JP2006044131A - Core base sheet, information recording medium using the same and manufacturing method of information recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a core base sheet which can be so processed as to attain a high image quality even under the atmospheric pressure and adheres firmly to an image recording body on the occasion of lamination therewith, and an information recording medium using the same and a manufacturing method of the information recording medium. <P>SOLUTION: The core base sheet has a core base and an adhesion layer provided on at least one side of the core base, and the adhesion layer contains at least a crystalline polyester resin having a melting point of 125°C or below and particulates having a volume average particle diameter of 5-35 μm. The information recording medium using the same and the manufacturing method of the information recording medium are also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a core substrate sheet for easily producing an information recording medium using an image recording body printed by electrophotography or the like, an information recording medium using the same, and a method for producing the information recording medium, In more detail, non-contact or contact-type personal information image information storage media such as cash card with face photo, employee ID card, student ID card, individual membership card, residence card, various driver's licenses, various qualification certificates, The present invention relates to a core base sheet that can be used for an RFID tag, an image sheet for personal verification used in a medical field, an image display board, a display label, and the like, an information recording medium using the same, and a method for manufacturing the information recording medium.

  In recent years, along with the development of image forming technology, means for forming images of the same quality in large quantities and at low cost by various printing methods such as intaglio printing, relief printing, planographic printing, gravure printing, and screen printing are known. Yes. Such a printing method is used to manufacture an information recording medium that can store predetermined information such as an IC card, a magnetic card, an optical card, or a combination of these, and can communicate with or without contact with an external device. Are often used.

  However, for example, the screen printing requires a large number of printing plates corresponding to the number of images to be printed, and in the case of color printing, printing plates corresponding to the number of colors are further required. Therefore, these printing methods are unsuitable for individually responding to individual identification information (face photo, name, address, date of birth, various licenses, etc.).

  The most mainstream image forming means for the above problems is an image forming method using a printer or the like employing a sublimation type or melting type thermal transfer system using an ink ribbon or the like. However, these can easily print personal identification information, but still have the problem that the resolution decreases when the printing speed is increased and the printing speed decreases when the resolution is increased.

  In contrast, in electrophotographic image formation (printing), the surface of the image carrier is uniformly charged, exposed in accordance with an image signal, and an electrostatic latent image due to a potential difference between an exposed portion and a non-exposed portion is generated. Then, a color powder (image forming material) called toner having a polarity opposite to (or the same as) the charge is electrostatically developed to form a visible image (toner image) on the surface of the image carrier. Done in the way. In the case of a color image, this process is repeated a plurality of times, or a plurality of image forming devices are arranged in parallel to form a visible color image, and these are transferred and fixed (fixed: mainly by heat) to the image recording medium. This is performed by a method of obtaining a color image by melting and solidifying the color powder by cooling.

  As described above, in the electrophotographic method, the electrostatic latent image on the surface of the image carrier is electrically formed by the image signal, so that not only the same image can be formed many times, but also different images can be easily handled. Image formation is possible. Further, the toner image on the surface of the image carrier can be transferred almost completely to the surface of the image recording body, and the toner image slightly remaining on the surface of the image carrier can be easily removed with a resin blade or a brush. Therefore, it is possible to easily produce printed materials for multi-product small-volume production.

  The toner is usually formed by melt-mixing a heat-meltable resin, a pigment, and optionally an additive such as a charge control agent, and pulverizing and finely pulverizing the kneaded product. Further, the electrostatic latent image in the electrophotographic method has a considerably higher resolution than the finely divided toner, and a sufficient resolution is expected even when compared with the resolution of the screen printing or thermal transfer method of the ink ribbon. it can.

  For color images, the four primary colors of cyan, magenta, yellow, and black are used as color toners, and these can be mixed to theoretically reproduce the same color as in printing. In the above color toner, since the toner resin and the pigment can be blended relatively freely, it is easy to increase the image concealment by the toner.

  Almost no consideration has been given to the heat resistance and light resistance of information recording media that are intended for outdoor use. However, if a driver's license is placed in a place exposed to direct sunlight in a vehicle, As a result, a thermal transfer type image using a dye is faded. However, in color images formed by electrophotography, pigments with excellent light resistance corresponding to each color of cyan, magenta, yellow, and black are used in the color toner. It is considered that the light resistance of the obtained image is sufficiently excellent. Similarly, if a heat-resistant toner is selected, it is considered that the heat resistance of an image formed on the information recording medium can be used outdoors.

  On the other hand, the base material (core) of various cards currently used most frequently is a vinyl chloride sheet because of its excellent printing characteristics and excellent embossing suitability (texture unevenness processing). This is because. However, the vinyl chloride sheet has a problem that dioxin is generated when the card to be disposed of due to expiration or the like is discarded using a heating furnace or the like. Various sheet films have begun to be used for the purpose.

  When it is assumed that the embossing is not performed when the card is manufactured, a conventional biaxially stretched PET (polyethylene terephthalate) film or the like can be used. However, embossing is often indispensable in order to continue the functions of conventional cards, and at present, ABS resin films and polyolefin resin films that soften at a relatively low temperature, and at least ethylene glycol, terephthalic acid, and 1,4 -A modified PET resin film called PET-G copolymerized with cyclohexanedimethanol, an integrally formed film of a modified PET resin film and a PET film, an amorphous PET resin film, or a polycarbonate resin film has come to be used. .

Examples of printing various cards using the electrophotographic apparatus described above include the following.
For example, in addition to various personal information, an invisible barcode is printed on a 250 μm-thick vinyl chloride sheet or a 280 μm-thick polyester sheet by electrophotography, overlaid on the printed surface, and laminated with a hot press. There is a method (for example, refer to Patent Document 1).

  However, in the above sheet, the inter-sheet friction coefficient is too large and the sheets are closely adhered to each other, so that the sheet transportability is poor, the electrophotographic apparatus stops, or the insulator (sheet) having a thickness of 250 μm or more as described above. In some cases, the image forming material (toner) cannot be sufficiently transferred and image defects increase. In addition, when an image is formed by using the resin film that softens at a relatively low temperature in an electrophotographic apparatus, the fixing process is higher in temperature than the softening temperature of the film in the fixing process, so that the adhesiveness appears and the film is wound around the fixing apparatus. There is a problem that jam occurs. Further, if the image forming material is offset to the fixing device or the fixing of the 250 μm thick sheet is continued, the fixing device may be damaged more than necessary at the edge (corner) of the sheet.

Further, there is a method in which personal identification information is printed on a light-transmitting sheet and the above printing is performed as a mirror image (for example, see Patent Document 2). However, in Patent Document 2, it is preferable that at least a part of the light-transmitting laminate sheet is a biaxially stretched polyester film, or a film made of ABS or polyester / biaxially stretched polyester film. It is only described as good.
Even if the image can be printed on the light-transmitting sheet, when laminating, air tends to remain between the sheets, resulting in bubbles and deteriorating the image quality.

  Therefore, in this specification, since the film is merely an insulator, the image quality is deteriorated due to poor transfer of the image forming material to the film surface or residual bubbles, and it is impossible to obtain the same resolution as the thermal transfer method. In this device, which focuses on improving productivity, the laminate sheet used is in the form of a roll, so it can be used for emergency or multi-product production such as different printing for one to several cards. Therefore, there is a problem that a lot of loss and waste occur.

  On the other hand, it has been reported that a urethane-polyester resin is used for a card sheet (see, for example, Patent Document 3). This technology uses a thermal crosslinking agent as a receiving layer (image receiving layer) for sublimation transfer printing. As a result, there is a problem that the pot life of the coating liquid for surface treatment is short, and the receiving layer is tacked. Force may be generated, resulting in a problem of conveyance failure in the sublimation transfer printer. In addition, if the surface is roughened to reduce the friction coefficient in order to improve the transportability, there is a problem that the image quality print quality deteriorates.

JP 2001-92255 A JP-A-11-334265 JP 2001-205945 A

The object of the present invention is to solve the above-mentioned problems of the prior art.
That is, the present invention provides a core substrate sheet that can be processed with high image quality even under atmospheric pressure and that adheres firmly when laminated with an image recording body, an information recording medium using the same, and a method for manufacturing the information recording medium For the purpose.

That is, the present invention
<1> A core base sheet having a core base and an adhesive layer provided on at least one side of the core base, wherein the adhesive layer has a crystalline polyester resin having a melting point of 125 ° C. or lower. And a core substrate sheet containing fine particles having a volume average particle diameter of 5 μm to 35 μm.

  <2> The core substrate sheet according to <1>, wherein the core substrate is transparent or opaque.

  <3> The core substrate sheet according to <1>, wherein at least one surface of the core substrate includes a polyester resin obtained by copolymerizing at least ethylene glycol, terephthalic acid, and a 1,4-cyclohexanedimethanol component.

  <4> An information chip capable of reading information by using at least one means selected from an electric means, a magnetic means, and an optical means is disposed inside or on the surface of the core substrate. It is a core base material sheet as described in <1>.

  <5> The core chip sheet according to <4>, wherein the information chip is an IC chip.

  <6> A core base material sheet having a core base material and an adhesive layer provided on at least one surface of the core base material, and image information bonded to the core base material via the adhesive layer is formed. An information recording medium comprising: an image recording medium, wherein the adhesive layer includes at least a crystalline polyester resin having a melting point of 125 ° C. or less and fine particles having a volume average particle diameter of 5 μm to 35 μm. It is a medium.

  <7> The information recording medium according to <6>, wherein the image information is a toner image formed by electrophotography.

  <8> The information recording medium according to <6>, wherein the image recording body is transparent or opaque.

  <9> The information recording medium according to <6>, wherein at least one surface of the image recording material includes a polyester resin obtained by copolymerizing at least ethylene glycol, terephthalic acid, and a 1,4-cyclohexanedimethanol component.

  <10> The image information is formed as a mirror image on the transparent image recording body, and the surface of the image recording body on which the image information is formed faces the adhesive layer of the core base sheet. The information recording medium according to <6>, which is adhered.

  <11> The surface of the image recording material opposite to the surface on which the image information is formed is selected from functions that control glossiness, light resistance, antibacterial properties, flame retardancy, release properties, and chargeability. The information recording medium according to <6>, wherein a functional layer having at least one function is provided.

  <12> An information chip capable of reading information by using at least one means selected from electrical means, magnetic means, and optical means is disposed inside or on the surface of the core substrate. <6> The information recording medium according to <6>.

  <13> The information recording medium according to <12>, wherein the information chip is an IC chip.

  <14> The information recording medium according to <12>, wherein the information is variable information.

  <15> The information recording medium according to <14>, wherein the variable information includes personal information.

  <16> A core base sheet having a core base and an adhesive layer provided on at least one side of the core base, and image information adhered to the core base through the adhesive layer. The adhesive layer is a method for producing an information recording medium comprising at least a crystalline polyester resin having a melting point of 125 ° C. or less and fine particles having a volume average particle diameter of 5 μm to 35 μm. An information recording process comprising: an image forming process for forming image information on the image recording body; and a laminating process for heat-pressing the image recording body on which the image information has been formed to the core substrate via the adhesive layer. It is a manufacturing method of a medium.

  <17> The image information is formed as a mirror image on the transparent image recording body, and the surface of the image recording body on which the image information is formed faces the adhesive layer of the core base sheet. Thus, it is a manufacturing method of the information recording medium as described in <16> which carries out thermocompression bonding.

  <18> The surface of the image recording body opposite to the surface on which the image information is formed is selected from functions that control glossiness, light resistance, antibacterial properties, flame retardancy, release properties, and charging properties. The method for producing an information recording medium according to <16>, wherein the functional layer having at least one function is provided.

  <19> The information recording medium manufacturing method according to <16>, wherein the image information is a toner image formed by electrophotography.

  <20> The method for producing an information recording medium according to <19>, wherein in the laminating step, thermocompression bonding is performed so that a surface temperature of the image recording body is equal to or lower than a heat melting temperature of the toner forming the toner image. .

  <21> The information recording medium manufacturing method according to <16>, wherein the thermocompression bonding is performed in a reduced pressure state in the laminating step.

  ADVANTAGE OF THE INVENTION According to this invention, the core base material sheet which can be adhere | attached firmly when it laminates, the information recording medium using the same, and the manufacturing method of an information recording medium can be provided.

Hereinafter, the core base sheet of the present invention, an information recording medium using the same, and a method for manufacturing the information recording medium will be described in detail.
<Core substrate sheet>
The core substrate sheet of the present invention has a core substrate and an adhesive layer provided on at least one side of the core substrate, and the adhesive layer has a crystalline polyester resin having a melting point of 125 ° C. or lower. And fine particles having a volume average particle diameter of 5 μm to 35 μm.

  According to the present invention, when a core substrate sheet and an image recording body to be described later (hereinafter, the image recording body may be referred to as a laminate film) can be firmly bonded to each other. In other words, the adhesive layer contains a crystalline polyester resin that decreases to an appropriate viscosity when thermocompression-bonded and exhibits a large adhesive force between the core substrate sheet and the image recording body after cooling. Good adhesion can be obtained even for instantaneous lamination (high-speed lamination conditions) using a roll or the like. In particular, when an adhesive layer is provided on the surface of a relatively thick core substrate sheet, the adhesive layer can be easily provided thicker than the thickness of a toner image layer formed on the surface of an image recording body described later. By doing so, the toner image can be sufficiently embedded in the adhesive layer at the time of laminating, and a decrease in adhesiveness due to the toner image layer being interposed at the adhesive interface can be avoided.

  In the present invention, the crystalline polyester resin refers to a polyester resin having a clear softening point. Furthermore, the crystallinity means that a melting point peak is observed by differential scanning calorimetry (temperature increase rate 20 ° C./min.), And the crystal melting energy is preferably 2 mJ / mg from the viewpoint of maintaining crystallinity. Or more, more preferably 4 mJ / mg or more. Further, the ratio (softening point / peak temperature) between the softening point and the maximum peak temperature of the heat of fusion is approximately 0.9 or more and less than 1.1. Non-crystalline means that the ratio of the softening point to the maximum peak temperature of heat of fusion (softening point / peak temperature) is 1.1 or more.

  The method for synthesizing the crystalline polyester resin used in the present invention is not particularly limited, but it can usually be obtained by subjecting a polybasic acid component having two or more carboxyl groups to a condensation reaction.

As the polybasic acid, divalent basic acid aromatic dicarboxylic acids can be used. For example, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,5-naphthalic acid, etc. are used. It is done. Also, aromatic oxycarboxylic acids such as p-oxybenzoic acid and p- (hydroxyethoxy) benzoic acid, and tri- and tetra-aromatic carboxylic acids such as trimellitic acid and pyromellitic acid can be used in combination.
Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, and dimer acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and its anhydride.

Further, dicarboxylic acids having a polymerizable unsaturated double bond can also be used. For example, α, β-unsaturated dicarboxylic acids include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, unsaturated double bonds. As the alicyclic dicarboxylic acid containing a bond, 2,5-norbornene dicarboxylic acid anhydride, tetrahydrophthalic anhydride, or the like can be used. Most preferred among these are fumaric acid, maleic acid, itaconic acid, and 2,5-norbornene dicarboxylic acid anhydride.
Furthermore, hydroxycarboxylic acids such as hydroxypivalic acid, γ-butyrolactone, and ε-caprolactone can be used as necessary.
These components can be used alone or in combination of two or more.

On the other hand, the glycol component can be at least one selected from aliphatic glycols having 2 to 10 carbon atoms, alicyclic glycols having 6 to 12 carbon atoms, and ether bond-containing glycols.
Examples of aliphatic glycols having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1, Examples include 6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, hydroxypivalic acid neopentylglycol ester, dimethylolheptane, and the like. .

Examples of alicyclic glycols having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol and tricyclodecane dimethylol.
Examples of the ether bond-containing glycols include diethylene glycol, triethylene glycol, dipropylene glycol, and glycols obtained by adding 1 to several moles of ethylene oxide or propylene oxide to two hydroxyl groups bonded to the aromatic ring of bisphenols, An example is 2,2-bis (4-hydroxyethoxyphenyl) propane. Polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can also be used as necessary.

  The crystalline polyester resin can be synthesized by a known method, for example, in a solvent at a reaction temperature of 20 to 150 ° C. in the presence of a catalyst such as amines and organotin compounds, or in the absence of a catalyst. Examples of the solvent that can be used at this time include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate.

  In the adhesive layer according to the core substrate sheet of the present invention, these crystalline polyester resins may be used alone or in combination of two or more. Further, in order to further improve the adhesiveness or improve the blocking property, a conventionally known resin can be mixed as necessary and used as a resin material constituting the adhesive layer.

When the crystalline polyester resin used in the present invention has a melting point of 125 ° C. or higher, when a later-described image recording body is thermocompression-bonded to the core base sheet of the present invention, the toner image or the like formed on the image recording body The image information may melt and the image may be distorted. This is because when the image forming material used for image formation is a color toner, the melting temperature of the color toner is generally around 120 ° C., and in this case, the surface temperature of the image recording medium is around 120 ° C. This is because the melting point temperature of the crystalline polyester resin contained in the adhesive layer needs to be at least 125 ° C. or lower in order to ensure the adhesiveness when heated to the (heat melting temperature). In addition, if the melting point of the crystalline polyester resin is higher than 125 ° C., the sandwiched air tends to remain between the resins having high viscosity during lamination.
The melting point of the crystalline polyester resin used in the present invention is preferably in the range of 20 ° C to 115 ° C, more preferably in the range of 80 ° C to 110 ° C.
If the melting point temperature is 20 ° C. or higher, the adhesive layer does not have viscosity at room temperature, and problems such as sticking out of the laminated part after lamination and shifting of the adhered material hardly occur.

  The adhesive layer according to the core substrate sheet of the present invention contains fine particles having a volume average particle diameter of 5 μm to 35 μm. The fine particles are preferably contained at least on the surface of the adhesive layer.

  In addition, when the fine particles are laminated, the surface of the core base sheet is improved in order to improve the transportability in the registering apparatus that superimposes the core base sheet of the present invention and the image recording body on which the image is formed. Part of the core base sheet is exposed to the outside of the surface of the core base sheet so that the coefficient of friction can be lowered, and is fixed to the surface of the core base sheet so as not to easily fall off. preferable.

The size of the fine particles used for such a purpose needs to be in the range of 5 to 35 μm in volume average particle diameter when added to a coating layer such as an adhesive layer. In addition, the volume average particle diameter of the fine particles can be selected according to the thickness of the adhesive layer to which the fine particles are added so that the fine particles are easily fixed on the surface of the core sheet. If the volume average particle size is less than 5 μm, the fine particles are almost buried in the adhesive layer, and the coefficient of friction on the surface of the core substrate sheet cannot be lowered. If it exceeds 35 μm, the fine particles can be visually confirmed, and the image quality after lamination deteriorates.
The preferred volume average particle size of the fine particles used in the present invention is preferably in the range of 15 to 30 μm.

  Further, the particle size distribution of the fine particles used in the present invention is preferably narrow in order to achieve the above object, and ideally it is preferably monodisperse. The particle size distribution of the fine particles can be represented by, for example, a volume average particle size distribution index GSDv. In the fine particles used in the present invention, GSDv is preferably 3 or less, and more preferably 1.8 or less.

  The volume average particle size and particle size distribution index of the fine particles in the present invention are measured using a Coulter counter TA-II (manufactured by Beckman-Coulter), and the electrolyte is measured using ISOTON-II (manufactured by Beckman-Coulter). can do.

  As a measuring method, 0.5 to 50 mg of a measurement sample was added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant, and this was added to 100 to 150 ml of the electrolytic solution. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the particle size is 0.6 to 100 μm using the Coulter Counter TA-II type aperture having an aperture diameter of 100 μm. The particle size distribution of particles in the range was measured.

For the measured particle size distribution, a cumulative distribution is drawn from the smaller diameter side with respect to the divided particle size range (channel), and the particle size that becomes 16% cumulative is defined as the volume average particle size D16v, which becomes 50% cumulative. The particle diameter is defined as a volume average particle diameter D50v (the volume average particle diameter of the fine particles described above indicates this). Similarly, the particle diameter that is 84% cumulative is defined as the volume average particle diameter D84v. Using these, the volume average particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 .

  The fine particles used in the present invention are not particularly limited. In the case of those composed of organic resin particles, specifically, styrenes such as styrene, vinyl styrene and chlorostyrene; ethylene, propylene, butylene, isobutylene and the like. Monoolefins; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate; methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate , Esters of α-unsaturated fatty acid monocarboxylic acids such as ethyl methacrylate, butyl methacrylate, dodecyl methacrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether; vinyl methyl ketone, vinyl hexyl Ketones, vinyl ketones such as vinyl isopropenyl ketone; isoprene, can be exemplified 2-one diene monomer chloro butadiene or of two or more polymerized obtained homopolymer or copolymer.

  Of these, styrenes and esters of α-unsaturated fatty acid monocarboxylic acids are preferred. When using a heat-meltable resin as fine particles, it can be used as fine particles constituting the adhesive layer by coating with a solvent that does not dissolve these resins. Preferably, a crosslinker or the like is added to these heat-meltable resins. More preferably, fine particles obtained by adding a thermosetting resin, a photocurable resin, an electron beam curable resin, or the like having a cross-linked structure to which the resin is added are added.

  When the fine particles are composed of inorganic fine particles, specific examples include mica, talc, silica, calcium carbonate, zinc white, halocyto clay, kaolin, hydrochloric acid magnesium carbonate, quartz powder, titanium dioxide, sulfuric acid. Examples include barium, calcium sulfate, and alumina.

The shape of the fine particles is generally spherical particles, but may be a plate shape, a needle shape, or an indefinite shape.
As described above, in order to improve the transportability of the core substrate sheet, it is necessary to reduce the friction on the surface of the core substrate sheet due to the fine particles, but in actual use, the static friction coefficient of the core substrate sheet surface is It is preferably 2 or less, and more preferably 1 or less. The dynamic friction coefficient of the core base sheet surface is preferably in the range of 0.2 to 1, and more preferably in the range of 0.3 to 0.65.

  The mass ratio of the fine particles to the crystalline polyester resin in the adhesive layer (fine particles: crystalline polyester resin) is preferably in the range of 0.3: 1 to 3: 1, and 0.5: 1 to 2: 1. More preferably, it is the range. When the proportion of the fine particles is within the above range, the image quality after lamination is stably obtained with high quality, but when it is less than the above range, tackiness is manifested and each core base sheet is formed by stacking sheets. May adhere. When the amount is larger than the above range, the adhesive strength after laminating an image recording material described later may not be sufficiently exhibited.

The resin used for the core substrate of the core substrate sheet is a polystyrene resin, a vinyl chloride resin, an ABS resin, an AS (acrylonitrile-styrene) resin, a polyethylene terephthalate (PET), or a polyolefin resin such as polyethylene or polypropylene. There are resins, vinyl chloride resins, etc., but polyvinyl chloride that has been used as a base material (core) for cards in the past is not good for the environment as it generates dioxins by burning when combustibles are discarded. Since it has been recognized and is no longer used, in the present invention, in consideration of the use of the above-mentioned base material containing no chlorine, as an additional material, in the present invention, in particular, PET (polyethylene terephthalate) using ethylene glycol and terephthalic acid is used. About 1,4-half of the ethylene glycol component It is preferred to use a cyclohexane dimethanol component replaced copolymerized allowed polyester resin (may be abbreviated as follows PET-G resin). In addition, it is preferable to use an alloy obtained by mixing the PET-G with a polycarbonate resin or a polyarylate resin.
When PET-G is used, it is preferable that at least one surface of the core base material includes a polyester resin obtained by copolymerizing at least ethylene glycol, terephthalic acid and a 1,4-cyclohexanedimethanol component. Since PET-G itself has heat sealability, it has excellent adhesion after lamination with a film holding an image. Therefore, by inserting an image between the film and the core base sheet or sandwiching a hologram printed material, it is difficult to tamper with the image, and an excellent security can be achieved.

  The polyester resin obtained by copolymerizing at least ethylene glycol, terephthalic acid and 1,4-cyclohexanedimethanol component is a crystalline polyester resin contained in a coating solution used when forming an adhesive layer on the surface of the core substrate. Since it is excellent in compatibility with such components, the surface of the base material containing the PET-G resin and the adhesive layer provided in contact with the base material surface can be firmly bonded to prevent peeling. Moreover, even if it peels, it cannot peel cleanly in an interface part. For this reason, when a laminate film is laminated on a core substrate sheet to form a card (information recording medium), forgery can be reliably prevented.

  In addition, PET-G resin is not only excellent in compatibility with the coating liquid, but among the resins that can be used as the core substrate, it is possible to produce a laminate film or a card using the same using an existing apparatus. Easy. In addition, compared to the vinyl chloride resin that has been used as a material for the core substrate, information recording media manufactured using laminated films such as sunlight and fluorescent lamps are exposed under normal usage conditions. It is hard to turn yellow against light and has excellent light resistance.

  The core substrate may be transparent or opaque, but when opaque, it is preferably colored white. Here, the term “transparent” means, for example, the property of transmitting a certain amount of light in the visible light region. In the present invention, at least the formed image is a core substrate from the surface opposite to the surface on which the image is formed. It means that it can be visually observed through the material. The term “opaque” refers to, for example, the property of blocking a certain amount of light in the visible light region. In the present invention, at least the formed image has a core base from the surface opposite to the surface on which the image is formed. It means that it is not visible through the material. The meanings of transparency and opaqueness in the present invention are the same hereinafter.

When a transparent core substrate is used, an information recording medium can be obtained, for example, by using a white sheet as an image recording body carrying an image and laminating the image bearing surface on the outside with the core substrate sheet.
On the other hand, when the core base material is white, a white or transparent sheet can be used as an image recording medium carrying an image. When the image recording body is a transparent sheet film, the image carrying surface is set to the outside or the inside. An information recording medium can be obtained by laminating with the core substrate sheet. In addition, when laminating with the image carrying surface on the inside, it is necessary to print the image on a mirror image. Further, when laminating with the image carrying surface on the inside, there is an advantage that a functional layer described later can be provided on the side opposite to the image carrying surface.

  As a method for making the core substrate opaque, for example, a method of mixing metal oxide fine particles such as silicon oxide, titanium oxide, and calcium oxide, organic white pigment, polymer particles and the like into the core substrate can be used. In addition, when making it opaque to colors other than white, a commonly used organic pigment or the like can be used.

The core substrate used in the present invention is preferably composed of two or more layers from the viewpoint of laminating properties.
In this case, for example, an adhesive layer containing a crystalline polyester resin is provided on at least one of the surfaces forming the outer surface of the core base material, and the other surface is a layer made of only PET-G resin. Good. In this case, since the softening point temperature of PET-G resin is around 80 ° C., heat fusion is easy, and even a layer of only PET-G resin is excellent in laminating properties. In the case of a specification that takes measures to prevent forgery that cannot be recognized by humans.

In the softening point temperature region of the PET-G resin, a layer containing the PET-G resin, particularly a base material made only of the PET-G resin, is easily deformed. In order to suppress such deformation, the image recording material laminated with the core base material sheet is preferably composed of a layer containing a PET-G resin and a layer made of other components. That is, it is preferable that at least one surface of the image recording body includes a polyester resin obtained by copolymerizing at least ethylene glycol, terephthalic acid, and 1,4-cyclohexanedimethanol component. As a material constituting the latter layer, a plastic film can be used. Specifically, for example, polyacetate film, cellulose triacetate film, nylon film, polyester film, polycarbonate film, polystyrene film, polyphenylene sulfide film, polypropylene film which are light transmissive films that can be used as OHP films , Polyimide film, cellophane, ABS (acrylonitrile-butadiene-styrene) resin film, and the like.
In the present invention, it is preferable to use a polyester resin having a softening point temperature higher than that of the PET-G resin. Examples of such a material include polycarbonate, polyarylate, and a mixture or copolymer thereof, or polyethylene. Terephthalate (PET) is desirable. In particular, when PET is used, a biaxially stretched film is strong when heated and is resistant to deformation. By laminating with such an image recording film containing PET-G resin, an information recording body resistant to deformation during heating can be produced.

  The polycarbonate resin is a polycondensate obtained from bisphenols and carbonic acid, and the polyarylate is a polyester obtained by polycondensation of bisphenols and an aromatic dicarboxylic acid. Polyarylate generally has higher heat resistance than polycarbonate because it contains a rigid aromatic ring in the main chain at a high density.

  Examples of the bisphenols include bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol C (4,4 ′-(1-methylethylidene) bis (2-methylphenol)), bisphenol AP (4 , 4 ′-(1-phenylethylidene) bisphenol), bisphenol Z (4,4′-cyclohexylidenebisphenol), 4,4′-cyclohexylidenebis (3-methylphenol), 5,5 ′-(1 -Methylethylidene) (1,1'-biphenyl) -2-ol, (1,1'-biphenyl) -4,4'-diol, 3,3'-dimethyl (1,1'-biphenyl) -4, 4'-diol, 4,4 '-(1,4-phenylenebis (1-methylethylidene)) bisphenol), 4,4'-(1,4-phenyle) Bis (1-methylethylidene) bis (2-methylphenol)), 4,4 '-(1,3-phenylenebis (1-methylethylidene) bis (2-methylphenol)), bisphenol S (4,4' -Bis (dihydroxydiphenylsulfone), etc. are mentioned, but those of bisphenol A are often used, and these may be used alone or in combination of two or more.

  Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, itaconic acid, azelaic acid, sebacic acid, icodic acid diacid, naphthalenedicarboxylic acid, diphenic acid, dodecanediic acid. Examples include acids and cyclohexanedicarboxylic acid. These raw materials are not necessarily used alone, and two or more of them may be copolymerized. Among these, as a preferable example, a mixture of a terephthalic acid component and / or an isophthalic acid component is preferable in terms of melt processability and overall performance of the resulting polyarylate. In such a mixture, the mixing ratio can be arbitrarily selected, but terephthalic acid component / isophthalic acid component = 9/1 to 1/9 (molar ratio) is preferable, particularly in terms of the balance between melt processability and performance. 7/3 to 3/7 (molar ratio), more preferably 1/1 (molar ratio).

  As the core substrate used in the present invention, a film made of a plastic having a thickness of 50 to 5000 μm is preferably used, and a PET-G resin film having a thickness of 100 to 1000 μm is more preferably used.

  In the present invention, an information chip capable of reading information by using at least one means selected from an electric means, a magnetic means, and an optical means is disposed in or on the core base material. It is preferable that

The information chip is not particularly limited as long as it has information having some kind of identification function and can be read by using at least one means selected from electrical means, magnetic means, and optical means. . This information chip may be dedicated to reading information, but may be one that can both read and write information (including “rewriting”) as necessary. A specific example of such an information chip is an IC chip (semiconductor circuit) when the information recording medium is used as an IC card, for example.
Details of these information chips, the arrangement method on the core substrate sheet, and the like will be described later in the information recording medium.

The adhesive layer containing at least a crystalline polyester resin and specific fine particles is formed on the surface of the core substrate by the following method.
The adhesive layer is prepared by mixing a crystalline polyester resin and fine particles using an organic solvent or water, and uniformly dispersing the mixture with an apparatus such as an ultrasonic wave, a wave blower, an attritor or a sand mill, The coating solution can be formed by coating or impregnating the surface of the core substrate as it is.

  As coating or impregnation methods, blade coating methods, wire bar coating methods, spray coating methods, dip coating methods, bead coating methods, air knife coating methods, curtain coating methods, roll coating methods, screen printing methods, etc. are usually used. Method is adopted.

  However, in the preparation of the coating liquid, it is preferable to use a good solvent that dissolves the surface of the core substrate as the solvent. When such a good solvent is used, the surface of the core base material dissolves, that is, the surface of the core substrate itself works as a binder resin and becomes very high, and it becomes easy to stably hold the fine particles.

Here, a good solvent for the surface of the core substrate means that when the solvent contacts the surface of the core substrate, it has some effect on the core substrate, and the surface of the core substrate is slightly affected (solvent removal). After that, it means that the surface has a slightly higher solubility.
From such a viewpoint, the surface of the core base material on which the adhesive layer is formed should contain a PET-G resin excellent in compatibility with a general solvent used in the coating liquid. Preferably, it is more preferably covered with these resins.

  The solvent for extracting the compatibility between the PET-G resin contained in the core substrate surface and the resin contained in the coating layer is not particularly limited as long as it is a solvent used for preparing a known coating solution. Specific examples include aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and chlorobenzene, ketones such as methyl ethyl ketone and cyclohexanone, tetrahydrofuran, ethyl acetate, mixtures of these solvents, and other poor A mixed solvent with a solvent may be used.

  The drying at the time of forming the coating layer on the surface of the core substrate may be air drying, but can be easily dried by heat drying. As the drying method, a commonly used method such as a method of placing in an oven, a method of passing through an oven, or a method of contacting with a heating roller is employed.

  The thickness of the adhesive layer in the core substrate sheet of the present invention is preferably in the range of 2 to 60 μm, and more preferably in the range of 5 to 30 μm. If the thickness is less than 2 μm, the layer thickness required for the adhesive layer cannot be obtained, and the toner image cannot be embedded sufficiently and the image is crushed more than necessary, resulting in a bold (deteriorated) image and poor image reproducibility. There is. On the other hand, if it exceeds 60 μm, the amount of adhesive may exceed the required amount or the image may be deteriorated.

<Method of manufacturing information recording medium>
Next, a method for manufacturing the information recording medium of the present invention will be described.
The method for producing an information recording medium of the present invention comprises an image forming step for forming image information on an image recording body, and an image recording body on which the image information is formed, via the adhesive layer of the core substrate sheet of the present invention. Laminating step of thermocompression bonding to the substrate.

(Image formation process)
In the case where an image is formed on a laminate film as an image recording body by an electrophotographic method, image formation on an unprinted laminate film by an electrophotographic method is performed on the surface of an electrophotographic photoreceptor (image carrier). After uniformly charging and charging, the obtained image information is exposed on the surface to form an electrostatic latent image corresponding to the exposure. Next, the electrostatic latent image is visualized and developed with the toner (toner image is formed) by supplying toner as an image forming material from the developing device to the electrostatic latent image on the surface of the electrophotographic photoreceptor. . Further, the formed toner image is transferred to the surface of the unprinted laminate film where the image receiving layer is formed, and finally the toner image is fixed on the surface of the image receiving layer by heat, pressure, etc. Is formed.

  As a material constituting the image receiving layer, a heat-meltable polyester resin is preferably used. Generally, a heat-meltable polyester can be produced by a reaction between a polyvalent hydroxy compound and a polybasic carboxylic acid or a reactive acid derivative thereof. Examples of the polyvalent hydroxy compound constituting the polyester include diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and neopentyl glycol. However, it is particularly preferable to use ethylene glycol and neopentyl glycol as the polyester used in the present invention.

  Examples of the polybasic carboxylic acid include malonic acid, succinic acid, adipic acid, sebacic acid, alkyl succinic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, and cyclohexanedicarboxylic acid. , Isophthalic acid, terephthalic acid, and other divalent carboxylic acids. In the present invention, isophthalic acid and terephthalic acid can be used particularly preferably in view of production, material availability and cost. In general, phthalic acid has structural isomers of isophthalic acid and terephthalic acid. Therefore, in the production of polyester, both of the above are inevitably mixed at a ratio of approximately half.

In the present invention, it is particularly desirable that the ratio of ethylene glycol and neopentyl glycol (ethylene glycol: neopentyl glycol) in the polyvalent hydroxy compound is in the range of 3: 7 to 1: 9 in terms of molar ratio.
The number average molecular weight of the heat-meltable polyester is preferably in the range of 12000 to 45000, and more preferably in the range of 20000 to 30000. If the number average molecular weight is 12000 or more, the softening point of the resin can be increased by suppressing the molar ratio of ethylene glycol and neopentyl glycol within a desired range, and the development of viscosity at room temperature can be suppressed. When the number average molecular weight is 45000 or less, the softening temperature can be suppressed to an appropriate height, and the fixability of the image (toner) is improved.
By using these materials, the image receiving layer can be excellent in adhesiveness with the toner.

  The toner image transferred to the image receiving layer of the laminate film is formed according to image information exposed to the electrophotographic photoreceptor. This information may be image information or character information. In the present invention, the term “formed according to image information” means “formed as a real image or formed as a mirror image” unless otherwise specified.

  The image information may include variable information. That is, in the image formation, the toner images formed on the surface of the unprinted laminate film are not the same in, for example, a plurality of image formations, and are different toner images depending on information that is variable information for each sheet. May be.

  For the image receiving layer provided on the surface of the laminate film, a material having good adhesiveness with the toner is selected. Therefore, the toner is sufficiently fixed on the surface of the laminate film at a temperature lower than the temperature at which the toner melts and becomes viscous.

  For this reason, it is preferable to fix the toner image formed on the surface of the laminate film so that the temperature of the surface of the laminate film (image forming surface) is equal to or lower than the melting temperature of the toner. Considering the melting temperature of normal toner, it is preferable that the surface temperature of the laminate film be 130 ° C. or lower, more preferably 110 ° C. or lower.

  As an image forming method that can be used in the present invention, intaglio printing, relief printing, lithographic printing, gravure printing, screen printing, a printer employing a thermal transfer method, electrophotography, etc. can be used, but a variety of small-scale production is possible. Therefore, it is preferable to use an electrophotographic method.

Similar to the core substrate, the laminate film may be transparent or opaque, but this laminate film is transparent, and the image forming surface (the surface on which the image receiving layer is provided) is defined as the laminate surface. In this case, the image formed on the image receiving layer of the unprinted laminate film needs to be a reverse image (mirror image). When an electrostatic latent image is formed on the surface of the photoconductor, it is preferable that mirror image information is provided as image information exposed on the surface of the photoconductor.
When the laminate film has an image receiving layer on one side and a functional layer (functionality control means) described later on one side, the image forming side is used as the laminate side and the functionality is It is preferable to laminate the layers with the layers outside to impart various functions to the information recording medium.

  On the other hand, when the laminate film is opaque, an image is formed by a normal development method, and in the lamination with the core substrate sheet, a surface without an image is used as a laminate surface. In this case, since it is not necessary to provide a functional layer, costs associated therewith can be suppressed.

  The functional layer preferably has at least one function selected from the functions of controlling glossiness, light resistance, antibacterial properties, flame retardancy, releasability, and chargeability. In contrast to the surface opposite to the image-carrying surface, gloss, light resistance, antibacterial properties, flame retardancy, releasability, conductivity, more preferably moisture resistance, heat resistance, water repellency, abrasion resistance And provided to add and / or improve various functions such as scratch resistance. Thereby, the information recording medium having the functional layer can be resistant to various use conditions.

As the functional layer, for example, it may be provided as a coating layer on the substrate surface, or a function may be directly imparted to the substrate surface by subjecting the substrate surface to mechanical treatment.
Thus, the film thickness of the coating layer (functional control layer) functioning as a functional layer formed on the surface of the substrate is preferably in the range of 0.1 to 20 μm, and preferably in the range of 1.0 to 10 μm. A range is more preferable.

(Lamination process)
The information recording medium of the present invention is manufactured by heat-pressing the image recording body on which image information is formed, to the core substrate via the adhesive layer of the core substrate sheet of the present invention. In this case, the image information is formed as a mirror image on the transparent image recording body, and the surface of the image recording body on which the image information is formed faces the adhesive layer of the core base sheet. Thus, it is preferable to heat-press. Thereby, image information can be clamped between a core base material and an image recording body.

  The lamination film and the core substrate sheet may be overlapped by holding and aligning the laminate film and the core substrate sheet by hand, or may be laminated on a collating tray or the like provided after the image formation. The film and the core base sheet may be discharged sequentially and automatically aligned.

  In the laminating step, any of various conventionally known laminating techniques and laminating apparatuses can be suitably employed. For example, after a laminated body in which the core base material and the laminate film are overlapped is disposed between a pair of pressing plate materials, the laminated body is pressed while being heated through the pair of pressing plate materials. A heat press method (hereinafter sometimes abbreviated as “plate material press”) can be used. However, in the production of the information recording medium of the present invention, a laminate in which a laminate film and a core base material sheet are superposed, for example, a heat press method (hereinafter referred to as a heat press method) is inserted while heating between a pair of rolls. It is preferable to use a “roll press” in some cases.

  In the laminating step, it is preferable that the surface pressure of the image recording body is thermocompression-bonded so as to be equal to or lower than the heat melting temperature of the toner forming the toner image. By laminating under these conditions, the interface between the adhesive layer and the image recording body can be securely and firmly adhered while maintaining the image quality in a relatively low temperature range where the toner image softens without flowing. .

  Specifically, considering the melting temperature of normal toner, it is preferable that the temperature at the bonding interface is 130 ° C. or lower, more preferably 110 ° C. or lower.

  When a laminate film (unfixed laminate film) in which a toner image is formed on the film surface without performing the fixing described above is used in the laminating process, the laminating temperature is slightly higher than when a laminated film that has been fixed is used. By making it higher, it is possible to ensure the color developability of the toner.

  Moreover, in this invention, it is preferable to perform the thermocompression bonding in the said lamination process in a pressure-reduced state. By performing bonding under these conditions, bubbles that tend to remain at the interface of the bonding can be reliably driven out, so that a higher-quality information recording medium can be manufactured. As specific decompression conditions, it is preferable to perform thermocompression bonding at about 4000 Pa or less, more preferably about 1333 Pa or less.

  The laminated body can be used as it is as the information recording medium of the present invention. However, when a plurality of individual images are formed on the laminate film, the laminate is cut for each image, and a plurality of pieces of information of a predetermined size are obtained. A recording medium can be obtained.

<Information recording medium>
Next, an information recording medium using the core substrate sheet of the present invention will be described.
An information recording medium of the present invention includes the core base sheet of the present invention and an image recording body on which image information is formed, which is bonded to the core base of the core base sheet via an adhesive layer. It is.
Specifically, as such an information recording medium, for example, (1) a laminate film in which a toner image corresponding to image information is formed on a laminate surface, and a transparent or opaque core that is overlapped and adhered to the laminate film A core substrate sheet having a substrate, and (2) a laminate film having a toner image formed on a laminate surface, and a transparent or opaque core substrate that is laminated and adhered to the laminate film. Arranged in at least one of the core substrate sheet, the inside of the core substrate, the surface of the core substrate opposite to the laminate surface, and the adhesive surface between the laminate film and the core substrate. Information by utilizing at least one means selected from electrical means, magnetic means and optical means Reading the information chip capable, it includes at least comprises configure.

  In addition, it is preferable that at least the crystalline polyester resin described above is included in at least the surface on the laminate side of the laminate film used for the production of the information recording medium of the present invention. In this case, when the laminate film and the core substrate sheet are laminated, both can be bonded more firmly.

  In the information recording medium of the present invention, the image information is formed as a mirror image on the transparent image recording body, and the surface of the image recording body on which the image information is formed and the adhesive layer of the core substrate sheet are bonded to face each other. It is preferable that it is an aspect. Thereby, image information can be protected.

  In the information recording medium shown in (1) above, the toner image partially or entirely serves as information having some kind of identification function, and includes a toner image that functions as identifiable information such as image information and character information. If it is, it will not specifically limit. Further, the identification of the toner image as information is not particularly limited as to whether the toner image can be visually identified, and may be mechanically identifiable.

  In the information recording medium shown in (2) above, the information chip has information having some kind of identification function, and at least one means selected from electrical means, magnetic means and optical means is used. If it is readable by this, it will not be specifically limited. This information chip may be dedicated to reading information, but may be one that can both read and write information (including “rewriting”) as necessary. A specific example of such an information chip is an IC chip (semiconductor circuit).

  Note that the toner image formed when the above-described information chip is used as the information source of the information recording medium is not particularly limited as to whether or not a part or all of the toner image has information having some kind of identification function.

On the other hand, the information included in the toner image or the information chip is not particularly limited as long as it can be identified, but may include variable information. The variable information means that information held by individual information recording media is different among a plurality of information recording media manufactured based on the same standard or standard.
For example, when the toner image includes variable information, the toner image corresponding to the variable information can be a different toner image for each information recording medium.

  Further, the variable information may include personal information. In this case, the information recording medium of the present invention can be applied to cash cards, employee cards, student cards, individual membership cards, residence cards, various driver's licenses, various qualification certificates, etc. In this case, the personal information includes, for example, a face photograph, personal identification image information, name, address, date of birth, and combinations thereof.

  Further, when the information recording medium of the present invention is used as an IC card or the like using an information chip such as an IC chip, as described above when the information recording medium is finally produced, The information chip may be disposed at least one of the inside, the surface of the core substrate opposite to the laminate surface, and the adhesive surface between the laminate film and the core substrate. However, in production, a material having an information chip inside or on the surface of the core substrate can be used practically.

  As a method of incorporating an information chip inside the core substrate, a method called an inlet in which an information chip is fixed is sandwiched between sheet materials constituting the substrate, and heat fusion and integration are generally performed by hot pressing. Are preferably used. In addition, a method in which the information chip is directly arranged without the inlet sheet and similarly heat-sealed and integrated is also possible.

In addition, it is possible to bond sheets constituting the base material together using an adhesive such as hot melt, and to incorporate an information chip in the same manner, but not limited to these. For example, any method that incorporates an information chip in an information recording medium can be applied as a method for manufacturing a core substrate sheet.
Furthermore, if there is no problem in use as an information recording medium, it is possible to arrange the information chip exposed on the surface rather than inside the core substrate.

  When the information recording medium of the present invention is used not only as an IC card but also as a magnetic card or the like, an antenna, a magnetic stripe, an external terminal, or the like may be embedded in the core base sheet as necessary. Moreover, a magnetic stripe, a hologram, etc. may be printed and required character information may be embossed.

Next, specific examples of the information recording medium described above will be described with reference to the drawings. FIG. 1 is a schematic perspective view showing an example of the information recording medium of the present invention. In FIG. 1, 100 represents a first laminate film, 200 represents a core substrate sheet, and 300 represents a second laminate film.
The information recording medium shown in FIG. 1A has a configuration in which a laminate film 100 and a core base sheet 200 that is a laminated body are laminated and bonded. Further, as shown in FIG. 1B, another laminate film may be superposed and bonded to the configuration illustrated in FIG. 1A. Specifically, both surfaces of the core base sheet 200 are bonded. The first laminate film 100 and the second laminate film 300 may be superposed and bonded to each other. Furthermore, it is good also as a structure which provided the sheet | seat, layer, etc. other than the above as needed.

  In the information recording medium shown in FIGS. 1A and 1B, the core base sheet of the present invention is used as the core base sheet 200.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In the following Examples and Comparative Examples, “part” means “part by mass”.

Example 1
A core substrate sheet (core substrate 1) was produced as follows. Hereinafter, the manufacturing method is demonstrated for every process.

<Preparation of adhesive layer coating solution A-1>
30 parts of crystalline polyester resin (Toyobo Co., Ltd .: Byron GA-6400, melting point 86 ° C., crystal melting energy: 2.1 mJ / mg, softening point / peak temperature ratio is 1.06) 35 parts of methyl ethyl ketone as a solvent The mixture was mixed with 35 parts of cyclohexanone and stirred while heating to 60 ° C. to obtain a resin liquid having a solid content concentration of 30%. To this resin liquid, 50 parts of crosslinked methacrylate copolymer fine particles (manufactured by Soken Chemical Co., Ltd .: MX-2000, volume average particle diameter: 20 μm) as fine particles and 115 parts of methyl ethyl ketone as a solvent are added and mixed, and stirred sufficiently. An adhesive layer coating solution A-1 was prepared.

<Preparation of core substrate sheet>
The adhesive layer coating solution A is applied to one side of a B4 size white sheet (Mitsubishi Resin Co., Ltd .: Deacrail W2012, total thickness: 500 μm) having a three-layer structure in which both sides are PET-G resin layers and the inside is A-PET. -1 was coated using an applicator, dried at 30 ° C. for 1 hour, and the other side was subjected to the same treatment to form an adhesive layer having a thickness of 16 μm on the front and back surfaces. 210 mm × 297 mm) to produce a core substrate sheet 1.

<Preparation of laminate film 1>
(Preparation of image-receiving layer coating solution B-1)
10 parts of polyester resin (manufactured by Soken Chemical Co., Ltd .: Foret FF-4M, solid content 30% by mass in methyl ethyl ketone solution), cross-linked methacrylate copolymer fine particles (manufactured by Soken Chemical Co., Ltd .: MX-300, volume average) as a matting agent (Particle size: 3 μm) 0.05 part and 0.2 part of a surfactant (manufactured by NOF Corporation: Elegan 264WAX) were added to a mixed solvent of 10 parts of toluene and 30 parts of methyl ethyl ketone, and sufficiently stirred. Image-receiving layer coating solution B-1 was prepared.

(Preparation of functional layer coating solution C-1)
10 parts of a silicone resin (SI Toshiba 801, SI coating 801, solid content 33% by mass) as a thermosetting resin, and polydimethylsiloxane fine particles (GE 145 manufactured by GE Toshiba Silicone: TP145, volume average particle size: 4. 0.4 part, 0.2 part as a charge control agent (manufactured by Takemoto Yushi Co., Ltd .: Pionein B144V), and 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole (Sumitomo) as an ultraviolet absorber Chemical: Sumisorb 200) 0.3 parts, calcium phosphate based inorganic antibacterial agent carrying silver as an antibacterial agent (Sangi: Apacider AW) 0.03 part, cyclohexanone and methyl ethyl ketone in a mass ratio of 10:90 Add to 30 parts of the mixed liquid and stir well, and the coating layer when it is formed will have mold release and light resistance. A fine antimicrobial, to prepare a functional layer coating liquid C-1 capable of holding the surface resistance of the surface to ^{1.0 × 10 8 ~1.0 × 10 13} Ω / □ in the range of.

<Manufacture and image formation of laminate film 1>
Using a transparent PET film (manufactured by Toray Industries Inc .: Lumirror 100T60: thickness 100 μm) as a substrate, the functional layer coating solution C-1 was applied to one side of the substrate using a wire bar and dried at 120 ° C. for 80 seconds. A functional layer having a thickness of 1 μm was formed. Further, the image receiving layer coating liquid B-1 was applied to the other surface (untreated surface) of this substrate using a wire bar and dried at 120 ° C. for 30 seconds to form an image receiving layer having a thickness of 2 μm. Then, it was cut into A4 size (210 mm × 297 mm) to produce a laminate film 1.

  Next, on the surface of the image receiving layer of the laminate film 1, a color copier DocuColor 1255 remodeled machine manufactured by Fuji Xerox Co., Ltd. (modified so that the surface temperature of the laminate film at the time of fixing is in the range of 95 to 100 ° C.) A laminated film 1-U in which 10 color-sized mirror image images including a solid image are formed on a single A4 size card, and 10 mirror image characters of only character information are similarly formed on a laminated film 1-U. D was produced.

<Production of information recording medium>
The image forming surface of the laminate film 1-U is overlaid on one side of the core substrate sheet 1, and the image forming surface of the laminate film 1-D is overlaid on the other side so that the four corners of each film are aligned. The both sides were overlapped by being sandwiched by a set of mirror-specific pressing plates made of SUS steel.
A laminate (pressing plate material 1 / laminate film 1-U / core substrate sheet 1 / laminate film 1-D / pressing plate material 1) subjected to the above positioning and superposition is vertically 120 ° C., 5 kgf / cm ² , Lamination was performed by a hot press under a condition of 30 seconds, and after cooling to room temperature, the pressing plate 1 was removed to obtain an information recording medium 1.

<Evaluation of core substrate sheet>
20 core substrate sheets 1 obtained as described above are stacked and allowed to stand in an environment of 40 ° C. and 90% RH for 24 hours, and the tack (adhesion) properties of the 20 core substrates are examined to evaluate the storability. It went as follows.
◯: There was no tack force at all, and all 20 sheets were separated without problems.
Δ: A slight tack force was felt, but all 20 sheets could be separated (separated) without requiring a large force.
X: Tacking force was obvious, and the sheet was separated (separated) with a large force or one of 20 sheets that could not be separated was generated.
<Performance evaluation of information recording media>
The information recording medium 1 was evaluated for image quality, laminate quality (bubbles remaining, dust resistance), laminating property (peeling strength), and light resistance evaluation according to the following criteria, and the performance as an information recording medium was confirmed.

-Image quality evaluation-
The image quality evaluation was performed by measuring the rate of change (enlargement) of characters after laminating by applying thermal pressure to the characters at the time of image output to the laminate film, and evaluating the accurate print reproducibility as follows.
A: A change rate of less than 3% was shown.
(Triangle | delta): What showed the change rate of less than 3-7%.
X: The rate of change was 7% or more.

-Evaluation of laminate quality (residual air bubbles)-
Regarding the laminate quality, regarding the information recording medium 1 after the lamination, the remaining of air bubbles between the laminate film 1-U and the core substrate 1 and between the laminate film 1-D and the core substrate 1 are visually checked as follows. It was evaluated with.
○: Residual bubbles cannot be confirmed.
Δ: Slightly residual bubbles can be confirmed.
X: Many or large bubbles can be confirmed.

-Evaluation of laminate quality (contamination of dust and dirt)-
Concerning the laminate quality, with respect to the information recording medium 1 after lamination, the dust contamination between the laminate film 1-U and the core substrate 1 and between the laminate film 1-D and the core substrate 1 is visually checked as follows. Evaluated by criteria.
○: Dust contamination cannot be confirmed.
Δ: Slight dust can be confirmed.
X: Many dusts can be confirmed.

-Evaluation of laminate properties (peel strength)-
Regarding the laminating property, with respect to the information recording medium 1 after lamination, the interface between the laminate film 1-U and the core substrate 1 and the laminate film 1-D and the core substrate 1 is peeled off with a cutter knife, and the portion is held. The evaluation was made according to the following criteria depending on the situation when it was peeled off by hand.
(Double-circle): It does not peel at all.
○: The laminate film 1 is torn off immediately after peeling.
(Triangle | delta): Although the laminate film peels off, the image of the peeled surface is disordered and it seems that forgery is difficult.
X: The laminate film 1 is easily peeled easily except the above.

-Light resistance evaluation-
In the light resistance evaluation, a laminate film 1 with a solid image printed side down was placed in a light resistance tester (Toyo Seiki Co., Ltd .: SUNTEST CPS +), and 760 W / mm with a Xe lamp in a 63 ° C. atmosphere. Irradiated for 100 hours at an intensity of m ² . Next, the image density of the solid image before and after the irradiation was measured. A solid image having a difference in image density of less than 0.1 is indicated by ◎, a difference by 0.1 or more and 0.5 or less by ○, and 0.5 or more by 1. A value of 0 or less was evaluated as Δ, and a value exceeding 1.0 was evaluated as ×. The image density was determined by measuring the solid image portion with an X-Rite967 densitometer (manufactured by X-Rite).
The above results are summarized in Table 1.

(Comparative Example 1)
Instead of the crystalline polyester resin used in the adhesive layer coating solution A-1 for the core substrate sheet of Example 1, a crystalline polyester resin having a melting point of 136 ° C. (by Toyobo Co., Ltd .: Byron GA-2310 was used. Except for this, the adhesive layer coating solution A-2 was prepared in the same manner as the adhesive layer coating solution A-1 used in Example 1, and the core substrate sheet 2 was prepared in the same manner as in Example 1 using this. Was made.
Using this core substrate sheet 2, an information recording medium 2 was obtained in the same manner as in Example 1. In the evaluation of the obtained information recording medium 2, the adhesiveness after lamination was poor, and laminate films 1-U and 1 were obtained. -D easily causes peeling on the core base sheet 2. These results are summarized in Table 1.

(Comparative Example 2)
The adhesive layer coating was carried out in the same manner as in Example 1 except that the crosslinked methacrylate copolymer fine particles, which were fine particles used in the adhesive layer coating solution A-1 for the core substrate sheet of Example 1, were not used. The working liquid A-3 was prepared, and using this, the core substrate sheet 3 was produced in the same manner as in Example 1.
The evaluation of the core base sheet 3 was performed in the same manner as in Example 1. However, the storage property was poor, and there was a portion where some sheets could not be tucked and separated. In addition, an information recording medium 3 was obtained in the same manner as in Example 1 by using the core base sheet 3. In the evaluation of the obtained information recording medium 3, the quality after lamination is poor, and many bubbles remain between the laminate film 1-U and the core substrate sheet 3 and between the laminate film 1-D and the core substrate sheet 3. did. These results are summarized in Table 1.

(Comparative Example 3)
Cross-linked methacrylate copolymer fine particles, which are fine particles used in the adhesive layer coating solution A-1 for the core substrate sheet of Example 1, have a volume average particle diameter of 40 μm (manufactured by Soken Chemical Co., Ltd .: MX4000). The adhesive layer coating solution A-4 was prepared in the same manner as in Example 1 except that it was used instead of this, and using this, the core substrate sheet 4 having an adhesive layer of 30 μm was prepared in the same manner as in Example 1. did.
The evaluation of the core substrate sheet 4 was performed in the same manner as in Example 1. However, in the evaluation of the information recording medium using the core substrate sheet 4, after the lamination, the image portion has image quality defects such as color loss due to fine particles. Occurred. In addition, an information recording medium 4 was obtained in the same manner as in Example 1 by using the core substrate sheet 4. In the evaluation of the obtained information recording medium 4, portions where air bubbles slightly remained were observed near the fine particles between the laminate film 1 -U and the core substrate sheet 4 and between the laminate film 1 -D and the core substrate sheet 4. It was. These results are summarized in Table 1.

(Comparative Example 4)
Instead of the crystalline polyester resin used in the adhesive layer coating solution A-1 for the core substrate sheet of Example 1, a crystalline polyester resin having a melting point of 141 ° C. (by Toyobo Co., Ltd .: Byron GA-1200) is used. Except for the above, the adhesive layer coating solution A-5 was prepared in the same manner as the adhesive layer coating solution A-1 used in Example 1, and the core substrate sheet was prepared in the same manner as in Example 1 using this. 5 was produced.
The evaluation of the core substrate sheet 5 was performed in the same manner as in Example 1. However, in the evaluation of the information recording medium 5 using the core substrate sheet 5, the adhesiveness after lamination was poor, and the laminate film 1-U and 1-D easily causes peeling on the core substrate sheet 5. These results are summarized in Table 1. Further, many residual bubbles were observed between the laminate film 1-U and the core substrate sheet 5, and between the laminate film 1-D and the core substrate sheet 5. These results are summarized in Table 1.

(Example 2)
<Preparation of adhesive layer coating solution A-6>
50 parts of cyclohexanone, 0.1 part of a surfactant (manufactured by Nippon Oil & Fats Co., Ltd .: Elegan 264WAX) as a charge control agent, and fine particles of cross-linked methacrylate ester copolymer (manufactured by Soken Chemical Co., Ltd .: MX-3000, volume average particle) 50 parts of diameter: 30 μm) is added and mixed. Further, a crystalline polyester resin (Toyobo Co., Ltd .: Byron 30P, melting point 125 ° C., crystal melting energy: 2.5 mJ / mg, softening point / peak temperature ratio is 1 0.03) 50 parts and 180 parts of methyl ethyl ketone were added and sufficiently stirred and dissolved while maintaining at 80 ° C. to prepare an adhesive layer coating solution A-6.

<Preparation of core substrate sheet>
In the same manner as in Example 1, the adhesive layer coating liquid A-6 was applied to a white sheet of B4 size (Made by Mitsubishi Plastics: Diafix PG-WHI, total thickness: 560 μm) composed of a PET-G resin layer. The adhesive layer having a thickness of 25 μm was formed on the front and back surfaces, and this was cut into A4 size (210 mm × 297 mm) to prepare the core base sheet 6.

<Preparation of laminate film 2>
(Preparation of image-receiving layer coating solution B-2)
10 parts of polyester resin (manufactured by Soken Chemical Co., Ltd .: Foret FF-4M, solid content 30% by mass in methyl ethyl ketone solution), cross-linked methacrylate copolymer fine particles (manufactured by Soken Chemical Co., Ltd .: MX-300, volume average) as a matting agent Particle size: 5 μm) 0.3 part, surfactant (manufactured by NOF Corporation: ELEGAN 264WAX) 0.4 part, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole (Sumitomo) as UV absorber Chemical Co., Ltd .: Sumisorb 200) 0.3 parts, and antibacterial glass fine particles (Nippon Sheet Glass Co., Ltd .: Amoclin P-05, average particle size 5 μm) 0.05 parts as a mixed solvent of toluene 40 parts and methyl ethyl ketone 4 parts Image-receiving layer coating solution B-, which is added and stirred well to control the image-receiving layer, light resistance, chargeability and antibacterial functionality 2 was prepared.

<Manufacture and image formation of laminate film 2>
Film (Teijin DuPont film) with PET as a base and a PET-G resin layer (thickness of about 16 μm) formed by copolymerizing ethylene glycol, terephthalic acid and 1,4-cyclohexanedimethanol components on both sides The image-receiving layer coating solution B-2 is applied to one side of a product made by the company: Melinex 342 and a total thickness of 102 μm using a wire bar and dried at 70 ° C. for 60 seconds to form an image-receiving layer having a thickness of 0.5 μm. Formed. Further, the image receiving layer coating solution B-2 was similarly applied to the other surface (untreated surface) of this substrate using a wire bar, dried at 70 ° C. for 60 seconds, and a film thickness of 0.5 μm. An image receiving layer / functional layer was formed. The film thus obtained was cut into A4 size to produce a laminate film 2.

  Next, on the surface of the image receiving layer of the laminate film 2, a color copier DocuColor 1255 remodeled machine manufactured by Fuji Xerox Co., Ltd. A laminate film 2-U in which 10 color-sized mirror image images including a solid image are formed on one A4 size card image and a 10-image laminate image in which only character information is formed. D was produced.

<Production of information recording medium>
In the same manner as in Example 1, the image forming surface of the laminate film 2-U is placed on one side of the core base sheet 6 and the image forming surface of the laminate film 2-D is placed on the other side so that the four corners of each film are aligned. Then, the two sides were overlapped by sandwiching both sides with a pair of pressing plate members of specular specification made of SUS steel plate.
Laminate (pressing plate material 1 / laminate film 2-U / core substrate sheet 6 / laminate film 2-D / pressing plate material 1) subjected to the above positioning and superimposing is 125 ° C., 5 kgf / cm ² above and below, Lamination was performed by a hot press under a condition of 30 seconds, and after cooling to room temperature, the pressing plate material 1 was removed to obtain an information recording medium 6.

<Evaluation of core substrate sheet and information recording medium>
The core substrate sheet 6 and the information recording medium 6 were evaluated in the same manner as in Example 1. The evaluation results are summarized in Table 1.

(Example 3)
Instead of the crystalline polyester resin (Toyobo Co., Ltd .: Byron 30P) in the adhesive layer of the core substrate sheet 6 of Example 2, a crystalline polyester resin having a melting temperature of 113 ° C. (Toyobo Co., Ltd .: Byron GA-5200, crystal melting) The adhesive layer coating solution A-7 was prepared in the same manner as in Example 2 except that energy: 2.4 mJ / mg and the softening point / peak temperature ratio was 1.06). Thus, a core base sheet 7 was produced, and an information recording medium 7 was obtained using the same as in Example 2.

<Evaluation of core substrate sheet and information recording medium>
The core substrate sheet 7 and the information recording medium 7 were evaluated in the same manner as in Example 1. The evaluation results are summarized in Table 1.

Example 4
Instead of the crystalline polyester resin (Toyobo Co., Ltd .: Byron 30P) in the adhesive layer of the core substrate sheet 6 of Example 2, a crystalline polyester resin having a melting point of 100 ° C. (Toyobo Co., Ltd .: Byron GA6300, crystal melting energy: The adhesive layer coating solution A-8 was prepared in the same manner as in Example 2 except that 2.1 mJ / mg and the softening point / peak temperature ratio was 1.07). A core substrate sheet 8 was produced, and an information recording medium 8 was obtained in the same manner as in Example 2 using this.

<Evaluation of core substrate sheet and information recording medium>
The core substrate sheet 8 and the information recording medium 8 were evaluated in the same manner as in Example 1. The evaluation results are summarized in Table 1.

(Example 5)
Instead of the crystalline polyester resin (Toyobo Co., Ltd .: Byron 30P) in the adhesive layer of the core substrate sheet 6 of Example 2, a crystalline polyester resin having a melting point of 107 ° C. (Toyobo Co., Ltd .: Byron GM-920, crystal melting) The adhesive layer coating solution A-9 was prepared in the same manner as in Example 2 except that energy: 2.3 mJ / mg, and the softening point / peak temperature ratio was 1.05). Thus, a core base sheet 9 was produced, and an information recording medium 9 was obtained in the same manner as in Example 2 using this.

<Evaluation of core substrate sheet and information recording medium>
The core substrate sheet 9 and the information recording medium 9 were evaluated in the same manner as in Example 1. The evaluation results are summarized in Table 1.

(Example 6)
30 parts of crystalline polyester resin (manufactured by Toyobo Co., Ltd .: Byron GA-6400, melting point 86 ° C.) is mixed with 35 parts of methyl ethyl ketone and 35 parts of cyclohexanone as a solvent, stirred while heating to 60 ° C., and a solid content concentration of 30% A resin solution was obtained. To this resin liquid, 100 parts of crosslinked methacrylate copolymer fine particles (manufactured by Soken Chemical Co., Ltd .: MX-1000, volume average particle size: 10 μm) as fine particles and 150 parts of methyl ethyl ketone as a solvent are added and mixed, and sufficiently stirred. Then, an adhesive layer coating solution A-10 was prepared, and a core substrate sheet 10 was produced in the same manner as in Example 2 and an information recording medium 10 was obtained in the same manner as in Example 2 using this.

<Evaluation of core substrate sheet and information recording medium>
Evaluation similar to Example 1 was performed about the core base material sheet 10 and the information recording medium 10. FIG. The evaluation results are summarized in Table 1.

(Example 7)
30 parts of crystalline polyester resin (manufactured by Toyobo Co., Ltd .: Byron GA-6400, melting point 86 ° C.) is mixed with 35 parts of methyl ethyl ketone and 35 parts of cyclohexanone as a solvent, stirred while heating to 60 ° C., and a solid content concentration of 30% A resin solution was obtained. To this resin solution, 100 parts of urethane-modified polyester resin solution (Toyobo Co., Ltd .: Byron UR-2300, solid content concentration 30%), and crosslinked methacrylic acid ester copolymer fine particles (manufactured by Soken Chemical Co., Ltd .: MX-500). , 50 parts by volume average particle diameter: 5 μm), 30 parts by weight cross-linked methacrylate copolymer fine particles (manufactured by Soken Chemical Co., Ltd .: MX-3000, volume average particle diameter: 30 μm), and 200 parts methyl ethyl ketone as a solvent. After mixing and stirring sufficiently, the adhesive layer coating solution A-11 was prepared, and the core base sheet 11 was prepared in the same manner as in Example 2 and information recording was performed in the same manner as in Example 2 using this. Medium 11 was obtained.

<Evaluation of core substrate sheet and information recording medium>
The core substrate sheet 11 and the information recording medium 11 were evaluated in the same manner as in Example 1. The evaluation results are summarized in Table 1.

(Examples 8 to 14)
As a core substrate sheet, a PET film inlet sheet in which 10 IC chips and antennas are formed in A4 size is laminated with PET-G with a thickness of about 200 μm on both sides, and a total thickness of 550 μm core substrate sheet (Dai Nippon Printing) The core substrate sheets 12 to 18 were produced in the same manner as in Example 2 using the adhesive layer coating liquids used in Examples 1 to 7 on the front and back of the product. In addition, IC cards 12 to 18 as information recording media were obtained using these core substrate sheets 12 to 18 in the same manner as in Example 2.

<Evaluation of card core substrate and IC card>
Evaluation similar to Example 1 was performed about the core base material sheets 12-18 and the IC cards 12-18. The evaluation results are summarized in Table 1.

It is a schematic perspective view which shows an example of the laminate film for electrophotography of this invention.

Explanation of symbols

100 First laminated film 200 Core substrate 300 Second laminated film

Claims (6)

A core substrate;
An adhesive layer provided on at least one side of the core substrate;
A core substrate sheet having
The adhesive layer is a core substrate sheet containing at least a crystalline polyester resin having a melting point of 125 ° C. or less and fine particles having a volume average particle diameter of 5 μm to 35 μm. A core substrate sheet having a core substrate and an adhesive layer provided on at least one side of the core substrate;
An image recording body on which image information is formed bonded to the core substrate via the adhesive layer;
An information recording medium having
The adhesive layer is an information recording medium containing at least a crystalline polyester resin having a melting point of 125 ° C. or less and fine particles having a volume average particle diameter of 5 μm to 35 μm.   The information recording medium according to claim 2, wherein the image information is a toner image formed by electrophotography. A core substrate sheet having a core substrate and an adhesive layer provided on at least one surface of the core substrate, and an image recording body on which image information is formed, which is adhered to the core substrate via the adhesive layer And the adhesive layer comprises at least a crystalline polyester resin having a melting point of 125 ° C. or lower and fine particles having a volume average particle diameter of 5 μm to 35 μm,
An image forming step of forming image information on the image recording body;
A laminating step in which the image recording body on which image information is formed is thermocompression-bonded to the core substrate via the adhesive layer;
Manufacturing method of information recording medium having The image information is formed as a mirror image on the transparent image recording body,
The method for producing an information recording medium according to claim 4, wherein the surface of the image recording body on which the image information is formed and the pressure-sensitive adhesive layer of the core base sheet are heat-pressed.   The method of manufacturing an information recording medium according to claim 4, wherein the image information is a toner image formed by electrophotography.

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