WO2011145589A1 - カード用シート及びカード - Google Patents
カード用シート及びカード Download PDFInfo
- Publication number
- WO2011145589A1 WO2011145589A1 PCT/JP2011/061251 JP2011061251W WO2011145589A1 WO 2011145589 A1 WO2011145589 A1 WO 2011145589A1 JP 2011061251 W JP2011061251 W JP 2011061251W WO 2011145589 A1 WO2011145589 A1 WO 2011145589A1
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- WIPO (PCT)
- Prior art keywords
- card
- sheet
- less
- resin
- polycarbonate resin
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/40—Manufacture
- B42D25/405—Marking
- B42D25/425—Marking by deformation, e.g. embossing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/40—Manufacture
- B42D25/45—Associating two or more layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
- G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
- G06K19/02—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the selection of materials, e.g. to avoid wear during transport through the machine
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
- G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
- G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
- G06K19/06187—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with magnetically detectable marking
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
- G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
- G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
- G06K19/067—Record carriers with conductive marks, printed circuits or semiconductor circuit elements, e.g. credit or identity cards also with resonating or responding marks without active components
- G06K19/07—Record carriers with conductive marks, printed circuits or semiconductor circuit elements, e.g. credit or identity cards also with resonating or responding marks without active components with integrated circuit chips
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- B42D2033/30—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42P—INDEXING SCHEME RELATING TO BOOKS, FILING APPLIANCES OR THE LIKE
- B42P2241/00—Parts, details or accessories for books or filing appliances
- B42P2241/26—Environmental aspects
- B42P2241/28—Materials, e.g. biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
Definitions
- the present invention relates to a card sheet and a card produced using the same, and more specifically, an environment-friendly type resin mainly composed of a resin mainly composed of plant-derived materials (also referred to as “plant material resin”).
- plant material resin also referred to as “plant material resin”.
- the present invention relates to a card sheet and a card produced using the same.
- PVC polyvinyl chloride resin
- a magnetic stripe card is obtained by superimposing a transparent oversheet temporarily bonded with a magnetic tape on a printed white core sheet, and heat-sealing the sheets with a hot press (hereinafter referred to as “laminate”). After that, it is cut into a card shape with a punching blade, and finally, a letter stamp (hereinafter referred to as “emboss”) is applied with an embosser.
- a PVC sheet is a material suitable for a card, which can be produced in a large amount by a calendar method, and has excellent printability, laminateability and embossability.
- polyester material which is a non-PVC card material for example, a sheet made of an amorphous polyester resin which is a dehydrated condensate of terephthalic acid, ethylene glycol and cyclohexanedimethanol has been proposed. ing.
- This material has processing suitability for cards close to PVC sheets, and can be made into cards using the same equipment as PVC sheets, so it is said that it is the favorite sheet material to replace PVC, but when embossed under the same conditions as PVC There was a problem that the embossed curl became large. If the emboss curl is large, the card may not only look bad, but it may be difficult to insert the card into a reader / writer. Therefore, a sheet that can reduce the emboss curl even when embossed under the same conditions as PVC has been desired. .
- Patent Document 1 discloses a card oversheet made of a composition containing a substantially non-crystalline polyester resin as a main component and a polycarbonate resin, a polyarylate resin, or a mixture thereof.
- Patent Document 2 mainly comprises a substantially non-crystalline polyester resin obtained by substituting a part of ethylene glycol, which is a component of polyethylene terephthalate, with 1,4-cyclohexanedimethanol.
- a card sheet containing an inorganic filler and polybutylene terephthalate or a copolymer thereof is disclosed.
- lactic acid polymers made from lactic acid obtained by fermenting starch obtained from plants. If the amount of plant raw material resin increases, not only can it contribute to the reduction of carbon dioxide emissions, but also the amount of exhaustible resources can be reduced, greatly contributing to the recycling of resources.
- Lactic acid-based polymers are excellent in transparency, rigidity, etc., and because they have already been established in fermentation and synthesis technology, they can be industrially mass-produced, so they are attracting attention as alternative raw materials for polyethylene terephthalate and polyvinyl chloride. In the field of manufacturing information recording cards, proposals have been made to use such lactic acid polymers as raw materials.
- Patent Document 3 discloses a biodegradable card formed by laminating a core layer and an over layer composed mainly of a composition comprising polylactic acid and a biodegradable aliphatic polyester having a glass transition temperature of 0 ° C. or less. Has been.
- Patent Document 4 discloses a card resin composition containing a lactic acid polymer, an amorphous aromatic polyester resin, and a thermoplastic elastomer, and a card sheet using the same.
- Patent Document 5 discloses a card formed by laminating a layer made of a substantially non-crystalline aromatic polyester resin composition and a layer made of a thermoplastic resin having a high heat resistance using a polycarbonate resin in the composition. A sheet and a card using the same are disclosed.
- an object of the present invention is to provide a card sheet and a card which are excellent in all of heat resistance, weather resistance, rigidity, punching workability and embossability and which use a plant raw material resin.
- the present inventors have found that a card sheet using a resin composition containing as a main component a polycarbonate resin containing a structural unit derived from a specific dihydroxy compound and having a glass transition temperature of less than 130 ° C. And it discovered that the card produced using it and the said subject could be solved, and came to complete this invention. That is, the present invention is as follows.
- a card sheet having a layer comprising:
- the polycarbonate resin (A) contains the structural unit (a) in a proportion of 80 mol% or more and 99 mol% or less in the structural units derived from all dihydroxy compounds, and has a glass transition temperature of 90 ° C. or higher.
- the structural unit (c) derived from the polyalkylene glycol having a mass average molecular weight of 1000 or less in the polycarbonate resin (A) is 1 mol% or more and 20 mol% or less in the structural units derived from all dihydroxy compounds.
- the card according to [11] which is an IC card produced using an IC chip.
- a card sheet and a card that are excellent in all of heat resistance, weather resistance, rigidity, punching workability, and embossability and that use a plant raw material resin.
- main component means that the ratio of the target component in the composition is 50% by mass or more, preferably 75% by mass or more, more preferably 90% by mass or more (including 100% by mass). Say something.
- Polycarbonate resin (A) As the polycarbonate resin (A) used in the present invention, a polycarbonate resin containing a structural unit (a) derived from a dihydroxy compound represented by the following formula (1) and having a glass transition temperature of less than 130 ° C. is used.
- the dihydroxy compound represented by the formula (1) is an ether diol that can be produced from a saccharide using a biogenic substance as a raw material, and specifically includes isosorbide, isomannide, isoide, and the like having a stereoisomeric relationship. . These may be used alone or in combination of two or more. Among them, isosorbide can be produced at low cost by hydrogenating and dehydrating D-glucose obtained from starch, and can be obtained in abundant resources. For these reasons, it is optimal to use isosorbide as the main constituent.
- a structural unit derived from cyclohexanedimethanol in order to improve the impact resistance of the polycarbonate resin (A), as a structural unit other than the structural unit (a), a structural unit derived from cyclohexanedimethanol ( It is preferable to include b). At this time, it is preferable that the content ratio of the structural unit (b) in the structural unit derived from all the hydroxy compounds of the polycarbonate resin (A) is 45 mol% or more and 65 mol% or less.
- the lower limit of the ratio of the structural unit (b) is more preferably 48 mol% or more, and further preferably 50 mol% or more.
- the upper limit of the ratio of the structural unit (b) is more preferably 62 mol% or less, and still more preferably 60 mol% or less.
- the structural unit derived from the dihydroxy compound of the polycarbonate resin (A) is preferably composed of the structural unit (a) and the structural unit (b), but within the range not impairing the effects of the present invention.
- a structural unit derived from a dihydroxy compound may be contained.
- Examples of other dihydroxy compounds other than the dihydroxy compound represented by the formula (1) and the cyclohexanedimethanol include aliphatic dihydroxy compounds described in International Publication No. 2004/111106, and International Publication No. 2007/148604. Can be mentioned.
- the aliphatic dihydroxy compound is preferably selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.
- the alicyclic dihydroxy compound preferably contains a 5-membered ring structure or a 6-membered ring structure.
- the six-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. Since the alicyclic dihydroxy compound has a 5-membered ring structure or a 6-membered ring structure, there is no risk of excessively lowering the heat-resistant temperature while imparting flexibility and impact resistance to the obtained polycarbonate. It is suitable for designing required products.
- the number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, more preferably 30 or less.
- Examples of the alicyclic dihydroxy compound containing the 5-membered ring structure or the 6-membered ring structure include those described in the above-mentioned International Publication No. 2007/148604. Among them, tricyclodecane dimethanol, adamantanediol, and Pentacyclopentadecane dimethanol can be suitably exemplified, and tricyclodecane dimethanol is most preferable from the viewpoints of economy and heat resistance. These may be used alone or in combination of two or more.
- the content ratio of the structural unit (a) is 80 mol% or more in the structural unit derived from the total hydroxy compound of the polycarbonate resin (A). Is preferable, 85 mol% or more is more preferable, and 90 mol% or more is particularly preferable.
- the content ratio is within the above range, the ratio of the plant raw material is further increased, the heat resistance is excellent, and other various required characteristics are satisfied. Therefore, it can be suitably used for the card sheet of the present invention. .
- the content rate of the said structural unit (a) is It is preferably 99 mol% or less, more preferably 98 mol% or less, and particularly preferably 97 mol% or less.
- the polycarbonate resin (A) further includes a structural unit (c) derived from a polyalkylene glycol having a mass average molecular weight of 1000 or less in a structural unit derived from all dihydroxy compounds at a ratio of 1 mol% or more and 20 mol% or less. Preferably it comprises.
- polyalkylene glycol examples include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polybutylene glycol, polypentene glycol, polyhexene glycol, block of ethylene oxide and propylene oxide. Or a random copolymer etc. are mentioned. Of these, polyethylene glycol is particularly preferably used.
- the mass average molecular weight of the polyalkylene glycol is preferably 1000 or less, more preferably 800 or less, and particularly preferably 600 or less.
- the mass average molecular weight is within the range, the mass ratio occupied by the polyalkylene glycol in the polycarbonate resin (A) is not excessively increased, and physical properties necessary for the card sheet such as heat resistance and rigidity are impaired. There is no.
- the lower limit of the content ratio of the structural unit (c) in the structural units derived from all dihydroxy compounds of the polycarbonate resin (A) is preferably 1 mol% or more, and more preferably 3 mol% or more. It is preferably 5 mol% or more, particularly preferably.
- the upper limit of the content ratio of the structural unit (c) is preferably 20 mol% or less, more preferably 15 mol% or less, and particularly preferably 10 mol% or less. By having such a content ratio, it is possible to achieve both heat resistance and impact resistance suitable for the card sheet of the present invention.
- the structural unit derived from the dihydroxy compound of the polycarbonate resin (A) is preferably composed of the structural unit (a) and the structural unit (c), but within the range not impairing the object of the present invention.
- a structural unit derived from a dihydroxy compound may be contained.
- Examples of other dihydroxy compounds other than the dihydroxy compound represented by the formula (1) and the polyalkylene glycol include, for example, aliphatic dihydroxy compounds described in International Publication No. 2004/111106, and International Publication No. 2007/148604. Can be mentioned.
- the aliphatic dihydroxy compound is preferably selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.
- the alicyclic dihydroxy compound preferably contains a 5-membered ring structure or a 6-membered ring structure.
- the six-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. Since the alicyclic dihydroxy compound has a 5-membered ring structure or a 6-membered ring structure, there is no risk of excessively lowering the heat-resistant temperature while imparting flexibility and impact resistance to the obtained polycarbonate. It is suitable for designing required products.
- the number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, more preferably 30 or less.
- Examples of the alicyclic dihydroxy compound containing the 5-membered ring structure or the 6-membered ring structure include those described in the above-mentioned International Publication No. 2007/148604, and among them, cyclohexanedimethanol, tricyclodecanedimethanol.
- Adamantanediol and pentacyclopentadecane dimethanol can be preferably exemplified, and among them, cyclohexane dimethanol or tricyclodecane dimethanol is most preferable from the viewpoint of economy and heat resistance, and these are used alone or in combination of two or more. It may be used.
- cyclohexanedimethanol 1,4-cyclohexanedimethanol which is easily available industrially is particularly preferable.
- the reduced viscosity which is an index of the molecular weight of the polycarbonate resin (A), is usually 0.20 dl / g or more and 1.0 dl / g or less in both the first aspect and the second aspect, preferably It is in the range of 0.30 dl / g or more and 0.80 dl / g or less.
- the reduced viscosity is measured at a temperature of 20.0 ° C. ⁇ 0.1 ° C. using methylene chloride as a solvent, adjusting the polycarbonate concentration to 0.60 g / dl precisely.
- the glass transition temperature of the polycarbonate resin (A) is a strain distribution of 0.1%, a frequency of 10 Hz, a dynamic viscoelasticity temperature measurement under conditions of a heating rate of 3 ° C./min (JIS-K7198A method (1991)).
- the temperature is less than 130 ° C., more preferably 129 ° C. or less, and 128 ° C. It is particularly preferred that Moreover, it is preferable that it is 80 degreeC or more, It is more preferable that it is 90 degreeC or more, It is further more preferable that it is 95 degreeC or more, It is especially preferable that it is 100 degreeC or more.
- it has a single glass transition temperature.
- the glass transition temperature is 130 ° C. or higher, the inter-sheet adhesion between the oversheet and the core sheet during card production is insufficient, and the card sheet or card becomes hard and brittle, which is easy during embossing and bending deformation. Since it breaks, it is not preferable.
- the glass transition temperature is 130 ° C. or higher, the card sheet is excellent in heat resistance and can sufficiently withstand a thermal environment assumed during transportation, storage, use, and the like. Further, the card sheet is not crushed or flowed at the time of heat-sealing, and the card as a product is excellent in rigidity.
- the content rate of the structural unit (a) derived from the dihydroxy compound represented by the said Formula (1) in the said polycarbonate resin (A), or the structure derived from cyclohexane dimethanol is within the scope described in the present specification. It is possible to employ a method of adjusting appropriately so as not to impair the effects of the invention.
- the polycarbonate resin (A) can be produced by a generally used polymerization method, and may be either a phosgene method or a transesterification method in which it reacts with a carbonic acid diester.
- a polymerization catalyst in the presence of a polymerization catalyst, the dihydroxy compound represented by the formula (1), cyclohexanedimethanol or the polyalkylene glycol, and other dihydroxy compounds used as necessary are reacted with a carbonic acid diester.
- the transesterification method is preferred.
- the transesterification method comprises a basic catalyst comprising a dihydroxy compound represented by the formula (1), cyclohexanedimethanol or the polyalkylene glycol, another dihydroxy compound used as necessary, and a carbonic acid diester. Is a production method in which an acidic substance that neutralizes this basic catalyst is added to carry out a transesterification reaction.
- carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. Is mentioned. Of these, diphenyl carbonate is particularly preferably used.
- the resin composition (X) in the present invention is a resin composition containing the polycarbonate resin (A) as a main component.
- resins other than the polycarbonate resin (A) and additives other than resins are added to the resin composition (X) constituting the card sheet of the present invention.
- resins such as polyester resins, polyethers, polyamides, polyolefins, polymethylmethacrylates, and rubbery modifiers such as core-shell type, graft type or linear random and block copolymers.
- the compounding amount of the resin or additive other than the polycarbonate resin (A) is 1 to the resin composition (X) constituting the card sheet of the present invention as long as the effects of the present invention are not impaired.
- blend in the ratio of mass% or more and 30 mass% or less, It is more preferable to mix
- the resin composition (X) constituting the card sheet of the present invention can be blended with a heat stabilizer in order to prevent a decrease in molecular weight and a deterioration in hue during molding.
- a heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.
- triphenyl phosphite tris (nonylphenyl) phosphite, tris (2 , 4-Di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-) tert Butylphenyl) o
- the blending amount of the heat stabilizer is preferably 0.0001% by mass or more and 1% by mass or less with respect to the resin composition (X) constituting the card sheet of the present invention. It is more preferable to mix
- antioxidants normally known for the purpose of antioxidant can be mix
- antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4
- the amount of the antioxidant to be blended is preferably 0.0001% by mass or more and 1% by mass or less with respect to the resin composition (X) constituting the card sheet of the present invention. It is more preferable to mix
- a lubricant can be blended for the purpose of imparting surface lubricity to the resin composition (X) constituting the card sheet of the present invention.
- the lubricant include higher fatty acid esters of mono- or polyhydric alcohol, higher fatty acid, paraffin wax, beeswax, olefin wax, olefin wax containing carboxyl group and / or carboxylic anhydride group, silicone oil, organopoly Examples thereof include siloxane.
- the higher fatty acid ester is preferably a partial ester or a total ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.
- Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, behenic acid monoglyceride, behenyl behenate, Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate
- stearic acid monoglyceride stearic acid triglyceride, pentaerythritol tetrastearate and behenyl behenate are preferably used.
- a saturated fatty acid having 10 to 30 carbon atoms is preferable.
- Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like. These lubricants may be used alone or in combination of two or more.
- the blending amount of the lubricant is preferably 0.0001% by mass or more and 1% by mass or less with respect to the resin composition (X) constituting the card sheet of the present invention. % Or more and 0.5% by mass or less is more preferable, and 0.001% by mass or more and 0.2% by mass or less is more preferable.
- the polycarbonate resin (A) hardly absorbs light in the visible light to near-ultraviolet wavelength region, there is an advantage that yellowing deterioration with time does not occur even if a special ultraviolet absorber is not blended.
- the core sheet absorbs ultraviolet rays transmitted through the oversheet and suppresses the deterioration of the core sheet from yellowing.
- the necessary minimum ultraviolet absorber can be blended in the resin composition (X) in the present invention.
- the ultraviolet absorber known ones such as various commercially available ones can be used without particular limitation. Especially, what is normally used for the addition to well-known aromatic polycarbonate resin can be used conveniently.
- the melting point of the ultraviolet absorber is particularly preferably in the range of 120 ° C to 250 ° C.
- the molded product surface becomes dirty due to a bleed-out phenomenon in which the UV absorber aggregates on the surface of the molded product over time, or when molding is performed using a die or a metal roll. Prevents bleed out of them and makes it easier to reduce and improve haze on the surface of the molded product.
- 2- (2′-hydroxy-5′-methylphenyl) benzotriazole 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole 2- [2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2-methylenebis [4 -(1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl)] phenol, benzo such as 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole Hydroxyl compounds such as triazole ultraviolet absorbers and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxy-phenol Nyltriazine-based UV absorbers can be preferably used, and among these, 2- (2-hydroxy-3,5-dicumyl
- the blending amount of the ultraviolet absorber is preferably 0.0001% by mass or more and 1% by mass or less with respect to the resin composition (X) constituting the card sheet of the present invention. It is more preferable to mix
- the weather resistance can be improved without causing bleeding of the ultraviolet absorber to the surface of the card sheet and deterioration of the mechanical properties of the card sheet.
- an epoxy compound can be blended.
- the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexyl Carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexyl carboxylate, 2,3-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexyl carboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) butyl-3 ', 4'-epoxycyclohexyl
- the amount of the epoxy compound is preferably 0.0001% by mass or more and 5% by mass or less based on the resin composition (X) constituting the card sheet of the present invention. It is more preferable to mix
- the resin composition (X) in the present invention preferably further contains an inorganic filler.
- the resin composition (X) in the present invention has a visible light transmittance for the purpose of improving impact resistance and punching workability. Is preferably added.
- the term “having visible light permeability” as used herein means a state in which the facing side is sufficiently visible from one side of the sheet even when the inorganic filler is contained in the card sheet of the present invention. Specifically, it refers to a state in which the total light transmittance of the sheet measured at a thickness of 0.2 mm (200 ⁇ m) is 80% or more based on JIS-K7105 (1981).
- the inorganic filler having visible light permeability to be added to the card oversheet conventionally known ones can be used, and among them, silicic acid, magnesium silicate, glass flakes and the like can be preferably used.
- the average particle diameter of the inorganic filler is preferably 5 ⁇ m or less, and more preferably 4 ⁇ m or less.
- the content of the inorganic filler in the card oversheet is preferably 0.5% by mass or more, and 1.0% by mass or more with respect to 100% by mass of the resin composition (X). More preferably. Moreover, it is preferable that it is 5.0 mass% or less, and it is more preferable that it is 4.0 mass% or less.
- the card produced using the card oversheet of the present invention is ensured in transparency and further resistant.
- the impact property is improved, the embossed portion is not cracked, and the punching processability is improved to obtain a flat punched section.
- the card sheet of the present invention when used as a core sheet, it is preferable to add an inorganic filler to the resin composition (X) of the present invention for the purpose of improving rigidity and suppressing emboss curl.
- the inorganic filler added to the card core sheet conventionally known ones can be used, and among them, talc, magnesium silicate, calcium carbonate, silica, mica and the like can be suitably used. These may be used alone or in combination of two or more.
- the average particle size of the inorganic filler is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less.
- the content of the inorganic filler in the card core sheet is preferably 2% by mass or more and more preferably 4% by mass or more with respect to 100% by mass of the resin composition (X). Moreover, it is preferable that it is 10 mass% or less, and it is more preferable that it is 8 mass% or less.
- the card produced using the card core sheet of the present invention has improved rigidity and is embossed.
- the embossed curl that occurs can be suppressed, and the impact resistance is further improved, and the embossed portion is not cracked.
- a resin composition (X) in this invention contains a coloring agent, for example, an organic pigment, an inorganic pigment, etc. can be mentioned.
- inorganic pigments having a refractive index of 2 or more such as titanium oxide, lead titanate, potassium titanate, zircon oxide, zinc sulfide, antimony oxide, and zinc oxide are preferable, and among them, titanium oxide having a high refractive index is particularly preferable. preferable.
- the core sheet can be made into an opaque white sheet. For example, if the inlet sheet described later is laminated so as to be sandwiched between the core sheets, the antenna base of the inlet sheet Etc. can be hidden so that they cannot be seen.
- Titanium oxide includes anatase type, rutile type, and brookite type, but it is preferable to use a rutile type having a large refractive index.
- titanium oxide manufactured by the chlorine method process and titanium oxide manufactured by the sulfuric acid method process can be used.
- the titanium oxide is preferably one whose surface is coated with at least one inert inorganic oxide selected from silica, alumina, and zirconia. Since the photocatalytic action of titanium oxide can be suppressed by coating with an inert inorganic oxide, the polycarbonate resin (A) is prevented from being depolymerized by the photocatalytic action of titanium oxide during production and use. Can do.
- the surface of the titanium oxide is at least one kind selected from a siloxane compound, a silane coupling agent or the like, at least one kind selected from a polyol or polyethylene glycol. It is even more preferable to use titanium oxide surface-treated with an organic compound.
- the range of the average particle diameter of titanium oxide is preferably 0.1 ⁇ m or more and 1 ⁇ m or less, and more preferably 0.2 ⁇ m or more and 0.5 ⁇ m or less. If the average particle diameter of titanium oxide is within such a range, excellent concealability can be imparted without deteriorating the mechanical properties of the card of the present invention.
- the content of the colorant in the card core sheet of the present invention is preferably 1% by mass or more and 20% by mass or less with respect to 100% by mass of the resin composition (X).
- a lower limit 3 mass% or more is preferable, and 5 mass% or more is more preferable.
- an upper limit 15 mass% or less is more preferable, and 10 mass% or less is further more preferable.
- additives such as a light stabilizer and a plasticizer can be further blended in the resin composition (X) constituting the card sheet of the present invention.
- seat of this invention has a layer which consists of the said resin composition (X), It is characterized by the above-mentioned. At this time, only a single layer of the resin composition (X) may be used as a card sheet. However, in the resin composition (X), the composition ratio of the polycarbonate resin (A) and the resin composition ( One or more layers each having a different content ratio of each component constituting X) may be laminated to form a card sheet.
- the resin composition different from the resin composition (X) is a resin composition mainly containing a resin other than the polycarbonate resin (A), and is not particularly limited as long as the characteristics of the present invention are not impaired. It is not a thing.
- the resin that can be used as the main component include polycarbonate resins, acrylic resins, alicyclic polyolefin resins, styrene resins, and polyester resins that do not contain a structural unit derived from the dihydroxy compound represented by the formula (1).
- Polyvinyl chloride resin, phenol resin, melamine resin, epoxy resin and the like can be exemplified.
- the card sheet of the present invention is prepared by directly mixing the polycarbonate resin (A) and, if necessary, raw materials such as an ultraviolet absorber, an inorganic filler and a colorant, other resins, and additives into an extruder. Or forming a pellet by melting and mixing the raw materials using a twin-screw extruder and extruding it into a strand shape, and then charging the pellet into an extruder. .
- raw materials such as an ultraviolet absorber, an inorganic filler and a colorant, other resins, and additives
- forming a pellet by melting and mixing the raw materials using a twin-screw extruder and extruding it into a strand shape, and then charging the pellet into an extruder.
- it is necessary to consider a decrease in molecular weight due to hydrolysis of the polycarbonate resin (A) and the latter is preferably selected for uniform mixing. Therefore, the latter manufacturing method will be described below.
- the polycarbonate resin (A) and other raw materials blended as necessary are sufficiently dried to remove moisture, mixed with a ribbon blender, tumbler, Henschel mixer, etc., and then melt-kneaded using a twin screw extruder. , Extruded into a strand shape to produce pellets.
- other raw materials to be blended as necessary may be continuously or sequentially supplied from a feeder into an extruder in which the polycarbonate resin (A) is melt-kneaded to produce pellets.
- it is preferable to appropriately adjust the melt-kneading temperature so as not to excessively increase in consideration of shearing heat generation when the resin is plasticized, changes in viscosity depending on the composition ratio and blending ratio of each raw material.
- the molding temperature is preferably 200 ° C. or higher and 260 ° C. or lower, more preferably 210 ° C. or higher and 250 ° C. or lower, and further preferably 220 ° C. or higher and 240 ° C. or lower.
- the pellet may be prepared to be the resin composition (X) constituting the present invention, or prepared as a high-concentration master batch of other raw materials to be blended as necessary.
- the card sheet When the card sheet is produced, it may be appropriately blended with the polycarbonate resin (A) for dilution and other resins to obtain a card sheet comprising the resin composition (X) having a desired composition ratio. .
- seat of this invention can be shape
- molding by T-die cast extrusion method is suitable especially.
- the pellets after the pellets are sufficiently dried, they can be heated and melted in an extruder, extruded from a T-die slit, and formed into a film from a cast roll to a cooling roll.
- the extrusion temperature is preferably set as appropriate in the range of 200 ° C. or higher and 260 ° C. or lower.
- different resin compositions can be coextruded using a multi-manifold die, a feed block, or the like to form a laminated sheet.
- 50 degreeC or more is preferable for sufficient roll surface transcription
- 130 degreeC or less is preferable in order to prevent roll winding
- 120 degrees C or less is preferable. More preferred is 110 ° C. or less.
- the 10-point average roughness of at least one surface of the sheet is preferably in the range of 3 ⁇ m or more and 30 ⁇ m or less.
- the lower limit value of the 10-point average roughness is more preferably 10 ⁇ m or more.
- the upper limit of the 10-point average roughness is more preferably 20 ⁇ m or less.
- a mirror surface sheet may be formed first, and then the surface may be processed using a mat roll or the like, or the cast roll may be used as a mat roll or the like during sheet extrusion molding.
- the surface may be processed by changing and performing extrusion molding. For example, a sheet extruded from a die is sandwiched between a metal mat roll having fine irregularities on the surface and a rubber roll having minute irregularities on the surface (hereinafter referred to as “mat forming roll”), and pressure
- mat forming roll a metal mat roll having fine irregularities on the surface and a rubber roll having minute irregularities on the surface
- the sheet for cards with mat processing applied to the front and back surfaces of the sheet is transferred by rotating the mat forming roll while passing the sheet and transferring the irregularities on the surface of the mat forming roll to the sheet surface.
- the method of performing mat processing is not limited to the method described here.
- the card sheet of the present invention can be provided with a printing layer on at least one surface.
- the printing layer is provided by a known printing method such as gravure printing, offset printing, or screen printing.
- the pattern of the print layer is arbitrary, such as a stone pattern, a wood grain, or a geometric pattern or an abstract pattern. Partial printing or full surface solid printing may be used, and both a partial printing layer and a solid printing layer may be provided.
- the pigment and solvent contained in the printing ink used for the printing layer are not particularly limited, and those commonly used can be applied.
- those containing acrylic resin, urethane resin, vinyl chloride-vinyl acetate copolymer and the like can be used to produce the card of the present invention without any trouble such as delamination even when a printing layer is provided. Therefore, it is preferable.
- the thickness is not particularly limited, but is usually preferably 20 ⁇ m or more and 150 ⁇ m or less. If the thickness is excessively smaller than the above range, there may be a problem that rigidity is insufficient, cracking occurs during embossing, and surface hardness is insufficient. On the other hand, if the thickness is excessively larger than the above range, the product thickness may become too thick, or the embossed marking may become unclear.
- the thickness is not particularly limited, but it is usually preferably 25 ⁇ m to 250 ⁇ m for a thin material and 250 ⁇ m to 800 ⁇ m for a thick material.
- a plurality of the thin sheets may be laminated to form a thick sheet.
- an inlet sheet having an IC chip or an antenna circuit is disposed therein, such a laminated core sheet is often configured. If it is excessively thinner than the above range, there may be a problem that the rigidity is insufficient or the impact resistance is insufficient. On the other hand, if the thickness is excessively larger than the above range, the product thickness may become too thick, or the embossed marking may become unclear.
- the card sheet of the present invention is a sheet having excellent rigidity and impact resistance.
- the value of the flexural modulus serving as an index of rigidity and impact resistance is preferably 2200 MPa or more, more preferably 2300 MPa or more, and preferably 3000 MPa or less, more preferably 2900 MPa or less. That's fine.
- the flexural modulus is 2200 MPa or more, emboss curl when embossing the card of the present invention can be suppressed, and when it is 3000 MPa or less, the card of the present invention is embossed. This is preferable because the embossed portion can be prevented from cracking.
- the content ratio of each structural unit in the polycarbonate resin (A) in the present invention, the average particle diameter of the inorganic filler added to the resin composition (X), the added amount, etc. can be achieved by adjusting within the range described in this specification.
- the card sheet of the present invention has excellent weather resistance, particularly UV discoloration resistance.
- the color difference ⁇ YI after irradiation for 50 hours of UV which is an index thereof, is preferably 1.0 or less, more preferably 0.9 or less, and even more preferably 0.8 or less.
- the color difference ⁇ YI is within such a range, it is possible to provide a card sheet in which the color tone is maintained without being yellowed even when used outdoors for a long time or in an environment irradiated with UV.
- the color difference ⁇ YI can be set to such a range by adjusting the composition of the resin composition (X) in the present invention and the thickness of the card sheet of the present invention within a preferable range described in the present specification.
- the card sheet of the present invention is excellent in surface hardness, and the pencil hardness as an index thereof is preferably F or more, and more preferably H or more.
- the pencil hardness is within such a range, a card having excellent scratch resistance can be provided.
- pencil hardness can be made into the range which adjusts the thickness of a sheet
- the card of the present invention is produced using the card sheet of the present invention.
- the card sheet of the present invention may be applied only as an oversheet, may be applied only as a core sheet, or may be applied to both an oversheet and a core sheet. Among these, it is particularly preferable to apply the card sheet of the present invention to at least the oversheet.
- the core sheet laminated on the card sheet of the present invention or the resin constituting the oversheet is The resin is not particularly limited as long as it does not interfere with the features of the invention.
- polycarbonate resin (A) polycarbonate resin, acrylic resin, alicyclic polyolefin resin, styrene resin, polyester resin, polyvinyl chloride.
- resins such as resins, lactic acid polymers, phenol resins, melamine resins, and epoxy resins can be used.
- the lactic acid-based polymer is a resin derived from plant raw materials like the polycarbonate resin (A), and when the card sheet of the present invention is applied as an oversheet, lactic acid is used as a resin constituting the core sheet.
- the polymer resin is preferable from the viewpoint that the ratio of the plant-derived raw material of the card of the present invention can be increased and the environmental load can be further reduced.
- a lactic acid polymer is a polymer obtained by condensation polymerization of a monomer containing lactic acid as a main component. Specifically, poly (L-lactic acid) having a structural unit of L-lactic acid and a structural unit of D-lactic acid. Poly (D-lactic acid), poly (DL-lactic acid) whose structural unit is composed of both L-lactic acid and D-lactic acid, or a mixture composed of a combination of two or more of these is preferably used.
- Lactic acid has two types of optical isomers, L-lactic acid and D-lactic acid, and the crystallinity of the lactic acid polymer varies depending on the ratio of these two structural units.
- a random copolymer having a ratio of L-lactic acid to D-lactic acid of approximately 90:10 to 10:90 has no crystallinity and becomes a completely non-crystalline polymer that softens around a glass transition temperature of 60 ° C.
- a random copolymer having a ratio of L-lactic acid to D-lactic acid of approximately 100: 0 to 90:10 or 10:90 to 0: 100 has a glass transition temperature of about 60 ° C. as in the former.
- the ratio of L-lactic acid to D-lactic acid in the lactic acid polymer is 99: 1 to 92: 8 or 1:99 to 8:92, particularly 98. : 2 to 94: 6 or 2:98 to 6:94, particularly preferably 97: 3 to 95: 5 or 3:97 to 5:95.
- the reason is as follows.
- lactic acid-based polymer sheets mainly composed of lactic acid-based polymers are heated and pressed together and fused together, lactic acid-based polymers with high crystallinity are If the heating temperature is set to near the state where the lactic acid polymer is completely melted due to crystallization, or the lactic acid polymer is completely melted, the lactic acid polymer melts and flows during hot pressing, A lactic acid polymer having high crystallinity is not preferred because it is difficult to obtain a product with a good appearance.
- a hot press machine is manufactured so as to be suitable for fusion of a vinyl chloride resin that has been used exclusively in the past, and the normal use temperature range is usually about 100 to 170 ° C., preferably about 120 to 150 ° C.
- a lactic acid polymer that can be sufficiently fused in the temperature range is preferable. In consideration of these points, the range of the ratio is preferable.
- the ratio of L-lactic acid and D-lactic acid may be used solely by the lactic acid polymer resin obtained in this ratio, or by mixing a plurality of lactic acid polymers having different ratios, and depending on the mass average fraction of the mixture. The mixture may be adjusted so that the ratio is within the above range.
- lactic acid-based polymer a copolymer of lactic acid and another hydroxycarboxylic acid can also be used.
- the non-aliphatic carboxylic acid such as terephthalic acid
- the non-aliphatic diol such as bisphenol-A or its ethylene oxide adduct
- a hydroxycarboxylic acid other than lactic acid may be contained as a small amount copolymerization component. Small amounts of chain extender residues may be included.
- polylactic acid-based polymer As the polymerization method for the lactic acid-based polymer, a condensation polymerization method, a ring-opening polymerization method, and other known polymerization methods can be employed.
- the condensation polymerization method polylactic acid having a desired composition can be obtained by directly dehydrating condensation polymerization of L-lactic acid, D-lactic acid or a mixture thereof.
- the ring-opening polymerization method lactide method
- lactide which is a cyclic dimer of lactic acid, with a polymerization regulator or the like as necessary.
- lactic acid polymer examples thereof include “Lacia” series manufactured by Mitsui Chemicals, “Ingeo” series manufactured by Nature Works, and the like.
- an amorphous aromatic polyester resin or a thermoplastic elastomer disclosed in Patent Document 4 may be blended. By doing so, adhesion may be improved when an aromatic polyester resin sheet, a printing layer, or the like is provided.
- the card sheet of the present invention to both the oversheet and the core sheet of the card of the present invention, the ratio of plant-derived raw materials of the card of the present invention can be increased and the environmental load can be further reduced.
- the card of the present invention may be laminated with other layers as long as the essence of the invention is not further impaired.
- an inlet sheet having an IC chip or an antenna circuit, an adhesive layer, and the like can be given.
- the manufacturing method is not limited to this.
- the card of the present invention is, for example, a core sheet, an oversheet, and, if necessary, an inlet sheet to be described later are stacked in a predetermined stacking order, and are heat-sealed by applying pressure under heating with a press machine to bond the sheets together. After cooling to room temperature, it can be manufactured by punching into a card shape.
- the oversheet is most suitable, for example, a configuration in which oversheets are stacked on both sides of the core sheet, an inlet sheet is sandwiched between core sheets, and an oversheet is stacked on both sides of the front and back. If it is on the surface layer, the others can take any configuration.
- a known laminating method such as a dry lamination method or a wet lamination method can be employed in addition to the above-described hot pressing method.
- the inlet sheet can be configured by forming an antenna circuit on a support made of resin, for example, and mounting an electronic component such as an IC chip or a capacitor on the antenna circuit.
- a known resin as described in the present specification can be used in addition to the polycarbonate resin (A) in the present invention.
- the card of the present invention is a card having small emboss curl and excellent embossability when embossing such as characters is performed.
- the embossed curl generated after embossing the card of the present invention at 23 ° C. using embossed encoder DC9000 (manufactured by Nippon Data Card Co., Ltd.) with 3 lines of 7B font and 19 characters on each line is preferably 2.5 mm or less. More preferably, it is 2.2 mm or less, and more preferably 2.0 mm or less.
- the embossing aptitude can be evaluated by the height of the embossed characters (hereinafter referred to as “embossing height”).
- the lower limit of the embossing height is preferably 0.40 mm, more preferably 0.42 mm.
- the upper limit of the emboss height is not particularly limited, but is preferably 0.48 mm or less so as not to cause a problem depending on the use of the card of the present invention.
- the card of the present invention is produced using the card sheet of the present invention in at least one layer, and is excellent in all of heat resistance, weather resistance, rigidity, punching workability, embossability, and environmental load. Since it can be reduced, it can be suitably used for cards used in large quantities, particularly magnetic stripe cards produced using magnetic tape, IC cards produced using IC chips, and the like.
- Aromatic polycarbonate resin (trade name “Iupilon S3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd.) was kneaded at 260 ° C. using a 40 mm ⁇ co-directional twin screw extruder, extruded from a T die, and then cast onto a 130 ° C. casting roll. While cooling rapidly, the mating process was performed by bringing the mating roll into contact with the surface in contact with the cast roll to produce a card oversheet (PC) having a thickness of 100 ⁇ m. The 10-point average roughness of the mat processed surface was 16 ⁇ m.
- a concealed printing layer was formed on one side of the card core sheet produced in the production example by screen printing using a vinyl chloride-vinyl acetate copolymer ink. Then, the two core sheets were overlapped so that the concealed printing layer faced outside. Furthermore, so that the combination of the following Table 2 is used, the two oversheets for the card produced in the production example are used above and below the overlapped core sheets so that the mat processed surface of the oversheet faces outward. These four sheets are sandwiched between two chrome-plated plates, pressed at 130 ° C. for 10 minutes at a sheet surface pressure of 9.8 ⁇ 10 5 Pa, cooled to room temperature, and taken out. A substrate sample was obtained.
- the dumbbell No. 1 test piece was punched from a card base material sample in accordance with JIS-K6251 (2004), and the defect that the cross section of the test piece was roughed or cracked occurred 10 times. Evaluated as “ ⁇ ” when there were more than 1 times, “ ⁇ ” when the failures were 3 times or more and 7 times or less, and “ ⁇ ” when the failures were less than 2 times or when there were no failures. .
- embossed encoder DC9000 manufactured by Nippon Data Card Co., Ltd.
- the embossed character pattern was “123... 90123.
- the card after embossing was placed on the surface plate, and the height from the surface plate surface to the highest position of the non-embossed surface of the card was measured, and this was taken as the value of emboss curl. Based on JIS-X6301 (1998), those having an embossed curl of 2.5 mm or less were evaluated as “ ⁇ ”, and those having an embossed curl exceeding 2.5 mm were evaluated as “X”.
- Embossing suitability (embossing height)
- the card embossed in (6) was placed on a surface plate, and the embossed height from the non-embossed portion to the top of the embossed character was measured.
- evaluation was made with an emboss height in the range of 0.4 mm to 0.48 mm as “ ⁇ ”, and an evaluation with less than 0.4 mm as “x”.
- the card configurations of Examples 1 to 3 using the card sheet of the present invention are all excellent in all of heat resistance, weather resistance, rigidity, punching workability, and embossability. It can be seen that the degree of planting is also high.
- the card configuration of Comparative Example 1 is inferior in punching workability and embossing curl, and inferior in weather resistance with respect to the over layer, and is not a plant-derived material. Further, the card configuration of Comparative Example 2 is inferior in punching workability, and embossing is extremely difficult, and heat resistance is not sufficient.
- C-3 Amorphous polylactic acid resin (manufactured by Nature Works, trade name “Ingeo 4060D”, glass transition temperature: 55 ° C.) 40% by mass, and crystalline polylactic acid resin (manufactured by Nature Works, trade name “ Ingeo 4032D ”, glass transition temperature: 55 ° C.) 60% by mass dry-blended and formed into a film having a thickness of 100 ⁇ m by a melt extrusion method.
- C-4 Aromatic polycarbonate resin (“Novalex 7022” manufactured by Mitsubishi Engineering Plastics Co., Ltd.) formed into a film with a thickness of 100 ⁇ m by a melt extrusion method.
- a concealed printing layer was formed on one side of each core sheet by screen printing using an ink of a vinyl chloride-vinyl acetate copolymer system. Then, the two core sheets were overlapped so that the concealed printing layer faced outside. Further, as shown in Table 3, the both sides of the overlapped core sheet were sandwiched between two oversheets, the entire sheet was sandwiched between chrome plated plates, and the sheet surface pressure was 9.8 ⁇ 10 5 Pa at 130 ° C. for 10 minutes. After pressing, it was cooled to room temperature and taken out, and this was used as a card substrate sample.
- embossed encoder DC9000 manufactured by Nippon Data Card Co., Ltd.
- the embossed character pattern was “123... 90123.
- the card after embossing was placed on the surface plate, and the height from the surface plate surface to the highest position of the non-embossed surface of the card was measured, and this was taken as the value of emboss curl. Based on JIS-X6301 (1998), an emboss curl of 2.5 mm or less was accepted.
- Embossing suitability (embossing height)
- the embossed card was placed on a surface plate, and the emboss height from the non-embossed portion to the top of the embossed character was measured. Based on JIS-X6302 (1998), those having an emboss height in the range of 0.4 mm to 0.48 mm were accepted.
- the cards of Examples 4 to 6 have a high plant raw material resin ratio and satisfy all of the heat resistance, impact resistance, embossing characteristics, interlayer adhesion, and weather resistance of the oversheet. Yes.
- the cards of Comparative Examples 3 and 4 were inferior to the Examples in any of heat resistance, impact resistance, embossing properties, interlayer adhesion, and oversheet weather resistance.
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Abstract
Description
このように従来の技術においては、カード用途に植物原料樹脂を用いる比率を高めることが十分にできていなかった。
すなわち本発明は以下の通りである。
本発明に用いるポリカーボネート樹脂(A)としては、下記式(1)で表されるジヒドロキシ化合物に由来する構造単位(a)を含み、ガラス転移温度が130℃未満であるポリカーボネート樹脂が用いられる。
尚、シクロヘキサンジメタノールの中でも、工業的に入手が容易である、1,4-シクロヘキサンジメタノールが好ましい。
また、後述する共重合成分により、前記ポリカーボネート樹脂(A)のガラス転移温度を、本発明のカードを作製するのに好ましい範囲とする必要があることから、前記構造単位(a)の含有比率は99モル%以下であることが好ましく、98モル%以下がより好ましく、97モル%以下が特に好ましい。
また、前記構造単位(c)の含有比率の上限は20モル%以下であることが好ましく、15モル%以下であることがより好ましく、10モル%以下であることが特に好ましい。係る含有比率であることによって、本発明のカード用シートに好適な、耐熱性と耐衝撃性を両立することができる。
一方、ガラス転移温度を80℃以上とすることによって、カード用シートは耐熱性に優れ、搬送時、保管時、使用時などで想定される熱環境に十分耐えることができる。また、熱融着時にカード用シートが潰れたり流れたりすることもなく、製品としてのカードも剛性に優れたものとなる。
本発明における樹脂組成物(X)は、前記ポリカーボネート樹脂(A)を主成分とする樹脂組成物である。
成形加工性や諸物性のさらなる向上・調整を目的として、本発明のカード用シートを構成する樹脂組成物(X)に対して、前記ポリカーボネート樹脂(A)以外の樹脂や、樹脂以外の添加剤を配合することも出来る。例えば、ポリエステル系樹脂、ポリエーテル、ポリアミド、ポリオレフィン、ポリメチルメタクリレート等の樹脂やコア-シェル型、グラフト型又は線状のランダム及びブロック共重合体のようなゴム状改質剤などが挙げられる。前記ポリカーボネート樹脂(A)以外の樹脂、あるいは、添加剤の配合量としては、本発明の効果を損なわない範囲で、本発明のカード用シートを構成する樹脂組成物(X)に対して、1質量%以上、30質量%以下の割合で配合することが好ましく、3質量%以上、20質量%以下の割合で配合することがより好ましく、5質量%以上、10質量%以下の割合で配合することがさらに好ましい。
本発明のカード用シートを構成する樹脂組成物(X)には、成形時における分子量の低下や色相の悪化を防止するために熱安定剤を配合することができる。かかる熱安定剤としては、亜リン酸、リン酸、亜ホスホン酸、ホスホン酸およびこれらのエステル等が挙げられ、具体的には、トリフェニルホスファイト、トリス(ノニルフェニル)ホスファイト、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジデシルモノフェニルホスファイト、ジオクチルモノフェニルホスファイト、ジイソプロピルモノフェニルホスファイト、モノブチルジフェニルホスファイト、モノデシルジフェニルホスファイト、モノオクチルジフェニルホスファイト、ビス(2,6-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト、2,2-メチレンビス(4,6-ジ-tert-ブチルフェニル)オクチルホスファイト、ビス(ノニルフェニル)ペンタエリスリトールジホスファイト、ビス(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、トリブチルホスフェート、トリエチルホスフェート、トリメチルホスフェート、トリフェニルホスフェート、ジフェニルモノオルソキセニルホスフェート、ジブチルホスフェート、ジオクチルホスフェート、ジイソプロピルホスフェート、4,4’-ビフェニレンジホスフィン酸テトラキス(2,4-ジ-tert-ブチルフェニル)、ベンゼンホスホン酸ジメチル、ベンゼンホスホン酸ジエチル、ベンゼンホスホン酸ジプロピル等が挙げられる。なかでも、トリスノニルフェニルホスファイト、トリメチルホスフェート、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト、ビス(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト、およびベンゼンホスホン酸ジメチルが好ましく使用される。
また、本発明のカード用シートを構成する樹脂組成物(X)には、酸化防止の目的で通常知られた酸化防止剤を配合することができる。かかる酸化防止剤としては、例えばペンタエリスリトールテトラキス(3-メルカプトプロピオネート)、ペンタエリスリトールテトラキス(3-ラウリルチオプロピオネート)、グリセロール-3-ステアリルチオプロピオネート、トリエチレングリコール-ビス[3-(3-tert-ブチル-5-メチル-4-ヒドロキシフェニル)プロピオネート]、1,6-ヘキサンジオール-ビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、ペンタエリスリトール-テトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)ベンゼン、N,N-ヘキサメチレンビス(3,5-ジ-tert-ブチル-4-ヒドロキシ-ヒドロシンナマイド)、3,5-ジ-tert-ブチル-4-ヒドロキシ-ベンジルホスホネート-ジエチルエステル、トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)イソシアヌレート、4,4’-ビフェニレンジホスフィン酸テトラキス(2,4-ジ-tert-ブチルフェニル)、3,9-ビス{1,1-ジメチル-2-[β-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ]エチル}-2,4,8,10-テトラオキサスピロ(5,5)ウンデカン等の1種又は2種以上が挙げられる。
また、本発明のカード用シートを構成する樹脂組成物(X)に対して表面滑性の付与を目的として、滑剤を配合することができる。前記滑剤としては、一価または多価アルコールの高級脂肪酸エステル、高級脂肪酸、パラフィンワックス、蜜蝋、オレフィン系ワックス、カルボキシル基および/ またはカルボン酸無水物基を含有するオレフィン系ワックス、シリコーンオイル、オルガノポリシロキサン等が挙げられる。
前記ポリカーボネート樹脂(A)は、可視光~近紫外波長領域での光吸収が殆ど無いため、特段の紫外線吸収剤を配合しなくても経時的な黄変劣化が起こらない利点がある。しかし本発明のカード用シートをオーバーシートとして用いて本発明のカードを作製するとき、当該オーバーシートを透過した紫外線がコアシートで吸収されて、コアシートが黄変劣化することを抑制するために、本発明における樹脂組成物(X)に必要最低限の紫外線吸収剤を配合することができる。
さらに、本発明のカード用シートを構成する樹脂組成物(X)の耐加水分解性をさらに向上するため、エポキシ系化合物を配合することができる。エポキシ系化合物の具体例としては、エポキシ化大豆油、エポキシ化アマニ油、フェニルグリシジルエーテル、アリルグリシジルエーテル、t-ブチルフェニルグリシジルエーテル、3,4-エポキシシクロヘキシルメチル-3’,4’-エポキシシクロヘキシルカルボキシレート、3,4-エポキシ-6-メチルシクロヘキシルメチル-3’,4’-エポキシ-6’-メチルシクロヘキシルカルボキシレート、2,3-エポキシシクロヘキシルメチル-3’,4’-エポキシシクロヘキシルカルボキシレート、4-(3,4-エポキシ-5-メチルシクロヘキシル) ブチル-3’,4’-エポキシシクロヘキシルカルボキシレート、3,4-エポキシシクロヘキシルエチレンオキシド、シクロヘキシルメチルー3,4-エポキシシクロヘキシルカルボキシレート、3,4-エポキシ-6-メチルシクロヘキシルメチル-6’-メチルシロヘキシルカルボキシレート、ビスフェノールAジグリシジルエーテル、テトラブロモビスフェノールAグリシジルエーテル、フタル酸のジグリシジルエステル、ヘキサヒドロフタル酸のジグリシジルエステル、ビス-エポキシジシクロペンタジエニルエーテル、ビス-エポキシエチレングリコール、ビス-エポキシシクロヘキシルアジペート、ブタジエンジエポキシド、テトラフェニルエチレンエポキシド、オクチルエポキシタレート、エポキシ化ポリブタジエン、3,4-ジメチル-1,2-エポキシシクロヘキサン、3,5-ジメチル-1,2-エポキシシクロヘキサン、3-メチル-5-t-ブチル-1,2-エポキシシクロヘキサン、オクタデシル-2,2-ジメチル-3,4-エポキシシクロヘキシルカルボキシレート、N-ブチル-2,2-ジメチル-3,4-エポキシシクロヘキシルカルボキシレート、シクロヘキシル-2-メチル-3,4-エポキシシクロヘキシルカルボキシレート、N-ブチル-2-イソプロピル-3,4-エポキシ-5-メチルシクロヘキシルカルボキシレート、オクタデシル-3,4-エポキシシクロヘキシルカルボキシレート、2-エチルヘキシル-3’,4’-エポキシシクロヘキシルカルボキシレート、4,6-ジメチル-2,3-エポキシシクロヘキシル-3’,4’-エポキシシクロヘキシルカルボキシレート、4,5-エポキシ無水テトラヒドロフタル酸、3-t-ブチル-4,5-エポキシ無水テトラヒドロフタル酸、ジエチル-4,5-エポキシ-シス-1,2-シクロヘキシルジカルボキシレート、ジ-N-ブチル-3-t-ブチル-4,5-エポキシ-シス-1,2-シクロヘキシルジカルボキシレートなどが挙げられる。ビスフェノールAジグリシジルエーテルが相溶性などの点から好ましい。
本発明における樹脂組成物(X)は、さらに無機充填剤を含むことが好ましい。このうち、本発明のカード用シートをオーバーシートとして用いる場合には、耐衝撃性や打ち抜き加工性を向上する目的で、本発明における樹脂組成物(X)に可視光透過性を有する無機充填剤を添加することが好ましい。なお、ここでいう「可視光透過性を有する」とは、該無機充填剤を本発明のカード用シートに含有させた場合でも、シートの一方の面から対面側が十分視認可能となるような状態であって、具体的にはJIS-K7105(1981年)に基づいて、厚み0.2mm(200μm)で測定された当該シートの全光線透過率が80%以上である状態を指す。
本発明のカード用シートをコアシートとして用いる場合、本発明における樹脂組成物(X)には着色剤を含有させることが好ましく、例えば有機顔料や無機顔料などを挙げることができる。中でも、屈折率が2以上である無機顔料、例えば酸化チタン、チタン酸鉛、チタン酸カリウム、酸化ジルコン、硫化亜鉛、酸化アンチモン、酸化亜鉛などが好ましく、その中でも、屈折率が高い酸化チタンが特に好ましい。
酸化チタンなどの屈折率が高い顔料を含有させることにより、コアシートを不透明な白色シートとすることができ、例えば後述するインレットシートをコアシート間で挟むように積層すれば、インレットシートのアンテナ基盤等が見えないように隠蔽することができる。
本発明のカード用シートは、前記樹脂組成物(X)からなる層を有することを特徴とする。この時、前記樹脂組成物(X)からなる層の単層のみでカード用シートとしても良いが、前記樹脂組成物(X)において前記ポリカーボネート樹脂(A)の組成比や、前記樹脂組成物(X)を構成する各成分の含有比率が異なる層を各1層以上積層してカード用シートとしても良い。
前記樹脂組成物(X)とは異なる樹脂組成物は、前記ポリカーボネート樹脂(A)以外の樹脂を主成分とする樹脂組成物であって、本発明の特徴を損なうことがなければ特に限定されるものではない。主成分とすることができる樹脂としては、前記式(1)で表されるジヒドロキシ化合物に由来する構造単位を含まないポリカーボネート樹脂、アクリル樹脂、脂環式ポリオレフィン系樹脂、スチレン系樹脂、ポリエステル系樹脂、ポリ塩化ビニル樹脂、フェノール樹脂、メラミン樹脂及びエポキシ樹脂等を例示することができる。
また、キャストロールの温度は、樹脂の種類及び組成によって調整するのが好ましいが、十分なロール面転写のために50℃以上が好ましく、ロール巻き付きを防ぐために130℃以下が好ましく、120℃以下がより好ましく、110℃以下が特に好ましい。
本発明のカードは、本発明のカード用シートを用いて作製されることを特徴とする。本発明のカードにおいては、本発明のカード用シートをオーバーシートとしてのみ適用しても、またコアシートとしてのみ適用してもよく、オーバーシートとコアシートの両方に適用してもよい。このうち、特に本発明のカード用シートを少なくともオーバーシートに適用することが好ましい。
本発明のカードに、23℃においてエンボスエンコーダーDC9000(日本データカード株式会社製)を用いて7Bフォントの文字を3行、各行19文字エンボスを施した後に生じるエンボスカールは、好ましくは2.5mm以下であり、より好ましくは2.2mm以下であり、さらに好ましくは2.0mm以下であればよい。
各種測定値・評価についての測定方法・評価方法は、以下の通りである。
各製造例におけるカード用シートをサンプルとして、粘弾性スペクトロメーターDVA-200(アイティー計測制御株式会社製)を用い、歪み0.1%、周波数10Hz、昇温速度3℃/分にて動的粘弾性の温度分散測定(JIS-K7198A法(1991年)の動的粘弾性測定)を行った。そして損失正接(tanδ)の主分散のピークを示す温度をガラス転移温度とした。
試験機としてアイスーパUVテスターSUV-W151(岩崎電気製)を用いて、UV照射強度:75mW/cm2、照射温度:63℃、照射湿度:50%の条件により各製造例におけるカード用シートをサンプルとしてUVを照射した。UV照射前と照射50時間後のサンプルのYI値(黄色度)をJIS-K7103(1977年)に基づいて分光測色計(「SC-T」、スガ試験機株式会社製)を用いて測定し、測定前後の差である色差ΔYIを算出し、ΔYIが0以上1.0未満のものを「○」、ΔYIが1.0以上のものを「×」として評価した。
各実施例及び比較例におけるカード用シートを38mm×38mmのサイズに切り出して試験片とした。テーバー式ステフネステスター(テーバー社製)を用いて、JIS-P8125(2000年)に準拠して曲げ角度15°における曲げこわさF(単位:g・cm)を測定した。これを下記の計算式(I)に代入して、曲げ弾性率(単位:Pa)を算出した。但し、試験片の厚みをd(cm)とする。
曲げ弾性率(Pa)=2×0.01×F/(d3×9.8) (I)
カード用シートの表面について、JIS-B0601(1994年)に基づいて、表面粗さ計「サーフコーダーSE-40D」(株式会社小坂研究所製)を用い、送り速さが0.5mm/sec、基準長さが8mm、カットオフ値が0.8mmの条件下で測定し、カード用シートの10点平均粗さ(単位:μm)を求めた。
イソソルビドに由来する構造単位:1,4-シクロヘキサンジメタノールに由来する構造単位=40:60(モル%)の比率で構成されるポリカーボネート樹脂を、40mmφ同方向二軸押出機を用いて220℃で混練した後、Tダイより押出し、次いで80℃のキャスティングロールにて急冷しながら、キャストロールに接触する面の対面をマットロールに接触させてマット加工し、厚み100μmのカード用オーバーシート(A-1)を作製した。マット加工面の10点平均粗さは15μmであった。
イソソルビドに由来する構造単位:1,4-シクロヘキサンジメタノールに由来する構造単位=50:50(モル%)の比率で構成されるポリカーボネート樹脂を、40mmφ同方向二軸押出機を用いて220℃で混練した後、Tダイより押出し、次いで80℃のキャスティングロールにて急冷しながら、キャストロールに接触する面の対面をマットロールに接触させてマット加工し、厚み100μmのカード用オーバーシート(A-2)を作製した。マット加工面の10点平均粗さは14μmであった。
芳香族ポリカーボネート樹脂(三菱エンジニアリングプラスチックス社製、商品名「ユーピロンS3000」)を、40mmφ同方向二軸押出機を用いて260℃で混練した後、Tダイより押出し、次いで130℃のキャスティングロールにて急冷しながら、キャストロールに接触する面の対面をマットロールに接触させてマット加工し、厚み100μmのカード用オーバーシート(PC)を作製した。マット加工面の10点平均粗さは16μmであった。
非晶性ポリ乳酸樹脂(Nature Works社製、商品名「Ingeo 4060D」、ガラス転移温度:55℃)40質量%と、結晶性ポリ乳酸樹脂(Nature Works社製、商品名「Ingeo 4032D」、ガラス転移温度:55℃)60質量%とをドライブレンドし、40mmφ同方向二軸押出機を用いて200℃で混練した後、Tダイより押出し、次いで50℃のキャスティングロールにて急冷しながら、キャストロールに接触する面の対面をマットロールに接触させてマット加工し、厚み100μmのカード用オーバーシート(PLA)を作製した。マット加工面の10点平均粗さは15μmであった。
製造例1に用いた樹脂100質量%と、着色剤としてルチル型酸化チタン(KRONOS社製、商品名「KRONOS2230」)10質量%とをドライブレンドし、40mmφ同方向二軸押出機を用いて220℃で混練した後、Tダイより押出し、次いで80℃のキャスティングロールにて急冷し、厚み150μmのカード用コアシート(A-コア)を作製した。
非晶性ポリ乳酸樹脂(Nature Works社製、商品名「Ingeo 4060D」、ガラス転移温度:55℃)40質量%と、結晶性ポリ乳酸樹脂(Nature Works社製、商品名「Ingeo 4032D」、ガラス転移温度:55℃)60質量%と、着色剤としてルチル型酸化チタン(KRONOS社製、商品名「KRONOS2230」)10質量%とをドライブレンドし、40mmφ同方向二軸押出機を用いて200℃で混練した後、Tダイより押出し、次いで50℃のキャスティングロールにて急冷し、厚み150μmのカード用コアシート(PLA-コア)を作製した。
カード基材サンプルからJIS-K6251(2004年)に準拠してダンベル1号試験片を打ち抜き、試験片の加工断面が荒れたりクラックが入ったりする不具合が10回試行中8回以上あるものを「×」、前記不具合が3回以上7回以下あるものを「△」、前記不具合が2回以下あるか又は前記不具合が1回もなかったものを「○」として評価した。
カード基材サンプルをカード形状に打ち抜いてから、23℃においてエンボスエンコーダーDC9000(日本データカード株式会社製)を用いて7Bフォントの文字を3行、各行19文字エンボスを施した。エンボス文字のパターンは「123・・・90123・・・789」とした。エンボス後のカードを定盤上に置き、定盤面からカードの非エンボス面の最も高い位置までの高さを測定し、これをエンボスカールの値とした。JIS-X6301(1998年)に基づきエンボスカールが2.5mm以下のものを「○」、2.5mmを超えるものを「×」として評価した。
(6)でエンボスを施したカードを定盤上に置き、非エンボス部分からエンボス文字の頂部までのエンボス高さを測定した。JIS-X6302(1998年)に基づき、エンボス高さが0.4mm~0.48mmの範囲のものを「○」、0.4mm未満のものを「×」として評価した。
前記カード基材サンプルを作製する際に、あらかじめプレスにより熱融着しない部分を残しておき、熱融着された部分と熱融着しない部分を共に含んだ試験片を作製した。この試験片を用いて、JIS-K6854-2(1999年)に基づきオーバーシートとコアシートの180°剥離試験を行なった。全く剥離しなかったものや、剥離しようとしてカード基材が破壊されたものを「○」、カード基材が破壊されずに剥離したものを「×」として評価した。
作製したカードにおいてオーバー層・コア層ともに植物由来原料を使用しているものを「○」、一方のみに使用しているものを「△」とした。
本発明におけるカード用オーバーシートとして、以下の材料を用いた。
(C-1)イソソルビド:ポリエチレングリコール(分子量400)=97:3のモル比率で共重合されてなる、ポリカーボネート樹脂(ガラス転移温度:127℃)を溶融押出法で厚さ100μmに製膜したもの。
(D-1)イソソルビド:1,4-シクロヘキサンジメタノール=50:50のモル比率で共重合されてなる、ポリカーボネート樹脂(ガラス転移温度101℃)100質量%と、ルチル型酸化チタン(KRONOS社製「KRONOS2230」)10質量%とをドライブレンドし、溶融押出法で厚さ150μmに製膜したもの。
1)耐熱性
磁気ストライプ付きクレジットカード規格JIS-X6310(1996年)に準拠して、60℃の温水中に5分間浸漬した時の、カード表面の変化と収縮性を観察した。合わせて80℃でも同様の試験を行った。何れの温度でも表面変化と収縮が認められなかったものを「○」、何れかの温度で表面変化または収縮が認められたものを「×」と判定した。
磁気ストライプ付きクレジットカード規格JIS-X6310(1996年)に準拠して、衝撃強さを測定した。即ちカードを堅固な水平板上に置き、500gの鋼球を30cmの高さから自由落下させた時の、カードの割れとひびを観察した。割れとひびが認められなかったものを「○」、割れまたはひびが認められたものを「×」と判定した。
カード基材サンプルをカード形状に打ち抜いてから、23℃においてエンボスエンコーダーDC9000(日本データカード株式会社製)を用いて7Bフォントの文字を3行、各行19文字エンボスを施した。エンボス文字のパターンは「123・・・90123・・・789」とした。エンボス後のカードを定盤上に置き、定盤面からカードの非エンボス面の最も高い位置までの高さを測定し、これをエンボスカールの値とした。JIS-X6301(1998年)に基づきエンボスカールが2.5mm以下のものを合格とした。
エンボスを施したカードを定盤上に置き、非エンボス部分からエンボス文字の頂部までのエンボス高さを測定した。JIS-X6302(1998年)に基づき、エンボス高さが0.4mm~0.48mmの範囲のものを合格とした。
カードシート間に切り込みを入れ、シート同士を剥離させた。切り込み部以外剥離しないか、切り込み部が千切れたものを「○」、脆性剥離したものを「△」、密着面が容易に剥離したものを「×」と判定した。
試験機として岩崎電気製アイスーパUVテスターSUV-W151を用いて、UV照射強度:75mW/cm2、照射温度:63℃、照射湿度:50%の条件により、各オーバーシートをサンプルとしてUVを照射した。UV照射前と照射50時間後のサンプルのYI値(黄色度)をJIS-K7103(1977年)に基づいて分光測色計(「SC-T」、スガ試験機(株)製)を用いて測定し、測定前後の差であるΔYIを算出した。ΔYIが0以上1.0未満のものを「○」、ΔYIが1.0以上のものを「×」と判定した。
作製したカードにおいて、植物原料樹脂を使用した層を記入した。
Claims (14)
- 前記ポリカーボネート樹脂(A)がさらに、シクロヘキサンジメタノールに由来する構造単位(b)を含有する、請求項1に記載のカード用シート。
- 前記ポリカーボネート樹脂(A)が、前記構造単位(b)を全ジヒドロキシ化合物に由来する構造単位中45モル%以上、65モル%以下の比率で含有する、請求項2に記載のカード用シート。
- 前記ポリカーボネート樹脂(A)が、前記構造単位(a)を全ジヒドロキシ化合物に由来する構造単位中80モル%以上、99モル%以下の比率で含有し、ガラス転移温度が90℃以上、130℃未満である、請求項1に記載のカード用シート。
- 前記ポリカーボネート樹脂(A)が、質量平均分子量が1000以下のポリアルキレングリコールに由来する構造単位(c)を、全ジヒドロキシ化合物に由来する構造単位中1モル%以上、20モル%以下の比率で含有する、請求項4に記載のカード用シート。
- 前記樹脂組成物(X)がさらに紫外線吸収剤を含有する、請求項1から5のいずれか1項に記載のカード用シート。
- 前記樹脂組成物(X)がさらに無機充填剤を含有する、請求項1から6のいずれか1項に記載のカード用シート。
- カード用オーバーシートであって、少なくとも一方の表面に10点平均粗さが3μm以上、30μm以下であるマット加工が施されている、請求項1から7のいずれか1項に記載のカード用シート。
- カード用コアシートであって、前記樹脂組成物(X)が着色剤を含有する、請求項1から7のいずれか1項に記載のカード用シート。
- 曲げ弾性率が2200MPa以上、3000MPa以下である、請求項1から9のいずれか1項に記載のカード用シート。
- 請求項1から10のいずれか1項に記載のカード用シートを用いて作製されるカード。
- さらに磁気テープを用いて作製される磁気ストライプカードである、請求項11に記載のカード。
- さらにICチップを用いて作製されるICカードである、請求項11に記載のカード。
- 前記カードに23℃にてエンボス加工を施した際に生じるエンボスカールが2.5mm以下である、請求項11から13のいずれか1項に記載のカード。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014159542A (ja) * | 2013-01-24 | 2014-09-04 | Mitsubishi Chemicals Corp | 遊技機部材、パーティション、タッチパネル、カード用シート、キーボード部品、ボタン部品、スイッチ部品、建物用窓又は車両用窓 |
Families Citing this family (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107263960A (zh) * | 2010-03-03 | 2017-10-20 | 三菱化学株式会社 | 树脂片包覆金属叠层体及其制造方法 |
KR20130090798A (ko) | 2010-07-14 | 2013-08-14 | 미쓰비시 가가꾸 가부시키가이샤 | 폴리카보네이트 수지 조성물, 및 이것을 사용한 성형품, 필름, 플레이트, 사출 성형품 |
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WO2014079478A1 (en) | 2012-11-20 | 2014-05-30 | Light In Light Srl | High speed laser processing of transparent materials |
JP2014106600A (ja) * | 2012-11-26 | 2014-06-09 | Toppan Printing Co Ltd | 非接触icカードの製造方法 |
EP2754524B1 (de) | 2013-01-15 | 2015-11-25 | Corning Laser Technologies GmbH | Verfahren und Vorrichtung zum laserbasierten Bearbeiten von flächigen Substraten, d.h. Wafer oder Glaselement, unter Verwendung einer Laserstrahlbrennlinie |
US9701564B2 (en) | 2013-01-15 | 2017-07-11 | Corning Incorporated | Systems and methods of glass cutting by inducing pulsed laser perforations into glass articles |
EP2781296B1 (de) | 2013-03-21 | 2020-10-21 | Corning Laser Technologies GmbH | Vorrichtung und verfahren zum ausschneiden von konturen aus flächigen substraten mittels laser |
JP6476543B2 (ja) * | 2013-12-06 | 2019-03-06 | 大日本印刷株式会社 | カード、カードの製造方法 |
US10442719B2 (en) | 2013-12-17 | 2019-10-15 | Corning Incorporated | Edge chamfering methods |
US9517963B2 (en) | 2013-12-17 | 2016-12-13 | Corning Incorporated | Method for rapid laser drilling of holes in glass and products made therefrom |
US11556039B2 (en) | 2013-12-17 | 2023-01-17 | Corning Incorporated | Electrochromic coated glass articles and methods for laser processing the same |
US9815730B2 (en) | 2013-12-17 | 2017-11-14 | Corning Incorporated | Processing 3D shaped transparent brittle substrate |
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US9701563B2 (en) | 2013-12-17 | 2017-07-11 | Corning Incorporated | Laser cut composite glass article and method of cutting |
US9850160B2 (en) | 2013-12-17 | 2017-12-26 | Corning Incorporated | Laser cutting of display glass compositions |
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TWI730945B (zh) | 2014-07-08 | 2021-06-21 | 美商康寧公司 | 用於雷射處理材料的方法與設備 |
EP3169635B1 (en) | 2014-07-14 | 2022-11-23 | Corning Incorporated | Method and system for forming perforations |
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US10526234B2 (en) | 2014-07-14 | 2020-01-07 | Corning Incorporated | Interface block; system for and method of cutting a substrate being transparent within a range of wavelengths using such interface block |
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WO2016105998A1 (en) * | 2014-12-22 | 2016-06-30 | 3M Innovative Properties Company | Compositions and films comprising polylactic acid polymer, polyvinyl acetate polymer and plasticizer |
JP2018507154A (ja) | 2015-01-12 | 2018-03-15 | コーニング インコーポレイテッド | マルチフォトン吸収方法を用いた熱強化基板のレーザー切断 |
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JP2018516215A (ja) | 2015-03-27 | 2018-06-21 | コーニング インコーポレイテッド | 気体透過性窓、および、その製造方法 |
JP6680036B2 (ja) * | 2015-03-31 | 2020-04-15 | 三菱ケミカル株式会社 | 積層体 |
JP6578711B2 (ja) * | 2015-04-03 | 2019-09-25 | 三菱ケミカル株式会社 | 積層フィルム、その製造方法、偏光子保護フィルムの製造方法、偏光板の製造方法及び液晶表示装置の製造方法 |
JP6578723B2 (ja) * | 2015-04-20 | 2019-09-25 | 三菱ケミカル株式会社 | 積層フィルム及び、それから得られる偏光板保護フィルム |
WO2016171194A1 (ja) * | 2015-04-21 | 2016-10-27 | 三菱化学株式会社 | ポリカーボネート樹脂フィルム |
EP3319911B1 (en) | 2015-07-10 | 2023-04-19 | Corning Incorporated | Methods of continuous fabrication of holes in flexible substrate sheets and products relating to the same |
MY194570A (en) | 2016-05-06 | 2022-12-02 | Corning Inc | Laser cutting and removal of contoured shapes from transparent substrates |
US10410883B2 (en) | 2016-06-01 | 2019-09-10 | Corning Incorporated | Articles and methods of forming vias in substrates |
US10794679B2 (en) | 2016-06-29 | 2020-10-06 | Corning Incorporated | Method and system for measuring geometric parameters of through holes |
JP7090594B2 (ja) | 2016-07-29 | 2022-06-24 | コーニング インコーポレイテッド | レーザ加工するための装置および方法 |
KR102423775B1 (ko) | 2016-08-30 | 2022-07-22 | 코닝 인코포레이티드 | 투명 재료의 레이저 가공 |
KR102078294B1 (ko) | 2016-09-30 | 2020-02-17 | 코닝 인코포레이티드 | 비-축대칭 빔 스폿을 이용하여 투명 워크피스를 레이저 가공하기 위한 기기 및 방법 |
EP3848333A1 (en) | 2016-10-24 | 2021-07-14 | Corning Incorporated | Substrate processing station for laser-based machining of sheet-like glass substrates |
US10752534B2 (en) | 2016-11-01 | 2020-08-25 | Corning Incorporated | Apparatuses and methods for laser processing laminate workpiece stacks |
US10688599B2 (en) | 2017-02-09 | 2020-06-23 | Corning Incorporated | Apparatus and methods for laser processing transparent workpieces using phase shifted focal lines |
US11078112B2 (en) | 2017-05-25 | 2021-08-03 | Corning Incorporated | Silica-containing substrates with vias having an axially variable sidewall taper and methods for forming the same |
US10580725B2 (en) | 2017-05-25 | 2020-03-03 | Corning Incorporated | Articles having vias with geometry attributes and methods for fabricating the same |
US10626040B2 (en) | 2017-06-15 | 2020-04-21 | Corning Incorporated | Articles capable of individual singulation |
US11554984B2 (en) | 2018-02-22 | 2023-01-17 | Corning Incorporated | Alkali-free borosilicate glasses with low post-HF etch roughness |
WO2023228804A1 (ja) * | 2022-05-27 | 2023-11-30 | 三菱ケミカル株式会社 | 樹脂組成物、フィルム、カード、及びパスポート |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999009102A1 (fr) * | 1997-08-19 | 1999-02-25 | Mitsubishi Plastics Inc. | Composition de resine pour cartes, et feuilles et cartes ainsi produites |
JP2000141955A (ja) | 1998-06-03 | 2000-05-23 | Mitsubishi Plastics Ind Ltd | 生分解性カード |
JP2002036765A (ja) | 2000-07-21 | 2002-02-06 | Mitsubishi Plastics Ind Ltd | カード用オーバーシート |
JP2002249652A (ja) | 2001-02-27 | 2002-09-06 | Mitsubishi Plastics Ind Ltd | カード用シート |
JP2003154606A (ja) * | 2001-11-20 | 2003-05-27 | Dainippon Printing Co Ltd | 耐熱性プラスチックカード、およびその製造方法 |
WO2004111106A1 (ja) | 2003-06-16 | 2004-12-23 | Teijin Limited | ポリカーボネートおよびその製造方法 |
WO2007148604A1 (ja) | 2006-06-19 | 2007-12-27 | Mitsubishi Chemical Corporation | ポリカーボネート共重合体及びその製造方法 |
JP2008285518A (ja) * | 2007-05-15 | 2008-11-27 | Teijin Ltd | 導電性樹脂組成物 |
JP2009040052A (ja) | 2008-08-26 | 2009-02-26 | Mitsubishi Plastics Inc | カード用シートおよびこれを用いて製造されたカード |
JP2009161746A (ja) * | 2007-12-12 | 2009-07-23 | Mitsubishi Chemicals Corp | ポリカーボネートの製造方法およびポリカーボネート成形物 |
JP2009235172A (ja) | 2008-03-26 | 2009-10-15 | Mitsubishi Plastics Inc | カード用樹脂組成物及びカード用シート |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2007289584A1 (en) * | 2006-08-28 | 2008-03-06 | Teijin Limited | Polycarbonate resin composition comprising plant-derived component |
US7666972B2 (en) * | 2007-10-18 | 2010-02-23 | SABIC Innovative Plastics IP B., V. | Isosorbide-based polycarbonates, method of making, and articles formed therefrom |
EP2543510B1 (en) * | 2010-03-03 | 2016-05-04 | Mitsubishi Chemical Corporation | Laminate |
CN107263960A (zh) * | 2010-03-03 | 2017-10-20 | 三菱化学株式会社 | 树脂片包覆金属叠层体及其制造方法 |
-
2011
- 2011-05-16 KR KR1020127029603A patent/KR20130079395A/ko not_active Application Discontinuation
- 2011-05-16 EP EP11783523.1A patent/EP2573137B1/en active Active
- 2011-05-16 CN CN201180024169.5A patent/CN102892833B/zh active Active
- 2011-05-16 WO PCT/JP2011/061251 patent/WO2011145589A1/ja active Application Filing
- 2011-05-17 TW TW100117156A patent/TWI511884B/zh active
- 2011-05-18 JP JP2011111616A patent/JP5844548B2/ja active Active
-
2012
- 2012-11-19 US US13/680,696 patent/US20130075480A1/en not_active Abandoned
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999009102A1 (fr) * | 1997-08-19 | 1999-02-25 | Mitsubishi Plastics Inc. | Composition de resine pour cartes, et feuilles et cartes ainsi produites |
JP2000141955A (ja) | 1998-06-03 | 2000-05-23 | Mitsubishi Plastics Ind Ltd | 生分解性カード |
JP2002036765A (ja) | 2000-07-21 | 2002-02-06 | Mitsubishi Plastics Ind Ltd | カード用オーバーシート |
JP2002249652A (ja) | 2001-02-27 | 2002-09-06 | Mitsubishi Plastics Ind Ltd | カード用シート |
JP2003154606A (ja) * | 2001-11-20 | 2003-05-27 | Dainippon Printing Co Ltd | 耐熱性プラスチックカード、およびその製造方法 |
WO2004111106A1 (ja) | 2003-06-16 | 2004-12-23 | Teijin Limited | ポリカーボネートおよびその製造方法 |
WO2007148604A1 (ja) | 2006-06-19 | 2007-12-27 | Mitsubishi Chemical Corporation | ポリカーボネート共重合体及びその製造方法 |
JP2008285518A (ja) * | 2007-05-15 | 2008-11-27 | Teijin Ltd | 導電性樹脂組成物 |
JP2009161746A (ja) * | 2007-12-12 | 2009-07-23 | Mitsubishi Chemicals Corp | ポリカーボネートの製造方法およびポリカーボネート成形物 |
JP2009235172A (ja) | 2008-03-26 | 2009-10-15 | Mitsubishi Plastics Inc | カード用樹脂組成物及びカード用シート |
JP2009040052A (ja) | 2008-08-26 | 2009-02-26 | Mitsubishi Plastics Inc | カード用シートおよびこれを用いて製造されたカード |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014159542A (ja) * | 2013-01-24 | 2014-09-04 | Mitsubishi Chemicals Corp | 遊技機部材、パーティション、タッチパネル、カード用シート、キーボード部品、ボタン部品、スイッチ部品、建物用窓又は車両用窓 |
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Publication number | Publication date |
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KR20130079395A (ko) | 2013-07-10 |
TWI511884B (zh) | 2015-12-11 |
CN102892833B (zh) | 2016-01-06 |
CN102892833A (zh) | 2013-01-23 |
EP2573137B1 (en) | 2023-08-30 |
JP5844548B2 (ja) | 2016-01-20 |
EP2573137A4 (en) | 2016-07-27 |
JP2012030574A (ja) | 2012-02-16 |
TW201210824A (en) | 2012-03-16 |
EP2573137A1 (en) | 2013-03-27 |
US20130075480A1 (en) | 2013-03-28 |
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