Patent Application
20190256706
The present invention relates to a resin composition that has high durability and heat resistance and can be easily processed, a resin sheet for a card produced by using the same, and a multilayer sheet.
Resin films are conventionally used for ID cards, e-passports, contactless IC cards, etc. It is known that as materials of such resin films, for example, polyvinyl chloride (PVC), polyethylene terephthalate-based PET-G, etc. are used.
It is also known that polyester resin compositions are used as resin compositions for various cards (see Patent Document 1). Patent Document 1 discloses a polyester resin composition which contains a polyester resin mainly composed of PET and an aromatic polycarbonate resin.
Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-97361
When using PVC, PET-G or the like as a resin composition for cards, the problem of mechanical strength of cards may arise since durability and heat resistance of these resins are not necessarily sufficient.
Patent Document 1 describes that the above-described polyester resin composition is excellent in heat resistance, impact resistance, etc. However, the polyester resin composition has poor transparency and the resolution of printed portions is reduced.
The present inventors diligently made researches in order to solve the above-described problems and found that a predetermined resin composition containing a polycarbonate has high durability and heat resistance and maintains transparency while having excellent easiness of processing, and thus the present invention was achieved.
Specifically, the present invention relates to a resin composition, a resin sheet for a card formed by using a polycarbonate resin composition and a multilayer sheet described below.
Bi(1-x)MxOy (I)
wherein: M is at least one metal selected from gadolinium and neodymium; x is a value satisfying 0.001<x<0.5; and y is a value satisfying 1<y<2.5.
The resin composition of the present invention contains an aliphatic polyester compound and a polycarbonate resin, and when it is processed into a sheet shape, it is not easily broken. It has excellent impact resistance, and has high durability particularly with respect to bending fatigue. Moreover, the resin composition of the present invention is also excellent in heat resistance and transparency, and is easily processed by heating. The resin composition of the present invention that has the above-described excellent characteristics is suitably used, in particular, as a material for a resin sheet for cards and a multilayer sheet, and for example, it is suitable for the production of an ID card, an e-passport, a contactless IC card, etc.
Further, the resin composition of the present invention is also excellent in adhesiveness to a film formed with another resin, in particular, a film formed with a polyester resin as the main component such as a PET-G film, and therefore is also suitable for the production of a laminate including such a film.
Hereinafter, the present invention will be described in detail. Note that the present invention is not limited to the below-described embodiments, and can be arbitrarily changed and then carried out within a range in which the effects of the present invention are exerted.
The resin composition of the present invention contains: 2% by mass or more but less than 9% by mass of an aliphatic polyester compound; and a polycarbonate resin. The type, etc. of each of the aliphatic polyester compound and the polycarbonate resin are as described later, and the content of the aliphatic polyester compound in the resin composition is more preferably 3% by mass or more but less than 9% by mass, even more preferably 3% by mass or more but 7% by mass or less, and particularly preferably 3% by mass or more but 5% by mass or less.
Thus, the resin composition of the present invention contains, as the main component, the polycarbonate resin that is excellent in durability and heat resistance and has high transparency, and therefore has these excellent characteristics. Moreover, the resin composition of the present invention contains a predetermined amount of the aliphatic polyester compound which is described in detail later, and for this reason, the resin composition is also excellent in easiness of processing.
The glass transition temperature of the resin composition of the present invention is preferably 100° C. to 135° C., more preferably 105° C. to 130° C., and even more preferably 110° C. to 128° C. In particular, from the viewpoint of easiness of processing of the resin composition, the glass transition temperature is 128° C. or lower, and preferably 120° C. or lower.
The aliphatic polyester compound contained in the resin composition of the present invention comprises a lactone compound as a constituent monomer. The aliphatic polyester compound may comprise, as the constituent monomer, a plurality of types of the above-described compounds, or may comprise only one type of the compound.
Among the above-described compounds, the aliphatic polyester compound preferably comprises a lactone compound as a monomer. In this regard, in all the monomers constituting the aliphatic polyester compound, the lactone compound is used in an amount of preferably 70 mol % or more, and more preferably 90 mol % or more.
Further, the lactone compound as the monomer of the aliphatic polyester compound includes ϵ-caprolactone, β-propiolactone and δ-valerolactone. The monomer of the aliphatic polyester compound may comprise a plurality of types of these lactone compounds, or only one type may be used.
Further, among the above-described lactone compounds, ϵ-caprolactone is preferably used as the monomer of the aliphatic polyester compound. In this regard, in the lactone compounds, ϵ-caprolactone is used in an amount of preferably 70 mol % or more, and more preferably 90 mol % or more.
Thus, the aliphatic polyester compound preferably comprises a polycaprolactone whose main constituent monomer is ϵ-caprolactone, and more preferably, as the aliphatic polyester compound, a polycaprolactone whose monomer is only ϵ-caprolactone is used. Note that the main constituent monomer means that it accounts for 50 mol % or more of the total of constituent monomers.
The weight-average molecular weight of the aliphatic polyester compound is preferably 10,000 to 90,000. The weight-average molecular weight of the aliphatic polyester compound is more preferably 10,000 to 60,000, and particularly preferably 10,000 to less than 40,000.
The polycarbonate resin contained in the resin composition of the present invention is not particularly limited as long as it contains a carbonate bond in the main chain of the molecule, i.e., it contains a —[O—R—OCO]— unit (R includes an aliphatic group, an aromatic group, or both of the aliphatic group and the aromatic group, and further has a linear structure or a branched structure), but the below-described polycarbonate is particularly preferably used.
That is a polycarbonate having a bisphenol A skeleton.
The weight-average molecular weight of the polycarbonate resin is preferably 20,000 to 60,000, more preferably 23,000 to 55,000, and even more preferably 25,000 to 50,000.
Further, the glass transition temperature of the polycarbonate resin is preferably 120 to 160 (° C.), and more preferably 130 to 155 (° C.).
The polycarbonate resin having a weight-average molecular weight or glass transition temperature within the above-described ranges contributes to realization of high heat resistance and impact resistance of the resin composition.
Further, the resin composition preferably contains the polycarbonate resin in an amount of 90% by mass or more based on the mass of the whole resin composition. The resin composition contains the polycarbonate resin in an amount of more preferably 93% by mass or more, and particularly preferably 95% by mass or more of the aliphatic polyester compound based on the mass of the whole resin composition.
The resin composition may further contain a white pigment. The resin composition containing the white pigment is suitably used as a material for a white sheet, for example, a white sheet for forming a core layer including an antenna of an ID card or the like. As the white pigment, titanium oxide, talc, kaolin, clay, mica or the like is used, and titanium oxide is preferably used.
The content of the white pigment is preferably 10 to 30% by mass, more preferably 13 to 25% by mass, and even more preferably 15 to 20% by mass based on the mass of the whole resin composition.
The resin composition may further contain a laser color former. The resin composition containing the laser color former is suitably used, for example, as a material for a laser marking sheet (laser marking layer) which enables printing by means of marking treatment for cards requiring prevention of falsification particularly. As the laser color former, carbon black, antimony-doped tin oxide, a bismuth oxide-based color former or the like is used, and preferably, carbon black is used.
Further, as a metal oxide-based laser color former, a bismuth oxide-based color former is preferred, and more preferred is a bismuth oxide-based color former which contains, as a metal component, neodymium or gadolinium in addition to bismuth.
For example, as the metal oxide that is the laser color former, those represented by formula (I) below are preferred:
Bi(1-x)MxOy (I)
(In formula (I): M is at least one metal selected from gadolinium and neodymium; x is a value satisfying 0.001<x<0.5, and preferably a value satisfying 0.01<x<0.3; and y is a value satisfying 1<y<2.5, and preferably a value satisfying 1.5<y<2.1.)
The content of the laser color former is preferably 0.0001 to 0.2% by mass, more preferably 0.0005 to 0.15% by mass, and even more preferably 0.001 to 0.1% by mass based on the mass of the whole resin composition.
For example, when using carbon black as the laser color former, the content of carbon black is preferably 1 to 100 mass ppm (0.0001 to 0.01% by mass), and more preferably less than 40 mass ppm, for example, 5 to 35 mass ppm based on the mass of the whole resin composition. Further, when using the metal oxide-based particle as the laser color former, the content of the laser color former is, for example, 50 to 5000 mass ppm (0.005 to 0.5% by mass), preferably 80 to 3000 mass ppm, and more preferably 100 to 2000 mass ppm based on the mass of the whole resin composition. Regarding the laser color former, use of a laser color former having characteristics in which a light of 1064 nm that is a wavelength of laser is not easily transmitted, and in addition, a light having a wavelength of about 500 nm is not easily transmitted specifically provides marvelous effects to laser marking performance. For example, the above-described laser color former can realize the effect of enabling clear printing even when just a slight amount of the laser color former is contained in the resin composition. Examples of the laser color former that realizes the effect include the above-described carbon black and those containing bismuth oxide.
The resin composition may contain the below-described additives in addition to the above-described components. Specifically, they are at least one additive selected from the group consisting of a thermal stabilizer, an antioxidant, a flame retardant, a flame retardant auxiliary agent, an ultraviolet absorber, a mold release agent and a coloring agent, etc.
Moreover, an antistatic agent, a fluorescent brightener, an antifog additive, a flowability improving agent, a plasticizer, a dispersant, an antimicrobial agent, etc. may also be added as long as desired physical properties are not significantly impaired.
However, in the case of an organophosphorus compound such as a phosphazene flame retardant, when an excess amount thereof is added to the resin composition, durability of a sheet formed by using the resin composition may be reduced. For this reason, it is preferred that in the resin composition, the content of the organophosphorus compound is, for example, less than 2000 mass ppm, and the content of phosphorus is, for example, less than 100 mass ppm.
Further, when a material containing an organic sulfonic acid phosphonium salt such as an alkylbenzene sulfonic acid phosphonium salt is added to the resin composition as the antistatic agent, durability after card forming may be significantly reduced due to its low molecular weight. Accordingly, there is a case where it is preferred to avoid the addition of an additive which may adversely affect performance of a resin sheet for a card.
Moreover, also in the case of adding glass flakes or the like or a liquid additive such as a phenyl group-containing silicone oil to the resin composition, the problem of reduction in durability after card forming may arise. In particular, when glass flakes are added, the problem of reduction in outer appearance (transparency) of the resin composition may also arise. Accordingly, there is a case where it is preferred to also avoid use of these additives.
Since the resin composition of the present invention is excellent in heat resistance and durability and can be easily processed as described above, it is suitably used as a material for a resin sheet for a card. Specifically, by using the resin composition of the present invention, a sheet for a card, for example, an antenna chip-embedded sheet or a laser marking sheet can be produced.
In the process of producing a sheet using the resin composition of the present invention, as a method for processing the resin composition to form a layer shape (sheet shape), a conventional technique can be employed. Examples thereof include methods using extrusion molding or cast molding.
For example, in a method using extrusion molding, the resin composition of the present invention in the form of pellet, flake or powder is melted and kneaded by an extruder and then extruded from a T-die or the like, and a sheet in a semi-melted state obtained is cooled and solidified while being compressed by rolls, thereby forming a sheet.
The multilayer sheet of the present invention has two or more laminated thermoplastic resin sheets, and at least one layer thereof contains the resin composition of the present invention. More specifically, a card that is a multilayer sheet (laminate) can be produced by laminating a plurality of sheets formed by using the resin composition of the present invention, for example, the above-described sheets for a card.
In a preferred embodiment of the multilayer sheet of the present invention, for example, at least one of thermoplastic resin sheets (resin sheets) contains one material selected from the group consisting of PET-G, polycarbonate, PCT-G, PCT and a mixture of at least two of them (alloy). Specifically, preferred specific examples of the thermoplastic resin sheets (resin sheets) include a PET-G sheet, a polycarbonate (PC) resin sheet, a PCT-G sheet, a PCT sheet and a sheet mainly composed of an alloy of any two of these resins. In particular, as the above-described alloy, an alloy of PC resin and PET-G resin is preferred.
Further, a sheet formed by using the resin composition of the present invention containing polycarbonate, such as the above-described antenna chip-embedded sheet and laser marking sheet, is not only excellent in adhesiveness to other polycarbonate resin sheets to be laminated, but also excellent in adhesiveness to the above-described PET-G sheet and sheet of the alloy of PC resin and PET-G resin.
As the thermoplastic resin sheets (resin sheets) constituting the multilayer sheet, a polycarbonate/polyester sheet (sheet of resin containing both a polycarbonate and a polyester) may also be used.
The PET-G sheet is a sheet formed with a polyethylene terephthalate-based PET-G resin (PETG resin), i.e., a polyester containing a dicarboxylic acid unit mainly composed of a terephthalic acid unit, an ethylene glycol unit and a glycol unit mainly composed of a cyclohexanedimethanol unit (1,4-cyclohexanedimethanol unit). For example, the terephthalic acid unit accounts for 50% or more of all the dicarboxylic acid units on a molar basis, and ethylene glycol accounts for 50% or more of all the glycol units (the total of the ethylene glycol unit and the cyclohexanedimethanol unit) on a molar basis.
Further, as a material for the thermoplastic resin sheets, other polyethylene terephthalate-based resins such as PCT-G resin (PCTG resin) and PCT resin may also be used.
The PCT-G resin is also a polyester containing a dicarboxylic acid unit mainly composed of a terephthalic acid unit, an ethylene glycol unit and a glycol unit mainly composed of a cyclohexanedimethanol unit (1,4-cyclohexinedimethanol unit), but differs from the PET-G resin on the point that the cyclohexanedimethanol unit accounts for 50% or more of all the glycol units (the total of the ethylene glycol unit and the cyclohexanedimethanol unit) on a molar basis.
Further, the PCT resin (polycyclohexylene dimethylene terephthalate resin) is a polyester containing a dicarboxylic acid unit mainly composed of a terephthalic acid unit and a glycol unit mainly composed of a cyclohexanedimethanol unit (1,4-cyclohexanedimethanol unit), and does not contain any ethylene glycol unit.
The sheets formed by using the above-described polyethylene terephthalate-based resins, i.e., the PET-G sheet, the PCT-G sheet and the PCT sheet are excellent in adhesiveness to (compatibility with) the polycarbonate resin sheet and suitably used for a laminate using the polycarbonate resin sheet.
The polycarbonate/polyester sheet is a sheet containing a polymer alloy (mixture) of a polycarbonate and a polyester. As the polycarbonate, the same material as that for the polycarbonate resin contained in the resin composition of the present invention can be used. As the polyester, the above-described aliphatic polyester compound, polyethylene terephthalate-based PETG resin, PCTG resin, PCT resin, etc. can be used. Specifically, as a material of the thermoplastic resin sheet included in the multilayer sheet, a polymer alloy containing at least two of the above-described polycarbonate resin, PETG resin, PCTG resin, PCT resin and aliphatic polyester may be used.
Specific examples of the multilayer sheet include an ID card 10 shown in
The first surface layer 12 and the second surface layer 14 are colorless and transparent, and on the first laser marking layer 16 and the second laser marking layer 18, it is possible to provide printing by means of irradiation of a laser light L. The first core layer 20 and the second core layer 22 are white because the white pigment is contained therein, and in the first core layer 20, an antenna chip 24 is embedded. The information of an IC chip (not shown) is overwritten in response to an electromagnetic wave from outside received by the antenna chip 24.
The resin composition of the present invention can be used in each of these layers. In particular, by forming the first surface layer 12 and the second surface layer 14 with use of the resin composition of the present invention, the ID card 10 whose surface is excellent in durability and heat resistance can be produced.
Moreover, by using the resin composition of the present invention which contains the laser color former, the first laser marking layer 16 and the second laser marking layer 18 which are excellent in laser markability can be formed.
Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the below-described examples, and can be arbitrarily changed and then carried out without departing from the gist of the present invention.
The glass transition temperature (Tg) of the resin was measured using a differential scanning calorimeter EXSTAR DSC 7020 (DSC) manufactured by Hitachi High-Tech Science Corporation. In the measurement, the temperature was increased to a temperature at which the resin component was melted under nitrogen atmosphere (270° C.) at a rate of 15° C./min, decreased to 30° C. at a rate of 20° C./min, and then increased again at a rate of 15° C./min (2nd run). The glass transition temperature was obtained from the obtained DSC curve according to the starting point method.
The adhesiveness of the resin composition to the PETG film in each of Examples and Comparative Examples was evaluated using a sample prepared as described below.
A 50 μm film was prepared using the resin composition to be measured, and it was overlaid on a 100 μm film similarly prepared using PETG (S2008: manufactured by SK Chemicals). The two-layer film to be measured was sandwiched between two laminated plates, in each of which a 0.5 mm SUS plate, a 1 mm silicone rubber sheet, a 100 μm SUS plate and a 0.78 mm Teflon (registered trademark) sheet were layered. Specifically, the film to be measured was sandwiched between the above-described two laminated plates so that the Teflon sheet of one of the laminated plates contacted with the sample film side of the film to be measured and the Teflon sheet of the other laminated plate contacted with the PETG film side of the film to be measured. Further, while the film to be measured was sandwiched between the two laminated plates, it was further sandwiched between a pair of pressing plates of a pressing machine from the side of the 0.5 mm SUS plate positioned at the outermost position of each of the two laminated plates, and using a pneumatic heating press (IMC-1839 type: manufactured by Imoto Machinery Co., Ltd.), it was pressed at 120° C. and an air pressure of 0.2 MPa for 60 seconds, thereby preparing a laminate.
The obtained laminate was attached to an adhesive tape peeling test apparatus by Autograph (AGS-X: manufactured by Shimadzu Corporation), and a peeling test, wherein the 50 μm film of the resin composition to be measured was peeled from the 100 μm PETG film (90° peeling test at a peeling rate of 152.4 mm/min), was conducted. The adhesiveness was evaluated as follows:
The durability of the resin composition of each of Examples and Comparative Examples was evaluated as described below. A card having a thickness of 0.78 mm was prepared using the target resin composition. A card bending test was conducted using an IC card bending/torsion test machine (manufactured by Toyo Seiki Seisaku-sho, Ltd.), and the number of times of bending until a crack was generated in the card was measured. The number of times of bending of the card was measured in accordance with JIS X6305-1, and evaluation was made based on the number of times as follows:
The transparency of the resin composition of each of Examples and Comparative Examples was evaluated as described below. A film having a thickness of 0.3 mm was formed using the resin composition to be measured. The Haze value thereof was measured using a Haze meter (HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd.), and the transparency was evaluated as described below.
The film of each of Examples 4-7 and Comparative Examples 6-13, which will be described in detail later, was subjected to a laser marking process, and the blackness was evaluated as described below. Firstly, using the resin composition to be measured, a laser marking film having a thickness of 0.1 mm containing carbon black or a metal oxide was formed. Further, using the resin composition to be measured not containing carbon black and a metal oxide, a 0.1 mm overlay film was formed. Further, titanium oxide (“White DCF-T-17007” manufactured by Resino Color Industry Co., Ltd.) was added to the resin composition used for forming the overlay film so that the amount of titanium oxide in the whole resin composition became 15 wt %, and using this resin composition, a white core film having a thickness of 0.2 mm was formed.
Regarding the prepared films, the overlay film, the laser marking film and the white core film were layered in this order. The three-layer film to be measured was sandwiched between two laminated plates, in each of which a 0.5 mm SUS plate, a 1 mm silicone rubber sheet, a 100 μm SUS plate and a 0.78 mm Teflon (registered trademark) sheet were layered. Specifically, the film to be measured was sandwiched between the above-described two laminated plates so that the Teflon sheet of one of the laminated plates contacted with the overlay film side of the film to be measured and the Teflon sheet of the other laminated plate contacted with the white core film side of the film to be measured. Further, while the film to be measured was sandwiched between the two laminated plates, it was further sandwiched between a pair of pressing plates of a pressing machine from the side of the 0.5 mm SUS plate positioned at the outermost position of each of the two laminated plates, and using a pneumatic heating press (IMC-1839 type: manufactured by Imoto Machinery Co., Ltd.), it was pressed at 160° C. and an air pressure of 0.2 MPa for 60 seconds, thereby preparing a laminate.
Using a laser marking apparatus (“EasyMarIV-E10” manufactured by Rofin-Baasel), laser marking was provided to the laminate obtained by pressing from the overlay film layer side under the below-described irradiation conditions. The printed portion was measured by a spectral density meter (“X-Rite504” manufactured by X-Rite Inc.), and the obtained maximum value was regarded as the blackness.
Scan Speed: 1,000 mm/s
Output Energy: 21 to 30 A
Pulse Frequency: 10 to 100 kHz
In the judgment of laser color developing property, Examples or Comparative Examples in which the value of the blackness was 1.70 (threshold) or more were evaluated as “good”, and Examples or Comparative Examples in which the value of the blackness was less than the threshold were evaluated as “poor”. Note that Examples and Comparative Examples in which carbon black and a metal oxide were not contained and laser markability was not possessed were evaluated as “none” of laser color developing property.
Each of the resin compositions in Examples 1-3 and Comparative Examples 1-5 was produced as described below. Specifically, to a resin represented by an abbreviation described below as shown in Table 1, polycaprolactone (poly(e-caprolactone), weight average molecular weight: 10000) and a phosphazene flame retardant (“Rabitle (registered trademark) FP-110” manufactured by Fushimi Pharmaceutical Co., Ltd.) were added in amounts respectively shown in Table 1, thereby obtaining a homogeneous resin composition.
Each of the resin compositions in Examples 4-7 and Comparative Examples 6-13 were produced as described below. Specifically, to a resin represented by an abbreviation described below as shown in Table 1, polycaprolactone (poly(ϵ-caprolactone), weight average molecular weight: 10000), carbon black (“MONARCH (registered trademark) 800” manufactured by Cabot Corporation) and a metal oxide (“42-920A” manufactured by Tokan Material Technology Co., Ltd.) were added in amounts respectively shown in Table 1, and the mixture was stirred, thereby obtaining a homogeneous resin composition.
Further, to a resin shown in Table 1 below, polycaprolactone (Capa (registered trademark) 6800 manufactured by Perstorp, weight average molecular weight: 80,000) and the above-described carbon black were added in amounts respectively shown in Table 1, and the mixture was stirred, thereby producing the resin composition of Example 8.
Note that the above-described metal oxide (“42-920A”) is a mixture of bismuth trioxide (Bi2O3) and neodymium trioxide (Nd2O3), and specifically, it is a mixture containing about 98 to 99% by mass of Bi2O3 and about 0.3 to 1.0% by mass of Nd2O3.
Bisphenol A-Type Aromatic Polycarbonate Resin
(“Iupilon (registered trademark) E-2000” manufactured by Mitsubishi Engineering-Plastics Corporation, thermal deformation temperature (glass transition temperature): 150° C.)
Modified Polyethylene Telephthalate Resin
(“SKYGREEN (registered trademark) 52008” manufactured by SK Chemicals, thermal deformation temperature (glass transition temperature): 80° C.)
Mixture of the above-described (PC) and (PETG) at a weight ratio of 50:50
Using each of the resin compositions in Examples 1-7 and Comparative Examples 1-13, a sheet for a test piece was produced as described below. Firstly, using a T-die melt extruder composed of a twin screw extruder with a barrel diameter of 32 mm and screw L/D=31.5, a sheet having a width of 300 mm was formed at a discharge rate of 20 kg/hour and at a screw rotation speed of 200 rpm. The cylinder/die head temperature was set at 280° C. in Examples 1-7 and Comparative Examples 2, 4-9, 11 and 13, and at 260° C. in Comparative Examples 1, 3, 10 and 12. As the sheet, a sheet in which both the surfaces are a mirror surface was produced. For the above-described evaluation of adhesiveness, durability and transparency, films with four thicknesses, i.e., 50 μm (0.05 mm), 100 μm (0.1 mm), 300 μm (0.3 mm) and 780 μm (0.78 mm), were formed using each of the resin compositions, and the above-described measurements were carried out.
10 ID card (multilayer sheet)
12 first surface layer
14 second surface layer
16 first laser marking layer
18 second laser marking layer
20 first core layer
22 second core layer
24 antenna chip
| Number | Date | Country | Kind |
|---|---|---|---|
| 2016-204712 | Oct 2016 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2017/037580 | 10/17/2017 | WO | 00 |
