JP2019183092A - Resin composition, and resin sheet for card based on the same - Google Patents

Abstract

To provide a polycarbonate resin composition having characteristics suitable for card applications, and a resin sheet for a card based on the same.SOLUTION: According to one embodiment, a resin composition comprises a polyester resin comprising a constitutional unit derived from a diol represented by the general formula (1) in the figure, and a polycarbonate resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition suitable for card applications and a resin sheet for cards using the same.

  In recent years, as a method of writing characters, barcodes, images, etc. on the surface of a plastic card such as a non-contact IC card, a method of marking by irradiating a laser beam instead of embossing or printing has been adopted. It has become. For example, by writing information on a card using a YAG laser or the like, it is possible to prevent the written information from being lost due to wear or aging. As a result, in many industries now, conventional ink systems are moving to laser marking systems.

  For laser marking, a CO2 laser, an Nd: YAG laser, or the like is used, but an Nd: YAG laser is mainly used to enable fine printing. However, when laser marking is performed on a resin molded product with an Nd: YAG laser, almost all major resin molded products cannot provide markings with sufficient quality in terms of visibility and fineness, and few resins cannot be printed at all. Absent.

  As a conventional material for a card subjected to laser marking, a polyvinyl chloride resin (PVC resin) composition has been mainly used from the viewpoints of printability, embossability, and laminateability. However, when the PVC resin composition is irradiated with a laser, chlorine gas may be generated from the heating part, and there are many complicated problems such as special separation and collection required at the time of disposal. For this reason, polycarbonate resins have attracted attention as suitable resins that can replace PVC resins (Patent Documents 1 to 3).

  Polycarbonate resin has high laser marking properties in addition to impact properties, dimensional stability, and transparency, and can be said to be a suitable resin that can replace PVC resin in card applications where laser marking is performed. However, polycarbonate resin has a problem that its molding temperature is higher than that of PVC resin, and its adoption in Japan is delayed. Accordingly, there is a need for a polycarbonate resin material suitable for card applications that can solve the above problems.

JP 2003-246925 A Patent No. 5864571 Japanese Patent Laying-Open No. 2015-83621

  An object of this invention is to provide the polycarbonate resin composition which has the characteristic suitable for a card use, and the resin sheet for cards using the same.

The present invention is as follows, for example.
[1] A resin composition comprising a polyester resin containing a structural unit derived from a diol represented by the following general formula (1) and a polycarbonate resin:
(Where
R ₁ and R ₂ are a hydrogen atom or an optionally substituted alkyl group or aryl group, and R ₁ and R ₂ may be bonded to form a ring;
R ₃ and R ₄ are an alkyl group or an aryl group which may have a substituent;
Each X is independently an alkylene group which may have a substituent;
p and q are integers from 0 to 4;
m and n are integers of 1 or more, and 2 ≦ m + n ≦ 6).
[2] The resin composition according to [1], wherein the polyester resin includes a structural unit derived from the diol represented by the general formula (1) at a ratio of 30 to 100 mol%.
[3] The resin composition according to [1] or [2], wherein the resin composition includes the polyester resin in an amount of 0.5 to 98% by mass and the polycarbonate resin in an amount of 2 to 99.5% by mass. .
[4] The resin composition according to any one of [1] to [3], wherein m and n are both 1.
[5] The resin composition according to any one of [1] to [4], wherein X is selected from the group consisting of a methylene group, an ethylene group, and a butylene group.
[6] The resin composition according to any one of [1] to [5], further including a laser light energy absorber.
[7] The resin composition according to [6], wherein the laser light energy absorber is carbon black.
[8] The resin composition according to any one of [1] to [7], wherein the glass transition temperature is 100 to 135 ° C.
[9] The resin composition according to any one of [1] to [8], wherein the haze value measured for a molded product having a thickness of 1.0 mm is less than 16%.
[10] A resin sheet for cards, molded using the resin composition according to any one of [1] to [9].
[11] A security card or ID card formed using the card resin sheet according to [10].

  ADVANTAGE OF THE INVENTION According to this invention, the polycarbonate resin composition which has the characteristic suitable for a card use, and the resin sheet for cards using the same can be provided.

Sectional drawing which shows the specific example of an ID card.

Hereinafter, embodiments of the present invention will be described in detail.
According to one embodiment of the present invention, there is provided a resin composition comprising a polyester resin containing a structural unit derived from a diol represented by the following general formula (1) and a polycarbonate resin:
(Where
R ₁ and R ₂ are a hydrogen atom or an optionally substituted alkyl group or aryl group, and R ₁ and R ₂ may be bonded to form a ring;
R ₃ and R ₄ are an alkyl group or an aryl group which may have a substituent;
Each X is independently an alkylene group which may have a substituent;
p and q are integers from 0 to 4;
m and n are integers of 1 or more, and 2 ≦ m + n ≦ 6).

  According to the present invention, a polycarbonate resin composition having a relatively low glass transition temperature can be obtained by using a polyester resin having the above specific structure in combination with a polycarbonate resin. Therefore, it becomes possible to perform molding at a relatively low temperature. In addition, the resin composition of the present invention is excellent in laser marking properties while maintaining the impact resistance, dimensional stability, and transparency inherent in the polycarbonate resin. Therefore, when marking is performed on the molded article using the resin composition of the present invention by laser light irradiation, it is possible to mark with good contrast to such an extent that marks such as letters and symbols can be clearly recognized visually. The resin composition having such characteristics can be suitably used as a card material for laser marking.

Hereinafter, the components of the resin composition of the present invention will be described in order.
(1) Polyester resin The resin composition of this invention contains the polyester resin containing the structural unit derived from the diol represented by following General formula (1). The polyester resin includes a structural unit derived from a diol and a structural unit derived from a dicarboxylic acid, and the structural unit derived from the diol includes a structural unit represented by the following general formula (1).

In Formula (1), R ₁ and R ₂ are a hydrogen atom or an alkyl group or an aryl group which may have a substituent, and R ₁ and R ₂ may be bonded to form a ring. . The alkyl group may be linear or branched, and is preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. , An isobutyl group, a sec-butyl group, a tert-butyl group, or a phenyl group, more preferably a hydrogen atom, a methyl group, or a phenyl group, and most preferably a hydrogen atom or a methyl group. preferable. In one embodiment, R ₁ and R ₂ are both methyl groups.

R ₃ and R ₄ are an alkyl group or an aryl group which may have a substituent, and specific examples of the alkyl group or the aryl group are the same as those of R ₁ and R ₂ .
X is independently an alkylene group which may have a substituent, preferably an alkylene group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. It is. Specifically, a methylene group, an ethylene group, a propylene group, or a butylene group is preferable, a methylene group, an ethylene group, or a propylene group is more preferable, and an ethylene group is particularly preferable. The alkylene group may be linear or branched.

p and q are integers of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. In one embodiment, p and q are both 0.
m and n are integers of 1 or more and satisfy the relationship of 2 ≦ m + n ≦ 6. m and n are preferably both integers of 1 to 3, more preferably 1 or 2, and particularly preferably 1.

The structural unit derived from the diol represented by the formula (1) is preferably derived from a compound represented by the following formula (2).

  The structural unit derived from the diol represented by the formula (1) is preferably contained in an amount of 30 to 100 mol%, more preferably 40 to 100 mol%, based on all the structural units constituting the polyester resin. 50-100 mol% is further more preferable, 60-100 mol% is still more preferable, and 70-100 mol% is especially preferable. The polyester resin may contain one or more structural units derived from the diol represented by the formula (1).

  The polyester resin may contain a structural unit derived from a diol other than the structural unit represented by the formula (1). Such a structural unit is not particularly limited, but alkylene glycol (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol (1,4-butanediol), hexanediol, neo Those derived from linear or branched C2-12 alkylene glycols such as pentyl glycol, octanediol and decanediol) and (poly) oxyalkylene glycols (eg, diethylene glycol, triethylene glycol, dipropylene glycol) Illustrated. Among these, a structural unit derived from ethylene glycol is particularly preferable. The structural unit derived from the diol other than the structural unit represented by the formula (1) is preferably 0 to 80 mol%, more preferably 0 to 50 mol%, more preferably based on all structural units constituting the polyester resin. It is preferably contained in an amount of 0 to 40 mol%, particularly preferably 0 to 30 mol%. The polyester resin may contain one or more structural units derived from a diol other than the structural unit represented by the general formula (1).

  The structural unit derived from dicarboxylic acid contained in the polyester resin is not particularly limited, but is aromatic such as naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, biphenyldicarboxylic acid, tetralindicarboxylic acid, etc. Dicarboxylic acid; oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decalindicarboxylic acid Acid, norbornane dicarboxylic acid, tricyclodecane dicarboxylic acid, pentacyclododecane dicarboxylic acid, 3,9-bis (1,1-dimethyl-2-carboxyethyl) -2,4,8,10-tetraoxaspiro [5. 5] Undecane, - carboxy-5-ethyl-2- (1,1-dimethyl-2-carboxyethyl) -1,3-dioxane, aliphatic dicarboxylic acids such as dimer acid; structural units derived from and derivatives preferred. Examples of these dicarboxylic acid derivatives include esters, acid anhydrides, and acid halides. Specifically, dimethyl esters of the above-mentioned dicarboxylic acids are preferable, and dimethyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, and dimethyl adipate are particularly preferable. The dicarboxylic acid structural unit constituting the polyester resin may be composed of one type of the exemplified structural units, or may be composed of two or more types.

The content ratio of the polyester resin with respect to the resin composition of the present invention is preferably 0.5 to 98% by mass, more preferably 10 to 49% by mass, and particularly preferably 20 to 40% by mass. . From the viewpoint of taking advantage of the preferable properties of the polycarbonate resin as described above, it is preferable that the content ratio of the polycarbonate resin is higher than that of the polyester resin. Therefore, the content ratio of the polyester resin is less than 50% by mass with respect to the resin composition. It is preferable.
The weight average molecular weight of the polyester resin is preferably 10,000 to 200,000, more preferably 20,000 to 150,000, and particularly preferably 40,000 to 100,000.

  The polyester resin can be produced by a conventionally known method by reacting a compound that generates a structural unit derived from a diol with a compound that generates a structural unit derived from a dicarboxylic acid. Examples of the reaction method include various methods such as a melt polymerization method such as a transesterification method and a direct polymerization method, a solution polymerization method, and an interfacial polymerization method.

(2) Polycarbonate resin The polycarbonate resin contained in the resin composition of the present invention is a — [O—R—OCO] unit containing a carbonate bond in the molecular main chain (wherein R is an aliphatic group, aromatic It is not particularly limited as long as it includes an aliphatic group or a group containing both an aliphatic group and an aromatic group, and may be linear or branched. A polycarbonate resin containing an aromatic group is preferred, and a polycarbonate having a bisphenol A skeleton is more preferred.

  The polycarbonate resin can be produced by a conventionally known method. For example, the raw material is melt polycondensed in the presence of a basic compound catalyst or a transesterification catalyst or a mixed catalyst composed of both, or in the absence of a catalyst. Can be manufactured.

The weight average molecular weight of the polycarbonate resin is preferably 20,000 to 60,000, and more preferably 23,000 to 55,000. More preferably, it is 25,000-50,000.
Moreover, as a glass transition temperature of polycarbonate resin, 120-160 (degreeC) is preferable and 130-155 (degreeC) is more preferable.
A polycarbonate resin having a weight average molecular weight and / or a glass transition temperature within the above range is preferred from the viewpoints of heat resistance and impact resistance.

  Moreover, it is preferable that the content rate of polycarbonate resin with respect to the resin composition of this invention is 2-99.5 mass%, It is more preferable that it is 51-90 mass%, It is that it is 60-80 mass%. Particularly preferred. From the viewpoint of taking advantage of the preferable properties of the polycarbonate resin as described above, it is preferable that the content ratio of the polycarbonate resin is higher than that of the polyester resin. Therefore, the content ratio of the polycarbonate resin is 50% by mass or more based on the resin composition. It is preferable.

(3) Laser light energy absorber The resin composition of the present invention may contain a laser light energy absorber. A resin composition containing a laser light energy absorber is suitably used as a material for a laser marking sheet (laser marking layer) that enables printing by a marking process, for example, in a card that particularly requires tampering prevention. As the laser light energy absorber, carbon black, antimony-doped tin oxide, metal oxide-based material, or the like is used, and preferably carbon black is used.
As the metal oxide laser energy absorber, a bismuth oxide material is preferable, and a bismuth oxide material containing neodymium or gadolinium in addition to bismuth as a metal component is more preferable.

More specifically, the metal oxide laser light energy absorber is preferably represented by the following formula (I).
Bi (1-x) MxOy (I)
(In formula (I), M is at least one metal selected from gadolinium and neodymium. X is a value satisfying the relationship of 0.001 <x <0.5, preferably 0.01 < x is a value that satisfies the relationship of x <0.3, and y is a value that satisfies the relationship of 1 <y <2.5, and preferably a value that satisfies the relationship of 1.5 <y <2.1. )

  The content of the laser light energy absorber is preferably 0.0001 to 0.2% by mass, more preferably 0.0005 to 0.15% by mass, and still more preferably based on the mass of the entire resin composition. 0.001 to 0.1% by mass. For example, when carbon black is used as the laser light energy absorber, the carbon black content is preferably 1 to 100 mass ppm (0.0001 to 0.01 mass%) based on the mass of the entire resin composition. ), More preferably less than 40 ppm by mass, for example, 5 to 35 ppm by mass. Moreover, when using the above-mentioned metal oxide type laser beam energy absorber, the content of the laser beam energy absorber is, for example, 50 to 5000 ppm by mass (0.005 based on the mass of the entire resin composition). -0.5 mass%), preferably 80-3000 mass ppm, more preferably 100-2000 mass ppm.

  In addition to making it difficult to transmit the 1064 nm light that is the wavelength of the laser, laser marking energy is improved by using a laser light energy absorber that has a property that it is difficult to pass light with a wavelength around 500 nm specifically. be able to. Such a laser light energy absorber having a light blocking property can provide a resin molded body capable of clear printing even if the amount contained in the resin composition is small. Examples of the laser light energy absorber that realizes such a preferable effect include carbon black and bismuth oxide.

(4) Other additives The resin composition of the present invention may contain the following additives in addition to the components described above. That is, it is at least one additive selected from the group consisting of a heat stabilizer, an antioxidant, a catalyst deactivator, a flame retardant, a flame retardant aid, an ultraviolet absorber, a release agent, and a colorant. 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. Among these, it is preferable to add at least an antioxidant and / or a catalyst deactivator. Antioxidants include phenolic antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants, but it is preferable to use phosphorus-based antioxidants. When adding antioxidant, 1 type may be added and 2 or more types of antioxidants may be added in combination. When the antioxidant is added, the amount thereof is preferably 0.01 to 0.5% by mass, more preferably 0.02 to 0.1% by mass with respect to the resin composition. It is especially preferable that it is 0.025-0.075 mass%.

  Examples of the catalyst deactivator include a phenol-based catalyst deactivator, a sulfur-based catalyst deactivator, and a phosphorus-based catalyst deactivator. It is preferable to use a phosphorus-based catalyst deactivator. When adding a catalyst deactivator, one type may be added and two or more types of catalyst deactivators may be added in combination. When adding a catalyst deactivator, the amount is preferably 0.01 to 0.5% by weight, more preferably 0.02 to 0.1% by weight, based on the resin composition, It is especially preferable that it is 0.025-0.075 mass%.

(5) Resin composition and molded article The resin composition of the present invention preferably has a glass transition temperature of 100 to 135 ° C, more preferably 100 to 130 ° C, and particularly preferably less than 120 ° C (eg, 100 ° C). And less than 120 ° C.). Since the glass transition temperature of polycarbonate resin is generally about 150 ° C., it can be said that the resin composition of the present invention has a glass transition temperature lower than that, and is therefore excellent in moldability.
The resin composition of the present invention is also excellent in transparency, and the haze value measured for a resin molded product having a thickness of 1.0 nm is preferably less than 16%, more preferably 8% or less, and particularly preferably less than 3%. is there.
Furthermore, the resin composition of the present invention is also excellent in laser marking properties, and preferably has a blackness of 1.50 or more (for example, 1.50 to 2.0), more preferably a blackness of 1.60 or more (for example, 1.60-2.0), laser marking can be applied.

  The resin composition of the present invention is suitably used as a material for a card resin sheet. Therefore, according to one Embodiment of this invention, the resin sheet for cards shape | molded using the resin composition of this invention is provided. That is, by using the resin composition of the present invention, a resin sheet for cards, for example, a sheet in which an antenna chip is embedded, a laser marking sheet, and the like can be produced.

The resin composition of the present invention can be produced by mixing (for example, melt mixing) the above-described materials. As a method of processing the obtained resin composition into a sheet shape, a conventionally known method can be adopted, and examples thereof include methods by extrusion molding, cast molding, and the like.
As an example of extrusion molding, pellets, flakes or powders of the resin composition of the present invention are melted and kneaded with an extruder, extruded from a T-die, etc., cooled while sandwiching the resulting semi-molten sheet with a roll, A method of forming a sheet by solidifying is mentioned.

  By combining the resin sheet for cards of the present invention with a sheet made of another material to form a multilayer sheet, a card suitable for the application can be produced. For example, a security card, an ID card, etc. are mentioned. Examples of other resin sheet materials used in combination with the resin sheet of the present invention include PET-G, polycarbonate, PCT-G, PCT, and a mixture (alloy) of at least two of these.

  The PET-G sheet is a polyethylene terephthalate-based PET-G resin (PETG resin), that is, a dicarboxylic acid unit mainly composed of terephthalic acid units, an ethylene glycol unit, and a cyclohexanedimethanol unit (1,4-cyclohexanedimethanol unit). ) Is a sheet formed of polyester containing glycol units mainly. The terephthalic acid unit accounts for 50% or more of all dicarboxylic acid units on a molar basis, for example, and ethylene glycol is 50% of all glycol units (total of ethylene glycol units and cyclohexanedimethanol units) on a molar basis. It is preferable to occupy the above.

  The PCT-G resin is also a polyester containing a dicarboxylic acid unit mainly containing a terephthalic acid unit, an ethylene glycol unit, and a glycol unit mainly containing a cyclohexanedimethanol unit (1,4-cyclohexanedimethanol unit). The dimethanol unit differs from the PET-G resin in that it occupies 50% or more of all glycol units (total of ethylene glycol unit and cyclohexane dimethanol unit) on a molar basis.

  PCT resin (polycyclohexylene / dimethylene / terephthalate resin) contains a dicarboxylic acid unit mainly composed of terephthalic acid units and a glycol unit mainly composed of cyclohexanedimethanol units (1,4-cyclohexanedimethanol units). It is a polyester and does not contain ethylene glycol units.

Sheets formed using the above-mentioned polyethylene terephthalate resin, that is, PET-G sheets, PCT-G sheets, and PCT sheets are excellent in adhesiveness (compatibility) with the resin sheet of the present invention. It is preferable for forming a multilayer sheet.
Moreover, you may combine polycarbonate / polyester resin sheets other than the resin sheet of this invention. In this case, as the polycarbonate resin, those similar to the polycarbonate resin contained in the resin composition of the present invention can be used. As the polyester resin, aliphatic polyester resin, polyethylene terephthalate-based PETG resin, PCTG resin, and PCT resin or the like can be used.

A specific example of the multilayer sheet is the ID card 10 shown in FIG. The ID card 10 is a laminate including a first surface layer 12, a second surface layer 14, a first laser marking layer 16, a second laser marking layer 18, a first core layer 20, and a second core layer 22.
The first surface layer 12 and the second surface layer 14 are colorless and transparent, and the first laser marking layer 16 and the second laser marking layer 18 can be printed by irradiating the laser beam L. The first core layer 20 and the second core layer 22 are white because they contain a white pigment, and the antenna chip 24 is embedded in the first core layer 20. Information of an IC chip (not shown) is overwritten in accordance with an external electromagnetic wave received by the antenna chip 24.
In any of these layers, it is possible to use the resin composition of the present invention, but it is preferable to use it in any of the laser marking layers since it has the property of being excellent in laser marking properties.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not limited by this.
<Production Examples 1 to 7 and Comparative Production Examples 1 to 3: Production of polyester resin>
The amount of monomers listed in Table 1 was added to a 6 liter (L) polyester production apparatus equipped with a packed column rectification column, a partial condenser, a full condenser, a cold trap, a stirring blade, a heating device, and a nitrogen introduction pipe. Was charged. Manganese acetate tetrahydrate and germanium dioxide were added to 0.03 mol% and 0.05 mol% of the dicarboxylic acid component, respectively, and the temperature was raised to 225 ° C. under normal pressure and nitrogen atmosphere to carry out the transesterification reaction. It was. After the reaction conversion rate of the dicarboxylic acid component was 90 mol% or more, 0.1 mol% of trimethyl phosphate was added to the dicarboxylic acid component. Then, the polycondensation reaction was finally performed at 270 to 300 ° C. and 0.3 kPa or less while gradually raising the temperature and reducing the pressure, and withdrawing ethylene glycol from the system. When the viscosity of the reaction product gradually increased and reached an appropriate melt viscosity, the reaction was terminated to obtain polyester resins (Production Examples 1 to 7 and Comparative Production Examples 1 to 3).

The polyester resin of Preparation 1-7 produced above, to determine the amount of diol constituent units and dicarboxylic acid constitutional units in the polyester resin at ^{1 H-NMR.} The measurement was performed at 400 MHz using NM-AL400 manufactured by JEOL Ltd. Deuterated chloroform was used as the solvent. The results are shown in Table 2.

<Examples 1-7, Comparative Examples 1-3: Production of Resin Sheet>
As described below, a resin composition was produced using the polyester resin produced above, and was molded to produce a resin sheet. As the polycarbonate resin, a polycarbonate resin (trade name: Iupilon E-2000N) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used.

(1) Production of master batch containing laser light energy absorber Polycarbonate resin (Iupilon E-2000N) 99.87% by mass, carbon black (MONARCH 800, manufactured by Cabot Corporation) 0.1% by mass, and phosphorus-based oxidation 0.03% by mass of an inhibitor (AS2112, manufactured by ADEKA) was mixed with a tumbler. The obtained resin mixture was melt-mixed using a twin screw extruder (screw diameter = 30 mm, L / D = 31.5) under the conditions of a cylinder temperature of 260 to 290 ° C. and a screw rotation speed of 200 rpm, and a master batch. Manufactured.

(2) Manufacture of resin composition Master batch containing polycarbonate resin, polyester resin, laser light energy absorber manufactured in the above (1), antioxidant (AS2112, ADEKA) And a catalyst deactivator (AX-71, manufactured by ADEKA) were mixed with a tumbler. The obtained resin mixture was melt-mixed using a twin screw extruder (screw diameter = 30 mm, L / D = 31.5) under the conditions of a cylinder temperature of 230 to 260 ° C., a die temperature of 260 ° C., and a screw rotation speed of 200 rpm. did.

(3) Production of resin sheet Using the twin-screw extruder (screw diameter = 32 mm, L / D = 31.5), the resin composition obtained in (2) above has a cylinder temperature of 230 to Extrusion was performed under the conditions of 260 ° C., T-die temperature of 260 to 270 ° C., screw rotation speed of 100 rpm, and a 0.1 mm thick resin sheet was produced.

About the resin sheet shape | molded using the resin composition of this invention, it evaluated in accordance with the following evaluation methods. The results are shown in Table 3.
<Evaluation of workability>
Glass transition temperature (Tg) was measured using DSC-60 (DSC) manufactured by Shimadzu Corporation, a differential thermal scanning calorimeter. In the measurement, the temperature was raised at 15 ° C./min to a temperature at which the resin component melts in a nitrogen atmosphere (265 ° C.), then cooled to 30 ° C. at 20 ° C./min, and then raised again at 15 ° C./min (2nd run). Based on the obtained DSC curve, the glass transition temperature was calculated by the starting point method.
Based on the calculated glass transition temperature, workability was evaluated as follows.
Tg less than 120 ° C: ○
Tg 120 ° C or higher: ×

<Evaluation of transparency>
A film having a thickness of 1.0 mm was formed using the resin composition obtained above, and the haze value was measured using a haze value measuring apparatus (model: COH-400) manufactured by Nippon Denshoku Industries Co., Ltd. The haze value was measured according to JIS K7105.
Based on the measured haze value, the transparency was evaluated as follows.
Haze value less than 3%: ○
Haze value 3% or more and less than 16%: △
Haze value 16% or more: ×

<Evaluation of laser marking properties>
A laser marking film having a thickness of 0.1 mm was molded using the resin composition obtained above. Moreover, 0.1 mm overlay film was shape | molded using polycarbonate resin (Iupilon (trademark) E-2000N, Mitsubishi Engineering-Plastics Co., Ltd. product). Furthermore, titanium oxide (white DCF-T-17007, manufactured by Resino Color Industry Co., Ltd.) is added to the resin composition used for molding the overlay film in an amount of 15% by mass with respect to the total mass of the resin composition and titanium oxide. Using the prepared composition, a white core film having a thickness of 0.2 mm was formed.

  The prepared film was stacked in the order of an overlay film, a laser marking film, and a white core film. The upper and lower sides of the obtained laminated film were respectively sandwiched by laminated plates of 4 layers of 0.5 mm SUS plate, 1 mm silicon rubber sheet, 100 μm SUS plate, and 0.78 mm Teflon (registered trademark) sheet. . That is, the laminated plate 2 so that the Teflon (registered trademark) sheet of one laminated plate is in contact with the overlay film side of the laminated film and the Teflon (registered trademark) sheet of the other laminated plate is in contact with the white core film side of the laminated film. The laminated film was sandwiched between sheets. This was sandwiched by a press machine, and a laminate was prepared by pressing for 90 seconds at 180 ° C. and an air pressure of 0.2 MPa using a pneumatic heating press (IMC-1839 type: manufactured by Imoto Seisakusho).

Laser marking was carried out on the laminate obtained above from the overlay film layer side using the laser marking device (EasyMark IV-E10, manufactured by Roffin Basel) under the following irradiation conditions. The printed part was measured using a spectral densitometer (X-Rite 504, manufactured by X-Rite Co., Ltd.), and the maximum value obtained was defined as blackness.
(Laser marking conditions)
・ Scan Speed: 1,000mm / s
・ Output Energy: 21-30A
・ Pulse Frequency: 10-100kHz
Based on the obtained blackness value, the laser marking property was evaluated as follows.
Blackness of 1.60 or more: ◎
Blackness 1.50 or more and less than 1.60: ○
Blackness: Less than 1.50: ×

The evaluation results are shown in Table 3.

From Table 3, it can be said that the resin composition according to the example is excellent in molding processability because the glass transition temperature is lower than 120 ° C., which is lower than that of a general polycarbonate resin. Moreover, since haze value is less than 3%, it is excellent also in transparency. Furthermore, when the card | curd is manufactured using the resin composition of this invention for a laser marking layer, the outstanding laser marking property is obtained and it can print with sufficient contrast.
As represented by Example 6, when using a polyester resin containing a large amount of structural units derived from the diol represented by the formula (1), the proportion of the polycarbonate resin in the resin composition is made higher and highly evaluated. The resin composition can be obtained. A high proportion of the polycarbonate resin in the resin composition is preferable in that the polycarbonate resin originally has excellent properties such as impact resistance, dimensional stability, and transparency.

  Although several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

  DESCRIPTION OF SYMBOLS 10 ... ID card (multilayer sheet), 12 ... 1st surface layer, 14 ... 2nd surface layer, 16 ... 1st laser marking layer, 18 ... 2nd laser marking layer, 20 ... 1st core layer, 22 ... 2nd core layer 24 ... Antenna chip.

Claims (11)

A resin composition comprising a polyester resin containing a structural unit derived from a diol represented by the following general formula (1) and a polycarbonate resin:
(Where
R ₁ and R ₂ are a hydrogen atom or an optionally substituted alkyl group or aryl group, and R ₁ and R ₂ may be bonded to form a ring;
R ₃ and R ₄ are an alkyl group or an aryl group which may have a substituent;
Each X is independently an alkylene group which may have a substituent;
p and q are integers from 0 to 4;
m and n are integers of 1 or more, and 2 ≦ m + n ≦ 6).   The said polyester resin is a resin composition of Claim 1 which contains the structural unit derived from the diol represented by the said General formula (1) in the ratio of 30-100 mol%.   The resin composition according to claim 1 or 2, wherein the resin composition contains the polyester resin in an amount of 0.5 to 98% by mass and the polycarbonate resin in an amount of 2 to 99.5% by mass.   The resin composition according to any one of claims 1 to 3, wherein both m and n are 1.   X is a resin composition as described in any one of Claims 1-4 selected from the group which consists of a methylene group, an ethylene group, and a butylene group.   Furthermore, the resin composition as described in any one of Claims 1-5 containing a laser beam energy absorber.   The resin composition according to claim 6, wherein the laser light energy absorber is carbon black.   The resin composition as described in any one of Claims 1-7 whose glass transition temperature is 100-135 degreeC.   The resin composition as described in any one of Claims 1-8 whose haze value measured about the molded article of thickness 1.0mm is less than 16%.   The resin sheet for cards shape | molded using the resin composition as described in any one of Claims 1-9.   A security card or an ID card molded using the resin sheet for cards according to claim 10.