WO2018074482A1

WO2018074482A1 - Resin film for card, sheet, and laminate for card

Info

Publication number: WO2018074482A1
Application number: PCT/JP2017/037582
Authority: WO
Inventors: 聖英武田; 鈴木　健太郎; 敬一造田; 淳也浅野; 博巳山室; 太二渡邉
Original assignee: 三菱瓦斯化学株式会社; Ｍｇｃフィルシート株式会社; サトーホールディングス株式会社
Priority date: 2016-10-18
Filing date: 2017-10-17
Publication date: 2018-04-26
Also published as: JP2019214633A; TW201827504A

Abstract

The present invention addresses the problem of suppressing the generation of carbon dioxide in a resin film for a card, a laminate for a card having a large thickness as a result of comprising a plurality of resin films, and the like during incineration. The abovementioned problem is solved by a resin film for a card containing a carbon dioxide generation-suppressing substance that suppresses the generation of carbon dioxide during combustion.

Description

Resin film for card, sheet, and laminate for card

The present invention relates to a card resin film, a sheet having a card resin film, and a card laminate.

In order to reduce the amount of carbon dioxide emitted when incinerated and discarded, it has been proposed to add a carbon dioxide-absorbing substance in stretch films, labels, thermal paper, ink ribbons, and the like (Patent Document 1 and Patent Document 2).

JP 2016-111401 A Japanese Patent No. 5830034

Conventionally, carbon dioxide-absorbing substances have been added for packaging materials and label applications such as stretch films. However, since it is generally thicker than a stretch film or the like, a carbon dioxide-absorbing substance has not been added to a resin film that generates a large amount of carbon dioxide per unit area when incinerated during disposal. For this reason, it is necessary to suppress the generation of carbon dioxide during incineration in a card laminate having a large thickness because it has a plurality of resin films for a resin film, particularly for cards such as ID cards. It was.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have suppressed the generation of predetermined carbon dioxide in a resin film for a card containing a resin, a sheet having a resin film for a card, and a laminated body for a card. It has been found that the amount of carbon dioxide gas generated during incineration can be suppressed by adding a substance, and the present invention has been completed.
That is, this invention relates to the resin film for cards shown below, the sheet | seat which has the resin film for cards, and the laminated body for cards.

(1) carbon dioxide generation inhibitor,
A resin film for cards, containing at least one resin selected from polycarbonate, PETG, and PCTG.
(2) The above-mentioned (1), containing 0% by mass to 50% by mass of PETG, 0% by mass to 50% by mass of PCTG, and 50% by mass to 100% by mass of polycarbonate based on the total mass of the resin film. The resin film for cards described in 1.
(3) The resin film for cards according to (1) above, comprising PETG and polycarbonate, wherein PETG: polycarbonate, which is a mass ratio of PETG to polycarbonate, is in the range of 10:90 to 50:50.
(4) The card resin film according to (1) above, comprising PCTG and polycarbonate, wherein PCTG: polycarbonate, which is a mass ratio of PCTG to polycarbonate, is in the range of 10:90 to 50:50.
(5) The above (1), wherein the carbon dioxide generation-suppressing substance contains at least one of the group consisting of metal hydroxide, metal oxide, aluminosilicate, titanate compound and lithium silicate. The resin film for card | curd in any one of (4).
(6) The resin film for card | curd as described in said (5) in which the said carbon dioxide generation suppression substance contains aluminosilicate.
(7) The card resin according to any one of (1) to (6), comprising 0.1 to 10% by mass of the carbon dioxide generation-inhibiting substance based on the total mass of the resin film. the film.
(8) The resin film for cards according to any one of the above (1) to (7), wherein the tensile yield stress is 45 MPa or more.
(9) The card resin film according to any one of (1) to (8), wherein the resin film has a thickness of 0.05 to 1 (mm).
(10) The resin film for cards according to any one of the above (1) to (9), wherein the resin film forms a transparent layer.
(11) The card resin film according to any one of (1) to (10) above, containing 10% by mass to 30% by mass of a white pigment based on the total mass of the resin film.
(12) An embedded sheet having the resin film according to (11) and a layer having an antenna and / or a chip.
(13) The card resin film according to any one of (1) to (11) above, containing 0.0001 to 0.5% by mass of a laser color former based on the total mass of the resin film.
(14) A laser marking film having the resin film according to (13).
(15) The resin film for cards according to any one of the above (1) to (11) and (13), wherein the carbon dioxide reduction rate based on JIS K 7217: 1983 is 30% or more.
(16) A card resin film according to any one of (1) to (11), (13) and (15) above, and a laminate comprising a non-transparent layer containing a resin,
The non-transparent layer contains a white pigment, and printing is performed on at least one surface of the non-transparent layer, so as to cover at least a part of the printed surface of the non-transparent layer that has been printed. A card laminate, wherein the card resin containing a carbon dioxide generation-inhibiting substance is laminated.
(17) The card laminate according to (16) above, wherein all the layers constituting the laminate contain the carbon dioxide generation-inhibiting substance.

In the card resin film, sheet, and card laminate of the present invention, the amount of carbon dioxide gas generated during incineration can be suppressed. In particular, in the card laminate, it is possible to significantly reduce the amount of carbon dioxide gas generated at the time of incineration by providing a carbon dioxide generation suppressing function in all the layers (sheets) constituting the card.

It is sectional drawing which shows the specific example of the laminated body for cards (ID card) containing the resin film for cards.

Hereinafter, the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, In the range which has the effect of invention, it can change arbitrarily and can implement.

[Resin film for cards]
The resin film for card | curd of this invention contains the carbon dioxide generation suppression substance which suppresses generation | occurrence | production of the carbon dioxide at the time of combustion, and at least 1 resin selected from a polycarbonate, PETG, and PCTG.

<Polycarbonate resin>
The polycarbonate resin that can be contained in the resin film for card is a — [O—R—OCO] -unit (R is an aliphatic group, an aromatic group, or an aliphatic group and an aromatic group containing a carbonate bond in the molecular main chain. It is not particularly limited as long as it includes both of the groups, and further includes those having a straight chain structure or a branched structure, but it is particularly preferable to use the following polycarbonates.
That is, it 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. More preferably, it is 35,000 to 50,000.
The glass transition temperature of the polycarbonate resin is preferably 120 to 160 (° C.), more preferably 130 to 155 (° C.).

<PETG resin and PCTG resin>
In the resin film for cards, as described above, a polyethylene terephthalate-based PETG resin and a PCTG resin can be included as a polyester resin in addition to the polycarbonate resin.
The PETG resin is a polyester copolymer composed of a dicarboxylic acid unit mainly composed of terephthalic acid units, an ethylene glycol unit, and a glycol unit mainly composed of 1,4-cyclohexanedimethanol unit. That is, the PETG resin is a resin obtained by copolymerizing cyclohexanedimethanol in addition to dicarboxylic acid and ethylene glycol, which are monomers of PET (polyethylene terephthalate) resin. In the PETG resin, terephthalic acid units occupy, for example, all dicarboxylic acid units on a molar basis, and 1,4-cyclohexanedimethanol units occupy, for example, less than 50% of all glycol units on a molar basis.
PCTG resin is a polyester copolymer in which the diol component of polycyclohexanedimethylene terephthalate is partially replaced with ethylene glycol. That is, the PCTG resin is a resin obtained by copolymerizing cyclohexanedimethanol in addition to dicarboxylic acid and ethylene glycol, which are monomers of PET (polyethylene terephthalate) resin. In the PCTG resin, for example, terephthalic acid units occupy all dicarboxylic acid units on a molar basis, and 1,4-cyclohexanedimethanol units occupy 50% or more of all glycol units on a molar basis, for example.

<Resin components other than polycarbonate>
The resin film for cards may contain a resin other than polycarbonate, PETG, and PCTG. For example, in the resin film for cards, PBT (polybutylene terephthalate), polycaprolactone, or the like may be included as a polyester resin other than PETG and PCTG. Moreover, ABS etc. may be contained as resin other than a polycarbonate and polyester.

<Ratio of resin component>
The resin film for card preferably contains 0% by mass to 50% by mass of PETG, 0% by mass to 50% by mass of PCTG, and 50% by mass to 100% by mass of polycarbonate based on the mass of the entire resin film. .
The resin film for cards contains more preferably 0% by mass to 45% by mass, and still more preferably 0% by mass to 40% by mass of PETG. The resin film for card contains more preferably 0% by mass to 45% by mass, and still more preferably 0% by mass to 40% by mass of PCTG. The card resin film more preferably contains 55% by mass to 100% by mass, and more preferably 60% by mass to 100% by mass of polycarbonate.

The card resin film preferably contains PETG and polycarbonate. In this case, PETG: polycarbonate, which is the mass ratio of PETG to polycarbonate, is more preferably in the range of 10:90 to 50:50, and PETG: polycarbonate is more preferably 20:80 to 40:60.

The resin film for cards preferably contains PCTG and polycarbonate. In this case, PCTG: polycarbonate, which is the mass ratio of PCTG and polycarbonate, is more preferably within the range of 10:90 to 50:50, and PCTG: polycarbonate is more preferably 20:80 to 40:60.

<Carbon dioxide generation inhibitor>
The amount of carbon dioxide generated when the film is burned can be suppressed by the carbon dioxide generation-suppressing substance contained in the card resin film. The carbon dioxide generation inhibitor is preferably added to the card resin film after the carbon dioxide generation inhibitor and the dispersion aid are mixed and subjected to a dispersion treatment.

The carbon dioxide generation inhibiting substance in the present invention is a substance that adsorbs carbon dioxide chemically or physically. The carbon dioxide generation suppressing substance suppresses the generation amount of carbon dioxide gas generated by the combustion of the combustible material by at least the following two effects. In other words, it promotes carbonization of flammable gas generated by decomposition of combustible materials during combustion, prevents binding to oxygen, and reacts chemically with carbon dioxide at high temperatures during combustion, resulting in nano-sized porosity. This is an effect of adsorbing carbon dioxide gas by forming a body.
Examples of carbon dioxide generation inhibiting substances having excellent effects as described above include, for example, inorganic hydroxides, metal hydroxides, metal oxides, aluminosilicates, titanic acid compounds, lithium silicates, silica gels, alumina and activated carbon, organic Specific examples of the compound include coconut mesocarp fiber.

Examples of the metal hydroxide include lithium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide.
Examples of the metal oxide include magnesium oxide, calcium oxide, and zinc oxide.
Examples of the aluminosilicate include amorphous aluminosilicate, natural zeolite, synthetic zeolite, and the like, preferably sodium aluminosilicate.
Examples of the titanate compound include barium titanate and barium orthotitanate.

The above-mentioned dispersion aid may be any substance as long as it can efficiently disperse the carbon dioxide generation inhibiting substance, which is an inorganic compound or an organic compound, in the resin. For example, fatty acid metal salts, polymeric surfactants and amphiphilic lipids are preferred.

Examples of the fatty acid metal salt include calcium stearate, zinc stearate, magnesium stearate, aluminum stearate, barium stearate, lithium stearate, sodium stearate, potassium stearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate. , 12-hydroxy magnesium stearate, 12-hydroxy aluminum stearate, 12-hydroxy barium stearate, 12-hydroxy lithium stearate, sodium 12-hydroxy stearate, potassium 12-hydroxy stearate and the like.
Examples of the polymeric surfactant include sodium polyacrylate, sodium polycarboxylate, olefin / maleic acid copolymer sodium salt, polyoxyethylene type gemini type surfactant (POE30-10-ODEs, POE20-10ODEs, POE10). -10-ODEs), phosphate type gemini surfactants (POH-10-ODEs), dicarboxylic acid type gemini surfactants (DC-10-ODEs), and the like.
Examples of the amphipathic lipid include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, egg yolk lecithin, hydrogenated egg yolk lecithin, glycerophospholipid such as soybean lecithin, hydrogenated soybean lecithin, sphingomyelin And sphingophospholipids such as ceramide phosphorylethanolamine and ceramide phosphorylglycerol.

The dispersion treatment described above may be any method as long as the surface of the carbon dioxide generation inhibiting substance is efficiently covered with a dispersion aid and a dispersion in which the carbon dioxide generation inhibiting substance is uniformly dispersed can be prepared. For example, a carbon dioxide generation inhibitor such as sodium aluminosilicate is preferably encapsulated in very fine phospholipid capsules and dispersed as liposomes in the resin so as to be substantially uniform.
Moreover, it is preferable to perform a supercritical fluid process, an ultrasonic irradiation process, and a stirring process as a dispersion process.

水 The solvent of the dispersion is preferably water or an organic solvent. Specific examples of the organic solvent include ethanol, dichloromethane, hexane and the like.

In the supercritical fluid treatment, the dispersibility of the carbon dioxide generation suppressing substance is improved by exposing a mixture of the carbon dioxide generation suppressing substance and the dispersion aid to the supercritical fluid. As the supercritical fluid, carbon dioxide in a supercritical state is preferable.
The supercritical carbon dioxide means carbon dioxide in a supercritical state having a critical temperature of 30.98 ° C. and a critical pressure of 7.3773 MPa or more. Note that carbon dioxide in which critical temperature alone or critical pressure alone is a critical condition is not a supercritical state.

Moreover, it is preferable that a carbon dioxide generation inhibitor is added to the resin film for cards as a transparent layer arrange | positioned, for example on the outer surface of a laminated body. Since the resin film for cards has high transparency, it is suitably used as a material for the transparent layer.
However, the amount of carbon dioxide generated at the time of incineration can be greatly suppressed by adding a carbon dioxide generation inhibitor to all layers of the multilayer body, the details of which will be described later.

The content of the carbon dioxide generation inhibiting substance in the card resin film is 0.1 to 10% by mass, preferably 0.1 to 5% by mass, based on the mass of the card resin film. When the amount of the carbon dioxide generation inhibiting substance exceeds 10% by mass, the strength of the resin film for cards tends to decrease. Further, if the amount of the carbon dioxide generation suppressing substance is less than 0.1% by mass, the carbon dioxide generation suppressing ability may be insufficient.

<Reduction rate of carbon dioxide>
By adding the carbon dioxide generation inhibiting substance, a carbon dioxide reduction rate of 30% or more based on JIS K 7217: 1983 can be realized in the resin film for cards. In the resin film for cards, more preferably, a carbon dioxide reduction rate of 40%, more preferably 50%, particularly preferably 60% can be achieved according to JIS K 7217: 1983.

<White pigment>
The resin film for cards may further contain a white pigment. Thus, the card | curd resin film containing a white pigment is used suitably as a material of the white sheet | seat which forms the sheet | seat (core layer) containing at least one of antennas and chips | tips, such as an ID card. In this case, for example, an embedding sheet in which a resin film for a card as a transparent layer not containing a white pigment and an antenna or a chip or a sheet (non-transparent layer) containing an antenna and a chip can be formed.

As the white pigment, titanium oxide, talc, kaolin, clay, mica and the like are used, and preferably titanium oxide is used.
The content of the white pigment is 10 to 30% by mass, preferably 13 to 25% by mass, more preferably 15 to 20% by mass, based on the mass of the entire non-transparent layer.

<Laser color former>
The resin film for cards may further contain a laser color former. Thus, a resin film for a card containing a laser color former is suitably used as a material for a laser marking film (laser marking layer) that enables printing by a marking process, for example, in a card that requires tampering prevention. The As the laser color former, carbon black, antimony-doped tin oxide, bismuth oxide color former or the like is used, and preferably carbon black is used.
The content of the laser color former is 0.0001 to 0.5% by mass, preferably 0.0005 to 0.3% by mass, more preferably 0.001 to 0%, based on the mass of the entire resin composition. .2% by mass.
For example, when carbon black is used as the laser color former, the content of carbon black is 1 to 100 ppm by mass, preferably 5 to 20 ppm by mass, based on the total mass of the resin composition. When the metal oxide laser color former described above is used, the content of the laser color former is, for example, 100 to 5000 ppm by mass, preferably 300 to 3000 mass, based on the mass of the entire resin composition. ppm, more preferably 500 to 2000 ppm by mass.

<Additive of resin composition>
The resin composition may contain the following additives in addition to the components described above. That is,
And at least one additive selected from the group consisting of heat stabilizers, antioxidants, flame retardants, flame retardant aids, ultraviolet absorbers, mold release agents and colorants.
In addition, an antistatic agent, a fluorescent whitening agent, an antifogging agent, a fluidity improving agent, a plasticizer, a dispersing agent, an antibacterial agent and the like may be added as long as desired physical properties are not significantly impaired.

[Properties of resin film for cards]
The resin film for cards preferably has a tensile yield stress of 45 (MPa) or more, more preferably 50 (MPa) or more, and particularly preferably 55 (MPa) or more.
The thickness of the resin film for cards is preferably 0.01 (mm) to 1 (mm), preferably 0.02 (mm) to 0.9 (mm), more preferably 0.03 (mm). Is 0.84 (mm). The resin film for cards of the present invention is excellent in durability and heat resistance, and is suitable for applications such as cards such as ID cards, particularly security cards. In many cases, the thickness of the laminate including the resin film is approximately 1.0 (mm) or less.

[Card laminate]
The laminated body for cards of the present invention is a multilayer body having at least one layer of the above-mentioned resin film for cards (resin film) and a non-transparent layer laminated on the resin film for cards. The card resin film contains a carbon dioxide generation-inhibiting substance and a polycarbonate resin.
In the above-described laminate, the non-transparent layer is made non-transparent, for example, with a white pigment, the surface of the non-transparent layer is printed, and the card resin film (for example, the transparent layer) is non-transparent. The transparent layer is laminated so as to cover the printed surface, that is, the printed surface.
Thus, in the card laminate formed as a multilayer body, preferably, all layers constituting the laminate contain a carbon dioxide generation-suppressing substance. For example, during combustion such as incineration, carbon dioxide The generation of gas is greatly suppressed.

[Transparent layer]
The above-mentioned resin film for cards (resin film) forms, for example, a transparent layer of the above-described laminate. The transparent layer is a colorless and transparent layer containing no pigment. Therefore, when a carbon dioxide generation inhibitor is added to the transparent layer, it is preferable to select a carbon dioxide generation inhibitor that can maintain transparency. The transparent layer preferably contains mainly a thermoplastic resin such as polycarbonate, but may contain a thermosetting resin. The transparent layer is laminated so as to cover the surface on which the non-transparent layer is printed, that is, the printed surface.

[Non-transparent layer]
The non-transparent layer contains a resin and is colored with a pigment or the like, for example, the above-described white pigment.
The non-transparent layer preferably contains a resin (thermoplastic resin) such as polycarbonate resin, PETG resin, or PCTG resin as the main component, as in the case of the card resin film (transparent layer). Specifically, the non-transparent layer is made of, for example, 70% by mass or more, preferably 80% by mass or more of a thermoplastic resin.
As described above, as the resin forming the non-transparent layer, for example, the thermoplastic resin, in addition to polycarbonate, PETG resin, and PCTG resin, any resin selected from polyester or a mixture of a plurality of resins is used. Also good.

A specific example of the resin laminate is the ID card 10 shown in FIG. The ID card 10 includes a first transparent layer 12, a second transparent layer 14, a first laser marking transparent layer 16, a second laser marking transparent layer 18, a first non-transparent layer 20, and a second non-transparent layer 22. Is the body.
The first transparent layer 12, the second transparent layer 14, the first laser marking layer 16, and the second laser marking layer 18 are colorless and transparent, and each contain a carbon dioxide generation suppressing substance. The first laser marking transparent layer 16 and the second laser marking transparent layer 18 further contain a laser color former, and printing by irradiating the laser beam L is possible. The first non-transparent layer 20 and the second non-transparent layer 22 contain a white pigment and are white and non-transparent. The surface of the first non-transparent layer 20 on the first laser marking transparent layer 16 side, that is, the first non-transparent layer 20. The surface covered with the laser marking transparent layer 16 is a printing surface printed (not shown) with ink. In the first non-transparent layer 20, an antenna chip 24 is embedded. Information of an IC chip (not shown) is overwritten in accordance with an external electromagnetic wave received by the antenna chip 24.
Any of these layers can be formed of, for example, a thermoplastic resin mainly composed of polycarbonate, and may be formed of a resin other than polycarbonate, for example, PETG resin. And the ID card 10 excellent in surface durability and heat resistance can be manufactured by forming the 1st transparent layer 12 and the 2nd transparent layer 14 using polycarbonate resin.
Further, by forming the first laser marking transparent layer 16 and the second laser marking transparent layer 18 with a polycarbonate resin, or with a resin preferably containing a polycarbonate resin as a main component, an area irradiated with laser light can be obtained. Black is clearly printed, and the contrast of the printed surface can be improved.
In addition, the durability of the ID card 10 is improved by forming the first non-transparent layer 20 and the second non-transparent layer 22 from a polycarbonate resin, or a resin preferably containing a polycarbonate resin as a main component. Is also possible.
Further, not only the transparent layer but also the first laser marking transparent layer 16, the second laser marking transparent layer 18, the first non-transparent layer 20, and the second non-transparent layer 22 are added with a carbon dioxide generation inhibiting substance. Also good.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

<Calculation of CO ₂ reduction rate>
A sample of the film was burned, and the reduction rate from the reference value was measured as follows for the amount of carbon dioxide generated by the burning. That is, the reduction rate of carbon dioxide was measured according to JIS K 7217: 1983 using a plastic combustion tester (manufactured by Sugia Magen Co., Ltd.). In the measurement, a 0.1 g sample was burned for 10 minutes under the conditions of a gas supply rate of 0.5 L / min and a set temperature of 750 ° C., and the total emission amount of carbon dioxide generated at that time was measured. The reduction rate was calculated from the total carbon dioxide emissions of Examples 1 to 10 and Comparative Examples 1 to 4 with the total oxygen dioxide emission measured using a polycarbonate test piece weighing 0.1 g as 100%. .

<Print surface protection>
The print protection properties of the resin films and laminates of each example and comparative example were not measured under the following conditions using a flat wear tester (equipment used: “PA-300A” manufactured by Daiei Scientific Instruments). Evaluation was made by carrying out a scratch test in which the printed surface side printed on the transparent layer was damaged while being loaded with steel wool.
(Test conditions)
Jig reciprocation frequency: 10 reciprocation stroke: 150 mm
Test speed: 10 reciprocations per minute Upper side: Steel wool # 0000
Lower side: Printed non-transparent layer Sample size: 40 mm x 300 mm
(Operating procedure)
In a state where the steel wool set on the upper side and the printed non-transparent layer film set on the lower side are overlapped so that the printing surface side is in contact with the steel wool, a rubbing test is performed by applying a load of 1000 g, and printing is performed. The presence or absence of scratches was determined.
(Evaluation of printing protection)
If there was one or more scratches on the printed surface, it was judged as “None”.
When no scratch was generated on the printed surface, it was judged as “good”.
However, since Example 1 and Comparative Examples 1, 2, and 4 where no printing surface exists were not printed in the first place, it was determined as “None” without performing a scratch test.
On the other hand, in Examples 1 and 3 to 10 and Comparative Example 3, the print protection property was confirmed by the scratch test.

<Shielding>
The shielding properties of the resin films and laminates of each Example and Comparative Example were evaluated as follows using the total light transmittance measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory) as an index. did. The total light transmittance was measured in accordance with JIS K 7361.
Total light transmittance <20%: Good Total light transmittance 20% or more: None

<Laser marking characteristics>
The resin film of each Example and the comparative example, and the laser marking characteristic of a laminated body were evaluated as follows. Using a laser marking device (“EasyMark IV-E10” manufactured by Lofine Basel), laser marking was performed on the film directly and on the laminate from the transparent layer side under the following irradiation conditions. After laser marking processing, the non-printed part is measured using a spectral colorimeter (“SD6000” manufactured by Nippon Denshoku Industries Co., Ltd.), and the obtained L value L0 is obtained by measuring the printed part. When the value L0 / L1 obtained by dividing by L1 was 2 or more, the laser marking characteristic was judged as “good”, and when L0 / L1 was less than 2, the laser marking characteristic was judged as “none”. Here, the L value refers to the L value indicated by the CIE 1976 (L * a * b *) color system.
Conditions for laser marking processing Scan Speed: 1,000 mm / s
Output Energy: 21-30A
Pulse Frequency: 10-100kHz

<Tensile yield stress>
The tensile yield stress of the resin film of each Example and Comparative Example and the laminate was measured using an autograph (“AGS-X” manufactured by Shimadzu Corporation). The tensile yield stress was measured according to JIS K 7161.

<Manufacture of film (laminate)>
The films of Example 1 and Comparative Examples 1 to 3 were produced as follows. That is, a carbon dioxide generation inhibiting substance (sodium aluminosilicate) and a laser color former (carbon black) are added to the following polycarbonate resins in the contents shown in Table 1 to obtain a uniform thermoplastic resin (polycarbonate resin). It was.
Bisphenol A type aromatic polycarbonate resin ("Iupilon (registered trademark) E-2000F" manufactured by Mitsubishi Engineering Plastics Co., Ltd., heat distortion temperature (glass transition temperature) 150 ° C)
A transparent layer was produced as follows using the thermoplastic resin described above. First, using a T-die melt extruder composed of a twin screw extruder having a barrel diameter of 32 mm and a screw L / D = 31.5, a sheet having a discharge amount of 20 kg / h and a screw rotation speed of 200 rpm was formed into a sheet having a width of 300 mm. Cylinder and die head temperatures were 280 ° C. in Examples 1 to 8, including Examples 2 and below, details of which will be described later, 240 ° C. in Examples 9 and 10, and 220 ° C. in Comparative Examples 4 to be described in detail later. It was done with the setting. A film having both mirror surfaces was used. The film thickness was formed to be 100 μm.
In Examples 5 to 8, the above-described aromatic polycarbonate resin (PC resin), PETG resin (“SKYGREEN (registered trademark) S2008” manufactured by SK Chemicals), and PCTG resin (“SKYGREEN (registered trademark) manufactured by SK Chemicals) ) J2003 ") at the ratio (mass ratio) shown in Table 1 to produce a transparent layer.
Moreover, in the transparent layer of Example 9, the cylinder die head temperature was set to 240 ° C. using the above-described PETG resin, and in the transparent layer of Comparative Example 4, PE resin (polyethylene resin: manufactured by Nippon Polyethylene Co., Ltd. “ A transparent layer was produced in the same manner as in Example 1 and Comparative Examples 1 to 3 except that the cylinder die head temperature was set to 220 ° C. using Novatec HD (registered trademark) HY540 ”.

Further, in Examples 2 to 10, Comparative Example 2 and Comparative Example 3, 15% by mass of a white pigment (titanium oxide) was added to the above polycarbonate resin, and a non-transparent layer was formed in the same manner as the transparent layer. Molded. In Examples 3 to 10 and Comparative Example 3, a transparent film (transparent layer) and a non-transparent film (non-transparent layer) were stacked and sandwiched between upper and lower SUS plates, and a pneumatic hot press (IMC-1839 type: The transparent layer and the non-transparent layer were laminated by pressing for 60 seconds at 200 ° C. and an air pressure of 0.2 MPa using Imoto Seisakusho.

It was confirmed that the film of each example provided with a transparent layer containing any one of PC resin, PETG resin, and PCTG resin and an appropriate amount of carbon dioxide generation-suppressing substance is excellent in CO ₂ reduction effect during combustion. It was. In this way, in the transparent layer excellent in the CO ₂ reduction effect at the time of combustion, a synergistic effect that the printing becomes more durable while reliably preventing rewriting can be expected by further adding a laser color former ( Laser marking characteristics). In addition, by providing a non-transparent layer, characteristics that prevent the inside of the film from being visually recognized (shielding property), and by covering the printing surface of the non-transparent layer with the transparent layer, the printing surface can be visually recognized from the outside. It was confirmed that it can be reliably protected with (printing surface protection). Further, by using any one of PC resin, PETG resin, and PCTG resin, it was possible to realize a film having a high tensile yield stress value and excellent durability.
On the other hand, in the film of each comparative example, generally satisfactory properties such as no CO ₂ reduction effect during combustion were not obtained.

10 ID card (card laminate)
12 1st transparent layer 14 2nd transparent layer 16 1st laser marking transparent layer 18 2nd laser marking transparent layer 20 1st non-transparent layer 22 2nd non-transparent layer 24 Antenna chip

Claims

Carbon dioxide generation inhibitor,
A resin film for cards, containing at least one resin selected from polycarbonate, PETG, and PCTG.
The card according to claim 1, comprising 0 to 50% by mass of PETG, 0 to 50% by mass of PCTG, and 50 to 100% by mass of polycarbonate based on the total mass of the resin film. Resin film.
The card resin film according to claim 1, comprising PETG and polycarbonate, wherein PETG: polycarbonate, which is a mass ratio of PETG to polycarbonate, is within a range of 10:90 to 50:50.
The card resin film according to claim 1, comprising PCTG and polycarbonate, wherein PCTG: polycarbonate, which is a mass ratio of PCTG and polycarbonate, is within a range of 10:90 to 50:50.
The carbon dioxide generation-suppressing substance contains any one or more members selected from the group consisting of metal hydroxides, metal oxides, aluminosilicates, titanate compounds, and lithium silicates. The resin film for cards according to claim.
The card resin film according to claim 5, wherein the carbon dioxide generation-inhibiting substance contains an aluminosilicate.
The card resin film according to any one of claims 1 to 6, comprising 0.1 to 10% by mass of the carbon dioxide generation-inhibiting substance based on the total mass of the resin film.
The resin film for cards according to any one of claims 1 to 7, wherein the tensile yield stress is 45 MPa or more.
The card resin film according to any one of claims 1 to 8, wherein the resin film has a thickness of 0.05 to 1 (mm).
The card resin film according to any one of claims 1 to 9, wherein the resin film forms a transparent layer.
The card resin film according to any one of claims 1 to 10, comprising 10% by mass to 30% by mass of a white pigment based on the total mass of the resin film.
An embedded sheet comprising the resin film for cards according to claim 11 and a layer having an antenna and / or a chip.
12. The card resin film according to claim 1, comprising 0.0001 to 0.5% by mass of a laser color former based on the total mass of the resin film.
A laser marking film comprising the card resin film according to claim 13.
The card resin film according to any one of claims 1 to 11 and 13, wherein a carbon dioxide reduction rate in accordance with JIS K 7217: 1983 is 30% or more.
A card resin film according to any one of claims 1 to 11, 13, and 15, and a laminate comprising a non-transparent layer containing a resin,
The non-transparent layer contains a white pigment, and printing is performed on at least one surface of the non-transparent layer, so as to cover at least a part of the printed surface of the non-transparent layer that has been printed. A card laminate, wherein the card resin containing a carbon dioxide generation-inhibiting substance is laminated.
The laminated body for cards of Claim 16 in which all the layers which comprise the said laminated body contain the said carbon dioxide generation suppression substance.