JP6493113B2 - Printing sheet, printing sheet with release layer, and decorative sheet - Google Patents

Description

  The present invention relates to a printing sheet, a printing sheet with a release layer, and a decorative sheet obtained by printing the printing sheet.

When decorating the glass surface used for modules such as touch panels (decoration), directly decorating the glass increases the yield and costs, so a sheet decorated with printing (decoration sheet) is molded. May stick to product surface. Thereby, designability can be provided to molded articles, such as a touch panel, or the molded article surface can be protected.

As such a decorative sheet, a pressure-sensitive adhesive sheet with a decorative print layer in which a hard coat layer is provided on one surface of a base film and a decorative print layer and an adhesive layer are further provided has been proposed (patent) Reference 1).

JP2011-093977

  However, the pressure-sensitive adhesive sheet with a decorative print layer described in Patent Document 1 has a problem that adhesion between the hard coat layer (resin layer) and the decorative print layer is poor. Further, the sheet before forming the decorative printing layer is usually wound in a continuous belt-like state and conveyed and stored as a roll, but there is a problem that the resin layer breaks during winding. Furthermore, the resin layer and the substrate film adjacent to the resin layer are likely to stick to each other during winding (blocking), and as a result, printing failures such as ink loss are likely to occur.

Therefore, in order to solve such a technical problem, the present inventors have obtained a printing sheet having good bending resistance so that the adhesiveness with the printing layer is good and the resin layer does not break when winding. The study was advanced as a purpose.

As a result of studies aimed at solving such problems, the present inventors can solve the problems by defining the glass transition temperature of the resin composition forming the resin layer within a specific range. I found out. Furthermore, by having a configuration with a dimensional change rate in a specific range, even after the heating process in decorative printing, a printing sheet that is less likely to cause thermal shrinkage and curling and has excellent handling properties is obtained. The present invention has been completed.
The present invention has the following modes as means for solving the problems.

[1] A printing sheet laminated in the order of a primer resin layer and an adhesive layer,
The primer resin layer is a cured layer of a resin composition having a glass transition temperature of 0 ° C. to 100 ° C.,
A printing sheet having a lateral heating dimensional change rate of −0.01 to + 1% measured based on JIS K 7133.
[2] The printing sheet according to [1], wherein the bending resistance measured based on JIS-K5600-5-1 is 4 mmφ or less.
[3] The printing sheet according to [1] or [2], wherein the 180 ° glass adhesive strength of the adhesive layer is 2 to 40 N / 25 mm.
[4] The printing sheet with a release layer according to any one of [1] to [3], wherein a release layer is further laminated on at least one of the primer resin layer and the adhesive layer.
[5] A decorative sheet in which a printing layer is further laminated on the primer resin layer of the printing sheet according to any one of [1] to [3].

ADVANTAGE OF THE INVENTION According to this invention, the printing sheet which is excellent in printability, bending resistance, and handleability, and also can be reduced in thickness can be provided.

It is a schematic sectional drawing which shows the structure of the printing sheet of this invention. It is a schematic sectional drawing which shows the structure of the printing sheet with a peeling layer of this invention. It is a schematic sectional drawing which shows the structure of the decorating sheet of this invention.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Print sheet]
FIG. 1 is a cross-sectional view showing a configuration of a printing sheet according to an embodiment of the present invention.
The printing sheet 10 of this example has a primer resin layer 11 and an adhesive layer 12 formed on the primer resin layer 11, and the lateral heating dimensional change rate measured based on JIS K 7133 is − 0.01 to + 1%.
The lateral heating dimensional change rate measured based on JIS K 7133 is preferably -0.01% to + 1%, more preferably -0.005% to + 0.5%, and 0.0 to +0. 3% is more preferable. Since the rate of change in the horizontal heating dimension is within the above range, appearance defects due to heat shrinkage and the like do not occur even when heat treatment is performed in a subsequent process such as printing. The horizontal dimensional change rate of the heating dimension can be adjusted by changing the degree of curing according to the composition ratio of the primer resin layer forming composition described later, the drying temperature, and the irradiation amount of the active energy ray.

  The thickness of the printing sheet 10 is preferably 5 to 40 μm, and more preferably 10 to 25 μm. The thickness can be measured by using a stylus thickness meter (for example, ABS Digimatic Indicator D-C112A with a peak hold function manufactured by Mitutoyo Corporation).

  The printing sheet of the present invention has a flex resistance measured based on JIS-K5600-5-1 of 4 mmφ or less, and more preferably 2 mmφ or less. When the bending resistance is not more than the above, the primer resin layer is not broken in a processing step such as printing, and can be bonded to an adherend having a curved surface as well as a flat surface without any problem.

<Primer resin layer>
The primer resin layer 11 is a layer obtained by curing a resin composition having a glass transition temperature of 0 ° C. to 100 ° C. The glass transition temperature is more preferably 20 to 90 ° C, further preferably 40 to 80 ° C. Since the glass transition temperature is within the above range, the adhesiveness with the printed layer is good, and when it is wound, the glass transition temperature that can be easily wound without sticking to the anti-coating surface is a resin composition. By adjusting the kind, composition ratio, polymerization conditions, and the like, it is possible to make it within the above range. The glass transition temperature can be measured by methods such as thermogravimetric-differential thermal analysis, differential scanning calorimetry, and thermomechanical analysis.
As will be described in detail later, the primer resin layer 11 can be obtained by coating the primer resin layer forming composition on a release sheet and curing the coating film by heating or irradiation with active energy rays.

The resin composition may be either a thermosetting resin or an active energy ray curable resin. Examples of the thermosetting resin include polyester urethane resin, polyester resin, acrylic resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, silicon resin, Examples thereof include polysiloxane resins.
Examples of the active energy ray-curable resin include urethane acrylic resin, acrylic resin, polyester acrylic resin, and epoxy acrylic resin. The urethane acrylic resin has a polyoxyalkylene segment and / or a saturated polyester segment connected via a urethane bond, and has acryloyl groups at both ends.
Among the above resins, a polyester urethane resin, an acrylic resin, a urethane acrylic resin, and a polyester acrylic resin are preferable from the viewpoint of adhesion to the printing layer.

The content of the resin in the primer resin layer 11 is preferably 20 to 100% by mass, more preferably 60 to 98% by mass, and further 80 to 98% by mass in 100% by mass of the solid content of the resin composition. preferable. If it is in the said range, adhesiveness with a printing layer will be favorable and it has sufficient intensity | strength as a primer layer.

(Other ingredients)
The primer resin layer-forming composition preferably contains a crosslinking agent (thermosetting agent) or a photopolymerization initiator in order to promote curing. As a crosslinking agent, an isocyanate compound, an epoxy compound, an oxazoline compound, an aziridine compound, a metal chelate compound, a butylated melamine compound, etc. are mentioned, for example, These may use 2 or more types together as needed.
Of these crosslinking agents, isocyanate compounds and epoxy compounds are preferred. Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diester. Glycidyl ether, tetraglycidyl xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. Can be mentioned. As the photopolymerization initiator, known ones can be used, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2 dimethoxy- 21-phenylacetophenone, 2,2-diethoxy-21-phenylacetophenone, 2-hydroxy-21-methyl-11-phenylphenyl-11-one, 11-hydroxycyclohexyl phenylketone, 2-methyl-11- [41- (methylthio) phenyl] 1 21 morpholinopropane-1 1-one, 4 1 (2 1 hydroxyethoxy) phenyl 2 (hydroxy 2 1 prop) ketone, benzophenone, p 1 phenylbenzophenone, 4 4'-diethylaminobenzophenone, propiophenone, dichlorobenzophenone, 21-methylanthraquinone, 2-ethylanthraquinone, 2-nightly shallow butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, and the like. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

0.5-10 mass parts is preferable in the solid content of 100 mass parts of the composition for primer resin layer formation, and, as for the compounding quantity of a crosslinking agent or a photoinitiator, 2-8 mass parts is more preferable. Since it is hard to produce the hardening defect of the primer resin layer 11 as it is 0.5 mass part or more, it is preferable. Further, even if the photopolymerization initiator is blended in an amount exceeding 10% by mass with respect to the total mass of the solid content of the primer resin layer forming composition, a curing accelerating effect corresponding to the blending amount cannot be obtained, and the cost is also increased. Get higher. In addition, the photopolymerization initiator may remain in the primer resin layer 11 to cause yellowing or bleed out.
In addition to the photopolymerization initiator, a photosensitizer can be further contained.
Examples of the photosensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.

The composition for primer resin layer formation may contain other components other than the above as long as it does not impair the effects of the present invention. For example, the primer resin layer 11 is used for imparting other functions (antibacterial properties, antifouling properties, antistatic properties, ultraviolet ray shielding properties, antiglare properties, hardness, etc.) other than ink adhesion and anti-blocking properties. Known additives can be included. Examples of such additives include antibacterial agents for imparting antibacterial properties, silicone-based antifouling agents and fluorine-based antifouling agents for imparting antifouling properties, and silicone-based lubricants for imparting slipperiness. And fluorine-based lubricants, leveling agents for improving coating suitability, metal oxide fine particles for imparting antistatic performance, antistatic resins, conductive polymers, metal oxide fine particles for imparting ultraviolet shielding properties , Ultraviolet absorbers, light stabilizers, antiglare properties, inorganic fine particles for imparting hardness, organic fine particles and the like. Inorganic fine particles and organic fine particles may be contained in order to improve blocking resistance.

The composition for primer resin layer formation may contain a solvent.
Examples of the solvent include methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, n-hexane, n-butyl alcohol, methyl isobutyl ketone, methyl butyl ketone, ethyl butyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl. Ether acetate, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, N-methyl-2-monopyrrolidone and the like are used. These may be used alone or in combination of two or more.
In particular, since it is possible to reduce coating unevenness, it is preferable to use two or more solvents having different evaporation rates in combination. For example, it is preferable to use a mixture of at least two selected from methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, and toluene.

(Function of primer resin layer)
The primer resin layer 11 plays a role of improving adhesion between the print layer and the primer resin layer 11 when the print layer is formed on the primer resin layer 11 of the printing sheet 10.

(Primer resin layer thickness)
The film thickness of the primer resin layer 11 can be adjusted in the range of 0.1 to 100 μm.
As for the film thickness of the primer resin layer 11, 3-25 micrometers is more preferable, and 5-15 micrometers is still more preferable. When the thickness of the primer resin layer 11 is less than 0.1 μm, the strength of the primer resin layer 11 itself is weak and it is easy to tear due to shear stress or the like. Further, the function of the primer resin layer 11 is not exhibited, and when the printing sheet 10 is printed, that is, when the printing layer is laminated on the primer resin layer 11, the primer resin layer 11 and the printing layer Adhesion decreases. On the other hand, when the thickness of the primer resin layer 11 exceeds 100 μm, the transparency of the primer resin layer itself is lowered.

<Adhesive layer>
The printing sheet 10 of the present invention has an adhesive layer 12. Examples of the pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer 12 include natural rubber-based pressure-sensitive adhesives, synthetic rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. Moreover, any of solvent system, emulsion system, and water system may be sufficient. Among these, acrylic adhesives are particularly preferable from the viewpoints of transparency, weather resistance, durability, cost and the like when used for optical system applications.

  The acrylic pressure-sensitive adhesive is mainly composed of an acrylic copolymer. The acrylic copolymer is obtained by copolymerizing a (meth) acrylic acid alkyl ester having no functional group and a (meth) acrylic monomer having a reactive functional group. The (meth) acrylic monomer having a reactive functional group serves as a reaction point when a cross-linking agent is used, and enables control of adhesive force, cohesive force, and heat resistance by cross-linking. It is preferable that content of the monomer which has a reactive functional group shall be 0.1-20 mass% with respect to the total mass of the monomer which comprises an acrylic copolymer. More preferably, it is 0.5-15 mass%, More preferably, it is 1-10 mass%.

  Examples of the monomer of (meth) acrylic acid alkyl ester having no functional group constituting the acrylic copolymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth). (Meth) acrylic acid alkyl esters such as acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, etc. Although a body is mentioned, these may use 2 or more types together as needed.

  Examples of the reactive functional group include a carboxy group, an amide group, an amino group, a hydroxy group, and a glycidyl group.

  Examples of the (meth) acrylic monomer having a carboxy group include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, and fumaric anhydride. Examples of the (meth) acrylic monomer having an amide group or amino group include (meth) acrylamide, morpholyacrylamide, and allylamide. Examples of the (meth) acrylic monomer having an amino group include N, N-dimethylaminoethyl acrylate and N-tert-butylaminoethyl acrylate. In addition, these may use together 2 or more types as needed.

  When polymerizing an acrylic copolymer, for example, a solution polymerization method can be applied. Examples of the solution polymerization method include an ionic polymerization method and a radical polymerization method. Examples of the solvent used at that time include tetrahydrofuran, chloroform, ethyl acetate, toluene, hexane, acetone, methyl ethyl ketone, and the like.

The acrylic copolymer used in the present invention can be subjected to a crosslinking treatment by blending a crosslinking agent.
As a crosslinking agent, an isocyanate compound, an epoxy compound, an oxazoline compound, an aziridine compound, a metal chelate compound, a butylated melamine compound, etc. are mentioned, for example, These may use 2 or more types together as needed.
Among these crosslinking agents, an isocyanate compound and an epoxy compound are preferable because the acrylic copolymer can be easily crosslinked. Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diester. Glycidyl ether, tetraglycidyl xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. Can be mentioned.
It is preferable that the content of the crosslinking agent is appropriately selected according to the desired pressure-sensitive adhesive properties.

Other auxiliary agents may be added to the adhesive as necessary. Other auxiliaries include tackifiers, silane coupling agents, metal corrosion inhibitors, antioxidants, UV absorbers, thickeners, pH adjusters, tackifiers, binders, cross-linking agents, adhesive fine particles, Examples include foaming agents, antiseptic / antifungal agents, pigments, inorganic fillers, stabilizers, wetting agents, wetting agents and the like.
Examples of the tackifier include rosin resin, terpene resin, terpene phenol resin, coumarone indene resin, styrene resin, xylene resin, phenol resin, and petroleum resin. Examples of the silane coupling agent include mercaptoalkoxysilane compounds (for example, mercapto group-substituted alkoxy oligomers). As the metal corrosion inhibitor, a type that prevents a corrosion by forming a complex with a metal and forming a film on the metal surface is preferable, and a benzotriazole-based metal corrosion inhibitor is particularly preferable. In particular, when a conductive film patterned with metal or a conductive surface of a glass with a conductive layer is bonded onto the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer preferably contains a metal corrosion inhibitor.
The antioxidant is preferably an antioxidant typified by a hindered phenol compound. Antioxidants are generally classified into primary antioxidants called radical chain terminators and secondary antioxidants that act as peroxide decomposers. Examples of the primary antioxidant include hindered phenol antioxidants, amine antioxidants, and lactone antioxidants. Examples of secondary antioxidants include phosphorus antioxidants and sulfur antioxidants. These antioxidants may be used alone or in combination of two or more.
The ultraviolet absorber is preferably a benzotriazole compound, a benzophenone compound, a triazine compound, or the like.

  The content of the additive used in combination is preferably 0.01 to 5 parts by mass and more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the acrylic copolymer. If the content is equal to or higher than the lower limit, the effect of the additive is exhibited, and if the content is equal to or lower than the upper limit, the additive bleed-out hardly occurs.

The thickness of the adhesive layer 12 is preferably 3 to 100 μm, more preferably 5 to 50 μm, and still more preferably 5 to 25 μm. When the thickness is 3 μm or more, a sufficient adhesive force can be secured, and even when used for a long time, it is difficult for floating and peeling. In addition, the thickness can be easily controlled and is less likely to be uneven. If the thickness of the pressure-sensitive adhesive layer is 100 μm or less, there is an advantage that troubles such as an increase in the defect rate due to adhesion of the pressure-sensitive adhesive to the cutting blade when the pressure-sensitive adhesive sheet is cut to the size of the display are obtained.
Here, the film thickness of the pressure-sensitive adhesive layer 12 refers to the distance from the interface between the pressure-sensitive adhesive layer 12 and a release layer 13 described later to the interface between the pressure-sensitive adhesive layer 12 and the primer resin layer 11. The thickness of the adhesive layer 12 can be measured using a stylus type film thickness meter (ABS Digimatic Indicator D-C112A with a peak hold function manufactured by Mitutoyo Corporation).

  180 degree | times adhesive force with respect to glass of the printing sheet | seat of this invention is 2-40 N / 25mm. The lower limit value is more preferably 8 N / 25 mm or more, and further preferably 10 N / 25 mm or more. The 180 ° adhesive strength to glass was peeled off at a pulling speed of 300 mm / min by the 180 ° peeling method defined in accordance with JIS Z0237 after 1 day had passed since the alkali glass plate and the adhesive layer were bonded. It means the adhesive strength (N / 25 mm) at the time.

The haze value of the printing sheet 10 is preferably 1% or less, and the total light transmittance is preferably 87% or more. If the haze value and the total light transmittance are within the above ranges, the printing sheet 10 can be suitably used as an optical application.

The haze value is a value measured according to JISK7136. The haze value of the printing sheet 10 is 0.044 rad (2.5 mm from the incident light due to scattering in the transmitted light that passes through the test piece using the CIE standard light D65 as a light source using a sample of 100 mm × 100 mm. Degree) or more can be measured by a method defined as the percentage of transmitted light deviated.
The haze value is preferably 1.0% or less, and more preferably 0.8% or less.

The total light transmittance is a value measured according to JISK7361. The total light transmittance of the printing sheet 10 is defined as a ratio of a total transmitted light beam integrated by an integrating sphere to a parallel incident light beam of a test piece using a sample of 100 mm × 100 mm as a light source of CIE standard light D65. It can be measured by the method. The total light transmittance is preferably 87% or more, and more preferably 89% or more.
The haze value and total light transmittance of the printing sheet 10 can be adjusted by the type of the resin composition forming the primer resin layer 11 and the Ra of the surface of the primer resin layer 11.

[Print sheet with release layer]
<Peeling layer>
A release layer 13 and a release layer 14 may be further formed on the surface of the primer resin layer 11 and / or the adhesive layer 12 of the printing sheet 10 of the present invention. If the primer resin layer 11 or the adhesive layer 12 is exposed, it may adhere to an unintended article or the primer resin layer 11 or the adhesive layer 12 itself may deteriorate. Therefore, in order to physically and chemically protect the primer resin layer 11, a release layer 13 or a protective layer is provided on the surface of the primer resin layer 11, and the release layer 13 or the protective layer is peeled off when used. Thus, the primer resin layer 11 is exposed, and decorative printing or the like can be performed. Similarly, in order to physically and chemically protect the adhesive layer 12, a release layer 14 is provided on the surface of the adhesive layer 12, and the adhesive layer 14 is exposed by peeling the release layer 14 when used. Can be attached to other members. Generally, since the printing layer 21 is provided and then bonded to the adherend, it is preferable to make the peeling force of the peeling layer 13 or the protective layer lighter than the peeling layer 14.

Examples of the release layer include those in which a release agent layer such as silicone is applied to various plastic films to form a release agent layer, and a polypropylene film alone, which is used as a release sheet for ordinary pressure-sensitive adhesive sheets Can be used.
Examples of the protective layer include those in which a pressure-sensitive adhesive layer is formed by applying a pressure-sensitive adhesive such as a urethane-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, and a silicone pressure-sensitive adhesive to various plastic films, a polyethylene film, a polypropylene film alone, etc. What is used as a protective sheet can be used.

<Manufacturing method of printing sheet with release layer>
The printing sheet 10 can be manufactured as follows, for example.
First, a primer resin layer forming composition is prepared. As solid content concentration of the composition for primer resin layer formation, it is preferable that it is 10-100 mass% with respect to the total mass of the composition for primer resin layer formation, and it is more preferable that it is 20-70 mass%. .
Next, the primer layer-forming composition is applied to the release sheet (release layer 13), and the primer resin layer 11 is formed on the release sheet by curing the coating film by heating or irradiation with active energy rays ( Formation of primer resin sheet).
Next, the pressure-sensitive adhesive layer 12 is formed on another release sheet (release layer 14) by applying a pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer 12 and curing the coating film by heating or irradiation with active energy rays. Formed (formation of adhesive sheet).
Finally, the primer resin sheet and the pressure-sensitive adhesive sheet are stacked so that the primer resin layer 11 and the pressure-sensitive adhesive layer 12 are in contact with each other, and are subjected to pressure bonding to obtain a printed sheet 10 ′ with a release layer.

Examples of the coating method for the primer resin layer forming composition include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and a printing machine. And the like. The coating amount of the curable resin layer forming composition is appropriately set according to the thickness of the primer resin layer 11 to be formed.

When the primer resin layer forming composition is an active energy ray-curable resin, the coating film can be cured by irradiation with active energy rays.
Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, visible rays, and γ rays. Among them, ultraviolet rays are preferable from the viewpoint of versatility. As the ultraviolet light source, for example, a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, or the like can be used. As the electron beam, for example, an electron beam emitted from various electron beam accelerators such as a cockloftwald type, a bandecraft type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used.
Curing by irradiation with active energy rays is preferably performed in the presence of an inert gas such as nitrogen. The irradiation amount of the active energy ray is preferably 100~1000mJ / cm ^2, more preferably 150~500mJ / cm ^2.
Curing may be performed in one stage, or may be performed in two stages, a preliminary curing process and a main curing process.

When the composition for forming the primer resin layer is a thermosetting resin, it can be cured by heating using a heating furnace or an infrared lamp. As heating conditions, it is preferable to carry out at 60-120 degreeC for 1 to 5 minutes, and it is more preferable to carry out at 70-100 degreeC for 2 to 3 minutes.

In the method of directly applying the primer resin layer to the cured pressure-sensitive adhesive layer, the primer resin layer-forming composition is cured following the unevenness of the pressure-sensitive adhesive layer, so that it is difficult to obtain a smooth surface. Also, in the method of directly applying the adhesive to the cured primer resin layer, the strength of the primer resin layer is weak, and the primer resin layer is torn when it comes into contact with the roll in the process of winding as a winding process in the manufacturing process. There were drawbacks.
Further, in the method in which the primer resin layer forming composition and the adhesive layer forming composition are simultaneously applied and laminated, a mixed layer of the primer resin layer and the adhesive layer is inevitably formed, and both resins are contained in the mixed layer. Problems such as whitening due to reaction of components may occur.

[Decorative sheet]
FIG. 3 is a cross-sectional view showing a configuration of a decorative sheet 20 which is an embodiment of the present invention.
In the decorative sheet 20 of this example, a printing layer 21 is laminated on the primer resin layer 11 of the printing sheet 10 shown in FIG.

<Print layer>
The print layer 21 is mainly applied for decoration or the like.
Examples of the printing layer 21 include a layer in which a pattern, characters, a photograph, and the like are printed with printing ink. As shown in FIG. 3, the print layer 21 may be formed on the entire surface of the primer resin layer 11, or may be formed on a part of the surface of the primer resin layer 11.
The printing layer 21 includes, for example, a colorant (pigment, dye) and a binder (polyvinyl resin, polyamide resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, polyester resin, cellulose ester. It can be formed by printing a colored ink containing a resin or an alkyd resin. In the case of forming a metal color, metal particles such as aluminum, titanium and bronze, and a pearl pigment obtained by coating mica with titanium oxide can be used. That is, it is preferable that the printing layer 21 includes a colorant and a binder.

The thickness of the printing layer 21, that is, the distance from the interface of the primer resin layer 11 to the outermost surface of the printing layer 21 (interface with air) in FIG. 3 is preferably 0.1 to 50 μm, and preferably 1 to 30 μm. More preferred. The film thickness can be specifically measured using a stylus type film thickness meter (ABS Digimatic Indicator ID-C112A with a peak hold function manufactured by Mitutoyo Corporation).

<Method for producing decorative sheet>
The decorative sheet 20 is obtained, for example, by printing the printing sheet 10 using a lithographic printing plate (lithographic plate), a screen printing method, a thermal transfer printing method, or the like. For example, printing is performed by bringing the planographic printing plate and the primer resin layer 11 of the printing sheet 10 into contact with each other, and the printing layer 21 is formed on the primer resin layer 11.

<Member>
A member may be further laminated on the surface of the pressure-sensitive adhesive layer 12 of the printing sheet 10 of the present invention. Examples of the member include a glass member and a resin plate. The printing sheet of the present invention can exhibit good adhesion to such a member.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.

(Preparation of primer resin layer forming composition A)
Polyester urethane resin A (trade name: Byron UR-1350, concentration 33%, manufactured by Toyobo Co., Ltd.) having a glass transition temperature (Tg) of 46 ° C., 100 parts by mass, an HDI curing agent (trade name: Coronate HXR) The primer resin layer forming composition A was prepared by mixing 0.66 parts by mass of Tosoh Corporation.

(Preparation of primer resin layer forming composition B)
Polyester urethane resin B (trade name: Byron UR-4125, concentration: 23%, manufactured by Toyobo Co., Ltd.) having a Tg of 68 ° C., an HDI curing agent (trade name: Coronate HXR, Tosoh Corp.) as a thermosetting agent (Manufactured) 0.46 parts by mass was mixed to prepare primer resin layer forming composition B.

(Preparation of primer resin layer forming composition C)
Polyester resin C (trade name: Byron UR-1700, concentration 30%, manufactured by Toyobo Co., Ltd.) having a Tg of 92 ° C., an HDI-based curing agent (trade name: Coronate HXR, manufactured by Tosoh Corporation) as a thermosetting agent ) 0.6 parts by mass was mixed to prepare a primer resin layer forming composition C.

(Preparation of primer resin layer forming composition D)
Polyester urethane resin D (trade name Byron UR-3500, concentration 40%, manufactured by Toyobo Co., Ltd.) having a Tg of 10 ° C., an HDI-based curing agent (trade name: Coronate HXR, Tosoh Corp.) as a thermosetting agent (Manufactured) 0.8 parts by mass was mixed to prepare a primer resin layer forming composition D.

(Preparation of primer resin layer forming composition E)
Polyester urethane resin E (trade name: Byron UR-8300, concentration: 30%, manufactured by Toyobo Co., Ltd.) having a Tg of 23 ° C., an HDI curing agent (trade name: Coronate HXR, Tosoh Corporation) as a thermosetting agent (Manufactured) A primer resin layer forming composition E was prepared by mixing 0.6 parts by mass.

(Preparation of primer resin layer forming composition F)
100 parts by mass of urethane acrylic resin F (trade name: 8UA-017, concentration: 50%, manufactured by Taisei Fine Chemical Co., Ltd.) having a Tg of 50 ° C., 1 part by mass of a photopolymerization initiator (trade name: IRGACURE184 BASF Co., Ltd.) By mixing, a primer resin layer forming composition F was prepared.

(Preparation of primer resin layer forming composition G)
Urethane acrylic resin G (trade name: 8UA-301, concentration: 30%, manufactured by Taisei Fine Chemical Co., Ltd.) 100 parts by mass, photopolymerization initiator (trade name: IRGACURE184 BASF Co., Ltd.) 0.6 mass Parts were mixed to prepare a primer resin layer forming composition G.

(Preparation of primer resin layer forming composition H)
Polyester urethane H (trade name: Byron UR-4800, concentration: 32%, manufactured by Toyobo Co., Ltd.) 100 parts by mass with a Tg of 106 ° C., HDI-based curing agent (trade name: Coronate HXR, manufactured by Tosoh Corp.) ) 0.64 parts by mass were mixed to prepare primer resin layer forming composition H.

(Preparation of primer resin layer forming composition I)
Polyester urethane I (trade name Byron UR-3200, concentration 30%, manufactured by Toyobo Co., Ltd.) 100 parts by mass with Tg of −3 ° C., HDI curing agent (trade name Coronate HXR, Tosoh Corp.) as thermosetting agent (Product) A composition I for forming a primer resin layer was prepared by mixing 0.6 parts by mass.

(Preparation of primer resin layer forming composition J)
Mixing 100 parts by mass of acrylic resin J (trade name Aronix M403, 100% concentration, manufactured by Toagosei Co., Ltd.) with a photopolymerization initiator (trade name: IRGACURE184 BASF Co., Ltd.) having a Tg of 250 ° C. or higher. Thus, a primer resin layer forming composition J was prepared.

(Preparation of primer resin layer forming composition K)
Mixing 100 parts by mass of acrylic resin K (trade name Aronix M306, concentration 100%, manufactured by Toagosei Co., Ltd.) and 2 parts by mass of a photopolymerization initiator (trade name: IRGACURE184 BASF Co., Ltd.) having a Tg of 250 ° C. or higher Thus, a primer resin layer forming composition K was prepared.

(Preparation of intermediate layer forming composition L)
Urethane acrylic resin L (trade name Art Resin UN-9200A, concentration 100%, manufactured by Negami Kogyo Co., Ltd.) 100 parts by mass, photopolymerization initiator (trade name: IRGACURE 184 BASF Co., Ltd.) 2 parts by mass is mixed. Layer forming composition L was prepared.

(Preparation of adhesive solution 1)
Nitrogen gas was sealed in a reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and then ethyl acetate as a solvent was added. Next, in the reactor, 65 parts by mass of butyl acrylate as an acrylic monomer, 35 parts by mass of methyl acrylate, 2 parts of acrylic acid, and 0.1 mass of 2,2′-azoisobutyronitrile as a polymerization initiator. Parts were added. Then, it superposed | polymerized at the reflux temperature of the solvent for 8 hours in nitrogen gas stream, stirring. After completion of the reaction, toluene was added to obtain an acrylic polymer solution. Next, 0.1 parts by mass of tolylene diisocyanate (trade name Coronate L, manufactured by Tosoh Corporation) as a cross-linking agent was mixed with 100 parts by mass of the acrylic polymer solid content to obtain a pressure-sensitive adhesive solution 1. .

(Preparation of adhesive solution 2)
2-ethylhexyl acrylate (Toagosei Co., Ltd.) 50 parts by mass, 2-hydroxypropyl acrylate (Osaka Organic Chemical Co., Ltd.) 50 parts by mass, 2-hydroxy-3-acryloyloxypropyl methacrylate (trade name 701A, parent Nakamura) Chemical Co., Ltd.) 0.5 parts by mass and photopolymerization initiator (trade name: IRGACURE184 BASF Co., Ltd.) 3 parts by mass were mixed to obtain an adhesive solution 2.

<Example 1>
(Preparation of printing sheet)
The coating thickness after drying of the composition A for forming the primer resin layer is 15 μm by a knife coater on the surface of the separator A (trade name E7002, 100 μm manufactured by Toyobo Co., Ltd.). It was coated as described above and dried at 100 ° C. for 2 minutes to form a primer resin layer, thereby preparing a primer resin sheet.
In addition, the adhesive solution 1 was applied to the surface of the separator B (trade name E7001, manufactured by Toyobo Co., Ltd. 100 μm) with a knife coater so that the coating thickness after drying was 25 μm. And dried at 100 ° C. for 2 minutes to form an adhesive layer, thereby producing an adhesive sheet.
Next, the primer resin sheet and the pressure-sensitive adhesive sheet were overlapped and pressure-bonded so that the primer resin layer and the pressure-sensitive adhesive layer were in contact with each other to obtain a printing sheet with a release layer.
Thereafter, the separator A on the primer layer side and the separator B on the adhesive layer side were peeled off to obtain a printing sheet.

<Example 2>
A printing sheet was prepared in the same manner as in Example 1 except that the primer resin layer forming composition A was changed to the primer resin layer forming composition B.

<Example 3>
A printing sheet was prepared in the same manner as in Example 1 except that the primer resin layer forming composition A was changed to the primer resin layer forming composition C.

<Example 4>
A printing sheet was prepared in the same manner as in Example 1 except that the primer resin layer forming composition A was changed to the primer resin layer forming composition D.

<Example 5>
A printing sheet was prepared in the same manner as in Example 1 except that the primer resin layer forming composition A was changed to the primer resin layer forming composition E.

<Example 6>
The coating thickness after drying of the composition F for forming the primer resin layer is 15 μm with a knife coater on the surface of the separator A (trade name E7002, 100 μm manufactured by Toyobo Co., Ltd.). And then dried at 100 ° C. for 2 minutes, using a high-pressure mercury lamp ultraviolet ray irradiator (manufactured by Eye Graphics Co., Ltd.) under the conditions of an irradiation intensity of 200 mW / cm ² and an integrated light quantity of 300 mJ / cm ^2. Irradiated. In addition, the adhesive solution 1 was applied to the surface of the separator B (trade name E7001, manufactured by Toyobo Co., Ltd. 100 μm) with a knife coater so that the coating thickness after drying was 25 μm. And dried at 100 ° C. for 2 minutes to form an adhesive layer.
Next, the primer resin sheet and the pressure-sensitive adhesive sheet were overlapped and pressure-bonded so that the primer resin layer and the pressure-sensitive adhesive layer were in contact with each other to obtain a printing sheet with a release layer.
Thereafter, the separator A on the primer resin layer side and the separator B on the adhesive layer side were peeled off to obtain a printing sheet.

<Example 7>
A printing sheet was prepared in the same manner as in Example 6 except that the primer resin layer forming composition F was changed to the primer resin layer forming composition G.

<Example 8>
A printing sheet was produced in the same manner as in Example 1 except that the thickness of the primer resin layer was changed to 50 μm.

<Example 9>
A printing sheet was produced in the same manner as in Example 1 except that the thickness of the primer resin layer was changed to 100 μm.

<Example 10>
A printing sheet was prepared in the same manner as in Example 1 except that the thickness of the primer resin layer was changed to 1 μm.

<Example 11>
A printing sheet was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was changed to 50 μm.

<Example 12>
A printing sheet was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was changed to 80 μm.

<Example 13>
The coating thickness after drying of the composition A for forming the primer resin layer is 15 μm with a knife coater on the surface of the separator A (trade name E7002, 100 μm manufactured by Toyobo Co., Ltd.). The primer resin layer was formed by coating at 100 ° C. for 2 minutes.
Further, the adhesive solution 2 was applied to the surface of the separator B (trade name E7001, manufactured by Toyobo Co., Ltd. 100 μm) by a knife coater so that the coating thickness after drying was 30 μm. Then, using a high pressure mercury lamp ultraviolet ray irradiator (manufactured by Eye Graphics Co., Ltd.), ultraviolet rays were irradiated under the conditions of an irradiation intensity of 200 mW / cm ² and an integrated light amount of 300 mJ / cm ² to form an adhesive layer.
Next, the primer resin sheet and the pressure-sensitive adhesive sheet were overlapped and pressure-bonded so that the primer resin layer and the pressure-sensitive adhesive layer were in contact with each other to obtain a printing sheet with a release layer.
Thereafter, the separator A on the primer resin layer side and the separator B on the adhesive layer side were peeled off to obtain a printing sheet.

<Comparative Example 1>
A printing sheet was prepared in the same manner as in Example 1 except that the primer resin layer forming composition A was changed to the primer resin layer forming composition H.

<Comparative example 2>
A printing sheet was prepared in the same manner as in Example 1 except that the primer resin layer forming composition A was changed to the primer resin layer forming composition I.

<Comparative Example 3>
The coating thickness after drying of the primer resin layer forming composition J is 15 μm with a knife coater on the surface of the separator A (trade name E7002, 100 μm manufactured by Toyobo Co., Ltd.). Then, using a high-pressure mercury lamp ultraviolet ray irradiator (manufactured by Eye Graphics Co., Ltd.), ultraviolet rays were irradiated under conditions of an irradiation intensity of 200 mW / cm ² and an integrated light amount of 300 mJ / cm ² . In addition, the adhesive solution 1 was applied to the surface of the separator B (trade name E7001, manufactured by Toyobo Co., Ltd. 100 μm) with a knife coater so that the coating thickness after drying was 25 μm. And dried at 100 ° C. for 2 minutes to form an adhesive layer.
Next, the primer resin sheet and the pressure-sensitive adhesive sheet were overlapped and pressure-bonded so that the primer resin layer and the pressure-sensitive adhesive layer were in contact with each other to obtain a printing sheet with a release layer.
Thereafter, the separator A on the primer resin layer side and the separator B on the adhesive layer side were peeled off to obtain a printing sheet.

<Comparative example 4>
A printing sheet was prepared in the same manner as in Comparative Example 3 except that the primer resin layer forming composition J was changed to the primer resin layer forming composition K.

<Comparative Example 5>
The adhesive solution 1 was applied to the surface of the separator B (trade name E7001, manufactured by Toyobo Co., Ltd. 100 μm) with a knife coater so that the coating thickness after drying was 25 μm. And dried at 100 ° C. for 2 minutes to form an adhesive layer.
Next, base material A (trade name T-60, manufactured by Toray Industries, Inc., 25 μm) is used as a primer resin sheet, and the base material A, which is the primer resin sheet, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet are stacked, pressure-bonded and peeled off. A layered printing sheet was obtained.
Thereafter, the separator B on the adhesive layer side was peeled off to obtain a printing sheet.

<Comparative Example 6>
The coating thickness after drying of the composition F for forming the primer resin layer is 80 μm with a knife coater on the surface of the separator A (trade name E7002, 100 μm manufactured by Toyobo Co., Ltd.). Thus, a primer resin layer was formed.
In addition, the adhesive solution 2 was applied to the surface of the separator B (trade name E7001, manufactured by Toyobo Co., Ltd. 100 μm) by a knife coater so that the coating thickness after drying was 30 μm. Then, using a high pressure mercury lamp ultraviolet ray irradiator (manufactured by Eye Graphics Co., Ltd.), ultraviolet rays were irradiated under the conditions of an irradiation intensity of 200 mW / cm ² and an integrated light amount of 50 mJ / cm ² to form an adhesive layer.
Next, the intermediate layer forming composition L was applied onto the primer resin layer with a knife coater so that the coating thickness after drying was 70 μm, and the adhesive layer was layered thereon and pressure-bonded thereon. Furthermore, using a high-pressure mercury lamp ultraviolet ray irradiator (manufactured by Eye Graphics Co., Ltd.), ultraviolet rays were irradiated under the conditions of an irradiation intensity of 200 mW / cm ² and an integrated light amount of 600 mJ / cm ² to obtain a printed sheet with a release layer.
Thereafter, the separator A on the primer resin layer side and the separator B on the adhesive layer side were peeled off to obtain a printing sheet.

<Comparative Example 7>
The primer resin layer-forming composition A was applied to a base material A (trade name T-60, 25 μm manufactured by Toray Industries, Inc.) with a knife coater so that the coating thickness after drying was 15 μm. The primer resin sheet was formed by drying at 2 ° C. for 2 minutes.
In addition, the adhesive solution 1 was applied to the surface of the separator B (trade name E7001, manufactured by Toyobo Co., Ltd. 100 μm) with a knife coater so that the coating thickness after drying was 25 μm. And dried at 100 ° C. for 2 minutes to form an adhesive layer.
Next, the primer resin sheet and the pressure-sensitive adhesive sheet were stacked and pressure-bonded so that the substrate A of the primer resin sheet and the pressure-sensitive adhesive layer were in contact with each other, and then the separator B on the pressure-sensitive adhesive layer side was peeled off to obtain a printing sheet.

<Measurement of dimensional change rate and heat shrinkage>
The printing pressure-sensitive adhesive sheet was cut into a size of 120 mm long × 120 mm wide, and the dimensional change rate (%) in the horizontal direction after processing at 150 ° C. for 30 minutes in accordance with JIS K 7133 was calculated.
Thereafter, as the evaluation of thermal shrinkage, the case where the dimensional change rate was −0.01 to + 1% was evaluated as ◯, and the case where it was smaller than −0.01% was evaluated as ×.

<Measurement of heat-resistant curl>
The printing pressure-sensitive adhesive sheet was cut into a size of 100 mm length × 100 mm width, treated at 150 ° C. for 30 minutes, and allowed to stand for 1 day in an environment of 23 ° C. and humidity 50% RH. Thereafter, the floating of the four corners was measured, and the average value was calculated as curl. The case where the curl was 0 to 5 mm was rated as ◯, the case where the curl was 5 to 20 mm as Δ, and the case where the curl was 20 mm or more as ×.

<Evaluation of bending resistance>
Based on JIS-K5600-5-1, the bending resistance of the printing sheet was tested with a cylindrical mandrel bending tester manufactured by Cortec Co., Ltd. with a mandrel diameter of 4 mmφ and 2 mmφ, and the primer resin layer did not break at 2 mmφ. Were not cracked at 4 mmφ, but were cracked at 2 mmφ, and those at 4 mmφ were marked as x.

<Evaluation of adhesive strength>
The produced printing sheet was aged for 7 days in an environment of a temperature of 23 ° C. and a humidity of 50%, and then a test piece having a width of 25 mm and a length of 100 mm was sampled from the film. On the other hand, an alkali glass plate was prepared by washing the surface with ethanol and leaving it for 3 hours or more in an environment of a temperature of 23 ° C. and a humidity of 50% RH. What peeled off the peeling film from the test piece was bonded together by making it reciprocate on the surface of an alkali glass plate with the pressurization roller of mass 2kg. After 30 minutes from the pasting, the adhesive strength (N / 25 mm) was measured by peeling at a tensile rate of 300 mm / min by the 180-degree peeling method defined in JIS Z0237.

<Evaluation of ink adhesion>
Ink A was prepared by mixing 100 parts by mass of ink (trade name MRX HF-919 black, Teikoku Ink Co., Ltd.) and 5 parts by mass of a curing agent (trade name 210 curing agent, Teikoku Ink Co., Ltd.).
Separately, 100 parts by mass of ink (trade name MRX HF-619 white, manufactured by Teikoku Ink) and 5 parts by mass of a curing agent (trade name 210 curing agent, manufactured by Teikoku Ink) were mixed to prepare ink B. did.
Screen printing was performed on the surface of the primer resin layer of the printing sheet using ink A and ink B, respectively, and dried at 80 ° C. for 1 hour to form a printing layer having a thickness of 15 μm on the primer resin layer.
In accordance with JIS K 5600-5-6, a cross-cut adhesion test was performed as follows.
Cellophane tape (trade name CT28, manufactured by Nichiban Co., Ltd.) was peeled off after being brought into close contact with the printed layer as if pressed from above with a finger. Of 100 squares, 100/100 is the case where the printed layer is not peeled off at all squares, and 0/100 is the case where the printed layer is peeled off at all squares. The ink adhesion was evaluated according to the following evaluation criteria.
A: 96/100 to 100/100
B: 50/100 to 95/100
C: 0/100 to 49/100

<Evaluation of sticking>
The adhesion when the primer resin layer surface was placed on the surface of the separator A that was not subjected to the release treatment was visually confirmed. At this time, the case where sticking did not occur on the surface on which it was placed was indicated by ◯, the case where sticking occurred partially was indicated by Δ, and the case where sticking occurred on the front surface was indicated by ×.

<Evaluation of ease of peeling of separator A>
When the separator A is peeled off from the primer resin layer side, the case where the primer resin layer can be peeled off without being broken is marked as ◯, the case where the primer resin layer can be peeled off almost without being broken, and the primer layer is broken. The case where it was done was set as x.

The evaluation results of Examples 1 to 13 are shown in Table 1, and the evaluation results of Comparative Examples 1 to 7 are shown in Table 2.

In Examples 1 to 13, good results were obtained in all evaluations, whereas Comparative Example 1 in which the glass transition temperature of the primer resin layer was high was inferior in ink adhesion. In Comparative Example 2, the glass transition temperature was low, and sticking occurred and it was difficult to wind up. Comparative Examples 3, 4, and 6 had very high glass transition temperatures and poor ink adhesion and flex resistance. In Comparative Example 5, heat shrinkage occurred and the ink adhesion was inferior. In Comparative Example 7, heat shrinkage occurred similarly to Comparative Example 5. Further, curling occurred and the handling property was inferior.

DESCRIPTION OF SYMBOLS 10 Printing sheet 10 'Printing sheet with peeling layer 11 Primer resin layer 12 Adhesive layer 13 Release layer 14 Release layer 20 Decorating sheet 21 Print layer

Claims (5)

It is a printing sheet laminated in the order of a primer resin layer and an adhesive layer,
The primer resin layer is a cured layer of a resin composition having a glass transition temperature of 0 ° C. to 100 ° C.,
The adhesive layer is provided only on one side of the primer resin layer,
A printing sheet having a lateral heating dimensional change rate of −0.01 to + 1% measured based on JIS K 7133. Printing sheet according to claim 1 bending resistance which is measured based on JIS-K5600-5-1 is less than 4 mm diameter. The printing sheet according to claim 1 or 2, wherein the adhesive layer has a 180 ° glass adhesive force of 2 to 40 N / 25 mm. At least on one of, printing sheet according to claim 1, further peeling layer are stacked in the primer resin layer and the adhesive layer. The decorative sheet | seat on which the printing layer was further laminated | stacked on the primer resin layer of the printing sheet of any one of Claims 1-3.

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