JP2015196269A - Resin sheet and method of producing protective layer formation material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin sheet which is used by pressure-adhering to the surface of a protective layer formation material in which a protective layer is formed on the surface of a to-be-transferred body (medium) and peeling from the protective layer and allows exclusive removal of burr (protective layer) in the peripheral edge of the medium and dust adhered to the surface of the protective layer without influence on the protective layer on the medium.SOLUTION: A resin sheet at least includes a resin layer 10 to be pressure-adhered to a protective layer of a medium and a substrate 11 supporting the resin layer 10, and the resin layer 10 contains a hardened resin formed by hardening a polyvinyl butyral resin and/or a polyvinyl acetal resin with an isocyanate-based hardener. The resin layer contains the isocyanate-based hardener in a mol equivalent ratio (-NCO/-OH) of the isocyanate group of the isocyanate-based hardener to hydroxy groups of the polyvinyl butyral resin and/or the polyvinyl acetal resin of 0.03-0.90.

Description

  The present invention relates to a resin sheet that is used after being pressure-bonded to the surface of a protective layer forming body having a protective layer provided on the surface of a medium, and then peeled off from the protective layer.

  Individual information such as face photos, addresses, and names are recorded on the surface of ID cards such as identification cards and cash cards such as banks. The recorded information is recorded on the surface of such IC cards. In order to protect the hologram and the hologram, a protective layer is provided using a protective layer transfer sheet.

  The protective layer transfer sheet has a configuration in which a transferable hard coat layer is provided on a support, and a hard coat layer (protective layer) of the protective layer transfer sheet is provided on the surface of a transfer target such as an IC card. By transferring, hard coat performance can be imparted to the surface of the transfer object. As such a protective layer transfer sheet, in general, an ultraviolet curable resin layer, an intermediate layer subjected to pattern printing or the like on a support such as a PET film via a release layer or a release layer, and an adhesive layer Those having a layer structure in which are stacked in order.

  In recent years, in order to improve security, OA devices and information terminals are often managed by ID cards, etc., and IDs provided with a conventional protective layer with the increasing frequency of use of ID cards etc. Even in the case of cards, images have been worn out due to wear or the like. Therefore, in order to further improve the image wear resistance, the protective layer is made thick. However, when a protective layer is transferred to a transfer target using a protective layer transfer sheet, if the protective layer is thickened as described above, an ID card or the like as shown in FIG. In some cases, burrs 24 called tailing occur at the end of the protective layer forming body 40.

  For the above-mentioned problems, a protective film having a certain thickness is provided on the surface of the transfer object by repeatedly performing the transfer twice using a normal thickness protective layer transfer sheet with good transferability. Can be considered. For example, in Japanese Patent Application Laid-Open No. 2001-138664 (Patent Document 1), using a protective layer transfer sheet having a cured layer (photocured resin layer) having a thickness of about 5 to 25 μm, the transfer is performed twice or more. It has been proposed to transfer a cured layer to the body.

JP 2001-138664 A

  However, although the method proposed in Japanese Patent Application Laid-Open No. 2001-138664 can suppress the generation of burrs when the protective layer is transferred, the number of steps is larger than that of a normal step, and thus a protective layer formed body is manufactured. There was a cost problem when doing so.

  The present inventors have now transferred a protective layer to the surface of a medium (transfer object), and then pressure-bonded a resin sheet made of a resin having a specific composition to the surface of the protective layer formed on the medium. By removing the resin sheet from the medium, it is possible to remove only burrs (protective layer) on the peripheral edge of the medium and dust attached to the surface of the protective layer without affecting the protective layer formed on the medium. Obtained knowledge. The present invention is based on this finding.

  Therefore, an object of the present invention is to provide a resin sheet that can remove only burrs (protective layer) on the peripheral edge of the medium and dust adhered to the surface of the protective layer without affecting the protective layer formed on the medium. Is to provide.

  Another object of the present invention is to provide a method for producing a protective layer forming body using the resin sheet.

The resin sheet according to the present invention is a resin sheet that is used after being pressure-bonded to the surface of the protective layer of the protective layer forming body provided with a protective layer on the surface of the medium, and then peeled off from the protective layer,
A resin layer to be pressure-bonded to the protective layer of the medium, and at least a base material that supports the resin layer,
The resin layer comprises a curable resin obtained by curing a polyvinyl butyral resin and / or a polyvinyl acetal resin with an isocyanate curing agent;
The molar equivalent ratio (-NCO / -OH) of the isocyanate group of the isocyanate curing agent to the hydroxyl group of the polyvinyl butyral resin and / or polyvinyl acetal resin is in the range of 0.03 or more and 0.90 or less. It contains an isocyanate curing agent.

  In the resin sheet by this invention, it is preferable that the glass transition temperature of the said polyvinyl butyral resin and / or polyvinyl acetal resin is 65 degreeC or more and 95 degrees C or less.

  Moreover, in the resin sheet by this invention, it is preferable that the said resin layer contains a thermoplastic elastomer in the range of 1% or more and 5% or less by mass reference | standard.

Moreover, the manufacturing method of the protective layer formation body by another aspect of this invention is the following.
A method for producing a protective layer forming body in which a protective layer is provided on the surface of a medium,
Forming a protective layer on the surface of the medium;
A step of pressing the resin sheet on the surface of the protective layer so that the protective layer and the resin layer face each other;
Peeling the resin sheet from the protective layer;
Is included.

  In the production method according to the present invention, it is preferable that the pressure bonding is performed under heating at 170 ° C. or higher and 210 ° C. or lower.

  In the production method according to the present invention, the protective layer is preferably formed by thermally transferring the protective layer to the medium surface.

  In the production method according to the present invention, the protective layer is preferably made of an ionizing radiation curable resin and / or a thermosetting resin.

  Moreover, in this invention, the protective layer formation body obtained by the said manufacturing method is also provided.

  After the protective layer is transferred to the surface of the medium (transfer object), the resin sheet according to the present invention is pressure-bonded to the surface of the protective layer formed on the medium, and the resin sheet is peeled off from the protective layer. It is possible to remove only burrs (protective layer) on the peripheral edge of the medium and dust attached to the surface of the protective layer without affecting the protective layer formed on the top.

The cross-sectional schematic diagram by one Embodiment of the resin sheet of this invention. The schematic cross section by one Embodiment of the protective layer transfer sheet used for manufacture of a protective layer formation body. The schematic cross section by other embodiment of the protective layer transfer sheet used for manufacture of a protective layer formation body. The schematic diagram which showed a part of process of forming a protective layer and manufacturing a protective layer formation body. The surface view which showed the tailing which generate | occur | produces in the edge part of a protective layer formation body. The schematic diagram which showed a part of process of manufacturing a protective layer formation body using a resin sheet.

<Resin sheet>
Embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view of a resin sheet according to the present invention. As shown in FIG. 1, the resin sheet 1 according to the present invention includes at least a resin layer 10 and a base material 11 that supports the resin layer 10. The resin layer serves as a surface for pressure-bonding the resin sheet to the surface of a protective layer forming body, which will be described later.

  The resin layer is mainly composed of a curable resin obtained by curing a polyvinyl butyral resin and / or a polyvinyl acetal resin with an isocyanate curing agent, but does not exclude the inclusion of a resin other than the curable resin.

  The above-mentioned polyvinyl butyral resin and / or polyvinyl acetal resin preferably has a hydroxyl value of 9% by mass or more and 25% by mass or less. When the resin is cured with an isocyanate-based curing agent by using a resin having a hydroxyl value in the above range, the heat resistance is further improved, and the periphery of the protective layer is not affected without affecting the surface of the protective layer forming body. Only dust and the like adhering to the burrs and the protective layer surface can be removed more efficiently. Examples of such a polyvinyl acetal resin having a hydroxyl value include SLECK BX-L, BX-1, BX-5, KS-1, KS-3, KS-5, and KS-10 manufactured by Sekisui Chemical Co., Ltd. . Examples of such a polyvinyl butyral resin include ESREC BM-5, BH-3, BH-6, and BL-S. In the present specification, “hydroxyl value” means the ratio of the monomer component having a hydroxyl group in the resin polymer, and the ratio of the mass of the monomer component having a hydroxyl group to the mass of the entire resin polymer (mass). %).

  As the polyvinyl butyral resin and / or polyvinyl acetal resin constituting the resin layer, those having a weight average molecular weight of 30,000 or more and 500,000 or less can be preferably used, and a more preferable weight average molecular weight is 50,000 or more, 10 10,000 or less. In addition, a weight average molecular weight shows the value of standard polystyrene molecular weight conversion measured by GPC. Moreover, it is preferable that the glass transition temperature of polyvinyl butyral resin and / or polyvinyl acetal resin is the range of 65 degreeC or more and 95 degrees C or less. When the glass transition temperature of the polyvinyl butyral resin and / or polyvinyl acetal resin is less than 65 ° C., a part of the resin layer forms a protective layer when the resin sheet is peeled off after being thermocompression bonded to the surface of the protective layer forming body. It may remain on the surface of the body. On the other hand, when a polyvinyl butyral resin and / or polyvinyl acetal resin having a glass transition temperature exceeding 95 ° C. is used, the solubility of the resin in a solvent decreases or the viscosity increases when used as a coating liquid. The processability at the time of formation may be inferior.

  A polyisocyanate resin can be preferably used as the isocyanate curing agent for curing the resin by reacting with the hydroxyl groups of the polyvinyl butyral resin and / or polyvinyl acetal resin. Various polyisocyanate resins are conventionally known, and among them, it is desirable to use an adduct of aromatic isocyanate. As aromatic polyisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, Examples include p-phenylene diisocyanate, trans-cyclohexane, 1,4-diisocyanate, xylylene diisocyanate, triphenylmethane triisocyanate, and tris (isocyanatephenyl) thiophosphate, especially 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. Or, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is preferable.

  The isocyanate curing agent has a molar equivalent ratio (-NCO / -OH) of the isocyanate group of the isocyanate curing agent to the hydroxyl group of the polyvinyl butyral resin and / or polyvinyl acetal resin in the range of 0.03 or more and 0.90 or less. As such, it is blended in a polyvinyl butyral resin and / or a polyvinyl acetal resin. When the molar equivalent ratio of isocyanate groups is less than 0.03, the resulting resin sheet has an effect of removing burrs and dust on the surface of the protective layer forming body, but the heat resistance of the resin sheet is high. Therefore, when the resin sheet is peeled after being thermocompression bonded to the surface of the protective layer forming body, a part of the resin layer may remain on the surface of the protective layer forming body. On the other hand, when the molar equivalent ratio of isocyanate groups exceeds 0.90, the resin sheet is excellent in heat resistance, but the resin sheet has insufficient removability such as burrs and dust. A preferred molar equivalent ratio of isocyanate groups is 0.05 or more and 0.70 or less.

  The resin layer may contain other resins in addition to the resin obtained by curing the polyvinyl butyral resin and / or the polyvinyl acetal resin as long as the gist of the present invention is not hindered. For example, a resin having self-adhesiveness and removability can be included. A thermoplastic elastomer can be suitably used as such a resin. The inclusion of the thermoplastic elastomer in the resin layer further improves the removal of burrs (protective layer) at the peripheral edge of the protective layer and dust adhering to the surface of the protective layer.

  Examples of the thermoplastic elastomer include conventionally known styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, polyamide elastomers, 1,2-polybutadiene elastomers, vinyl chloride elastomers, and the like. These thermoplastic elastomers may be used alone or in combination of two or more. Among these, block copolymer (SBS) of styrene and butadiene, block copolymer (SIS) of styrene and isoprene, styrene-ethylene / butylene-styrene (SEBS) obtained by hydrogenating a part of SBS, and the like. It can be preferably used.

  The blending amount of the thermoplastic elastomer in the resin layer is preferably 1% or more and 5% or less on the mass basis with respect to the entire resin layer. If the content of the thermoplastic elastomer is too large, the adhesiveness when the resin sheet is thermocompression bonded to the surface of the protective layer forming body becomes too strong, and it may be formed in some cases when the resin sheet is subsequently peeled off. A part of the protective layer may be peeled off by the resin sheet.

For the resin layer, a coating solution obtained by dissolving the above resin in an appropriate solvent is applied to one surface of a base material described later, and the coating film is heated and dried to cure the polyvinyl butyral resin and / or the polyvinyl acetal resin. It can be formed by caulking. The coating method is not particularly limited, and a conventionally known method can be applied. Examples of the coating method include conventionally known coating methods such as a gravure coater, a roll coater, and a wire bar. The coating amount of the coating liquid at that time is preferably 0.2 g / m ² or more and 1.0 g / m ² or less, more preferably 0.3 g / m ² or more, 0 in terms of the coating amount at the time of drying. 0.7 g / m ² or less. In addition, the heating temperature of the drying conditions after coating is not particularly limited as long as the curing reaction of the polyvinyl butyral resin and / or the polyvinyl acetal resin and the isocyanate curing agent proceeds. It is preferable to dry at a temperature of 120 ° C. or lower.

  The resin layer is supported by a base material as shown in FIG. The substrate is not particularly limited as long as it can support the resin layer. For example, polyester such as polyethylene terephthalate, polyarylate, polycarbonate, polyurethane, polyimide, polyetherimide, cellulose derivative, polyethylene, ethylene / vinyl acetate Polymer, polypropylene, polystyrene, acrylic, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene / perfluoroalkyl vinyl ether, polyvinyl fluoride, Tetrafluoroethylene / ethylene, tetrafluoroethylene / hexafluoropropylene, polychlorotrifluoroethylene, polyvinylidene Various plastic films or sheets such as Ruoraido like. Moreover, you may use the composite film or sheet | seat which laminated | stacked 2 or more types of above-described resin. The thickness of the substrate may be appropriately changed depending on the material so that the strength and heat resistance are appropriate, but is usually 10 μm or more and 50 μm or less.

<Method for producing protective layer forming body>
The method for producing a protective layer forming body according to the present invention includes: i) a step of forming a protective layer on the surface of the medium; ii) the above-described resin sheet on the surface of the protective layer formed on the medium; And iii) a step of peeling the resin sheet from the protective layer as essential steps. Hereinafter, each step will be described.

(Protective layer forming step)
The protective layer formed on the surface of the medium is formed by thermally transferring the protective layer to the medium surface using a protective layer transfer sheet or the like. Examples of the medium include an ID card such as an ID card and an IC card such as a cash card such as a bank. However, the medium is not limited to this, and by providing a protective layer on the surface, the surface of the medium may be damaged. Any device may be used as long as generation is suppressed.

  As shown in FIG. 2, the protective layer transfer sheet 2 includes a support 20 and a protective transfer layer 22 provided on one surface of the support 20. The protective transfer layer 22 is on the support 10 side. The release layer 23 and the protective layer 24 are stacked in this order. In the protective layer transfer sheet 2, the protective layer transfer layer 22 is peeled off from the support 20 and transferred onto the surface of the medium by heating means such as a thermal head, a heat roller, or a hot stamp. By providing such a protective layer on the surface of the medium, it is possible to prevent character information, image information, and the like recorded on the medium from being worn or discolored by using the medium.

  As the protective layer transfer sheet, a conventionally known one can be used, and any conventionally known resin can be used as the protective transfer layer as long as the resin is excellent in durability and transparency. A thermosetting resin or a thermosetting resin can be preferably used. As will be described later, when removing the tail (burrs) and the like generated at the end of the protective layer forming body using the resin sheet according to the present invention, heat is applied from the substrate side of the resin sheet. By applying this heat, curing of the ionizing radiation curable resin or thermosetting resin of the protective layer further proceeds, so that the durability of the protective layer can be improved. Examples of the ionizing radiation curable resin include acrylic resins, and examples of the thermosetting resin include polyvinyl acetal resins and epoxy resins.

The protective layer is, for example, a protective layer coating solution obtained by dissolving or dispersing the above resin in a suitable solvent or dispersion, and the coating amount is 0.5 g / m ² or more on the surface of the support or release layer. It can form by apply | coating so that it may become about 15 g / m < ² > or less (dry basis), and making it dry. The thickness of the protective layer is preferably 1 μm or more and 15 μm or less, more preferably 0.3 μm or more and 30 μm or less.

  As the support for the protective layer transfer sheet, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and polymethylpentene, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene Polyfluorinated ethylene resin such as -4 fluoroethylene copolymer, polyamide resin such as nylon 6, nylon 6.6, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, Ethylene / vinyl alcohol copolymers, vinyl polymers such as polyvinyl alcohol and vinylon, cellulose resins such as cellulose triacetate and cellophane, methyl polymethacrylate, ethyl polymethacrylate, polyethyl acrylate, butyric acrylate Acrylic resin, etc., synthetic resin sheets such as polystyrene, polycarbonate, polyarylate, polyimide, etc., or paper such as fine paper, thin paper, glassine paper, sulfuric acid paper, single layer such as metal foil, or lamination of two or more layers The body is mentioned. The thickness of the support is preferably in the range of 5 μm to 100 μm, more preferably 10 μm to 50 μm.

  Further, a receiving layer 25 may be provided on the upper surface of the protective layer 24 of the protective layer transfer sheet 2 as shown in FIG. When such a receiving layer 25 is provided, before transferring the protective layer 24 to the medium, desired image information, character information, or the like is printed in advance on the receiving layer 25 using a thermal transfer sheet or the like. The protective layer 24 can be transferred to the medium together with the receiving layer 25 on which character information or the like is printed. The receiving layer 25 can be formed directly on the protective layer 24 or via a primer layer (not shown). The receiving layer has a different configuration of the receiving layer depending on the recording method of hot melt transfer recording and sublimation transfer recording. In addition, in thermal melt transfer recording, a colored transfer layer can be thermally transferred directly from a thermal transfer sheet or the like to a protective layer (thermal transfer layer) without providing a receiving layer. The receiving layer by the hot melt transfer recording method or the sublimation transfer recording method has a function of receiving the color material transferred from the heat transfer sheet by heating. In particular, in the case of a sublimation dye, it receives and develops a color. At the same time, it is desirable not to resublimate once received dye. In general, the receiving layer has transparency so that the image of the image receiving layer transferred to the surface of the medium can be clearly observed through the protective layer. However, it is also possible to characterize the retransfer image by artificially making the receiving layer turbid or lightly colored.

The receiving layer is generally composed mainly of a thermoplastic resin. Examples of the material for forming the receiving layer include polyolefin resins such as polypropylene, vinyl chloride / vinyl acetate copolymers, ethylene / vinyl acetate copolymers, halogenated polymers such as polyvinylidene chloride, polyvinyl acetate, and polyacrylic. Examples include polyester resins such as esters, polystyrene resins, polyamide resins, copolymers of olefins such as ethylene and propylene and other vinyl monomers, cellulose resins such as ionomers and cellulose diacetates, and polycarbonate resins. Particularly preferred among these are polyester resins, vinyl chloride / vinyl acetate copolymers, and mixtures thereof. Further, as conventionally known, a release agent such as silicone oil may be blended in the receiving layer. Receiving layer can be dissolved in a suitable organic solvent with additives such as release agents added as necessary, or dispersion dispersed in organic solvent or water can be used for gravure coating, gravure reverse coating, roll coating, etc. It is formed by coating on the protective layer and drying by a known forming means. In forming the receiving layer, the receiving layer may be of any thickness, but generally has a thickness such that the coating amount is 1 g / m ² or more and 10 g / m ² or less in a dry state.

  In order to form the protective layer 22 on the surface of the medium 30 using the protective layer transfer sheet 2 as described above, for example, as shown in FIG. For example, the heat roller 32 and the heat roller 32 are supported while being heated by a heating unit such as the heat roller 32 from the support 20 side of the protective layer transfer sheet 2. The protective layer transfer sheet 2 and the medium 30 are thermocompression bonded by the roller 33, and then the protective layer 22 is peeled from the support 20 of the protective layer transfer sheet 2. Thus, the protective layer forming body 40 in which the protective layer 22 is formed on the surface of the medium 30 can be obtained. By using an embossed one on the surface of the heat roller 32, a protective layer having an arbitrary shape (for example, a stripe shape) can be transferred to the medium surface. In addition to the method described above, the protective layer can be formed by a known transfer method using a protective layer transfer sheet. For example, hot stamping by hot stamping (heat stamping) or a thermal head (thermal printing head) The thermal transfer may be performed using a thermal printer or the like equipped with a).

  When the protective layer 22 is peeled from the support 20 of the protective layer transfer sheet 2 using the protective layer transfer sheet as described above, the surface of the protective layer 22 of the protective layer transfer sheet 2 contacts the surface of the medium 30. It is ideal that only the part that has been peeled off from the support 20 is actually called tailing as shown in FIG. 5 at the end of the protective layer forming body 40 on which the protective layer 22 is formed. Burr 24 may occur. In addition, dust or dust may adhere to the surface of the protective layer 22. In this invention, the burr | flash which generate | occur | produced in the protective layer formation body, the dust of the surface, dust, etc. can be effectively removed by implementing the process mentioned later using the above-mentioned resin sheet.

(Resin sheet crimping process)
After forming a protective layer on the surface of the medium, it is then subjected to a resin sheet pressing step. Dust and dust are attached to the surface of the medium (protective layer forming body 40) on which the protective layer 22 is formed, or burrs 24 are attached to the end portions as described above. The protective layer forming body 40 and the resin sheet 1 in such a state are arranged so that the protective layer 22 of the protective layer forming body 40 and the resin layer of the resin sheet 1 face each other, and the guide roller 41 and the like Thus, the two are arranged in a parallel state and can be pressed. Next, the resin sheet 1 and the protective layer forming body 40 are thermocompression bonded by the heat roller 42 and the support roller 43 while applying heat from the substrate side of the resin sheet 1 by a heating means such as the heat roller 42.

  The temperature at the time of thermocompression bonding the protective layer forming body 40 and the resin sheet 1 can be controlled by the temperature of the heat roller 42, and the surface temperature of the heat roller 42 is in the range of 170 ° C. or higher and 210 ° C. or lower. Is preferred. When the surface temperature of the heat roller 42 is too low, the burrs 24 at the end of the protective layer forming body 40 and the dust and dirt on the surface may not be completely removed. On the other hand, if the surface temperature is too high, a part of the resin layer of the resin sheet may adhere to the surface of the protective layer forming body or may cause thermal damage to the protective layer forming body. Moreover, the pressure in the thermocompression bonding can be controlled by the distance between the heat roller 42 and the support roller 43. For example, in the case of the protective layer forming body (IC card or the like) as described above, the heat roller 42 and the support roller A resin sheet is pressure-bonded to the protective layer forming body 40 so that the distance between the distances 43 is 0.2 mm or more and 0.7 mm or less. If the pressure bonding force is too low, the burr 24 at the end of the protective layer forming body 40 and the dust on the surface may not be completely removed. On the other hand, if the pressure bonding force is too high, the protective layer forming body is deformed. There is a case.

(Resin sheet peeling process)
After the resin sheet 1 is pressure-bonded to the surface of the protective layer forming body 40, the resin sheet 1 is peeled from the protective layer 22 of the protective layer forming body 40. The resin sheet 1 is peeled off from the protective layer 22 while the burrs 24 at the end of the protective layer forming body 40 and the dust and dirt on the surface adhere to the surface of the resin layer. As a result, only the burrs 24 at the end of the protective layer forming body 40 generated during the formation of the protective layer, dust and dirt on the surface, etc. are generated without affecting the surface of the protective layer forming body 40 (that is, the protective layer 22). Can be removed.

  It goes without saying that the above-described protective layer forming step or resin sheet peeling step may be carried out as a continuous series of steps.

  EXAMPLES Next, although an Example is given and this invention is demonstrated still in detail, this invention is not limited to these Examples. Unless otherwise specified, parts or% is based on mass.

<Production of resin sheet>
Example 1
Polyvinyl butyral resin (BM-5, glass transition temperature 67 ° C., hydroxyl value 22% by weight, manufactured by Sekisui Chemical Co., Ltd.) and isocyanate curing agent (Bernock D750, solid content 45%, isocyanate group equivalent 13% by weight, DIC Corporation) Are mixed so that the molar equivalent ratio (-NCO / -OH) of the isocyanate curing agent to the hydroxyl group of the polyvinyl butyral resin is 0.05, and the solvent (methyl ethyl ketone / toluene 1: 3 coating solvent) to prepare a coating solution 1.

On one surface of a base material made of a polyethylene terephthalate film (Lumirror, manufactured by Toray Industries, Inc.) having a thickness of 25 μm, the coating liquid obtained as described above has a thickness when dried of 0.5 g / m ^2. Thus, it apply | coated with the gravure printing machine, the resin was hardened by making it dry at 85 degreeC, the resin layer was formed, and the resin sheet was produced.

Example 2
A coating liquid 2 was prepared in the same manner as in Example 1 except that the blending ratio of the polyvinyl butyral resin and the isocyanate curing agent was changed so that the -NCO / -OH ratio was 0.30, and a resin sheet was produced. did.

Example 3
A coating liquid 3 was prepared in the same manner as in Example 1 except that the blending ratio of the polyvinyl butyral resin and the isocyanate curing agent was changed so that the —NCO / —OH ratio was 0.70, and a resin sheet was produced. did.

Example 4
A coating liquid 4 was prepared in the same manner as in Example 1 except that BX-1 (glass transition temperature 90 ° C., hydroxyl value 16% by weight, manufactured by Sekisui Chemical Co., Ltd.) was used as the polyvinyl butyral resin instead of BM-5. The resin sheet was prepared.

Example 5
A coating liquid 5 was prepared in the same manner as in Example 4 except that the blending ratio of the polyvinyl butyral resin and the isocyanate curing agent was changed so that the —NCO / —OH ratio was 0.30, and a resin sheet was produced. did.

Example 6
A coating liquid 6 was prepared in the same manner as in Example 4 except that the blending ratio of the polyvinyl butyral resin and the isocyanate curing agent was changed so that the —NCO / —OH ratio was 0.70, and a resin sheet was produced. did.

Example 7
SEBS (Tuftec M-1913, manufactured by Asahi Kasei Chemicals), which is a thermoplastic elastomer, is 1% by mass with respect to the entire solid content of the coating liquid (total amount of polyvinyl butyral resin, isocyanate curing agent and thermoplastic elastomer). A coating liquid 7 was prepared in the same manner as in Example 5 except that the resin sheet was added to prepare a resin sheet.

Example 8
SEBS (Tuftec M-1913, manufactured by Asahi Kasei Chemicals), which is a thermoplastic elastomer, was added so as to be 5% by mass with respect to the entire solid content of the coating liquid (total amount of polyvinyl butyral resin and isocyanate curing agent). A coating liquid 8 was prepared in the same manner as in Example 5 except that a resin sheet was produced.

Example 9
As a polyvinyl butyral resin, a coating liquid 9 was prepared in the same manner as in Example 2 except that BL-S (glass transition temperature 61 ° C., hydroxyl value 15% by weight, manufactured by Sekisui Chemical Co., Ltd.) was used instead of BM-5. The resin sheet was prepared.

Example 10
As a polyvinyl butyral resin, a coating liquid 10 was prepared in the same manner as in Example 2 except that KS-3 (glass transition temperature 110 ° C., hydroxyl value 12% by weight, manufactured by Sekisui Chemical Co., Ltd.) was used instead of BM-5. The resin sheet was prepared.

Example 11
A coating liquid 8 was prepared in the same manner as in Example 5 except that SEBS (Tuftec M-1913, manufactured by Asahi Kasei Chemicals), which is a thermoplastic elastomer, was added so that the solid content was 10% with respect to the total solid content of the coating liquid. The resin sheet was prepared.

Comparative Example 1
A coating liquid 12 was prepared in the same manner as in Example 1 except that the blending ratio of the polyvinyl butyral resin and the isocyanate curing agent was changed so that the —NCO / —OH ratio was 0.01, and a resin sheet was produced. did.

Comparative Example 2
A coating liquid 13 was prepared in the same manner as in Example 1 except that the blending ratio of the polyvinyl butyral resin and the isocyanate curing agent was changed so that the -NCO / -OH ratio was 1.00, and a resin sheet was produced. did.

Comparative Example 3
A resin sheet was produced in the same manner as in Example 1 except that the resin layer was not formed.

<Preparation of protective layer transfer sheet>
A polyethylene terephthalate film (Lumirror, manufactured by Toray Industries, Inc.) with a thickness of 25 μm is used as a support, and a release layer coating solution having the following composition is applied to one surface thereof by gravure coating to a thickness after drying of 1.5 μm. It was applied and dried to form a release layer.
<Composition of release layer coating solution>
Norbornene resin (Nippon Synthetic Rubber Co., Ltd., Arton G) 40 parts Acrylic polyol resin 10 parts (Trade name Thermolac SU-100A, manufactured by Soken Chemical Co., Ltd.)
Solvent (methyl ethyl ketone: toluene = 2: 8) 50 parts

  Next, on the release layer formed as described above, a coating liquid for forming a protective layer having the following composition is applied by gravure coating so that the thickness after drying becomes 6 μm, and dried to form a coating film. Formed.

<Coating liquid composition for protective layer formation>
50 parts of urethane oligomer (trade name NK Oligo U-6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.)
25 parts of polyfunctional oligomer (trade name NK ester UA-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.)
30 parts of methacrylic resin (trade name Parapet GF, manufactured by Kuraray Co., Ltd.)
5 parts of photopolymerization initiator (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
200 parts of methyl ethyl ketone

Using a UV exposure device (Fusion UV, F600V, LH10 lamp, H bulb, and reflector is a cold type) on the coating film formed as described above, the integrated exposure amount is 70 mJ under the condition of a peak illuminance of 150 mW / cm ^2. Irradiation with ultraviolet rays was performed so as to be / cm ² . The peak illuminance and the integrated exposure amount were measured using a microcure model MC-2 with a UV illuminance meter microcure data reader manufactured by Fusion UV Systems Japan.

On the protective layer formed as described above, an intermediate layer coating solution having the following composition is applied by gravure coating so that the thickness after drying becomes 2.0 μm, and then subjected to aging at 50 ° C. for 24 hours. Thus, an intermediate layer was formed.
<Composition liquid composition for intermediate layer formation>
100 parts of methacrylic acid (trade name Parapet GF, manufactured by Kuraray Co., Ltd.)
100 parts of methyl ethyl ketone

Subsequently, on the intermediate layer formed as described above, a coating liquid for forming an adhesive layer having the following composition was applied by gravure coating, dried to a thickness of 1.0 μm, dried and bonded. A protective layer transfer sheet having a layer structure of support / protective layer / intermediate layer / adhesive layer was obtained.
<Composition liquid composition for forming adhesive layer>
Vinyl chloride-vinyl acetate copolymer 20 parts Acrylic resin 10 parts Solvent (ethyl acetate: toluene = 2: 5) 70 parts

<Preparation of protective layer forming body>
The protective layer transfer sheet obtained as described above is laminated so that the adhesive layer faces one surface of the card substrate made of polyvinyl chloride, and is thermocompression bonded from the support side of the protective layer transfer sheet by a heat roller. Then, the protective layer was peeled from the support of the protective layer transfer sheet to form a protective layer on the entire surface of the card substrate. Tail (burrs) occurred in a part of the periphery of the obtained protective layer forming body.

<Evaluation of resin sheet>
The protective layer forming body and the resin sheet are overlapped so that the protective layer of the protective layer forming body and the resin layer of the resin sheet face each other. The resin sheet was peeled from the layer forming body.

  The durability of the protective layer of the subsequent protective layer forming body was evaluated by an abrasion resistance test according to JIS K 7204. The case where the wear of the protective layer reached the card base material after 1000 times was evaluated as Δ, and the case where the wear of the protective layer did not reach the card base material at 1000 times was evaluated as ○. As Comparative Example 4, the same test as described above was performed on the protective layer formed body before the resin sheet was pressure bonded.

  Moreover, the adhesiveness of the protective layer of the protective layer forming body was evaluated by a cross-cut peel test based on JIS K 5600. In the tape peeling test, the case where peeling was observed was indicated by Δ, and the case where peeling was not observed was indicated by ○. As Comparative Example 4, the same test as described above was performed on the protective layer formed body before the resin sheet was pressure bonded.

  Further, tailing (burrs) of the protective layer forming body that occurred during the formation of the protective layer and the presence or absence of dust or dirt attached to the surface of the protective layer forming body were visually confirmed. X indicates that burrs, dust, dust, etc. are attached, ◯ indicates that there are no burrs, but dust, dust, etc. are attached, and ◎ indicates that no burrs, dust, dust, etc. are attached. did. As Comparative Example 4, the same test as described above was performed on the protective layer formed body before the resin sheet was pressure bonded.

  Further, it was visually observed whether a part of the resin layer of the resin sheet remained on the surface of the protective layer forming body, and when there was a residue, the degree of adhesion to the surface of the protective layer forming body was also confirmed. . The resin layer remains mostly and cannot be easily peeled off from the surface of the protective layer forming body. ×, The resin layer remains but can be easily removed from the surface of the protective layer forming body. Δ, the case where no residual resin layer was observed was marked with ○.

  Further, it was visually confirmed whether a part of the surface of the protective layer forming body (protective layer) was not peeled off when the resin sheet was peeled off. The case where a part of the protective layer adhered to the resin sheet was evaluated as x, and the case where the protective layer did not adhere to the resin sheet at all was indicated as ◯.

  Moreover, the processability (resin solubility of the resin and the applicability of the coating solution) of the resin layer when producing the resin sheet was evaluated. Low solubility in solvent and time required for preparation of coating liquid, or high viscosity of coating liquid and application amount could not be constant x, time for preparation of coating liquid Those which were not required and had a uniform coating amount were marked with ◯.

  The evaluation results were as shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 Resin sheet 2 Protective layer transfer sheet 10 Resin layer 11 Base material 20 Support body 22 Protective transfer layer 23 Peeling layer 24 Protective layer 25 Receptive layer 30 Medium 40 Protective layer formation body

Claims (8)

A resin sheet that is used after being pressure-bonded to the surface of the protective layer of the protective layer forming body provided with a protective layer on the surface of the medium, and then peeled off from the protective layer,
A resin layer to be pressure-bonded to the protective layer of the medium, and at least a base material that supports the resin layer,
The resin layer comprises a curable resin obtained by curing a polyvinyl butyral resin and / or a polyvinyl acetal resin with an isocyanate curing agent;
The molar equivalent ratio (-NCO / -OH) of the isocyanate group of the isocyanate curing agent to the hydroxyl group of the polyvinyl butyral resin and / or polyvinyl acetal resin is in the range of 0.03 or more and 0.90 or less. A resin sheet comprising an isocyanate curing agent.   The resin sheet of Claim 1 whose glass transition temperature of the said polyvinyl butyral resin and / or polyvinyl acetal resin is 65 degreeC or more and 95 degrees C or less.   The resin sheet according to claim 1 or 2, wherein the resin layer contains a thermoplastic elastomer in a range of 1% to 5% on a mass basis. A method for producing a protective layer forming body in which a protective layer is provided on the surface of a medium,
Forming a protective layer on the surface of the medium;
The step of pressure-bonding the resin sheet according to any one of claims 1 to 3 so that the protective layer and the resin layer face each other on the surface of the protective layer,
Peeling the resin sheet from the protective layer;
Comprising a method.   The method according to claim 4, wherein the pressure bonding is performed under heating at 170 ° C. or more and 210 ° C. or less.   The method according to claim 4, wherein the protective layer is formed by thermally transferring the protective layer to a medium surface.   The method according to claim 4, wherein the protective layer is made of an ionizing radiation curable resin and / or a thermosetting resin.   The protective layer formation body obtained by the method as described in any one of Claims 4-7.

Images