JP7700515B2 - Resin composition for cards or passports, film for cards or passports, cards, and passports - Google Patents

Description

The present invention relates to a resin composition for cards or passports, a film for cards or passports, a card, and a passport.

Cards such as credit cards, cash cards, ID cards, tag cards, and insurance cards are generally manufactured by stacking multiple resin sheets, heat fusing them, and then punching them out. Passports are also generally manufactured by stacking multiple resin sheets in a similar manner. Resin sheets used in cards or passports often use thermoplastic resin compositions containing polyester, aromatic polycarbonate, and the like as the resin component.

For example, Patent Document 1 discloses a thermoplastic resin composition for cards, which is a mixture of one or more thermoplastic resins selected from polyesters and aromatic polycarbonates and an inorganic plate-like filler. In Patent Document 1, the polyesters used include those in which the glycol units are ethylene glycol units (I) and 1,4-cyclohexanedimethanol units (II) in a molar ratio (I)/(II) of 70/30, and those in which the ethylene glycol units (I) and 1,4-cyclohexanedimethanol units (II) in a molar ratio (I)/(II) of 35/65.
Patent Document 1 also discloses a resin composition using these polyesters in combination with an aromatic polycarbonate.

Japanese Patent Application Publication No. 11-001607

When manufacturing cards or passports by heat-sealing multiple resin sheets, low-temperature fusion properties that enable heat fusion at low temperatures may be required. In addition, the resin sheet requires solvent resistance because adhesives may be required if it has poor heat fusion properties with other sheets, and it may have an image-receiving layer used when printing face photographs, etc., or it may come into contact with ink when designs or security printing is performed.

However, when aromatic polycarbonate is used as a resin component, it is difficult to achieve good low-temperature fusion properties and solvent resistance. On the other hand, the polyester used in Patent Document 1 has good low-temperature fusion properties, but insufficient heat resistance, and a sheet formed from that polyester has a large thermal expansion rate. Therefore, when a sheet formed from polyester is laminated with a highly heat-resistant sheet, such as an aromatic polycarbonate sheet, to produce a card or passport, problems such as large dimensional changes, poor workability, and warping of the finished card or passport may occur. Furthermore, the solvent resistance may be insufficient.

In addition, in Patent Document 1, the resin composition using polyester and polycarbonate in combination has improved heat resistance compared to the resin composition using polyester alone, but this is not sufficient, and the solvent resistance is also insufficient.

The present invention aims to provide a resin composition for cards or passports that has excellent low-temperature fusion properties and solvent resistance, excellent heat resistance, and small dimensional changes during the production of the cards or passports.

As a result of extensive investigations, the present inventors have found that the above problems can be solved by using a specific polyester resin (A-1) in combination with a polycarbonate resin (B), and have completed the present invention as described below. That is, the present invention provides the following [1] to [12].
[1] A resin composition containing a resin component including a polyester resin (A-1) and a polycarbonate resin (B),
The polyester resin (A-1) contains a structural unit derived from a chain dihydroxy compound,
The polyester resin (A-1) has a glass transition temperature of 90° C. or higher.
[2] The resin composition for cards or passports according to the above [1], which has a storage modulus at 100° C. of 1×10 ⁹ Pa or more.
[3] The resin composition for cards or passports according to the above [1] or [2], wherein the polyester resin (A-1) contains a structural unit derived from an alicyclic dihydroxy compound.
[4] The resin composition for cards or passports according to the above [3], wherein the polyester resin (A-1) contains a structural unit derived from a chain dihydroxy compound and a structural unit derived from an alicyclic dihydroxy compound, and the proportion of the structural unit derived from the alicyclic dihydroxy compound is more than 65 mol % in a total of 100 mol % of the structural units derived from the chain dihydroxy compound and the structural units derived from the alicyclic dihydroxy compound.
[5] The resin composition for cards or passports according to any one of the above [1] to [4], wherein the polyester resin (A-1) contains a structural unit derived from ethylene glycol and a structural unit derived from cyclohexanedimethanol.
[6] The resin composition for cards or passports according to any one of the above [1] to [5], wherein the polyester resin (A-1) contains a structural unit derived from ethylene glycol, a structural unit derived from cyclohexanedimethanol, and a structural unit derived from tetramethylcyclobutanediol.
[7] The resin composition for cards or passports according to any one of the above [1] to [6], wherein the content ratio ((A-1)/(B)) of the polyester resin (A-1) to the polycarbonate resin (B) is 3/97 or more and 97/3 or less in mass ratio.
[8] The resin composition for cards or passports according to any one of [1] to [7] above, which contains recycled raw materials.
[9] A card or passport film comprising the resin composition according to any one of [1] to [8] above.
[10] A card comprising the film described in [9] above.
[11] A passport comprising the film described in [10] above.
[12] A method for producing a resin composition according to any one of [1] to [8] above, comprising blending recycled raw materials into the resin composition.

The present invention provides a resin composition for cards or passports that has excellent low-temperature fusion properties and solvent resistance, as well as excellent heat resistance and small dimensional changes during the production of the cards or passports.

FIG. 2 is a schematic diagram showing a layer structure of a card. FIG. 2 is a schematic diagram showing a layer structure of a passport.

The present invention will be described in detail below with reference to the embodiments. However, the present invention is not limited to the embodiments described below. In addition, the terms "film" and "sheet" used in the following description are not clearly distinguished from each other, and the term "film" includes "sheet," and the term "sheet" includes "film."

<Resin composition for cards or passports>
The resin composition of the present invention is a resin composition for cards or passports, and contains a resin component including a polyester resin (A-1) and a polycarbonate resin (B).

[Polyester resin (A-1)]
The polyester resin (A-1) contains a structural unit derived from a chain dihydroxy compound and has a glass transition temperature of 90° C. or higher. The polyester resin (A-1) has excellent heat resistance when used in combination with a polycarbonate resin (B) described later, and the dimensional change when a film formed from the resin composition is heated is small. Therefore, the workability when producing a card or passport is improved, and further, the produced card or passport is less likely to warp. In addition, the polyester resin (A-1) contains a structural unit derived from a chain dihydroxy compound, which makes the low-temperature fusion property of the resin composition easy to be good. Furthermore, the resin composition contains the polyester resin (A-1), which makes the solvent resistance good. In addition, when the resin composition contains a colorant described later, the laser printability is also easy to be good.

The polyester resin (A-1) is a polyester obtained by polycondensation of a dicarboxylic acid and a dihydroxy compound. As the dicarboxylic acid, a dicarboxylic acid derivative such as an ester or an acid halide of the dicarboxylic acid may be used for the synthesis of the polyester resin (A-1).
From the viewpoint of heat resistance, it is preferable to use an aromatic dicarboxylic acid as the dicarboxylic acid used to obtain the polyester resin (A-1), and therefore, it is preferable that the polyester resin (A-1) contains a structural unit derived from an aromatic dicarboxylic acid.
The aromatic dicarboxylic acid is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, anthracene dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, 3-sodium sulfoisophthalate, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, and 2-methylterephthalic acid. Of these, terephthalic acid and isophthalic acid are preferred, and terephthalic acid is more preferred from the viewpoint of transparency.
The aromatic dicarboxylic acids may be used alone or in combination of two or more kinds.

The polyester resin (A-1) may also contain a small amount (usually 40 mol % or less, for example 30 mol % or less, preferably 20 mol % or less) of structural units derived from an aliphatic dicarboxylic acid. There are no particular limitations on the aliphatic dicarboxylic acid, and examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3 or 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and 4,4'-dicyclohexyldicarboxylic acid. The aliphatic dicarboxylic acids may be used alone or in combination of two or more.

The aromatic dicarboxylic acid-derived structural units are preferably contained in the dicarboxylic acid-derived structural units in the polyester resin (A-1) in an amount of 80 mol % or more, and more preferably 90 mol % or more. There is no particular upper limit, and it is sufficient if it is 100 mol % or less, but it is most preferably 100 mol %.

The chain dihydroxy compound used in the polyester resin (A-1) may be linear or may have a branched structure. Specific examples of the chain dihydroxy compound include chain dihydroxy compounds having about 2 to 18 carbon atoms, such as ethylene glycol (EG), diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, triethylene glycol, 1,2-hexadecanediol, and 1,18-octadecanediol, and polyglycols, such as polytetramethylene ether glycol, polypropylene glycol, and polyethylene glycol. Among these, a chain dihydroxy compound having 2 to 12 carbon atoms is preferred, and one or more selected from ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferred, with ethylene glycol (EG) being particularly preferred.
The chain dihydroxy compound may be used alone or in combination of two or more kinds.

The polyester resin (A-1) is preferably a copolymer polyester resin using two or more dihydroxy compounds as copolymerization components. Specifically, it is preferable to use an alicyclic dihydroxy compound in addition to a chain dihydroxy compound as the dihydroxy compound used to obtain the polyester resin (A-1). Therefore, it is preferable that the polyester resin (A-1) has a structural unit derived from an alicyclic dihydroxy compound in addition to a structural unit derived from a chain dihydroxy compound. By using an alicyclic dihydroxy compound, the heat resistance, solvent resistance, laser printability, etc. tend to be good.
Specific examples of alicyclic dihydroxy compounds include tetramethylcyclobutanediol, cyclohexanedimethanol (CHDM), tricyclodecane dimethanol, adamantanediol, and pentacyclopentadecanedimethanol. Of these, tetramethylcyclobutanediol and cyclohexanedimethanol are preferred. Examples of cyclohexanedimethanol include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol, with 1,4-cyclohexanedimethanol being preferred from the viewpoint of industrial availability. In addition, 2,2,4,4-tetramethyl-1,3-cyclobutanediol is generally used as tetramethylcyclobutanediol.
The alicyclic dihydroxy compound may be used alone or in combination of two or more. As the alicyclic dihydroxy compound, it is preferable to use at least cyclohexanedimethanol, and it is more preferable to use tetramethylcyclobutanediol and cyclohexanedimethanol in combination.

In the polyester resin (A-1), the ratio of the structural units derived from the alicyclic dihydroxy compound is preferably more than 65 mol% out of the total 100 mol% of the structural units derived from the chain dihydroxy compound and the structural units derived from the alicyclic dihydroxy compound. When the ratio of the structural units derived from the alicyclic dihydroxy compound exceeds 65 mol%, the heat resistance is excellent and the storage modulus of the resin composition in a high temperature environment is high. Therefore, the value of the thermal expansion and contraction rate of the film formed from the resin composition of the present invention is likely to be low.
The above proportion of structural units derived from an alicyclic dihydroxy compound is more preferably 70 mol % or more, even more preferably 80 mol % or more, and even more preferably 90 mol % or more.
In addition, from the viewpoint of improving low-temperature fusion properties by incorporating a certain amount or more of a chain dihydroxy compound, the above-mentioned proportion of structural units derived from an alicyclic dihydroxy compound is preferably 99 mol % or less, more preferably 98 mol % or less, and even more preferably 95 mol % or less.

As the dihydroxy compound used in the polyester resin (A-1), a dihydroxy compound other than a chain dihydroxy compound and an alicyclic dihydroxy compound (also referred to as "other dihydroxy compound") may be used within a range that does not impair the effects of the present invention. In the polyester resin (A-1), the content of the structural unit derived from the other dihydroxy compound is, for example, 20 mol % or less, preferably 10 mol % or less, more preferably 5 mol % or less, and most preferably 0 mol % in 100 mol of the structural units derived from the dihydroxy compound in the polyester resin (A-1).
Other dihydroxy compounds include p-xylylenediol, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), tetrabromobisphenol A, tetrabromobisphenol A-bis(2-hydroxyethyl ether), α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (bisphenol M), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (bisphenol AF), and 1,1-bis(4-hydroxyphenyl)decane.

From the viewpoints of low-temperature fusion property, heat resistance, solvent resistance, and the like, among the above, polyester resin (A-1) preferably contains structural units derived from ethylene glycol and structural units derived from cyclohexanedimethanol, and particularly preferably contains structural units derived from ethylene glycol, structural units derived from cyclohexanedimethanol, and structural units derived from tetramethylcyclobutanediol.

In the polyester resin (A-1), the content of the structural units derived from ethylene glycol is preferably 1 mol % or more, more preferably 2 mol % or more, and even more preferably 5 mol % or more, and is preferably 30 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less, based on 100 mol % of the structural units derived from the dihydroxy compound.
In addition, the content of the structural units derived from cyclohexanedimethanol is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more, and is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, based on 100 mol% of the structural units derived from the dihydroxy compound.
Furthermore, the content of the structural unit derived from tetramethylcyclobutanediol is preferably less than the content of the structural unit derived from cyclohexanedimethanol. The content of the structural unit derived from tetramethylcyclobutanediol is preferably 4 mol% or more, more preferably 8 mol% or more, even more preferably 13 mol% or more, particularly preferably 15 mol% or more, and is preferably 49 mol% or less, more preferably 38 mol% or less, even more preferably 30 mol% or less, particularly preferably 25 mol% or less, based on 100 mol% of the structural unit derived from the dihydroxy compound.

(Glass Transition Temperature)
The glass transition temperature (Tg) of the polyester resin (A-1) is 90° C. or higher, as described above. If the glass transition temperature is less than 90° C., the heat resistance will be insufficient even when the polycarbonate resin (B) is used in combination, the thermal expansion rate will be high, the dimensional stability will be reduced, and the dimensional change during the preparation of a card or passport will be large. As a result, the workability during the preparation of a card or passport will be reduced, and the card or passport will be warped. Furthermore, even if the resin composition contains a colorant, it will be difficult to improve the laser printability.
From the viewpoint of improving heat resistance and improving dimensional stability, laser printability, and the like, the glass transition temperature (Tg) of the polyester resin (A-1) is preferably 93° C. or higher, more preferably 95° C. or higher, even more preferably 98° C. or higher, and even more preferably 100° C. or higher. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the polyester resin (A-1) is better to be higher, but from the viewpoint of low-temperature fusion property, the lower the glass transition temperature (Tg), and it is preferably 130° C. or lower, more preferably 120° C. or lower, and even more preferably 115° C. or lower.
The glass transition temperature can be obtained for each resin by measuring the temperature dispersion of dynamic viscoelasticity in a tensile mode at a strain of 0.07%, a frequency of 1 Hz, a heating rate of 3°C/min, and a viscoelasticity spectrometer in accordance with JIS K7244-4:1999, and determining the temperature at the peak top of the loss modulus.

The polyester resin (A-1) is preferably an amorphous polyester, since the use of an amorphous polyester tends to improve adhesion to other members such as resin films.
The amorphous polyester may be any polyester that is substantially amorphous. As the substantially amorphous polyester (including low crystallinity), polyesters that do not show a clear crystal fusion peak when heated by differential scanning calorimetry (DSC), polyesters that have crystallinity but have a slow crystallization rate and do not become highly crystalline when molded by extrusion film forming method, and polyesters that have crystallinity but have a low crystal fusion heat (ΔHm) of 10 J/g or less when heated by differential scanning calorimetry (DSC) can be used. That is, the amorphous polyester in the present invention also includes "crystalline polyester in a non-crystalline state".
The polyester resin (A-1) may be used alone or in combination of two or more kinds.

[Polycarbonate resin (B)]
The resin composition of the present invention contains, as a resin component, the above-mentioned polyester resin (A-1) and, in addition, a polycarbonate resin (B). By containing the polycarbonate resin (B), the resin composition of the present invention, coupled with the use of the above-mentioned specific polyester resin (A-1), has excellent heat resistance.
The polycarbonate resin (B) is not particularly limited, but it is preferable to use a bisphenol-based polycarbonate, which can easily provide various mechanical properties and heat resistance excellent.

Bisphenol-based polycarbonate refers to a polycarbonate in which 50 mol% or more, preferably 70 mol% or more, and more preferably 90 mol% or more of the structural units derived from dihydroxy compounds are structural units derived from bisphenol. Bisphenol-based polycarbonate may be either a homopolymer or a copolymer. Bisphenol-based polycarbonate may have a branched structure or a linear structure, or may be a mixture of a resin having a branched structure and a resin having only a linear structure.

Specific examples of bisphenols include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), bis(4-hydroxyphenyl)diphenylmethane (bisphenol BP), 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol C), 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E), bis(4-hydroxyphenyl)methane (bisphenol F), 2,2-bis( 4-hydroxy-3-isopropylphenyl)propane (bisphenol G), 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene (bisphenol M), bis(4-hydroxyphenyl)sulfone (bisphenol S), 1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene (bisphenol P), 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-ol]propane (bisphenol PH), 1,1-bis(4-hydroxyphenyl)3,3,5-trimethylcyclohexane (bisphenol TMC), and 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z). Bisphenols may be used alone or in combination of two or more.

As the bisphenol, 2,2-bis(4-hydroxyphenyl)propane, ie, bisphenol A, is preferably used, but a part of bisphenol A may be replaced with another bisphenol.
Of the structural units derived from the dihydroxy compound, the structural units derived from bisphenol A are preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 90 mol % or more, and most preferably 100 mol %. Therefore, as the polycarbonate resin (B), bisphenol A homopolycarbonate is most preferable.

The bisphenol-based polycarbonate used as the polycarbonate resin (B) may be produced by any known method such as the phosgene method, the ester exchange method, or the pyridine method.
For example, the transesterification method is a production method in which bisphenol and a carbonic acid diester are subjected to melt transesterification condensation polymerization in the presence of a basic catalyst and an acidic substance that neutralizes the basic catalyst.
Specific examples of the carbonate diester include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate, with diphenyl carbonate being particularly preferred.

From the viewpoints of mechanical properties and moldability, the melt flow rate (300°C, 1.2 kgf) of polycarbonate resin (B) is preferably 1 g/min or more, more preferably 2 g/min or more, even more preferably 3 g/min or more, and preferably 60 g/min or less, more preferably 50 g/min or less, even more preferably 40 g/min or less. The melt flow rate of polycarbonate resin (B) can be measured in accordance with ASTM D1238.

The mass average molecular weight of the polycarbonate resin (B) is usually 10,000 or more, preferably 30,000 or more, and usually 100,000 or less, preferably 80,000 or less, in consideration of the balance between mechanical properties and moldability. The mass average molecular weight can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.
The viscosity average molecular weight of the polycarbonate resin (B) is usually 12000 or more, preferably 15000 or more, more preferably 20000 or more, and even more preferably 22000 or more, in consideration of the balance between mechanical properties and moldability, and is usually 40000 or less, preferably 35000 or less, more preferably 30000 or less, and even more preferably 28000 or less. The viscosity average molecular weight can be measured by using dichloromethane as a solvent, determining the intrinsic viscosity ([η]) (unit: dl/g) at a temperature of 20° C. using an Ubbelohde viscometer, and calculating from Schnell's viscosity formula: η = 1.23 × 10 ^-4 M ^0.83 .

The glass transition temperature of the polycarbonate resin (B) is preferably higher than the glass transition temperature of the polyester resin (A-1), and is, for example, 110° C. or higher and 200° C. or lower. It is also preferably 125° C. or higher, more preferably 135° C. or higher, and even more preferably 140° C. or higher, and is also preferably 175° C. or lower, more preferably 170° C. or lower, and even more preferably 165° C. or lower.
By setting the glass transition temperature to the above lower limit or more, it becomes easy to impart appropriate heat resistance and to reduce dimensional changes during the production of cards or passports. In addition, by setting the glass transition temperature to the above upper limit or less, moldability and the like become good. The polycarbonate resin (B) usually has a single glass transition temperature.

The content ratio ((A-1)/(B)) of the polyester resin (A-1) and the polycarbonate resin (B) is preferably 3/97 or more and 97/3 or less in mass ratio. When the content ratio ((A-1)/(B)) is 3/97 or more, low-temperature fusion property and solvent resistance are easily improved. Furthermore, when the content ratio ((A-1)/(B)) is 97/3 or less, heat resistance is easily improved.
From these viewpoints, the content ratio ((A-1)/(B)) is more preferably 6/94 or more, even more preferably 10/90 or more, even more preferably 15/85 or more, even more preferably 30/70 or more, and even more preferably 40/60 or more. In addition, the content ratio ((A-1)/(B)) is more preferably 94/6 or less, even more preferably 90/10 or less, even more preferably 85/15 or less, even more preferably 80/20 or less, and even more preferably 75/25 or less.

[Polyester resin (A-2)]
The resin composition of the present invention may contain a polyester resin (A-2) other than the above-mentioned polyester resin (A-1) as a resin component. The polyester resin (A-2) is a polyester obtained by polycondensation of a dicarboxylic acid and a dihydroxy compound. As the dicarboxylic acid, a dicarboxylic acid derivative such as an ester or an acid halide of a dicarboxylic acid may be used for the synthesis of the polyester resin (A-2). By containing the polyester resin (A-2) in addition to the polyester resin (A-1), the resin composition tends to have various properties, for example, low-temperature fusion properties and printability tend to be improved. In addition, even if a relatively large amount of the polycarbonate resin (B) is contained, the low-temperature fusion properties are easily maintained.
In the following description, the polyester resin (A-1) and the polyester resin (A-2) may be collectively referred to as the polyester resin (A).

In the polyester resin (A-2), it is preferable to use an aromatic dicarboxylic acid as the dicarboxylic acid from the viewpoint of heat resistance, and therefore, it is preferable that the polyester resin (A-2) contains a structural unit derived from an aromatic dicarboxylic acid. Specific examples of the aromatic dicarboxylic acid are as described in the polyester resin (A-1), and the same applies to suitable compounds. The aromatic dicarboxylic acid may be used alone or in combination of two or more kinds.
In the polyester resin (A-2), the structural units derived from aromatic dicarboxylic acids are preferably contained in the structures derived from dicarboxylic acids in the polyester resin (A-1) in an amount of 80 mol % or more, more preferably 90 mol % or more, and preferably 100 mol % or less, and most preferably 100 mol %.
The polyester resin (A-2) may contain a small amount (usually in the range of 20 mol % or less) of a structural unit derived from an aliphatic dicarboxylic acid. Specific examples of the aliphatic dicarboxylic acid are as described in the polyester resin (A-2).

The polyester resin (A-2) is preferably a copolymer polyester resin using two or more dihydroxy compounds as copolymerization components. The polyester resin (A-2) may use at least one of a chain dihydroxy compound and an alicyclic dihydroxy compound as the dihydroxy compound, but it is preferable to use both of them. Therefore, the polyester resin (A-2) preferably contains a structural unit derived from a chain dihydroxy compound and a structural unit derived from an alicyclic dihydroxy compound.
Specific examples of the chain dihydroxy compound used in the polyester resin (A-2) are as described in the polyester resin (A-1), but are preferably one or more selected from ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.
Specific examples of the alicyclic dihydroxy compound used in the polyester resin (A-2) are as described for the polyester resin (A-1), but are preferably one or more selected from tetramethylcyclobutanediol and cyclohexanedimethanol, more preferably cyclohexanedimethanol. As for the cyclohexanedimethanol, 1,4-cyclohexanedimethanol is preferred, as described above.

In the polyester resin (A-2), the proportion of structural units derived from alicyclic dihydroxy compounds is preferably 65 mol % or less, more preferably 50 mol % or less, and more preferably 40 mol % or less, based on the total of 100 mol % of structural units derived from chain dihydroxy compounds and structural units derived from alicyclic dihydroxy compounds. When the proportion of structural units derived from alicyclic dihydroxy compounds is reduced as described above, the content of structural units derived from chain dihydroxy compounds in the polyester resin (A-2) increases, which makes it easier to improve the low-temperature fusion properties of the resin composition.
In addition, from the viewpoint of improving heat resistance by incorporating a certain amount or more of an alicyclic dihydroxy compound, the above-mentioned proportion of structural units derived from an alicyclic dihydroxy compound is preferably 5 mol % or more, more preferably 15 mol % or more, and even more preferably 20 mol % or more.

The glass transition temperature (Tg) of the polyester resin (A-2) is preferably less than 90° C., but is preferably 88° C. or less, more preferably 85° C. or less, and even more preferably 82° C. or less. From the viewpoint of improving the heat resistance and impact resistance of the resin composition, the glass transition temperature (Tg) of the polyester resin (A-2) is preferably 70° C. or more, more preferably 73° C. or more, and even more preferably 75° C. or more. The method for measuring the glass transition temperature (Tg) is as described above.
The polyester resin (A-2) is preferably an amorphous polyester, since the use of an amorphous polyester tends to improve adhesion to other members such as resin films.

(Content of Polyester Resins (A-1) and (A-2))
The content of polyester resin (A-1) in the resin composition is preferably 20 parts by mass or more relative to 100 parts by mass of the total amount of polyester resin (A-1) and polyester resin (A-2). By making the content of polyester resin (A-1) a certain amount or more, it is possible to maintain good heat resistance while improving low-temperature fusion properties, and dimensional changes are unlikely to occur during heat processing. Therefore, the workability when producing a card or passport is improved, and it is possible to prevent warping of the obtained card or passport. Furthermore, solvent resistance is also likely to be good. In addition, impact resistance is also likely to be good, and reliability in long-term use is also likely to be improved.
The content of polyester resin (A-1) in the resin composition is, relative to 100 parts by mass of the total amount of polyester resin (A-1) and polyester resin (A-2), more preferably 25 parts by mass or more, even more preferably 35 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 60 parts by mass or more, and even more preferably 70 parts by mass or more.
In addition, the resin composition of the present invention may not contain the polyester resin (A-2) as described above. Therefore, the content of the polyester resin (A-1) in the resin composition may be 100 parts by mass or less per 100 parts by mass of the total amount of the polyester resin (A-1) and the polyester resin (A-2).
However, in order to easily exert the effect of including the polyester resin (A-2) when the polyester resin (A-2) is contained in the resin composition, the content of the polyester resin (A-2) is preferably a certain amount or more. Therefore, the content of the polyester resin (A-1) is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 85 parts by mass or less, relative to 100 parts by mass of the total amount of the polyester resin (A-1) and the polyester resin (A-2).

(Content ratio of resins (A) and (B))
The content ratio (A/B) of the polycarbonate resin (B) to the total content of the polyester resin (A-1) and the polyester resin (A-2) (i.e., the content of the polyester resin (A)) is preferably 10/90 or more and 97/3 or less in mass ratio. When the content ratio ((A)/(B)) is 10/90 or more, a certain amount or more of the polyester resin (A) can be contained in the resin composition, which makes it easier to improve low-temperature fusion properties and solvent resistance. In addition, when the content ratio ((A)/(B)) is 97/3 or less, a certain amount or more of the polycarbonate resin (B) can be contained in the resin composition, which tends to improve heat resistance.
From these viewpoints, the content ratio ((A)/(B)) is more preferably 20/80 or more, even more preferably 30/70 or more, and even more preferably 35/65 or more. The content ratio ((A)/(B)) is more preferably 90/10 or less, even more preferably 85/15 or less, and even more preferably 80/20 or less.

[Coloring agent]
The resin composition of the present invention may further contain a colorant. By containing a colorant, the resin composition of the present invention can be printed by laser irradiation, and the printability is also improved. In addition, in laser printing, the resin composition containing the colorant absorbs laser light, generates heat, and the surrounding forming material is carbonized, thereby performing the desired printing.

As the colorant, either a pigment or a dye may be used, and examples thereof include titanium oxide, barium oxide, and zinc oxide as white pigments, iron oxide and titanium yellow as yellow pigments, iron oxide as red pigments, and cobalt blue ultramarine as blue pigments, and the dye is preferably a white dye, which may be mixed with a fluorescent whitening dye or the like.
Examples of fluorescent brightening dyes include fluorescein compounds, thioflavin compounds, eosin compounds, rhodamine compounds, coumarin compounds, imidazole compounds, oxazole compounds, triazole compounds, carbazole compounds, pyridine compounds, imidazolone compounds, naphthalic acid derivatives, stilbene disulfonic acid derivatives, stilbene tetrasulfonic acid derivatives, stilbene hexasulfonic acid derivatives, dazolone derivatives, etc. In terms of the effects of the present invention, stilbene disulfonic acid derivatives, etc. are preferable.
The colorants may be used alone or in combination of two or more.
Among the above-mentioned colorants, white dyes and white pigments, which have outstanding contrast, are preferred. The white dyes and white pigments may be used alone or in combination.
The colorant is more preferably a white pigment, and particularly preferably titanium oxide.
The average particle size of the pigment is not particularly limited, but is, for example, 0.01 μm to 10 μm, preferably 0.03 μm to 5 μm, more preferably 0.07 μm to 3 μm, and even more preferably 0.1 μm to 1.0 μm. The average particle size refers to the volume moment average diameter obtained by laser diffraction particle size distribution measurement.

Examples of titanium oxide include rutile titanium oxide and anatase titanium oxide, and rutile titanium oxide is more preferable. By using rutile titanium oxide as a white pigment, the effect of suppressing deterioration of the polyester resin (A) is high.

If desired, titanium oxide may be surface-treated by various known methods using a hydrous oxide or oxide of at least one metal selected from silicon, titanium, zirconium, tin, cerium, etc. For example, as a method for surface treatment with the hydrous oxide or oxide of the above metal, a method can be adopted in which a water-soluble compound of the above metal is added to an aqueous slurry of titanium oxide, followed by neutralization to precipitate the hydrous oxide of the metal on the surface of titanium oxide particles, followed by filtration and drying.
In addition, when titanium oxide is used, the resin composition may contain, in addition to titanium oxide, other colorants such as organic pigments and dyes, and may also contain a fluorescent whitening dye or the like as a white dye to adjust the color tone.

The content of the colorant in the resin composition is preferably 0.01 parts by mass or more and 40 parts by mass or less per 100 parts by mass of the resin component. When the content of the colorant is 0.01 parts by mass, the resin composition can be appropriately colored, and the laser printability can be easily improved. Furthermore, the design of the film formed from the resin composition can be improved and the concealing property can be imparted. In addition, by making the content 40 parts by mass or less, an effect commensurate with the content can be exhibited, and the deterioration of the physical properties of the film formed from the resin composition can also be suppressed.
From the above viewpoints, the content of the colorant in the resin composition is more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of the resin component, and more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.

[Lubricant]
The resin composition may contain a lubricant. By containing a lubricant, the surface resistivity of a film made of the resin composition is reduced, and charging is suppressed. In addition, the surface slipperiness of the film is improved, and the problem of adhesion to another film or press plate and difficult to peel off is unlikely to occur. In addition, when the surface resistivity is low, static electricity is unlikely to occur when the film is unwound from the roll, and it is possible to prevent sparks from occurring during unwinding and scratching the surface of the film, etc., and further, due to the improvement of slipperiness and the decrease in surface resistivity, it is possible to prevent the film from meandering or slanting when unwound from the roll and unwound from causing misalignment, twisting, wrinkles, etc., when the film is unwound from the roll and unwound. Therefore, the handling and processability are improved. Furthermore, when the surface resistivity is low, floating dust is attracted by static electricity and adheres to the surface of the film, etc., and problems such as foreign matter being mixed into the obtained laminated film or card are unlikely to occur, and the dustproofness is improved. In addition, since the slipperiness is good, the film surface is unlikely to be scratched even when rubbed, and it is also excellent in abrasion resistance.
Furthermore, it is presumed that the improved wettability due to the lubricant improves printability when printing is performed on a film made of a resin composition. The printability means the compatibility of the ink with the film when printing is performed on the surface of the film made of a resin composition. When the printability is improved, the ink can be printed neatly on the film without repelling or the like.

Lubricants generally include compounds having polar moieties such as acids, esters, hydroxyl groups, amide groups, and metal salts in the molecule, and non-polar moieties such as aliphatic groups. In addition, compounds other than these compounds that improve the sliding properties with other materials such as metals and resins can be used as lubricants. The use of a lubricant having a polar moiety makes it easier to lower the surface resistivity. The use of a lubricant having a non-polar moiety makes it easier to suppress sticking of press plates, etc.
Specific examples of the lubricant include polyalkylene glycol, fatty acid ester, metal salt having an aliphatic group, fluorine-based polymer, fatty acid amide, aliphatic alcohol, fatty acid, aliphatic hydrocarbon compound, etc. By adding these lubricants to the polyester resin (A), the above-mentioned various performances are easily exhibited. Among these, the lubricant is preferably at least one selected from polyalkylene glycol, fatty acid ester, metal salt having an aliphatic group, and fluorine-based polymer.

(Polyalkylene glycol)
The polyalkylene glycol may be polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, or a copolymer of ethylene oxide and propylene oxide. The polyalkylene glycol may have a branch in the molecular skeleton. Among these, polyethylene glycol is preferred.
The polyalkylene glycol is preferably a solid wax that is solid at room temperature (23°C). A solid wax is preferable because it is easily mixed with pellets and is less likely to volatilize due to the heat required for processing into a sheet. The polyalkylene glycol that becomes the solid wax has a number average molecular weight of, for example, 500 to 5000. The number average molecular weight refers to the number average molecular weight calculated based on the hydroxyl value measured in accordance with JIS K1577:2007.
The polyalkylene glycols may be used alone or in combination of two or more kinds.

(Fatty acid ester)
The fatty acid ester may be any known fatty acid ester used as a lubricant. The fatty acid ester is an ester made from fatty acids and various alcohols, and preferably has a long-chain aliphatic group and an ester group in the molecule.
Specific examples of fatty acid ester lubricants include higher fatty acid esters of monohydric alcohols, higher fatty acid esters or partial esters of polyhydric alcohols, or partially saponified products thereof, etc. The higher fatty acids used in the higher fatty acid esters have, for example, 10 or more carbon atoms, preferably 12 or more carbon atoms, more preferably 16 or more carbon atoms, and even more preferably 20 or more carbon atoms, and preferably 36 or less carbon atoms, more preferably 32 or less carbon atoms.
Specifically, examples of such fatty acids include montanic acid esters, partially saponified montanic acid esters, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl erucate, methyl behenate, butyl laurate, butyl stearate, isopropyl myristate, isopropyl palmitate, octyl palmitate, coconut fatty acid octyl esters, octyl stearate, cow fatty acid octyl esters, lauryl laurate, stearyl stearate, behenyl behenate, cetyl myristate, neopentyl polyol fatty acid esters such as neopentyl glycol dioleate and neopentyl glycol dicaprate, and trimeyl polyol fatty acid esters such as trimethylolpropane trioleate. Examples of such fatty acid esters include various trimethylolpropane fatty acid esters such as trimethylolpropane trifatty acid esters and trimethylolpropane difatty acid esters such as trimethylolpropane dicaprate, pentaerythritol fatty acid esters such as pentaerythritol tetraoleate, dipentaerythritol fatty acid esters such as dipentaerythritol hexaisononanoate, fatty acid glycerides such as stearate monoglyceride, stearate diglyceride, stearate triglyceride, oleate monoglyceride, oleate diglyceride, oleate triglyceride, pentaerythritol fatty acid condensation esters, and trimethylolpropane fatty acid condensation esters. Among these, montanic acid esters are preferred.
The fatty acid esters may be used alone or in combination of two or more.

(Metal Salts Having Aliphatic Groups)
The metal salt used as the lubricant may be a metal salt having an aliphatic group. By using a metal salt having an aliphatic group, it becomes easier to reduce the surface resistivity and to exhibit various effects. Examples of the aliphatic group include an aliphatic hydrocarbon group and an aliphatic acyl group. The aliphatic group is not particularly limited, but preferably has 8 or more carbon atoms, more preferably has 10 or more carbon atoms, and preferably has 30 or less carbon atoms, more preferably has 24 or less carbon atoms, and even more preferably has 16 or less carbon atoms.
Specific examples of the metal salt include metal salts of fatty acids and metal salts of alkylbenzenesulfonic acids, with metal salts of alkylbenzenesulfonic acids being preferred.

The fatty acid metal salts are salts of fatty acids, for example, higher fatty acids having about 8 to 30 carbon atoms, preferably 10 to 24 carbon atoms, such as stearic acid, lauric acid, myristic acid, and castor oil fatty acid, with metals such as aluminum, calcium, zinc, magnesium, lead, and barium. Preferred examples include calcium stearate, zinc stearate, and magnesium stearate.
The metal alkylbenzenesulfonate includes metal alkylbenzenesulfonates having an alkyl group with preferably 8 to 24 carbon atoms, more preferably 10 to 16. The metal used is preferably sodium, calcium, magnesium, potassium, etc., and particularly preferably sodium.
A specific example of a suitable metal salt of alkylbenzenesulfonate is sodium dodecylbenzenesulfonate.
The metal salts may be used alone or in combination of two or more kinds.

(Fluorine-based polymer)
Examples of the fluorine-based polymer include fluorine resins having a carbon-fluorine bond in the molecule, specifically, polytetrafluoroethylene, polytrifluoroethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoroalkylvinyl ether copolymer, fluorine-based polymers having fluoroalkyl groups at both ends or one end of the polymer chain, perfluorocarboxylic acid ester, etc.
Among these, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, and the like are preferable.
The fluorine-based polymers may be used alone or in combination of two or more kinds.

(Aliphatic amide)
Examples of fatty acid amides include known fatty acid amides that can be used as lubricants. Fatty acid amides are amides consisting of fatty acids and amines, and have a long-chain aliphatic group and an amide group in the molecule, and are also called fatty acid amides. Specific examples include monoamides, substituted amides, bisamides, methylol amides, ethanol amides, ester amides, substituted ureas, and polycondensates of fatty acids and amines. The fatty acids used may be saturated or unsaturated. The number of carbon atoms of the fatty acid is, for example, about 8 to 30, and preferably 10 to 24.
Preferred examples of the fatty acid amide include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, stearyl erucic acid amide, ethylene bis erucic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, N-oleyl palmitamide, and ethylene diamine-stearic acid-sebacic acid polycondensates.
The fatty acid amides may be used alone or in combination of two or more.

(Fatty alcohol)
The fatty alcohol may be any known fatty alcohol that can be used as a lubricant. The fatty alcohol may, for example, be an fatty alcohol having 6 to 30 carbon atoms, preferably 10 to 24 carbon atoms. Specific examples of the fatty alcohol include caproyl alcohol, caprylyl alcohol, capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, etc., and preferably stearyl alcohol.
The fatty acid alcohols may be used alone or in combination of two or more.

(fatty acid)
The fatty acid may be any known fatty acid that can be used as a lubricant. For example, the fatty acid may be a fatty acid having 6 to 30 carbon atoms, preferably 10 to 24 carbon atoms. Specific examples of the fatty acid include saturated fatty acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid, and unsaturated fatty acids such as oleic acid and erucic acid, with stearic acid being preferred.

(Aliphatic hydrocarbon compounds)
Examples of the aliphatic hydrocarbon compound include known aliphatic hydrocarbon compounds that can be used as lubricants. Specific examples of the aliphatic hydrocarbon compound include paraffin waxes such as liquid paraffin, microcrystalline wax, natural paraffin, and synthetic paraffin having 16 or more carbon atoms, polyolefin waxes such as polyethylene wax, and partial oxides, fluorides, and chlorides thereof.
The aliphatic hydrocarbon compounds may be used alone or in combination of two or more kinds.

In the resin composition, the lubricant may be used alone or in combination of two or more.When using two or more, for example, it is preferable to use polyalkylene glycol and a metal salt having an aliphatic group in combination, and it is more preferable to use polyethylene glycol and a metal salt of alkylbenzenesulfonic acid in combination.By using these two types of lubricants in combination, the film made of the resin composition of the present invention is less likely to adhere to not only other resin films but also press plates, so that the handling and processability are more excellent.
When a polyalkylene glycol and a metal salt having an aliphatic group are used in combination, the ratio of the polyalkylene glycol to the metal salt having an aliphatic group (polyalkylene glycol/metal salt), in terms of mass ratio, is preferably 1/9 or more and 9/1 or less, more preferably 1/5 or more and 5/1 or less, and even more preferably 1/3 or more and 3/1 or less.

It is also preferable to use a fatty acid ester and a fluoropolymer in combination. By using these two types of lubricants in combination, the film made of the resin composition of the present invention is less likely to adhere to not only the resin film but also the press plate, resulting in better handling and processability. When a fatty acid ester and a fluoropolymer are used in combination, the ratio of the fluoropolymer to the fatty acid ester (fluoropolymer/fatty acid ester) is preferably 1/9 or more and 9/1 or less, more preferably 1/6 or more and 6/1 or less, even more preferably 1/4 or more and 4/1 or less, and even more preferably 1/3 or more and 3/1 or less, by mass.

Three or more types of lubricants may be used in combination, for example, four types of lubricants may be used in combination: polyalkylene glycol, metal salt having an aliphatic group, fatty acid ester, and fluoropolymer. When four types of lubricants are used in combination in this way, the content ratio of polyalkylene glycol to metal salt, and the content ratio of fatty acid ester to fluoropolymer may be as described above.

The content of the lubricant in the resin composition is preferably 0.01 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the resin component contained in the resin composition. By being 0.01 parts by mass or more, the surface resistivity of the film formed from the resin composition is reduced, charging is prevented, and the slipperiness is improved, and the processability, handling property, dust resistance, scratch resistance, etc. are easily improved. In addition, it is estimated that the wettability is appropriately increased and the printability is easily improved. In addition, by making it 5 parts by mass or less, it is possible to exert an effect commensurate with the content, and it is also possible to suppress the deterioration of the physical properties of the film formed from the resin composition and the deterioration of the printability.
From the above viewpoints, the content of the lubricant in the resin composition is more preferably 0.1 parts by mass or more, even more preferably 0.4 parts by mass or more, even more preferably 0.6 parts by mass or more, and particularly preferably 0.9 parts by mass or more, relative to 100 parts by mass of the resin component. Also, it is more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, and particularly preferably 1.5 parts by mass or less.

[Impact resistance improver]
The resin composition of the present invention may contain an impact modifier. The resin composition using the polyester resin (A) may lack long-term reliability in practical use, but by blending an impact modifier, the influence caused by external impact such as bending and impact in practical use is mitigated, and the reliability in long-term use is improved.
Examples of the impact resistance improver include soft styrene-based resins and elastomers. The elastomer may be a core-shell type elastomer. The impact resistance improver may be used alone or in combination of two or more kinds.
Among the above, the core-shell type elastomer is preferred as the impact resistance improver. By using the core-shell type elastomer, the impact resistance is further improved, and the reliability in long-term use is further improved.

Examples of the soft styrene-based resin include a block copolymer containing a styrene polymer block and a conjugated diene polymer block, and a block copolymer containing a styrene polymer block and an acrylonitrile block.
The styrene content in the soft styrene-based resin is, for example, 5% by mass or more and 80% by mass or less, preferably 10% by mass or more and 50% by mass or less, and more preferably 15% by mass or more and 30% by mass or less. By having the styrene content in the above range, the effect of imparting impact resistance is further improved.

As the conjugated diene polymer block used in the soft styrene-based resin, a homopolymer of butadiene, isoprene, 1,3-pentadiene, or the like, a copolymer thereof, or a copolymer containing a monomer copolymerizable with the conjugated diene monomer in the block, or the like can be used.
Specific examples of soft styrene resins include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), silicone-acrylic composite rubber-acrylonitrile-styrene copolymers (SAS), methyl methacrylate-maleic anhydride-styrene copolymers (SMM), acrylonitrile-styrene copolymers (AS), acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile-styrene-acrylic rubber copolymers (ASA), acrylonitrile-ethylene propylene rubber-styrene copolymers (AES), etc. Specific examples of commercial products include the "Kraton D" series manufactured by Kraton Polymers, the "AR-100" series manufactured by Aronkasei, the "Dialac" series manufactured by UMG ABS, and the "Delpet" series manufactured by Asahi Kasei Chemicals. As the soft styrene-based resin, the "Dynaron" series manufactured by JSR Corporation, the "Tuftec" series manufactured by Asahi Kasei Chemicals Corporation, the "Hybler" series manufactured by Kuraray Co., Ltd., and the like can be used as the styrene-based elastomer described below.

The block copolymer includes pure block, random block, tapered block, etc., and the copolymerization form is not particularly limited. The block unit may also have multiple repeating units. Specifically, in the case of a styrene-butadiene block copolymer, the block unit may be repeated multiple times, such as a styrene-butadiene copolymer, a styrene-butadiene-styrene block copolymer, or a styrene-butadiene-styrene-butadiene block copolymer.

Hydrogenated styrene-butadiene-styrene block copolymers (SEBS) and hydrogenated styrene-isoprene-styrene block copolymers (SEPS), in which some or all of the double bonds in the conjugated diene polymer blocks of SBS and SIS are hydrogenated, can also be used. Specific examples of such products include the "Tuftec H" series manufactured by Asahi Kasei Chemicals Corporation and the "Kraton G" series manufactured by Kraton Polymers.

A functional group having polarity can be added to the soft styrene-based resin. Specific examples of the functional group having polarity include an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid amide group, a carboxylate group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid amide group, a sulfonate group, an epoxy group, an amino group, an imide group, and an oxazoline group. Among these, it is preferable to add an acid anhydride group or an epoxy group.
As the soft styrene-based resin to which a polar functional group is added, modified products of SEBS and SEPS are preferably used. Specific examples include maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, epoxy-modified SEBS, and epoxy-modified SEPS. Specific commercial products include the "Tuftec M" series manufactured by Asahi Kasei Chemicals Corporation, the "Dynaron" series manufactured by JSR Corporation, and the "Epofriend" series manufactured by Daicel Chemical Industries, Ltd.

The soft styrene-based resin may also be a styrene-based elastomer containing an elastomer component. Specifically, among the above, there are block copolymers of a styrene component and butadiene, isoprene, 1,3-pentadiene, etc., and modified products or hydrogenated products of these may also be used. More specifically, there are SBS, SIS, SEBS, SEPS, etc.

The elastomer may be other than a styrene-based elastomer, and examples thereof include known elastomers such as polyester-based elastomers, polyolefin-based elastomers, diene-based elastomers, acrylic-based elastomers, polyamide-based elastomers, polyurethane-based elastomers, fluorine-based elastomers, and silicone-based elastomers. The elastomer is generally a thermoplastic elastomer. The elastomer is preferably a polyester-based elastomer or the above-mentioned styrene-based elastomer.

The polyester elastomer is a thermoplastic polyester that has rubber properties at room temperature, and is preferably a thermoplastic elastomer whose main component is a polyester block copolymer, and is preferably a block copolymer having a high melting point and high crystallinity aromatic polyester as a hard segment and an amorphous polyester or amorphous polyether as a soft segment. The soft segment content of the polyester elastomer is at least 20 to 95 mol% of the total segments, and in the case of a block copolymer of polybutylene terephthalate and polytetramethylene glycol (PTMG-PBT copolymer), it is 50 to 95 mol%. The preferred soft segment content is 50 to 90 mol%, particularly 60 to 85 mol%. Among them, polyester ether block copolymers, particularly PTMG-PBT copolymers, are preferred because they reduce the drop in transmittance.

The core-shell type elastomer is composed of an innermost layer (i.e., a core) and one or more outer layers (i.e., shells) covering the innermost layer. The core-shell type elastomer is preferably a core-shell type graft copolymer in which a monomer component capable of being graft-copolymerized with the core is graft-copolymerized as the shell.

The core-shell type graft copolymer has a polymer component, usually called a rubber component, as the core. In the core-shell type graft copolymer, it is preferable that the polymer component constituting the core and a monomer component copolymerizable with this polymer component are graft copolymerized as the shell.
The core-shell type graft copolymer may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., and the copolymerization method may be one-stage grafting or multi-stage grafting. However, commercially available core-shell type elastomers can usually be used as they are. Examples of commercially available core-shell type elastomers will be given later.

Specific examples of the polymer components forming the core include butadiene-based rubbers such as polybutadiene and styrene-butadiene copolymers, isoprene-based rubbers, acrylic rubbers such as polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate-2-ethylhexyl acrylate copolymers, silicone-based rubbers such as polyorganosiloxane rubber, butadiene-acrylic composite rubbers, silicone-acrylic composite rubbers such as IPN (Interpenetrating Polymer Network)-type composite rubbers consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, ethylene-α-olefin-based rubbers such as ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-octene copolymers, ethylene-acrylic rubbers, and fluororubbers. These may be used alone or in combination of two or more. Among these, in terms of mechanical properties and surface appearance, at least one selected from butadiene-based rubber, acrylic-based rubber, silicone-based rubber, and silicone-acrylic composite rubber is preferred, and among these, at least one selected from butadiene-based rubber and silicone-acrylic composite rubber is more preferred.

Specific examples of the monomer component constituting the shell and capable of graft copolymerization with the polymer component of the core include aromatic vinyl compounds; vinyl cyanide compounds; (meth)acrylic compounds such as (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, and epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and anhydrides thereof (e.g., maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, and (meth)acrylic compounds are preferred from the standpoint of mechanical properties and surface appearance, and more preferably aromatic vinyl compounds and (meth)acrylic compounds, and especially (meth)acrylic acid ester compounds.
Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, and halogenated styrenes. Among these, styrene and α-methylstyrene are more preferred.
Specific examples of the (meth)acrylic acid ester compound include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, etc., of which methyl (meth)acrylate and ethyl (meth)acrylate, which are relatively easily available, are preferred, and methyl (meth)acrylate is more preferred. Note that "(meth)acrylic" is a general term for "acrylic" and "methacrylic".

As the core-shell type elastomer, a core-shell type graft copolymer is particularly preferred, which is composed of a core made of at least one polymer component selected from butadiene rubber, acrylic rubber, silicone rubber, and silicone-acrylic composite rubber, and a shell formed by graft copolymerizing a (meth)acrylic compound such as a (meth)acrylic acid ester or an aromatic vinyl compound around the core. The content of the polymer component in the core in the core-shell type graft copolymer is preferably 40% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.
In addition, the total content of the (meth)acrylic compound (particularly, the (meth)acrylic acid ester) component and the aromatic vinyl compound component in the shell of the core-shell type graft copolymer is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and even more preferably 70% by mass or more. In the shell, either the (meth)acrylic compound or the aromatic vinyl compound may be used alone, or these may be used in combination.

Specific preferred examples of core-shell elastomers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber-styrene copolymer, methyl methacrylate-(acrylic-silicone composite rubber) copolymer, etc.

Commercially available core-shell type graft copolymers include, for example, "Paraloid EXL2602", "Paraloid EXL2603", "Paraloid EXL2690", "Paraloid EXL2691J", "Paraloid EXL2650J", "Paraloid EXL2655", "Paraloid EXL2311", "Paraloid EXL2313", "Paraloid EXL2315", "Paraloid KM330", "Paraloid KM336P", and "Paraloid Examples of such polymers include "KCZ201" manufactured by Mitsubishi Chemical Corporation, "Metablen C-223A", "Metablen E-901", "Metablen S-2001", "Metablen W-450A", and "Metablen SRK-200" manufactured by Mitsubishi Chemical Corporation, and "Kane Ace M-210", "Kane Ace M-511", "Kane Ace M-600", "Kane Ace M-400", "Kane Ace M-580", "Kane Ace M-590", "Kane Ace M-711", "Kane Ace MR-01", and "Kane Ace M-300" manufactured by Kaneka Corporation.
These impact resistance improvers such as core-shell type graft copolymers may be used alone or in combination of two or more kinds.

In the resin composition, the content of the impact resistance improver is preferably 1 part by mass or more and 40 parts by mass or less per 100 parts by mass of the resin component. When the content of the impact resistance improver is 1 part by mass or more, the influence caused by external impact is moderately alleviated, and long-term reliability is improved. By setting the content to 40 parts by mass or less, an effect commensurate with the content can be exhibited, and various physical properties such as heat resistance of the film formed from the resin composition can also be prevented from being deteriorated.
From these viewpoints, the content of the impact modifier in the resin composition is more preferably 2.5 parts by mass or more, even more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, based on 100 parts by mass of the resin component, and is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 16 parts by mass or less, and particularly preferably 12 parts by mass or less.

[Laser coloring agent]
The resin composition may contain a laser coloring agent. The laser coloring agent is not particularly limited as long as it has the function of generating heat by irradiation with a laser beam, and may be a so-called self-coloring type coloring agent that generates color by itself by irradiation with a laser beam, or may not generate color by itself. The laser coloring agent can promote carbonization of the surrounding forming material by generating heat, and further improve the laser printability. Furthermore, when a self-coloring laser coloring agent is used, the coloring of the laser coloring agent and the coloring of the carbonized material generated by carbonization of the forming material are synergistic, and a print with a deep color and excellent visibility can be displayed. When the laser coloring agent generates color, the color is not particularly limited, but from the viewpoint of visibility, it is preferable to use a laser coloring agent that can generate a deep color including black, navy blue, and brown.

The laser coloring agent may be a metal oxide or a compound other than a metal oxide. The metal oxide is not limited as long as it has a laser coloring effect, and examples of the metal oxide include iron oxide, copper oxide, zinc oxide, tin oxide, cobalt oxide, nickel oxide, bismuth oxide, indium oxide, antimony oxide, tungsten oxide, neodymium oxide, mica, hydrotalcite, montmorillonite, and smectite.
Laser coloring agents other than metal oxides may also be used, including metals such as iron, copper, zinc, tin, gold, silver, cobalt, nickel, bismuth, antimony, and aluminum, and metal salts thereof such as iron chloride, iron nitrate, iron phosphate, copper chloride, copper nitrate, copper phosphate, zinc chloride, zinc nitrate, zinc phosphate, nickel chloride, nickel nitrate, bismuth subcarbonate, and bismuth nitrate, metal hydroxides such as magnesium hydroxide, lanthanum hydroxide, nickel hydroxide, and bismuth hydroxide, and metal borides such as zirconium boride, titanium boride, and lanthanum boride. Among the metal borides, hexaborides have near-infrared absorption ability, and among them, lanthanum hexaboride is preferred because it has excellent laser light absorption efficiency. In addition, dye systems represented by leuco dyes such as fluoran, phenothiazine, spiropyran, triphenylmethaphthalide, and rhodamine lactam, and carbon black can also be used.
As the laser coloring agent, it is preferable to use a bismuth-based metal oxide such as bismuth oxide or a metal oxide containing bismuth and at least one metal selected from Zn, Ti, Al, Zr, Sr, Nd, and Nb.
The laser color developing agent may be used alone or in combination of two or more kinds.

[Antioxidants]
The resin composition may contain an antioxidant. The antioxidant has an effect of suppressing the transesterification reaction between the polyester resin and the polycarbonate resin, and can suppress foaming due to the transesterification reaction in the resin composition. In addition, the antioxidant can also prevent yellowing of molded products such as films molded from the resin composition.
As the antioxidant, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, etc. can be used. Among them, a phenol-based antioxidant and a phosphorus-based antioxidant are preferable. The antioxidant may be used alone or in combination of two or more kinds. By using two or more kinds of antioxidants, it is possible to effectively suppress the molecular weight reduction and yellowing during molding. In addition, by using two or more kinds of antioxidants, it is possible to achieve both stability during molding and long-term stability after molding.

Examples of phenol-based antioxidants include α-tocopherol, 4-methoxyphenol, 4-hydroxyphenyl (meth)acrylate, β-tocopherol, 2,6-di-tert-butylphenol, 2,6-di-tert-4-methoxyphenol, 2-tert-butyl-4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol (dibutylhydroxytoluene, BHT), and stearyl-β-propionate (3,5-di-tert-butyl-4-hydroxyphenyl). Of these, 2,6-di-tert-butyl-4-methylphenol (dibutylhydroxytoluene, BHT) is preferred.

Examples of phosphorus-based antioxidants include tris(2,5-di-tert-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris[2,4-bis(1,1-dimethylpropyl)phenyl]phosphite, tris(mono- or di-tert-butylphenyl)phosphite, 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecylphosphite), cyclic neopentanetetraylbis(2,6-di-t-butyl-4-methylphenylphosphite), tris(nonylphenyl)phosphite, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, and trisalkylphosphites such as trisstearylphosphite. Among these, trisalkyl phosphites such as trisstearyl phosphite are preferred.

Examples of sulfur-based antioxidants include thiodipropionic acid, dilauryl thiodipropionate, distearyl thiodipropionate, laurylstearyl thiodipropionate, dimyristyl thiodipropionate, distearyl-β,β'-thiodibutyrate, thiobis(β-naphthol), thiobis(N-phenyl-β-naphthylamine, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, and nickel dibutyldithiocarbamate.

The content of the antioxidant in the resin composition is preferably 0.05 parts by mass or more and 4 parts by mass or less, more preferably 0.07 parts by mass or more and 3 parts by mass or less, even more preferably 0.1 parts by mass or more and 2 parts by mass or less, and even more preferably 0.15 parts by mass or more and 1.5 parts by mass or less, relative to 100 parts by mass of the resin component. By making the content of the antioxidant equal to or more than the above lower limit, foaming and yellowing due to the transesterification reaction can be effectively suppressed. Furthermore, by making the content equal to or less than the above upper limit, an effect commensurate with the content can be exhibited.

(Other ingredients)
The resin composition may contain known additives used in resin materials other than those mentioned above, such as heat stabilizers, process stabilizers, ultraviolet absorbers, light stabilizers, matting agents, processing aids, metal deactivators, residual polymerization catalyst deactivators, antibacterial and antifungal agents, antiviral agents, antistatic agents, flame retardants, and fillers.

In addition, the resin composition of the present invention may use only the polyester resin (A) and the polycarbonate resin (B) as resin components, but may contain resins other than the polyester resin (A) and the polycarbonate resin (B) within the scope of the present invention. As such resins, it is preferable to use known resins that are generally used, but it is preferable to use resins that are compatible with the polyester resin (A) and the polycarbonate resin (B). In this specification, the resin components do not include those used as the impact resistance improvers described above.
The resin constituting the resin composition may contain a polyester resin (A) and a polycarbonate resin (B) as main components, and the total content of the polyester resin (A) and the polycarbonate resin (B) is preferably 70 mass% or more, more preferably 90 mass% or more, and most preferably 100 mass% based on the total amount of the resin components contained in the resin composition.

(Storage Modulus)
The resin composition of the present invention preferably has a storage modulus at 100° C. of 1×10 ⁹ Pa or more. When the storage modulus at 100° C. is 1×10 ⁹ Pa or more, deformation is unlikely to occur when heated, and workability when producing cards or passports is improved. Furthermore, cards and passports are unlikely to warp. In addition, durability that can withstand long-term use is likely to be obtained. The storage modulus at 100° C. of the resin composition is more preferably 1.1×10 ⁹ Pa or more, and even more preferably 1.3×10 ⁹ Pa or more.
The upper limit of the storage modulus is not particularly limited, but is, for example, 1×10 ¹¹ Pa or less, preferably 5×10 ¹⁰ Pa or less, more preferably 3×10 ¹⁰ Pa or less, and further preferably 1×10 ¹⁰ Pa or less.

The storage modulus is the value of the tensile storage modulus obtained from dynamic viscoelasticity measurement in accordance with JIS K7244-4:1999, and is described in detail in the Examples. The test piece for obtaining the tensile storage modulus may be prepared by, for example, press molding or extrusion molding of a film from the resin composition, and the film may be used as the test piece. In the case of extrusion molding, the film should be prepared so as not to be stretched, but if there is directionality, it is recommended to measure in the MD. In the case of no directionality such as press molding, measurement is made in only one direction, and the measured value is taken as the storage modulus. Note that MD (Machine Direction) is the flow direction of the resin, and TD (Transverse Direction) is the direction perpendicular to the MD along the surface direction of the film.

(Recycled raw material)
The resin composition of the present invention may contain recycled raw materials. By using recycled raw materials, it is possible to contribute to global environmental protection, such as reducing waste and energy consumption. The recycled raw materials may be raw materials that have been regenerated from recovered products, waste, etc. by a chemical regeneration method involving chemical reactions. In addition, the recycled raw materials may be raw materials that have been regenerated from recovered products, waste, etc. by a physical regeneration method (mechanical recycling).
As for the recycled raw materials, it is preferable to use recycled raw materials for at least a part of the polyester resin (A-1) and the polyester resin (A-2), and it is more preferable to use recycled raw materials for at least a part of the polyester resin (A-1).
It is also preferable to use recycled raw materials for at least a part of the polycarbonate resin (B).
In addition, polyester resin (A-1), polyester resin (A-2), and polycarbonate resin (B) made from recycled raw materials are also referred to as recycled polyester resin (A-1), recycled polyester resin (A-2), and recycled polycarbonate resin (B), respectively.

The total content of the recycled polyester resin (A-1), recycled polyester resin (A-2), and recycled polycarbonate resin (B) in the resin composition is, for example, 30% by mass or more, preferably 50% by mass or more, and more preferably 70% by mass or more, based on the total amount of the polyester resin (A-1), polyester resin (A-2), and polycarbonate resin (B). From the viewpoint of protecting the global environment, the higher the content of the recycled raw materials, the better, and there is no particular restriction as long as it is 100% by mass or less.

The recycled polyester resin (A-1) or the recycled polyester resin (A-2) may be one that has been regenerated by a chemical regeneration method as described above. Specifically, the recycled polyester resin (A-1) or the recycled polyester resin (A-2) can be obtained by depolymerizing a discarded polyester resin or the like, and repolymerizing the resulting intermediate or monomer to synthesize the polyester resin (A-1) or the polyester resin (A-2).
The recycled polycarbonate resin (B) may also be one that has been recycled by a chemical recycling method.

The recycled polyester resin (A-1), recycled polyester resin (A-2), or recycled polycarbonate resin (B) may be one that has been recycled by a physical recycling method as described above. Specifically, the recycled polyester resin (A-1), recycled polyester resin (A-2), or recycled polycarbonate resin (B) is obtained by recovering polyester resin products, polycarbonate resin products, and scraps generated during the production process, and then performing processing such as melting and pulverization after sorting and washing as necessary, and then appropriately performing processing such as granulation, micronization, pelletization, and flaking, and using it as a recycled raw material in a form that can be used as a raw material for resin compositions such as powder, granules, pellets, and flakes.
In addition, in the recycled polyester resin (A-1) and the recycled polyester resin (A-2), the molecular weight may be increased by solid-phase polymerization or the like in the process of obtaining the recycled raw material by a physical regeneration method. That is, the recycled polyester resin (A-1) or the recycled polyester resin (A-2) may be one that has been regenerated by a physical regeneration method that does not involve a chemical reaction, or the molecular weight may be increased by a chemical change while being regenerated by a physical regeneration method.

The recycled polyester resin (A-1) or the recycled polyester resin (A-2) is preferably a recycled polyester resin recycled from scraps generated during the production process. Similarly, the polycarbonate resin (B) is preferably a recycled polyester resin recycled from scraps generated during the production process.
Scraps generated during the production process have a relatively stable raw material composition, and the raw material composition is often known, making them easy to recycle as recycled raw materials.
The scraps generated during the production process refer to polyester resin or polycarbonate resin that is generated during the process from synthesized polyester resin or polycarbonate resin to a specified product form (any product form such as film, sheet, fiber, strand, block, pellet, powder, or other molded product) and is not used as a product.

There are no particular limitations on the resin composition as long as it is used for at least a part of either a card or a passport. For example, as described below, it can be used as either a core sheet, a laser marking sheet, or a protective sheet for a card or passport, and it is preferable to use it as either a core sheet or a laser marking sheet.
A laser marking sheet is a sheet provided for laser marking a card or passport. For example, when a resin composition containing a colorant, a laser coloring agent, or both is used in a laser marking sheet, it becomes easier to improve the laser printability on the laser marking sheet.
Furthermore, since core sheets generally contain a colorant from the viewpoints of design and concealment, for example, a resin composition containing a colorant is suitable for use in the core sheet. When a resin composition containing a colorant is used in the core sheet, it is preferable to perform laser printing on the core sheet, so that a laser marking sheet does not have to be provided in the card or passport, but may be provided.
Furthermore, the core sheet, laser marking sheet, and protective sheet of each card or passport may be constructed by stacking multiple resin layers (films) as described below, in which case at least one of the multiple resin layers (films) should be constructed from the above-mentioned resin composition.

(Method for producing resin composition)
The resin composition of the present invention may be obtained by mixing raw materials constituting the resin composition, such as the polyester resin (A-1), the polycarbonate resin (B), the polyester resin (A-2) which is optionally blended, a colorant, a lubricant, an impact resistance improver, a laser coloring agent, an antioxidant, and other additives.
In addition, when the resin composition contains recycled raw materials, the recycled raw materials may be blended into the resin composition and mixed with other raw materials to obtain the resin composition.
The raw materials may be mixed by melt kneading while heating in an extruder, a plastomill or the like, but the raw materials constituting the resin composition may also be dry-blended in a tumbler or the like and used as is.
The melt-kneading temperature is appropriately adjusted depending on the type and mixing ratio of the resin, the presence or absence and type of additives, but from the viewpoint of productivity, etc., it is preferably 220° C. or higher, more preferably 240° C. or higher, and even more preferably 250° C. or higher. It is also preferably 300° C. or lower, more preferably 280° C. or lower, and even more preferably 270° C. or lower. If the melt-kneading temperature is within the range, it is easy to sufficiently flow the resin while suppressing decomposition and crosslinking.

<Card or passport film>
The card or passport film of the present invention (hereinafter sometimes referred to as "the film") is a film made of the above-mentioned resin composition. The thickness of the film is not particularly limited and may be appropriately adjusted depending on the purpose of use, but is, for example, 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more, and is 1000 μm or less, preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 200 μm or less.
The present film may constitute a monolayer structure or may constitute one layer of a multilayer laminate, in which only one layer may be composed of the present film, or two or more layers may be composed of the present film.
As will be described later, cards or passports are generally constructed by stacking a number of resin layers, and it is preferable that the present film constitutes at least one of these layers.

(heating expansion/contraction rate)
The present film preferably has a thermal expansion/contraction rate of -1.7% or more when heated at 110° C. for 10 minutes, as expressed by the following formula. The thermal expansion/contraction rate may be calculated by marking a standard line on a measurement sample and measuring the distance between the standard lines before and after the heat treatment.
Heat expansion/contraction rate (%) = [standard line spacing after heat treatment - standard line spacing before heat treatment] / standard line spacing before heat treatment x 100

The thermal expansion rate is a negative value when it shrinks due to heating, and a positive value when it expands due to heating. Generally, resin films shrink when heated, so the thermal expansion rate of the present film is usually a negative value, but the lower the absolute value, the less the shrinkage when heated. Therefore, if the thermal expansion rate of the present film when heated at 110°C for 10 minutes is set to -1.7% or more as described above, the dimensional change when producing a card or passport will be small, and the deterioration of workability and the occurrence of warping can be prevented.
From these viewpoints, the thermal expansion rate when heat-treated at 110° C. for 10 minutes is more preferably −1.4% or more, even more preferably −1.0% or more, even more preferably −0.8% or more, even more preferably −0.5% or more, and even more preferably −0.3% or more. On the other hand, as described above, the thermal expansion rate is preferably closer to 0%, and therefore the upper limit of the thermal expansion rate when heat-treated at 110° C. for 10 minutes is generally 0%.

The present film preferably has a thermal expansion/contraction ratio represented by the above formula of -3.5% or more when heat-treated at 140°C for 10 minutes. If the present film has a thermal expansion/contraction ratio of -3.5% or more when heat-treated at 140°C for 10 minutes, warping is further prevented from occurring during the preparation of cards or passports, and workability is improved. The thermal shrinkage ratio when heat-treated at 140°C for 10 minutes is more preferably -3% or more, more preferably -2% or more, even more preferably -1.5% or more, and even more preferably -1.2% or more.
The thermal expansion/contraction rate described above should be measured in two directions, one in the plane direction of the film and the other perpendicular to that direction, and the lower value (i.e., the value with the greater thermal shrinkage) should be used. However, if the MD and TD directions are known, it is advisable to measure the thermal expansion/contraction rate in both the MD and TD directions.

(Method of manufacturing card or passport film)
The card or passport film (the present film) can be produced by a known method, but it is preferable to obtain a resin composition for forming the present film as described above and form the resin composition into a film. The method for forming the resin composition into a film is not particularly limited, and may be press molding or extrusion molding, but extrusion molding is preferred from the standpoint of productivity and cost.
When forming a multi-layer laminate using the present film, a plurality of resin films may be laminated by a known lamination method, or a resin composition for forming another resin layer may be melt-extruded onto a resin film, or a multi-layer structure may be formed by co-extrusion.

<Cards and passports>
The card of the present invention comprises the above-mentioned present film, and the passport of the present invention comprises the above-mentioned present film.
Examples of cards include IC cards, magnetic cards, driver's licenses, residence cards, qualification certificates, employee ID cards, student ID cards, My Number cards, seal registration certificates, vehicle inspection certificates, tag cards, prepaid cards, cash cards, credit cards, ETC cards, SIM cards, and B-CAS cards.
The card or passport may include a core sheet. The card or passport may also include, in addition to the core sheet, one or both of a laser marking sheet and a protective sheet.

(card)
A preferred layer structure of the card will be described in more detail below. The card is preferably laminated with a laser marking sheet on both sides of the core sheet. Specifically, the card 20A shown in FIG. 1(a) is made up of a laser marking sheet 1/core sheet 2/laser marking sheet 1, or the card 20B shown in FIG. 1(b) is made up of a protective sheet 4/laser marking sheet 1/core sheet 2/laser marking sheet 1/protective sheet 4. The laser marking sheet 1 may be omitted, or the card 20C shown in FIG. 1(c) is made up of a protective sheet 4/core sheet 2/protective sheet 4.
In each of the cards 20A to 20C, the layer structures provided on both sides of the core sheet 2 are the same, but may be different on each side. For example, the laser marking sheet 1 and the protective sheet 4 may be provided in this order on one side of the core sheet 2, and only the protective sheet 4 may be provided on the other side of the core sheet 2.

The laser marking sheet 1 may be composed of a single resin layer, but is preferably a laminate of a multi-layer structure composed of multiple resin layers. The laser marking sheet 1 preferably includes a resin layer containing a laser coloring agent, and when composed of a single resin layer, it is preferable that one of the resin layers contains a laser coloring agent. Also, when it is a multi-layer structure, it is preferable that one or more of the multiple resin layers contains a laser coloring agent.

The core sheet 2 is usually made of a single resin layer, but may be made of multiple resin layers. The thickness of the core sheet is, for example, about 400 to 700 μm. The core sheet is preferably a colored sheet that contains an appropriate amount of colorant. Specific examples of colorants used in the core sheet are as described above.

A dye-sublimation thermal transfer image receiving layer may be provided on the outermost surface of the laser marking sheet, or on the outermost surface of the core sheet when the laser marking sheet is omitted. In the laser marking sheet and the core sheet, the dye-sublimation thermal transfer image receiving layer is preferably provided on the front surface, which is the visible side, and therefore the dye-sublimation thermal transfer image receiving layer provided on the laser marking sheet is preferably provided on the opposite side to the core sheet. The same applies to passports, which will be described later.

The dye-sublimation thermal transfer image-receiving layer may be a conventionally known one, for example, made by adding various additives such as a release agent, a stabilizer, and an ultraviolet absorber, as necessary, to a varnish mainly composed of a resin that is easy to transfer or dye a coloring material.
Resins that are easily dyeable and are used in the sublimation thermal transfer image receiving layer include polyolefin resins such as polypropylene, halogenated resins such as polyvinyl chloride and polyvinylidene chloride, vinyl resins such as polyvinyl acetate and polyacrylic esters, and copolymers thereof, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, copolymers of olefins such as ethylene and propylene with other vinyl monomers, ionomers, cellulose derivatives, etc., used alone or in mixtures, and among these, polyester resins and vinyl resins are preferred.
The dye-sublimation type thermal transfer image receiving layer can be formed by dissolving and dispersing the above-mentioned resin in a solvent such as an organic solvent or water, and then coating the solution.

The protective sheet is laminated to protect the card. The protective sheet may be composed of a single resin layer, or may be a laminate having a multi-layer structure composed of a plurality of resin layers. The protective sheet is also called an oversheet, and generally constitutes the outermost layer of the card.
When the protective sheet is laminated on the outside of the laser marking sheet 1, it suppresses so-called "blistering" in which foaming occurs in the laser-marked portion due to irradiation with laser light.

The card may be manufactured by stacking the core sheet, laser marking sheet, and protective sheet as appropriate to form the layer structure described above, pressing and heat fusing them, and then performing a punching process or the like. Alternatively, the sheets may be bonded together using an appropriate adhesive or the like instead of heat fusing.

(passport)
Next, a preferred layer structure of the passport will be described in more detail. The film is preferably used for a passport, which is a so-called electronic passport equipped with an IC chip. In particular, when the data page is made of plastic, it is preferable that the passport is provided with a hinge sheet and a core sheet provided on each side of the hinge sheet, and a laser marking sheet is further laminated on the surface of the core sheet. In addition, the passport is preferably provided with a protective sheet, and a protective sheet is further laminated on the surface of the laser marking sheet to protect the laser marking sheet. Specifically, a passport 10A shown in FIG. 2(a) consisting of a laser marking sheet 1/core sheet 2/hinge sheet 3/core sheet 2/laser marking sheet 1, or a passport 10B shown in FIG. 2(b) consisting of a protective sheet 4/laser marking sheet 1/core sheet 2/hinge sheet 3/core sheet 2/laser marking sheet 1/protective sheet 4 is preferable. Furthermore, the laser marking sheet 1 may be omitted, and a card 10C may be used which is composed of a protective sheet 4/core sheet 2/hinge sheet 3/core sheet 2/protective sheet 4 as shown in FIG. 2(c).
In each of the passports 10A, 10B, and 10C, the layer configurations on both sides of the hinge sheet 3 are the same, but may be different on each side. For example, the core sheet 2, the laser marking sheet 1, and the protective sheet 4 may be provided in this order on one side of the hinge sheet 3, while the core sheet 2 and the marking sheet 1 may be provided in this order on the other side of the hinge sheet 3, with the protective sheet 4 omitted.

The passport may have a dye-sublimation thermal transfer image receiving layer as described above for the card. The passport may also have a sheet on which various information is stored in a storage medium such as an IC chip, that is, a so-called inlet sheet. The inlet sheet may be provided, for example, between the hinge sheet and the core sheet.
The hinge sheet is a sheet that holds the recording layer, the core sheet, the inlet sheet, etc., and plays a role in firmly binding the cover of the passport together with other visa sheets, etc. Therefore, it is preferable that the hinge sheet has a strong heat fusion property, a suitable flexibility, heat resistance during the heat fusion process, etc.

The hinge sheet may be a known one, and may be a resin sheet made of a thermoplastic resin or a thermoplastic elastomer, such as a thermoplastic polyester resin, a thermoplastic polyester elastomer, a thermoplastic polyamide resin, a thermoplastic polyamide elastomer, a thermoplastic polyurethane resin, or a thermoplastic polyurethane elastomer, or may be made of a woven fabric, a knitted fabric, or a nonwoven fabric, or may be a composite material of a woven fabric, a knitted fabric, or a nonwoven fabric and a thermoplastic resin or a thermoplastic elastomer. The core sheet in the passport is the same as above, except that it is preferably 50 to 200 μm thick. The protective sheet in the passport is as described above.
In the case of a passport, the core sheet, the laser marking sheet and the protective sheet are preferably laminated together in the above-mentioned layer structure and then pressed and heat-sealed. Alternatively, the sheets may be bonded together with an adhesive instead of heat-sealing.

At least one of the core sheet, laser marking sheet, and protective sheet provided on the card or passport may comprise the above-mentioned present film. By providing at least one of these sheets with the present film, it becomes easier to fuse the sheets together at low temperatures. In addition, since there is little dimensional change when heated, the workability of manufacturing the card or passport is improved, and warping of the card or passport can also be prevented.

As described above, the present film is preferably provided on either the laser marking sheet or the core sheet. For example, in the configurations shown in Figures 1(a) and (b) or 2(a) and (b), it is more preferable to provide the present film on either the core sheet 2 or the laser marking sheet 1. In addition, when the resin composition of the present invention contains a colorant, it is preferable to provide the present film on the laser marking sheet 1. In addition, in the configurations shown in Figures 1(c) and 2(c), it is preferable to provide the present film on the core sheet 2.

In cards or passports, the core sheet, laser marking sheet and protective sheet may have a multi-layer structure as described above, in which case at least one layer should preferably be made of the present film. The present film should also be disposed as the outermost layer of each sheet. A sheet having the present film disposed as the outermost layer will be laminated to other sheets via the present film, so that it can be reliably fused to other sheets even by low-temperature heating.

In addition, in the card or passport, at least one of the resin layers constituting the core sheet, the laser marking sheet, and the protective sheet may be formed from this film, and the other resin layers may not be formed from this film. In such a case, the resin used for the other resin layer is not particularly limited as long as it is a thermoplastic resin, but examples thereof include polycarbonate resin, polyester resin, and mixtures thereof.

The following examples and comparative examples are provided, but the present invention is not limited in any way by these.

The evaluation and measurement methods are as follows:

(1) Low-temperature fusion properties Using a compression molding machine "NF-37" (manufactured by Shinto Metal Industries Co., Ltd.), the films (size 100 mm x 300 mm) obtained in each example and comparative example were stacked and sandwiched between stainless steel plates, and the pressing pressure was 1.5 MPa, the pressing time was 5 minutes, and the subsequent cooling was performed for about 5 minutes until the temperature dropped to room temperature, and heat fusion was performed. After that, the fused film was removed from the stainless steel plate, and the films were peeled off from each other to confirm whether the film was non-peeling (whether the material was broken). The heating temperature during pressing was increased in 10°C increments, and those that were non-peeling (those that had material destruction) were judged to be fused, and the minimum temperature at which they were fused (material destruction temperature) was obtained. This material destruction temperature is the temperature at which the film is properly fused, and the lower the temperature, the better the low-temperature fusion properties.

(2) Solvent resistance In a room temperature environment, a piece of film from each Example and Comparative Example was immersed in a petri dish containing a solvent for 1 minute, and the appearance was visually confirmed and evaluated according to the following evaluation criteria. This test was carried out using ethyl acetate, toluene, and methyl ethyl ketone (MEK) as the solvent. Those rated "OK" are presumed to be at a level that does not pose a problem when used as an actual product.
OK: Becomes cloudy within 30 seconds to 1 minute NG: Dissolves within 30 seconds

(3) Glass transition temperature (Tg)
For each resin used, a viscoelasticity spectrometer "DVA-200" (manufactured by IT Measurement & Control Co., Ltd.) was used to measure the temperature dispersion of dynamic viscoelasticity in accordance with JIS K7244-4: 1999, at a strain of 0.07%, a frequency of 1 Hz, a heating rate of 3°C/min, and in a tensile mode. The peak top temperature of the loss modulus was determined as the glass transition temperature.

(4) Storage Modulus A test piece of 4 mm x 25 mm (thickness 100 μm) was cut out from the film obtained in each Example and Comparative Example to obtain a measurement sample. The measurement sample was used to measure the tensile storage modulus at 100°C in MD in accordance with JIS K7244-4:1999 using a viscoelasticity spectrometer "DVA-200 (manufactured by IT Measurement & Control Co., Ltd.)" at a frequency of 1 Hz, a strain of 0.07%, and a temperature rise rate of 3°C/min from -100 to 180°C.

(5) Thermal expansion/contraction rate Test pieces measuring 120 mm x 120 mm were cut out from the films obtained in each Example and Comparative Example, a standard line measuring 100 mm x 100 mm was marked in the center of the obtained test pieces, and the test pieces were heat-treated in an oven at 110°C or 140°C for 10 minutes, and the thermal expansion/contraction rate was calculated using the following formula from the standard line spacing in MD and TD before and after the treatment. The standard line spacing was measured at the center of the standard line.
Heat expansion rate (%) = [standard line spacing after heat treatment (mm) - 100 (mm)] / 100 (mm) x 100
The closer the thermal expansion/contraction rate of a film is to 0, the more excellent its heat resistance is.

The raw materials used in the examples and comparative examples are as follows.
(Polyester resin)
PCTG: A copolymer polyester resin (amorphous) of a dicarboxylic acid consisting of terephthalic acid and a dihydroxy compound consisting of ethylene glycol (EG), 1,4-cyclohexanedimethanol (1,4-CHDM), and 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), dihydroxy compound (EG = 8 mol%, 1,4-CHDM = 74 mol%, TMCD = 18 mol%), recycled polyester resin recycled from scraps, glass transition temperature (Tg) = 100°C
PETG: A copolymer polyester resin (amorphous) of a dicarboxylic acid component consisting of terephthalic acid and a dihydroxy compound consisting of EG and 1,4-CHDM, dihydroxy compound (EG = 70 mol%, 1,4-CHDM = 30 mol%), glass transition temperature (Tg) = 78°C
(Polycarbonate resin)
PC1: "Caliber 301-4" manufactured by Sumika Polycarbonate Co., Ltd., melt flow rate (300°C, 1.2 kgf) = 4 g/min (catalog value), glass transition temperature (Tg) = 150°C
PC2: Bisphenol A homopolycarbonate, melt flow rate (300°C, 1.2 kgf) = 20 g/min, recycled polycarbonate resin recycled from scraps, glass transition temperature (Tg) = 150°C
(Coloring Agent)
Titanium oxide (lubricant)
Polyethylene glycol (number average molecular weight 3000): sodium dodecylbenzenesulfonate = 2:1 (mass ratio)
(Impact modifier)
Impact resistance improver: Core-shell type elastomer, Mitsubishi Chemical Corporation's "Metablen S-2001", Core: Silicone-acrylic composite rubber (antioxidant)
Antioxidant: phenol-based antioxidant (dibutylhydroxytoluene (BHT): phosphorus-based antioxidant (trisstearyl phosphite) = 1:1 (mass ratio)

[Examples 1 to 3, Comparative Examples 1, 3, and 4]
According to the formulation shown in Table 1, the resin or the resin and additives were charged into a twin-screw extruder and kneaded, and the resin composition was extruded at 270° C. using the twin-screw extruder to obtain a film having a thickness of 100 μm.

[Comparative Example 2]
The same procedure as in Example 1 was repeated except that the composition was changed as shown in Table 1 and the extrusion temperature was changed from 270°C to 250°C.

As shown in Table 1, the resin compositions of Examples 1 to 3 contained polyester resin (A-1) that contained structural units derived from a chain dihydroxy compound and had a glass transition temperature of 90°C or higher, and thus had good low-temperature fusion properties and also good solvent resistance. Furthermore, by containing polycarbonate resin (B) in addition to polyester resin (A-1), the storage modulus at 100°C was high and heat resistance was excellent, so that the thermal expansion rate when heated to 110°C and 140°C was a low value close to 0%. Therefore, it can be understood that when using this resin composition to manufacture cards or passports, the size change during thermal processing is small, workability is high, and the occurrence of warping can be suppressed.

In contrast, the resin composition of Comparative Example 1 contained the polycarbonate resin (B) but did not contain the polyester resin (A-1), and therefore had good heat resistance, but could not achieve good low-temperature fusion property and solvent resistance. Also, the resin composition of Comparative Example 2 did not contain either the polycarbonate resin (B) or the polyester resin (A-1), and therefore could not achieve good heat resistance and solvent resistance.
In addition, Comparative Example 2 is excellent in low-temperature fusion properties by using polyester resin (A-2) having a glass transition temperature of less than 90°C. When the films of Comparative Example 2 are fused to each other at a low temperature, size change is suppressed and workability is good, but only cards or passports with low heat resistance are obtained. On the other hand, when the film of Comparative Example 2 is fused to a film with high heat resistance (e.g., a polycarbonate film) to increase the heat resistance of the card or passport, it is necessary to increase the fusion temperature. However, if the fusion temperature is high, size change occurs in the film of Comparative Example 2, workability is reduced, and warping occurs. In other words, it can be understood that when the resin composition of Comparative Example 2 is used, it is difficult to achieve the effects of the present invention even when combined with other films.

The resin compositions of Comparative Examples 3 and 4 contain polyester resin (A) and polycarbonate resin (B), but polyester resin (A-1), which contains structural units derived from a chain dihydroxy compound and has a glass transition temperature of 90°C or higher, was not used as polyester resin (A). As a result, the solvent resistance, or the solvent resistance and heat resistance, were not good.

1 Laser marking sheet 2 Core sheet 3 Hinge sheet 4 Protective sheet 20A, 20B, 20C Card 10A, 10B, 10C Passport

Claims (10)

A resin composition containing a resin component including a polyester resin (A-1) and a polycarbonate resin (B),
the polyester resin (A-1) contains structural units derived from a chain dihydroxy compound and an alicyclic dihydroxy compound , and the proportion of the structural units derived from the alicyclic dihydroxy compound is 90 mol % or more in a total of 100 mol % of the structural units derived from the chain dihydroxy compound and the structural units derived from the alicyclic dihydroxy compound;
The polyester resin (A-1) has a glass transition temperature of 90° C. or higher. The resin composition for cards or passports according to claim 1, which has a storage modulus at 100° C. of 1×10 ⁹ Pa or more. The resin composition for cards or passports according to claim 1 or 2 , wherein the polyester resin (A-1) contains a structural unit derived from ethylene glycol and a structural unit derived from cyclohexanedimethanol. The resin composition for cards or passports according to any one of claims 1 to 3 , wherein the polyester resin (A-1) contains a structural unit derived from ethylene glycol, a structural unit derived from cyclohexanedimethanol, and a structural unit derived from tetramethylcyclobutanediol. The resin composition for cards or passports according to any one of claims 1 to 4 , wherein a content ratio ((A-1)/(B)) of the polyester resin (A-1) to the polycarbonate resin (B) is 3/97 or more and 97/3 or less in mass ratio. The resin composition for cards or passports according to any one of claims 1 to 5 , which contains recycled raw materials. A card or passport film comprising the resin composition according to any one of claims 1 to 6 . A card comprising the film of claim 7 . A passport comprising the film of claim 7 . A method for producing a resin composition according to any one of claims 1 to 6 , comprising blending a recycled raw material into the resin composition.