WO2006038438A2 - Materiau d'enregistrement thermique reversible, et support de communication comportant une couche d'affichage et un materiau d'enregistrement - Google Patents

Materiau d'enregistrement thermique reversible, et support de communication comportant une couche d'affichage et un materiau d'enregistrement Download PDF

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Publication number
WO2006038438A2
WO2006038438A2 PCT/JP2005/016832 JP2005016832W WO2006038438A2 WO 2006038438 A2 WO2006038438 A2 WO 2006038438A2 JP 2005016832 W JP2005016832 W JP 2005016832W WO 2006038438 A2 WO2006038438 A2 WO 2006038438A2
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WIPO (PCT)
Prior art keywords
layer
display
communication medium
adhesive layer
recording material
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PCT/JP2005/016832
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English (en)
Japanese (ja)
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WO2006038438A1 (fr
WO2006038438A3 (fr
Inventor
Yasuhiro Monobe
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Oji Paper Co
Yasuhiro Monobe
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Application filed by Oji Paper Co, Yasuhiro Monobe filed Critical Oji Paper Co
Priority to JP2006539204A priority Critical patent/JPWO2006038438A1/ja
Publication of WO2006038438A1 publication Critical patent/WO2006038438A1/fr
Publication of WO2006038438A2 publication Critical patent/WO2006038438A2/fr
Publication of WO2006038438A3 publication Critical patent/WO2006038438A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating

Definitions

  • Reversible thermosensitive recording medium communication medium having display layer, and recording medium
  • the present invention relates to a reversible thermosensitive recording material capable of repeatedly displaying a colored state and a decolored state reversibly by heat.
  • the present invention also relates to a communication medium having printability equipped with RFID (Radio Frequency Identification).
  • RFID Radio Frequency Identification
  • the present invention relates to a recording body excellent in recording properties and difficult to bend and wrinkled, and further to a recording body containing an identification tag.
  • Display media that can replace paper include cathode ray tube monitors such as personal computers and liquid crystal panels.
  • electronic devices such as electronic paper using liquid crystal systems and electrophoresis have been proposed.
  • thermosensitive recording media capable of recording and erasing by heat have come to be put into practical use as promising candidates because of their listability, flexibility, and texture close to those of paper.
  • thermosensitive recording medium has been mounted on a magnetic card and used to display a store point in a chain store.
  • non-contact IC cards for reuse-type commuter passes are mounted on lift tickets at ski fields and used to display expiration dates.
  • these are relatively hard media limited to the shape of a card, and it has been thought that it would be sufficient if it could be reused several tens of times.
  • display medium for paper it is generally required to have a larger size than A6, which is more flexible. Folding, which is almost a problem with card size, Deformation has occurred and has emerged as a practical durability issue.
  • Patent Document 2 introduces that the thermal support recording layer and the heating body for heat application are improved by an elastic layer having a rubber elasticity of 0.2 to 20 microns having a rubber elasticity on the support. Regarding the print quality, it is disclosed that the quality is improved if the adhesion is improved.
  • Patent Document 3 proposes a reversible thermosensitive recording medium characterized by providing one or more elastic layers, each of which has a rubber elastic polymer as a main component, separate from the support. It has been done. This is intended to improve the reproducibility failure based on the poor adhesion between the heat-sensitive recording layer and the heating body for applying heat, and to obtain a clear image with good reproducibility and a sufficiently decolored state over a long period of time. It is.
  • the force of laminating a 100mm polyester film with a 5mm and 20mm elastic layer is not possible with this combination to prevent the penetration of flaws during cleaning and the prevention of folding-type penetration. This is not supposed to be a countermeasure against reprinting or deformation on the crease.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-294073 (Claim 1 and others)
  • Patent Document 2 JP-A-5-221152
  • Patent Document 3 Japanese Patent Laid-Open No. 2001-130135
  • a bar code is an information on the arrangement state of images (bars), and the information can be read with a dedicated bar code reader. For this reason, for example, product management and physical distribution management are performed by attaching a barcode displaying product information to the product.
  • a large amount of information is stored in a semiconductor (IC) chip, and a planar antenna that transmits and receives information is connected to the IC chip.
  • IC semiconductor
  • a planar antenna that transmits and receives information is connected to the IC chip.
  • the stored information of the internal IC chip is transmitted to the reader via the antenna according to the radio wave.
  • update information from the reader It is sent to the IC chip via the antenna, and the information stored in the IC chip is updated (hereinafter referred to as the “IC inlet”).
  • An IC inlet serving as a communication medium is first put into practical use as an IC card.
  • an IC card in which the IC module is held in a hard plastic is manufactured by sandwiching the IC inlet with a plastic film or the like and performing appropriate thermocompression bonding.
  • the IC card is provided to the user's mobile phone as appropriate, for example, as an employee ID card.
  • the IC card is used for personal authentication, etc.-and the information stored in the IC chip of the IC card issued to the individual is appropriately rewritten and used.
  • Information on the card face displayed on the IC card When printed and displayed, there is little rewriting.
  • IC chips used in IC cards are often reinforced to cope with external stresses to protect information.
  • IC tags used for merchandise management, logistics management, etc. are inserted into a box or pasted by attaching the IC inlet to a film or synthetic paper or paper to form a label. used.
  • Internal information is read by a reader / writer, abbreviated as RZW, and rewritten as necessary.
  • RZW a reader / writer
  • the IC chip in the IC tag has the same record and display on the bill surface, and the information is printed on the display layer and simultaneously the information is written on the IC chip.
  • IC tags have a large area and become large.
  • sticky labels have been proposed. Because these IC tags are printed, the printed display cannot be rewritten, so they are usually disposable and inexpensive. Therefore, they are often used without reinforcing the chip. Recently, however, recycling has been screaming, and media that can be used any number of times have been considered.
  • various reversible thermosensitive recording media capable of recording and erasing by heat are attracting attention and are being put into practical use. By using these reversible thermosensitive recording media for the display layer, the display layer display can be rewritten any number of times. In order to effectively use the rewritable performance of the IC chip 100,000 times, such a combination has been studied.
  • thermosensitive recording media are being put into practical use for office applications such as medical records, field instructions in factories and logistics, and kanban. It can be used only about tens of times due to dirt, deformation, breakage, etc. that occur during actual use even though it is supposed to be 500 to 1000 times. However, it was divided.
  • Patent Document 4 discloses a relatively soft color display body in which a specific base material and a holding layer are combined.
  • a flexible display body is obtained by using a soft base material on one side, and such a display body is considered to be effective against deformation and breakage.
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2004-226488
  • dirt is also generated when handling with dirty hands, adhering to the surface of water or oil, adhering dust due to static electricity, or using in an oil atmosphere.
  • instructions are handled by work gloves with oil on them, resulting in partial oil contamination.
  • oil stains penetration into the media occurred, causing the media to swell and curl or partially swell, indicating that printing characteristics are likely to deteriorate and jamming is likely to occur inside the printer.
  • office applications such as medical records, it is used in a relatively clean and mild environment, so there are relatively few inconveniences.
  • it is used in a relatively clean and mild environment, so there are relatively few inconveniences.
  • it is used in a relatively clean and mild environment, so there are relatively few inconveniences.
  • the thermal head or transport roller in the printer Since the dirt is re-transferred to the next medium surface, the contamination will spread to other media.
  • cleaning When using a large amount of media, it is difficult to determine whether the media is dirty or not. The cleaning will be repeated regularly. Although it depends on the dirt adhering to the medium, cleaning can be divided into a case where it is performed every time after use and a case where it is periodically performed according to a predetermined number of uses.
  • This cleaning process itself is one of the causes of media deformation, so we investigated the effective methods for extending the media life.
  • the cleaning time is delayed, it becomes easy to saturate the medium, and it has become a major obstacle to introducing a reversible thermosensitive recording medium with a short medium life as an alternative to paper.
  • the medium in order to meet the potential life of a reversible thermosensitive recording layer, which is said to be able to withstand reuse of 500 times, the medium may be deformed or washed by oil, chemicals, etc. assumed for factory use. The purpose is to improve the resistance to bending, rubbing, and deformation.
  • an IC tag or the like that uses a reversible thermosensitive recording layer used in the process management or distribution management as a display layer is likely to be used tens or hundreds of times.
  • the environment in which it is used is likely to be stressed by the chip.
  • the IC chip is not reinforced, the reliability of the medium will be reduced, and the IC chip that cannot withstand daily use may be broken. To prevent this, it is necessary to reinforce the IC chip.
  • the reinforcement of an IC chip is often performed by bonding a metal plate to the IC chip with an adhesive.
  • thermosensitive recording medium for the display layer
  • various stresses such as stress on the IC chip in the transport path and stress applied to the IC chip by the print head are generated, and it is necessary to consider the protection of the IC chip.
  • cards and IC tags that are soft and flexible like paper are proposed.
  • the printer transport path even if the media is large, can have a compact design, space can be used effectively, and even if the transport path is twisted. Economical.
  • the IC chip becomes more susceptible to pressure on the transport path.
  • Patent Document 4 discloses a relatively soft display body in which a specific base material and a holding layer are combined. By using a soft base material on one side, a flexible display is obtained. Among them, it is also disclosed that an identification tag is built in the display body. However, this document does not give any specific reinforcement to the IC chip, and it is highly likely that the IC chip will be damaged when stress is applied to the chip. In other words, it may be necessary to reinforce the IC chip depending on how many times it is used and depending on the environment in which it is used.
  • the present inventors have tried to reinforce the IC or the like when the IC tag is built in the display itself. If a reinforcing plate is used to reinforce a hard card such as an IC card, the way the bending of the reinforcing plate and the medium differs depending on the contact between the transport path and the print head, or when performing contact printing such as thermal printing, It was discovered that there was a problem that printing could not be done cleanly due to unevenness in the thermal head for printing. Among these, the platen roll and supply roll opposite the printing section perform printing clearly in such a situation, so that a certain amount of pressure is applied and the medium is pressed against the head.
  • the printed bar code and merchandise management items can be faulty, resulting in trouble with merchandise management.
  • the present invention provides a communication medium that has an IC chip built therein, is strong against external stress, and has excellent printability even when the IC chip has a recording layer. It is aimed.
  • the present inventors have found that a commercially available mesh cloth such as a polyester fiber or a nylon fiber is used as a material positioned on the surface side.
  • the inventors have found that curling of the recording material can be effectively prevented by reducing the difference in linear expansion coefficient from the material located on the back surface side, thus completing the present invention.
  • a reversible thermosensitive recording material comprises (1) a display substrate mainly comprising polyethylene terephthalate (PET) having a reversible thermosensitive recording layer, and (2) polybutylene terephthalate (PBT). Mainly polyester elastomers with node segments, polyester elastomers with aliphatic polyester as soft segment, or polyester elastomers with polybutylene naphthalate (PBN) as node segments and aliphatic polyester or aliphatic diol as soft segments.
  • a support as a component; and (3) an adhesive layer for bonding the display substrate and the support.
  • volume swelling ratio A when immersed in the machine oil of the display substrate and the volume swelling ratio B when immersed in the machine oil of the support is within IB-AI force. It is preferable because it is difficult to warp!
  • the display substrate has a tensile modulus of 2000 MPa or more and a volume swelling ratio of 2% or less when immersed in machine oil.
  • the soft segment of the support is PBT
  • the soft segment is poly-force prolacton (PCL)
  • the hard segment is PBN
  • the soft segment is PCL or polytetramethylene ether glycol (PTMG). It is preferable because it has excellent oil resistance and can be used as a reversible thermosensitive recording material for a long period of time and has excellent reusability.
  • the entire elastomer is softened and the tensile elastic modulus can be adjusted, which is preferable.
  • the second polyester resin has at least an aromatic dicarboxylic acid and a diol having 5 or more carbon atoms.
  • the aromatic dicarboxylic acid power of the second polyester resin is more preferably phthalic acid or isophthalic acid in terms of the adjustment as described above.
  • thermosensitive recording body with RFID Since at least an identification tag including RFID or the like can be held in the adhesive layer, a reversible thermosensitive recording body with RFID can be easily obtained.
  • a communication medium comprises a display substrate and a display member comprising a display layer on the display substrate;
  • An IC inlet mounted with an IC chip to which a reinforcing plate meeting the following mechanical conditions is disposed, which is disposed on the display substrate side of the display member;
  • a holding layer disposed on the side of the IC chip covering the IC inlet
  • the deflection in the three-point bending test of the test method is 3 mm or more when the load is 0.2 N with a distance between fulcrums of 50 mm.
  • the holding layer may be formed of a holding layer adhesive layer.
  • the holding layer is composed of an adhesive layer for holding layer support and a holding layer support.
  • the holding layer support is a fiber-containing layer.
  • the reinforcing plate resin that joins the reinforcing plate and the IC chip has a flexural modulus of 10 to 2000 MPa and an adhesive strength of 1 N or more, defects may occur during printing. More preferable.
  • the display layer is a thermosensitive recording layer. Furthermore, if the holding layer has a flexural modulus of 10 to LOOOMPa, it is preferable to maintain good printability if an ordinary display member is used.
  • the recording body of the present invention is a recording body capable of preventing the occurrence of curling due to a change in ambient temperature.
  • the recording body includes a display layer provided with a recording layer on one surface of a substrate.
  • An anti-curl layer provided on the other surface side of the base material in the display layer, and the anti-curl layer is provided on the adhesive layer located on the base material side and the adhesive layer.
  • the ratio of the linear expansion coefficient is 5: 1 to 1: 5, and the force is at least one of the adhesive layer and the holding layer in the storage elastic modulus according to JIS K 7244-1998.
  • the storage elastic modulus is 0.01 to 1.5 GPa.
  • the present invention is also characterized in that, in the recording medium having the above-described characteristics, the anti-curl layer includes a mesh cloth having an open structure.
  • the present invention is characterized in that, in the recording medium having the above-mentioned characteristics, the base material is a polyester biaxially stretched film having a storage elastic modulus of 4 GPa or more in the display layer.
  • the present invention is characterized in that in the recording medium having the above-described characteristics, the mesh cloth force is inherent in the holding layer.
  • the present invention is also characterized in that, in the recording medium having the above-described characteristics, the mesh cloth is present in the adhesive layer.
  • the present invention is a recording body capable of preventing the occurrence of curling, the recording body comprising a display layer provided with a recording layer on one surface of a polyethylene terephthalate film substrate; An anti-curl layer provided on the other surface side of the base material in the display layer, and the anti-curl layer is laminated on the adhesive layer located on the base material side and the adhesive layer
  • a mesh cloth is present in the retaining layer. At this time, the mesh cloth preferably has an open structure in the range of 0.5 mm to 20 mm.
  • the present invention is characterized in that the display layer is a reversible thermosensitive recording layer.
  • the present invention is characterized in that in the recording medium having the above-described characteristics, an identification tag is disposed at least in the adhesive layer.
  • thermosensitive recording material of the present invention With the reversible thermosensitive recording material of the present invention, a recording material excellent in oil resistance, durability at the time of washing, etc., and excellent in reusability can be obtained.
  • the communication medium of the present invention is strong against external stress even if the IC chip is built in, and is excellent in printability even when a recording layer is provided in a part where the IC chip is located.
  • the recording material of the present invention is a recording material that hardly curls even when the temperature changes.
  • FIG. 1 is a cross-sectional view showing an example of a reversible thermosensitive recording material of the present invention.
  • FIG. 2 is a cross-sectional view showing another example of the reversible thermosensitive recording material of the present invention.
  • FIG. 3 is a sectional view of Example 5 as an example of the communication medium of the present invention.
  • FIG. 4 is a cross-sectional view of an IC inlet.
  • FIG. 5 is a sectional view of Example 6 as an example of the communication medium of the present invention.
  • FIG. 6 is a sectional view of Example 7 as an example of the communication medium of the present invention.
  • FIG. 7 is a cross-sectional view of a first example of the recording material of the present invention.
  • FIG. 8 is a cross-sectional view of a second example of the recording material of the present invention.
  • FIG. 9 is a cross-sectional view of a third example of the recording material of the present invention.
  • FIG. 10 is a cross-sectional view of a fourth example of the recording medium of the present invention.
  • FIG. 11 is a cross-sectional view of an IC inlet.
  • FIG. 12 is a sectional view of a fifth example of the recording medium of the present invention.
  • FIG. 1 is a sectional view of an example of the reversible thermosensitive recording material of the present invention.
  • the reversible thermosensitive recording material of the present invention is mainly composed of a display substrate la and a support lc that supports the display substrate la and an adhesive layer 1 It is composed!
  • the reversible thermosensitive recording layer is a display device using a thermosensitive dye, a polymer, or magnetic particles.
  • a deviation can be used as long as the two react to cause coloration.
  • the thermorewrite type thermal rewrite layer is also suitable for reuse.
  • the thermolite recording layer is a display device using a thermosensitive dye, polymer, or magnetic particles.
  • a leuco dye and a reversible developer are melt-mixed to form a PET (polyethylene telephoto) substrate.
  • the reversible thermosensitive recording medium is provided with a layer such as an overcoat layer, a protective layer, an ultraviolet absorbing layer, and an anchor layer in addition to the recording layer on the display substrate.
  • the support is softened.
  • Various types of soft base materials that can be used for the support can include various materials. Elastomers can be used to achieve uniform performance.
  • Oil stains were divided into two cases: partial adhesion and full adhesion.
  • partial adhesion occurs, the part where the oil adheres receives oil penetration and begins to swell.
  • the part where the oil is not attached is not swollen, only the swollen part is swollen and becomes a hump.
  • the permeated oil takes time to volatilize, so keep it as it is. Even if the surface is wiped off or cleaned, the hump does not become small. As a result, jamming occurs in the transport path for printing, and printing precision is lost, resulting in poor printing.
  • the difference in the swelling rate between the display substrate and the support exceeds 2%, large warpage may occur, or jamming may occur in the transport path for printing immediately, or it may become cylindrical, and printing may not be possible. . For this reason, it was found that the difference in swelling rate should be within 2%.
  • thermosensitive recording media are often provided with a thermosensitive recording layer and an overcoat layer, protective layer, ultraviolet absorption layer, anchor layer, etc. on the display substrate. , Need to layer.
  • the display base material is resistant to heat and ultraviolet rays in order to prevent the base material from extending during processing, and requires high tensile strength, that is, high tensile elastic modulus.
  • the tensile elastic modulus is measured according to ISK7113-1995.
  • the recording layer, overcoat layer, protective layer, UV absorption layer, and anchor layer paints can be diluted with solvents, aqueous solutions, emulsions, etc.
  • the drying temperature during coating is about 120 ° C
  • the heat resistance of the display substrate may be about 120 ° C.
  • a tensile modulus of 2000 MPa or more is generally considered appropriate for such coating. Note that if it exceeds 8000 MPa, the material is too hard, so if it is bent like a crease, it will not break or is too hard. In particular, if a display substrate with high heat resistance and high strength, which has higher heat resistance and tensile modulus than necessary, is selected, it becomes very expensive and is not suitable for practical use.
  • Display substrates include fine paper, art paper, coated paper, cast-coated paper, kraft paper, polyethylene laminate paper, impregnated paper, foamed paper, polyolefins (eg, polyethylene, polypropylene, etc.), polysalt ⁇ Bull (for example, soft poly vinyl chloride, rigid polyvinyl chloride), polyester (for example, polyethylene terephthalate, modified polyethylene terephthalate (commercialized as PET-G), etc.), polyethylene naphthalate, poly Strength-A film composed mainly of a single resin such as sulfonate, polystyrene, polyurethane, and cellophane, a composite, a mixture of copolymers, etc., a foamed film in which a foaming agent is blended and foamed, and the resin.
  • polyolefins eg, polyethylene, polypropylene, etc.
  • polysalt ⁇ Bull for example, soft poly vinyl chloride, rigid polyvinyl chloride
  • polyester for example,
  • Films such as porous films in which voids are formed by blending inorganic pigments and organic pigments , Or synthetic paper such Ya nonwoven acids, and the like further laminated sheet was if attached them.
  • a biaxially stretched polyester film excellent in thermal dimensional stability is suitable.
  • a film with high crystallinity such as oriented polypropylene (OPP) or PET having a high tensile elastic modulus is often used among the display substrates.
  • OPP is weaker than PET, and generally PET is often used.
  • PET is made by biaxially stretching molten polyester resin.
  • the "swelling in oil test” shows that the swelling rate is 2% or less, and the tensile modulus is 2000MPa or more.
  • a layer having a tensile elastic modulus lower than the tensile elastic modulus of the display substrate is selected and combined with one reversible thermosensitive recording medium.
  • a reversible thermosensitive recording material it becomes easy to bend, and a layer with a low tensile elastic modulus has a property of extending with respect to stress compared with a layer with a high tensile elastic modulus.
  • the recording body is bent so as to have a crease at 180 degrees, for example, it has become easy to restore. Therefore, it was possible to control how external stress was applied by combining layers with different tensile moduli when constructing a reversible thermosensitive recording material.
  • the proportion of the tensile modulus of the support is suitably 25% or less of the tensile modulus of the display substrate. When the ratio of the tensile modulus of the support exceeds 25%, the effect is recognized but not so large. Further, if it exceeds 50%, the difference from the tensile modulus of elasticity with the display base material is difficult to obtain, and a surplus effect cannot be obtained.
  • the lower limit of the ratio of tensile strength of the support is required to be 1% or more. If it is less than 1%, the tensile modulus of the display substrate that is actually considered to be used is about several thousand. Even if it bends with eyes, it is difficult to restore.
  • a "folded crease spot printability test” was established in order to evaluate the printability, including the effect of wrinkles remaining with such bendability. This is done by bending the reversible thermosensitive recording body into the press machine so that it does not fold before pressing, applying a load of 49N (5kgf), creating a crease, and releasing the pressure after 30 seconds. This is an evaluation sample.
  • a printing test was conducted on a sample left for 1 hour after the pressure was released using a thermal printer (PR31 printer for rewriting manufactured by Sanwa-Utec). The sample was folded so that it could pass through the printer and returned to a flat state due to poor resilience. The sample was flattened manually to prepare a sample for this evaluation test.
  • Bar codes were printed with a thermal printer, including the bent parts of the sample, and the missing or reproducible prints were evaluated. Bar code can be read ⁇ , bar code can not be read, but characters can be read ⁇ , bar code and characters can not be read The one was rated as X. The barcode was read with a WELCAT barcode reader RHT-100-01.
  • the support has a property of expanding and contracting, has a relatively low tensile elastic modulus, and an elastomer is considered as a material having a low oil expansion rate and a high oil resistance.
  • the main components are styrene elastomers, olefin elastomers, polyamide elastomers, urethane elastomers, polyester elastomers, etc., among which polyester elastomers are excellent in heat resistance and the like. Yes.
  • polyester-based elastomers mainly from hard segments of aromatic polyesters such as polybutylene terephthalate (PBT) and polybutylene naphthalate (PBN) and soft segments such as aliphatic polyesters and aliphatic diols.
  • PBT polybutylene terephthalate
  • PBN polybutylene naphthalate
  • soft segments such as aliphatic polyesters and aliphatic diols.
  • a polyester block copolymer of polyester constituted by selecting “mainly” PBT as the hard segment and selecting “mainly” one of the aliphatic polyesters, such as polystrength prolatatone, as the soft segment.
  • the term “mainly” as used herein means a component having a weight ratio of 80% or more, and some impurities or by-products during synthesis may be present.
  • the PBT was specified as “main” PBT as the hard segment, and the poly force prolataton (PCL) was used as the soft segment, it was explained earlier that oil swelling hardly occurs.
  • the soft segment may be combined with the aliphatic polyester in the same manner as described above, as the hard segment and the polyester bond. In this case, a higher tensile modulus can be obtained than with PBT.
  • aliphatic glycols and aliphatic diols such as polytetramethylene ether glycol (PTMG) that will have a polyether bond can be combined as a soft segment. Oil resistance can be obtained. In this case, essentially, the polyester bond is superior in oil resistance and superior to the polyether bond.
  • PBN is better in oil resistance than PBT in terms of material, so that even if it is a polyether bond, sufficient oil resistance can be obtained when combined with PBN.
  • PBN is selected as the hard segment of the polyester elastomer, and PCL and PTMG are combined as the soft segment. It is very suitable for such tests.
  • PBT or PBN is used as the hard segment of a polyester elastomer, the elastomer tends to be hard as a whole due to its crystallinity. Therefore, it may be useful to adjust the tensile modulus by softening the entire elastomer by the following method. This method can be softened by adding a second polyester resin, which is completely different from the above-mentioned polyester elastomer, especially phthalic acid, isophthalic acid and diol power of 5 or more carbon atoms.
  • polyester resin increases the oil resistance.
  • the amount of added calories of the second polyester resin is appropriate between 5% and 70% of the first polyester resin, and if the upper limit of the range is exceeded, the characteristics of the first polyester elastomer will be manifested. become. If the lower limit is not reached, almost no effect will be seen.
  • the polyester elastomer that is the main component of the support is also called polyester resin in a broad sense. Therefore, it is also the power that considered this as the first polyester resin.
  • the adhesive layer is a layer that joins the display base and the support having different tensile elastic moduli.
  • an adhesive, a pressure-sensitive adhesive, a thermoplastic film, or the like that can be bonded firmly to the display substrate and the support can be considered as the adhesive layer.
  • the material of the adhesive layer include, for example, vinyl acetate resin, chlorinated resin, acrylic resin, olefin resin, gen resin resin, natural rubber, gelatin, eucalyptus, abietic resin, and cellulose derivative resin.
  • polyester-based resin modified polyester-based resin, epoxy resin, burpetylal resin, polyurethane-based resin, polyamide-based resin, alkyd resin, melamine-based resin, urea-based resin, phenolic formalin
  • polyurethane-based resin polyamide-based resin
  • alkyd resin alkyd resin
  • melamine-based resin urea-based resin
  • phenolic formalin There are single, mixture, copolymer, etc., such as system resin, petroleum resin, and maleic acid copolymer.
  • Materials to be added to the adhesive or pressure-sensitive adhesive or thermoplastic film include dispersants, thickeners, fats and oils, cross-linking agents, curing agents, plasticizers, mold release materials, antioxidants, stabilizers, and UV absorbers. Agents, stilts, foamed particles, conductive agents, fiber fillers, rubber-like particles, colored pigments, opaquers, catalysts, etc. are appropriately used within the range where the insulating properties are not impaired.
  • the volume resistivity should be 10 12 ⁇ ⁇ or higher.
  • curing agent within the range in which adhesion
  • the cross-linking reaction proceeds after bonding due to moisture in the air, and moisture-curing urethane resin containing isocyanate groups obtained by delaying the required hardness in time provides sufficient fluidity for bonding. It is preferably used because it can be cured over time to obtain the required strength.
  • partially spray the curing agent The method of using and strengthening only a specific part is also used.
  • thermoplastic film may be used alone or as a mixture, and hot melt coating, water-based or solvent-based coating may be performed, and if necessary, hot air drying may be performed to obtain a film-like thermoplastic film.
  • the coating amount depends on the final thickness of the target display, but is usually 10 to 700 gZm 2 in dry weight and 5 to: LOOO / zm in thickness.
  • the glass transition point (TG) is suitably in the range of ⁇ 50 ° C. to 100 ° C.
  • polyurethane-based resin polyurethane-based resin
  • polyester-based resin adhesive moisture-curing hot melt (PUR: polyurethane reactive) adhesive or polyester-based hot melt adhesive
  • epoxy it is preferable to use rosin or the like because high adhesive force can be stably obtained even in oil.
  • Adhesive strength is appropriate as long as the display substrate and the support are pulled at 180 ° and either the display substrate or the support breaks, and the strength is 6 NZcm or more.
  • elastic epoxy resin bonding is performed because RFID can be easily embedded. It is preferable to use an agent, a hot melt adhesive or the like.
  • the present invention needs to increase the durability of the medium itself in order to give the reusable thermosensitive recording medium 500 times as much as possible, that is, to provide long-term reuse. In other words, it provides resistance to oil resistance and deformation such as bending and bending during cleaning. To that end, it is important to give specific oil resistance and elastic properties to the entire reversible thermosensitive recording material, and the oil resistance test, cleaning test, and crease spot printing described above for its physical properties. It was found that it satisfies the sex test.
  • FIG. 3 is a cross-sectional view of a first example of the communication medium of the present invention.
  • the base member 3b having the display layer 3a constitutes the display member 3s.
  • the holding layer adhesive layer 3c sandwiches the IC inlet 3d between the base material 3b and adheres to them to support them.
  • the adhesive layer 3c for the holding layer corresponds to the holding layer of claim 10.
  • Fig. 4 is a cross-sectional view of the IC inlet. It has antennas 4a and 4b formed on the insulating sheet 4, Since the antenna 4b is a spiral antenna, several cross sections appear in the drawing.
  • An IC chip 4e is electrically connected on the antenna.
  • the IC chip 4e has a reinforcing plate 4g bonded with a reinforcing resin 4f.
  • the antennas 4a and 4b are electrically joined up and down by through holes 4h.
  • FIG. 5 is a cross-sectional view of a second example of the communication medium of the present invention.
  • a display member 5s is constituted by a base material 5b having a display layer 5a. These display layer, base material, and display member are the same members as in FIG.
  • a communication medium is constituted by the adhesive layer 5c for the supporting member for the supporting layer for supporting the base material 5b, the IC inlet 3d and the supporting layer supporting member 5g which are included therein.
  • the IC inlet 3d exists so as to be sandwiched between the base material 5b and the adhesive layer 5c for the support for the holding layer.
  • the laminate of the adhesive layer 5c for the support for the support layer and the support layer support 5g corresponds to the support layer of claim 10.
  • FIG. 6 is a cross-sectional view of a third example of the communication medium of the present invention.
  • a display member 6s is constituted by a base material 6b having a display layer 6a. These display layer, base material, and display member are the same members as in FIG.
  • a communication medium is configured by the holding layer support adhesive layer 6c for supporting the base material 6b, the IC inlet 3d and the fiber-containing layer 6h included therein.
  • the IC inlet 3d exists so as to be sandwiched between the substrate 6b and the fiber-containing layer 6h.
  • the fiber-containing layer 6h is a kind of holding layer support 5g in FIG. In the example of this figure, the lamination of the adhesive layer 5c for the support for the support layer and the fiber-containing layer 6h corresponds to the support layer of Claim 10.
  • the bending elastic modulus of the communication medium of the present invention is preferably from lOOMPa to 2000 MPa. If the communication medium has an elastic modulus of less than lOOMPa, although it depends on the thickness, it will be handled because there is no flexibility in handling the communication medium by hand. Also, if it exceeds 2000MPa, the conveyance path of the printer etc. must be straightened, and the media will be bent, so it will be easy to scratch and wrinkle when used repeatedly and use repeatedly. This is likely to be unsuitable for the purpose of use.
  • the bending elastic modulus of the communication medium is measured with reference to the three-point bending test of the plastic bending property test method of JIS K 7171-1994.
  • Distance between fulcrum for communication medium 50 A 3-point bending test was performed at a speed of 5 mm / min using a specified indenter on a measuring support table of mm, and the flexural modulus was measured between two points with a deflection distance of 2 mm to 5 mm. If there is a difference in the measured values depending on the orientation of the front and back sides, the average of both is V as the flexural modulus. In particular, if the conditions are described! /, In this case, all the tests were performed under the same conditions.
  • the flexural modulus is obtained by the following equation.
  • Flexural modulus (cube distance cubed x load) / (4 x specimen width x thickness cubed x strain)
  • the above formula force Since it is inversely proportional, even if it has the same elastic modulus, if the thickness changes, the strain will also differ. Even if the same force is applied, the thinner the film, the better the distortion.
  • the softness of the communication medium is almost determined by the thickness of the base material and the holding layer and the flexural modulus.
  • the IC inlet that goes inside also has an effect, but the area can be made relatively small, and if the area is less than 30% of the surface area of the communication medium, the effect is small. In the case of 30% or more, the thickness and material of the substrate of the IC inlet are affected.
  • the flexural modulus of the inlet base material is relatively high, a soft communication medium can be obtained by using a thin inlet base material. If the inlet base material is soft, a relatively thick inlet base material can also be used.
  • the holding layer holds RFID and needs to have a certain thickness
  • a material having a lower bending elastic modulus than the inlet base material is used for the communication medium. It is considered important in determining softness.
  • the total thickness of the communication medium is preferably about 100 m to 2 mm. If it is less than 100 ⁇ m, it will be difficult to incorporate RFID. Even with a bending elasticity of 2000 MPa, the waist becomes too weak and the handling becomes worse. If the thickness exceeds 2 mm, the waist becomes strong and it is difficult to bend even if the elastic modulus is lOOMPa. In addition, there is no inconvenience when using a single sheet, but when many sheets are used, for example, when they are stacked and stocked, they are inconvenient because they cannot be stocked in small amounts when printing or reading / writing to IC chips. It is.
  • Printers that print or communicate on communication media often have a print head for printing and an RZW for communication. Furthermore, with heat-sensitive reversible printing communication media, In order to perform erasing and printing, it is convenient to have an erasing roll, a print head, and a cooling device in the same transport path. However, such a structure tends to require a longer transport path, which often requires more space for managing the temperature of the communication medium.
  • the printer transport path is preferably a straight transport path, but such a mechanism is a large device and requires a large space for installation, which may cause space problems. Therefore, the space can be reduced by bending the conveyance path and forming a bent conveyance path.
  • the RZW is a device that reads and writes information in the IC chip. Even a reader that simply reads can be sufficient. RZW always emits radio waves, and if there is a communication medium including IC inlet in the communication range of a certain strength, the communication medium can obtain power by this radio wave and send a response signal back to RZW for communication. Begins. The output of this radio wave is regulated by the standard, and it is necessary to devise ways to efficiently communicate with communication media. RZW is divided into an antenna unit that communicates with a communication medium and a main body that commands, controls, and analyzes the communication. Furthermore, it is possible to connect the main body with a shoe LAN or wireless communication.
  • the communication medium is often pressed by a platen roll in the conveyance path against the thermal print head for printing.
  • the transport path is angled with the platen roll at the top.
  • the more parts that are in contact with the platen roll the more the transport path is angled.
  • the more the part of the communication medium that the platen roll has a smaller diameter is in contact with the more the communication medium is bent and conveyed.
  • a large platen roll with a diameter of about 5 to 40 mm is used to make the printer smaller than practical.
  • the diameter of the platen roll is preferably 10 to 30 mm. Printing can be performed without adversely affecting the communication medium by setting the angle formed by the portion where the communication medium is wound around the platen roll to be in contact with it to about 5 to 30 °.
  • the communication medium of the present invention is a platen roll having the above dimensions, that is, a diameter of 10 to 30 mm, and is designed so that printing can be performed satisfactorily at a winding angle of about 5 to 30 °. .
  • the printer has a space-saving printer with a curved surface. Conveying rollers and platen rolls with a diameter of 15 to 25 mm are installed, and the print head is at an angle of about 10 to 20 ° to improve contact.
  • an insulating sheet having a thickness of 20 to LOO ⁇ m such as polyethylene terephthalate, polyethylene naphthalate, glycol-modified polyester, polypropylene, and polyethylene
  • Printed using conductive ink etc. on an insulating sheet such as an antenna or polyethylene terephthalate, polypropylene, polyethylene, etc., or a plate antenna with a metal such as copper or aluminum deposited on it.
  • the thickness of the antenna is preferably 40 to 80 ⁇ m.
  • various IC chips are mounted on the antenna as data storage and Z or calculation units.
  • the IC chip to be mounted is about 0.2 mm square to 5 mm square, and the thickness is 0.05 mm force and 0.5 mm thick.
  • the larger the force coil the longer the communication distance.
  • a system that can communicate with IC chips is read as RFID, and can communicate individual product information and distribution information.
  • the reinforcing plate is protected by bonding it to the IC chip with a reinforcing grease.
  • the reinforcing plate is preferably a metal plate, and a thicker plate is more robust against external stress.
  • the reinforcing adhesive is preferably strongly bonded to a stiff reinforcing plate.
  • the reinforcing plate of the IC chip is hard or thick, and if there is a soft adhesive layer or holding layer on the opposite side of the display layer, only the portion of the reinforcing plate has a different elastic modulus, and the bending force Therefore, when performing contact printing such as thermal printing, the When the pressure on the ten-roll was increased, the reinforcing plate did not bend like the surrounding members, so it was found that there was a phenomenon that the print head hit only that part and the print could not be printed cleanly. The bending and strain with respect to the stress of the reinforcing plate varies depending on the elastic modulus, thickness, and size of the reinforcing plate.
  • Test conditions Test speed lmm / min, Distance between fulcrums: 50mm, Test piece: Length 100mm, Width 10mm
  • the reinforcing plate having a thickness of 50 ⁇ m is approximately when the distance between fulcrums is 50 mm when a weight of 0.2 N is applied. I bent 5mm. If this is 100 m thick, it will bend only about 3 mm.
  • the communication medium of Example 1 described later was found to have a deflection of about 3 mm when a 0.2 N load was applied under the same conditions. This communication medium can be printed clearly even in places where there are reinforcing plates. The communication medium bends in the printer.
  • the reinforcing plate can be bent to the same extent, it can be presumed that it can be printed clearly. In other words, if the degree of deflection of the reinforcing plate is greater than the degree of deflection of the communication medium at the time of printing, it is considered that there will be no problem in printing.
  • the degree of the above-described deflection of the communication medium is such that the communication medium retains the bending elastic modulus in the above-described range within the thickness range described above, and is flexible under the bending condition. Almost, it was about 2-6mm in the measurement of surface force. If the communication medium bends when it is actually transported and printed by a printer, etc., it is considered that the reinforcement plate should be soft enough to bend more than the deflection of the communication medium at that time. The amount of deflection should be 3mm or more.
  • the deflection amount be equal to or greater than the deflection amount when the communication medium is conveyed by a printer or the like.
  • the thickness of the reinforcing plate is 30-100 m. If the amount of deflection of the reinforcing plate is too large to exceed 6 mm, the reinforcing plate will bend too much when stress is applied, making it difficult to obtain the original IC chip reinforcement effect. Therefore, it is preferable that the amount of deflection does not exceed 6 mm.
  • the thickness corresponding to such a deflection of 6 mm is a thickness of 30 ⁇ m on the stainless steel reinforcing plate. Therefore, if the metal reinforcing plate is less than 30 ⁇ m, it is difficult to obtain a reinforcing effect. Conversely, if the thickness of the metal reinforcing plate exceeds 150 m, the amount of deflection will decrease more than 3 mm, which may cause problems in printing.
  • the reinforcing plate is made of a non-metallic soft plastic resin material or the like, if the above-described deflection amount exceeds the deflection amount of the communication medium, the reinforcing plate can be used with a relatively large thickness. If the reinforcing plate becomes too thick, the thickness of the entire communication medium will also increase. Therefore, it is important to select the material and thickness of the reinforcing plate in consideration of the entire lance.
  • the present invention when a metal reinforcing plate is used, printing is performed on a communication medium in which the reversible thermosensitive recording layer is used as the display layer when the thickness exceeds 150 m.
  • the following problems arise because opportunities and communication to IC chips are often performed by RZW.
  • One is deterioration of the reversible thermosensitive recording medium. This is because the communication medium that contains a hard-to-bend object such as a reinforcing plate is rubbed only during printing or transportation. The surface becomes painful. The other is that the print becomes unclear. In order to make printing clearer, the printing head is often pressed against the thermal recording medium.
  • the printing surface will float and the print head will not hit only that part.
  • the print head does not hit the printing surface of the medium, and it is impossible to get a clear print! /!
  • the size of the reinforcing plate is considered to be large enough to hide the IC chip. However, a reinforcing plate that is too large is not good because the printing ability is impaired even if it has a reinforcing effect. Smaller ones than IC chips have good printability but are considered to be less effective.
  • a reinforcing plate having a size 1 to 1.5 times the diagonal of the chip to be used is preferable.
  • the shape can be freely selected from circles, ellipses, squares, rectangles, and the like. In order to bend in an arc shape, a circular or elliptical shape is preferable. For squares and rectangles, it is more preferable that the corners are rounded because the display layer is less likely to be damaged when bent.
  • the transport path is slightly angled.
  • the pressing pressure on the platen roll is preferably a linear pressure of 0.01 to 5 N / cm.
  • the reinforcing plate protects the IC chip against external stress, and at the same time, when the stress disappears, it needs to return to its original state. If the reinforcing plate does not return to its original state, it becomes distorted with external stress applied, which is not preferable in appearance. From the viewpoint of protecting the IC chip, the reinforcing plate should not be distorted when an external force is applied, but if it is too hard, the reinforcing plate will break. Depending on the thickness, too much strain can damage the chip. A highly elastic material such as metal is suitable.
  • the material examples include metals such as copper, lead, iron, aluminum, nickel, titanium, manganese, molybdenum, tin, zinc, conoretol, and chromium, and alloys such as stainless steel and steel. Of these, cold rolled stainless steel stainless steel for springs is often used. Furthermore, it is possible to raise the hardness and elastic modulus by tempering.
  • the reinforcing grease connects the IC chip and the reinforcing plate, but the reinforcing plate is larger than the IC chip! Because it is a size, it is not an IC chip! In some places, an IC inlet is formed! /, And the insulating sheet and the reinforcing plate are directly joined. Therefore, if the reinforcing grease is too hard like the reinforcing plate, there is a possibility that a printing defect may occur. Therefore, the reinforcing resin should have a low flexural modulus in order to bend easily together with the reinforcing plate, the display substrate, and the holding layer. In this case, the lower limit of the flexural modulus is not particularly defined because the reinforcing resin partially resides in the retaining layer.
  • the communication medium When the communication medium is transported by a roll such as a platen roll, if the bending elasticity of the reinforcing resin exceeds 2000 MPa, the internal IC inlet bends in the same way as the medium. In contrast, the strength of the reinforcing grease makes it difficult for the reinforcing plate to be bent. At this time, if the adhesive strength between the reinforcing plate and the insulating sheet of the IC inlet is weak, the reinforcing plate force is easily separated from the insulating sheet of the C inlet. Therefore, the reinforcing plate resin is easy to bend and the bending elastic modulus is preferably 2000MPa or less.
  • the thickness of the reinforcing resin it is sufficient that there is an interval of about 0 to 100 ⁇ m between the IC chip and the reinforcing plate. If the interval is more than 100 m, the reinforcing part of the IC chip becomes large and the print is easily affected. IC chips with a thickness of 30 ⁇ m to 200 ⁇ m are often used. Therefore, the thickness of the reinforcing resin other than the IC chip is about 30 ⁇ m to 300 ⁇ m.
  • the adhesive strength of the insulating sheet and the reinforcing plate may be 1N or more, but if it is less than 1N, it may come off or the reinforcing effect may be weakened immediately. Furthermore, it is preferable that the reinforcing plate and the insulating sheet are firmly joined to each other.
  • the reinforcing resin is not particularly limited in terms of material.
  • Adhesives such as adhesives, moisture curable adhesives, cationic curable adhesives, and EB curable adhesives can be used.
  • an epoxy resin that is stable in quality and has a low elastic modulus (5 MPa to 2000 MPa).
  • the holding layer is on the side of the display member where the IC inlet is located, and functionally (1) represents the IC inlet. Holds the display member, (2) enhances the printability of the display layer, and (3) softens the entire communication medium.
  • the holding layer adhesive layer 3c which is a holding layer, holds the IC inlet on the base material and also functions as the outermost layer on the back side of the communication medium. Display material of Fig. 3
  • the holding layer is composed of a holding layer support and an adhesive layer for the holding layer support.
  • the adhesive layer for the support for the support layer is located between the display layer and the support for the support layer.
  • the adhesive layer for the support for the support layer is a layer for bonding the support for the support layer and the display layer.
  • the support for the holding layer is the outermost layer on the back side of the communication medium. As shown in Fig. 5, when the holding layer is divided into the holding layer support and the adhesive layer for the holding layer support, even if one of the elasticity is high, the elasticity of the other is reduced. It is easy to control the flexural modulus as a communication medium.
  • the bending elastic modulus of the entire communication medium is not less than lOOMPa and not more than 20 OOMPa when combined with the display member described later. Experimentally gained. If the retention layer exceeds lOOOMPa, the bending elastic modulus of the entire communication medium tends to exceed 2000 MPa, and printing with a printer having a curved conveyance path cannot be performed neatly and defects tend to occur.
  • the support for the holding layer a plastic sheet, cloth, woven fabric, non-woven fabric, rubber, elastomer sheet, or the like is used.
  • the main component may be styrene elastomer, olefin elastomer, polyamide elastomer, urethane elastomer, polyester elastomer, and the like.
  • the elastomer which is a copolymer with the constituent molecules of the elastomer, has a low tensile elastic modulus and excellent heat resistance. Among them, polyester elastomers are excellent in heat resistance.
  • polyester elastomer a block copolymer composed mainly of a hard segment of an aromatic polyester such as tetramethylene terephthalate or polybutylene terephthalate and a soft segment such as an aliphatic polyether is used.
  • a block copolymer of PBT in the hard segment and polyether (aliphatic polyether) in the soft segment There are Toray 'DuPont's Hytrel series, Teijin Chemicals Co., Ltd.'s Nuberan B4000 series, and Toyobo Co., Ltd.'s Perprene P type.
  • the elastomer is a polyester block copolymer of polyester comprising a polybutylene terephthalate as a hard segment and a dicarboxylic acid and a diol as a soft segment
  • an elastic body can be obtained with a small residual elongation after elongation. Things are possible.
  • Products that have PBT in the hard segment and polyester block copolymer in the soft segment include the Nuberan P4100 series from Teijin Chemicals Limited and the Perprene S type from Toyobo Co., Ltd.
  • thermo printing by selecting a heat-resistant material as the main component of the holding layer in this way, curling, distortion and deformation due to heat during printing of the display body, and force during distortion during rewriting And the deformation can be reduced.
  • the support for the retaining layer has a property of expanding and contracting, has a relatively low tensile elastic modulus, and has a swelling ratio in oil.
  • Low, high oil resistance more preferred to choose materials. Examples of such a material include the elastomer described in the section of the support in the above-described reversible thermosensitive recording material.
  • an adhesive or pressure-sensitive adhesive such as thermoplastic resin
  • the material of the adhesive and the pressure-sensitive adhesive include the resin described in the section of the adhesive layer in the above-described reversible thermosensitive recording material.
  • the adhesive layer for the support for the holding layer is formed by calorie heating with a thermoplastic film sandwiched between the base material and the holding layer, or by applying an adhesive. Such a bonding process may be performed independently or separated into several processes.
  • the coating amount depends on the final thickness of the target display, but is usually 10 to 700 gZm 2 in dry weight and 5 to 1000 / ⁇ ⁇ in thickness.
  • a polyethylene or polyester material it is useful when reusing as a chemical raw material.
  • the fiber-containing layer 6 is flat, so-called flat such as cloth, non-woven fabric, and net.
  • a fiber layer laminate using a planar fiber layer and using it is mentioned.
  • a layer called a short fiber-containing layer which is a relatively short fiber such as a yarn pulp, is also included.
  • the fiber-containing layer is provided to improve the strength, durability, and physical properties of the communication medium itself.
  • the fiber layer laminate is made by infiltrating the planar fiber layer in a liquid resin using the same resin as the adhesive layer for the support for the holding layer, or the resin A material sandwiched between layers can be used.
  • the resin sheets mentioned for the support for the holding layer may also be infiltrated with a planar fiber layer in the same manner as the adhesive during the production of the sheet, or may be sandwiched between the resin sheets. Can be used.
  • the short fiber-containing layer is prepared by kneading relatively short fibers such as yarn and pulp using a resin similar to the above-mentioned adhesive layer for the support for the holding layer. You can get it.
  • the resin sheets mentioned for the support for the holding layer can also be obtained by kneading short fibers into the resin of the liquid resin sheet raw material during the production of the sheet.
  • the holding layer may be formed by laminating several kinds of the layers mentioned above.
  • the holding layer only needs to be able to hold the IC inlet in cooperation with the display member, but to improve slipperiness to improve transportability-paints and inks such as antifouling varnish and antistatic varnish
  • This layer can also be provided. It is also possible to knead the holding layer with a pigment, a conductive filler, an antistatic agent or the like. In practical use, characters and designs are printed and front / back identification marks are printed in a timely manner. A trigger for discriminating between the front and back can be added at any time.
  • Various display layers such as thermal recording, pressure sensitive recording, thermal transfer recording, and ink jet recording can be selected as the display layer.
  • the thermal recording that the display layer is preferred for various display layers is suitable for applications such as delivery slips, process control tables, IC cards, and IC tags because the printer device is simple and easy to carry.
  • a configuration having a thermosensitive recording layer is preferred. Any combination of a color former and a colorant for the heat-sensitive recording layer can be used as long as they react to cause coloration.
  • Thermolite recording layer that can print repeatedly such as a multicolor thermal recording layer that can perform thermal recording in two or more colors, and a reversible type thermal recording layer. Also included in terms of recycling.
  • the rewritable recording method is typically a thermolite recording layer.
  • the layers suitable for the recording and printing methods are appropriately and preferably formed so as to be compatible with a plurality of recording methods.
  • the layer is not limited to a single layer, and a plurality of layers may be formed, or the layer to be formed may be changed according to the recording site on the information medium surface. Further, providing such a reversible thermosensitive coloring layer on the entire surface of the communication medium is easy to record without any restriction.
  • the thermal head for printing is placed on the tag transport line, pressed with the back surface force of the communication medium, a platen roll, etc., and pressed against the display layer to transmit heat and develop color to perform printing.
  • a protective layer such as varnish is often provided.
  • Possible applications for the protective layer include UV resistance, abrasion resistance, stain resistance, curling resistance, electrostatic resistance, oil resistance, chemical resistance, and writing ability. Also, printing can be given for distinguishing between the front and back sides and the medium type.
  • the display layer is often formed of a relatively low-molecular polymer or the like, and in that case, the tensile elastic modulus becomes negligibly small.
  • the tensile modulus of the base material is larger than that of the display layer, the influence of the tensile modulus of the display layer is very small.
  • Display substrates include polyolefin (eg, polyethylene, polypropylene, etc.), polyvinyl chloride (eg, soft polyvinyl chloride, hard polyvinyl chloride), polyester (eg, polyethylene terephthalate, modified polyethylene terephthalate (PET— G))), etc.), polycarbonate, polystyrene, polyurethane, a film composed mainly of a resin, such as cellophane, a composite, a mixture of copolymers, etc.
  • polyolefin eg, polyethylene, polypropylene, etc.
  • polyvinyl chloride eg, soft polyvinyl chloride, hard polyvinyl chloride
  • polyester eg, polyethylene terephthalate, modified polyethylene terephthalate (PET— G)
  • PET— G polyethylene terephthalate
  • polycarbonate polystyrene
  • polyurethane a film composed mainly of a resin, such as cellophane
  • a foamed film a film such as a porous film in which a void is formed by blending an inorganic pigment or an organic pigment with the resin, a synthetic paper or a non-woven fabric, and a laminated sheet obtained by laminating these films Etc.
  • crystalline polyester film Is thin and suitable for easy processing. The appropriate thickness is 20 to 100 / ⁇ ⁇ . If the thickness is less than 20 m, it is too thin to be processed and difficult to process. If the thickness exceeds 100 m, the bending elasticity of the communication medium becomes too high and is not suitable. Absent.
  • FIG. 7 is a cross-sectional view of a first example of the recording material of the present invention.
  • a mesh cloth 7j is arranged in the holding layer 7g, and the holding layer 7g and the display layer 7s are bonded by the adhesive layer 7c. ing.
  • FIG. 8 is a cross-sectional view of a second example of the recording body of the present invention.
  • the display layer 8s is composed of the base material 8b having the recording layer 8a, and the adhesive layer 8c and the holding layer 8g are formed on the back side of the base material 8b.
  • an anti-curl layer having a layer structure that is sequentially laminated so as to sandwich the mesh cloth layer is provided.
  • one surface (lower surface) side is embedded in the holding layer, and the other surface (upper surface) side is bonded by the adhesive layer 8c.
  • FIG. 9 is a cross-sectional view of a third example of the recording medium of the present invention.
  • a mesh cloth is attached to one side of the holding layer 9g, and the holding layer 9g and the display layer 9s are bonded by the adhesive layer 9c so that the mesh cloth 9j is the outermost layer. .
  • FIG. 10 is a cross-sectional view of a fourth example of the recording medium of the present invention.
  • the display layer 10s is composed of the base material 10b having the recording layer 10a, similarly to the recording bodies of FIGS.
  • An adhesive layer 10c, a mesh cloth 10j, and a holding layer 10g are sequentially provided on the lower layer side of the display layer 10s.
  • An IC chip l ie is mounted in the adhesive layer 10c, and a reinforcing plate l
  • An IC inlet reinforced with lg is embedded, and this IC inlet exists so as to be sandwiched between the base material 10 b and the holding layer 10 g.
  • FIG. 11 is a cross-sectional view of the IC inlet.
  • This IC inlet has a top surface antenna 1 la and a bottom surface antenna 1 lb formed on an insulating sheet 11, and the bottom surface antenna 1 lb is a spiral antenna, so its cross section appears in several places in the drawing. .
  • An IC chip ie is electrically connected on the antenna.
  • a reinforcing plate 1 lg is adhered to the IC chip lie by a reinforcing resin 1 If.
  • the top antenna 1 la and bottom The antenna l ib is electrically joined up and down by a through hole l lh.
  • an insulating sheet on which electronic components such as an antenna and an IC are mounted is referred to as an IC inlet as a whole.
  • FIG. 12 is a cross-sectional view of a fifth example of the recording body of the present invention.
  • the recording body of the present invention shown in FIG. 12 is different from the recording bodies of FIGS. 7 to 9 in that the display layer 12s is composed of the base material 12b having the recording layer 12a.
  • An adhesive layer 12c including a mesh cloth 12j and a holding layer 12g are sequentially provided on the lower layer side of the display layer 12s.
  • the display layer in the recording material of the present invention comprises a substrate and a recording layer on the substrate.
  • Base materials include high-quality paper, art paper, coated paper, cascaded paper, kraft paper, polyethylene laminated paper, impregnated paper, foamed paper, polyolefins (eg, polyethylene, polypropylene, etc.), and poly salty paper.
  • the storage modulus of the substrate actually used is preferably 4 GPa or more and lOGPa or less. If it is less than 4 GPa, a practical display body has low rigidity and tends to be weak. Also 10
  • the thickness of the base material is actually in the range of about 6 m to 200 m.
  • the recording layer in the recording medium of the present invention is the same as the display layer in the communication medium described above, Also included is a thermolite reversible thermosensitive recording layer that can be repeatedly printed, such as a multicolor thermosensitive recording layer that can perform thermal recording in two or more colors, and a reversible type thermosensitive recording layer. And display methods using polymers or magnetic particles.
  • a thermolite reversible thermosensitive recording layer that can be repeatedly printed, such as a multicolor thermosensitive recording layer that can perform thermal recording in two or more colors, and a reversible type thermosensitive recording layer.
  • display methods using polymers or magnetic particles display methods using polymers or magnetic particles.
  • Another type of rewritable recording method is electronic paper. Electronic paper uses electrophoretic aggregation and diffusion of charged particles in microcapsules (if necessary, E. Kishi et al., SIDOO Digest, p. 24, 2000, or ! ⁇ or SA Swanson et al., SIDOO Digest, p.
  • two-color [displays by moving and rotating the coated spheres, so-called polymers filled with liquid crystal in micropores Dispersive liquid crystal, electochromism, or magnetic recording device that rotates and moves magnetized fine particles by controlling magnetism (if necessary, see LL Lee et al., SID76 Digest, p. 56, 1976) Power ⁇ Knowed!
  • Display layers using these rewritable recording methods can be used, but there are some layers that are vulnerable to bending due to the layer structure, and among these, thermolite methods using thermosensitive dyes, polymers, etc. Since the heat-sensitive recording layer has a simple structure and is inherently resistant to such bending, it can be used more preferably.
  • soft materials examples include mixtures of elastomers whose main components are styrene elastomers, olefin elastomers, polyamide elastomers, urethane elastomers, polyester elastomers, and the like.
  • this mesh cloth is a cloth having an open structure, and yarns having various material strengths can be selected, and the weaving method, thickness, and number of fibers can be appropriately selected.
  • the material include synthetic fibers such as polyester, nylon, vinylon, polyurethane, acrylic, carbon, teflon, polypropylene, and glass fibers, and natural fibers such as cotton, hemp, hair, and silk.
  • the yarn used may be either monofilament or multifilament.
  • weaving method of the mesh cloth weaving methods used in ordinary fabrics such as basic plain weave, twill weave and satin weave can be considered. Plain weave is industrially easy to produce.
  • the yarn diameter is preferably in the range of 1 to 900 dtex. The larger the yarn diameter, the more likely it will be affected during printing.
  • the opening is 0.5mn! A range of ⁇ 20 mm is preferable, and a range of 2 mm to 10 mm is more preferable. It is preferable to change the size according to the size of the recording medium. If the aperture is clogged, it will be affected by the mesh cloth material and it will be difficult to adjust the softness of the recording medium. If the opening is too large, it becomes difficult to control the linear expansion coefficient. Furthermore, in order to fix the opening in a state where the yarn is closed, it is preferable to bundle it with a sizing agent or heat treatment.
  • a melt laminating method in which the mesh cloth is pressed against the molten holding layer or the adhesive layer, and at least a part of the mesh cloth is pressed and bonded.
  • T-die extrusion lamination method, calendar molding method, etc. It is also possible to extrude a holding layer or an adhesive layer on a state in which the mesh cloth is partially pushed in and to make it exist inside. Alternatively, it is possible to put a mesh cloth in advance when bonding the holding layer and bond it to the adhesive layer at the same time as bonding.
  • a mesh cloth When a mesh cloth is present in the holding layer or adhesive layer constituting the anti-curl layer, it functions as an anti-curl layer due to its presence. As described above, it is preferable that the position where the mesh cloth is present is preferably as far as possible from the display layer in view of the anti-curl function.
  • the linear expansion coefficient of the holding layer constituting a part of the anti-curl layer is displayed.
  • the preferred range is defined by the ratio with the layer.
  • a material having a storage elastic modulus of 0.01 GPa to 1.5 GPa is suitable as the holding layer constituting the anti-curl layer. 0. If it is less than OlGPa, a practical display body is less rigid and tends to be weak. 1. Above 5 GPa, the flexibility is poor, and it is easy to cause defects such as cracking or chipping.
  • the adhesive layer and the holding layer constituting the anti-curl layer cause the softness of the recording medium. It is ideal and more preferable that both satisfy the above storage elastic modulus. Even if one of them does not exhibit the above storage elastic modulus, if the storage elastic modulus of the thicker layer is lower than that of one of the layers, the soft recording medium satisfies the performance. When embedding an identification tag or the like in the adhesive layer, the thickness of the adhesive layer becomes larger than that of the holding layer, and the adhesive layer is considered to be dominant immediately.
  • Examples of the material having the storage elastic modulus include styrene-based elastomers, olefin-based elastomers, polyamide-based elastomers, urethane-based elastomers, polyester-based elastomers, and the like.
  • the heat resistance varies greatly depending on the composition of the hard segment having crystallinity in the block copolymer and the soft segment in the non-crystalline part.
  • polyester elastomers are superior in heat resistance because they have a higher melting point and less elastic change due to temperature changes than other elastomers.
  • thermal printing characteristics in particular, by selecting a heat-resistant material as the main component of the holding layer, curling, distortion and deformation due to heat during printing of the display body, curling, distortion and deformation during rewriting Can be reduced.
  • Polyester elastomers are mainly composed of aromatic polyester hard segments such as polybutylene terephthalate (PBT) and polybutylene naphthalate (PBN), and soft segments such as aliphatic polyesters and aliphatic polyethers.
  • PBT polybutylene terephthalate
  • PBN polybutylene naphthalate
  • soft segments such as aliphatic polyesters and aliphatic polyethers.
  • the block copolymer is preferred.
  • commercially available products can be used as the synthetic resin constituting the retaining layer.
  • suitable commercially available products include mainly PBT as a hard segment and fat as a soft segment. Teijin Chemicals Co., Ltd., stabilize P4100 series, Toyobo Co., Ltd., Perprene S type, which is a block copolymer of aliphatic diol or aliphatic polyester.
  • the thickness of the anti-curl layer is suitably 50 ⁇ m to 1000 ⁇ m. 50 to 800 ⁇ m is preferable. If the anti-curl layer is thinner than 50 m, it will be difficult to flatten the mesh cloth, which will be described later, and it will be difficult to incorporate it. On the other hand, if it is thicker than 800 m, it becomes too thick as a whole display, and it becomes difficult to handle it when printing or transporting. Furthermore, it is preferable to adjust the overall thickness by thickening the holding layer or thinning the adhesive layer.
  • the adhesive layer in the recording material of the present invention is formed by sandwiching a thermoplastic film between the display layer and the holding layer and heating, or applying an adhesive. Such a bonding process may be performed alone or in several steps.
  • the adhesive used in the adhesive layer of the present invention what is called a thermoplastic film, an adhesive, or an adhesive can be used.
  • the storage elasticity is preferably from 0. OlGPa to 1.5 GPa. 0. If it is less than OlGPa, a practical display body is less rigid and tends to be weak. On the other hand, if it exceeds 1.5 GPa, the flexibility tends to be poor, and defects such as cracking and chipping tend to occur.
  • the material of the adhesive, the pressure-sensitive adhesive, and the thermoplastic film include those described in the description of the “adhesive layer” of the reversible thermosensitive recording layer.
  • RFID tags that use ICs with the adhesive layer and EAS (Electronic Article Surveillance) technology.
  • a tag used for theft prevention or the like can be integrated with the display body of the present invention.
  • Such tags are collectively referred to as “identification tags” in this specification.
  • RFID tags include the aforementioned IC inlet, which is the part that communicates with the reader / writer.
  • the IC inlet in the recording medium of the present invention is the same as the IC inlet of the communication medium described above. [0118] [Reinforcing plate and reinforcing resin]
  • the reinforcing plate and reinforcing resin in the recording medium of the present invention are the same as the reinforcing plate and reinforcing resin of the communication medium described above. There is no need to reinforce the tip if the tip is small or if the recording is difficult to apply pressure to the tip. Furthermore, even when the reinforcing resin is hard, the reinforcing resin may replace the action of the reinforcing plate, and the chip protection may be unnecessary.
  • Example 1 as an example of the display body of the present invention will be described with reference to FIG.
  • FIG. 1 is a cross-sectional view showing an example of the display body of the present invention.
  • Display substrate la Mitsubishi Paper Relite Film TFR85WA: 75 ⁇ m thick polyethylene terephthalate film with a 10 ⁇ m thick thermoreversible thermosensitive paint layer serving as the display layer
  • the rewritable film itself was subjected to tests such as the tensile elastic modulus, “oil drop adhesion suitability test”, and “swelling in oil test”.
  • Tensile modulus was 3700Ma measured value, oil droplet adhesion suitability was appropriate, and the volume swelling rate was 0.2% in the oil swelling test. It was confirmed that the values of the tensile modulus and the swelling test in oil were almost the same as those of the equivalent PET film with the same thickness.
  • Toyobo Perprene S1002 polyester elastomer, hard segment: PBT, soft segment: poly-strength prolatatone having a thickness of 300 ⁇ m was used.
  • the support was subjected to tests such as the tensile elastic modulus, “oil drop adhesion suitability test”, and “in-oil swelling test” described above.
  • Adhesive layer lb (manufactured by Toyo Morton Co., Ltd., main component AD-577 (polyester resin)) and hardener 10L (polyisocyanate) are mixed at a ratio of 5: 1.
  • the layer was obtained by coating and drying to a thickness of 6 m.
  • the resulting reversible thermosensitive recording material had a thickness force of S410 ⁇ m. This sample is cut into a size of 20 cm ⁇ 10 cm, and the reversible thermosensitive of the present invention A sample of Example 1 of the recording material was prepared.
  • FIG. 2 is a cross-sectional view showing another example of the display body of the present invention.
  • An inlet was used in which the top antenna 2f and bottom antenna 2g (material aluminum) were formed on the inlet base material 2e (material PET) and the my-d chip 2h was connected to it.
  • This inlet is commercially available as Infion's SR F55V10P square inlay (dimensions 48mm x 48mm).
  • Toyobo Perprene EN1000 polyester elastomer, hard segment: PBN, soft segment: PTMG
  • the tensile elastic modulus was 83 MPa
  • the oil droplet adhesion suitability was appropriate
  • the volume swelling ratio was 1.0%.
  • Cemedine EP-001 elastic epoxy adhesive, tensile modulus 20MPa catalog value manufactured by Cemedine Co., which will become the adhesive layer 2b, is coated, the inlet is placed, and the display substrate 2a is placed on the uppermost layer.
  • Rewrite film TFR33TA (Mitsubishi Paper Co., Ltd.)
  • a protective layer, etc. is appropriately provided on a 23 ⁇ m thick polyethylene terephthalate film with a 10 ⁇ m thick thermoreversible thermosensitive paint layer as the display layer.
  • a sample was obtained by pasting together.
  • RFID including such an IC or antenna is used, even if the antenna or the like is on the hard display substrate side, the inlet bulges slightly to the adhesive layer side, so that the inlet is easily embedded in the adhesive layer 2b.
  • the inlet can be embedded in the adhesive layer very easily.
  • the thickness of the reversible thermosensitive recording material obtained by this bonding was 800 ⁇ m, and the substantial thickness of the adhesive layer was 470 ⁇ m.
  • the pasted material is cut into a size of 20 cm x 10 cm, and the print area can be removed by removing the portion where the inlet is embedded.
  • a sample of Example 2 of an inverse thermosensitive recording material was prepared. In addition, it was confirmed that the reversible thermosensitive recording material of Example 2 was able to read the information on the chip with an Omron H-01 reader / writer even after each test.
  • Example 1 a reversible thermosensitive recording material was obtained in the same manner as in Example 1 except that a polyester elastomer as described below was used instead of Toyobo's Perprene S1002 used for the support lc. It was. The outline of the production method of the polyester elastomer used for the support is described below. 80 parts of polytetramethylene terephthalate and 20 parts of force prolatatone were placed in a reaction vessel and melt-reacted for 2 hours while stirring at 230 ° C. in nitrogen.
  • Example 3 a sample of the reversible thermosensitive recording material of Example 3 was prepared in the same manner as in Example 1.
  • Example 3 a support was obtained using the second polyester resin obtained by reacting 60 parts of terephthalic acid instead of isophthalic acid and 40 parts of propylene glycol instead of hexanediol.
  • a reversible thermosensitive recording material was prepared in the same manner as in Example 3 except that.
  • the tensile elastic modulus was 500 MPa
  • the oil droplet adhesion suitability was appropriate
  • the volume swelling ratio was 2.0%.
  • Example 1 instead of Toyobo's Perprene S1002 used for the support lc, Toyobo's Perprene ⁇ -450 ⁇ (polyester elastomer, hard segment PBT, soft segment: PTMG) with a thickness of 300 ⁇ m was used.
  • Comparative Example 1 A sample of a reversible thermosensitive recording material was prepared. The results of the above tests on the support were as follows: tensile modulus: 3000 MPa, oil droplet adhesion suitability, volume swell ratio: 0.5%.
  • Example 1 instead of Toyobo's Perprene S1002 used for support lc, Toyobo's Perprene ⁇ 70 mm (polyester elastomer, hard segment P BT, soft segment: PTMG) was used. A sample of the reversible thermosensitive recording material of Comparative Example 2 was prepared in the same manner as Example 1. The results of the above tests on this support were as follows: tensile modulus: 3000 MPa, oil droplet adhesion suitability, volume swelling rate: 2.5%.
  • test of each material and the test of each material and the test performed for each sample were as follows.
  • the obtained thermal recording medium sample is cut out to a card size (according to 85.5 mm X 54 mm JIS X 6301 (1998)), dipped in machine oil, and left for 7 days at a temperature of 23 ° C. Remove after 7 days, wipe off the oil, and measure the warpage according to the JIS X 6301 (1998) card warpage measurement method. The amount of warpage measured is shown in Table 2. 2mm or less was judged good.
  • Example 3 Compared to Example 1, the sample of Example 3 is very preferred, with no scratches observed during the cleaning test. This is presumably because the softness and softness of the second polyester resin were selected, so that the hard segment was relatively hard and the effect of compensating for the properties of PBT was obtained.
  • Example 4 the second polyester resin used in this example is presumed to be inferior to the crease test or the like because a relatively hard resin was selected.
  • Comparative Example 2 showed properties that were inferior in oil resistance to Comparative Example 1. This is presumed to be due to the fact that the proportion of PTMG with ether bonds was too large compared to Comparative Example 1.
  • Embodiment 5 will be described as an embodiment of the communication medium of the present invention with reference to the drawings.
  • FIG. 4 is a cross-sectional view of an example of an IC inlet used for the communication medium of the present invention.
  • the 38 ⁇ m-thick PET film was used as the insulating sheet 4 in advance, 30 m-thick aluminum foil was attached, resist ink was applied, and etching was performed to form antennas 4a and 4b on the insulating sheet.
  • an IC chip 4e (I-CODE SLI, manufactured by Philippe) is bonded onto the antenna 4b, and further, an epoxy resin (EP001 elastic epoxy adhesive manufactured by Cemedine, flexural modulus 20MPa) becomes a reinforcing resin 4f.
  • FIG. 3 is a cross-sectional view of Example 5 as an example of the communication medium of the present invention.
  • a rewrite film TFR85WA manufactured by Mitsubishi Paper Industries Co., Ltd. was used as a display member 3s composed of the base material 3b and the display layer 3a.
  • a 75 ⁇ m thick polyethylene terephthalate film constituting the substrate 3b is provided with a thermoreversible thermosensitive paint layer constituting the display layer 3a in a thickness of 10 m.
  • the IC inlet 3d is sandwiched by Toron Gosei PAL111EEW (polyester-based hot melt adhesive) made by Toagosei Co., Ltd. with a thickness of 300 ⁇ m to form the base material 3b and the holding layer 3c.
  • Toron Gosei PAL111EEW poly-based hot melt adhesive
  • the IC inlet, the display member, and the holding layer were integrated together to obtain an example of the communication medium of the present invention.
  • This display was capable of reading chip information with an Omron H-01 reader / writer.
  • a communication medium with a flexural modulus of 100 MPa (actual measurement) and a thickness of 380 ⁇ m was prepared.
  • FIG. 5 is a sectional view of Embodiment 6 of the communication medium of the present invention.
  • the IC inlet 3d used in Example 6 was the same as the IC inlet used in Example 5.
  • Cemedine EP-made by Cemedine Co., Ltd. which becomes the adhesive layer 5c for the support for the support layer in the Toilene clay noiterel 4047 (polyester elastomer: flexural modulus 70MPa catalog value) with a thickness of 300 ⁇ m as the support for the support layer 5g 001 (elastic epoxy adhesive, flexural modulus 20MPa) applied Then, the IC inlet 3d was sandwiched, and at that time, Cemedine EP-001 was applied to the side of the IC inlet 3d where the IC chip was not provided, and was bonded to the display member 5s.
  • a rewrite film TFR33TA manufactured by Mitsubishi Paper Industries Co., Ltd.
  • This rewritable film is a 23 m thick polyethylene terephthalate film constituting the substrate 5b and a thermoreversible thermosensitive paint layer constituting the display layer 5a having a thickness of 10 m.
  • a communication medium was created as described above. The thickness as a communication medium was 600 ⁇ m. The thickness of the adhesive layer 5c for the support for the holding layer is approximately 270 m. ⁇ ⁇ At the place where the UC inlet 3d was present, the support layer support 5g side was 250 m and the base material 5b side was 20 m except for the IC chip part.
  • the flexural modulus was 200 MPa when the rewritable film side force of the communication medium was pressed, and the flexural modulus was 130 MPa when the opposite surface force was pressed. (The average flexural modulus was 160 MPa.)
  • the display can be read with the OMRON H-01 reader / writer.
  • Embodiment 7 which is another embodiment of the communication medium of the present invention will be described with reference to FIG.
  • FIG. 6 is a cross-sectional view of Embodiment 7 of the communication medium of the present invention.
  • the IC inlet 3d used in Example 7 was the same as the IC inlet used in Example 5.
  • Torayen clay nobletler 4047 polyethylene elastomer: flexural modulus 70MPa catalog value
  • a plain weave 5B sandwiched between rubber sheets is used.
  • a communication medium was obtained in the same manner as in Example 5 except that a 400 ⁇ m thick composite sheet (measured value of flexural modulus: 300 MPa) manufactured by Elastomer Co., Ltd. was used.
  • the resulting communication medium had a thickness of 700 m and a flexural modulus of 300 MPa.
  • Example 6 instead of epoxy resin (EP001 made by Cemedine Co., Ltd.) as a reinforcing resin obtained by bonding a reinforcing plate and IC, main agent TA-180 0E and a curing agent as an adhesive made by Sanyo Chemical Industries A communication medium was prepared in the same manner as in Example 6 except that an epoxy resin adhesive mixed with TA-1800H (bending elastic modulus at curing 3000 MPa) was used. Obtained communication medium The body thickness was 600 ⁇ m and the flexural modulus was 160 MPa.
  • epoxy resin EP001 made by Cemedine Co., Ltd.
  • TA-1800H bending elastic modulus at curing 3000 MPa
  • Example 6 in place of Torayen clay noytrel 4047 as 5 g of retaining layer support, Torayen clay Hytrel 2751 (polyester elastomer bending elastic modulus 1250MPa catalog value) having a thickness of 300 ⁇ m was used.
  • a communication medium was prepared in the same manner as in Example 6. The resulting communication medium had a thickness of 600 ⁇ m and a flexural modulus of 1400 MPa.
  • Example 6 as reinforced plate 4g, SUS301 with thickness of 150 ⁇ m, 5mm ⁇ , 3-point bending test Similar to Example 6 except that a stainless steel plate exhibiting 0.5mm deflection at 0.2mm load was used. Created a communication medium. The resulting communication medium had a thickness of 600 m and a flexural modulus of 140 MPa.
  • Example 6 is the same as Example 6 except that an unstretched polyester film (bending elastic modulus 2300 MPa, catalog value) with a thickness of 300 ⁇ m was used instead of Torayen clay noitorel 4047 as 5 g of the retaining layer support.
  • a communication medium was created in the same manner as above.
  • the resulting communication medium had a thickness of 600 m and a flexural modulus of 2200 MPa.
  • the communication media of Examples and Comparative Examples were cut to a size of 100 mm ⁇ 200 mm, and thermal printing of barcodes was performed using a rewrite printer PR3101 manufactured by Sanwa New Tech Co., Ltd., and the printing state was examined.
  • Barcode printing is judged visually and the one with no interruption in printing is considered to be good, and the printing is reduced! /, But the one that can read the barcode is somewhat good, and the printing is interrupted and can be read as a barcode.
  • the product was judged to be defective (printing energy of the printer was standard). At the same time, erasure printing was repeated 200 times, and then the communication status was confirmed. Of the 5 cards, X was assigned when communication was impossible, and ⁇ was assigned when communication was possible. Results below
  • Example 380 100 4.8 20 20 O Good
  • Example 600 160 4.8 20 70 O Good
  • Comparative example 600 140 0.5 20 70 X Defect
  • Example 10 will be described with reference to FIG.
  • Display layer 7s Mitsubishi Paper Rewrite Film TFR8 5WA: Base 7b protected by a 75 ⁇ m thick polyethylene terephthalate film with a thermoreversible thermosensitive paint layer 10a thick as the recording layer 7a
  • Layer 7g is to melt the raw material pellets of Teijin Chemicals Ltd.
  • Nu one base run P4145 polyyester elastomer primary, linear expansion coefficient 19. 2 X 10- 5 1 / ° C, the storage modulus 0.
  • polyester fiber mesh cloth, mesh opening 5mm, yarn diameter 20 ⁇ m, 280 dtex is dropped on the chill roll surface side and sandwiched into a sheet first to create did.
  • Roll up the prepared original fabric melt the polyester raw material of the same raw material onto it and extrude it onto the mesh cloth surface, and hold the polyester elastomer with a thickness of 300 ⁇ m 7 g It was created.
  • Fiber expansion coefficient of the holding layer by having a mesh cloth 7j to middle 4 X 10- 5 1 / ° C , became a storage modulus 0. 85 GPa.
  • the display layer 7 s and the holding layer 7g adhesive layer 7c (Notepu Kogyo, moisture-curable hot-melt RHC- 100, the linear expansion coefficient 25 X 10- 5 1 / ° C , the storage modulus 0. lGPa) thickness It apply
  • the obtained reversible thermosensitive recording material had a thickness of 430 ⁇ m.
  • the sample was cut into a size of 10 cm ⁇ 10 cm, and the sample of Example 10 of the reversible thermosensitive recording material of the present invention (having the cross-sectional structure shown in FIG. 7). Created).
  • Example 10 when creating a retention layer, the raw material of Teijin Chemicals Ltd. Nu one base run P4145 (polyether ester elastomers, linear expansion coefficient 19. 2 X 10- 5 1 / .C , storage modulus 0. 45 GPa)
  • P4145 polyether ester elastomers, linear expansion coefficient 19. 2 X 10- 5 1 / .C , storage modulus 0. 45 GPa
  • a polyester fiber mesh cloth, mesh opening 5mm, yarn diameter 20 ⁇ m, 280 dtex is dropped onto the chill roll surface and sandwiched as it is, thickness 300 ⁇ m
  • a retaining layer of m polyester elastomer was prepared. The mesh cloth was almost buried in the elastomer.
  • Fiber expansion coefficient of the holding layer by having a main Sshukurosu is 4 X 10- 5 1 / ° C , it became a storage modulus 0. 85 GPa.
  • a sample of the recording material of the present invention having the cross-sectional structure shown in FIG. 8 was prepared in the same manner as in Example 10 except that this mesh cloth was positioned inside the holding layer (display layer side).
  • the resulting reversible thermosensitive recording material had a thickness of 430 m.
  • Example 10 when creating a retention layer, produced by Teijin Chemicals Ltd. Nu one base run P4145 (polyether ester elastomers, linear expansion coefficient 19. 2 X 10- 5 1 / ° C, the storage modulus 0. 45 GPa) of the material
  • P4145 polyether ester elastomers, linear expansion coefficient 19. 2 X 10- 5 1 / ° C, the storage modulus 0. 45 GPa
  • a sample of the recording material of the present invention having the cross-sectional structure shown in FIG. 9 was prepared in the same manner as in Example 10 except that this mesh cloth was positioned on the outer side (back side) of the holding layer. Created.
  • the resulting reversible thermosensitive recording material had a thickness of 430 m.
  • the recording material of the present invention shown in FIG. 10 having a structure in which an IC inlet is sandwiched between the display layer and the adhesive layer in Example 12 was prepared.
  • this IC inlet as shown in FIG. 11, a top surface antenna l la and a bottom surface antenna l ib (material aluminum) are formed on an insulating sheet 11 (material PET), and a my-d chip l ie is connected thereto.
  • IC inlet was used.
  • the IC inlet used was a commercially available SRF55V10P square-open inlay (size 48 mm x 48 mm) manufactured by Infion.
  • a 50 ⁇ m thick 5 mm ⁇ metal plate of SUS304 was mounted on the IC chip as a reinforcing plate llg using Cemedine EP001 (Cemedine), an elastic epoxy adhesive.
  • a sample of the recording material of the present invention having the sectional structure shown in FIG. 10 was prepared in the same manner as in Example 12 except that the thickness of the adhesive layer was 250 microns.
  • the resulting reversible thermosensitive recording material had a thickness of 630 m.
  • Example 15 will be described with reference to FIG.
  • Display layer 12s Mitsubishi Paper Relite Film TF R85WA: 75 ⁇ m thick polyethylene terephthalate film with a thermoreversible thermosensitive paint layer as a display layer with a thickness of 10 m, a protective layer, etc. are provided as appropriate. are commercially available products are.
  • Retaining layer 12g is to melt the raw material pellets of Teijin Chemicals Ltd.
  • Nu one base run P4145 polyyester elastomer primary, linear expansion coefficient 19. 2 X 10- 5 1 / .C , storage modulus 0.
  • Example 16 A display layer, an adhesive layer, and a holding layer were sandwiched between vacuum heat press machines, and heated vacuum press was performed to prepare a sample of a recording body having a thickness of 480 m as shown in FIG. This sample was cut into a size of 10 cm ⁇ 10 cm to prepare a sample of Example 15 (having the cross-sectional structure of FIG. 12) of the reversible thermosensitive recording material of the present invention.
  • Example 14 Oite using a raw material pellet in place of Teijin Chemicals Ltd. Nu one base run P4145 P4165 (polyester gills Sutoma linear expansion rate 13. 0 X 10- 5 1 / ° C, the storage modulus 2. OGPa) A sample was prepared in the same manner as in Example 14 except that. Linear expansion coefficient of the retained layer which is inherent mesh cloth 3. 0 X 10- 5 1 / ° C, were storage modulus 2. OGPa. The resulting reversible thermosensitive recording material had a thickness of 630 ⁇ m.
  • Example 10 the display layer and the holding layer were bonded together with an adhesive without sandwiching the mesh cloth, and a comparative sample was prepared.
  • the resulting reversible thermosensitive recording material had a thickness of 430 m.
  • Example 14 the display layer, the IC inlet, and the holding layer were bonded together with an adhesive without sandwiching the mesh cloth, and a comparative sample was prepared.
  • the obtained reversible thermosensitive recording material had a thickness force of S630 ⁇ m.
  • Example 10 instead of mesh cloth, a holding layer in which a plain fabric packed with 140 decitex polyester fibers was sandwiched was sandwiched (the fiber expansion coefficient of this holding layer was 3.5 X 10— 5 1 / ° C, storage elastic modulus was 0.990 GPa) and the display layer were bonded with an adhesive to prepare a comparative sample.
  • the resulting reversible thermosensitive recording material had a thickness force of 430 ⁇ m.
  • Rewrite film TFR60WA Mitsubishi Paper Co., Ltd.
  • display layer 7s thermo-reversible thermosensitive paint layer as a display layer on a 50 ⁇ m thick polyethylene terephthalate film with a thickness of 10 ⁇ m
  • linear expansion coefficient in the TD direction 2.
  • 2 GPa Teijin Chemicals thickness 300 m in the holding layer made null one base run P415 5 (polyester elastomer primary, linear expansion coefficient 15.
  • 5 X 10- 5 1 / ° C the storage modulus 1.
  • thermosensitive recording material 2 GPa
  • an adhesive layer (Notepu Kogyo, moisture-curable hot-melt RHC- 100, the storage elastic
  • the coating was applied to a thickness of 50 m and bonded together.
  • the obtained reversible thermosensitive recording material is The thickness was 410 ⁇ m.
  • This sample was cut into a size of lOcm ⁇ 10 cm to prepare a sample of Example 13 of the reversible thermosensitive recording material of the present invention.
  • test of each material and the test of each material and the test performed for each sample were as follows.
  • the communication media of Examples and Comparative Examples were cut to a size of lOOmm ⁇ 100 mm, and curling was observed at a high temperature of 40 ° C. and a low temperature of 4 ° C.
  • the four corners were placed on the table so that they warped upward, and the distance from the table surface to the tip of the four corners was measured. Less than 2mm ⁇ , 2mn! ⁇ less than ⁇ 5mm, and X more than 5mm.
  • the notation is 40 ° C high temperature evaluation Z4 ° C low temperature evaluation.
  • Each sample was a sample with no curl at 20 ° C before each test. If it is less than 5mm, it will not be a problem in handling with a printer! The cleaning machine is a little tricky. If it is less than 2mm, there will be no problem in printers and washing machines.
  • the communication media of Examples and Comparative Examples were cut to a size of lOOmmX200 mm, and barcode printing was performed with standard settings using a rewrite printer PR3101 manufactured by Sanwa New Tech Co., Ltd., and the printing state was examined.
  • Bar code printing was judged by visual inspection. If the printing was not interrupted, it was judged as ⁇ (good), and if printing was interrupted and could not be read as a barcode, it was judged as X (defect). The printing energy of the printer was standard.
  • Example 10 TKF85WA / Linear expansion rate RHC-100 / Linear expansion rate mesh cloth containing o / o o
  • Example 12 TRF85WA / Linear expansion coefficient RHC-100 / Linear expansion coefficient Mesh cloth containing retaining layer and ⁇ / ⁇ o
  • Example 13 TRF85 A / swelling coefficient RHC-1CI0 / linear expansion coefficient O / O o mesh layer containing retaining layer O / O o
  • Example 14 TRF85WA / Linear expansion rate rate- wo / Linear expansion rate Mesh / retained layer O / O o
  • Example 16 TRF85WA Linear expansion coefficient RHC-0 / Linear expansion coefficient Holding eyebrows with mesh cloth and O / O o
  • Example 10 shows curl and print evaluation. Although the price was ⁇ , it was a little hard to handle as a recording medium to be used over and over again. In Comparative Example 8, when the curl result was X, printing was possible even at high temperatures by correcting the force when printing.
  • the curl just after printing is almost absent in the examples, but in Comparative Examples 5, 6, and 8, large curls are generated immediately after printing due to the heat of printing. It showed superior characteristics.
  • the recording medium of the present invention is less likely to curl even when the air temperature changes. Particularly, in the case where the display layer is a reversible thermosensitive recording layer, the color development state or decoloration is caused by heat. The state can be displayed repeatedly.

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  • Laminated Bodies (AREA)

Abstract

La présente invention a trait à un matériau d'enregistrement thermique réversible à durabilité améliorée telle que la résistance à la flexion et la résistance à l'abrasion lors de la déformation ou du lavage d'un support, à un support de communication à circuit intégré incorporé résistant à la contrainte externe et présentant une excellente aptitude à l'impression. L'invention a trait à un matériau d'enregistrement comportant une structure de couche se prêtant difficilement au cintrage. Le matériau d'enregistrement thermique réversible présente une structure dans laquelle un matériau de base d'affichage contenant principalement du polyéthylène téréphtalate ayant une couche d'enregistrement thermique réversible et un support contenant principalement un élastomère polyester constitué d'un segment rigide et d'un segment souple reliés ensemble par une couche adhésive. Le support de communication comporte un organe d'affichage muni d'un matériau de base d'affichage et une couche d'affichage sur le matériau de base d'affichage, et une entrée de circuit intégré disposée sur le matériau de base d'affichage bordée par l'organe d'affichage et montée avec une puce de circuit intégré assemblée à une platine de renfort satisfaisant des conditions mécaniques spécifiques, et une couche de maintien recouvrant l'entrée de circuit intégré, le module d'élasticité en flexion du support de communication étant de 100 à 2000 MPa. Le matériau d'enregistrement comporte une couche d'affichage prévue sur la face avant d'un matériau de base, et une couche d'inhibition de cintrage prévue sur la face arrière du matériau de base, la couche d'inhibition de cintrage comprenant une couche adhésive positionnée sur le côté du matériau de base et une couche de maintien réalisée en résine synthétique déposée sur la couche adhésive, un rapport entre le coefficient de dilatation linéique de la couche d'affichage et d'au moins une parmi la couche adhésive et la couche de maintien est de 1:5 à 5:1 et le module d'élasticité de stockage d'au moins une parmi la couche adhésive et la couche de maintien est de 0,01 à 1,5 GPa.
PCT/JP2005/016832 2004-09-14 2005-09-13 Materiau d'enregistrement thermique reversible, et support de communication comportant une couche d'affichage et un materiau d'enregistrement WO2006038438A2 (fr)

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JP2010016362A (ja) * 2008-06-06 2010-01-21 Semiconductor Energy Lab Co Ltd 半導体装置の作製方法
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EP3316280A4 (fr) * 2015-06-29 2019-03-13 Mitsui Chemicals Tohcello, Inc. Film pour la fabrication de composants à semi-conducteur
WO2021159495A1 (fr) * 2020-02-14 2021-08-19 汉朔科技股份有限公司 Étiquette électronique de gondole et son procédé de fabrication
WO2023233784A1 (fr) * 2022-06-02 2023-12-07 ニッタ株式会社 Étiquette à circuit intégré et son procédé de fabrication

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JP2009122783A (ja) * 2007-11-12 2009-06-04 Krd Corporation Kk Ｉｃタグ
US8637932B2 (en) 2008-04-25 2014-01-28 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device and method for manufacturing the same
WO2009131132A1 (fr) * 2008-04-25 2009-10-29 Semiconductor Energy Laboratory Co., Ltd. Dispositif à semiconducteur et son procédé de fabrication
US8133749B2 (en) 2008-04-25 2012-03-13 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device and method for manufacturing the same
US8384209B2 (en) 2008-05-12 2013-02-26 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device and method for manufacturing semiconductor device
US9048277B2 (en) 2008-05-12 2015-06-02 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device and method for manufacturing semiconductor device
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JP2010016362A (ja) * 2008-06-06 2010-01-21 Semiconductor Energy Lab Co Ltd 半導体装置の作製方法
US8552498B2 (en) 2008-09-19 2013-10-08 Semiconductor Energy Laboratory Co., Ltd. Semiconductor device and method for manufacturing the same
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JP2017514253A (ja) * 2014-04-11 2017-06-01 コナック カンパニー リミテッドＫｏｎａｃ． Ｃｏ．， Ｌｔｄ 麻生地シートを含むカード及び製造方法
EP3316280A4 (fr) * 2015-06-29 2019-03-13 Mitsui Chemicals Tohcello, Inc. Film pour la fabrication de composants à semi-conducteur
US10858547B2 (en) 2015-06-29 2020-12-08 Mitsui Chemicals Tohcello, Inc. Film for manufacturing semiconductor parts
US11535776B2 (en) 2015-06-29 2022-12-27 Mitsui Chemicals Tohcello, Inc. Film for manufacturing semiconductor parts
WO2021159495A1 (fr) * 2020-02-14 2021-08-19 汉朔科技股份有限公司 Étiquette électronique de gondole et son procédé de fabrication
WO2023233784A1 (fr) * 2022-06-02 2023-12-07 ニッタ株式会社 Étiquette à circuit intégré et son procédé de fabrication
JP2023177662A (ja) * 2022-06-02 2023-12-14 ニッタ株式会社 Ｉｃタグ及びその製造方法

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