JP2005280042A - Intermediate transfer recording medium made antistatic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intermediate transfer recording medium which is made antistatic, to which dust from surroundings hardly sticks and which is free from defects of appearance such as an omission in transfer (printing, transfer), a nick or a dent and excellent in the long-time durability even in the surroundings of high humidity or high temperature and humidity. <P>SOLUTION: A base film 2, a release layer 3, a relief forming layer 4, a reflecting layer 5, a primer layer 6 and a dye accepting layer 8 are stacked sequentially. The primer layer 6 contains a metal ion conducting agent and the metal ion is preferably a lithium ion. The metal ion conducting agent is one or a plurality selected from the group consisting of a lithium ion conductive resin, lithium perfluoroalkyl sulfonate and lithium bisperfluoroalkyl sulfonimide. The primer layer 6 contains further an isocyanate compound (cured matter). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an intermediate transfer recording medium, and more particularly to an intermediate transfer recording medium having excellent antistatic properties.

In the present specification, “ratio”, “part”, “%” and the like indicating the composition are based on mass unless otherwise specified, and the “/” mark indicates that they are integrally laminated.
“PET” is “polyethylene terephthalate”, “ionizing radiation curable (resin) resin” is an abbreviation for “uncured ionizing radiation curable resin and cured ionizing radiation curable resin”, functional expression, common name, Or an industry term. The resin before curing is referred to as an ionizing radiation curable resin, the resin after curing is referred to as an ionizing radiation curable resin, and both of these are referred to as an ionizing radiation curable resin.

(Background Art) An intermediate transfer recording medium is composed of a plurality of layers. In particular, in order to express a relief forming layer and the relief effect formed on the relief forming layer more highly, a high refractive index or A reflective layer such as a low refractive index metal or metal oxide is formed. If the reflective layer is an insulator, the charge amount is large, or if it is a metal, it becomes a capacitor state and the charge amount is also large.
A large amount of charge is generated when the image is printed on the dye-receiving layer of the intermediate transfer recording medium with a sublimation transfer ink ribbon, or when the intermediate transfer recording medium is used to transfer to an object to be transferred. Attracts or adheres to the film, and may cause defective appearance such as missing (printing, transferring), chipping, or dent. Furthermore, the thermal head of the transfer device is destroyed, or a ribbon-like intermediate transfer recording medium is stuck to the transfer target and cannot be transported, resulting in transfer failure. In addition, it is required to have excellent long-term durability even during storage, at the time of transfer, or after transfer to a transfer medium, even in a high temperature or high temperature and high humidity environment.
The intermediate transfer recording medium is required to have excellent antistatic properties and excellent long-term durability even in a high temperature or high temperature and humidity environment.

(Prior Art) Conventionally, an intermediate transfer recording medium has a release layer, a hologram formation layer, a reflective reflection layer, and an adhesive layer formed in sequence on a base film, and forms an image for sublimation transfer on the adhesive layer. One having an image receiving and primer layer having thermal adhesiveness to a transfer body is known (for example, see Patent Document 1). However, when transferring a light diffraction structure such as a hologram or diffraction grating onto a transfer object such as a credit card or a cash card, for example, the transfer sheet and the transfer object are overlapped and heat-pressed from the substrate film side of the transfer sheet. By doing so, it is possible to form a hologram and / or diffraction grating with metallic luster due to the reflective layer on the transfer object, but since antistatic is not prevented, dust adheres during storage and transfer work, and when transferring There is a problem that transfer (printing, transfer) omission, chipping, dent, etc. are likely to occur, and the appearance of images and holograms by sublimation transfer is impaired.
In addition, conventionally used antistatic agents, for example, quaternary ammonium salts have a poor compatibility depending on the type, or a phenomenon called “bleed” in a short period of time in a high temperature and high humidity environment. Occurs, the antistatic property is lowered, and the environmental reliability in the long term is lacking.
In addition, a resin having a relatively low molecular weight and a large antistatic property is blended to form a polymer alloy and fixed in a matrix resin to exhibit a semipermanent antistatic property (for example, Patent Documents). 2-6.) However, since polyether ether amide resin, which is a hydrophilic resin, and special resins such as polyethylene oxide are blended, there is a limit in compatibility with the resin, and it is necessary to use a compatibilizer in combination. However, since a very large amount of addition is required to exert the antistatic effect, there is a problem that the cost is high.

Japanese Patent Laid-Open No. 06-255268 Japanese Patent Application Laid-Open No. 60-23435 JP-A-61-73753 JP-A-2-194052 JP-A-3-26756 JP-A-2-233743

  Accordingly, the present invention has been made to solve such problems. Its purpose is to contain a metal ion conductive agent in the primer layer provided on the reflective layer surface, to prevent electrification and to prevent dust from adhering to the environment, transfer (printing, transfer) omission, chipping, dents, etc. It is an object of the present invention to provide an intermediate transfer recording medium which has no appearance defect and is excellent in long-term durability even in a humid or hot and humid environment.

To solve the above problem,
The intermediate transfer recording medium according to the invention of claim 1 includes a base film, and at least a release layer, a relief forming layer, a reflective layer, a prelaminator layer, and a dye receiving layer are sequentially laminated on one surface of the base film. In this intermediate transfer recording medium, the primer layer contains a metal ion conductive agent.
The intermediate transfer recording medium according to the invention of claim 2 is such that the metal ion of the metal ion conductive agent is lithium ion.
In the intermediate transfer recording medium according to the invention of claim 3, the metal ion conductive agent is one or more selected from lithium ion conductive resin, lithium perfluoroalkyl sulfonate or lithium bisperfluoroalkyl sulfonimide. As you can see.
The intermediate transfer recording medium according to the invention of claim 4 is such that the primer layer further contains an isocyanate cured product.
The intermediate transfer recording medium according to the invention of claim 5 is such that the surface resistance value of the primer layer is in the range of 1 × 10 ⁹ to 1 × 10 ¹³ Ω / □.
The intermediate transfer recording medium according to the invention of claim 6 is such that the relief of the relief forming layer is a relief hologram and / or a diffraction grating.
The intermediate transfer recording medium according to the invention of claim 7 is such that a heat-resistant slipping layer is provided on the surface opposite to the release layer of the base film.

According to the first to third aspects of the present invention, by including a metal ion conductive agent in the primer layer, the antistatic property is excellent, dust and the like are hardly attached at the time of transfer, and are not easily affected by the transfer environment. There is no appearance defect such as omission, chipping, unevenness, dent, etc., and even if it is placed in a hot and humid environment for a long time, the antistatic agent is hard to bleed on its surface, so even in harsh environments There is provided an intermediate transfer recording medium that is less susceptible to gloss unevenness on the transfer surface and has high environmental reliability and excellent long-term durability.
According to the present invention of claim 4, since the peeling is light and has a stable peeling force, an intermediate transfer recording medium capable of obtaining a stable transfer property without unevenness or chipping is provided.
According to the present invention of claim 5, an intermediate transfer recording medium having excellent antistatic properties is provided.
According to the sixth aspect of the present invention, since the relief of the relief forming layer is composed of a hologram or a diffraction grating, the intermediate transfer recording has a design property due to a unique brightness and is excellent in security due to its manufacturing difficulty. A medium is provided.
According to the seventh aspect of the present invention, there is provided an intermediate transfer recording medium which is not easily affected by heat and stress during transfer, can be transferred at high speed, and can be stably transferred.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view showing an embodiment of the intermediate transfer recording medium of the present invention.

(Invention of Product) As shown in FIG. 1, the intermediate transfer recording medium 7 of the present invention has a release layer 3, a relief forming layer 4, a reflective layer 5, a primer layer 6, and a dye receiving layer 8 on a base film 2. Are sequentially stacked. That is, “heat resistant slipping layer (if necessary) 9 / base film 2 / release layer 3 / relief forming layer 4 / reflective layer 5 / primer layer 6 / dye receiving layer 8”.
The dye-receiving layer 8 is a layer that can receive a sublimation dye, and another known thermal transfer ink ribbon is superposed on the layer, and the dye-receiving layer 8 is heated in accordance with image information, and the dye-receiving layer 8 is thermally transferred with the dye. Is formed. The surface of the dye receiving layer 8 on which this image is formed and the transfer target are combined, and heat pressure is applied to the transfer target to release layer 3 / relief forming layer 4 / reflective layer 5 / primer layer 6 / dye receiving layer 8. An image and a relief can be formed on a transfer material by transferring a transfer layer comprising

Hereinafter, each layer constituting the intermediate transfer recording medium of the present invention will be described in detail.
(Base Film) The base film 2 can be the same base film as that used in conventional intermediate transfer recording media as it is, and is not particularly limited. Specific examples of preferred substrate films include thin paper such as glassine paper, condenser paper or paraffin paper, or heat resistance such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ketone or polyether sulfone. And stretched or unstretched films of plastics such as polyester, polypropylene, polycarbonate, cellulose acetate, polyethylene derivatives, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polymethylpentene, or ionomer. Moreover, the composite film which laminated | stacked 2 or more types of these materials can also be used. Although the thickness of a base film can be suitably selected according to material so that the intensity | strength, heat resistance, etc. may become appropriate, the thing about 1-100 micrometers is normally used normally.

  (Peeling layer) The peeling layer 3 provided on the base film 2 of the present invention is formed from the base film 2 to the dye receiving layer 8 or the like when transferring the dye receiving layer 8 or the like of the intermediate transfer recording medium to the transfer target. The transfer portion is easy to peel off, and further has a protective layer function as the outermost surface layer of the transfer portion transferred to the transfer target. As the release layer 3, cellulose derivatives such as ethyl cellulose, nitrocellulose, and cellulose acetate, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and polybutyl acrylate, polyvinyl chloride, and vinyl chloride-acetic acid are generally used. It can be formed using a thermoplastic resin such as a vinyl copolymer or polyvinyl butyral, or a thermosetting resin such as an unsaturated polyester resin, a polyurethane resin, or an aminoalkyd resin.

  Preferable release layer 3 is formed of a heat-resistant transparent resin having at least a norbornene structure, and preferably, a resin that is incompatible with the heat-resistant transparent resin is 5 to 30 with respect to the total solid content of the entire release layer. It is preferable to mix them at a ratio of%, and when an incompatible resin is added to the norbornene-based resin, a large number of dispersed particles or microdomains are formed in the release layer, improving the peelability during hologram transfer. As a result, unevenness in transfer is eliminated and the sharpness of the transfer edge portion is improved.

  The release layer is composed of the heat-resistant transparent resin having the norbornene structure described above, the resin incompatible with the heat-resistant transparent resin having the norbornene structure, a solvent, and other resins, waxes, surfactants, and the like as necessary. A coating liquid containing an additive is prepared, and can be formed by coating and drying by a known means such as a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. Its thickness is about 0.1 to 2 μm in a dry state.

〔式中、Ａ、Ｂ、ＣおよびＤは水素原子、炭素数１〜１０の炭化水素基、ハロゲン原子、ハロゲン原子で置換された炭素数１〜１０の炭化水素基、−（ＣＨ₂）ｎＣＯＯＲ₁、−（ＣＨ₂）ｎＯＣＯＲ₁、−（ＣＨ₂）ｎＯＲ₁、−（ＣＨ₂）ｎＣＮ、−（ＣＨ₂）ｎＣＯＮＲ₃Ｒ₂、−（ＣＨ₂）ｎＣＯＯＺ、−（ＣＨ₂）ｎＯＣＯＺ、−（ＣＨ₂）ｎＯＺ、−（ＣＨ₂）ｎＷ、またはＢとＣから構成された−ＯＣ−Ｏ−ＣＯ−、−ＯＣ−ＮＲ₄−ＣＯ−、もしくは（多）環状アルキレン基を示す。ここでＲ₁、Ｒ₂、Ｒ₃およびＲ₄は、炭素数１〜２０の炭化水素基、Ｚはハロゲン原子で置換された炭化水素基、ＷはＳｉＲ₅ｐＦ₃−ｐ（Ｒ₅は炭素数１〜１０の炭化水素基、Ｆはハロゲン原子、−ＯＣＯＲ₆または−ＯＲ₆（Ｒ₆は炭素数１〜１０の炭化水素基）、ｐは０〜３の整数を示す）、ｎは０〜１０の整数を示す〕 As the heat-resistant transparent resin having a norbornene structure contained in the release layer, a compound having a structural unit represented by the following general formula (1) is preferably used.

[Wherein, A, B, C and D are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, — (CH ₂ ) nCOOR ₁ , — (CH ₂ ) nOCOR ₁ , — (CH ₂ ) nOR ₁ , — (CH ₂ ) nCN, — (CH ₂ ) nCONR ₃ R ₂ , — (CH ₂ ) nCOOZ, — (CH ₂ ) nOCOZ, — _{(CH 2) nOZ, - (} CH 2) nW or B is composed of a C a -OC-O-CO, -, - shows the OC-NR ₄ -CO-, or (poly) cyclic alkylene group. Here, R ₁ , R ₂ , R ₃ and R ₄ are hydrocarbon groups having 1 to 20 carbon atoms, Z is a hydrocarbon group substituted with a halogen atom, W is SiR ₅ pF ₃ -p (R ₅ is carbon A hydrocarbon group having 1 to 10 carbon atoms, F is a halogen atom, -OCOR ₆ or -OR ₆ (R ₆ is a hydrocarbon group having 1 to 10 carbon atoms), p is an integer of 0 to 3, and n is 0 Represents an integer of -10)

The resin having a polynorbornene skeleton as described above is an amorphous polyolefin resin due to the structure of the resin, and preferably has a mass number average molecular weight in the range of 50,000 to 300,000. Examples thereof include ARTON G, ARTON F, and ARTON I manufactured by KK.
Further, a resin having a norbornene skeleton and a resin incompatible with the norbornene skeleton resin can be added and mixed.

(Incompatible resin) The resin incompatible with the resin having the norbornene skeleton is not particularly limited as long as it is an incompatible compound that does not completely dissolve in the norbornene addition type polymer. The incompatibility is determined according to a conventional method in the resin industry. For example, a composition obtained by melting and mixing 5 parts by mass of a compound with respect to 100 parts by mass of a norbornene-based resin is magnified 100,000 times with an electron microscope, and a domain or particle of 1 mm ² or more in a range of 10 cm × 15 cm. Those possessing at least one can be defined as incompatible.

  (Incompatible Compound) As the incompatible compound, other resins than the norbornene-based addition polymer are usually used. Examples of other resins that are incompatible with the norbornene resin include polyethers or polythioethers such as polyphenylene sulfide and polyphenylene ether; aromatic polyesters, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyether ketone, and the like. Polyester polymers of the chain; chain polyolefin polymers such as polyethylene, polypropylene, poly-4-methyl-pentene-1; general-purpose products such as polymethyl methacrylate, cyclohexyl methacrylate and methyl methacrylate copolymer, polyacrylonitrile styrene (AS resin) Transparent resin; acrylic resin; MS resin; liquid crystal plastic.

  When an incompatible compound is added to a transparent resin having a norbornene structure, in many cases, a large number of dispersed microdomains or particles are formed in a coating film formed by applying the compound. When forming microdomains, the average particle size [(major axis + minor axis) / 2] of the domain observed with an electron microscope is usually 5-30 μm, preferably 10-20 μm. Transparency and transferability at the time of thermally transferring a hologram or the like to a transfer target using a transfer sheet are preferable.

And it is preferable that the peeling layer in this invention contains 5-30% of resin incompatible with the heat-resistant transparent resin which consists of norbornene structures with respect to the total solid of a peeling layer. When the content ratio of the heat-resistant transparent resin having a norbornene structure and the incompatible resin is in the above range, the heat resistance and transparency of the release layer and the transferability at the time of thermal transfer to the transfer target of the hologram are well balanced. Can demonstrate.
The addition of a resin that is incompatible with the amorphous polyolefin, which is a heat-resistant transparent resin having a norbornene structure, is to improve the foil breakability at the time of peeling, and is incompatible with the total solid content of the peeling layer. If the resin content is less than 5%, the foil will not break. On the other hand, if the content exceeds 30%, the coating suitability will deteriorate due to incompatibility, and the base film film will be deformed by heat. The crack of the reflective layer that follows this occurs. Therefore, the incompatible resin is preferably contained at a ratio of about 5 to 20% with respect to the total solid content of the release layer.

(Additive to release layer) The release layer is composed of the heat-resistant transparent resin having the norbornene structure described above, the resin or compound incompatible with the heat-resistant transparent resin having the norbornene structure, and if necessary, waxes or surfactants. And the like. In addition, it is preferable to add an ionizing radiation curable resin or an isocyanate compound to the release layer, and a narrower and more stable release force can be obtained within the range of the release force. It is particularly preferable to add an isocyanate compound and include the cured product. The isocyanate compound is cured to form an isocyanate cured product, both of which are referred to as an isocyanate compound (cured) product. However, the isocyanate cured product is obtained by curing the isocyanate compound and mainly the other composition, but the whole or a part thereof may be a cured product.
For 100 parts by mass of the release layer composition (a heat-resistant transparent resin having a norbornene structure, or a resin or a compound incompatible with a heat-resistant transparent resin having a norbornene structure and containing no additives), further ionization It is preferable to add 1 to 10 parts by mass of the radiation curable resin, or 1 to 20 parts by mass of the isocyanate compound with respect to the main composition of the release layer (so-called out%).

(Ionizing radiation curable resin) As an ionizing radiation curable resin to be added to the release layer composition, an ionizing radiation curable resin described later can be applied, and when the relief forming layer is shaped and cured. Those that are simultaneously cured to become an ionizing radiation curable resin can be applied. The ionizing radiation curable resin is an uncured ionizing radiation curable resin at the time of application and becomes a cured ionizing radiation curable resin after relief molding. write.
The addition amount of the ionizing radiation curable resin is 1 to 10 parts by mass. If the amount is less than this range, there are few particles or microdomains dispersed in the release layer, and the release force is small. It tends to drop off, crack, transfer edge sharpness, and transfer unevenness. If this range is exceeded, there are too many particles or microdomains dispersed in the release layer, the release property during transfer is poor, and transfer irregularities and transfer abnormalities are likely to occur.

  (Isocyanate compound (cured) product) As the isocyanate compound to be added to the release layer composition, those conventionally used for polyurethane production can be used. Such polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), aliphatic polyisocyanates having 2 to 18 carbon atoms, and alicyclic rings having 4 to 15 carbon atoms. Formula polyisocyanate, aromatic aliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, Oxazolidone group-containing modified products and the like) and mixtures of two or more thereof.

  Aromatic polyisocyanates include, for example, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / Or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4 '-Diisocyanatodiphenylmethane, crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight) of a trifunctional or higher polyamine] Of the mixture]: polyallyl polyisocyanate (PA I)], 1,5-naphthylene diisocyanate, 4,4 ', 4 "- triphenylmethane triisocyanate, etc. m- and p- isocyanatophenyl sulfonyl isocyanate.

  Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc. Examples include aliphatic polyisocyanates.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanate). Natoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

Examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Examples of modified polyisocyanates include polyisocyanates such as modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI. Modified products and mixtures of two or more thereof [for example, combined use of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)] are included.
The polyol used for the production of the urethane-modified polyisocyanate [free isocyanate-containing prepolymer obtained by reacting excess polyisocyanate (TDI, MDI, etc.) and polyol] is a polyol having an equivalent weight of 30 to 200, such as ethylene glycol, Examples include glycols such as propylene glycol, diethylene glycol and dipropylene glycol; triols such as trimethylolpropane and glycerine; high functional polyols such as pentaerythritol and sorbitol; and adducts thereof with alkylene oxide (ethylene oxide and / or propylene oxide). . Of these, preferred are those having 2 to 3 functional groups.

  The free isocyanate group content of the modified polyisocyanate and prepolymer is usually 8 to 33%, preferably 10 to 30%, particularly preferably 12 to 29%. Of these, preferred are diisocyanates and crude MDI, and particularly preferred are MDI, HDI, IPDI, and HDI.

  The addition amount of the isocyanate compound is 1 to 20 parts by mass, and if it is less than this range, there are few particles or microdomains dispersed in the release layer, the release force is small, and the transfer part falls off or cracks during storage. The edge of the transfer edge is likely to be sharp and uneven. If this range is exceeded, there are too many particles or microdomains dispersed in the release layer, the release property during transfer is poor, and transfer irregularities and transfer abnormalities are likely to occur.

  When an ionizing radiation curable resin or particularly preferably an isocyanate compound (cured) is added to the release layer, the release force at the time of transfer is 0.1 to 0.2 N / 25.4 mm width. An intermediate transfer recording medium that can be easily obtained and can reduce the difference between the maximum value and the minimum value of the peeling force with a peeling force within this range, and can be used for extremely stable transfer operations. can get.

  (Relief Forming Layer) The relief forming layer 4 in the intermediate transfer recording medium of the present invention is a layer in which fine irregularities such as a diffraction grating and a hologram are formed on one surface of a synthetic resin layer. As a typical example of a light diffraction structure, a hologram can be used with a planar hologram. Specific examples include a relief hologram, a full-nel hologram, a Fraunhofer hologram, a lensless Fourier transform hologram, a laser reproduction hologram (image hologram, etc.), white Examples include an optical reproduction hologram (rainbow hologram or the like), a color hologram, a computer hologram, a hologram display, a multiplex hologram, a holographic stereogram, a holographic diffraction grating, and the like.

  (Ionizing radiation curable resin) An ionizing radiation curable resin composition (also referred to as a precursor) that is cured with ionizing radiation constituting the relief forming layer is a photopolymerization initiator and / or photopolymerization in the case of UV curing. In the case of electron beam curing having a high energy by adding an accelerator, it may not be added, and if an appropriate catalyst is present, it can be cured by thermal energy. The thickness of the relief forming layer is preferably in the range of 0.1 to 6 μm, and more preferably in the range of 0.1 to 4 μm.

When hardening after application | coating of an ionizing radiation curable resin composition is performed by ultraviolet irradiation, a photoinitiator and a photoinitiator are added. As photopolymerization initiators, acetophenones, benzophenones, benzoins, thioxanthones, aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metathelone compounds, benzoin sulfonic acid esters, etc., are used alone or as a mixture. Depending on the photosensitizer, for example, n-butylamine, triethylamine, tri-n-butylphosphine and the like are added. More specifically, benzoin methyl ether, Michler benzoyl benzoate, α-amyloxime ester, tetramethyl meuram monosulfide, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] ] Propanone}, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2,2-dimethoxy-1,2-diphenylethanone, benzyl Dimethyl ketal, methylbenzophenone derivative, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzyl, 1- [4- (2-hydroxy Ethoxy) -phenyl] -2-hydroxy-2-methyl There is a 1-propane-1-one. These photopolymerization initiators are available from Ciba Specialty Chemicals Co., Ltd. under trade names such as [Irgacure 184], [Irgacure 907], [Irgacure 2959].
In the case of a resin system having a cationic polymerizable functional group, as a photopolymerization initiator,
In addition, by using a plurality of photopolymerization initiators and photosensitizers, the range of curing responsiveness to the UV wavelength of the curable composition can be expanded, and the range of viscosity adjustment of the curable composition can be expanded. . The addition amount of a photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of curable resin compositions.

  The ionizing radiation curable resin is obtained by curing a curable resin composition (also referred to as a precursor) with ionizing radiation, and the curable resin composition has at least one that reacts by polymerization (also referred to as curing) with ionizing radiation. A curable component having a functional group may be contained. As the curable component, a compound having a radical polymerizable unsaturated double bond can be applied, and examples thereof include a monofunctional monomer, a bifunctional or higher polyfunctional monomer, a functional oligomer, and a functional polymer. The functional group that is polymerized (also called cured) by ionizing radiation is an acryloyl group, a methacryloyl group, an allyl group, or an epoxy group.

  Examples of monofunctional monomers include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, -2-ethylhexyl acrylate, isobutyl acrylate, methyl methacrylate, 2-hexyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxy. Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, nonylphenol EO adduct acrylate (DNPA), phenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate (HPPA), 3-ethyl-3-hydroxymethyloxetane, (Meth) acrylates such as the above, or alkyl or aryl esters thereof, styrene, methylstyrene, styrene acrylonitrile and the like can be applied.

  Moreover, in this specification, (meth) acrylic acid means acrylic acid or methacrylic acid. (Meth) acrylate means acrylate or methacrylate, and the same notation applies to this.

  Examples of the bifunctional monomer include 1,6-hexanediol acrylate (HDDA), ethylene glycol diacrylate, diethylene glycol diacrylate (DEGDA), neopentyl glycol diacrylate (NPGDA), tripropylene glycol diacrylate (TPGDA), and polyethylene. Glycol 400 diacrylate (PEG400DA), hydroxypivalate ester neopentyl glycol diacrylate (HPNDA), bisphenol AEO modified diacrylate, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, etc. are applicable .

  As a polyfunctional monomer, a bifunctional or higher (meth) acryloyl monomer obtained by reacting a bifunctional or higher compound such as ethylene glycol, glycerin, pentaerythritol, or an epoxy resin with (meth) acrylic acid or a derivative thereof, etc. For example, trimethylolpropane acrylate (TMPTA), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate (PEHA), dipentaerythritol pentaacrylate, trimethylolpropane EO modified triacrylate, Examples thereof include dimethylolpropane tetraacrylate.

  The functional oligomer (also referred to as prepolymer) has a molecular weight (weight average) of about 300 to 5000, and a radical polymerizable double chain such as (meth) acryloyl group, methacryloyl group, allyl group, or epoxy group in the molecule. Polyurethanes having a bond, polyesters, polyethers, polycarbonates, poly (meth) acrylic acid esters can be applied. For example, unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, polyesters ( (Meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, urethane (meth) acrylate, isocyanurate (meth) acrylate, polyester-urethane (meth) acrylate, epoxy (meth) acrylate, etc. (Meth) acrylates include, cationic polymerizable epoxy compounds.

  The functional polymer has a molecular weight (weight average) of about 1000 to 300,000, and has urethane (meth) acrylate, isocyanurate (having radical polymerizable double bonds such as acryloyl group, methacryloyl group, allyl group, or epoxy group) (Meth) acrylate, polyester-urethane (meth) acrylate, and epoxy (meth) acrylate can be applied.

  The curable monomer and / or oligomer and / or polymer described above may be contained in the curable resin composition. These curable components are, for example, 5% by weight or more, preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on the amount excluding components that do not affect the function of the curable resin composition. By containing, ionizing radiation curability is imparted.

  Further, the curable resin composition may contain at least one monomer, or may further contain a monomer called a reactive diluent. The monomer is a monofunctional reactive diluent having a (meth) acryloyl group, a methacryloyl group, an allyl group, or an epoxy group. Here, the reactive diluent is different from a general organic solvent such as toluene. That is, in this specification, a solvent excludes a reactive diluent, and a non-solvent (no solvent) described later does not contain a solvent such as a general organic solvent such as toluene. Means. Usually, the curable resin composition has a high viscosity and cannot be applied unless the viscosity is reduced with an organic solvent. However, when the monomer is contained in the curable resin, the viscosity of the curable resin composition is lowered, and it is not necessary to use a solvent, and it can be used in a non-solvent (no solvent). The oligomer also has the same effect.

  Furthermore, monomers and oligomers can increase the speed of the polymerization reaction, and oligomers and polymers can adjust the crosslinking density and cohesion after curing. For this reason, it is preferable to use a monomer and / or an oligomer and / or a polymer for the curable resin composition. Furthermore, they are preferably used in combination, and the blending ratio is appropriately changed to obtain the performance of the cured resin according to the use and purpose. Furthermore, you may add additives, such as a polymerization inhibitor and anti-aging agent, to a curable resin composition as needed. In the curable resin composition, if necessary, a plasticizer, a lubricant, a colorant such as a dye or a pigment, a filler such as an extender pigment or a resin for increasing weight or preventing blocking, a surfactant, an antifoaming agent, Additives such as leveling agents and thixotropic agents may be added as appropriate.

  (Relief) The relief can be formed on the relief forming layer made of the above-described resin by a conventionally known method using the above-mentioned materials. For example, when recording a diffraction grating or hologram interference fringes as a relief with surface irregularities, an original plate on which diffraction gratings or interference fringes are recorded in an irregular shape is used as a press mold, and the original plate is overlaid on the resin layer. Then, by suitably heat-pressing both of them by a suitable means such as a heating roll, the concave / convex pattern of the original plate is shaped and can be duplicated.

  When the relief forming layer is an ionizing radiation curable resin during or after forming the concavo-convex pattern, the relief is fixed as an ionizing radiation curable resin by irradiating with ionizing radiation, and heat or external force is applied. It will not easily return. The ionizing radiation may be classified according to the quantum energy of the electromagnetic wave, but in this specification, all ultraviolet rays (UV-A, UV-B, UV-C), visible rays, gamma rays, X-rays, electrons It is defined as including a line. Therefore, as ionizing radiation, electron beam (EB), gamma ray, X-ray, ultraviolet ray (UV), or visible light can be applied, but EB or UV (also referred to as active energy rays in combination) is preferable, UV is more preferable in terms of handling and cost.

  As an EB irradiation device, an electron beam accelerator is used to generate an electron beam. For example, a cockroft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, or a linear type, a dynamitron type, a high frequency type Using various electron beam accelerators, etc., the electron beam is irradiated by the ecultron curtain method, beam scanning method, etc. An apparatus “Electro Curtain” (trade name) that can irradiate a uniform electron beam in the form of a curtain from a linear filament is preferable. The electron beam is irradiated with electrons having an energy of 100 to 1000 keV, preferably 100 to 300 keV, with an irradiation amount of about 0.5 to 20 Mrad.

As a UV irradiation apparatus (also referred to as a UV lamp) used for UV curing, a chemical reaction chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a visible light halogen lamp, or the like is used. The UV irradiation amount is preferably such that the integrated energy at a wavelength of 200 to 600 nm is 0.01 to 10 J / cm 2. The UV irradiation atmosphere may be air or an inert gas atmosphere such as nitrogen or argon.
The wavelength of the ultraviolet light is about 200 to 400 nm, and the wavelength may be selected according to the adhesive composition. The irradiation amount may be irradiated according to the material and amount of the composition, the output of the UV lamp, and the processing speed.

  (Reflection layer) As the reflection layer 5 of the intermediate transfer recording medium, a transparent material having a refractive index difference from that of the hologram layer can be used. The reflective layer can be formed by a known method such as sublimation, vacuum deposition, sputtering, reactive sputtering, ion plating, chemical vapor deposition (CVD), or electroplating.

As the reflective layer forming the transparent type hologram, any material can be used as long as it is light transmissive so as to exhibit the hologram effect. For example, a transparent material having a refractive index different from that of the resin of the relief forming layer can be used. The refractive index in this case may be larger or smaller than the refractive index of the resin of the relief forming layer, but the difference in refractive index is preferably 0.1 or more, more preferably 0.5 or more, and 1.0 The above is optimal. In addition to the above, there is a metallic reflective film of 20 nm or less. Examples of the transparent type reflective layer that can be suitably used include titanium oxide (TiO ₂ ), zinc sulfide (ZnS), and Cu—Al composite metal oxide.
When a transparent type reflective layer is used as the reflective layer 5, an image printed on the dye receiving layer 8 described later can be observed through the hologram, and security can be improved.

  (Primer layer) The primer layer 6 has an antistatic property that the intermediate transfer recording medium 7 is difficult to be charged and can be easily diffused even once charged to reduce the charge amount. In order to develop the antistatic property, the primer layer 6 contains a metal ion conductive agent. As the metal ion conductive agent, the metal ion of the metal ion conductive agent is preferably lithium, and more preferably, the lithium ion conductive agent is a lithium ion conductive resin, lithium perfluoroalkyl sulfonate, or lithium bis One or more selected from perfluoroalkylsulfonimides.

(Antistatic property) Relief forming layer and reflecting layer made of a metal or metal oxide having a high refractive index or a low refractive index on the relief forming surface in order to enhance the effect of the relief formed on the relief forming layer. Is deposited. If the reflective layer is an insulator, the charge amount is large, or if it is a metal, it becomes a capacitor state and the charge amount is also large.
However, by using the primer layer 6 having antistatic properties, the amount of charge can be reduced, and when an image is printed with a sublimation transfer ink ribbon onto the dye receiving layer of the intermediate transfer recording medium of the present invention, or the intermediate transfer recording Even when transferring to a transfer medium using a medium, environmental dust is not attracted or adhered, so that appearance defects such as transfer (printing, transfer) omission, chipping, and dent are unlikely to occur. Further, there is no transfer failure such as destruction of the thermal head of the transfer device or the transfer of the ribbon-like intermediate transfer recording medium to the transfer target.
In addition, it has excellent long-term durability during storage, transfer, or after transfer to the transfer target, even in high-temperature or high-temperature and high-humidity environments. Or the sticking of the ribbon is less likely to cause a defect that causes a conveyance failure.

  (Primer layer material) Examples of the material of the primer layer 6 include polyurethane resin, polyester resin, polyamide resin, epoxy resin, phenol resin, polyvinyl chloride resin, polyvinyl acetate resin, Vinyl chloride-vinyl acetate copolymer, acid-modified polyolefin resin, copolymer of ethylene and vinyl acetate or acrylic acid, (meth) acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, polybutadiene resin, rubber A compound having oxygen or nitrogen, or a compound having a reactive isocyanate compound, such as an acrylic resin, a urethane resin, an amide resin, an epoxy resin, an ionomer resin, or a rubber-based resin. It is known as a conventional adhesive.

(Additive to primer layer) Mainly one or more of the above-mentioned resins or monomers, oligomers or prepolymers thereof, and if necessary, for example, various stabilizers, fillers, reaction initiators In addition, one or a plurality of additives such as a curing agent or a crosslinking agent may be arbitrarily added, or a main component and a curing agent may be combined to use either one-component curable type or two-component curable type. Can do.
A preferable curing agent is an isocyanate compound, and the cured product is included in the primer layer 6. However, the isocyanate cured product is obtained by curing the isocyanate compound and mainly the other composition, but the whole or a part thereof may be a cured product.
As the isocyanate compound, the isocyanate compound used in the release layer 3 can be applied. Thus, by adding an isocyanate compound (cured) product, the antistatic property is excellent and the long-term durability is excellent even in a high temperature or high temperature and high humidity environment.
The addition amount of the isocyanate compound (cured) is 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on the main composition of the primer layer 6 (main component not containing additives) (so-called , Out as%).

  (Metal ion conductive agent) As the metal ion conductive agent to be contained in the primer layer 6, the metal ion of the metal ion conductive agent is preferably lithium, more preferably the lithium ion conductive agent is a lithium ion conductive resin. Or one or more selected from lithium perfluoroalkylsulfonate or lithium bisperfluoroalkylsulfonimide.

The metal ion conductive agent takes lithium ions (Li ⁺ ) into a coordination field such as crown ether formed by ether oxygen or urethane nitrogen of the resin constituting the matrix with the main component of the primer layer 6 and dissociates. The ionic species are easily moved by molecular vibration of ether oxygen or urethane nitrogen, and when an electric field is applied from the outside, they move toward the corresponding pole (ion movement) and exhibit ionic conductivity. I guess that.

Further, preferable lithium perfluoroalkyl sulfonate, lithium bisperfluoroalkyl sulfonimide, preferred examples of lithium perfluoroalkyl sulfonate include lithium trifluoromethyl sulfonate, lithium pentafluoroethyl sulfonate, and the like. Preferred examples of the lithium bisperfluoroalkylsulfonimide include lithium bistrifluoromethanesulfonimide and lithium bispentafluoroethanesulfonimide. Among these, a cured product prepared from a resin composition containing lithium bistrifluoromethanesulfonimide or lithium bispentafluoroethanesulfonimide is preferably applied because it is particularly excellent in environmental reliability. However, it is excellent in environmental reliability that the lithium ion conductive agent is lithium in a coordination field such as crown ether formed by ether oxygen or urethane nitrogen of the resin constituting the matrix with the main component of the primer layer 6. This is probably because ions (Li ⁺ ) are taken in.

  By including these lithium ion conductive agents in the resin composition, the resulting cured product is imparted with conductivity to improve antistatic properties, and is compatible with the resin composition and the resulting cured product. Long-term environmental reliability can be provided. In particular, regarding environmental reliability, a cured product prepared from a resin composition containing a lithium ion conductive agent is placed in a hot and humid environment, and even after a long period of time, a lithium ion conductive agent is present on the surface of the cured product. It is difficult to bleed. Therefore, haze (cloudiness) hardly occurs in the cured product, and desired transparency can be maintained over a long period of time, so that environmental reliability can be improved.

  The content of the lithium ion conductive agent is determined according to the required properties, but is usually preferably 0.1 to 10 parts by mass, particularly preferably 100 parts by mass of the primer layer composition. Is in the range of 0.5 to 5 parts by mass.

  The upper limit of the content of the lithium ion conductive agent is determined from the viewpoint of generation of bleeding of the lithium ion conductive agent on the surface of the cured product. That is, since the lithium ion conductive agent is a conductive material, the surface resistance value of the cured product that is obtained decreases as the content increases, and the antistatic property is improved. This is because the lithium ion conductive agent bleeds and the luster or the like changes, which may reduce environmental reliability. For example, the upper limit of the lithium ion conductive agent is, for example, lithium bistrifluoromethanesulfone so that the difference between the gloss after leaving in an environment of temperature 60 ° C. and humidity 95% and the gloss before leaving is 15% or less. In the case of containing imide, about 1.0 part by mass can be contained as an upper limit value with respect to 100 parts by mass of the resin composition.

On the other hand, the lower limit value of the content of the lithium ion conductive agent may be an amount that can ensure the required surface resistance value, taking into consideration the type of the resin composition and the prepolymer / monomer content contained therein. It is determined. For example, since an intermediate transfer recording medium requires a surface resistance value of about 1 × 10 ¹⁴ Ω / □ or less, for example, when lithium bistrifluoromethanesulfonimide is contained, 100 parts by mass of an ionizing radiation curable resin composition About 0.5 parts by mass can be contained as a lower limit value.

  These resins are appropriately dissolved or dispersed in a solvent, and sufficiently kneaded as necessary to prepare a coating agent composition (ink, coating solution), which is applied by a known coating method and dried. Alternatively, the primer layer 6 is obtained by drying, or aging (curing) treatment after drying, or reacting (curing) with ionizing radiation. The primer layer 6 has a thickness of about 0.05 to 50 μm, preferably 0.1 to 10 μm.

  (Heat resistant slipping layer) In the intermediate transfer recording medium 7 of the present invention, if necessary, a hologram portion is provided on the back surface of the base film, that is, the surface opposite to the surface on which the release layer, the relief forming layer, and the reflective layer are provided. In order to prevent adverse effects such as sticking and wrinkles due to heat from a thermal head or a heat roll as a means for transferring to a transfer target, a heat resistant slipping layer 9 can be provided. The resin for forming the heat resistant slipping layer may be any conventionally known resin, such as polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polyether resin, polybutadiene resin, Styrene-butadiene copolymer, acrylic polyol, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, urethane or epoxy prepolymer, nitrocellulose resin, cellulose nitrate resin, cellulose acetopropionate resin, cellulose acetate butyrate Resin, cellulose acetate hydrodiene phthalate resin, cellulose acetate resin, aromatic polyamide resin, polyimide resin, polycarbonate resin, chlorinated polyolefin Fin resins, and chlorinated polyolefin resins.

  The slipperiness imparting agent added to or overcoated with the heat resistant slipping layer made of these resins includes phosphate ester, silicone oil, graphite powder, silicone graft polymer, fluorine graft polymer, acrylic silicone graft polymer, acrylic siloxane, aryl Examples thereof include silicone polymers such as siloxane, but a layer made of a polyol, for example, a polyalcohol polymer compound, a polyisocyanate compound, and a phosphate ester compound, and a filler is more preferably added. The heat resistant slipping layer is prepared by dissolving or dispersing the above-described resin, slipperiness imparting agent, and filler with an appropriate solvent to prepare a heat resistant slipping layer forming ink. It can apply | coat to the back surface of a material film film with formation means, such as the reverse coating method using a gravure printing method, a screen printing method, and a gravure plate, and can dry and form.

  (Dye Receiving Layer) The dye receiving layer 8 is provided as a part of the transfer portion constituting the intermediate transfer recording medium 7 so as to be positioned on the outermost surface of the transfer sheet. On this receiving layer, an image is formed by thermal transfer from a thermal transfer sheet having a color material layer by thermal transfer. Then, the transfer portion of the intermediate transfer recording medium 7 on which the image is formed is transferred to the transfer target, and as a result, a printed matter is formed. For this reason, as a material for forming the receiving layer, a conventionally known resin material that can easily receive a heat transferable color material such as a sublimation dye or a heat-meltable ink can be used. For example, polyolefin resin such as polypropylene, halogenated resin such as polyvinyl chloride or polyvinylidene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer or polyacrylate Vinyl resins, polyester resins such as polyethylene terephthalate or polybutylene terephthalate, polystyrene resins, polyamide resins, copolymers of olefins such as ethylene or propylene and other vinyl polymers, cellulose resins such as ionomers or cellulose diastases Polycarbonate, etc., and vinyl chloride resin, acrylic-styrene resin or polyester resin is particularly preferable.

  When the dye-receiving layer is transferred to the transfer target, it is preferable to form the dye-receiving layer using a resin material having adhesiveness by heating, such as vinyl chloride-vinyl acetate copolymer. In the case of having a layer, the adhesiveness of the dye receiving layer itself is not necessarily required. For the dye-receiving layer, one or more materials selected from the above-mentioned materials and various additives as necessary are added and dissolved or dispersed in an appropriate solvent such as water or an organic solvent. A coating solution can be prepared, and this can be formed by applying and drying by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. Its thickness is about 1 to 10 μm in a dry state.

  The above-described embodiment is an exemplification, and has any configuration that has substantially the same configuration as the technical scope described in the claims of the present invention and that exhibits the same operational effects. Are also included in the technical scope of the present invention.

  (Manufacturing method) The manufacturing method of the intermediate transfer recording medium of the present invention includes (a) a step of forming a release layer on one surface of the substrate film, and (b) forming a relief forming layer on the surface of the release layer. A step, (c) a step of shaping a relief on the surface of the relief forming layer, (d) a step of irradiating and curing ionizing radiation during or after the shaping, and (e) the cured relief A step of forming a reflective layer on the surface of the forming layer, (f) a step of forming a primer layer on the surface of the reflective layer, and (g) a step of forming a dye-receiving layer on the surface of the primer layer. In the step of forming on the surface of the release layer, it is preferable to use a solvent that does not dissolve the material of the release layer as the solvent of the relief forming layer coating composition used when forming by the coating method.

  In the method for producing a transfer sheet of the present invention, the steps (a), (c), (d), (e), (f), and (g) are omitted because they have been described in the material description, and (b) ionizing radiation is applied to the release layer surface. The step of forming a relief forming layer made of a curable resin will be described.

  When forming the relief forming layer on the surface of the release layer, the relief forming layer composition is dispersed or dissolved in a solvent, applied as a coating liquid (ink), and dried. As soon as the coating liquid (ink) is applied, the composition of the relief forming layer and the solvent come into contact with the release layer. At this time, when the solvent of the relief forming layer uses a solvent (for example, toluene) that dissolves the release layer, the solvent (for example, toluene) causes the very thin release layer to swell or partly disperse or dissolve. This is not clear, but it seems to have molecular gaps. A part of the relief forming layer made of an ionizing radiation curable resin enters the release layer into the gap, and is compatible or eroded. After the relief is formed, when the ionizing radiation curable relief forming layer is cured with ionizing radiation, a reaction occurs at the interface between the base film film and the release layer, and the release force varies.

  (Solvent) In order to solve this problem, it has been found that the peeling fluctuation can be suppressed by using a solvent that does not swell, disperse or dissolve the material of the release layer as the solvent of the coating solution when forming the relief forming layer. The solvent that does not swell, disperse or dissolve does not have to swell, disperse or dissolve between application and drying, and includes those that swell, disperse or dissolve somewhat depending on heating and time. Even those that slightly swell, disperse or dissolve usually have a short function from application to drying, and can often function.

  By doing in this way, the peeling force at the time of transfer can secure a width of 0.1 to 0.2 N / 25.4 mm, has a stable peeling performance, and is stable even at the time of producing a transfer sheet. And an intermediate transfer recording medium having high lot-to-lot stability. If the peeling force is less than this range, it is easy to crack even if the transfer sheet can be removed or transferred before the transfer sheet is stored or transferred during transfer. If this range is exceeded, burrs or chipping may occur during transfer, or transfer may become impossible.

(Modification) The present invention includes the following modifications.
(1) As a relief structure, you may comprise uneven | corrugated patterns, such as a wrinkle pattern, a satin, a hairline, a moth eye, etc., and an uneven | corrugated pattern which expresses antireflection.
(2) The relief forming layer may be configured not to be formed with a concavo-convex pattern such as a hologram or a diffraction grating. There is no relief structure, and for example, the same function can be obtained as a protective layer.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this.

A PET film having a thickness of 25 μm (manufactured by Toray Industries, Inc., Lumirror) is used as a base material, and a release layer, a relief forming layer, a reflective layer, a primer layer, and a dye receiving layer are sequentially formed on one surface under the following conditions. Thus, an intermediate transfer recording medium of Example 1 was obtained.
The release layer was formed by applying and drying with a coating liquid having the following composition by gravure coating so as to have a thickness of 1.0 μm when dried.
(Release layer coating solution)
・ Norbornene resin (Nippon Synthetic Rubber Co., Ltd., Arton G) 80 parts ・ Acrylic polyol resin 20 parts ・ Polyethylene WAX 5 parts ・ UV curing agent 5 parts ・ Solvent (methyl ethyl ketone: toluene = 1: 1) 100 parts Nickel on which a hologram pattern is formed by forming a relief forming layer on a formed release layer by applying a gravure coating with a coating liquid having the following composition to a thickness of 2.0 μm when dried and forming a relief layer. The pressed plate and the relief forming layer were combined and heated and pressed to form irregularities on the relief forming layer, and the relief forming layer was cured by UV exposure to form a relief hologram.
(Relief forming layer coating solution)
・ Acrylic resin 60 parts ・ Urethane acrylate oligomer 40 parts ・ Silicone 0.5 part ・ Photopolymerization initiator 5 parts ・ Solvent (isopropyl alcohol: methyl ethyl ketone = 1: 1) 100 parts Also, on the relief forming layer formed above A reflective layer having a thickness of 500 mm was formed by sputtering TiO ₂ .
On the reflective layer, a primer layer composition having the following composition was applied by gravure coating to a thickness of 1.0 μm when dried, dried, and then aged at 45 ° C. for 24 hours. A layer was formed.
(Primer layer composition working solution)
・ Polyester resin 3.3 parts ・ Vinyl chloride-vinyl acetate copolymer 2.7 parts ・ Isocyanate compound (The Inktec, XEL curing agent) 1 part ・ Lithium ion conductive resin (Sanko Chemical Industries, PEO) -20T) 0.03 parts · Toluene 5 parts · Methyl ethyl ketone 5 parts On the primer layer, by applying a gravure coating with a coating liquid of the following composition, dried to a thickness of 2 µm and dried to receive the dye A layer was formed.
(Receptive layer solution)
・ Vinyl chloride-vinyl acetate copolymer (The Inktec Co., Ltd., HND # 8) 15 parts ・ Epoxy-modified silicone oil (Shin-Etsu Chemical Co., Ltd., KP-1800U) 0.225 parts ・ Toluene 3 parts ・ Methyl ethyl ketone 3 Part

An intermediate transfer recording medium was obtained in the same manner as in Example 1 except that the following primer layer composition working solution was used.
(Primer layer composition working solution)
・ Polyester resin 3.3 parts ・ Vinyl chloride-vinyl acetate copolymer 2.7 parts ・ Isocyanate curing agent (The Inktec Co., Ltd., XEL curing agent) 1 part ・ Lithium ion conductive resin (Sanko Chemical Industry Co., Ltd.) , PEO-20T) 0.12 parts · Toluene 5 parts · Methyl ethyl ketone 5 parts

An intermediate transfer recording medium was obtained in the same manner as in Example 1 except that the following primer layer composition working solution was used.
(Primer layer composition working solution)
・ Polyester resin 3.3 parts ・ Vinyl chloride-vinyl acetate copolymer 2.7 parts ・ Isocyanate curing agent (The Inktec Co., Ltd., XEL curing agent) 1 part ・ Lithium ion conductive resin (Sanko Chemical Industry Co., Ltd.) , PEO-20T) 0.24 parts · Toluene 5 parts · Methyl ethyl ketone 5 parts

An intermediate transfer recording medium was obtained in the same manner as in Example 1 except that the following primer layer composition working solution was used.
(Primer layer composition working solution)
-Polyester resin 3.3 parts-Vinyl chloride-vinyl acetate copolymer 2.7 parts-Lithium ion conductive resin (manufactured by Sanko Chemical Co., Ltd., PEO-20T) 0.12 parts-Toluene 5 parts-Methyl ethyl ketone 5 parts

An intermediate transfer recording medium was obtained in the same manner as in Example 1 except that the following primer layer composition working solution was used.
(Primer layer composition working solution)
・ Polyester resin 3.3 parts ・ Vinyl chloride-vinyl acetate copolymer 2.7 parts ・ Isocyanate curing agent (The Inktec Co., Ltd., XEL curing agent) 1 part ・ Lithium bistrifluoromethanesulfonimide (Sumitomo 3M Co., Ltd.) Trade name; Florard TM HQ-115) 0.03 parts, toluene 5 parts, methyl ethyl ketone 5 parts

An intermediate transfer recording medium was obtained in the same manner as in Example 1 except that the following primer layer composition working solution was used.
(Primer layer composition working solution)
・ Polyester resin 3.3 parts ・ Vinyl chloride-vinyl acetate copolymer 2.7 parts ・ Isocyanate curing agent (XEL curing agent manufactured by The Inktec Co., Ltd.) 1 part ・ Lithium bispentafluoroethanesulfonimide (Sumitomo 3M ( Co., Ltd.
Product name: Florard TM L-13858 (BETI) 0.06 parts · Toluene 5 parts · Methyl ethyl ketone 5 parts

An intermediate transfer recording medium was obtained in the same manner as in Example 1 except that the following primer layer composition working solution was used.
(Primer layer composition working solution)
・ Polyester resin 3.3 parts ・ Vinyl chloride-vinyl acetate copolymer 2.7 parts ・ Isocyanate curing agent (XEL curing agent manufactured by The Inktec Co., Ltd.) 1 part ・ Lithium trifluoromethylsulfonate (Sumitomo 3M Co., Ltd.) )
Product name: Florard TM FC-122) 0.06 parts, toluene 5 parts, methyl ethyl ketone 5 parts

(Comparative Example 1) An intermediate transfer recording medium was obtained in the same manner as in Example 1 except that the primer layer composition was prepared as follows.
(Primer layer composition working solution)
・ Polyester resin 3.3 parts ・ Vinyl chloride-vinyl acetate copolymer 2.7 parts ・ Isocyanate curing agent (XEL curing agent manufactured by The Inktec Co., Ltd.) 1 part ・ Toluene 5 parts ・ Methyl ethyl ketone 5 parts

(Comparative Example 2) An intermediate transfer recording medium was obtained in the same manner as in Example 1 except that the primer layer composition was prepared as follows.
(Primer layer composition working solution)
・ Polyester resin 3.3 parts ・ Vinyl chloride-vinyl acetate copolymer 2.7 parts ・ [C1 ₄ H ₂₉ N (CH ₃ ) ₂ CHC ₆ H ₅ ] ⁺ Cl ⁻ (quaternary ammonium salt) 0.12 parts・ Isocyanate curing agent (The Inktec Co., Ltd., XEL curing agent) 1 part ・ Toluene 5 parts ・ Methyl ethyl ketone 5 parts

(Evaluation method) The evaluation was performed on the surface electrical resistance value (before and after the environmental test), transferability, transportability, and surface quality of the transfer surface.
The surface electrical resistance value was measured using a Hiresta IP machine (trade name, manufactured by Mitsubishi Chemical Corporation) under the conditions of a temperature of 24 ° C. and a relative humidity of 40% RH at an applied voltage of 500 V and a measurement time of 10 seconds. Was measured.
In addition, the surface electrical resistance value was measured immediately after being left for 48 hours under the condition of a temperature of 60 ° C. and a relative humidity of 95% RH (hereinafter referred to as after an environmental test) to evaluate durability under high temperature and high humidity. Went.

The transportability is determined based on the intermediate transfer recording media of the above examples and comparative examples and the standard thermal transfer sheet for the VDS card printer CX210 (yellow, magenta, cyan dye layers, hot-melt black transfer layer on the substrate, In the VDS card printer CX210, the intermediate transfer recording medium conveyance path and the thermal transfer sheet conveyance path are overlapped and contacted with each other (from the position of the thermal head). Whether the intermediate transfer recording medium and the thermal transfer sheet are stuck to each other at the previous supply side position). Conveyance is that the intermediate transfer recording medium and the thermal transfer sheet are not stuck, and the one that was able to be transported satisfactorily is accepted as “○”, and sticking occurs, causing jamming (clogging), Those with a conveyance trouble were rejected and indicated by "x".
As for transferability, in the VDS card printer CX210, the intermediate transfer recording media of Examples and Comparative Examples and the vinyl chloride card as the transfer target were superposed to transfer, and the hologram was transferred to the vinyl chloride card. However, the surface temperature of the heating mold is 175 ° C., and the pressing time is 2 sec / inch. Moreover, the card | curd made from a vinyl chloride consists of the material composition shown below.
<Material composition of vinyl chloride card>
-100 parts of polyvinyl chloride compound (degree of polymerization 800) (contains about 10% of additives such as stabilizers)
-White pigment (titanium oxide) 10 parts-Plasticizer (DOP) 0.5 part The transferability of the transfer layer surface transferred to the vinyl chloride card was observed with the naked eye. Transferability is acceptable when there is no transfer unevenness (burr or chipping), and is marked with “○”. Although there is slight transfer unevenness, it is acceptable when there is no practical problem, and “△” is marked. Some were rejected and indicated by "x".
As for the surface quality of the transfer surface, the surface quality of the transfer layer surface transferred to the vinyl chloride card was observed with the naked eye. Conformations and distortions that may be caused by dust, deformation and distortion of the design such as holograms, and blemishes and distortions of the print are few. Passed and indicated by “x”.
The results are shown in “Tables 1 and 2”.

(Evaluation results)
In Examples 1 to 3 and 5 to 6, the surface electrical resistance values after the initial and environmental tests were both 1 × 10 ⁹ to 1 × 10 ¹⁴ Ω / □, and the surface quality and transferability were acceptable.
In Example 4, the transferability was Δ because the lithium ion conductive resin in the primer layer was slightly bleed on the surface.
In Comparative Example 1, the surface electrical resistance value was high and the transportability was also unacceptable.
The surface electrical resistance value of Comparative Example 2 was good initially, but deteriorated after the environmental test, and the transportability and transferability were also rejected due to bleeding of the antistatic agent.

  The antistatic intermediate transfer recording medium of the present invention uses a sublimation transfer type ink ribbon in advance to transfer a dye diffraction structure such as a hologram or a diffraction grating onto a transfer object such as a credit card. An arbitrary image is printed on the layer and transferred to the transfer target along with the relief such as the print and hologram, and even under the transfer or storage environment, dust is less likely to adhere and transfer of excellent surface quality The body is obtained. It can be used not only for credit cards and cash cards, but also for certificates, publications such as magazines and books, and packaging such as food and daily necessities.

1 is a cross-sectional view showing an embodiment of an intermediate transfer recording medium of the present invention.

Explanation of symbols

2: base film 3: release layer 4: relief forming layer 5: reflective layer 6: primer layer 7: intermediate transfer recording medium 8: dye receiving layer

Claims (7)

In an intermediate transfer recording medium in which a base film and at least a release layer, a relief forming layer, a reflective layer, a primer layer, and a dye receiving layer are sequentially laminated on one surface of the base film, the primer layer is a metal ion An intermediate transfer recording medium comprising a conductive agent. 2. The intermediate transfer recording medium according to claim 1, wherein the metal ions of the metal ion conductive agent are lithium ions. The metal ion conductive agent is one or more selected from lithium ion conductive resin, lithium perfluoroalkyl sulfonate, or lithium bisperfluoroalkyl sulfonimide. The intermediate transfer recording medium described in 1. The intermediate transfer recording medium according to claim 1, wherein the primer layer further contains an isocyanate cured product. 5. The intermediate transfer recording medium according to claim 1, wherein the primer layer has a surface resistance value in a range of 1 × 10 ⁹ to 1 × 10 ¹⁴ Ω / □. 6. The intermediate transfer recording medium according to claim 1, wherein a relief of the relief forming layer is a relief hologram and / or a diffraction grating. The intermediate transfer recording medium according to claim 1, wherein a heat-resistant slipping layer is provided on the surface opposite to the release layer of the base film.

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