JP3336482B2 - Laminated sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate sheet, and more particularly, to weather resistance, contamination, and the like for ID cards such as identification cards and sample cards such as restaurant menus.
The present invention relates to a laminate sheet capable of providing an image having excellent durability such as abrasion resistance.

[0002]

2. Description of the Related Art Conventionally, various thermal transfer methods are known.
Among them, a transfer sheet having a dye layer containing a sublimable dye and a binder on a base film is used, and the dye in the dye layer is sublimated by a heating means such as a thermal head or a laser in accordance with image information. Sublimation-type thermal recording system in which recording is performed after the transfer is performed. Further, using a transfer sheet provided with a hot-melt ink layer containing a coloring agent such as a pigment and a vehicle such as wax on a base film, the molten ink layer component softened by the same heating means is transferred to form an image. A heat melting type thermal recording system to be formed is known.
In these thermal transfer methods, various images can be easily formed, so that the printed sheets whose number of prints may be relatively small, such as cards such as identification cards, various certificates, sample cards such as restaurant menus, etc. Attempts have been made to use it.

[0003]

However, when an ID card such as an identification card is prepared using the above-described thermal transfer sheet, the use of a heat-melting type thermal transfer sheet results in a monotonous operation such as letters and numerals. Although images are easy to form, these images suffer from poor durability, especially poor abrasion resistance. On the other hand, when a sublimation transfer type thermal transfer sheet is used, a gradation image such as a face photograph can be precisely formed, but it is used daily in addition to the problem of poor abrasion resistance as described above. In the process, there is a problem that the color is faded due to the influence of light rays or the like.

As a means for solving the above-mentioned drawbacks, for example, there is a method of adding an ultraviolet absorber or an antioxidant to a dye-receiving layer and / or a laminate sheet. Even with such a method, although the light resistance of the transferred image is improved to some extent, in the method of simply adding the ultraviolet absorber to the laminate sheet, the ultraviolet absorber volatilizes or decomposes due to heat, and the ultraviolet light is absorbed. There is a problem that the effect of the agent decreases over time. Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art,
An object of the present invention is to provide a laminate sheet having the property that the durability of a thermal transfer image, particularly the light resistance, can be maintained for a long period of time.

[0005]

The above problems are achieved by the present invention described below. That is, the present invention provides a laminated sheet for protecting one or both sides of a thermal transfer image, wherein the sheet is formed by laminating an ultraviolet shielding layer and an adhesive layer on a transparent film, and the ultraviolet shielding layer reacts with a reactive ultraviolet absorbent. A laminate sheet characterized by containing a resin bonded thereto. Further, in a laminate sheet for protecting one side or both sides of the thermal transfer image, the sheet is formed by laminating an adhesive layer on a transparent film, and the adhesive layer contains a resin obtained by reacting and bonding a reactive ultraviolet absorber. It is a laminate sheet characterized by the following.

[0006]

[Function] By providing an ultraviolet blocking layer containing a resin obtained by reacting a reactive ultraviolet absorber between the transparent film and the adhesive layer, vaporization, divergence and decomposition of the ultraviolet absorber due to heat are reduced. The ultraviolet absorbing effect and the transparency can be maintained for a long time. In particular, when the laminate sheet of the present invention is laminated on a printing surface of a print having a dye image by an image forming method such as a sublimation transfer method,
Light resistance is improved along with friction resistance. Also, by providing an adhesive layer containing a resin obtained by reacting a reactive ultraviolet absorber on a transparent film, a laminated sheet having improved light resistance can be provided as described above.

Next, the present invention will be described in more detail with reference to the accompanying drawings, which schematically show preferred embodiments. FIG. 1 is a diagram schematically showing a cross section of a laminate sheet according to a preferred embodiment of the present invention. In the laminate sheet of this embodiment, an ultraviolet shielding layer 2 and an adhesive layer 3
The present invention is characterized in that the ultraviolet blocking layer 2 contains a resin obtained by reacting a reactive ultraviolet absorber with a reactive agent. On the other hand, FIG. 2 is a diagram schematically showing a cross section of a thermal transfer sheet according to another preferred embodiment. In this embodiment, an adhesive layer 4 having an ultraviolet blocking ability is provided on a transparent substrate film 1. In the present invention, a resin obtained by reacting a reactive ultraviolet absorber in the adhesive layer 4 is used. It is characterized by containing. FIG. 3 shows a laminate sheet of a more preferred embodiment of the type shown in FIG. 1, characterized in that a primer layer 5 is provided between the transparent base film 1 and the ultraviolet shielding layer 2. Things. This primer layer is necessary when the adhesion between the ultraviolet shielding layer and the transparent substrate film is not good, but may be omitted if the adhesion is good.

Next, the laminated sheet of the present invention will be described in more detail by using materials and forming methods. As the transparent substrate film used in the laminate sheet of the present invention, it suffices that the base thermal transfer image has a degree of transparency that can be observed through the transparent sheet or more, such as polyethylene, polypropylene, polyvinylidene chloride, and polyvinyl. Among films or sheets of alcohol, polyester, polycarbonate, polyamide, polystyrene, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ionomer, etc., colored or uncolored transparent or translucent ones, Mechanical strength,
In consideration of transparency, flexibility, heat resistance, and the like, polyester, polycarbonate, and polyamide films are preferable, and polyethylene terephthalate and polyethylene naphthalate films are particularly preferable. These films or sheets may contain UV absorbers, antioxidants, light stabilizers, etc. to further improve the light resistance, or may contain an antistatic agent in advance to prevent the adsorption of dust and the like. May be used. Further, coloring or matting treatment may be applied. The thickness of the sheet is usually 25 to
It is about 300 μm, preferably about 38 to 188 μm.

It is desirable that the laminate sheet of the present invention is provided with an ultraviolet blocking layer in order to improve the light resistance of the print. It is preferable that the ultraviolet shielding layer is formed between the transparent film and the adhesive layer. The ultraviolet absorbing layer used in the present invention is characterized by containing a resin obtained by reacting and binding a reactive ultraviolet absorbing agent. Specifically, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, nickel chelate-based, hindered amine-based non-reactive ultraviolet absorbers which are conventionally known organic ultraviolet absorbers, for example, vinyl group And an acryloyl group, an addition polymerizable double bond such as a methacryloyl group, or an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, or the like can be used. The reactive UV absorbers used can be used.

[0010]

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As a method for reacting and fixing the above reactive ultraviolet absorber to the resin, various methods can be used.
For example, by radical polymerization with a conventionally known monomer, oligomer, or resin component of a reactive polymer and a reactive ultraviolet absorber having an addition-polymerizable double bond as described above,
A copolymer can be obtained. Also, the reactive ultraviolet absorber is a hydroxyl group, an amino group, a carboxyl group, an epoxy group,
In the case of having an isocyanate group or the like, use a thermoplastic resin having the above-mentioned reactive group and a reactive group, and use a catalyst as necessary to fix the reactive ultraviolet absorber to the thermoplastic resin by heat or the like. can do. Examples of the monomer component copolymerized with the reactive ultraviolet absorber include the following.

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) ) Acrylate, lauryltridecyl (meth) acrylate,
Tridecyl (meth) acrylate, seryl stearyl (meth) acrylate, stearyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methacrylic acid, hydroxyethyl (meth) ) Acrylate, hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, tert-butylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylenedi (Meth) acrylate, diethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, tetra Lenglycol di (meth) acrylate, decaethylene glycol (meth) acrylate, pentadecaethylene (meth) acrylate, pentacontahector ethylene glycol (meth) acrylate, butylene di (meth) acrylate, allyl (meth) acrylate, trimethylolpropanetri (Meth) acrylate, hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Neopentyl glycol penta (meth) acrylate, phosphazenehexa (meth) acrylate and the like can be used.

The above-mentioned substances are not limited to monomers, and may be used as oligomers. Further, polyester acrylates comprising a polymer of the above substances or derivatives thereof,
Acrylic reactive polymers such as epoxy acrylates can also be used. These monomers, oligomers, and acrylic reactive polymers may be used alone or as a mixture.

A thermoplastic copolymer resin obtained by copolymerizing a monomer, oligomer, or acrylic reactive polymer of a thermoplastic resin with a reactive ultraviolet absorber as described above, and reacting and fixing the reactive ultraviolet absorber. Is obtained, but 10 to 90% by weight, preferably 30% by weight, is contained in the copolymerizable resin.
It is desirable to contain about 70% by weight of a reactive ultraviolet absorber. If the content is less than this, it is difficult to obtain satisfactory weather resistance, and if it is more than this, there are problems such as stickiness at the time of application and blurring of the image at the time of adhesion to the dye image. The molecular weight of the copolymer resin is 5
About 000 to 300,000, more preferably 9000
~ 250,000 is good. If the molecular weight is less than 5,000, the film strength is poor, and sufficient toughness as a laminate sheet cannot be obtained. On the other hand, if it exceeds 300,000, there is a problem that the viscosity increases and the handling becomes complicated. The ultraviolet blocking layer of the present invention is characterized by containing a resin obtained by reacting and binding the reactive ultraviolet absorbing product as described above, but this layer may be formed of the resin alone or if necessary. If desired, other resins may be mixed. An example of the structural formula of a thermoplastic resin obtained by copolymerizing the reactive ultraviolet absorber is shown, but the copolymer resin of the present invention is not limited to this.

[0015]

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When the above-described ultraviolet absorbing layer is formed on the transparent sheet, if the adhesiveness is poor, a primer layer can be formed. As a resin for forming such a primer layer, urethane resins, polyester resins, polypropylene resins, polyol resins, and reaction products of these resins with isocyanates can be used. As the isocyanates to be used, conventionally used diisocyanate compounds, triisocyanate compounds and the like can be used. The primer layer as described above is preferably formed to have a thickness in the range of 0.1 to 10.

Next, the adhesive layer provided on the outermost layer of the laminate sheet will be described. The adhesive layer is preferably formed of a resin having a good adhesive property when heated, and has a feature that, when adhered on an image, the image is not blurred, for example, an acrylic resin, a vinyl chloride resin, and vinyl acetate. Resin, vinyl chloride-vinyl acetate copolymer resin, polyester resin, polyamide resin, chlorinated polypropylene resin, polyurethane resin, etc.
It is preferable to form it in the range of 20 μm.

Further, as another embodiment of the present invention, a laminate sheet characterized by laminating an adhesive layer having an ultraviolet blocking ability on a transparent film is preferable. As an example of an adhesive layer having ultraviolet blocking ability, a layer containing an adhesive component and a resin obtained by reacting a reactive ultraviolet absorber as described above in the adhesive layer can be raised. By mixing and using the components, it is possible to form a thin laminate sheet and to reduce the cost, as compared with the case where the ultraviolet shielding layer and the adhesive layer are provided as separate layers. Furthermore, since an ultraviolet absorber exists near the dye image, the ultraviolet light can be absorbed more efficiently.

The ratio of the resin reactively bonded to the reactive ultraviolet absorber contained in the adhesive layer having the ultraviolet absorbing ability is 30 to 7 with respect to 100 parts by weight of the adhesive resin.
It is desirable to adjust so that the ratio becomes 0 parts by weight. If the amount of the UV-absorbing resin is less than the above range, the UV-absorbing ability is inferior. On the other hand, if the amount of the UV-absorbing resin is larger than this range, there are problems such as stickiness and bleeding of the dye image. In addition, when the resin obtained by reactive bonding of the reactive ultraviolet absorber has an adhesive property, the adhesive layer can be formed only with the resin obtained by reactive bonding of the reactive ultraviolet absorber. The resin does not have to be mixed.

As the transfer object on which an image is formed using the laminate sheet of the present invention, a plastic film such as a polyester resin, a vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer resin, and a polycarbonate resin can be used.
Especially for vinyl chloride resin, because the resin itself has dyeing properties,
The receiving layer can be omitted. When these plastic cards do not show sufficient dyeing properties with respect to the sublimable dye, a plasticizer or a lubricant may be added to the resin to adjust the dyeing properties or release properties. Further, as another transfer member, a plastic film or paper provided with a dye receiving layer, a woven fabric or a nonwoven fabric made of synthetic fibers such as polyester fiber, polyamide resin, polypropylene fiber, and vinylon fiber can be used. When a dye receiving layer is provided, any conventionally known sublimation type transfer recording receiving layer resin can be used,
In particular, polyester resin, vinyl chloride-vinyl acetate copolymer resin, polycarbonate resin, butyral resin and the like are preferable in terms of dyeing properties and image durability.

When the transfer sheet of the present invention is used for a card, it may be provided with an emboss, a writable layer for signing, an IC memory, a magnetic layer, and other printing in advance. Emboss, sign, IC after transfer
It is also possible to provide a memory, a magnetic layer, and the like.

A sublimable dye layer region of the thermal transfer sheet of the present invention is superimposed on the above-mentioned image receiving body, and a desired color image is formed based on image information by a heating means such as a thermal head and a laser. Further, if necessary, a desired character, symbol or the like is printed by overlapping the hot-melt ink layer in the same manner. Next, a laminate sheet is adhered on the formed image. As a heating means, a hot stamper, a heat roll, a line heater, an iron, or the like can be used.

[0023]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the description, parts and% are based on weight unless otherwise specified. Example 1 A 50 μm-thick PET (trade name: Lumirror Toray) was used as a base film, and one side was coated with the following ultraviolet blocking layer forming ink using a gravure coating method when dried. Is 3 g / m ^2, and an adhesive layer is further applied thereon by using an ink for forming an adhesive layer such that the dry coating amount is 1.5 g / m ^2. It was dried to form a laminate sheet. Adhesive layer-forming ink vinyl chloride - vinyl acetate copolymer (# 1000ALK · manufactured by Denki Kagaku Kogyo) 30 parts Toluene / methyl ethyl ketone = 1/1 copolymer reacted combine 70 parts of the ultraviolet blocking layer forming ink reactive UV absorber Resin (UVA635L, manufactured by BASF Japan) 30 parts Toluene / methyl ethyl ketone = 1/1 70 parts

Example 2 In Example 1, the coating amount at the time of drying was adjusted to 1 g / m ² by the gravure coating method using the following ink for forming a primer layer between the ultraviolet shielding layer and the transparent film. And dried. Ink polyester resin for forming primer layer (Vylon-200, manufactured by Toyobo) 30 parts Toluene / methyl ethyl ketone = 1/1 70 parts Example 3 Example 1 was repeated except that the following resin was used as the ultraviolet ray blocking layer in Example 1. A laminate sheet was obtained in the same manner as in No. 1. UV blocking layer forming ink Reactively bonded copolymer resin with reactive UV absorber (UVA935LH, manufactured by BASF Japan) 30 parts Toluene / methyl ethyl ketone = 1/1 70 parts

Example 4 In Example 1, an ink having the following composition was prepared in place of the adhesive layer except for the ultraviolet blocking layer, and the coating amount when dried by a gravure coating method was 4 g / m ^2.
And dried to obtain a laminate sheet. Ink for forming UV-absorbing adhesive layer Copolymer resin reactive with UV-absorbent (UVA635L, manufactured by BASF) 15 parts Vinyl chloride-vinyl acetate copolymer (# 1000ALK, manufactured by Denki Kagaku Kogyo) 15 parts Toluene / methyl ethyl ketone = 1/1 70 parts The laminated sheet of the above Examples 1 to 4 was prepared using MS pouch:
Using H-140 (manufactured by Meiko Shokai), the sheet was adhered on an image formed on the transfer target A described below under the condition of “SLOW”. Transfer object A (card type) (54 mm x 86 mm) The composition of the card base material is as follows. Polyvinyl chloride compound (having a degree of polymerization of 800 and containing about 10% of additives such as stabilizers) 100 parts White pigment (titanium oxide) 10 parts Plasticizer (dioctyl phthalate) ... 0.5 part The following thermal transfer sheet was used for image formation, and an image was formed using a thermal head.

(Formation of Thermal Transfer Sheet) A 6 μm-thick polyethylene terephthalate long film (Lumirror: manufactured by Toray Co., Ltd.) having a heat-resistant back surface and a sublimable dye layer having the following composition, A set was applied by a gravure coater. Yellow ink dye (FORON BRILLIANT YELLOW S-6GL) 5.5 parts Polyvinyl acetoacetal resin (KS-5: manufactured by Sekisui Chemical Co., Ltd.) 4.5 parts Polyethylene wax 0.1 parts Toluene / methyl ethyl ketone (1/1) 89 parts Instead of magenta ink yellow dye Magenta dye (MS RED-G 1.5
Parts, and 2.0 parts of MACROLEX RED VIORER). A cyan dye (Kayaset Blue 7) in place of the cyan ink yellow dye
The procedure was the same as the yellow ink except that 14) was used.

Comparative Example 1 A laminate sheet was formed in the same manner as in Example 1 except that the ultraviolet ray blocking layer was omitted. Comparative Example 2 In Example 4, a benzotriazole-based ultraviolet absorber (Tinuvin 32) was used instead of UVA635L.
8. Ciba Geigy) was added in the same amount as in Example 4 to form a laminate sheet. [Comparative Example 3] In Example 4, a benzotriazole-based ultraviolet absorber (Tinuvin 32) was used instead of UVA635L.
0.7 manufactured by Ciba Geigy Co., Ltd. (the composition was the same as that of Example 4) to form a laminate sheet.

The following test was performed using the card to which the above-mentioned laminate sheet was adhered. Light fastness test: Using a xenon fade meter (Atlas Ci35A), a black panel temperature of 45 ° C.
After storage under the condition of 200 kJ / m ² , the residual ratio of the formed image near the reflection density of 1.0 was measured. Optical density after irradiation Residual rate = ──────────── (%) Optical density before irradiation ○: 70% or more remaining ×: less than 70% remaining Bleeding test: 60 ° C. oven After storage in the medium for 100 hours, dot bleeding was visually observed. ：: no dot bleeding observed X: dot bleeding observed The results are shown in Table 1 below.

[0029]

[Table 1]

Further, after an image was formed in the same manner using the transfer-receiving member B as described below, a test was similarly performed on the double-sided pouch of the laminate of the example, and the same result as that of the transfer-receiving member A was obtained. Obtained. Transcripts B as (menu type) substrate, a synthetic paper (Yupo FPG-150, thickness 150
μm Oji synthetic oil synthetic paper) (size: 100mm x 14)
0 mm), and the other side was coated with an ink for forming a dye receiving layer having the following composition so that the coating amount at the time of drying was 4 g / m ² , followed by drying to form a dye receiving layer. Ink polyester resin for forming a dye receiving layer (Vylon 200, manufactured by Toyobo) 20 parts Amino-modified silicone oil (X-22-343, manufactured by Shin-Etsu Chemical) 1 part Epoxy-modified silicone oil (KF-393, manufactured by Shin-Etsu Chemical) 1 Parts toluene / methyl ethyl ketone = 1/1 80 parts

[0031]

According to the present invention, the ultraviolet absorbing effect and the transparency are maintained for a long period of time by providing an ultraviolet shielding layer containing a resin obtained by reacting a reactive ultraviolet absorbing agent between the transparent film and the adhesive layer. Can be. In particular, when the laminate sheet of the present invention is laminated on a printing surface of a print having a dye image by an image forming method such as a sublimation transfer method, the light resistance as well as the friction resistance are improved. Also, by providing an adhesive layer containing a resin obtained by reacting a reactive ultraviolet absorber on a transparent film, a laminate sheet with improved light resistance can be provided.

[Brief description of the drawings]

FIG. 1 is a diagram schematically illustrating a cross section of a laminate sheet of the present invention.

FIG. 2 is a diagram schematically illustrating a cross section of the laminate sheet of the present invention.

FIG. 3 is a diagram schematically illustrating a cross section of the laminate sheet of the present invention.

[Explanation of symbols]

 1: transparent base film 2: ultraviolet blocking layer 3: adhesive layer 4: adhesive layer having ultraviolet blocking ability 5: primer layer

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-257012 (JP, A) JP-A-7-148896 (JP, A) JP-A 8-2-2192 (JP, A) JP-A-7-257 276831 (JP, A) JP-A-7-290848 (JP, A) JP-A-7-304275 (JP, A) JP-A-58-149048 (JP, A) JP-A-4-142987 (JP, A) JP-A-5-212974 (JP, A) JP-A-6-115270 (JP, A) JP-A-6-148430 (JP, A) JP-A-7-314932 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B41M 5/38 B32B 7/12 B41M 7/00

Claims (2)

(57) [Claims] 1. A laminated sheet for protecting one or both sides of a thermal transfer image, wherein the sheet is formed by laminating an ultraviolet ray blocking layer and an adhesive layer on a transparent film, and the ultraviolet ray shielding layer binds a reactive ultraviolet ray absorbing agent. A laminated sheet characterized by containing a resin obtained. 2. A laminate sheet for protecting one side or both sides of a thermal transfer image, wherein the sheet is formed by laminating an adhesive layer on a transparent film, and the adhesive layer is formed by reacting a reactive ultraviolet absorber with a resin. A laminate sheet characterized by containing.