JP2006035740A - Over-sheet for card and card using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a card showing no warp even under a storage condition at a high temperature and to provide an over-sheet for the card. <P>SOLUTION: The over-sheet comprises at least tree layers of a welded layer (A) made of a polyester copolymer, a heat-resistant layer (B-1) made of a polycarbonate resin or a heat resistant layer (B-2) containing 70 to 40 pts.wt. of the polycarbonate resin and 30 to 60 pts.wt. of the polyester copolymer resin, and a surface layer (C) wherein the heat-resistant layer (B-1) is 15 to 50 μm thick or the heat resistant layer (B-2) is 30 to 60 μm thick, and the whole thickness of the sheet is 50 to 100 μm. By this the card shows no warp even under the storage condition at the high temperature. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a card and a card oversheet that do not warp even under high temperature storage conditions.

  In general, a plastic card is produced by laminating a transparent sheet called an oversheet on a white colored sheet called a core sheet. The lamination of the core sheet and the oversheet is performed by sticking heat-sealable resins together or using an adhesive.

  In general, vinyl chloride sheets have been used for these card sheets, but there are increasing cases in which polyester resins are used due to the problem of incineration. Among them, a copolymer polyester resin (poly (ethylene-1,4-cyclohexylenedimethylene terephthalate), PETG resin) obtained by substituting the ethylene glycol component of the polyethylene terephthalate resin with cyclohexanedimethanol is particularly often used. .

  However, the copolymer polyester resin obtained by substituting the ethylene glycol component of the polyethylene terephthalate resin with cyclohexanedimethanol has low heat resistance, so when the molded card is exposed to a high temperature, for example, 90 ° C. Has a problem of warping (for example, Patent Document 1).

  A card using a copolymerized polyester resin obtained by substituting the ethylene glycol component of a polyethylene terephthalate resin with cyclohexanedimethanol, and many techniques for suppressing warpage of the card due to heat have been reported. For example, Patent Documents 2 and 3 are cited. These have achieved a reduction in warpage due to heat of the card by blending a resin having a high glass transition temperature such as a polycarbonate resin. Although it is possible to suppress warping due to heat of the card by the methods described in these documents, these documents contain a resin having a high glass transition temperature in all or many regions constituting the card. Increasing the proportion of resin with a high glass transition temperature will adversely affect various properties other than heat resistance, such as an increase in fusing temperature and increased warpage when embossed characters are engraved. .

JP 2000-238475 A Japanese Patent No. 3045112 JP 2001-80251 A

  An object of the present invention is to provide a card that does not warp even under high-temperature storage conditions, and a card oversheet used therefor, which has a configuration that does not contain a resin having a high glass transition temperature as much as possible.

As a result of various investigations to solve the above problems, the present inventors have arranged a resin layer having high heat resistance on the surface layer side of the card, so that it will not warp more efficiently even under high temperature storage conditions. I found out that I could make a card.
That is, the present invention
(1) A card oversheet used as a surface layer of a card that does not warp even under high temperature storage conditions, wherein 10 to 70 mol% of the ethylene glycol component of the polyethylene terephthalate resin is replaced with cyclohexanedimethanol. Copolymerized polyester obtained by substituting 10 to 70 mol% of the ethylene glycol component of polyethylene terephthalate resin with a fusion layer (A) made of copolymerized polyester, a heat resistant layer (B-1) made of polycarbonate resin, and polyethylene terephthalate resin. For a card, comprising at least three surface layers (C) comprising: a heat-resistant layer (B-1) having a thickness of 17 to 50 μm, and a card oversheet having a total thickness of 50 to 100 μm. Oversheet,
(2) A card oversheet used as a card surface layer that does not warp even under high temperature storage conditions, wherein 10 to 70 mol% of the ethylene glycol component of the polyethylene terephthalate resin is replaced with cyclohexanedimethanol. Fusion layer (A) made of copolymerized polyester, 30 to 60 parts by weight of copolymerized polyester resin obtained by replacing 70 to 40 parts by weight of polycarbonate resin with 10 to 70 mol% of the ethylene glycol component of polyethylene terephthalate resin by cyclohexanedimethanol At least three layers of a heat-resistant layer (B-2) containing a part and a surface layer (C) made of a copolymerized polyester obtained by substituting 10 to 70 mol% of the ethylene glycol component of the polyethylene terephthalate resin with cyclohexanedimethanol. Including heat-resistant layer (B-2 Of a thickness of 32～60Myuemu, over sheet's cards over sheet total thickness for cards, characterized in that a 50 to 100 [mu] m,
(3) A card using the card oversheet according to any one of (1) to (2) on both sides of the card,
It is.

  According to the present invention, it is possible to provide a card that does not warp even under high temperature storage conditions.

  In the polyethylene terephthalate resin used in the present invention, a resin obtained by substituting 10 to 70 mol% of the ethylene glycol component with cyclohexanedimethanol is an amorphous polyester resin. The substitution amount of the ethylene glycol component is more preferably 20 to 35 mol%. When the substitution amount of the ethylene glycol component is less than 10 mol%, the resin does not become sufficiently amorphous, and thus when the sheet is made into a sheet, the elastic modulus of the sheet is lowered or weakened, or the moldability is poor. This is not preferable. Also, in applications that require heat fusion, recrystallization of the sheet proceeds at the time of cooling after being fused, and heat fusion properties are lost, so there is a problem that sufficient adhesive strength cannot be obtained. Arise. On the other hand, even when the substitution amount of the ethylene glycol component exceeds 70 mol%, the resin does not become sufficiently amorphous, which is not preferable for the same reason as when the substitution amount of the ethylene glycol component is less than 10 mol%.

  The polycarbonate resin used in the present invention is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted.

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) Bis (hydroxyaryl) alkanes such as tert-butylphenyl) propane, bis (hydroxy) such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane Aryl) cycloalkanes, 4,4′-dihydroxydiphenyl ether, Dihydroxy diaryl ethers such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, dihydroxy diaryls such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide Sulfides, 4,4′-dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy Examples include dihydroxydiaryl sulfones such as −3,3′-dimethyldiphenyl sulfone, and these may be used alone or in combination.

  Although there is no restriction | limiting in particular in the viscosity average molecular weight of the polycarbonate resin used for this invention, Usually, it is 10,000-100000, Preferably it is 15000-35000 from the surface of moldability, intensity | strength, and heat resistance. Moreover, when manufacturing such polycarbonate resin, a molecular weight regulator, a catalyst, etc. may be added as needed.

  On both sides of the heat-resistant layer of the card oversheet of the present invention, there are a fusion layer and a surface layer made of a copolymerized polyester resin obtained by substituting 10 to 70 mol% of the ethylene glycol component of the polyethylene terephthalate resin with cyclohexanedimethanol. Provided. As an advantage of providing the fusion layer, for example, the press temperature can be lowered. In general, the card core sheet is often made of a material that can be heat-sealed with a copolymerized polyester resin obtained by replacing 10 to 70 mol% of the ethylene glycol component of the polyethylene terephthalate resin with cyclohexanedimethanol. Therefore, when the card is produced by integrating the oversheet and the core sheet, the card can be obtained with low energy without using an adhesive. On the other hand, as an advantage of providing the surface layer, for example, the temperature during transfer printing can be lowered. In addition to this, in a card using magnetic tape as an information recording medium, the magnetic tape is embedded on either the front or back of the oversheet. By using the copolyester resin for the fusion layer and the surface layer, The magnetic tape can be easily embedded and a smoother card can be obtained.

  The heat-resistant layer of the card oversheet of the present invention is a polycarbonate resin or a polycarbonate resin containing a copolymerized polyester resin obtained by substituting 10 to 70 mol% of an ethylene glycol component of a polyethylene terephthalate resin with cyclohexanedimethanol. The content of the copolyester resin can vary depending on the heat resistance required for the card.

  In other words, the heat resistance required for the card is that the card does not undergo thermal deformation, but these are broadly divided into two types: that the card is not warped by heat and that the card is not recessed by heat. In the case of a contact type IC card or magnetic stripe card, these deformations are not preferable because resistance is generated when the card is inserted into and removed from the reader / writer. Further, even in a non-contact type IC card that does not require insertion / removal of the card into / from the reader / writer, it is not preferable that the card is deformed because the appearance is not beautiful.

  The heat-resistant temperature required for the card varies. For example, it is said that the temperature in the car in summer rises to nearly 80-90 ° C. For this reason, it may be required that the card does not warp even when left in the vehicle. In addition, the non-stop automatic toll collection system (ETC) on expressways automatically pays by wirelessly communicating information about tolls, etc. between the toll booth antenna and the onboard equipment mounted on the car. However, at this time, a dedicated ETC card needs to be inserted into the vehicle-mounted device. Even when this ETC card is left in a state where it is inserted into the vehicle-mounted device in summer, it is required that the card does not dent. In addition to this, heat resistance is also required for an IC card for process management in a factory, an IC card for recording measurement data at a construction site, and the like.

  In order to suppress thermal deformation of the card, a resin having a high glass transition temperature may be used. The card dent due to heat needs to increase the heat resistance of the entire core sheet and oversheet constituting the card. Whether the card is dented by heat can be evaluated by the Vicat softening temperature measured according to JIS K 7206. On the other hand, the warp of the card due to heat, which is a problem in the present invention, only needs to increase the heat resistance of the surface layer of the card, that is, the oversheet.

  When polycarbonate resin is used for the heat resistant layer of the oversheet (B-1), the thickness of the heat resistant layer needs to be 15 to 50 μm. Preferably it is 25-50 micrometers, More preferably, it is 45-50 micrometers. When the thickness of the heat-resistant layer made of polycarbonate resin is less than 15 μm, the warp of the card due to heat cannot be sufficiently suppressed. When the thickness exceeds 50 μm, the warp after embossing is required for a card that requires embossing of characters. It is not preferable because it becomes large and costs increase.

  In the case of using a resin containing a copolymerized polyester resin obtained by substituting 10 to 70 mol% of an ethylene glycol component of a polyethylene terephthalate resin with cyclohexanedimethanol for the heat-resistant layer of the oversheet (B-2), the heat-resistant layer Needs to be 30-60 μm. Preferably it is 35-60 micrometers, More preferably, it is 50-60 micrometers. If the thickness of the heat-resistant layer made of the polycarbonate resin containing the copolymerized polyester is less than 30 μm, the warp of the card due to heat cannot be sufficiently suppressed, and if it exceeds 60 μm, characters must be stamped by embossing. This is not preferable because there is a problem that warpage after embossing becomes large on a card, or that magnetic tape is insufficiently embedded on a card using a magnetic stripe as an information recording medium.

  The oversheet of the present invention has a thickness of 50 to 100 μm. Use of an oversheet with a thickness outside this range is preferable because there is a problem that the production efficiency of the card is deteriorated or the chip is transparent from the back side of the card in an IC card in which the concealing layer is not printed on the back side of the card. Absent.

  In any layer of the card oversheet of the present invention, additives usually used as desired, for example, compatibilizers, stabilizers, lubricants, reinforcing agents, processing aids, pigments, antistatic agents, antioxidants , Neutralizers, ultraviolet absorbers, dispersants, thickeners, other inorganic fillers, resin modifiers, and the like may be included. Further, the fusion layer and the surface layer of the card oversheet of the present invention have a high heat resistance resin and a high solvent resistance when it is desired to shift the press temperature to a high temperature side or to prevent sheet deterioration due to printing ink. A resin or the like may be contained.

Hereinafter, the present invention will be described by way of examples, but this is merely an example, and the present invention is not limited thereto. The raw materials used in the examples are as follows, and the raw materials shown in Tables 1 and 2 are as follows.
(1) PETG resin: poly (ethylene-1,4-cyclohexylenedimethylene terephthalate) resin, GN071, manufactured by Eastman Chemical Japan Co., Ltd. (2) PC resin: polycarbonate resin, Caliber 301-10, Sumitomo Dow ( Co., Ltd.

<Experimental Examples 1-8>
A single-layer sheet of PETG resin and PC resin was prepared using a single-screw extruder and a T-type die in order to study where the heat-resistant layer in the card can efficiently suppress the warp of the card due to heat. . The produced single-layer sheet was sandwiched between press plates having the configuration shown in Table 1, pressed at 110 ° C. for 10 minutes, and then punched out to a card size specified by ISO / IEC7810 to obtain a card-like sample. A cut was made in the obtained card-like sample, and it was confirmed whether or not the three sheets were peeled off, but none of the cards were peeled off. Next, the card-like sample was stood so that the long side of the card-like sample was at an angle of 45 degrees with respect to the horizontal plane so that the first layer in Table 1 was the upper surface, and left in an oven at 90 ° C. for 30 minutes. It cooled to room temperature and measured the curvature according to JISX6301. As a result, the warpage of the card when the total thickness of the heat-resistant layer (PC resin layer) is converted to 200 μm and the determination based on the following are shown in Table 1.
○: Warpage value when heat-resistant layer was converted to 200 μm was less than 1 Δ: Warpage value when heat-resistant layer was converted to 200 μm was less than 2 ×: Heat-resistant layer was converted to 200 μm From these experimental examples, it was found that the layer structure having the heat-resistant layers on both outer layers can effectively suppress the warp of the card.

<Examples 1-9 and Comparative Examples 1-4>
In order to investigate how many μm or more of the heat-resistant layer thickness of the oversheet can suppress the warp of the card due to heat, an oversheet and a core sheet were prepared as follows.

<Production of oversheet>
Using a single screw extruder and a T-type die, PETG resin was used for the fusion layer (A) and the surface layer (C), and the PC layer or PC resin was added to the heat-resistant layer (B). A three-layer oversheet using a resin (sheet laminated with C / B / A from the upper surface of the sheet, sheet thickness: 50 μm or 100 μm) was produced by a coextrusion method. The fusing layer (A) was embossed so that air would not accumulate during card production. In the case where the raw material of the heat-resistant layer was an alloy of PC resin and PETG resin, a multilayer sheet was prepared using pellets produced by melt-kneading using a biaxial kneading extruder in advance. The layer composition ratio of the sheet is shown in Table 2.

<Production of core sheet>
10 parts of a white pigment (titanium oxide, titanium CR-60, manufactured by Ishihara Sangyo Co., Ltd.) was blended with the PETG resin, and melt-kneaded using a twin-screw kneading extruder to produce pellets. 560 μm and 660 μm sheet-like samples were obtained from the manufactured pellets using a single screw extruder and a T-shaped die.

The prepared oversheet and core sheet are sandwiched between press plates in the form of oversheet / core sheet / oversheet, pressed at 110 ° C. for 10 minutes, and then punched to the card size specified by ISO / IEC7810 to obtain a card-like sample. It was. At this time, the sheets were overlapped so that the fused sheet of the oversheet and the core sheet were combined, and the oversheet and the core sheet were combined so that the card thickness after pressing was 760 μm. A cut was made in the obtained card-like sample, and it was confirmed whether or not the three sheets were peeled off, but none of the cards were peeled off. Subsequently, the magnitude | size of the curvature by the heat | fever of this card-like sample was measured by the method similar to an experiment example, and the result based on the following and the determination based on the following were shown in Table 2.
○: Warpage was 2.0 mm or less ×: Warpage exceeded 2.0 mm

  Various heat resistances are required for cards on the market depending on the application. According to the present invention, it is possible to provide a card and a card oversheet that do not warp even when stored at high temperatures, and the amount of high heat-resistant resin necessary to achieve the card is minimized. Therefore, the sacrifice of other characteristics due to an increase in the high heat resistant resin can be suppressed as much as possible. Furthermore, by controlling the thickness of the heat-resistant layer of the oversheet or the content of the high heat-resistant resin in the heat-resistant layer, it is possible to cope with various required heat-resistant temperatures.

Claims (3)

  A card oversheet used as a surface layer of a card that does not warp even under high temperature storage conditions, and is a copolymerized polyester obtained by substituting 10 to 70 mol% of an ethylene glycol component of a polyethylene terephthalate resin with cyclohexanedimethanol A surface comprising a copolyester obtained by substituting cyclohexane dimethanol for 10 to 70 mol% of the ethylene glycol component of a polyethylene terephthalate resin, and a heat-resistant layer (B-1) comprising a fusion resin layer (A) comprising A card oversheet comprising at least three layers (C), wherein the heat-resistant layer (B-1) has a thickness of 17 to 50 µm, and the overall thickness of the card oversheet is 50 to 100 µm.   A card oversheet used as a surface layer of a card that does not warp even under high temperature storage conditions, and is a copolymerized polyester obtained by substituting 10 to 70 mol% of an ethylene glycol component of a polyethylene terephthalate resin with cyclohexanedimethanol A fusion layer (A) comprising: 30 to 60 parts by weight of a copolyester resin obtained by replacing 10 to 70 mol% of an ethylene glycol component of a polyethylene terephthalate resin with cyclohexanedimethanol in 70 to 40 parts by weight of a polycarbonate resin Heat-resistant layer (B-2) and at least three layers of a surface layer (C) made of a copolyester obtained by substituting cyclohexanedimethanol for 10 to 70 mol% of the ethylene glycol component of the polyethylene terephthalate resin, Layer (B-2) thickness There is 32～60Myuemu, over sheet's cards over sheet total thickness for cards, characterized in that a 50 to 100 [mu] m. The card | curd which uses the oversheet for cards in any one of Claims 1-2 on both surfaces of a card | curd.