Resin film for cards or passports, inlet sheets, film laminates, cards and passports

Abstract

We provide a resin film for cards or passports that offers both transparency and flexibility. [Solution] A resin film for cards or passports comprising a polycarbonate resin (A) containing a structural unit (A1) derived from a dihydroxy compound having a part of its structure represented by the following formula (1), and an impact-resistant agent, wherein the impact-resistant agent is a core-shell type graft copolymer with an average primary particle size of 300 nm or less, and is a multilayer polymer composed of a core made of saturated or unsaturated rubber components and a shell made of monomer components including a (meth)acrylic compound, and the proportion of long relaxations when the sum of short relaxations and long relaxations measured by pulsed NMR of the resin film is normalized to 1 is 0.28 or less. JPEG2026101552000010.jpg1547 However, this excludes cases where the part represented by formula (1) is part of -CH2-OH.

Description

[Technical Field]

[0001] The present invention relates to a resin film for cards or passports, an inlet sheet having the film, a film laminate, a card, and a passport. [Background technology]

[0002] Conventionally, resin films mainly composed of polyester resin or polycarbonate resin have been widely used for cards or passports. Card or passport films are required to have good mechanical properties, particularly good bending resistance. Conventionally, in resin molded articles, resin sheets, etc., it has been proposed to use impact resistance modifiers in combination to improve bending resistance (for example, Patent Document 1). Furthermore, transparency is often required for the outermost layer of card sheets. Therefore, in recent years, there has been a growing demand for materials that offer both bend resistance and transparency for card applications. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2000-169684 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, while the addition of impact-resistant modifiers improves bending resistance, depending on the type of impact-resistant modifier used, the film's transparency may be insufficient.

[0005] Therefore, the objective of the present invention is to provide a film for cards or passports that can achieve both bend resistance and transparency, which are conflicting properties. [Means for solving the problem]

[0006] As a result of diligent research, the inventors have found that a resin composition containing a specific polycarbonate resin and an impact-resistant modifier having a specific configuration, and a resin film using the same, can achieve both flexibility and transparency, making it suitable as a film for cards or passports, and have completed the present invention as described below. That is, the present invention provides the following [1] to

[14] .

[0007] [1] A resin film containing a polycarbonate resin (A) having a structural unit (A1) derived from a dihydroxy compound having a part of the structure represented by the following formula (1), and an impact-resistant modifier, wherein the average primary particle size of the impact-resistant modifier is 300 nm or less, and is a core-shell type graft copolymer, which is a multilayer polymer composed of a core made of saturated or unsaturated rubber components and a shell made of monomer components including a (meth)acrylic compound, wherein the proportion of long relaxations when the sum of short relaxations and long relaxations measured by pulsed NMR of the resin film is normalized to 1 is 0.28 or less, for use as a card or passport resin film. [ka] However, this excludes cases where the part represented by formula (1) is part of -CH2-OH. [2] The resin film for cards or passports according to [1] above, wherein the core contains butadiene rubber. [3] The resin film for cards or passports as described in [1] or [2] above, wherein the number of times the resin film is folded is 25,000 or more. [4] A resin film for cards or passports as described in any of [1] to [3] above, wherein the film haze of the resin film is 25% or less. [5] A resin film for cards or passports as described in any of [1] to [4] above, wherein the tensile elongation at break of the resin film is 145% or more for both MD and TD. [6] A resin film for cards or passports according to any of [1] to [5] above, wherein the content of the impact-resistant improving agent is 1% by mass or more and 30% by mass or less. [7] A resin film for cards or passports according to any of [1] to [6] above, wherein the polycarbonate resin (A) has a mass-average molecular weight of 10,000 or more and 100,000 or less. [8] A resin film for cards or passports, as described in any of [1] to [7] above, used for the core sheet. [9] A resin film for cards or passports as described in any of [1] to [8] above, having a thickness of 20 μm or more and 500 μm or less.

[10] An inlet sheet equipped with a resin film for cards or passports as described in any of [1] to [9] above.

[11] A film laminate comprising a resin film for a card or passport as described in any of [1] to [9] above, and another resin film laminated on the resin film.

[12] A resin composition for cards or passports comprising a polycarbonate resin (A) containing a structural unit (A1) derived from a dihydroxy compound having a part of its structure represented by the following formula (1), wherein the impact-resistant agent is a core-shell type graft copolymer having an average primary particle size of 300 nm or less, and is a multilayer polymer composed of a core made of saturated or unsaturated rubber components and a shell made of monomer components including a (meth)acrylic compound, and a resin film molded from the resin composition is subjected to pulsed NMR measurement, and the proportion of long relaxations when the sum of short relaxations and long relaxations is normalized to 1 is 0.28 or less. [ka] However, this excludes cases where the part represented by formula (1) is part of -CH2-OH.

[13] A card comprising any one of the following: a resin film for cards or passports as described in any one of items [1] to [9] above, an inlet sheet as described in

[10] above, a film laminate as described in

[11] above, and a resin composition as described in

[12] above. A passport comprising any one of the resin films for cards or passports according to any one of [1] to [9] above, the inlet sheet according to

[10] above, the film laminate according to

[11] above, and the resin composition according to

[12] above.

Advantages of the Invention

[0008] According to the present invention, there is provided a resin film for cards or passports capable of achieving both bending resistance and transparency.

Brief Description of the Drawings

[0009] [Figure 1] It is a schematic cross-sectional view showing an example of an IC sheet.

Modes for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail with reference to embodiments. However, the present invention is not limited to the embodiments described below. In the following description, the terms "film" and "sheet" are not clearly distinguished, and the term "film" includes "sheet", and the term "sheet" includes "film".

[0011] <Resin Film for Cards or Passports> The resin film for cards or passports of the present invention (hereinafter sometimes simply referred to as "the present film") contains a polycarbonate resin and an impact modifier.

[0012] (Polycarbonate Resin (A)) As the polycarbonate resin used in the present film, there can be mentioned a polycarbonate resin (hereinafter sometimes referred to as polycarbonate resin (A)) containing a structural unit derived from a dihydroxy compound having a site represented by the following formula (1) in a part of its structure. The polycarbonate resin (A) may be used alone or in combination of two or more.

[0013] As described above, the polycarbonate resin (A) used is a polycarbonate resin that contains a structural unit derived from a dihydroxy compound having a part of its structure represented by the following formula (1) (hereinafter sometimes referred to as structural unit (A1)). Polycarbonate resin (A) containing structural unit (A1) can be manufactured from plant-derived raw materials, thereby reducing the environmental impact.

[0014] [ka] However, this excludes cases where the part represented by formula (1) is part of -CH2-OH. That is, the dihydroxy compound refers to one that contains two hydroxyl groups and at least the part represented by formula (1).

[0015] Dihydroxy compounds having a moiety represented by formula (1) as part of their structure are not particularly limited as long as they have the structure represented by formula (1) in their molecule, but specifically include 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene Examples include compounds having aromatic groups in the side chain and ether groups bonded to the aromatic groups in the main chain, such as 9,9-(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, and 9,9-(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene, as well as dihydroxy compounds having a cyclic ether structure, such as dihydroxy compounds represented by the following formula (2) and spiroglycols represented by the following formula (3).

[0016] Among the above, dihydroxy compounds having a cyclic ether structure are preferred, and anhydrous sugar alcohols represented by formula (2) are particularly preferred. More specifically, dihydroxy compounds represented by formula (2) include isosorbide, isomannide, and isoidette, which are stereoisomers of each other. In addition, dihydroxy compounds represented by the following formula (3) include 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane (common name: spiroglycol), 3,9-bis(1,1-diethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, and 3,9-bis(1,1-dipropyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane. These can be used individually, or two or more can be used in combination.

[0017] [ka] [ka] In formula (3), R1 to R4 are each independently alkyl groups having 1 to 3 carbon atoms.

[0018] The dihydroxy compound represented by formula (2) is an ether diol that can be produced from carbohydrates using plant-derived materials as raw materials. In particular, isosorbide can be produced inexpensively by hydrogenating and then dehydrating D-glucose obtained from starch, and it is readily available as a resource. For these reasons, isosorbide is the most preferred choice.

[0019] A polycarbonate resin containing structural unit (A1) may further contain structural units other than structural unit (A1) as structural units derived from dihydroxy compounds. For example, it is preferable to contain structural units derived from at least one dihydroxy compound selected from aliphatic dihydroxy compounds and alicyclic dihydroxy compounds (hereinafter sometimes referred to as structural unit (A2)).

[0020] The aliphatic dihydroxy compounds used in polycarbonate resins containing structural unit (A1) are not particularly limited in terms of the number of carbon atoms, but preferably aliphatic dihydroxy compounds having about 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms. Specifically, examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol, and the like. Preferably, at least one selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol is used, and more preferably, at least one selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol is used. In addition, structural units derived from aliphatic dihydroxy compounds can be used, for example, those described in International Publication No. 2004 / 111106.

[0021] The structural unit (A1) derived from the alicyclic dihydroxy compound used in the polycarbonate resin preferably includes at least one of a five-membered ring structure or a six-membered ring structure, and the six-membered ring structure may be fixed in a chair-like or boat-like shape by covalent bonds. By including structural units derived from alicyclic dihydroxy compounds of these structures, the heat resistance of the resulting polycarbonate resin can be improved. The number of carbon atoms in the alicyclic dihydroxy compound is, for example, 5 to 70, preferably 6 to 50, and more preferably 8 to 30. The above alicyclic dihydroxy compounds are preferably at least one selected from cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, and pentacyclopentadecanedimethanol. From the viewpoint of economy and heat resistance, cyclohexanedimethanol or tricyclodecanedimethanol is more preferred, and cyclohexanedimethanol is even more preferred. Of the cyclohexanedimethanol, 1,4-cyclohexanedimethanol is particularly preferred because it is readily available industrially. Furthermore, structural units derived from alicyclic dihydroxy compounds, as described in International Publication No. 2007 / 148604, can also be used.

[0022] In polycarbonate resins containing structural unit (A1), the content of structural unit (A1) is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 45 mol% or more, and preferably 75 mol% or less, more preferably 70 mol% or less, and even more preferably 65 mol% or less, of the structural units derived from dihydroxy compounds. By keeping it within this range, discoloration caused by the carbonate structure and discoloration caused by trace amounts of impurities due to the use of plant resource materials can be effectively suppressed. Furthermore, it tends to be possible to achieve a suitable balance of physical properties such as moldability, mechanical strength, and heat resistance, which is difficult to achieve with polycarbonate resins composed only of structural unit (A1). On the other hand, the content of structural unit (A2) in the polycarbonate resin containing structural unit (A1) is preferably 25 mol% or more, more preferably 30 mol% or more, even more preferably 35 mol% or more, and also preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 55 mol% or less, among the structural units derived from the dihydroxy compound.

[0023] A polycarbonate resin containing structural unit (A1) preferably consists of structural unit (A1) and structural unit (A2) derived from a dihydroxy compound, but may also contain structural units derived from other dihydroxy compounds. Specifically, this may involve copolymerizing a small amount of aromatic ring-containing dihydroxy compound, such as bisphenol, represented by 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A). Using aromatic ring-containing dihydroxy compounds is expected to efficiently improve heat resistance and moldability, but if added in large quantities, it tends to cause problems with weather resistance, so it is best to use it in an amount that does not cause problems with weather resistance. Examples of aromatic ring-containing dihydroxy compounds other than bisphenol A include 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.

[0024] Polycarbonate resins containing the above-described structural unit (A1) can be produced by commonly used polymerization methods, including the phosgene method and the transesterification method involving reaction with diester carbonate. Among these, the transesterification method is preferred, in which a dihydroxy compound having a part of its structure represented by formula (1) and other dihydroxy compounds are reacted with diester carbonate in the presence of a polymerization catalyst. The transesterification method is a polymerization method in which a dihydroxy compound, diester carbonate, a basic catalyst, and an acidic substance to neutralize the catalyst are mixed and a transesterification reaction is carried out. Specific examples of diester carbonates are as described above, with diphenyl carbonate being particularly preferred.

[0025] The mass-average molecular weight of polycarbonate resin (A) is typically 10,000 or more, preferably 30,000 or more, more preferably 38,000 or more, and even more preferably 40,000 or more, while also typically in the range of 100,000 or less, preferably 80,000 or less, considering the balance between mechanical properties and moldability. The mass-average molecular weight can be measured using gel permeation chromatography (GPC) with polystyrene as the standard substance. However, the polycarbonate resin (A) may also have a high molecular weight from the viewpoint of impact resistance, dynamic bending durability, and heat resistance such as load deflection temperature. From this viewpoint, it is preferable that the mass average molecular weight of the polycarbonate resin (A) be 37,000 or more, more preferably 40,000 or more, even more preferably 45,000 or more, even more preferably 50,000 or more, even more preferably 55,000 or more, even more preferably 58,000 or more, even more preferably 60,000 or more, and particularly preferably 63,000 or more. Furthermore, the mass-average molecular weight can be measured using gel permeation chromatography (GPC) with polystyrene as the standard substance.

[0026] Furthermore, the viscosity-average molecular weight of the polycarbonate resin (A) is typically 12,000 or more, preferably 15,000 or more, more preferably 20,000 or more, even more preferably 22,000 or more, even more preferably 26,000 or more, particularly preferably 29,000 or more, and also typically in the range of 50,000 or less, preferably 45,000 or less, more preferably 40,000 or less, and even more preferably 35,000 or less, based on a balance between mechanical properties and moldability.

[0027] The melt flow rate (300°C, 1.2 kgf) of polycarbonate resin (A) is preferably 1 g / 10 min or more, more preferably 3 g / 10 min or more, even more preferably 5 g / 10 min or more, even more preferably 6 g / 10 min or more, and also preferably 50 g / 10 min or less, more preferably 40 g / 10 min or less, even more preferably 30 g / 10 min or less, even more preferably 25 g / 10 min or less, and even more preferably 20 g / 10 min or less. The melt flow rate of polycarbonate resin (A) can be measured in accordance with ISO 1133.

[0028] The glass transition temperature of the polycarbonate resin (A) is, for example, 70°C or higher, preferably 80°C or higher, more preferably 85°C or higher, even more preferably 90°C or higher, and also, for example, 140°C or lower, preferably 130°C or lower, more preferably 125°C or lower, and even more preferably 120°C or lower. Furthermore, it is generally preferable that the polycarbonate resin (A) has a single glass transition temperature. By setting the glass transition temperature above the lower limit mentioned above, it becomes easier to impart appropriate heat resistance and reduce dimensional changes when manufacturing cards or passports. Furthermore, setting it below the upper limit also improves moldability and other properties. The glass transition temperature can be obtained by using a viscoelastic spectrometer and performing dynamic viscoelastic temperature dispersion measurements in tensile mode with a strain of 0.07%, a frequency of 1 Hz, and a heating rate of 3°C / min, in accordance with JIS K7244-4:1999, to determine the temperature of the peak of the loss modulus.

[0029] As described above, this film uses polycarbonate resin (A) as the resin, but it may be used alone or in combination with other resins. As such, it is good to use a commonly used known resin, but it is also good to use a resin that is easily compatible with polycarbonate resin, and it is preferable to use a thermoplastic resin, for example, it is preferable to use a polycarbonate resin other than polycarbonate resin (A) or a polyester resin, and among these, polyester resin is more preferable. Details of the polyester resin used in combination with polycarbonate resin will be described below. The resin constituting this film preferably contains polycarbonate resin (A) as its main component, and the content of polycarbonate resin (A) is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass, based on the total amount of resin constituting this film. The resin constituting this film may be a thermoplastic resin, but it may also contain components other than thermoplastic resins.

[0030] (Polyester resin) Examples of polyester resins include polyesters obtained by polycondensation of dicarboxylic acid and dihydroxy compounds. Dicarboxylic acid derivatives such as esters and acid halides may also be used as the dicarboxylic acid in the synthesis of the polyester resin. Using a polyester resin results in good low-temperature fusion properties, making it easier to adhere this film to other films by heat fusion at relatively low temperatures. It also facilitates improvements in processability.

[0031] From the viewpoint of heat resistance, aromatic dicarboxylic acids are preferred as the dicarboxylic acids used to obtain polyester resins, and therefore, it is preferable that the polyester resin contains structural units derived from aromatic dicarboxylic acids. There are no particular restrictions on the aromatic dicarboxylic acid, and examples 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, anthracenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5-sulfoisophthalic acid, sodium 3-sulfoisophthalate, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, etc. Among these, terephthalic acid and isophthalic acid are preferred, and terephthalic acid is more preferred. Aromatic dicarboxylic acids may be used individually or in combination of two or more.

[0032] It is even more preferable that the structural units derived from aromatic dicarboxylic acids are present in the polyester resin at a concentration of, for example, 60 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more. Furthermore, there is no particular upper limit, and it is acceptable as long as it is 100 mol% or less, but most preferably 100 mol%.

[0033] Furthermore, the polyester resin may contain a small amount of structural units derived from aliphatic dicarboxylic acids (usually 40 mol% or less, for example 30 mol% or less, preferably 20 mol% or less) in addition to structural units derived from aromatic dicarboxylic acids. There are no particular restrictions on the aliphatic dicarboxylic acids, and examples include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecanedionic acid, dimer acid, 1,3 or 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and 4,4'-dicyclohexyldicarboxylic acid. The aliphatic dicarboxylic acid may be used alone or in combination of two or more.

[0034] The polyester resin preferably contains structural units derived from chain-like dihydroxy compounds. The inclusion of these structural units in the polyester resin tends to result in good low-temperature fusion properties for the film. The chain-like dihydroxy compounds used in polyester resins may be linear or have a branched structure. Specific examples of chain-like dihydroxy compounds include chain-like dihydroxy compounds with approximately 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, as well as polyglycols such as polytetramethylene ether glycol, polypropylene glycol, and polyethylene glycol. Among these, chain-type dihydroxy compounds having 2 to 12 carbon atoms are preferred, and more preferably one or more selected from ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, with ethylene glycol (EG) being particularly preferred. The chain-type dihydroxy compounds may be used individually or in combination of two or more.

[0035] The polyester resin is preferably a copolymer polyester resin obtained by using two or more dihydroxy compounds as copolymer components. Specifically, it is preferable to use alicyclic dihydroxy compounds in addition to chain-type dihydroxy compounds as the dihydroxy compounds used to obtain the polyester resin. Therefore, it is preferable that the polyester resin has structural units derived from alicyclic dihydroxy compounds in addition to structural units derived from chain-type dihydroxy compounds. Using alicyclic dihydroxy compounds tends to result in good heat resistance, solvent resistance, etc. Specific examples of alicyclic dihydroxy compounds include tetramethylcyclobutanediol, cyclohexanedimethanol (CHDM), tricyclodecanedimethanol, adamantanediol, and pentacyclopentadecanedimethanol. Among these, tetramethylcyclobutanediol and cyclohexanedimethanol are preferred. Of the cyclohexanedimethanol compounds available, there are 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol, but 1,4-cyclohexanedimethanol is preferred due to its easy industrial availability. Generally, 2,2,4,4-tetramethyl-1,3-cyclobutanediol is used as the tetramethylcyclobutanediol. The alicyclic dihydroxy compound may be used alone or in combination of two or more. At least cyclohexanedimethanol is preferred as the alicyclic dihydroxy compound, and from the viewpoint of flexibility, tetramethylcyclobutanediol and cyclohexanedimethanol are preferred in combination.

[0036] In polyester resins, the proportion of structural units derived from alicyclic dihydroxy compounds is, for example, 5 mol% or more, preferably 15 mol% or more, more preferably 20 mol% or more, and also, for example, 99 mol% or less, preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 80 mol% or less, out of a total of 100 mol% of structural units derived from chain-type dihydroxy compounds. In polyester resins, particularly in terms of heat resistance such as storage modulus and thermal expansion coefficient under high-temperature environments, and solvent resistance, the proportion of structural units derived from alicyclic dihydroxy compounds is preferably more than 65 mol%, more preferably 70 mol% or more, even more preferably 80 mol% or more, and even more preferably 90 mol% or more, out of a total of 100 mol% of structural units derived from chain-type dihydroxy compounds and structural units derived from alicyclic dihydroxy compounds. Furthermore, in terms of low-temperature fusion properties, the proportion of structural units derived from alicyclic dihydroxy compounds is preferably 65 mol% or less, more preferably 55 mol% or less, even more preferably 45 mol% or less, and even more preferably 40 mol% or less, out of a total of 100 mol% of structural units derived from chain-type dihydroxy compounds and structural units derived from alicyclic dihydroxy compounds.

[0037] As the dihydroxy compound used in the polyester resin, dihydroxy compounds other than chain-type dihydroxy compounds and alicyclic dihydroxy compounds (also referred to as "other dihydroxy compounds") may be used, as long as they do not impair the effects of the present invention. In the polyester resin, the content of structural units derived from other dihydroxy compounds is, for example, 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, and most preferably 0 mol% per 100 moles of structural units derived from dihydroxy compounds in the polyester resin. Other dihydroxy compounds include p-xylenediol, 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.

[0038] Among the above, the polyester resin preferably contains structural units derived from ethylene glycol and structural units derived from cyclohexanedimethanol, from the viewpoint of low-temperature fusion properties, heat resistance, and solvent resistance, and also preferably contains structural units derived from ethylene glycol, structural units derived from cyclohexanedimethanol, and structural units derived from tetramethylcyclobutanediol.

[0039] The polyester resin is preferably amorphous polyester. Using amorphous polyester tends to improve the adhesion of this film to other components such as resin films. The amorphous polyester can be any polyester that is substantially non-crystalline. Examples of substantially non-crystalline polyesters (including those with low crystallinity) include polyesters that do not show a clear crystallization peak when heated by differential scanning calorimeter (DSC), polyesters that have crystalline properties but have a slow crystallization rate and do not become highly crystalline when molded by extrusion or other methods, and polyesters that have crystalline properties but have a low heat of crystallization (ΔHm) of 10 J / g or less when heated by differential scanning calorimeter (DSC). In other words, amorphous polyester in this invention also includes "crystalline polyester that is in a non-crystalline state."

[0040] [Layer structure of the film] This film may have a single-layer structure or a multi-layer structure. In the following description, a multi-layer film may be referred to as a laminated film. In the case of a multi-layer structure, each layer constituting the laminated film contains resin, and the details of the resin constituting each layer should be as described above. Therefore, it is preferable that the resins constituting each layer are thermoplastic resins, and it is preferable to use either polycarbonate resin or polyester resin, with the use of polycarbonate resin (A) being more preferable. In other words, it is preferable that the resins constituting each layer contain polycarbonate resin (A). The resins constituting each layer may be used individually or as a mixture of two or more types.

[0041] When using polycarbonate resin (A) in each layer, it may be used alone or mixed with resins other than polycarbonate resin (A). While it is preferable to use a commonly used, known resin other than polycarbonate resin (A), it is preferable to use a resin that is easily compatible with polycarbonate resin (A). For example, it is preferable to use a polycarbonate resin other than polycarbonate resin (A) or a polyester resin, with polyester resin being more preferable. Details of the polyester resin used in combination with polycarbonate resin (A) are as described above. The resin constituting each layer of this film preferably contains polycarbonate resin (A) as the main component, and the amount of polycarbonate resin (A) is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass, based on the total amount of resin constituting each layer.

[0042] The layer structure of the laminated film is not particularly limited and may consist of two or more layers, but it is preferable to have a surface layer / middle layer / surface layer structure in which surface layers are provided on both sides of the middle layer. When it has a surface layer / middle layer / surface layer structure, it may consist of three layers, but an adhesive layer or the like may be provided between the surface layer and the middle layer as appropriate, or two or more middle layers may be provided, resulting in a structure of three or more layers.

[0043] [Impact-resistant additive] This film contains an impact-resistant modifier as described above. Further inclusion of the impact-resistant modifier mitigates the effects of external impacts such as bending and impact during actual use, making it easier to maintain good bending resistance. Furthermore, it prevents the decrease in softening and fluidity during heating, which can occur due to the use of specific resins such as polycarbonate resin (A), making it easier to maintain good processability. In this specification, the impact-resistant modifier is not considered to be incorporated into the resin.

[0044] As the impact-resistant modifier, a core-shell type elastomer with an average primary particle size of 300 nm or less is used. The impact-resistant modifier may be used alone or in combination of two or more types. By using a core-shell type elastomer, impact resistance is further improved, and bending resistance is further enhanced.

[0045] Core-shell elastomers consist of an innermost layer (i.e., the core) and one or more outer layers (i.e., the shell) covering it. Core-shell elastomers are core-shell graft copolymers. Core-shell type graft copolymers use a polymer component called a rubber component as the core. In core-shell type graft copolymers, the polymer component constituting the core and monomer components copolymerizable with this polymer component are graft copolymerized as the shell. The transparency of the film can be appropriately adjusted by appropriately selecting the materials of the core-shell type graft copolymer; for example, the transparency can be appropriately adjusted by the type of rubber component of the core. The method for producing the core-shell type graft copolymer may be any of the following methods: bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. The copolymerization method may be single-stage grafting or multi-stage grafting. However, commercially available core-shell type elastomers can usually be used as is. Examples of commercially available core-shell type elastomers will be given later.

[0046] Specific examples of polymer components forming the core include saturated or unsaturated rubber components, specifically butadiene-based rubbers such as polybutadiene and styrene-butadiene copolymers, isoprene-based rubbers, acrylic-based 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 copolymer, ethylene-butene copolymer, and ethylene-octene copolymer, ethylene-acrylic rubber, and fluororubber. These may be used individually or in combination of two or more. Among these, at least one selected from butadiene-based rubber, acrylic rubber, butadiene-acrylic composite rubber, silicone-based rubber, and silicone-acrylic composite rubber is preferred in terms of mechanical properties and surface appearance. Furthermore, it is more preferable that the core contains butadiene rubber, and more specifically, at least one selected from butadiene rubber and butadiene-acrylic composite rubber is more preferable.

[0047] Specific examples of monomer components that can be graft copolymerized with the core polymer component that constitutes the shell include (meth)acrylic compounds. Examples of (meth)acrylic compounds include (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, and epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate. Specific examples of (meth)acrylic acid ester compounds include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate. Alkyl (meth)acrylates with approximately 1 to 8 carbon atoms in the alkyl group are preferred, with methyl (meth)acrylate and ethyl (meth)acrylate being preferred due to their relatively easy availability, methyl (meth)acrylate being more preferred, and methyl methacrylate being even more preferred. Note that "(meth)acrylic" is a general term encompassing both "acrylic" and "methacrylic". (Meth)acrylic compounds may be used individually or in combination of two or more.

[0048] From the viewpoint of transparency, the monomer components constituting the shell are preferably (meth)acrylic compounds alone. However, monomer components other than (meth)acrylic compounds, such as aromatic vinyl compounds; vinyl cyanide compounds; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; and α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, or their anhydrides (e.g., maleic anhydride), may be used in combination with (meth)acrylic compounds, as long as they do not impair the effects of the present invention. These monomer components other than (meth)acrylic compounds may be used individually or in combination of two or more. Among these, aromatic vinyl compounds and vinyl cyanide compounds are preferred in terms of mechanical properties and surface appearance, and aromatic vinyl compounds are more preferred.

[0049] Specific examples of aromatic vinyl compounds include styrene, α-methylstyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, or halogenated styrene, with styrene or α-methylstyrene being more preferred.

[0050] As the core-shell type elastomer, a core-shell type graft copolymer is particularly preferred, comprising a core consisting of at least one polymer component selected from butadiene rubber, acrylic rubber, silicone rubber, butadiene rubber-acrylic composite rubber, and silicone-acrylic composite rubber, and a shell formed by graft copolymerizing a (meth)acrylic compound such as a (meth)acrylic acid ester around the core. The content of the polymer component in the core of the core-shell type graft copolymer is preferably 40% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0051] Furthermore, the content of (meth)acrylic compounds (especially (meth)acrylic acid esters) 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, even more preferably 70% by mass or more, and most preferably 100% by mass. In other words, as described above, it is preferable to use (meth)acrylic compounds alone in the shell, but monomer components other than (meth)acrylic compounds may be used as long as they do not impair the effects of the present invention.

[0052] Preferred specific examples of core-shell type 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., and methyl methacrylate-(butadiene-acrylic composite rubber) copolymer, etc. Among these, methyl methacrylate-butadiene copolymer or methyl methacrylate-(butadiene-acrylic composite rubber) copolymer is preferred.

[0053] The average primary particle size of the impact-resistant additive must be 300 nm or less from the viewpoint of achieving both bending resistance and transparency. From the viewpoint of transparency, the average primary particle size is preferably 250 nm or less, more preferably 200 nm or less, particularly preferably 150 nm or less, and most preferably 120 nm or less. On the other hand, regarding the lower limit of the average primary particle size, from the viewpoint of ensuring impact resistance, it is preferably 50 nm or more, and more preferably 80 nm or more. Furthermore, the transparency of this film can be appropriately adjusted by the average primary particle size of the impact-resistant additive.

[0054] The average primary particle size is determined by diluting the sample (impact-resistant modifier) ​​with deionized water to a concentration of approximately 3%, and measuring the particle size using a particle size analyzer, such as the CHDF2000 model manufactured by MATEC Corporation of the United States. The median diameter is used as the average particle size.

[0055] Measurements can be performed under the following standard conditions recommended by MATEC. Cartridge: Dedicated capillary cartridge for particle separation (product name: C-202) Carrier fluid: Dedicated carrier fluid (product name: 2XGR500), pH of carrier fluid: nearly neutral Carrier fluid flow rate: 1.4 ml / min, carrier fluid pressure: approximately 4,000 psi (2,6 (00kPa), measurement temperature: 35℃, sample volume: 0.1ml. Furthermore, as a standard particle size material, monodisperse polystyrene with known particle size manufactured by DUKE, Inc. in the United States is used. Therefore, 12 types of particles with particle sizes ranging from 40 to 800 nm are used.

[0056] The impact-resistant agent content in the entire film is preferably 1% by mass or more and 30% by mass or less, based on the total amount of the film. A content of 1% by mass or more of the impact-resistant agent moderately mitigates the effects of external impacts, making it easier to improve bending resistance and other properties. Furthermore, it helps prevent a decrease in softening and fluidity during film heating, which can occur due to the type of resin used, thus maintaining good processability. On the other hand, by limiting the content to 30% by mass or less, the film can achieve effects commensurate with its content. Furthermore, it prevents a decrease in various physical properties of the film, such as heat resistance, and prevents the film from becoming too fluid during processing. From these viewpoints, the content of the impact-resistant improving agent in the entire film is more preferably 1.5% by mass or more, even more preferably 2% by mass or more, even more preferably 2.5% by mass or more, and particularly preferably 3% by mass or more. Furthermore, it is more preferably 20% by mass or less, even more preferably 15% by mass or less, and most preferably 10% by mass or less.

[0057] In the case of a laminated film, it is sufficient if at least one layer contains an impact-resistant modifier. While all layers of a laminated film may contain an impact-resistant modifier, it is preferable that at least the surface layer constituting the outermost layer of the film contains an impact-resistant modifier. Therefore, in a laminated film having a surface layer / middle layer / surface layer structure, it is preferable that both surface layers contain an impact-resistant agent, and thus, it is preferable that both surface layers contain an impact-resistant agent in addition to the polycarbonate resin (A). On the other hand, the middle layer may contain polycarbonate resin (A), but it is preferable that it does not contain an impact-resistant agent, or if it does, it contains an impact-resistant agent in a smaller amount than the other surface layers. In this way, by incorporating a relatively large amount of impact-resistant agent into both surface layers, it is possible to improve bending resistance and impact resistance, as well as processability, without having to increase the total impact-resistant agent content of the film as a whole, and to make it easier to embed IC chips and other components.

[0058] The impact-resistant additive content in each of the two surface layers is preferably 2% by mass or more, more preferably 4% by mass or more, even more preferably 6% by mass or more, even more preferably 8% by mass or more, and also preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less. On the other hand, as described above, the amount of impact-resistant modifier in the middle layer is preferably less than the amount of impact-resistant modifier in each of the surface layers, based on the mass of each layer, preferably less than 4% by mass, more preferably less than 2% by mass, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and most preferably 0% by mass.

[0059] (Antistatic agent) This film may contain an antistatic agent. The inclusion of an antistatic agent tends to improve handling by suppressing static charge buildup during transport and when layered with other films, and by reducing adhesion to press plates during heat pressing. Furthermore, the lower surface resistivity of the film reduces static electricity generation when unwinding the film from the film roll, effectively preventing sparks that could scratch the film surface, and preventing the film from meandering or skewing during feeding, resulting in misalignment, twisting, wrinkles, etc. Therefore, handling and processability are improved. In addition, lower surface resistivity reduces the likelihood of airborne dust being attracted by static electricity and adhering to the film surface, thus reducing the risk of foreign matter contamination in the resulting laminated films, cards, passports, and other products, thus improving dust resistance. Examples of antistatic agents include low-molecular-weight antistatic agents and high-molecular-weight antistatic agents. These may be ion-conducting or electron-conducting types.

[0060] Examples of low-molecular-weight antistatic agents include anionic antistatic agents, cationic antistatic agents, nonionic antistatic agents, amphoteric antistatic agents, complex compounds, metal alkoxides such as alkoxysilanes, alkoxytitanium, and alkoxyzirconium, and their derivatives, and coated silica. The amphoteric antistatic agent may be of the betaine type, but may also be of a different type, and may be any antistatic agent composed of a cation and anion, and may also be an ionic liquid. The polymeric antistatic agent may be various polymers, such as vinyl copolymers containing metal sulfonic acid salts, such as alkyl sulfonic acid metal salts or alkylbenzene sulfonic acid metal salts, within the molecule, or it may be a betaine type. Polyamide elastomers, polyester elastomers, etc., can also be used. Antistatic agents can be used individually or in combination of two or more types.

[0061] Among the above, antistatic agents composed of a cation and anion are preferred. Specifically, antistatic agents composed of an anion selected from a sulfonimide anion containing a fluorine atom and a sulfonate anion containing a fluorine atom, and a cation selected from a phosphonium cation, an ammonium cation, an imidazolium cation, and a pyridinium cation are preferred. Antistatic agents composed of cations and anions are preferably ionic liquids. Ionic liquids inherently possess high conductivity and are liquids at around room temperature, resulting in excellent dispersibility and superior antistatic performance. Furthermore, they exhibit excellent heat resistance, allowing for the suppression of property degradation due to thermal decomposition of the antistatic agent while providing excellent antistatic performance. An ionic liquid is defined as a compound consisting solely of ions with a melting point of 100°C or lower.

[0062] The anion selected from the above-mentioned sulfonimide anions and sulfonate anions containing a fluorine atom preferably includes an anion selected from perfluoroalkyl sulfonimide anions and perfluoroalkyl sulfonate anions. The anion tends to have improved transferability to the surface of the ionic liquid in the film by containing a fluorine atom, particularly a perfluoroalkyl group. Therefore, it becomes possible to impart high antistatic performance with a lower amount of additive.

[0063] As an antistatic agent composed of the above-mentioned anion and cation, an antistatic agent represented by the following formula (4) is preferred. [(R 11 )4P + ]·(R 12 SO2)(R 12 SO2)N - (4) (In the above formula (4), R 11 Each of these independently represents a hydrocarbon group, and R 12 Each of these independently represents a hydrocarbon group containing a fluorine atom.

[0064] In equation (4), R 11is preferably independently selected from a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkenyl group, and an aryl group, more preferably a linear or branched alkyl group, and even more preferably a linear alkyl group. R 11 each may have a substituent, but it is preferred that they do not have a substituent. R 11 The hydrocarbon group of has, for example, 1 to 20 carbon atoms, preferably 1 to 12, more preferably 1 to 8, even more preferably 1 to 6, and even more preferably 1 to 4. The hydrocarbon group is preferably an alkyl group as described above. Therefore, R 11 is most preferably an alkyl group having 1 to 4 carbon atoms. A plurality of R 11 in one molecule may be the same as or different from each other. A plurality of R 11 in one molecule, when they are different, it is preferred that the hydrocarbon groups of three R 11 have the same number of carbon atoms, and the hydrocarbon group of the other one R 11 preferably has a different number of carbon atoms. The number of carbon atoms of the hydrocarbon group of three R 11 is, for example, 9 or less, preferably 4 to 9, more preferably 5 to 8, and even more preferably 6 to 7. The number of carbon atoms of the hydrocarbon group of the other one R 11 is, for example, 10 or more, preferably 10 to 18, more preferably 11 to 16, and even more preferably 12 to 14. The hydrocarbon group is preferably an alkyl group as described above.

[0065] R 12 is preferably independently selected from a linear, branched or cyclic alkyl group containing a fluorine atom, a linear, branched or cyclic alkenyl group containing a fluorine atom, and an aryl group containing a fluorine atom, more preferably a linear or branched alkyl group containing a fluorine atom, and even more preferably a linear alkyl group containing a fluorine atom. In each R 12 the number of carbon atoms of the hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. More specifically, R 12 Each of these groups is preferably a perfluorohydrocarbon group, more preferably a perfluoroalkyl group, even more preferably a perfluoromethyl group or a perfluoroethyl group, and even more preferably a perfluoromethyl group. Multiple Rs within a single molecule 12 They may be the same as each other, or they may be different.

[0066] The antistatic agent represented by formula (4) is preferably a compound represented by the following formula (5). [ka]

[0067] In a single-layer film, it is preferable that the antistatic agent be contained in the single layer. In a laminated film, the antistatic agent only needs to be contained in at least one layer of the laminated film, or it may be contained in all layers. However, the antistatic agent is preferably contained in the surface layer. Therefore, in a laminated film having a surface layer / middle layer / surface layer structure, it is preferable that both surface layers contain the antistatic agent. By containing the antistatic agent in both surface layers, it becomes easier to obtain the above-mentioned effects, such as improved handling performance, by effectively suppressing static charge in the film.

[0068] The content of the antistatic agent in each layer containing the antistatic agent is preferably 0.1% to 3% by mass, more preferably 0.2% to 2.5% by mass, even more preferably 0.3% to 2% by mass, and even more preferably 0.4% to 1.5% by mass, if the antistatic agent is composed of cations and anions. If it is another type of antistatic agent, the content of the antistatic agent in each layer is preferably 0.1% to 5% by mass, more preferably 0.2% to 4% by mass, even more preferably 0.4% to 3% by mass, and even more preferably 0.5% to 2% by mass.

[0069] (filling material) This film may or may not contain fillers. The transparency of this film can be adjusted by omitting fillers or by appropriately adjusting the filler content. From the viewpoint of improving transparency and making it easier to adjust transparency with impact-resistant modifiers, it is preferable that this film contains no fillers or only a small amount of fillers. Here, a small amount of filler content means, for example, less than 8% by mass, preferably less than 5% by mass, more preferably less than 3% by mass, and even more preferably less than 1% by mass, based on the total amount of the film. Furthermore, this film does not need to contain fillers, and the lower limit of the filler content is 0% by mass. Here, the filler can be either an inorganic or organic filler, but examples of inorganic fillers include titanium dioxide, talc, mica, calcium carbonate, barium oxide, zinc oxide, carbon black, silica, lead titanate, potassium titanate, barium titanate, zircon oxide, magnesium oxide, calcium oxide, zinc sulfide, antimony oxide, zinc oxide, aluminum oxide, boron nitride, aluminum nitride, magnesium carbonate, and barium sulfate. The filler material may be used alone or in combination of two or more types. Furthermore, if the film is a laminated film, it is sufficient that the filler content in at least one of the multiple layers constituting the laminated film is within the above range, but it is preferable that the filler content in all layers is within the above range. In that case, the standard for the filler content in each layer may be the total amount of each layer instead of the total amount of the film.

[0070] (Other ingredients) This film may contain additives other than those listed above (other additives) that are commonly used in card or passport films. Examples of other additives include antioxidants, antiblocking agents, lubricants, process stabilizers, UV absorbers, light stabilizers, matting agents, processing aids, metal deactivators, residual polymerization catalyst deactivators, antibacterial and antifungal agents, antiviral agents, flame retardants, laser colorants, etc. If this film is a laminated film, at least one of the multiple layers constituting the laminated film may contain at least one of the other additives listed above, or all layers may contain at least one of the other additives.

[0071] The thickness of this film is not particularly limited and can be adjusted as appropriate depending on the intended use, but for example, it is 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, even more preferably 20 μm or more, and even more preferably 40 μm or more. Alternatively, it is 500 μm or less, preferably 300 μm or less, more preferably 250 μm or less, even more preferably 200 μm or less, and even more preferably 170 μm or less. Setting the film thickness above a certain level makes it easier to ensure opacity. On the other hand, setting the thickness below a certain level makes it easier to make cards and passports thinner.

[0072] Furthermore, when this film has a surface layer / middle layer / surface layer structure, the thickness ratio of each surface layer to the middle layer (each surface layer / middle layer) is preferably 0.03 to 0.85, more preferably 0.05 to 0.7, even more preferably 0.1 to 0.5, and even more preferably 0.15 to 0.35. By keeping the thickness ratio within the above range, the surface layer and middle layer can each perform their appropriate functions more easily. For example, as described above, by including an impact-resistant improving agent in the surface layer and making its content greater than that of the middle layer, the effects of using the impact-resistant improving agent can be effectively exerted while suppressing the total amount of impact-resistant improving agent in the film as a whole.

[0073] (Measurement of relaxation time (short relaxation, long relaxation) using pulsed NMR) When the sum of short relaxations and long relaxations obtained by pulsed NMR measurement of this film is normalized to 1, the proportion of long relaxations is 0.28 or less, preferably 0.25 or less, and more preferably 0.20 or less. In this invention, the resin film was viewed microscopically from the viewpoint of achieving both flexibility and transparency. Specifically, 1 This method measures the relaxation time of the H nucleus and evaluates the interaction state in a blend of a polycarbonate resin (A) having a specific structural unit (A1) in a solid state and an impact-resistant modifier. Focusing on the molecular mobility of the resin film, the method examines the length of the relaxation time using pulsed NMR. Long relaxation times are strongly influenced by components with high molecular mobility in the film and are a factor resulting from its soft physical properties. On the other hand, short relaxation times are strongly influenced by components with low molecular mobility and are a factor resulting from its rigid physical properties. In this invention, by keeping the proportion of long relaxation in the entire resin film to 0.28 or less, it is possible to significantly improve bending resistance. Furthermore, by keeping the proportion of long relaxation even lower, it is possible to further improve transparency, and it has been found that it is possible to achieve both bending resistance and transparency. As a specific means to keep the proportion of long relaxation in the entire film below the above-mentioned certain level, the present invention includes using a polycarbonate resin (A) having a specific structural unit (A1) in combination with an impact-resistant modifier having an average primary particle size of 300 nm or less. Furthermore, the proportion of long-term relaxation is not particularly limited in terms of its lower limit; it may be 0.01 or higher, or 0.05 or higher. Furthermore, as will be discussed later, the improvement in tensile fracture elongation suggests that the dispersibility between the polycarbonate resin (A) having a specific structural unit (A1) and the impact-resistant modifier is good.

[0074] (Film Haze) The film haze of this film is preferably 25% or less, more preferably 20% or less, even more preferably 10% or less, and particularly preferably 5% or less. By setting the film haze within the above range, the application can be appropriately selected according to the value of the film haze. For example, it can be used as a cover sheet for the outermost layer of a card, or as a core sheet or inlet used internally. The lower limit of the film haze is not particularly limited and should be 0% or more. The film haze can be measured by the method described in the examples.

[0075] (Tensile elongation at fracture) The tensile elongation at break of this film is preferably 145% or higher for both the medium-density (MD) and tangential (TD), and more preferably 160% or higher for both the MD and TD. The inclusion of an impact-resistant agent makes it easier to increase the tensile elongation at break of this film. While the tensile elongation at break is not particularly limited, it is preferable that it be 350% or lower for both the MD and TD. The tensile elongation at break can be measured by the method described in the examples.

[0076] (Card bending test (bending resistance)) The number of folds of this film is preferably 25,000 or more, more preferably 30,000 or more, particularly preferably 60,000 or more, and among those, 80,000 or more is preferable. The bending resistance of this film improves as the number of folds increases. The number of folds can be measured by a card bending test (evaluation of bending resistance), and specifically, by the method described in the examples.

[0077] (Method of manufacturing resin film for cards or passports) A resin film for cards or passports (this film) can be manufactured by known methods, but it is preferable to obtain a resin composition for forming this film and then make the resin composition into a film. The resin composition may be obtained by mixing, for example, a resin, an impact modifier, and optionally added antistatic agents, fillers, and other components. The mixing of the raw materials may be carried out by melt-kneading while heating in an extruder, plast mill, etc., but the raw materials constituting the resin composition may also be used as is after being dry-blended in a tumbler or the like. The method for forming the resin composition into a film is not particularly limited, but it may be done by press molding or extrusion molding, however, extrusion molding is preferred in terms of productivity and cost.

[0078] Furthermore, if the film is a laminated film, resin compositions for forming each layer may be prepared, and multiple resin layers may be laminated by a known lamination method while forming each resin layer from each resin composition. Alternatively, a resin composition for forming another resin layer may be melt-extruded and laminated onto a resin film formed from any of the resin compositions. A multilayer structure may also be formed by co-extrusion. From the viewpoint of productivity and cost, it is preferable to adopt the co-extrusion method. In a laminated film, the resin composition for forming each layer is preferably obtained by mixing components for forming each layer according to the composition of each layer. For example, in a laminated film having a surface layer / middle layer / surface layer structure, a resin composition for the surface layer containing at least a resin and an impact-resistant modifier for forming the surface layer, and a resin composition for the middle layer containing at least a resin for forming the middle layer are prepared, and the laminated film is formed using these resin compositions.

[0079] [Resin composition for cards or passports] The resin composition for cards or passports according to the present invention (hereinafter sometimes referred to as "the resin composition") is used to manufacture the above-described film. The resin composition contains the above-described polycarbonate resin (A) and an impact-resistant agent. The resin composition may also contain an antistatic agent. Furthermore, the resin composition may appropriately contain other additives other than the impact-resistant agent and the antistatic agent. Details of the impact-resistant modifier, antistatic agent, and other additives used in this resin composition are as described above, and the content of these components in this resin composition is also as described above for this film. Furthermore, this resin composition may or may not contain fillers, but their content is as described above. However, the content of the impact-resistant modifier and fillers, which was previously based on the total amount of this film, will now be based on the total amount of this resin composition. Similarly, the content of the antistatic agent, which was previously based on each layer, will now be based on the total amount of this resin composition.

[0080] The resin constituting this resin composition may consist solely of polycarbonate resin (A), or it may contain polycarbonate resin (A) in addition to resins other than polycarbonate resin (A). Details of polycarbonate resin (A) and resins other than polycarbonate resin (A) are as described above. In this resin composition, polycarbonate resin (A) is often the main component, and the content of polycarbonate resin (A) is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass, relative to the total amount of resin constituting this resin composition.

[0081] Furthermore, when pulsed NMR measurements are performed on a resin film molded from this resin composition, and the sum of short relaxations and long relaxations is normalized to 1, the proportion of long relaxations is 0.28 or less, preferably 0.25 or less, more preferably 0.20 or less, and may also be 0.01 or more, or 0.05 or more. By keeping the proportion of long relaxations measured as described above to 0.28 or less, this resin composition makes it possible to achieve both flexibility and transparency in the resin film molded from this resin composition. Pulsed NMR measurements performed on a resin film molded from this resin composition are preferably performed on a resin film with a thickness of, for example, 100 μm, prepared from this resin composition, as shown in the examples described later. The details are as described in the examples.

[0082] This resin composition may be used in single-layer films or multilayer films as described above. A single-layer film using this resin composition may be made of this resin composition. In a multilayer film, at least one layer may be made of this resin composition, but it is preferable that all layers be made of this resin composition.

[0083] [Laminated film] This film may be further laminated onto another resin film to form a film laminate. Generally, cards or passports are often constructed by laminating multiple resin films; therefore, the film laminate is suitable for use in cards or passports. The film laminate may comprise at least the aforementioned main film and other resin films laminated to it. The other resin films may be composed of the aforementioned main film or other resin films. In other words, the film laminate may consist of two or more layers of the main film laminated together, or it may consist of one or more layers of the main film laminated together with one or more resin films other than the main film.

[0084] The resins constituting the other resin films besides this film may be polyester resin, polycarbonate resin, or a combination of both. Details of the polyester resin are as described above. Among these, polycarbonate resin is preferred, and the polycarbonate resin (A) described above is more preferred. The film laminate is not particularly limited, but for example, it can be manufactured by overlapping two or more resin films (this film and other resin films) and integrating them by heat-pressing or other means. Of course, when integrating two or more resin films in the film laminate, adhesive may be used instead of heat-pressing to bond them together. The film laminate may be used, for example, as an inlet sheet as described later, or as a laminate that constitutes at least a part of a card or passport other than an inlet sheet as described later.

[0085] <Card or passport> The aforementioned film, film laminate, and resin composition are used for cards or passports. Examples of cards include IC cards, magnetic cards, driver's licenses, residence cards, qualification certificates, employee IDs, student IDs, My Number cards, seal registration certificates, vehicle registration certificates, tag cards, prepaid cards, cash cards, credit cards, ETC cards, SIM cards, and B-CAS cards. A card or passport (more specifically, a passport data page) may include a core sheet. In addition to the core sheet, the card or passport data page may also include at least one of a laser-marked sheet, a printed sheet, and a protective sheet. The passport data page or card may be manufactured by overlapping one or more sheets selected from the core sheet and other sheets, pressing them together, heat-sealing them, and then die-cutting them. Alternatively, instead of heat-sealing, an adhesive may be used to bond the sheets together as appropriate.

[0086] In the present invention, a card or passport comprises the above-described film. A card or passport usually comprises multiple resin films, and it is preferable that at least one of them be made of the film, but it is preferable that the film is used as a core sheet in the card or passport. In particular, it is preferable that the film constitutes an inlet sheet into which an inlet such as an IC chip or antenna is embedded, and it is more preferable that it constitutes an IC sheet into which an IC chip is embedded.

[0087] This film allows for appropriate adjustment of transparency, making it suitable for use in core sheets, particularly inlet sheets such as IC sheets, to effectively conceal inlets such as IC chips and antennas. Furthermore, as mentioned above, the film contains an impact-resistant additive, preventing softening and loss of fluidity during heating, thus maintaining good processability. Therefore, even when used in inlet sheets, this film is less likely to cause problems such as difficulty in embedding IC chips. When using this film as an inlet sheet for IC sheets, it is preferable to laminate two or more sheets, more preferably three or more sheets, and even more preferably four or more sheets. When laminating, the films may be laminated directly, or other layers such as adhesive layers may be present as needed. By laminating this film to form an inlet sheet, there is an advantage that it becomes easier to embed inlets such as IC chips and antennas compared to an inlet sheet made of a single layer of this film. In addition, although IC chips and the like are available in various thicknesses, by using an inlet sheet configuration such as that shown in Figure 1, which will be explained later, it is possible to adjust the thickness of the inner film according to the thickness of the IC chip, etc. Furthermore, since the films on both surfaces of the inlet sheet are positioned above and below the IC chip, etc., it is possible to appropriately adjust the transparency of the films on both surfaces to properly conceal inlets such as IC chips, etc.

[0088] Furthermore, as mentioned above, laminating two or more of this film to form an inlet sheet offers the advantage of making it easier to adjust the overall thickness of the product when laminating it with other resin films, such as laser marking sheets or printed sheets, to create actual products such as cards or passports.

[0089] Figure 1 shows an example of an IC sheet used as an inlet sheet to which this film is applied. As shown in Figure 1, the IC sheet (inlet sheet) 11 is made by laminating multiple resin films 10 so that an inlet such as an IC chip 12 is embedded inside. For example, it is preferable to sandwich the inlet between two or more resin films 10 and laminate them, then integrate them by heat fusion or the like. In Figure 1, the IC sheet (inlet sheet) 11 is formed from four resin films 10, but any number of resin films 10, two or more, is acceptable. Also, although only the IC chip 12 is shown as the inlet, other inlets such as an antenna may also be present. Furthermore, at least one of the multiple resin films 10 may be appropriately cut to form a hollow portion or notch according to the shape of the inlet (e.g., IC chip 12) so that the inlet can be properly embedded inside, and the multiple resin films may be laminated and integrated after the inlet is placed in the hollow portion or notch. For example, in the example of Figure 1, two of the four resin films 10 on the inside may be provided with hollow portions for placing the IC chip 12.

[0090] In an inlet sheet such as an IC sheet 11, at least one of the multiple resin films 10 may be the aforementioned film. For example, some of the multiple resin films 10 (for example, the resin films provided on both surfaces in the configuration of Figure 1) may be the aforementioned film, or all of them may be the aforementioned film. As described above, the aforementioned film can provide high opacity, so by being used as part or all of an inlet sheet such as an IC sheet 11, the inlet such as an IC chip 12 can be properly concealed.

[0091] The thickness of the inlet sheet (IC sheet) is not particularly limited, but is preferably 100 μm to 500 μm, more preferably 200 μm to 460 μm, even more preferably 250 μm to 440 μm, and even more preferably 280 μm to 420 μm. By making the inlet sheet thickness 100 μm or more, the inlet such as the IC chip can be properly concealed by the inlet sheet. Furthermore, by making it 500 μm or less, it becomes easier to add various functions to the data pages and cards by making the parts other than the inlet sheet thicker without making the passport data pages and cards unnecessarily thick.

[0092] In the case of a passport or card, the above-mentioned inlet sheet may be used as the core sheet, and a laser marking sheet may be further laminated on one or both sides thereof. The laser marking sheet is a sheet on which personal information, etc., is printed by laser printing. Personal information is information used to identify the passport or cardholder, and includes personal name, personal ID, card number, etc.

[0093] A laser marking sheet may consist of a single resin layer, but it is preferable to have a multilayer laminate structure consisting of multiple resin layers. The laser marking sheet preferably includes a resin layer containing a laser colorant, and if it consists of a single resin layer, one of the resin layers may contain the laser colorant. In the case of a multilayer structure, the laser marking sheet may, for example, have a structure in which surface layers are provided on both sides of the middle layer, and the middle layer may contain the laser colorant. The laser marking sheet typically consists of a transparent layer. The thickness of the laser marking sheet is not particularly limited, but is preferably 15 μm to 400 μm, more preferably 30 μm to 300 μm, even more preferably 40 μm to 250 μm, and even more preferably 60 μm to 200 μm. A thickness of 15 μm or more allows for appropriate printing of various information by laser. A thickness of 400 μm or less prevents the passport or card from becoming excessively thick.

[0094] The resin used in each resin layer constituting the laser marking sheet is not particularly limited and may be polyester resin, polycarbonate resin, or a combination of both. However, from the viewpoint of laser printability, polycarbonate resin is preferred. Details of the polyester resin are as described above. Furthermore, the polycarbonate resin (A) described above is preferred as the polycarbonate resin.

[0095] The laser colorant used in laser marking sheets is not particularly limited as long as it has the function of generating heat when irradiated with a laser beam. It may be a so-called self-coloring colorant that develops color itself when irradiated with laser light, or it may be one that does not develop color itself. By generating heat, the laser colorant can promote the carbonization of the surrounding forming material, thereby improving laser printability. Furthermore, if a self-coloring laser colorant is used, the color development of the laser colorant and the color development of the carbides produced by the carbonization of the forming material synergistically result in a dark color and a highly visible print. When the laser colorant develops color, the color is not particularly limited, but from the viewpoint of visibility, it is preferable to use a laser colorant that can develop dark colors including black, navy blue, and brown.

[0096] The laser colorant 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 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. Furthermore, laser colorants other than metal oxides may also be used, including metals such as iron, copper, zinc, tin, gold, silver, cobalt, nickel, bismuth, antimony, and aluminum; metal salts 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 metal borides, hexaborides have near-infrared absorption ability, and lanthanum hexaboride is preferred because it has excellent laser light absorption efficiency. In addition, dyes such as leuco dyes such as fluorane, phenothiazine, spiropyran, triphenyl metaphthalide, and rhodamine lactam, as well as carbon black, can also be used. As the laser colorant, it is preferable to use bismuth oxide or a bismuth-based metal oxide such as a metal oxide containing bismuth and at least one metal selected from Zn, Ti, Al, Zr, Sr, Nd, and Nb. Laser colorants may be used individually or in combination of two or more types.

[0097] A printing sheet is a sheet on which fixed information is printed before multiple sheets are laminated and integrated. This fixed information is information other than the personal information mentioned above, and it remains the same regardless of the card or passport. The fixed information may be printed on the printing sheet using known inks such as photocuring or thermocuring inks. The printing sheet is a colored sheet and may consist of a single layer of resin film or a laminated film consisting of multiple resin layers. The printing sheet is a sheet placed on the outside of the inlet sheet. If a laser marking sheet is also provided, the printing sheet may be placed between the inlet sheet and the laser marking sheet.

[0098] The protective sheet used in passports or cards, also known as an oversheet or cover sheet, generally constitutes the outermost layer on the data pages of the card or passport. Therefore, when laser marking sheets or printed sheets are laminated, the protective sheet is preferably laminated on the outside of these. When the protective sheet is laminated on the outside of the laser marking sheet, it suppresses the so-called "blistering" that occurs when the laser-printed area is irradiated with laser light. The protective sheet may consist of a single resin layer or a multilayer laminate consisting of multiple resin layers. The resin used in each resin layer constituting the protective sheet is not particularly limited and may be polyester resin, polycarbonate resin, or a combination of these, but polycarbonate resin is preferred from the viewpoint of transparency and heat resistance. Details of the polyester resin are as described above. Furthermore, the polycarbonate resin (A) described above is preferred as the polycarbonate resin. The protective sheet typically constitutes a transparent layer.

[0099] The stacked structure of the data pages or card in a passport is not particularly limited, but may have one of the following stacked structures, for example (1) to (6). (1) Protective sheet / Laser marking sheet / IC sheet (inlet sheet) / Printed sheet / Protective sheet (2) Protective sheet / Laser marking sheet / IC sheet (inlet sheet) / Laser marking sheet / Protective sheet (3) Protective sheet / Laser marking sheet / Printed sheet / IC sheet (inlet sheet) / Printed sheet / Laser marking sheet / Protective sheet (4) Protective sheet / Laser marking sheet / Printed sheet / IC sheet (Inlet sheet) / Laser marking sheet / Protective sheet (5) Protective sheet / Laser marking sheet / IC sheet (inlet sheet) / Protective sheet (6) Protective sheets / Laser marking sheets / Printed sheets / IC sheets (inlet sheets) / Protective sheets The passport or card preferably has the laminated structure of (1) above. In the laminated structures of (1) to (6) above, protective sheets are provided on both outermost surfaces, but one or both of the protective sheets may be omitted as appropriate.

[0100] Furthermore, the data pages and cards of the passport may be equipped with security features such as lenticular printing, hologram printing, and security threads, which may be appropriately placed, for example, between the protective sheet and the laser marking sheet, between the laser marking sheet and the printing sheet, or between the laser marking sheet and the inlet sheet.

[0101] Furthermore, a hinge sheet may be provided in the passport. The hinge sheet is a sheet that plays a role in securely binding the data pages together with the passport cover and other visa sheets, etc. The hinge sheet may be positioned to protrude from the inlet sheet, for example, so as to be connected to the inlet sheet that constitutes the core sheet. Alternatively, the hinge sheet may be placed, for example, between the inlet sheet and the printing sheet, laser marking sheet, or protective sheet, and laminated within the data pages so that a portion of it protrudes from the inlet sheet.

[0102] In addition to the above, the card or passport may also have decorative layers, such as a hologram layer, which may be placed between each sheet in the card or passport. The decorative layer may display any information or decoration.

[0103] Furthermore, although the above explanation of cards or passports was based on the assumption that this film is used for the core sheet, this film does not necessarily have to be used for the core sheet. It may also be used for any sheet used in the card or passport, such as a protective sheet (cover sheet), laser marking sheet, or printing sheet. As described above, this film can also be made highly transparent. Therefore, information, decorations, etc., placed inside this film can be easily seen from the outside through this film. For this reason, if this film is used, for example, as a protective sheet (cover sheet), various information and decorations displayed on printed sheets, laser-marked sheets, decorative layers, etc., can be easily seen through the protective sheet (cover sheet). The protective sheet (cover sheet) may constitute the outermost layer in a card or passport, but it does not have to be the outermost layer and may be placed in any position as long as it is on one side of the surface of the laser-marked sheet, printed sheet, decorative layer, or core sheet. [Examples]

[0104] Examples and comparative examples are shown below, but these do not limit the present invention in any way.

[0105] The evaluation method is as follows:

[0106] (1)Kinematic viscosity average molecular weight Using dichloromethane as the solvent, the intrinsic viscosity ([η]) (unit dl / g) at 20°C was determined using an Ubbelohde viscometer, and Schnell's viscosity formula was used: η = 1.23 × 10⁻⁶ -4 M 0.83 It can be calculated from the formula.

[0107] (2) Calculation of short and long relaxations using pulsed NMR Measurement device: Bruker, Model: minispec mq20 Observed nucleus: 1H NMR Pulse sequence: Solid-Echo method Acquisition scale: 0.1ms Recycle Delay (sec): 1 sec First 90° Pulse Separation: 0.01 ms Final Pulse Separation: 2.0 ms Total number of times: 256 Measurement temperature (℃): 40℃ *Standardization After normalizing the obtained relaxation profile by its maximum value, the profile was considered as a two-relaxation system with exponential properties, and the following equation was applied. Relaxation function M=ΣPi×exp(t / τi), i=2 Here, short relaxation time τ1, short relaxation fraction p1 Long relaxation time τ2, long relaxation fraction p2 However, p1 + p2 = 1, and t indicates the elapsed time of the test. The fitting was performed using the Levenberg-Marquadt iterative method implemented in Origin2022.

[0108] (3) Film haze Film haze was measured using a Tokyo Denshoku haze meter "TC-HIIIDPK," in accordance with JIS K 7136:2000.

[0109] (4) Tensile elongation at break Based on JIS K6734:1995, test specimens with a length of 120 mm, a width of 10 mm, and a thickness of 0.1 mm were prepared. Tensile tests were conducted at a test speed of 200 mm / min, and the elongation at the time of fracture was measured.

[0110] (5) Card bending test (folding evaluation) For cards made using this film, we bent them in the short-side direction with a maximum deflection of 10 mm, referring to JIS X 6320:2009, and confirmed the number of bends (folding count) until the card cracked under the condition of a test frequency of 0.5 Hz. The cards used in the card bending test were made by stacking multiple sheets of this film to a thickness of 800 μm, then using a hot press machine to obtain a laminate at 130°C, which was then punched out into a card shape (54 mm x 85 mm).

[0111] The raw materials used in this embodiment are as follows: PC:ISP; A plant-derived polycarbonate resin obtained by melt polymerization using isosorbide and 1,4-cyclohexanedimethanol as dihydroxy compounds, such that the ratio of structural units derived from isosorbide to those derived from 1,4-cyclohexanedimethanol is 50:50 (molar ratio). Glass transition temperature: 98°C, mass-average molecular weight: 68000

[0112] The present invention will be described in further detail below with reference to manufacturing examples and embodiments. However, the present invention is not limited in any way by the following embodiments. In the following embodiments, "parts" means "parts by mass" and "%" means "percent mass".

[0113] For impact-resistant modifiers a and d, core-shell type elastomers manufactured as follows were used.

[0114] [Manufacturing of polybutadiene rubber latex (R-1)] In a pressure-resistant autoclave, 100 parts of 1,3-butadiene (Bd), 0.3 parts of tert-dodecyl mercaptan, 0.28 parts of diisopropylbenzene hydroperoxide, 0.3 parts of tetrasodium pyrophosphate, 0.0036 parts of ferrous sulfate, 0.39 parts of sodium sulfate, 0.24 parts of glucose, 1.25 parts of potassium rosinate, 1.25 parts of potassium tallowate, and 200 parts of deionized water were charged and reacted at 53°C for 12 hours with stirring to obtain polybutadiene rubber latex (R-1).

[0115] [Production of acid group-containing copolymer latex (K-1)] In a glass reactor equipped with a reflux condenser, 1.67 parts potassium tallowate, 2.5 parts sodium dioctyl sulfosuccinate, 0.3 parts sodium formaldehyde sulfoxylate, 0.003 parts ferrous sulfate, 0.009 parts disodium ethylenediaminetetraacetate, and 196 parts deionized water were charged, and the temperature inside the glass reactor was raised while stirring until it reached 60°C. Next, a mixture consisting of 85 parts n-butyl acrylate, 15 parts methacrylic acid, and 0.5 parts cumene hydroperoxide was continuously added to the mixture of raw materials over 2 hours, and then polymerized by holding for another 2 hours to obtain an acid group-containing copolymer latex (K-1).

[0116] [Manufacturing Example 1] Manufacturing of impact-resistant agent a 222 parts of polybutadiene rubber latex (R-1) (70 parts as the starting monomer component) were placed in a glass reaction vessel (separable flask) equipped with a stirrer and reflux condenser. The atmosphere inside the separable flask was replaced with nitrogen by passing a stream of nitrogen gas through it. Next, the liquid temperature was raised to 80°C. Then, a mixture consisting of 30 parts of methyl methacrylate (MMA) and 0.11 parts of tert-butyl hydroperoxide was added dropwise to the reaction vessel over 60 minutes, and heating and stirring were continued for 120 minutes. In this way, vinyl monomers were graft polymerized onto the rubbery polymer to obtain impact-resistant latex (a). For tert-butyl hydroperoxide, we used the trade name "Perbutyl H, manufactured by NOF Corporation".

[0117] 288.18 parts of the obtained impact-resistant latex (a) were mixed with 2.2 parts of stabilizer emulsion. Then, an aqueous solution of 5 parts calcium acetate and 173 parts deionized water was heated to 90°C, and the impact-resistant latex containing the stabilizer emulsion was added to the aqueous solution to form a slurry. The liquid temperature was raised to 95°C and held for 5 minutes to cause the slurry to coagulate. The coagulated material was collected, immersed in 1500 parts of deionized water, and the dewatering process was repeated twice. Finally, it was dried at 60°C for 12 hours to obtain the powder of impact-resistant agent a.

[0118] [Manufacturing Example 2] Manufacturing of impact-resistant agent d 222 parts of polybutadiene rubber latex (R-1) (70 parts as the starting monomer component) were placed in a glass reaction vessel (separable flask) equipped with a stirrer and reflux condenser. The atmosphere inside the separable flask was replaced with nitrogen by passing a stream of nitrogen gas through it. 4.24 parts of acid group-containing copolymer latex (K-1) were added, and the temperature was raised to 40°C and held for 10 minutes. Next, an aqueous solution consisting of 0.94 parts of dipotassium alkenylsuccinate and 27 parts of deionized water was added, and the temperature was raised to 80°C. Furthermore, an aqueous solution consisting of 0.09 parts of sodium formaldehyde sulfoxylate dihydrate and 3.8 parts of deionized water was added. Subsequently, a mixture of 30 parts of methyl methacrylate (MMA) and 0.11 parts of tert-butyl hydroperoxide was added dropwise to the reaction vessel over 60 minutes, and heating and stirring were continued for 120 minutes. In this way, vinyl monomers were graft polymerized onto a rubbery polymer to obtain impact-resistant latex (d). Furthermore, the product name used for dipotassium alkenylsuccinate was "Latemul ASK, manufactured by Kao Corporation," and the product name used for tert-butyl hydroperoxide was "Perbutyl H, manufactured by NOF Corporation."

[0119] 288.18 parts of the obtained impact-resistant latex (d) were mixed with 2.2 parts of stabilizer emulsion. Then, an aqueous solution of 5 parts calcium acetate and 173 parts deionized water was heated to 90°C, and the impact-resistant latex (d) containing the stabilizer emulsion was added to the aqueous solution to form a slurry. The liquid temperature was raised to 95°C and held for 5 minutes to cause the slurry to coagulate. The coagulated material was collected, immersed in 1500 parts of deionized water, and the dewatering process was repeated twice. Finally, it was dried at 60°C for 12 hours to obtain the impact-resistant agent d powder.

[0120] For impact-resistant modifiers other than those a and d, the following core-shell type elastomers were used. b: Dow Chemical's "PARALOIDE XL-2650J" c: "Metablen C-950" manufactured by Mitsubishi Chemical Corporation e: Mitsubishi Chemical Corporation's "Metablen E-870A" The types of rubber components constituting the core of each impact-resistant modifier, the monomer components constituting the shell, and the average particle size are as shown in Table 1.

[0121] [Examples 1-4, Comparative Examples 1 and 2] Each component was blended according to the formulations shown in Table 1, kneaded using an extruder, extruded at 230°C, and rapidly cooled on a casting roll at approximately 120°C to obtain a single-layer resin film with a thickness of 100 μm. The obtained resin film was used for various evaluations. The evaluation results are shown in Table 1.

[0122] [Table 1] *Butadiene = Polybutadiene, Butanediene / BA = Butadiene-Acrylic (Polybutyl Acrylate) Composite Rubber MMA = Methyl acrylate, MMA / St = Methyl acrylate and styrene

[0123] As described above, in Examples 1 to 4, by using a specific impact-resistant modifier with an average primary particle size of 300 nm or less in combination with a polycarbonate resin (A) having a specific structural unit (A1), the bending resistance of the resin film was significantly improved by approximately 3 to 10 times in terms of the number of bending cycles compared to Comparative Example 1, and it was found that the transparency of the film could also be adjusted. In contrast, although the film of Comparative Example 2 contained an impact-resistant modifier, the proportion of long relaxations in pulsed NMR measurement was high, so while the bending resistance improved, the transparency of the film was drastically reduced, indicating that it is difficult to achieve both bending resistance and transparency. [Explanation of Symbols]

[0124] 10 Resin film 11 IC Sheet (Inlet Sheet) 12 IC chips

Claims

1. A polycarbonate resin (A) containing a structural unit (A1) derived from a dihydroxy compound having a portion represented by the following formula (1) in part of its structure, and a resin film containing an impact-resistant agent, The impact-resistant modifier is a core-shell type graft copolymer having an average primary particle size of 300 nm or less, and is a multilayer polymer composed of a core made of saturated or unsaturated rubber components and a shell made of monomer components containing (meth)acrylic compounds. A resin film for cards or passports, wherein, when the sum of short relaxations and long relaxations measured by pulsed NMR of the resin film is normalized to 1, the proportion of long relaxations is 0.28 or less. 【Chemistry 1】 However, the part represented by formula (1) above is -CH ２ Except when it is part of -O-H.

2. The resin film for a card or passport according to claim 1, wherein the core comprises butadiene rubber.

3. The resin film for a card or passport according to claim 1, wherein the number of times the resin film can be folded is 25,000 or more.

4. The resin film for cards or passports according to claim 1, wherein the film haze of the resin film is 25% or less.

5. The resin film for cards or passports according to claim 1, wherein the tensile elongation at break of the resin film is 145% or more for both MD and TD.

6. The resin film for cards or passports according to claim 1, wherein the content of the impact-resistant improving agent is 1% by mass or more and 30% by mass or less.

7. The resin film for cards or passports according to claim 6, wherein the mass-average molecular weight of the polycarbonate resin (A) is 10,000 or more and 100,000 or less.

8. A resin film for a card or passport, as described in claim 1, used as a core sheet.

9. A resin film for a card or passport according to claim 1, wherein the thickness is 20 μm or more and 500 μm or less.

10. An inlet sheet comprising a resin film for a card or passport as described in claim 1.

11. A film laminate comprising a resin film for a card or passport as described in claim 1, and another resin film laminated on the resin film.

12. A resin composition comprising a polycarbonate resin (A) containing a structural unit (A1) derived from a dihydroxy compound having a part of its structure represented by the following formula (1), and an impact resistance modifier, The impact-resistant modifier is a core-shell type graft copolymer having an average primary particle size of 300 nm or less, and is a multilayer polymer composed of a core made of saturated or unsaturated rubber components and a shell made of monomer components containing (meth)acrylic compounds. A resin composition for cards or passports, wherein, when a resin film molded from the aforementioned resin composition is subjected to pulse NMR measurement, the proportion of long relaxations is 0.28 or less when the sum of short relaxations and long relaxations is normalized to 1. 【Chemistry 2】 However, the part represented by formula (1) above is -CH ２ Except when it is part of -O-H.

13. A card comprising any one of the following: a resin film for a card or passport according to any one of claims 1 to 9, an inlet sheet according to claim 10, a film laminate according to claim 11, and a resin composition according to claim 12.

14. A passport comprising a resin film for cards or passports according to any one of claims 1 to 9, or an inlet sheet according to claim 10, a film laminate according to claim 11, or a resin composition according to claim 12.

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