Resin compositions, resin films, laminates, cards, and passports

Abstract

To provide resin compositions and resin films that do not cause printing defects or heat-sealing defects even when using specific polyester resins such as PCTG, particularly recycled PCTG, as raw materials. [Solution] A resin composition comprising a polyester resin (B) obtained by polycondensation of a dicarboxylic acid component mainly containing terephthalic acid and a glycol component mainly containing ethylene glycol and 1,4-cyclohexanedimethanol, and a polycarbonate resin (B), characterized in that no peak appears when the cold crystallization temperature is measured by DSC under measurement conditions of a heating rate of 10°C / min and a measurement temperature range of -70°C to 260°C.

Description

[Technical Field]

[0001] The present invention relates to resin compositions, resin films, laminates, cards, and passports. [Background technology]

[0002] Credit cards, cash cards, ID cards, tag cards, and insurance cards are generally manufactured by layering multiple resin sheets, heat-fusing them together, and then die-cutting them. Similarly, passports are also generally manufactured by layering multiple resin sheets. The resin sheets used in cards and passports often contain thermoplastic resin compositions, such as polyester and aromatic polycarbonate, as resin components.

[0003] In recent years, there has been a growing demand to reduce the consumption of fossil fuels and plastic waste in order to lessen the environmental burden. Therefore, it has been proposed to manufacture laminates containing sheets made from recycled PCTG (polycarbonate tungsten) for use in various types of cards, in order to reduce the environmental impact (see Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-160497 [Patent Document 2] Japanese Patent Publication No. 2024-21669 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, sheets made from certain polyester resins, such as PCTG, particularly recycled PCTG, sometimes experienced printing defects or thermal sealing defects during the manufacturing process.

[0006] Therefore, the object of the present invention is to provide a resin composition and a resin film that do not cause printing defects or heat-sealing defects even when using specific polyester resins such as PCTG, particularly recycled PCTG, as raw materials. [Means for solving the problem]

[0007] As a result of diligent research, the inventors have found that the above problems can be solved by using a resin composition with a specific configuration, and have completed the present invention as follows. That is, the present invention provides the following [1] to

[17] .

[0008] [1] A resin composition comprising a polyester resin (A) obtained by polycondensation of a dicarboxylic acid component mainly composed of terephthalic acid and a glycol component mainly composed of ethylene glycol and 1,4-cyclohexanedimethanol, and a polycarbonate resin (B), characterized in that no peak appears when the cold crystallization temperature is measured by DSC under measurement conditions of a heating rate of 10°C / min and a measurement temperature range of -70°C to 260°C. [2] The storage modulus at 170°C and 1 Hz is 1 × 10⁻⁶ 6 The resin composition described in [1] above, wherein the Pa is less than or equal to [1]. [3] The resin composition according to [1] or [2] above, wherein the number average molecular weight of the polycarbonate resin (B) is 18,000 or more. [4] The resin composition according to any one of [1] to [3] above, wherein the content of structural units derived from 1,4-cyclohexanedimethanol in the structural units derived from the glycol component is 50 mol% or more. [5] A resin composition according to any of [1] to [4] above, which includes recycled materials. [6] The resin composition according to any one of [1] to [5] above, wherein the polyester resin (A) contains recycled raw materials. [7] A film comprising any of the resin compositions described in [1] to [6] above. [8] The film according to [7] above, wherein the film haze change rate (ΔH) before and after heat treatment performed at 140°C for 30 minutes is 2.0% or less. [9] A laminate comprising a plurality of the films described in [7] above, wherein the plurality of films are laminated directly or through other layers.

[10] The laminate according to [9] above, wherein the other layer is a resin sheet containing a polycarbonate resin.

[11] The laminate according to [9] or

[10] above, wherein the other layer is a resin sheet containing a polycarbonate resin (C) having a structural unit (C1) derived from a dihydroxy compound represented by the following formula (1) in a part of the structure. [Chemical formula] However, it excludes the case where the part represented by the formula (1) is a part of -CH2-O-H.

[12] The film according to [7] or [8] above, which is for a card or a passport.

[13] A card comprising the film according to [7] or [8] above.

[14] A card comprising the laminate according to any one of [9] to

[11] above.

[15] A passport comprising the film according to [7] or [8] above.

[16] A passport comprising the laminate according to any one of [9] to

[11] above.

[17] A method for producing a laminate, wherein the films according to [7] or [8] above are stacked directly or through other layers and heat-pressed at a temperature below 170°C. [Advantages of the Invention]

[0009] According to the present invention, it is possible to provide a resin composition and a resin film that do not cause printing defects or heat fusion defects during the manufacturing process, even when using a specific polyester resin such as PCTG, particularly recycled PCTG, as a raw material. [Brief Description of the Drawings]

[0010] [Figure 1] It is a schematic diagram showing the layer structure in a card. [Figure 2] It is a schematic diagram showing the layer structure in a passport.

Mode for Carrying Out the Invention

[0011] 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 when referred to as "film", it includes "sheet", and when referred to as "sheet", it includes "film".

[0012] <Resin Composition> The resin composition of the present invention (hereinafter sometimes referred to as "the present resin composition") contains a polyester resin (A) and a polycarbonate resin (B).

[0013] (Polyester Resin (A)) The polyester resin (A) is a polyester obtained by polycondensing a dicarboxylic acid component containing terephthalic acid as a main component and a glycol component containing ethylene glycol and 1,4-cyclohexanedimethanol as main components. As the dicarboxylic acid component, dicarboxylic acid derivatives such as esters of dicarboxylic acids and acid halides may be used in the synthesis of the polyester resin. When the polyester resin (A) is used as the resin, the low-temperature fusion property is good, and the film formed from the present resin composition can be easily adhered to other films by heat fusion at a relatively low temperature. Also, it is easy to improve the processability and the like.

[0014] Polyester resin (A) has terephthalic acid as the main component in its dicarboxylic acid component, as described above. Here, having terephthalic acid as the main component means that the structural units derived from terephthalic acid should be 50 mol% or more of the dicarboxylic acid-derived structural units in polyester resin (A), and preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and even more preferably 90 mol% or more of the dicarboxylic acid-derived structural units in polyester resin (A). 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%.

[0015] In addition to terephthalic acid, other dicarboxylic acids may be used as the dicarboxylic acid component to obtain polyester resin (A). Specifically, aromatic dicarboxylic acids other than terephthalic acid and aliphatic dicarboxylic acids may be used. Aromatic dicarboxylic acids other than terephthalic acid are not particularly limited and include 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 which isophthalic acid is preferred.

[0016] 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. When using dicarboxylic acids other than terephthalic acid, one type may be used alone, or two or more types may be used in combination.

[0017] Polyester resin (A) has ethylene glycol and 1,4-cyclohexanedimethanol as the main components of its glycol component, as described above. By using these components as the main components, it becomes easier to improve the low-temperature fusion properties, heat resistance, and solvent resistance of this resin composition. Here, "mainly composed of ethylene glycol and 1,4-cyclohexanedimethanol" means that the total amount of structural units derived from ethylene glycol and 1,4-cyclohexanedimethanol is 50 mol% or more of the structural units derived from the glycol component in the polyester resin (A). The above total amount is preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and even more preferably 90 mol% or more, relative to the structural units derived from the glycol component. Furthermore, there is no particular upper limit, and it is sufficient if it is 100 mol% or less.

[0018] Structural units derived from 1,4-cyclohexanedimethanol are preferably present in the polyester resin (A) in an amount of 30 mol% or more, more preferably 40 mol% or more, even more preferably 45 mol% or more, and even more preferably 50 mol% or more, and also preferably 70 mol% or less, more preferably 65 mol% or less, even more preferably 60 mol% or less, and even more preferably 57 mol% or less. Having a certain amount or more of structural units derived from 1,4-cyclohexanedimethanol can improve heat resistance and other properties. Reducing the amount of structural units derived from 1,4-cyclohexanedimethanol below a certain amount can improve low-temperature fusion properties and other properties.

[0019] Furthermore, as the polyester resin (A), a polyester resin in which terephthalic acid-derived structural units account for all dicarboxylic acid-derived structural units on a molar basis, and 1,4-cyclohexanedimethanol-derived structural units account for, for example, 50% or more of all glycol-derived structural units on a molar basis (sometimes abbreviated as "PCTG") is also preferred. Using PCTG makes it easier to achieve a good balance of various properties such as heat resistance, low-temperature fusion resistance, and solvent resistance.

[0020] In polyester resin (A), structural units derived from ethylene glycol are preferably present in an amount of 20 mol% or more, more preferably 30 mol% or more, even more preferably 35 mol% or more, and even more preferably 40 mol% or more, and also preferably 70 mol% or less, more preferably 60 mol% or more, even more preferably 55 mol% or less, and even more preferably 50 mol% or less. Having a certain amount or more of structural units derived from ethylene glycol makes it easier to improve flexibility and low-temperature fusion properties. Conversely, keeping the amount of structural units derived from ethylene glycol below a certain level makes it easier to improve heat resistance and solvent resistance.

[0021] In addition to 1,4-cyclohexanedimethanol and ethylene glycol, glycol components other than 1,4-cyclohexanedimethanol and ethylene glycol (hereinafter also referred to as "other glycol components") may be used as glycol components to obtain polyester resin (A). Specifically, examples include chain-type dihydroxy compounds other than ethylene glycol and alicyclic dihydroxy compounds other than 1,4-cyclohexanedimethanol.

[0022] Chain-type dihydroxy compounds other than ethylene glycol may be linear or have a branched structure. Specific examples of chain-type dihydroxy compounds include chain-type dihydroxy compounds with approximately 2 to 18 carbon atoms, such as 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.

[0023] Specific examples of alicyclic dihydroxy compounds other than 1,4-cyclohexanedimethanol include cyclohexanedimethanol other than 1,4-cyclohexanedimethanol, tetramethylcyclobutanediol, tricyclodecanedimethanol, adamantanediol, and pentacyclopentadecanedimethanol. Examples of cyclohexanedimethanol include 1,2-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. Generally, 2,2,4,4-tetramethyl-1,3-cyclobutanediol is used as tetramethylcyclobutanediol. Other glycol components may be used individually or in combination of two or more. Furthermore, other glycol components are preferably chain-type dihydroxy compounds having 3 to 12 carbon atoms, and more preferably one or more selected from diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, with diethylene glycol being particularly preferred.

[0024] In polyester resin (A), structural units derived from other glycol components are preferably present in an amount of 10 mol% or less, more preferably 5 mol% or less, and even more preferably 3 mol% or less, within the total amount of structural units derived from glycol components in polyester resin (A). In polyester resin (A), structural units derived from other glycol components may or may not be present; therefore, the lower limit of the content of structural units derived from other glycol components is 0 mol%.

[0025] The polyester resin (A) is preferably an amorphous polyester. Using an amorphous polyester tends to improve the adhesion of the resin film formed from this resin composition to other components such as resin films, and to the interlayer adhesion in multilayer 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 crystal melting peak when heated by differential scanning calorimeter (DSC), polyesters that have crystallinity but have a slow crystallization rate and do not become highly crystalline when molded by extrusion film formation, and polyesters that have crystallinity but have a low heat of crystal melting (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." Among these, amorphous polyesters are preferable in that the heat of fusion (ΔHm) observed during heating by differential scanning calorimeter (DSC) of crystalline materials is 10 J / g or less. In the present invention, the crystalline nature of the polyester resin (A) as described above allows the effects of blending with the polycarbonate resin (B), which will be described later, to be appropriately exhibited. The DSC measurement procedure should be the same as the method for measuring the cold crystallization temperature and melting point described in the examples below.

[0026] When measuring the cold crystallization temperature of polyester resin (A) using DSC under measurement conditions of a heating rate of 10°C / min and a measurement temperature range of -70°C to 260°C, it is preferable that a peak appears. The appearance of a peak in the cold crystallization temperature allows the effects of blending with polycarbonate resin (B), described later, to be properly exhibited. The cold crystallization temperature of polyester resin (A) is not particularly limited, but for example, it is 150°C to 190°C, preferably 160°C to 185°C, and more preferably 167°C to 180°C. The detailed measurement conditions for DSC should be carried out as described in the examples.

[0027] The glass transition temperature of polyester resin (A) is typically lower than that of polycarbonate resin (B), preferably between 70°C and 110°C, more preferably between 75°C and 100°C, and even more preferably between 80°C and 95°C. Having the glass transition temperature within this range facilitates good thermal smability. The glass transition temperature of each resin can be obtained by measurement using DSC. Detailed measurement conditions should be as described in the examples.

[0028] (Polycarbonate resin (B)) In this invention, by using polycarbonate resin (B) in combination with the polyester resin (A) described above, the crystallization of polyester resin (A) is suppressed by polycarbonate resin (B), making it less likely for a peak to occur when measuring the cold crystallization temperature. Furthermore, even when a film or resin layer made of this resin composition is fused to another film or resin layer, it becomes easier to increase the adhesive strength between the fused film or other object, and it also becomes less likely for delamination to occur in multilayer films. In addition, it becomes easier to increase the adhesive strength to films or resin layers containing resin components other than polycarbonate resin (B). Moreover, it becomes less likely for printing defects to occur on films or resin layers made of this resin composition.

[0029] In the present invention, the polycarbonate resin (B) is preferably a polycarbonate having an aromatic ring, and more preferably a bisphenol-based polycarbonate. This resin composition contains a polyester resin (A) in addition to a polycarbonate resin having an aromatic ring, such as a bisphenol-based polycarbonate, which makes it easier to further increase the adhesive strength to layers and films containing resin components other than the polycarbonate resin (B). Furthermore, the inclusion of bisphenol-based polycarbonate in this resin composition makes it easier to improve the mechanical properties and heat resistance of the film. Moreover, the use of bisphenol-based polycarbonate in this resin composition makes it more compatible with polyester resin (A), and makes it less likely for peaks to occur when measuring the cold crystallization temperature.

[0030] Bisphenol-based polycarbonates are those in which 50 mol% or more, preferably 70 mol% or more, and more preferably 90 mol% or more of the structural units derived from dihydroxy compounds are derived from bisphenol. Bisphenol-based polycarbonates may be either homopolymers or copolymers. Furthermore, bisphenol-based polycarbonates may have a branched structure, a linear structure, or a mixture of a resin having a branched structure and a resin having only a linear structure.

[0031] Specific examples of bisphenols include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), bis(4-hydroxyphenyl)diphenylmethane (bisphenol BP), 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol C), 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E), bis(4-hydroxyphenyl)methane (bisphenol F), 2,2-bis( Examples include 4-hydroxy-3-isopropylphenyl)propane (bisphenol G), 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene (bisphenol M), bis(4-hydroxyphenyl)sulfone (bisphenol S), 1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene (bisphenol P), 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-ol]propane (bisphenol PH), 1,1-bis(4-hydroxyphenyl)3,3,5-trimethylcyclohexane (bisphenol TMC), and 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z). Bisphenols may be used individually or in combination of two or more types.

[0032] As the bisphenol, 2,2-bis(4-hydroxyphenyl)propane, i.e., bisphenol A, is preferably used, but a portion of the bisphenol A may be replaced with other bisphenols. Among the structural units derived from the dihydroxy compound, the structural units derived from bisphenol A are preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more, and most preferably 100 mol%. Therefore, bisphenol A homopolycarbonate is most preferred as the polycarbonate resin.

[0033] The method for producing bisphenol-based polycarbonates used as polycarbonate resins may be any known method, such as the phosgene method (interfacial polymerization), the transesterification method (melt polymerization), and the pyridine method. For example, the transesterification method is a manufacturing method that involves melt transesterification polymerization of bisphenol and diester carbonate using a basic catalyst, and further adding an acidic substance to neutralize this basic catalyst. Specific examples of diester carbonates include diphenyl carbonate, ditrile carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate, among which diphenyl carbonate is preferably used.

[0034] The glass transition temperature of polycarbonate resin (B) is typically higher than that of polyester resin (A), for example, between 110°C and 200°C. Preferably, it is 125°C or higher, more preferably 135°C or higher, even more preferably 140°C or higher, and also preferably 175°C or lower, more preferably 170°C or lower, and even more preferably 165°C or lower. Note that polycarbonate resin usually has a single glass transition temperature. By setting the glass transition temperature of polycarbonate resin (B) to 110°C or higher, the resin composition is more likely to exhibit appropriate heat resistance. On the other hand, setting it to 200°C or lower results in good low-temperature fusion properties. Furthermore, the moldability of the film is also easier to achieve.

[0035] The deflection temperature under load of the polycarbonate resin (B) is, for example, 90°C or higher, preferably 100°C or higher, more preferably 110°C or higher, even more preferably 120°C or higher, and also, for example, 170°C or lower, preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 145°C or lower. Setting the deflection temperature above the above lower limit makes it easier to obtain appropriate heat resistance. On the other hand, setting it to 170°C or lower improves low-temperature fusion properties. It also makes it easier to improve the moldability of the film. The temperature of deflection under load can be adjusted by appropriately selecting the ratio of each structural unit that makes up the polycarbonate resin (B). The temperature of deflection under load for each resin can be measured using the JIS K7191-2:2015A method (bending stress of 1.80 MPa applied to the test specimen).

[0036] The melt volume rate (300°C, 1.2 kgf) of the polycarbonate resin (B) is preferably 1 cm from the viewpoint of mechanical properties and moldability. 3 / 10 minutes or more, more preferably 2 cm 3 / 10 minutes or more, more preferably 3 cm 3 / 10 minutes or more, and preferably 60 cm 3 / 10 minutes or less, more preferably 50cm 3 / 10 minutes or less, and more preferably 40 cm 3 / 10 minutes or less, more preferably 30 cm 3 This is per 10 minutes. By setting the melt volume rate of polycarbonate resin (B) above a certain level, the crystallization of polyester resin (A) can be more effectively suppressed by the polycarbonate resin (B). The melt volume rate of polycarbonate resin can be measured in accordance with ISO 1133.

[0037] The number-average molecular weight (Mn) of the polycarbonate resin (B) is, for example, 15,000 or more, preferably 18,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more, and also preferably 50,000 or less, more preferably 40,000 or less. By setting the number-average molecular weight of the polycarbonate resin (B) to a certain level or higher, the crystallization of the polyester resin (A) can be more effectively suppressed by the polycarbonate resin (B).

[0038] Furthermore, the mass-average molecular weight of polycarbonate resin (B) is typically 20,000 or more, preferably 30,000 or more, and also typically 100,000 or less, preferably 80,000 or less, depending on the balance between mechanical properties and moldability. The mass-average molecular weight and number-average molecular weight can be measured using gel permeation chromatography (GPC) with polystyrene as the standard substance.

[0039] The viscosity-average molecular weight of polycarbonate resin (B) is typically 12,000 or more, preferably 15,000 or more, more preferably 20,000 or more, and even more preferably 22,000 or more, while also typically within the range of 40,000 or less, preferably 35,000 or less, more preferably 30,000 or less, and even more preferably 28,000 or less, based on a balance between mechanical properties and moldability. The viscosity-average molecular weight can be measured using dichloromethane as the solvent, determining the intrinsic viscosity ([η]) (unit dl / g) at 20°C using an Ubbelohde viscometer, and calculating it from Schnell's viscosity formula: η = 1.23 × 10⁻⁴ M 0.83. Furthermore, the degree of dispersion, expressed as the ratio of the mass-average molecular weight to the number-average molecular weight (Mw / Mn) of the polycarbonate resin, is not particularly limited, but is, for example, 1.1 or more and 10 or less, preferably 1.5 or more and 6 or less, more preferably 1.8 or more and 5 or less, and even more preferably 2 or more and 4 or less.

[0040] (Polycarbonate resin (C)) In the present invention, a polycarbonate resin (B) other than the bisphenol-based polycarbonate described above may be used as the polycarbonate resin (B). For example, it may be a polycarbonate resin (C) having a structural unit (A1) derived from a dihydroxy compound having a part of its structure represented by the following formula (1). [ka] However, this excludes cases where the part represented by formula (1) is part of -CH2-OH. In other words, the dihydroxy compound refers to one that contains two hydroxyl groups and at least the portion of formula (1) above.

[0041] Dihydroxy compounds having a site 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, and 9,9-bis(4-(2-hydroxyethoxy)-3-cyclo Examples include compounds having aromatic groups in the side chain and ether groups bonded to the aromatic groups in the main chain, such as hexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, and 9,9-bis(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).

[0042] 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. 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.

[0043] [ka]

[0044] [ka] In formula (3), R1 to R4 are each independently alkyl groups having 1 to 3 carbon atoms.

[0045] 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.

[0046] The polycarbonate resin (C) may further contain structural units other than structural unit (C1) as structural units derived from dihydroxy compounds, and it is preferable that it contains 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 (C2)).

[0047] Aliphatic dihydroxy compounds are not particularly limited in terms of the number of carbon atoms, but preferably have 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.

[0048] The structural units derived from alicyclic dihydroxy compounds preferably include 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 (C) 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. Preferably, the alicyclic dihydroxy compound is 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.

[0049] The content of structural units (C1) in the polycarbonate resin (C) is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 45 mol% or more, and preferably 80 mol% or less, more preferably 75 mol% or less, even more preferably 70 mol% or less, and even more preferably 65 mol% or less, within the structural units derived from the dihydroxy compound. By setting the content 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, making it easier to improve the transparency of the resin composition and prevent yellowing. 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 units (C1). On the other hand, the content of structural units (C2) in the polycarbonate resin (C) is preferably 20 mol% or more, more preferably 25 mol% or more, even more preferably 30 mol% or more, and 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.

[0050] The polycarbonate resin (C) preferably consists of structural units derived from dihydroxy compounds, namely structural unit (C1) and structural unit (C2). However, other structural units derived from dihydroxy compounds may also be included, as long as they do not impair the objectives of the present invention. Specifically, this may involve copolymerizing a small amount of aromatic ring-containing dihydroxy compounds, such as bisphenols like 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 excessive amounts tend to cause problems with weather resistance. Therefore, it is best to use them in an amount that does not impair 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.

[0051] The glass transition temperature of the polycarbonate resin (C) is, for example, 70°C or higher, preferably 80°C or higher, more preferably 85°C or higher, and 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 (C) has a single glass transition temperature. By keeping the glass transition temperature within the above range, it becomes easier to achieve low-temperature thermal fusion properties. The glass transition temperature can be adjusted by appropriately selecting the ratio of each structural unit that makes up the polycarbonate resin (C).

[0052] Polycarbonate resin (C) 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.

[0053] The molecular weight of the polycarbonate resin (C) can be expressed in terms of reduced viscosity. From the viewpoint of imparting mechanical strength, the reduced viscosity is preferably 0.3 dL / g or more, and more preferably 0.35 dL / g or more. From the viewpoint of improving productivity and moldability by increasing fluidity during molding, the reduced viscosity is preferably 1.2 dL / g or less, more preferably 1 dL / g or less, and more preferably 0.8 dL / g or less. The reduced viscosity is measured using a Ubbelohde viscometer at a temperature of 20.0°C ± 0.1°C, after precisely preparing the polycarbonate resin concentration to 0.6 g / dL using dichloromethane as the solvent.

[0054] In the present invention, the polycarbonate resin (B) can be any of the above-mentioned polycarbonate resins selected individually or in combination of two or more, but it is preferable to use at least bisphenol-based polycarbonate, and more preferably to use bisphenol-based polycarbonate alone.

[0055] The proportion of polycarbonate resin (B) in this resin composition is preferably 21% by mass or more, more preferably 25% by mass or more, even more preferably 28% by mass or more, and even more preferably 30% by mass or more, based on 100% by mass of the total amount of polyester resin (A) and polycarbonate resin (B). By including 21% by mass or more of polycarbonate resin (B), compatibility with the polyester resin (A) used in combination is increased, and the arrangement of molecular chains becomes less likely, thereby suppressing the acceleration of crystallization of polyester resin (A). As a result, when measuring the cold crystallization temperature by DSC, the peak is less likely to appear. Furthermore, it becomes possible to prevent the form containing polyester resin (A) from causing thermal fusion defects during the manufacturing process. In addition, the adhesive strength to other films containing resin components other than polycarbonate (B) resin, or to other resin layers in multilayer films, can be increased, making it easier to prevent delamination between fused films or delamination between layers in multilayer films. In addition, the mechanical strength of this film can be easily improved, and furthermore, printing defects will be less likely to occur.

[0056] Furthermore, the proportion of polycarbonate resin (B) in this resin composition is, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, and even more preferably 40% by mass or less, based on 100% by mass of the total amount of polyester resin (A) and polycarbonate resin (B). By keeping the proportion of polycarbonate resin (B) below a certain amount, it becomes easier to improve low-temperature fusion properties. Regarding the mixing ratio of polycarbonate resin (A) and polyester resin (A), it is possible to estimate this ratio by, for example, using model experiments to compare the ratio of peak intensities derived from each resin component using samples with varying mixing ratios of the two.

[0057] Furthermore, in this resin composition, the total amount of polyester resin (A) and polycarbonate resin (B) is, for example, 70% to 100% by mass, preferably 80% to 100% by mass, more preferably 90% to 100% by mass, and even more preferably 95% to 100% by mass, based on 100% by mass of the resin composition.

[0058] (Inorganic filler) This resin composition may or may not contain inorganic fillers. When used as a resin sheet, for example on the surface side of a laminate, it is preferable to have a transparent and visible resin composition that does not contain inorganic fillers, or has a low inorganic filler content. More specifically, the inorganic filler content is preferably less than 10 parts by mass, more preferably less than 8 parts by mass, even more preferably less than 5 parts by mass, and particularly preferably 0 parts by mass, per 100 parts by mass of the resin composition. Here, the surface side refers to, for example, the surface on which a pattern is viewed. Examples of patterns include those formed by printing a hologram layer or a coloring agent described later. The pattern also includes text. This resin composition, by containing an inorganic filler, has low light transmittance, which allows it to exhibit properties such as opacity. Therefore, this resin composition can be suitably used in cards and passports, and is particularly suitable for use in core sheets, as described later.

[0059] Examples of inorganic fillers include titanium dioxide, talc, mica, calcium carbonate, magnesium carbonate, barium oxide, carbon black, silica, lead titanate, potassium titanate, barium titanate, zircon oxide, magnesium oxide, calcium oxide, aluminum oxide, zinc sulfide, antimony oxide, zinc oxide, boron nitride, aluminum nitride, and barium sulfate. Among these, metal oxides are preferred as inorganic fillers.

[0060] As the inorganic filler, at least one selected from the inorganic fillers listed above with a refractive index of 2 or higher is preferred, more preferably 2.2 or higher, and even more preferably 2.4 or higher. Examples of inorganic fillers with a refractive index of 2 or higher include titanium dioxide, lead titanate, potassium titanate, barium titanate, zircon oxide, magnesium oxide, calcium oxide, zinc sulfide, antimony oxide, zinc oxide, aluminum oxide, boron nitride, aluminum nitride, calcium carbonate, magnesium carbonate, and barium sulfate. Using an inorganic filler with a refractive index of 2 or higher provides even better opacity and makes it easier to color the material white. From these viewpoints, titanium dioxide is more preferred as the inorganic filler. There are no particular limitations on titanium dioxide, but examples include rutile-type titanium dioxide and anatase-type titanium dioxide. The refractive index of the inorganic filler can be measured by the Becke line method.

[0061] The average particle size of the inorganic filler is not particularly limited, but is, for example, 0.01 μm or more and 1 μm or less, preferably 0.05 μm or more and 0.8 μm or less, more preferably 0.08 μm or more and 0.6 μm or less, even more preferably 0.1 μm or more and 0.5 μm or less, and even more preferably 0.12 μm or more and 0.4 μm or less. Note that the average particle size refers to the average primary particle size observed with a scanning electron microscope.

[0062] When the resin composition contains an inorganic filler, it is preferable that the inorganic filler content in the resin composition be such that it contains a certain amount or more of the inorganic filler. Specifically, it is preferable that the inorganic filler content be between 5 parts by mass and 90 parts by mass per 100 parts by mass of the resin component contained in the resin composition. By having an inorganic filler content of 5 parts by mass or more, the opacity of the film formed from the resin composition can be improved. Furthermore, by having an inorganic filler content of 90 parts by mass or less, it becomes easier to maintain good mechanical properties such as bending resistance. From these viewpoints, the inorganic filler content is more preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, and if higher opacity is required, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more. Furthermore, the inorganic filler content is more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less, but if higher opacity is not required, it may be 40 parts by mass or less.

[0063] As described above, the inorganic filler is preferably titanium dioxide. Therefore, the titanium dioxide content in this resin composition is preferably 5 parts by mass or more and 90 parts by mass or less per 100 parts by mass of the resin components contained in this resin composition. Furthermore, the titanium dioxide content is more preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more. Furthermore, the titanium dioxide content is more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 45 parts by mass or less, and may also be 40 parts by mass or less.

[0064] (Coloring agent) This resin composition may contain a coloring agent. By containing a coloring agent, the resin sheet formed from this resin composition can be colored, allowing for printing and other applications. The coloring agent is preferably a laser coloring agent. By containing a laser coloring agent, the resin sheet formed from this resin composition can be laser printed.

[0065] The laser colorant 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 emits color itself when irradiated with laser light, or it may not emit color itself. When the laser colorant generates heat, at least the surrounding forming material carbonizes, and the desired printing appears on the resin sheet. Furthermore, if a self-coloring laser colorant is used, the coloring of the laser colorant and the coloring of the carbonized material produced by the carbonization of the forming material of the resin sheet synergistically produce printing with a deep color and excellent visibility. When the laser colorant emits color, the color is not particularly limited, but from the viewpoint of visibility, it is preferable to use a laser colorant that can emit dark colors including black, navy blue, and brown.

[0066] 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. In addition to metal oxides, other laser colorants include metals such as iron, copper, zinc, tin, gold, silver, cobalt, nickel, bismuth, antimony, and aluminum, as well as their 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, as well as metal borides such as zirconium boride, titanium boride, and lanthanum boride, can also be used. Among metal borides, hexaborides are preferred because they have near-infrared absorption capabilities, and lanthanum hexaboride is particularly favored due to its excellent laser light absorption efficiency. Dyes and carbon black can also be used. The laser colorant may be used alone in the resin composition, or two or more may be used in combination.

[0067] (Impact-resistant additive) This resin composition may contain an impact-resistant agent. By containing an impact-resistant agent, this resin composition can mitigate the effects of external impacts such as bending and impact during actual use, thereby improving the bending durability of films and other materials formed from this resin composition. It can also prevent a decrease in softness and fluidity when heated, making it easier to maintain good processability.

[0068] Examples of impact-resistant modifiers include soft styrene resins and elastomers. The elastomer may be a core-shell type elastomer. The impact-resistant modifier may be used alone or in combination of two or more types. Among the above, core-shell type elastomers are preferred as impact-resistant modifiers. By using a core-shell type elastomer, impact resistance is further improved and bending durability is further enhanced.

[0069] Examples of flexible styrene-based resins include block copolymers containing styrene polymer blocks and conjugated diene polymer blocks, and block copolymers containing styrene polymer blocks and acrylonitrile blocks. The styrene content in the flexible styrene resin is, for example, 5% by mass or more and 80% by mass or less, preferably 10% by mass or more and 50% by mass or less, and more preferably 15% by mass or more and 30% by mass or less. Having a styrene content within this range further improves the impact resistance effect.

[0070] As conjugated diene polymer blocks used in flexible styrene resins, homopolymers such as butadiene, isoprene, and 1,3-pentadiene, copolymers thereof, or copolymers containing monomers copolymerizable with conjugated diene monomers within the block can be used. Specific examples of flexible styrene-based resins include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), silicone-acrylic composite rubber-acrylonitrile-styrene copolymer (SAS), methyl methacrylate-maleic anhydride-styrene copolymer (SMM), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene-acrylic rubber copolymer (ASA), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES). Specific products include the "Krayton D" series from Kraton Polymers, the "AR-100" series from Aron Kasei Co., Ltd., the "Dialac" series from UMG ABS, and the "Delpet" series from Asahi Kasei Chemicals. Furthermore, as flexible styrene-based resins, the following styrene-based elastomers can also be used, including the "Dynalon" series from JSR Corporation, the "Toughtech" series from Asahi Kasei Chemicals Corporation, and the "Hybral" series from Kuraray Corporation.

[0071] The block copolymer includes pure blocks, random blocks, tapered blocks, etc., and the form of copolymerization is not particularly limited. Furthermore, the block units themselves may consist of multiple repeating units. Specifically, in the case of styrene-butadiene block copolymers, the block units may be repeated multiple times, such as styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, and styrene-butadiene-styrene-butadiene block copolymer.

[0072] Furthermore, hydrogenated styrene-butadiene-styrene block copolymers (SEBS) and hydrogenated styrene-isoprene-styrene block copolymers (SEPS), in which some or all of the double bonds of the conjugated diene polymer blocks of SBS or SIS are hydrogenated, can also be used. Specific examples of such products include Asahi Kasei Chemicals' "ToughTec H" series and Kraton Polymers' "Kraton G" series.

[0073] It is also possible to impart polar functional groups to flexible styrene resins. Specific examples of polar functional groups include acid anhydride groups, carboxylic acid groups, carboxylic acid ester groups, carboxylic acid chloride groups, carboxylic acid amide groups, carboxylic acid bases, sulfonic acid groups, sulfonic acid ester groups, sulfonate chloride groups, sulfonic acid amide groups, sulfonic acid bases, epoxy groups, amino groups, imide groups, and oxazoline groups. Among these, it is preferable to impart acid anhydride groups or epoxy groups. Modified forms of SEBS and SEPS are preferred as soft styrene resins to which polar functional groups are added. Specifically, examples include maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, epoxy-modified SEBS, and epoxy-modified SEPS. Specific products include the "ToughTec M" series from Asahi Kasei Chemicals, the "Dynalon" series from JSR Corporation, and the "Epofriend" series from Daicel Chemical Industries, Ltd.

[0074] Furthermore, the flexible styrene resin may also be a styrene elastomer containing an elastomer component. Specifically, among those mentioned above, examples include a styrene component and block copolymers of butadiene, isoprene, 1,3-pentadiene, etc., and modified versions of these or hydrogenated versions may also be used. More specifically, examples include SBS, SIS, SEBS, and SEPS.

[0075] The elastomer may be anything other than a styrene-based elastomer, and known examples include polyester-based elastomers, polyolefin-based elastomers, diene-based elastomers, acrylic-based elastomers, polyamide-based elastomers, polyurethane-based elastomers, fluorine-based elastomers, and silicone-based elastomers. The elastomer is generally a thermoplastic elastomer. Preferably, the elastomer is a polyester-based elastomer or one of the styrene-based elastomers described above.

[0076] Polyester elastomers are thermoplastic polyesters that have rubber properties at room temperature, and are preferably thermoplastic elastomers mainly composed of polyester block copolymers, and are preferably block copolymers having a high melting point, high crystallinity aromatic polyester as the hard segment and amorphous polyester or amorphous polyether as the soft segment. The soft segment content of the polyester elastomer is at least 20 to 95 mol% of the total segments, and in the case of a block copolymer of polybutylene terephthalate and polytetramethylene glycol (PTMG-PBT copolymer), it is 50 to 95 mol%. The preferred soft segment content is 50 to 90 mol%, particularly 60 to 85 mol%. Among these, polyester ether block copolymers, and especially PTMG-PBT copolymers, are preferred.

[0077] A core-shell type elastomer consists of an innermost layer (i.e., a core) and one or more outer layers (i.e., a shell) covering it. Preferably, the core-shell type elastomer is a core-shell type graft copolymer in which monomer components capable of graft copolymerization with respect to the core are graft copolymerized as the shell.

[0078] Core-shell type graft copolymers typically have a polymer component called a rubber component as the core. In core-shell type graft copolymers, it is preferable that the polymer component constituting the core and monomer components copolymerizable with this polymer component are graft copolymerized as the shell. 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.

[0079] Specific examples of polymer components forming the core include 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, silicone-acrylic composite rubbers such as butadiene-acrylic composite rubbers and IPN (Interpenetrating Polymer Network) type composite rubbers consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, ethylene-α-olefin-based rubbers such as ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-octene copolymers, ethylene-acrylic rubbers, and fluororubber. These may be used individually or in combination of two or more. Among these, at least one selected from butadiene-based rubbers, acrylic-based rubbers, silicone-based rubbers, and silicone-acrylic composite rubbers is preferred in terms of mechanical properties and surface appearance, and at least one selected from butadiene-based rubbers and silicone-acrylic composite rubbers is more preferred.

[0080] Specific examples of monomer components that can be graft copolymerized with the polymer component of the core and constitute the shell include aromatic vinyl compounds; vinyl cyanide compounds; (meth)acrylic compounds such as (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, and epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; and α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and their anhydrides (e.g., maleic anhydride). These monomer components may be used individually or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, and (meth)acrylic compounds are preferred in terms of mechanical properties and surface appearance, and more preferably aromatic vinyl compounds, (meth)acrylic compounds, and especially (meth)acrylic acid ester compounds. 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. Specific examples of (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate. Among these, methyl (meth)acrylate and ethyl (meth)acrylate are preferred because they are relatively easy to obtain, with methyl (meth)acrylate being more preferred. Note that "(meth)acrylic" is a general term for "acrylic" and "methacrylic".

[0081] As the core-shell type elastomer, a core-shell type graft copolymer is particularly preferred, which consists of a core made of at least one polymer component selected from butadiene rubber, acrylic rubber, silicone rubber, and silicone-acrylic composite rubber, and a shell formed by graft copolymerizing a (meth)acrylic compound such as a (meth)acrylic acid ester or an aromatic vinyl compound around the core. The content of the polymer component in the core 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. Furthermore, the total content of (meth)acrylic compounds (especially (meth)acrylic acid esters) and aromatic vinyl compounds in the shell of the core-shell type graft copolymer is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and even more preferably 70% by mass or more. In the shell, either the (meth)acrylic compound or the aromatic vinyl compound may be used alone, or they may be used in combination.

[0082] 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, and methyl methacrylate-(acrylic / silicone composite rubber) copolymer.

[0083] Examples of commercially available core-shell graft copolymers include "Paraloid EXL2602", "Paraloid EXL2603", "Paraloid EXL2690", "Paraloid EXL2691J", "Paraloid EXL2650J", "Paraloid EXL2655", "Paraloid EXL2311", "Paraloid EXL2313", "Paraloid EXL2315", "Paraloid KM330", "Paraloid KM336P", and "Paraloid KCZ201" from Dow Chemical Japan, and "Metab" from Mitsubishi Chemical Corporation. Examples include "Ren C-223A", "Metabren E-901", "Metabren S-2001", "Metabren W-450A", "Metabren SRK-200", "Metabren E-870A", "Metabren S-2006", "Metabren W-377", and Kaneka's "Kaneace M-210", "Kaneace M-511", "Kaneace M-600", "Kaneace M-400", "Kaneace M-580", "Kaneace M-590", "Kaneace M-711", "Kaneace MR-01", and "Kaneace M-300". These impact-resistant modifiers, such as core-shell type graft copolymers, may be used individually or in combination of two or more types.

[0084] The content of the impact-resistant modifier in this resin composition is preferably 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the resin components contained in the resin composition. A content of 1 part by mass or more of the impact-resistant modifier moderately mitigates the effects of external impacts, improving bending durability and other properties. It also prevents a decrease in softening and fluidity during heating of the resin composition, which can be caused by the type of resin used, thus maintaining good processability. On the other hand, a content of 30 parts by mass or less allows the modifier to exert an effect commensurate with its content. Furthermore, it prevents a decrease in various physical properties of the resin composition, such as heat resistance, moisture resistance, and mechanical strength. Additionally, it prevents the resin composition from becoming excessively fluid during processing. The impact-resistant agent content in this resin composition is more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 8 parts by mass or more, even more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.

[0085] (Other resin components) This resin composition may contain resin components other than polyester resin (A) and polycarbonate resin (B) (also referred to as "other resin components"). Such resin components may be commonly used known resins, and it is preferable to use resins that are compatible with polyester resin (A) and polycarbonate resin (B). Other resin components may include any resin other than the polycarbonate resin (A), polycarbonate resin (B), and impact modifier mentioned above, and thermoplastic resins are preferred. Examples include polyester resins other than the polyester resin (A) mentioned above, polyolefin resins, acrylic resins, polystyrene resins, polyamide resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl alcohol resins, ethylene-vinyl alcohol resins, polycycloolefin resins, ethylene vinyl acetate copolymer resins, ethylene (meth)acrylate copolymer resins, polyphenylene ether resins, polyacetal resins, acrylonitrile-butadiene-styrene copolymer resins, polyaryl ether ketone resins, polyimide resins, polyphenylene sulfide resins, polyarylate resins, polysulfone resins, polyethersulfone resins, and fluororesins.

[0086] (Recycled materials) This resin composition may contain recycled materials. By including recycled materials, this resin composition can further reduce its environmental impact. Preferably, the recycled material is a recycled resin that constitutes at least a part of the resin components described above. In particular, it is more preferable that at least a portion of the polyester resin (A) and polycarbonate resin (B) are recycled materials, and even more preferable that at least a portion of the polyester resin (A) are recycled materials. Polyester resin (A) is highly recyclable, and recycled materials can be used relatively easily. Furthermore, recycled polyester resin (A) has a high thermal history, which leads to a decrease in molecular weight and makes it prone to crystallization. However, in this invention, even when using recycled polyester resin (A) that is prone to crystallization, printing defects and heat-sealing defects can be made less likely.

[0087] Recycled resin may be resin produced by chemical recycling methods involving chemical reactions from collected products or waste, or it may be resin produced by physical recycling methods (mechanical recycling) from collected products or waste. Resins recycled by chemical recycling methods, in the case of polyester resins, can be obtained by depolymerizing discarded polyester resins, and then repolymerizing the resulting intermediates or monomers to synthesize various polyester resins such as polyester resin (A). The resin recycled by the physical recycling method can be used as recycled resin by collecting various resin products such as polyester resin products and polycarbonate resin products, as well as scraps generated during the production process, sorting, separating, and washing as needed, then processing by melting and crushing, and then processing by granulation, micronization, pelletization, flakeization, etc. as appropriate, to form a material that can be used as a raw material for resin compositions such as powder, granules, pellets, and flakes.

[0088] When recycled materials are used as resin components, the entire amount of the resin components in this resin composition may be recycled, or only a portion may be recycled. Similarly, when recycled materials are used as polyester resin (A), the entire amount of polyester resin (A) may be recycled, or only a portion may be recycled. PCTG is preferred as the polyester resin (A) used as a recycled material. When recycled materials are used in polyester resin (A), the content of recycled materials in polyester resin (A) is, for example, 30% by mass or more, preferably 50% by mass or more, and more preferably 70% by mass or more. From the viewpoint of protecting the global environment, the higher the recycled material content, the better, and there is no particular limit as long as it is 100% by mass or less.

[0089] This resin composition may contain components other than resin components, fillers, colorants, impact modifiers, and ionic acid generators, for example, it may contain other additives (also called other additives). Other additives include, specifically, antioxidants, heat stabilizers, process stabilizers, UV absorbers, light stabilizers, matting agents, processing aids, metal deactivators, residual polymerization catalyst deactivators, antibacterial and antifungal agents, antiviral agents, antistatic agents, lubricants, flame retardants, pigments, dyes, and other colorants commonly used in a wide range of resin materials. For these as well, the amount added should be the amount typically used, depending on the intended purpose. These additives may be used individually or in combination of two or more.

[0090] This resin composition may be obtained by mixing, for example, polyester resin (A), polycarbonate resin (B), and other raw materials that constitute this resin composition, such as inorganic fillers, colorants, shock absorbers, and other additives as needed, as well as resin components other than polyester resin (A) and polycarbonate resin (B). The mixing of the raw materials may be carried out by melt kneading while heating in an extruder, plast mill, or the like. The temperature during kneading is, for example, 180°C to 320°C, preferably 200°C to 310°C, and more preferably 220°C to 300°C.

[0091] [Cold crystallization temperature] This resin composition is characterized by the absence of a peak when the cold crystallization temperature is measured by DSC under measurement conditions of a heating rate of 10°C / min and a measurement temperature range of -70°C to 260°C. The absence of a peak when measuring the cold crystallization temperature enhances the compatibility between polyester resin (A) and polycarbonate resin (B), making it difficult for molecular chains to align and suppressing the crystallization of polyester resin (A). As a result, films and resin layers made from this resin composition can be prevented from causing thermal fusion defects with other films and resin layers during the manufacturing process. Furthermore, printing defects are less likely to occur when printing is performed on films and resin layers made from this resin composition. In addition, since substantially no crystallization occurs even when this resin composition is heated, it is possible to prevent clouding after thermal fusion. The details of the measurement conditions for the crystallization temperature will be as shown in the examples described later. Also, the peak of the crystallization temperature can be prevented from appearing by appropriately selecting the types and blending amounts of the polyester resin (A) and the polycarbonate resin (B).

[0092] [Storage elastic modulus] This resin composition preferably has a storage elastic modulus of 1×10 6 Pa or less at 170°C and 1 Hz. By having a storage elastic modulus of 1×10 6 Pa or less, crystallization does not occur when heated, and a film or resin layer made of this resin composition is less likely to cause poor heat fusion with other films or other resin layers. Also, printing defects are less likely to occur when printing is performed on a film or resin layer made of this resin composition. The details of the measurement conditions for the storage elastic modulus are as described in the examples below. A film may be prepared according to the methods described in the examples and comparative examples, and the measurement may be performed on that film.

[0093] [Glass transition temperature] The glass transition temperature of this resin composition is preferably 80°C or higher and 130°C or lower, more preferably 85°C or higher and 120°C or lower, and even more preferably 90°C or higher and 110°C or lower. By having the glass transition temperature within the above range, the heat fusion property and heat resistance can be well balanced. The glass transition temperature of this resin composition can be obtained by measurement using DSC. The detailed measurement conditions may be carried out as described in the examples.

[0094] [Film] The film of the present invention (hereinafter also referred to as "this film") is made of this resin composition. This film may have a single-layer structure or a multilayer structure. The number of layers of the multilayer-structured this film is not particularly limited as long as it has two or more resin layers. The multilayer-structured this film may be such that each resin layer is made of this resin composition. For the multilayer-structured this film, the compositions of the resin compositions constituting each resin layer may be the same as or different from each other.

[0095] 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 may be 1000 μm or less, preferably 500 μm or less, more preferably 300 μm or less, even more preferably 250 μm or less, and even more preferably 200 μm or less. Setting the thickness of this film above a certain level makes it easier for the film to perform its appropriate function. For example, it makes it easier to ensure opacity when inorganic fillers are included. On the other hand, setting the thickness below a certain level makes it easier to make cards and passports thinner.

[0096] [Film haze change rate] The film preferably has a film haze change rate (ΔH) of 2.0% or less, more preferably 1.5% or less, and even more preferably 1.0% or less, before and after heat treatment at 140°C for 30 minutes. The lower limit of the film haze change rate (ΔH) is not particularly limited, but for example, it may be -10% or more, -5.0% or more, or -2.0% or more. By lowering the film haze change rate, the film does not crystallize and become cloudy when heated, which reduces the likelihood of poor heat fusion and printing defects. The haze value of this film before heating is not particularly limited, but if it is transparent, it may be, for example, 10% or less, preferably 5% or less, and more preferably 3% or less. The rate of change in film haze can be determined by measuring the haze of the film before heating and the haze of the film after heating at 140°C for 30 minutes, and then subtracting the haze before heating from the haze after heating.

[0097] (Method of manufacturing this film) Although this film can be manufactured by known methods, it is preferable to obtain the resin composition for forming this film as described above and then make the resin composition into a film. The method for making the resin composition into a film is not particularly limited, and may include press molding or extrusion molding, but extrusion molding is preferred in terms of productivity and cost.

[0098] Furthermore, if the film has a multilayer structure, 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 layer 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.

[0099] <Laminate> The laminate of the present invention (hereinafter also referred to as "this laminate") comprises a plurality of this film, wherein the plurality of this film is laminated directly or via other layers. Alternatively, this laminate may consist of only one this film; in that case, this laminate may be a laminate of this film and other layers. Because this film has good heat-sealing properties, it can be easily bonded to other layers or to each other by heat fusion.

[0100] The other layers are preferably resin sheets containing polycarbonate resin. As described above, this film has high heat-sealability and contains polycarbonate resin (B), so it can be easily heat-sealed to resin sheets containing polycarbonate resin. Here, examples of polycarbonate resins used for the other layers include polycarbonates having aromatic rings, and among these, bisphenol-based polycarbonates are preferred. Details of bisphenol-based polycarbonates are as described above, so their explanation will be omitted.

[0101] Furthermore, the polycarbonate resin used in other layers may be a polycarbonate resin (C) having a structural unit (A1) derived from a dihydroxy compound having a portion represented by formula (1) above as part of its structure. In the present invention, as described above, the film has high heat-sealability and contains polycarbonate resin (B), so even if the polycarbonate resin used in the resin sheet is polycarbonate resin (C), the film can be easily heat-sealed to the resin sheet. In the following explanation, a resin sheet containing polycarbonate resin (C) may be referred to as resin sheet A, and a resin sheet containing polycarbonate resin may be referred to as resin sheet B.

[0102] The resin sheet A used in this laminate may consist of a resin composition A containing a polycarbonate resin (C) having a structural unit derived from a dihydroxy compound having a part of its structure represented by formula (1) above. Details of the polycarbonate resin (C) are as described above. Resin composition A may use only polycarbonate resin (C) as the resin component, but may also contain resin components other than polycarbonate resin (C) to the extent that it does not contradict the spirit of the present invention. The resin components constituting resin composition A preferably contain polycarbonate resin (C) as the main component, and the amount of polycarbonate resin (C) 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 components contained in resin composition A.

[0103] Furthermore, the resin sheet B used in this laminate may be made of a resin composition B containing polycarbonate resin, and the polycarbonate resin is not particularly limited. In other words, known polycarbonate resins can be used. Therefore, the polycarbonate resin contained in the resin sheet B may be bisphenol-based polycarbonate, etc. However, a resin composition containing the above-mentioned polycarbonate resin (C) may be used as the resin composition B. By using polycarbonate resin (C) in the resin sheet B, the biomass content of the final product can be improved and the environmental burden can be reduced. In addition, because the resin sheet B contains polycarbonate resin (C), the film can be fused at a low temperature when hot-pressed, resulting in good hot-press suitability.

[0104] Resin composition B may use only polycarbonate resin as the resin component, but may also contain resin components other than polycarbonate resin as long as it does not contradict the spirit of the present invention. The resin components constituting resin composition B preferably contain polycarbonate resin as the main component, and the amount of polycarbonate resin 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 components contained in resin composition B.

[0105] In one preferred embodiment, the resin components constituting resin composition B may mainly contain bisphenol polycarbonate, and the amount of bisphenol polycarbonate 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 components contained in resin composition B. In another preferred embodiment, the resin components constituting resin composition B may mainly contain polycarbonate resin (C), and the amount of polycarbonate resin (C) 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 components contained in resin composition B.

[0106] The following describes resin composition A and resin composition B. When "resin composition X" is mentioned, it refers to both resin composition A and resin composition B. In addition to being used in resin sheets A and resin sheet B, resin composition X can also be used as a core sheet, overlay sheet, laser marking sheet, etc., as described later.

[0107] Resin composition X may or may not contain an inorganic filler. Details of the inorganic filler are as described above. When transparency is required for resin sheet A or resin sheet B, the inorganic filler may be omitted or its content reduced. In the embodiment where the inorganic filler content is reduced, the inorganic filler content is as described above for this resin composition. Furthermore, by containing a certain amount or more of inorganic filler, resin composition X can have reduced light transmittance, for example, exhibiting opacity. Therefore, resin composition X can be suitably used in cards and passports, and is particularly suitable for use in core sheets as described later. Details of the content in embodiments containing a certain amount or more of inorganic filler are as described above in the description of this resin composition.

[0108] Furthermore, resin composition X may appropriately contain colorants, ionic acid generators, impact-resistant modifiers, etc. Details of the colorants, ionic acid generators, and impact-resistant modifiers are as described above, and a detailed explanation of their content is also provided in this resin composition. Resin composition A may contain resin components other than polycarbonate resin (C). Such resin components may be commonly used known resins, and it is preferable to use resins that are compatible with polycarbonate resin (C). Similarly, resin composition B may contain resin components other than polycarbonate resin. Such resin components may include commonly used, known resins, and it is preferable to use resins that are compatible with polycarbonate resin. The resin other than polycarbonate resin (C) used in resin composition A may be a polycarbonate resin other than polycarbonate resin (C), a polyester resin such as polyester resin (A), or any other resin component. The resin other than polycarbonate resin used in resin composition B may be a polyester resin such as polyester resin (A), or any other resin component other than polyester resin or polycarbonate resin. Details of the other resin components are as described above.

[0109] Resin composition X may contain components other than resin components, fillers, colorants, impact modifiers, and ionic acid generators, for example, other additives (other additives). Examples of other additives include those commonly used in a wide range of resin materials, and specifically, additives other than the fillers, colorants, and ionic acid generators listed in the above-mentioned resin composition. Other additives should be added in amounts typically used depending on the intended purpose. These additives may be used individually or in combination of two or more.

[0110] The resin sheet A may have a single-layer structure or a multi-layer structure. In the case of a multi-layer resin sheet A, the number of layers is not particularly limited as long as it has two or more resin layers. In the case of a multi-layer resin sheet A, each resin layer may be made of the above-mentioned resin composition A. In the case of a multi-layer resin sheet A, the composition of the resin composition constituting each resin layer may be the same as or different from one another. Furthermore, like resin sheet A, resin sheet B may have a single-layer structure or a multi-layer structure. The number of layers in a multi-layer resin sheet B is not particularly limited, as long as it has two or more resin layers. In a multi-layer resin sheet B, each resin layer is preferably made of resin composition B containing the polycarbonate resin described above. In a multi-layer resin sheet B, the composition of the resin composition constituting each resin layer may be the same or different from one another.

[0111] The thickness of resin sheet A and resin sheet B is not particularly limited and can be adjusted as appropriate depending on the intended use, but for example, they are 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, and also, for example, 1000 μm or less, preferably 500 μm or less, more preferably 300 μm or less, even more preferably 250 μm or less, and even more preferably 200 μm or less. Setting the thickness of the resin sheet above a certain level makes it easier for the resin sheet to perform its appropriate function. For example, it makes it easier to ensure opacity when inorganic fillers are included. On the other hand, setting the thickness below a certain level makes it easier to make cards and passports thinner.

[0112] This laminate may also contain resin sheets other than the above-mentioned resin sheet A and resin sheet B as other layers, and the resin sheets are not particularly limited as long as they are resin sheets that can be used for cards and passports.

[0113] This laminate may also have a hologram layer as another layer. The hologram layer can be a volume-type hologram layer or a relief-type hologram layer, and either can be used in this invention, but a relief-type is preferred because it is easier to manufacture. The relief-type hologram layer can be any material having a surface with an uneven structure (relief structure) corresponding to interference fringes, and known materials can be used. Specifically, it is formed by using a photocurable resin, thermosetting resin, or thermoplastic resin to create a desired fine uneven pattern and then curing it. The thickness of the hologram layer is preferably within the range of 0.8 μm to 1.5 μm.

[0114] A relief (uneven surface) is formed on the surface of the relief-type hologram layer, and a reflective layer is deposited on the relief surface to improve visibility. The reflective layer can be made from a transparent coating material or a metal coating material. Examples of transparent coating materials include ZnS, TiO2, PbTiO2, ZrO, ZnTe, and PbCrO4. When using a metal coating material for the reflective layer, it is possible to use elements, mixtures, or alloys of chromium, nickel, aluminum, iron, titanium, silver, gold, or copper. The thickness of the reflective layer is preferably within the range of 50 nm to 100 nm.

[0115] The hologram layer may be laminated directly onto the resin sheet or the resin film. Furthermore, the hologram layer may be formed on a substrate, in which case the hologram layer can be easily bonded to the resin sheet or film via the substrate by heat fusion. Suitable resins for the substrate include polyester resin. While not particularly limited, polyester resins such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate) may be used.

[0116] The hologram layer may have an adhesive layer and be bonded to the resin sheet or the main resin film via the adhesive layer. If a substrate is provided, the adhesive layer may be provided on the side opposite to the side on which the substrate is provided. The hologram layer may have adhesive layers on both sides and be bonded to the resin film or the main film via the adhesive layers on both sides. The materials constituting the adhesive layer are not particularly limited as long as they have good adhesion to other resins. For example, thermoplastic resins such as propylene resin, polyethylene terephthalate resin, polyacetal resin, and polyester resin can be used. Furthermore, the adhesive layer material may also contain inorganic materials such as silica. While there are no particular limitations on the thickness of the adhesive layer, a range of 0.5 μm to 1.5 μm is preferred. A thickness of 0.5 μm or more ensures sufficient adhesive strength even when the surface of the adherend is rough.

[0117] Specific examples of this laminate include resin sheet A / main film / main film / resin sheet B, resin sheet A / main film / resin sheet B / main film / resin sheet B, film / adhesive layer / hologram layer / film / film, film / hologram layer / adhesive layer / film / resin film, film / adhesive layer / hologram layer / adhesive layer / film / film, etc. In the above laminate configuration, at least one "film" should be the main film, and the rest should be either resin sheet A or resin sheet B. Furthermore, the present invention is not limited to the above configuration, and when this laminate is used in cards, passports, etc., additional layers may be laminated. Also, the number of "films" that are laminated continuously is not limited to the above, and instead of one, there may be two or more, or instead of two, there may be one or three or more. In addition, layers other than the resin sheet A, resin sheet B, hologram layer, and adhesive layer described above may be laminated. Moreover, in each of the above laminated structures, the hologram layer may be formed on a substrate.

[0118] (Method of manufacturing a laminate) This laminate is best formed by overlapping one or more of the main film and other layers such as resin sheets and hologram layers as needed, and then bonding them together by heat pressing and press molding. In this case, if the laminate has multiple main films, the multiple main films should be overlapped directly or via other layers and then bonded together by press molding. Furthermore, if the hologram layer is to be bonded to other layers such as this film or a resin sheet via an adhesive layer, the hologram layer and this film or other layer may be bonded via the adhesive layer, and then further layered with other this film or resin sheets and laminated by press molding. As described above, this film contains polyester resin (A), so it can be pressed onto other resin sheets or this film even when heat-pressed at a relatively low temperature. Press molding is preferably performed by heat-pressing at a temperature of less than 170°C, more preferably at a temperature of about 120 to 160°C.

[0119] <Card or passport> This resin composition, this film, and this laminate are preferably used in cards or passports. As for cards, they can be used in various types of cards such as IC cards, magnetic cards, driver's licenses, residence cards, qualification certificates, employee IDs, student IDs, health insurance cards, My Number cards, seal registration certificates, vehicle registration certificates, tag cards, prepaid cards, cash cards, bank cards, credit cards, SIM cards, ETC cards, identification cards, information-carrying cards, smart cards, B-CAS cards, and memory cards. Furthermore, this film, this resin composition, or this laminate is preferably used in the data pages of passports.

[0120] The card or passport of the present invention (more specifically, the data page of a passport) may include the above-described film (or laminate). The card or passport is usually composed of multiple resin films, and it is preferable that at least one of them is the present film. The card or passport may include a core sheet. In addition to the core sheet, the card or passport may also include at least one of a laser-marked sheet and an oversheet. Passports or cards may be manufactured by die-cutting this laminate, or by overlapping this laminate with other sheets, pressing and heat-fusing them, and then die-cutting them. Alternatively, instead of heat-fusing, adhesives may be used to bond the sheets together as appropriate.

[0121] In the case where this film does not contain inorganic fillers, or contains inorganic fillers in an amount that does not impair transparency, the film may not contain a coloring agent in one embodiment, but it is also preferable to include a coloring agent. In the embodiment without a coloring agent, the film can be used as an oversheet, and in the embodiment with a coloring agent, the film can be used as a laser marking sheet. On the other hand, the film may also be made of a resin composition containing an inorganic filler in an amount of 5 to 90 parts by mass per 100 parts by mass of the resin component, in which case the film is preferably used as a core sheet.

[0122] Preferably, the card is a card 20A comprising a laser marking sheet 1 and a core sheet 2, as shown in Figure 1(a), with the laser marking sheet 1 on one or both sides of the core sheet 2. If a hologram layer is to be provided in the card 20A, for example, a hologram layer (not shown) may be provided between the laser marking sheet 1 and the core sheet 2. Furthermore, as shown in Figure 1(b), a card 20B is also preferable, which further includes an oversheet 4, with the oversheet 4 further laminated on the outside of the laser marking sheet 1 as a protective layer. In the case of card 20B, if a hologram layer is to be provided, for example, the hologram layer (not shown) may be placed between the laser marking sheet 1 and the oversheet 4. Furthermore, the laser marking sheet may be omitted, and the card may be a card 20C, for example, as shown in Figure 1(c), comprising a core sheet 2 and an oversheet 4 as a protective layer on one or both sides of the core sheet 2. In the case of card 20C, if a hologram layer is provided, for example, the hologram layer (not shown) may be provided between the core sheet 2 and the oversheet 4. Although Figure 1 shows a configuration in which the laser marking sheet 1, the oversheet 4, or both of these are provided on both sides of the core sheet 2, the laser marking sheet 1, the oversheet 4, or both of these may be provided on only one side of the core sheet 2. Furthermore, in each of the cards 20A to 20C, the layer structure provided on each side of the core sheet 2 was the same, but it may be different on each surface. For example, the laser marking sheet 1 and the oversheet 4 may be provided in that order on one side of the core sheet 2, and only the oversheet 4 may be provided on the other side of the core sheet 2.

[0123] Passports, especially electronic passports, often include a hinge sheet. For example, as shown in Figure 2(a), a passport 10A is preferably provided with a hinge sheet 3 and core sheets 2 provided on both sides of the hinge sheet 3, with a laser marking sheet 1 laminated on the outside of one or both of the core sheets 2. If a hologram layer is to be provided in the passport 10A, for example, a hologram layer (not shown) may be provided between the laser marking sheet 1 and the core sheet 2. Furthermore, as shown in Figure 2(b), a passport 10B is also preferable, which includes an oversheet 4, with the oversheet 4 further laminated as a protective layer on the outside of the laser marking sheet 1. In the case of the passport 10B, if a hologram layer is to be provided, for example, the hologram layer (not shown) may be placed between the laser marking sheet 1 and the core sheet 2. Furthermore, the laser marking sheet may be omitted, and the passport may be a passport 10C, as shown in Figure 2(c), comprising a hinge sheet 3, core sheets 2 provided on both sides of the hinge sheet 3, and an oversheet 4 as a protective layer on the outside of one or both of the core sheets 2. In the passport 10C, if a hologram layer is to be provided, it is preferable to provide a hologram layer (not shown) between the core sheet 2 and the oversheet 4.

[0124] Furthermore, while Figure 2 shows an embodiment in which the laser marking sheet 1, the oversheet 4, or both are provided on either side of the core sheet 2, the laser marking sheet 1, the oversheet 4, or both may be provided on only one side of the core sheet 2's exterior. Furthermore, in each passport 10A to 10C, the layered structures provided on the outside of the core sheet 2 were the same, but they may be different. For example, the laser marking sheet 1 and the oversheet 4 may be provided in that order on the outside of one of the core sheets 2, and only the oversheet 4 may be provided on the outside of the other core sheet 2.

[0125] Furthermore, while Figures 2(a) to 2(c) show a passport in which core sheets 2, 2 are arranged to sandwich the hinge sheet 3, this is not particularly limited, and the core sheets do not need to be arranged to sandwich the hinge sheet; there may be only one core sheet. Also, the core sheet may consist of multiple core sheets stacked together without sandwiching the hinge sheet. In addition, the hinge sheet 3 does not need to be in contact with the core sheets and may be placed at any position that does not touch the core sheets. The hinge sheet may be placed, but is not limited to, between core sheets, for example, between a core sheet and an oversheet, between a core sheet and a laser-marked sheet, or between a laser-marked sheet and an oversheet.

[0126] In a card or passport, the core sheet is preferably a resin film using polycarbonate resin, polyester resin, or a mixture thereof as the resin component, and it is also preferable that it contains a filler. The core sheet may be made up of multiple laminated core sheets. The thickness of each core sheet is preferably about 50 to 700 μm. Each core sheet may be a printed sheet for printing fixed information, or it may be an inlet sheet with a hollow section for housing an inlet such as an IC chip or antenna. It may also be a concealing sheet for hiding the inlet, etc. Furthermore, adhesive sheets may be placed between adjacent pairs of core sheets as appropriate, and adjacent pairs of core sheets may be bonded together by the adhesive sheets. Each core sheet may be composed of a single-layer film or a laminated film having two or more resin layers. The adhesive sheets may be placed between the core sheets and the oversheet or laser marking sheet, for example.

[0127] The laser marking sheet is preferably a resin film using polycarbonate resin, polyester resin, or a mixture thereof as the resin component. The laser marking sheet is a sheet on which personal information 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. Laser marking sheets are often formed from a resin film, which may be a single-layer film or a laminated film having two or more resin layers. Preferably, the laser marking sheet includes a resin layer containing a laser colorant. In the case of a single-layer film, the single resin layer may contain the laser colorant. In the case of a laminated film, the laser marking sheet may have a structure in which, for example, surface layers are provided on both sides of a middle layer, and the middle layer may contain the laser colorant. Laser marking sheets are typically transparent films. The thickness of the laser marking sheet is not particularly limited, but is preferably about 5 to 400 μm, and preferably 10 to 300 μm.

[0128] The oversheet generally forms the outermost layer on the data page of a card or passport, protecting the card or passport. When the oversheet is placed outside the laser marking sheet, as shown in Figures 1(b) and 2(b), it can suppress so-called "blistering," where the laser-printed area foams up due to laser irradiation. There are no particular restrictions on the resin used for the oversheet, but examples include polycarbonate resins, polyester resins, or mixtures thereof. The thickness of the oversheet is not particularly limited, but is preferably about 5 to 400 μm, and preferably 10 to 300 μm.

[0129] The hinge sheet in a passport is a sheet that securely binds the data pages together with the passport cover and other visa sheets. The hinge sheet can be made of any known material and may be a resin sheet made of thermoplastic resins or thermoplastic elastomers such as thermoplastic polyester resin, thermoplastic polyester elastomer, thermoplastic polyamide resin, thermoplastic polyamide elastomer, thermoplastic polyurethane resin, or thermoplastic polyurethane elastomer; it may be made of woven fabric, knitted fabric, or nonwoven fabric; or it may be a composite material of woven fabric, knitted fabric, or nonwoven fabric with thermoplastic resin or thermoplastic elastomer.

[0130] In a card or passport, the resin film used in the core sheet, laser marking sheet, and oversheet may be made of the film described above, but other resin films may be used as long as the card or passport has at least one of the films described above. Here, it is preferable that the card or passport uses the film described above in at least the core sheet. Furthermore, if the core sheet is composed of multiple core sheets, at least one of the multiple core sheets may be made of this film, or all of the core sheets may be made of this film. Similarly, if multiple laser marking sheets and oversheets are provided, at least one of the multiple sheets may be made of this film, or all of them may be made of this film. [Examples]

[0131] The following are examples and comparative examples, but these do not limit the present invention in any way.

[0132] The resins used in the examples and comparative examples, as well as the evaluation methods for the resin compositions and films obtained in the examples and comparative examples, are as follows.

[0133] The method for measuring the glass transition temperature of a resin is as follows: (Glass transition temperature) Using a differential scanning calorimeter "DSC8000" (manufactured by PerkinElmer), the glass transition temperature was measured in accordance with JIS K7121:2012 when the temperature was increased from -70°C to 260°C at a rate of 10°C / min, then decreased to -70°C at a rate of 10°C / min, and then increased again to 260°C at a rate of 10°C / min. The glass transition temperature was determined using the midpoint glass transition temperature (Tmg).

[0134] (Cold crystallization temperature and melting point) Using a differential scanning calorimeter "DSC8000" (manufactured by PerkinElmer), the temperature was increased from -70°C to 260°C at a rate of 10°C / min in accordance with JIS K7121:2012, then decreased to -70°C at a rate of 10°C / min, and then increased again to 260°C at a rate of 10°C / min. The cold crystallization temperature and melting point were measured during these processes. Whether or not a peak at the cold crystallization temperature was detected was determined by whether the absolute value of the heat quantity ΔHm, calculated from the exothermic peak area due to cold crystallization during reheating, was less than 0.5 J / g. Similarly, whether or not a peak at the melting point was detected was determined by whether the absolute value of the heat of fusion quantity ΔHm, calculated from the endothermic peak area due to crystal melting during reheating, was less than 0.5 J / g.

[0135] (Storage modulus at 170°C and 1 Hz) The storage modulus of each resin composition was measured using the "DVA-200 manufactured by IT Measurement Control Co., Ltd." Specifically, 4 mm × 30 mm test pieces were cut from the 250 μm thick films obtained in each example and comparative example to obtain measurement samples. Using these measurement samples, the temperature was increased from 0 to 260°C at a heating rate of 3°C / min in accordance with JIS K7244-4:1999, with a chuck distance of 20 mm, a frequency of 1 Hz, a strain of 0.1%, and the tensile storage modulus at 170°C was measured. Furthermore, under high-temperature conditions, crystallization originating from PCTG (polyester resin (A)) is promoted. When crystallization is promoted, a phenomenon was observed where the peak of the storage modulus rises again from the region above 150°C. Therefore, the presence or absence of a crystallization suppression effect was evaluated from a viscoelastic perspective using the following evaluation criteria. The storage modulus at 170°C and 1 Hz is 1 × 10⁻⁶ 6 If it is less than Pa, mark it with "〇", 1 x 10 6 If the value was Pa or higher, it was judged as "×".

[0136] (Haze change rate after heat treatment) The haze change rate was measured before and after heat treatment of the films obtained in the examples and comparative examples at 140°C for 30 minutes. The films were heated by leaving them in a constant temperature bath maintained at 140°C for 30 minutes. The haze was measured in accordance with JIS K 7136:2000 using a Tokyo Denshoku haze meter "TC-HIIIDPK".

[0137] (Heat fusion evaluation) Using the electric sealer "Impulse Sealer OPL-200-10" (manufactured by Fuji Impulse Co., Ltd.), the films obtained in each example and comparative example were heat-sealed together in a sheet width of 10 mm x length of 40 mm (heat-sealed length 10 mm, unheat-sealed length 30 mm) under the conditions of heating at 130°C for 5 seconds, followed by cooling at 40°C for 5 seconds, to obtain a laminated sheet (laminated body). Subsequently, a T-shaped peel test was performed by holding the unheat-sealed portion by hand, and the following evaluation criteria were used for evaluation. In the evaluation of heat-sealability, if the laminated sheet breaks without delamination between layers (between films), it means that the films are properly bonded to each other, the adhesive strength between the films is high, and the heat-sealability is good. "Breakdown" refers to a failure mode in which the laminated sheet is destroyed in a part other than between layers. (judgment criteria) ○: The material fractured without delamination between layers. ×: The laminated sheet ruptured in one component and partially delaminated between layers. Or, the laminated sheet completely delaminated between layers without any material rupture.

[0138] The raw materials used in the examples and comparative examples are as follows: (resin) PCTG: A copolymer polyester resin consisting of a dicarboxylic acid made of terephthalic acid and a glycol component made of ethylene glycol (EG), diethylene glycol (DEG), and 1,4-cyclohexanedimethanol (1,4-CHDM). Dihydroxy compounds (EG = 43 mol%, DEG = 2 mol%, 1,4-CHDM = 55 mol%), glass transition temperature (Tg) = 83°C, cold crystallization temperature = 174°C, heat of fusion (ΔHm) = 7.6 J / g PC1: Bisphenol A-based polycarbonate, Mn: 1.9 × 10 4Melt volume rate (300℃, 1.2kgf): 15cm 3 / 10 min, glass transition temperature (Tg) = 156℃ PC2: Bisphenol A-based polycarbonate, Mn: 2.4 × 10 4 Melt volume rate (300℃, 1.2kgf): 4cm 3 / 10 min, glass transition temperature (Tg) = 159°C PEs: Product name "FX100", manufactured by Eastman Chemical Company, TMCD copolymer polyester resin

[0139] [Example 1, Example 2] Each component listed in Table 1 was placed in a Laboplast Mill "4C150" manufactured by Toyo Seiki Seisakusho Co., Ltd., and melt-kneaded at 240°C, 60 rpm, and under a nitrogen atmosphere for 5 minutes. The resulting resin composition was press-molded at 240°C using a heated press "IMC-18DA" manufactured by Imoto Seisakusho Co., Ltd. to obtain a resin film with a thickness of approximately 250 μm. The obtained resin film was evaluated in various ways. The results are shown in Table 1.

[0140] [Comparative Example 1 to Comparative Example 3] Except for changing the resin composition as shown in Table 1, the resin film was manufactured in the same manner as in Example 1 to obtain a resin sheet with a thickness of 250 μm. The obtained resin film was evaluated in various ways. The results are shown in Table 1.

[0141] [Table 1] A "-" at the cold crystallization temperature and melting point indicates that no peak was observed.

[0142] The resin compositions of Examples 1 and 2 were found to use polycarbonate resin (B) as a crystallization inhibitor for polyester resin (A) (PCTG), which prevented the appearance of a peak at the cold crystallization temperature, maintained the transparency of the sheet even after heat treatment, and ensured heat-sealability. Furthermore, as shown in Comparative Example 1, when the amount of polycarbonate resin (B) used in combination was small, although there was a crystallization suppression effect, it was insufficient, a peak in the cold crystallization temperature appeared, and transparency and heat sealability after heat treatment could not be ensured. Similarly, as shown in Comparative Example 2, it was difficult to ensure transparency and heat sealability after heat treatment with polyester resin (A) (PCTG) alone. Moreover, in Comparative Example 3, a TMCD copolymer polyester resin was used in combination instead of polycarbonate resin (B), but crystallization was promoted, and the desired crystallization suppression effect could not be obtained. [Industrial applicability]

[0143] The resin film made from the resin composition of the present invention suppresses crystallization even when heated, thus maintaining good heat-sealability. Therefore, it is an industrially valuable technology because it can produce cards, passports, etc., with excellent adhesive properties. Furthermore, it is possible to use recycled polyester resin (B) (PCTG), which is prone to crystallization, as a raw material, thus contributing to a reduction in environmental impact, making it an industrially valuable technology. [Explanation of symbols]

[0144] 1 Laser Marking Sheet 2 core sheets 3 Hinge Seat 4 Oversheet 20A, 20B, 20C cards 10A, 10B, 10C Passport

Claims

1. A resin composition comprising a polyester resin (A) obtained by polycondensation of a dicarboxylic acid component mainly containing terephthalic acid and a glycol component mainly containing ethylene glycol and 1,4-cyclohexanedimethanol, and a polycarbonate resin (B), A resin composition characterized by the absence of a peak when the cold crystallization temperature is measured by DSC under measurement conditions of a heating rate of 10°C / min and a measurement temperature range of -70°C to 260°C.

2. The storage modulus at 170°C and 1 Hz is 1 × 10⁻⁶. ６ The resin composition according to claim 1, wherein the pressure is Pa or less.

3. The resin composition according to claim 1, wherein the number average molecular weight of the polycarbonate resin (B) is 18,000 or more.

4. The resin composition according to claim 1, wherein the content of structural units derived from 1,4-cyclohexanedimethanol in the structural units derived from the glycol component is 50 mol% or more.

5. The resin composition according to claim 1, comprising recycled materials.

6. The resin composition according to claim 1, wherein the polyester resin (A) contains recycled raw materials.

7. A film comprising the resin composition according to any one of claims 1 to 6.

8. The film according to claim 7, wherein the rate of change in film haze (ΔH) before and after heat treatment performed at 140°C for 30 minutes is 2.0% or less.

9. A laminate comprising a plurality of films according to claim 7, wherein the plurality of films are laminated directly or via other layers.

10. The laminate according to claim 9, wherein the other layer is a resin sheet containing polycarbonate resin.

11. The laminate according to claim 9, wherein the other layer is a resin sheet containing a polycarbonate resin (C) having a structural unit (C1) derived from a dihydroxy compound having a portion represented by the following formula (1) in part of its structure. 【Chemistry 1】 However, the part represented by formula (1) above is -CH ２ Except when it is part of -O-H.

12. The film according to claim 7, which is for use with cards or passports.

13. A card comprising the film described in claim 7.

14. A card comprising the laminate described in claim 9.

15. A passport comprising the film described in claim 7.

16. A passport comprising the laminate described in claim 9.

17. A method for manufacturing a laminate, comprising stacking multiple films according to claim 7 directly or via other layers and heat-pressing them at a temperature of less than 170°C.

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