by weight or more is preferable. On the other hand, if the weight ratio of atactic polypropylene increases too much, the film itself will be easily deformed, and the film will be deformed due to tension or heat when the film is passed through a printing machine, resulting in distorted pictures and multi-color printing. In such a case, a defect such as misregistration is likely to occur. Further, it is not preferable because the film is easily broken at the time of molding. The upper limit of the weight ratio of atactic polypropylene is 5 when a pattern can be printed on a usual rotary printing machine such as rotogravure printing, and when the film is processed by vacuum forming and simultaneous lamination of injection molding.
0% by weight or less, more preferably 40% by weight or less. In the present invention, any of three structural isomers of 1-butene, 2-butene and isobutylene can be used as the thermoplastic elastomer comprising an ethylene-propylene-butene copolymer. The copolymer is a random copolymer, and preferred specific examples of the above ethylene, propylene, and butene copolymer partially including an amorphous portion include the following (a) to (c). it can. (a) Copolymer described in JP-A-9-111055 This is a random copolymer which is a terpolymer of ethylene, propylene and butene. The weight ratio of the monomer components is 90% by weight or more of propylene. The melt index is 1 to 50 g / 10 min (230 ° C., 2.
1 kg) is preferred. Further, with respect to 100 parts by weight of such a ternary random copolymer, a transparent nucleating agent containing a phosphate aryl ester compound as a main component is used in an amount of 0.01 to 0.01%.
50 parts by weight of a fatty acid amide having 12 to 22 carbon atoms in an amount of 0.0
3 to 0.3 parts by weight are melt-kneaded and used. (b) Composition described in JP-A-5-77371 This is a terpolymer of ethylene, propylene and 1-butene, and is an amorphous polymer having a propylene component content of 50% by weight or more. Is 20 to 100% by weight and the crystalline polypropylene is 80 to 0% by weight. (c) Copolymer described in JP-A-5-77371 This is a terpolymer of ethylene, propylene and 1-butene, and has a propylene and / or 1-butene content of 50%.
A N-acylamino acid amine salt, based on 100 parts by weight of a mixed composition comprising 20 to 100% by weight of a low crystalline polymer of not less than 20% by weight and 80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene; It is obtained by adding 0.5% by weight of an oil gelling agent such as N acyl amino acid ester. Further, if necessary, the above (a), (b) and (c) may be further mixed with another olefin resin. Although the thickness of the film depends on the rigidity of the film due to the material and the film forming method,
Those having a thickness of from 200 to 200 μm are also preferable in terms of handling such as workability.

Further, the film which can be used in the invention of claim 2 is not necessarily required to be transparent, and an aluminum foil or the like can be used in addition to the thermoplastic resin. In the case of a thermoplastic resin film, a transparent or opaque colored film in which a pigment is kneaded can also be used. Then, by using a film made of the same resin as the molded product, the film can be directly welded to the molten resin by heat at the time of molding without using an adhesive layer. Taking into account strength, printability, dimensional stability, etc. that does not break during molding, biaxially stretched polyester (polyethylene terephthalate) film, cellulose triacetate film, biaxially stretched or unstretched polypropylene film, or polystyrene resin often used for molded products Can be preferably used. A desirable thickness of the film is 15 to 100 μm, though it depends on the physical properties of the film. If it is too thin, it will be broken or wrinkled during molding, making it impossible to obtain a sufficient molded product. On the other hand, if the thickness is too large, not only the cost is increased, but also the rigidity is too strong, so that printing with a picture layer becomes difficult.

The pattern layer provided on the image forming film may be of any type, such as a gravure plate, a silk screen plate, a flexographic plate using a relief plate, a lithographic offset, and a printing method such as rotary printing or sheet-fed printing. Gravure printing or lithographic offset printing is preferred from the viewpoint of obtaining a sophisticated image, and in consideration of a post-process such as lamination, a rotary printing method performed by winding is preferred.

The pigment and binder of the printing ink can be arbitrarily used from ordinary materials, but are preferably selected from those which do not discolor or dissolve at the temperature of the molding resin. As the pigment (including the dye) of the printing ink, any of inorganic and organic pigments can be used, but from the viewpoint of waste pollution, it can be selected from materials that do not contain harmful metals such as cadmium and lead. For example, carbon black, iron oxide (Sepiya,
Black), navy blue, quinacridone red, phthalocyanine blue, indanthrone blue, phthalocyanine green,
Isoindoline yellow, chromophthalo yellow and the like can be preferably used. The binder is preferably a thermoplastic polyester, a vinyl chloride-vinyl acetate copolymer, a two-component reactive resin of polyurethane and the like and a polyisocyanate as a binder. Alternatively, a water-soluble primer layer or a resist layer may be provided in a pattern to form a metallic pattern layer of partial vapor deposition by metal aluminum vapor deposition.

The uncured ionizing radiation-curable resin composition for forming the surface protective layer may be either uncured or non-tacky as long as it has coating applicability. Can be used. Then, a prepolymer or oligomer having an ethylenically unsaturated bond in the molecule, for example, an unsaturated polyester, a polyester (meth) acrylate (here, acrylate and methacrylate are described as (meth) acrylate), epoxy (Meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, polyol (meth)
There are various (meth) acrylates such as acrylate and melamine (meth) acrylate. Then, one or more of these (meth) acrylates and a monomer having an ethylenically unsaturated bond in the molecule, for example, styrene,
Styrene-based monomers such as α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl-hexyl (meth) acrylate, methoxyethyl (meth) acrylate , Ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, lauryl (meth) acrylate, and phenylethyl (meth) acrylate. Further, unsaturated carboxylic acid amides such as (meth) acrylamide, methyl (2-N, N-dimethylamino) (meth) acrylate, methyl (2-N, N
-Diethylamino) (meth) acrylate, methyl (2
—N, N-dibenzylamino) (meth) acrylate,
Ethyl (2-N, N-dimethylamino) (meth) acrylate, ethyl (2-N, N-diethylamino) (meth) acrylate, ethyl (2-N, N-dibenzylamino) (meth) acrylate, propyl ( 2-N, N-
There are amino-substituted (meth) acrylates such as dimethylamino) (meth) acrylate. Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neobenzyl glycol di (meth)
Acrylate, 1,6-hexanediol (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Polyfunctional compounds such as dipropylene glycol di (meth) acrylate, and / or polythiol compounds having two or more thiol groups in the molecule, for example, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate And pentaerythritol tetrathioglycolate.

The composition of the surface protective resin layer composed of the above ionizing radiation curable resin is not particularly limited,
Those which are soluble in general-purpose solvents and can have ordinary coating suitability are preferred. Further, the coating liquid comprising the above composition,
Unlike the invention disclosed in Japanese Patent Publication No. 4-19924, there is no need to form a curable resin in a non-adhesive state after coating. Accordingly, it is preferable to use not only a solid or high-viscosity composition soluble in a solvent but also a low-viscosity one. Then, if necessary, to improve the solubility of the entire coating liquid, and to obtain a thixotropic coating liquid having a viscosity suitable for coating, various solid resins, for example, an acrylic resin, a polyester resin, a urethane-based resin. A resin, a cellulose derivative, a rubber, or the like is selected and blended to provide coating suitability. Then, it is dissolved and diluted with a solvent having an evaporating property and a drying rate according to the coating method to prepare a coating liquid.

Since the surface protective layer forms the outermost layer of the molded product, in order to satisfy the surface properties of the formed product, a lubricating agent or a fine powder made of fine powder of spherical α-alumina, silica or the like is used. It is preferable to add a matting agent, a slip agent, an antistatic agent, an antibacterial agent and the like. In the coating liquid for the surface protective layer, a reducing agent such as hydroquinone, hydroquinone monomethyl ether, or benzoquinone is added as a stabilizer for the purpose of preventing the ionizing radiation-curable resin composition from curing before electron beam irradiation. You can also.

As a method of applying the surface protective layer, an ordinary application method can be applied according to the state of the shaping sheet and the coating solution. For example, natural roll coat, reverse roll coat,
Gravure coat, air knife coat, curtain coat,
It can be appropriately selected from bar coats and the like. The surface protective layer can be laminated with a release film in an uncured state after coating, wound up, cut into a desired size, and supplied as an uncured cured label.

The surface protective layer is formed of not only an ionizing radiation-curable resin but also a heat-curable composition, a two-part reactive resin composition,
It can be selected from a crosslinked resin composition and the like. in any case,
After coating, it is laminated with a release film to form an uncured surface-curable label when molding a plastic molded product or labeling the molded product, and after laminating, irradiating with an electron beam, irradiating infrared rays, or heating. Alternatively, it is a label cured by aging.

Examples of the heat-curable resin include a polyester of a reactive monobasic acid or polybasic acid and a polyhydric alcohol, an alkyd resin, an amino alkyd, and a styrene-modified or methyl methacrylate-modified alkyd resin. There are also cured products of linear polyesters, polyethers and polyurethanes with polyisocyanates, and crosslinked products of unsaturated polyesters.

Reactive natural monobasic acids that form the surface protective layer include double bonds such as linoleic acid, linolenic acid, dehydrated ricinoleic acid, and eleostearic acid, and fatty acids containing a conjugated double bond. . And, polybasic acids for polymerizing polyester include phthalic anhydride, isophthalic acid,
Terephthalic acid, succinic anhydride, malonic acid, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromphthalic anhydride, tetrachlorophthalic anhydride, heptanic anhydride, endmethylenetetrahydrophthalic anhydride Acids and the like.

Polyhydric alcohols which react with the above-mentioned acids include ethylene glycol, propylene glycol, 1,
3-butylene glycol, 1,6-hexanediol,
Examples include diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol A, bisphenol dihydroxypropyl ether, glycerin, trimethylolpropane, and pentaeristol.

The release film is used to prevent blocking when the uncured surface-curable label is wound up, and to prevent contamination of the surface until the surface protective layer is hardened by applying energy to the surface protective layer. belongs to. The release film obtained after the molded product is obtained and cured, has a function as a protective film during the transfer of the molded product and until post-processing, but is anyway peeled and discarded. Therefore, it is selected from materials which do not adhere to the resin of the surface protective layer and which are inexpensive and hardly deteriorated by heat during molding. For example, a stretched or unstretched polypropylene film or polyethylene film is preferred. The thickness is 15 to 50 μm which does not hinder the work.

The molding resin used in the present invention includes thermoplastic resins such as polyethylene, polypropylene, polyester, polycarbonate, polystyrene, ABS, methyl methacrylate, melamine formaldehyde resin, diallyl phthalate resin, unsaturated polyester, epoxy resin and the like. It can be applied to a molded product of a curable resin such as a resin or a molding process using these resins. In addition, it can also be used as a label having the same hardness as those materials for glassware, pottery, and the like.

The adhesive layer of the present invention is preferably a heat-sensitive adhesive mainly composed of a thermoplastic resin, such as acrylic resin, polystyrene, vinyl chloride / vinyl acetate copolymer, urethane resin, chlorinated polypropylene, polyamide, Examples include an ethylene / vinyl acetate copolymer. In addition, rosin, rosin-modified maleic resin, rosin-modified phenol resin, etc. and esters of glycene or pentaerythritol as tackifiers, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate ester There are a pressure-sensitive adhesive composed of a copolymer, a natural or synthetic wax and the like, and a so-called hot lacquer which forms an adhesive layer by heating and dissolving and coating a gel-like substance obtained by dispersing the same in an organic solvent. The thickness of the adhesive layer depends on the material to be used and the forming method, but is 1 to 30 μm. In the case of coating, the thickness can be reduced.

In the case where the molding resin is a polyolefin resin, an anchor coating agent such as polyester / isocyanate, alkyl titanate, titanium acylate and titanium chelate is provided in the adhesive layer in addition to the above-mentioned heat-sensitive adhesive. It can be bonded to the molten molding resin.

By providing a primer layer between the respective layers of the present invention, the adhesion can be firmly and stabilized. The primer layer can be composed of a resin varnish which does not contain a particulate matter in principle. For example, there are isocyanates, saturated polyesters, urethane resins, vinyl chloride / vinyl acetate copolymers, and acrylic resins. The coating can be performed by a usual method such as a gravure coat, a roll coat, and a bar coat.
The coating amount is the smoothness of the coating surface (for example, the pattern layer surface is rough because pigment particles are precipitated).
Although it depends, it is 0.5 to 3 g / m ² .

Hereinafter, the present invention will be described in more detail with reference to examples. Example 1 As shown in FIG. 1, a 1: 1 mixture of acrylic and vinyl chloride / vinyl acetate copolymer was used as a binder on an acrylic film (image forming film 1) having a thickness of 100 μm. Was used to form a woodgrain pattern layer 2 by gravure printing. Next, an adhesive having a vinyl chloride-vinyl acetate copolymer as a main component was applied at ² g / m 2 on the surface of the picture layer 2 to form an adhesive layer 4. Further, a coating solution having the following composition is applied to the surface opposite to the adhesive layer 4 of the acrylic film 1 at 5 g / m ² to form an uncured surface protective layer 3 and a biaxially oriented polypropylene having a thickness of 20 μm. The untreated surface of the film (release film 5) was laminated to produce an uncured surface-curable label 15 shown in FIG. 1 (A). (Coating liquid) 45 parts by weight of oligoester acrylate (trade name of Alonix M8030, Toagosei Co., Ltd.) 50 parts by weight of epoxy acrylate (trade name of epoxy VR90 manufactured by Showa Polymer Co., Ltd.) 0.5 part by weight of hydroquinone Methyl ethyl ketone 20 parts by weight Release film 5 of uncured surface-curable label 15
Was mounted on a mold of an injection molding machine, and preheated to a mold shape by heating with a hot plate and vacuum suction at the same time. Then, the mold was closed and an acrylic resin was injection molded. In a nitrogen gas atmosphere, the obtained molded product is applied to the surface of the release film 5 with a curtain electron beam of 150 KeV-15 mA.
By irradiating Mrad, the surface protective layer 3 is cured, the release film 5 is peeled off, and the surface-cured label 1 shown in FIG.
Thus, a molded product 20 equipped with No. 0 was constructed. Obtained molded product 2
No. 0 has a hard surface hardness, does not scratch even if scratched with a nail, and has a luster or even if rubbed 50 times with a cotton cloth moistened with ethyl acetate, toluene, methyl ethyl ketone, ethyl alcohol,
No change was observed in the picture layer.

(Embodiment 2) As shown in FIG.
On the treated surface of the colored unstretched polypropylene film having a thickness of μm (image forming film 1), a wood-grain pattern layer 2 was provided with a two-part curable gravure ink using urethane composed of polyester polyol and hexamethylene diisocyanate as a binder. Next, 5 g / m ^{2 of the} coating liquid used in the example was applied to the surface of the pattern layer 2, and the uncured surface protective layer 3 was applied.
FIG. 2 (A) is obtained by laminating a 20 μm-thick isotactic polypropylene hard segment and an atactic polypropylene soft segment in a 70:30 weight ratio and mixing an olefin-based thermoplastic elastomer film. Uncured surface-curable label 1)
5 was created. The release film 5 of the uncured surface-curable label 15 was mounted on a mold of an injection molding machine, and pre-formed into a mold shape by heating with a hot plate and vacuum suction at the same time. Then, the mold was closed, and polypropylene was injection molded. The obtained molded product is placed in a nitrogen gas atmosphere.
The surface of the release film 5 is irradiated with 5 Mrad by a 150 KeV-15 mA curtain electron beam, so that the surface protective layer 3 is formed.
Was cured, and the release film 5 was peeled off to form a molded product 20 on which the surface-curable label 10 was mounted. The obtained molded product 20 has a high surface hardness and is not damaged even when scratched with a nail.
In addition, no change was observed in the gloss and the pattern layer even when rubbed with ethyl acetate, toluene, methyl ethyl ketone and ethyl alcohol 50 times with a wet cotton cloth. And even if it did not provide an adhesive layer between an image forming film and a molding resin, it had sufficient adhesive strength (non-peelable).

(Embodiment 3) As shown in FIG.
On a polyethylene terephthalate film (image forming film 1) of μm, a stone pattern pattern layer 2 was provided by gravure printing with an ink using a polyester polyol and a hexamethylene diisocyanate-based resin as a binder. Then
An adhesive layer 4 is formed on the surface of the picture layer 2 by applying 2 g / m ^{2 of} an adhesive mainly composed of a mixture of acrylic and vinyl chloride / vinyl acetate copolymer at a weight ratio of 1: 1. did. Further, the adhesive layer 4 of polyethylene terephthalate 1
Although not shown on the opposite side, an isocyanate-based resin varnish was provided as a 0.5 g / m ² primer layer, a coating solution having the following composition was applied at 5 g / m ² , and an uncured surface protective layer 3 was formed.
Was formed and laminated with an olefin-based thermoplastic film (release film 5) made of an ethylene / propylene / butene copolymer having a thickness of 20 μm to prepare an uncured surface-curable label 15 shown in FIG. 1 (A). . (Coating liquid) 70 parts by weight of short oil alkyd 30 parts by weight of butylated melamine resin Release film 5 of uncured surface-curable label 15 described above
Was mounted on a mold of an injection molding machine, and preheated into a mold shape by vacuum suction from a female mold simultaneously with heating by a hot platen. Then, the mold was closed and the unsaturated polyester was injection molded. The obtained molded article is placed in a 100 ° C. atmosphere for 20 minutes.
Then, the surface protective layer 3 was cured and the release film 5 was peeled off to form a molded article 20 to which the surface-cured label 10 shown in FIG. 1B was attached. The obtained molded article 20 has a high surface hardness and is not damaged even when scratched with a nail.Even if it is rubbed 50 times with a cotton cloth moistened with ethyl acetate, toluene, methyl ethyl ketone, or ethyl alcohol, the gloss and the pattern layer are reduced. No change was noted.

(Comparative Example 1) A label without the surface protective layer 3 was formed and molded in the same process using the same image forming film as in Example 1. The surface of the obtained molded article was inferior in surface hardness that was easily damaged by nails. In addition, solvents such as ethyl acetate, toluene, and methyl ethyl ketone were inferior in solvent resistance to lose gloss on the surface.

(Comparative Example 2) A label without the release film 15 was formed and molded in the same process using the same image forming film as in Example 2. After molding, when the male and female molds were opened and the molded product was taken out, a part of the surface protective layer 3 adhered to the mold surface side and was removed. On the surface of the obtained molded article, the surface protective layer became patchy, and the lacking portion of the surface protective layer was inferior in surface hardness, which was easily damaged by nails including the picture layer. Further, the solvent resistance such that a part of the picture layer on the surface disappeared by a solvent such as ethyl acetate, toluene and methyl ethyl ketone was poor.

[0030]

As described in detail above, the present invention provides an image-forming film having good printability, particularly good surface smoothness, by providing a fine pattern layer on the image-forming film, further comprising an ionizing radiation-curable resin,
Alternatively, a surface protective layer made of a heat-curable resin is provided and laminated with a release film to form an uncured surface-curable label. Therefore, even if the label is not only non-adhesive at room temperature but also uses an ionizing radiation-curable resin having an adhesive property, a surface protective layer is not adhered at the time of molding and is not removed. Therefore, there is an effect that a surface protective layer having various characteristics can be formed by expanding the options of the ionizing radiation-curable resin. Further, since the surface protective layer in an uncured state is molded and then the surface protective layer is cured, the surface protective layer does not crack or break even when molded into a three-dimensional shape. Therefore, the picture layer provided on the film having excellent surface smoothness of the present invention has an effect that a fine picture layer can be realized and a label having the surface characteristics of the curable resin can be formed.

[Brief description of the drawings]

FIG. 1A is a conceptual sectional view of an uncured surface-curable label of the present invention. (B) is a conceptual sectional view showing a state where an uncured label is laminated with a molding resin, and a release film is peeled off after curing.

FIG. 2A is a conceptual cross-sectional view of another uncured surface-curable label of the present invention. (B) is a conceptual sectional view showing a state in which the uncured label is laminated with a molding resin, and a release film is peeled off after curing.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Image forming film 2 Picture layer 3 Surface protective layer 4 Adhesive layer 5 Release film 6 Molding resin 10 Surface cured label 15 Uncured surface cured label 20 Molded article

Claims (2)

[Claims] 1. A transparent image-forming film provided with a pattern layer and an adhesive layer on at least one side in order, and then an ionizing radiation-curable resin or a heat-curable reaction type serving as a surface protective layer on the other side. After laminating the adhesive layer of the uncured surface-curable label formed by laminating the release film via the resin and the molding resin, the surface protective layer reacts by irradiating or heating ionizing radiation from the release film side. A method for forming a surface-cured label, comprising peeling off a release film from a cured surface-cured label. 2. A pattern layer is formed on one surface of an image forming film, and then an ionizing radiation-curable resin or a heat-curable reaction-type resin serving as a surface protective layer and a release film are sequentially laminated on the pattern layer. After laminating the formed uncured surface-curable label image forming film and the molten molding resin, the surface protective layer is separated from the surface-cured label that has reacted and cured the surface protective layer by irradiating or heating with ionizing radiation from the release film side. A method for forming a surface-cured label, comprising removing and removing a shaped film.