JP7831008B2 - Laminates, composite laminates, cards, and passports - Google Patents

Description

This invention relates to laminates, composite laminates, cards, and passports, and more particularly to laminates usable in applications such as oversheets, as well as composite laminates, cards, and passports having laminates.

In recent years, in order to reduce the environmental burden, there has been consideration to replace some of the resin raw materials from fossil fuel-derived resins with plant-derived resins. The use of plant-derived resins is also being considered for resin films used in cards and passports. For example, Patent Document 1 describes the consideration of using a resin composition mainly composed of polycarbonate resin with a glass transition temperature of less than 130°C, having structural units derived from isosorbide or its stereoisomers, for use in card sheets (see Patent Document 1).

Cards, passports, and similar items are typically manufactured by laminating multiple resin films and integrating them using heat pressing. The layer structure may include, for example, a structure where multiple core sheets are laminated between a pair of oversheets, or a structure where a laser-printed sheet is further placed between the oversheets and core sheets. Generally, the core sheet thickness accounts for a large proportion of the overall product thickness.

Japanese Patent Publication No. 2012-30574

In recent years, there has been a growing demand to increase the proportion of plant-derived raw materials (biomass content) in resin raw materials and final products in order to further reduce environmental impact. While applying plant-derived raw materials to all layers might be considered for creating cards and passports with a high biomass content, the inventors' research has revealed that applying the plant-derived resin (isosorbide polycarbonate resin) described in Patent Document 1 to all layers results in insufficient mechanical properties, particularly in terms of repeated bending durability.

Therefore, the inventors further investigated and attempted to apply isosorbide polycarbonate resin to the core sheet with a high thickness ratio, and use general polycarbonate resin for the other oversheets and laser-printed sheets. However, there was a significant difference in glass transition temperature (Tg) between isosorbide polycarbonate resin and general polycarbonate resin, requiring the press temperature during hot pressing to be adjusted to match the higher Tg of the general polycarbonate resin. Consequently, it was found that the isosorbide polycarbonate resin, with its lower Tg, would flow out during hot pressing, resulting in problems such as shrinkage and failure to achieve the desired thickness.

Further investigation revealed that we attempted to use a general polycarbonate resin for the core sheet and isosorbide polycarbonate resin for the oversheet and laser-printed sheet. However, we found that using isosorbide polycarbonate resin for the oversheet significantly affected the bending durability due to the surface resin, resulting in insufficient performance when higher bending durability was required. On the other hand, we also found that using isosorbide polycarbonate resin for the laser-printed sheet was undesirable because it sometimes reduced laser printability.

Therefore, the objective of this invention is to provide a laminate that improves low-temperature fusion properties during hot pressing, thereby increasing the biomass content of the final product, without causing problems such as the plant-derived resin flowing or shrinking during pressing, and also achieving good bending durability.

As a result of diligent research, the inventors have discovered that the above problems can be solved by, for example, making a multilayered resin film used in an oversheet, using a polycarbonate resin (A) containing specific structural units in at least one resin layer of the film, and using a high molecular weight resin other than polycarbonate resin (A) in another resin layer. Based on this discovery, the inventors have completed the present invention. That is, the present invention provides the following [1] to [18].

[1] A resin layer (a) containing a polycarbonate resin (A) which includes a structural unit (A1) derived from a dihydroxy compound having a part of its structure represented by the following formula (1),
The resin layer (a) comprises a resin layer (b) containing a resin (B) other than the polycarbonate resin (A) contained in the aforementioned resin layer (a),
A laminate in which the mass-average molecular weight of the resin (B) is 40,000 or more.

However, this excludes cases where the portion represented by formula (1) is part of _-CH2 -O-H.
[2] The laminate according to [1] above, wherein the glass transition temperature (Tg) of the resin (B) is 132°C or higher.
[3] The laminate according to [1] or [2] above, wherein the resin (B) is a polycarbonate resin other than the polycarbonate resin (A).
[4] The laminate according to any one of [1] to [3] above, wherein the polycarbonate resin (A) contains 30 mol% or more of the structural unit (A1) derived from the dihydroxy compound.
[5] The laminate according to any one of [1] to [4] above, wherein the polycarbonate resin (A) contains 75 mol% or less of the structural unit (A1) derived from the dihydroxy compound.
[6] The laminate according to any one of [1] to [5] above, wherein the resin layer (a) is provided on both sides of the resin layer (b).
[7] The laminate according to any one of [1] to [6] above, wherein the resin layer (a) contains an impact resistance modifier.
[8] The laminate according to any one of [1] to [7] above, wherein the resin layer (b) contains a laser colorant.
[9] The laminate according to any one of [1] to [8] above, wherein the glass transition temperature of the polycarbonate resin (A) is lower than the glass transition temperature of the resin (B), and is 80°C or more and 140°C or less.
[10] A laminate according to any of [1] to [9] above, to be used as an oversheet.
[11] A laminate according to any of [1] to [10] above, to be used for a card.
[12] A laminate described in any of [1] to [10] above, for use in a passport.
[13] A composite laminate comprising a laminate according to any one of [1] to [12] above and a resin layer (c).
[14] The composite laminate according to [13], wherein the resin layer (c) contains a polycarbonate resin containing the structural unit (A1).
[15] The composite laminate according to [13] or [14], wherein the resin layer (c) contains a filler in an amount of 1% by mass or more and 60% by mass or less.
[16] A method for manufacturing a composite laminate according to any one of [13] to [15] above,
A method for manufacturing a composite laminate, comprising laminating the laminate by fusing it to a resin sheet made of the resin layer (c).
[17] A card comprising a laminate according to any of [1] to [11] above, or a composite laminate according to any of [13] to [15] above.
[18] A passport comprising a laminate according to any of [1] to [10] and [12] above, or a composite laminate according to any of [13] to [15] above.

According to the present invention, even when the low-temperature fusion properties during hot pressing are improved and the biomass content of the final product is increased, the plant-derived resin does not flow or shrink during hot pressing, and bending durability is also improved.

This is a schematic diagram showing the layer structure of a card. This is a schematic diagram showing the layer structure of a passport.

The present invention will be described in detail below with reference to embodiments. However, the present invention is not limited to the embodiments described below. Furthermore, the terms "film" and "sheet" used in the following description are not clearly distinguished; the term "film" includes "sheet," and vice versa.

<Laminated structure>
The laminate of the present invention (hereinafter referred to as "this laminate") is a laminate having at least two layers, a resin layer (a) and a resin layer (b). The resin layer (a) and the resin layer (b) will be described in detail below.

[Resin layer (a)]
The resin layer (a) contains a polycarbonate resin (A) which includes a structural unit (hereinafter sometimes referred to as structural unit (A1)) derived from a dihydroxy compound having a portion represented by the following formula (1) in part of its structure.

However, this excludes cases where the part represented by formula (1) is part of _-CH2 -O-H. In other words, the dihydroxy compound means one that contains two hydroxyl groups and at least the part of formula (1).

In the present invention, by using a polycarbonate resin (A) having the above structure in the resin layer (a), the low-temperature fusion properties and suitability for hot press molding can be improved. Therefore, it is possible to perform heat fusion at low temperatures, and it is possible to prevent the plant-derived resin contained in the laminate or another resin layer laminated to the laminate (for example, resin layer (c) described later) from flowing during pressing, and to prevent shrinkage problems in the laminate and the other resin layer. Furthermore, as described later, by using a resin (B) with a larger mass-average molecular weight than the polycarbonate resin (A) contained in resin layer (a) in resin layer (b), the bending durability of the laminate and the final product such as a card or passport containing the laminate can also be improved.
Furthermore, by including polycarbonate resin (A) in the resin layer (a), it can be manufactured using plant-derived raw materials, thereby improving the biomass content of the laminate and the final products such as cards and passports containing this laminate. In addition, by using polycarbonate resin (A) in the resin layer (a) of this laminate, the solvent resistance of the resin layer (a), i.e., the laminate itself, can be improved.

Dihydroxy compounds having a moiety represented by formula (1) as part of their structure are not particularly limited as long as they have the structure represented by formula (1) in their molecule, but specifically include 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl) Examples include compounds having aromatic groups in the side chains and ether groups bonded to the aromatic groups in the main chain, such as dihydroxy compounds represented by formula (2) below and spiroglycols represented by formula (3) below.

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.

In formula (3), _R1 to _R4 are each independently alkyl groups having 1 to 3 carbon atoms.

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.

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

The aliphatic dihydroxy compound is not particularly limited in terms of the number of carbon atoms, but preferably has 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. Furthermore, structural units derived from aliphatic dihydroxy compounds, for example, those described in International Publication No. 2004/111106, can also be used.

The structural units derived from the alicyclic dihydroxy compound 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 (A) 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.

The content of structural units (A1) in polycarbonate resin (A) is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 45 mol% or more, and preferably 75 mol% or less, more preferably 70 mol% or less, and even more preferably 65 mol% or less, among the structural units derived from dihydroxy compounds. 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 laminate. 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 resin composed only of structural units (A1).
On the other hand, the content of structural units (A2) in the polycarbonate resin (A) is preferably 25 mol% or more, more preferably 30 mol% or more, even more preferably 35 mol% or more, and also preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 55 mol% or less, among the structural units derived from the dihydroxy compound.

The polycarbonate resin (A) preferably consists of structural units derived from dihydroxy compounds, namely structural unit (A1) and structural unit (A2). 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 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.

The glass transition temperature of the polycarbonate resin (A) is, for example, 70°C or higher, preferably 80°C or higher, more preferably 85°C or higher, even more preferably 90°C or higher, and also, for example, 140°C or lower, preferably 130°C or lower, more preferably 125°C or lower, and even more preferably 120°C or lower. Furthermore, it is generally preferable that the polycarbonate resin (A) has a single glass transition temperature.
By keeping the glass transition temperature within the above range, it becomes easier to achieve low-temperature thermal fusion, and furthermore, it becomes easier to impart heat resistance to the laminate.
The glass transition temperature can be adjusted by appropriately selecting the ratio of each structural unit constituting the polycarbonate resin (A). The glass transition temperatures of resins (A) and (B) can be obtained by measurement using a differential scanning calorimeter. Detailed measurement conditions should be as described in the examples.

Furthermore, it is preferable that the glass transition temperature of the polycarbonate resin (A) is lower than that of the resin (B), which will be described later. By raising the glass transition temperature of resin (B) while lowering the glass transition temperature of resin (A), it is possible to provide the laminate with a certain degree of heat resistance and bending durability while also achieving good low-temperature fusion properties.
The difference between the glass transition temperature of polycarbonate resin (A) and resin (B) is not particularly limited, but is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, even more preferably 20°C or higher, even more preferably 25°C or higher, and also preferably 80°C or lower, more preferably 75°C or lower, even more preferably 70°C or lower, and even more preferably 65°C or lower.

Polycarbonate resin (A) can be produced by commonly used polymerization methods, and can be produced by either the phosgene method or the transesterification method, which involves reacting it 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.
Examples of diester carbonates include diphenyl carbonate, ditriyl 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.

The molecular weight of the polycarbonate resin (A) 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 viscous tube at a temperature of 20.0°C ± 0.1°C, after precisely adjusting the polycarbonate resin concentration to 0.6 g/dL using dichloromethane as the solvent.

The resin layer (a) may use only polycarbonate resin (A) as the resin, but may also contain resins other than polycarbonate resin (A) to the extent that it does not contradict the spirit of the present invention. As such a resin, it is good to use a commonly used known resin, but it is preferable to use a resin that is compatible with polycarbonate resin (A). Using a compatible resin tends to prevent a decrease in the transparency of the laminate.
The resin constituting the resin layer (a) preferably contains polycarbonate resin (A) as the main component, and the amount of polycarbonate resin (A) is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass, based on the total amount of resin contained in the resin layer (a).

(Impact-resistant agent)
The resin layer (a) may further contain an impact-resistant modifier. By further containing an impact-resistant modifier, the resin layer (a) can mitigate the effects of external impacts such as bending and impact during actual use, thereby improving the bending durability of the laminate. In addition, it can prevent a decrease in softening and fluidity when heated, making it easier to maintain good processability.

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 resistance modifiers. Using core-shell type elastomers further improves impact resistance and provides even better bending durability.

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.

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 examples of 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, such as the "Dynalon" series from JSR Corporation, the "Toughtech" series from Asahi Kasei Chemicals Corporation, and the "Hybral" series from Kuraray Corporation.

Furthermore, block copolymers include pure blocks, random blocks, tapered blocks, etc., and the form of copolymerization is not particularly limited. Also, 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.

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.

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.
As soft styrene resins to which polar functional groups are added, modified forms of SEBS and SEPS are preferably used. 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.

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.

The elastomer may be anything other than a styrene-based elastomer, including known elastomers such as polyester-based elastomers, polyolefin-based elastomers, diene-based elastomers, acrylic-based elastomers, polyamide-based elastomers, polyurethane-based elastomers, fluorine-based elastomers, and silicone-based elastomers. Generally, the elastomer is a thermoplastic elastomer. Preferably, the elastomer is a polyester-based elastomer or one of the styrene-based elastomers described above.

Polyester elastomers are thermoplastic polyesters that possess rubber properties at room temperature. Preferably, they are thermoplastic elastomers primarily 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%. A preferred soft segment content is 50 to 90 mol%, particularly 60 to 85 mol%. Among these, polyester ether block copolymers, especially PTMG-PBT copolymers, are preferred.

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

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 core-shell type graft copolymer can be manufactured using 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.

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

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, and methyl (meth)acrylate is more preferred. Note that "(meth)acrylic" is a general term for "acrylic" and "methacrylic".

As the core-shell type elastomer, a core-shell type graft copolymer is particularly preferred, which 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.

Preferred 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.

Examples of commercially available core-shell type 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", all manufactured by Dow Chemical Japan. Examples include Mitsubishi Chemical's "Metabren C-223A,""MetabrenE-901,""MetabrenS-2001,""MetabrenW-450A,""MetabrenSRK-200," and "Metabren E-870A," and Kaneka's "Kaneace M-210,""KaneaceM-511,""KaneaceM-600,""KaneaceM-400,""KaneaceM-580,""KaneaceM-590,""KaneaceM-711,""KaneaceMR-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.

The impact-resistant agent content in each resin layer (a) is preferably 2% by mass or more and 40% by mass or less, based on the total amount of each resin layer (a). A content of 2% by mass or more of the impact-resistant agent moderately mitigates the effects of external impacts, making it easier to improve bending durability and other properties. Furthermore, it helps prevent a decrease in softening and fluidity during film heating, which can occur due to the type of resin used, thus maintaining good processability.
On the other hand, by limiting the content to 40% by mass or less, the effect commensurate with the content can be achieved. Furthermore, it is possible to prevent a decrease in various physical properties such as the heat resistance of the resin layer (a), a decrease in the biomass content of the laminate, and excessive fluidity of the resin layer (a) during processing.
From these viewpoints, the content of the impact-resistant modifier in the resin layer (a) is more preferably 4% by mass or more, even more preferably 6% by mass or more, even more preferably 8% by mass or more, even more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[Resin layer (b)]
The resin layer (b) contains a resin other than the polycarbonate resin (A) contained in the resin layer (a) (hereinafter also referred to as resin (B)). In this laminate, the mass-average molecular weight of resin (B) is 40,000 or more. If the mass-average molecular weight is less than 40,000, it becomes difficult to achieve good bending durability. From the viewpoint of improving bending durability, the mass-average molecular weight is preferably 50,000 or more, more preferably 54,000 or more, even more preferably 57,000 or more, even more preferably 60,000 or more, and even more preferably 65,000 or more. Furthermore, from the viewpoint of moldability and the like, the above mass-average molecular weight is preferably 120,000 or less, more preferably 100,000 or less, even more preferably 90,000 or less, even more preferably 86,000 or less, and even more preferably 83,000 or less.

The number-average molecular weight (Mn) of resin (B) is preferably 10,000 or more, more preferably 14,000 or more, even more preferably 18,000 or more, and even more preferably 20,000 or more, from the viewpoint of improving bending durability. Furthermore, from the viewpoint of increasing fluidity during molding and improving productivity and moldability, it is preferably 40,000 or less, more preferably 35,000 or less, even more preferably 30,000 or less, and even more preferably 28,000 or less.

The molecular weight distribution (Mw/Mn) of the polycarbonate resin (A) is preferably 1.8 or higher, more preferably 2 or higher, even more preferably 2.2 or higher, even more preferably 2.4 or higher, preferably 4 or lower, more preferably 3.6 or lower, even more preferably 3.3 or lower, and even more preferably 3 or lower.

Furthermore, the glass transition temperature (Tg) of resin (B) is preferably 132°C or higher. A glass transition temperature (Tg) of 132°C or higher makes it easier to improve bending durability and also improves heat resistance. When heat resistance is improved, for example, when a laser coloring agent is contained in the resin layer (B), sheet foaming is less likely to occur even when irradiated with high-power laser light, resulting in good laser printability and appearance. The glass transition temperature (Tg) of resin (B) is more preferably 137°C or higher, even more preferably 142°C or higher, and even more preferably 145°C or higher.
Furthermore, from the viewpoint of moldability and other factors, the glass transition temperature (Tg) of resin (B) is preferably 200°C or lower, more preferably 175°C or lower, even more preferably 170°C or lower, and even more preferably 165°C or lower.
Furthermore, resin (B) may have a single glass transition temperature or multiple glass transition temperatures, but resin (B) usually has a single glass transition temperature. If multiple glass transition temperatures are observed, it is preferable to adopt the lower glass transition temperature.

The resin (B) is preferably a thermoplastic resin, and examples include polycarbonate resin, polyester resin, polyolefin resin, acrylic resin, polystyrene resin, polyamide resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, ethylene-vinyl alcohol resin, polycycloolefin resin, ethylene vinyl acetate copolymer resin, ethylene (meth)acrylate copolymer resin, polyphenylene ether resin, polyacetal resin, acrylonitrile-butadiene-styrene copolymer resin, polyaryl ether ketone resin, polyimide resin, polyphenylene sulfide resin, polyarylate resin, polysulfone resin, polyethersulfone resin, and fluororesin.
Among these, resin (B) is preferably an amorphous thermoplastic resin from the viewpoint of film-forming properties and suitability for processing such as hot pressing, and polycarbonate resin is more preferable among them. Using polycarbonate resin results in good bending durability. It also makes it easier to achieve good heat resistance. Note that the polycarbonate resin used as resin (B) may be referred to as polycarbonate resin (B1) in the following description.

As the polycarbonate resin (B1), any polycarbonate resin other than the polycarbonate resin (A) having the above-described structural unit (A1) may be used, but it is preferable to use bisphenol-based polycarbonate. Using bisphenol-based polycarbonate results in improved various mechanical properties, and the bending durability described above is also easier to achieve. Furthermore, heat resistance and, if laser colorants are included, laser color development are also excellent.

Bisphenol-based polycarbonate refers to a material 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 polycarbonate may be either a homopolymer or a copolymer. Furthermore, bisphenol-based polycarbonate may have a branched structure, a linear structure, or be a mixture of a resin with a branched structure and a resin with only a linear structure.

Specific examples of bisphenols include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), bis(4-hydroxyphenyl)diphenylmethane (bisphenol BP), 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol C), 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E), bis(4-hydroxyphenyl)methane (bisphenol F), 2,2-bis( 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.

As the bisphenol, 2,2-bis(4-hydroxyphenyl)propane, i.e., bisphenol A, is preferably used, but a portion of bisphenol A may be replaced with other bisphenols.
In 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 (B1).

The method for producing the bisphenol-based polycarbonate used as polycarbonate resin (B1) may be any known method, such as the phosgene method, the transesterification method, or the pyridine method.
For example, the transesterification method is a manufacturing method that involves melt transesterification polymerization of bisphenol and diester carbonate with a basic catalyst and an acidic substance to neutralize the basic catalyst. Specific examples of diester carbonate are listed in the above-mentioned polycarbonate resin (A), with diphenyl carbonate being particularly preferred.

(Laser colorant)
The resin layer (b) may contain a laser coloring agent. By containing a laser coloring agent in the resin layer (b), the laminate can be used as a laser marking sheet that develops color when irradiated with a laser.
The laser colorant contained in the resin layer (b) 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 itself develops color when irradiated with laser light, or it may not develop color itself. When the laser colorant generates heat, at least the surrounding forming material carbonizes, and the desired printing appears on the resin layer (b). Furthermore, if a self-coloring laser colorant is used, the color development of the laser colorant and the color development of carbides produced by the carbonization of the forming material of the laminate synergistically result in printing with a deep color and excellent visibility. When the laser colorant develops color, the color is not particularly limited, but from the viewpoint of visibility, it is preferable to use a laser colorant that can develop into a deep color including black, navy blue, and brown.

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. Furthermore, dyes such as leuco dyes like fluorane, phenothiazine, spiropyran, triphenylmetaphthalide, and rhodamine lactam, as well as carbon black, can also be used.
Laser colorants may be used individually or in combination of two or more types.

From the viewpoint of laser printability, it is preferable to use a metal oxide as the laser colorant used in the resin layer (b). In particular, from the viewpoint of laser coloration effect and cost, it is preferable to use a bismuth-based metal oxide such as bismuth oxide or a metal oxide containing bismuth and at least one metal selected from Zn, Ti, Al, Zr, Sr, Nd, and Nb. Bismuth-based metal oxides produce good coloration even in relatively small amounts, thus enabling excellent laser coloration without impairing the transparency of the resin layer (b).

The average particle size of the laser colorant is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, and particularly preferably 2 μm or less. If the particle size is 10 μm or less, there is no risk of a significant decrease in transparency. Here, particle size refers to the median diameter (d50) determined by laser diffraction/scattering. The lower limit of the average particle size of the laser colorant is not limited, but from the viewpoint of printing performance and productivity, it is preferably 0.05 μm or more, more preferably 0.1 μm or more, and even more preferably 0.3 μm or more.
Examples of commercially available metal oxides include the product names "42-903A" and "42-920A" from TOMATEC Corporation, and "Iliotec 8820" and "Iliotec 8825" from Merck Performance Materials.
When using metal oxides as laser colorants, metal oxides alone may be used, but metal oxides and compounds other than metal oxides may also be used in combination.

The content of the laser colorant in the resin layer (b) is preferably 0.5 μg/ ^cm² or more per unit area. By setting the content of the laser colorant to above the lower limit, printability can be improved. From the viewpoint of printability, the content of the laser colorant is more preferably 3 μg/ ^cm² or more, even more preferably 7 μg/ ^cm² or more, even more preferably 10 μg/ ^cm² or more, even more preferably 30 μg/ ^cm² or more, even more preferably 40 μg/ ^cm² or more, and particularly preferably 50 μg/ ^cm² or more.
Furthermore, the content of the laser colorant in the resin layer (b) is preferably 350 μg/ ^cm² or less. By keeping the content below the above upper limit, the transparency and mechanical properties of the laminate can be improved. From these viewpoints, the content of the laser colorant is more preferably 320 μg/ ^cm² or less, even more preferably 300 μg/ ^cm² or less, even more preferably 280 μg/ ^cm² or less, and particularly preferably 260 μg/ ^cm² or less.

Furthermore, while the content of the laser colorant in the resin layer (b) is not particularly limited, it is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, even more preferably 0.06% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.8% by mass or less, based on the total amount of the resin layer (b).

When a laser colorant other than carbon black is used, the content is as described above. However, when carbon black is used as the laser colorant, the carbon black content is preferably 0.002 μg/ ^cm² or more, more preferably 0.009 μg/ ^cm² or more, even more preferably 0.018 μg/ ^cm² or more, and particularly preferably 0.1 μg/ ^cm² or more. Furthermore, it is preferably 14 μg/cm² or ^less , more preferably 7 μg/ ^cm² or less, even more preferably 1.4 μg/ ^cm² or less, and particularly preferably 0.7 μg/ ^cm² or less.

Furthermore, when carbon black is used as a laser colorant in the resin layer (b), the content is not particularly limited, but preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, preferably 0.1% by mass or less, more preferably 0.05% by mass or less, even more preferably 0.01% by mass or less, and particularly preferably 0.005% by mass or less, based on the total amount of resin layer (b).

When polycarbonate resin (B1) is used as the resin for the resin layer (b), only polycarbonate resin (B1) may be used, but other resins may be included as long as they do not contradict the spirit of the present invention. Such resins may be appropriately selected from the resins mentioned above, but it is preferable to use a resin that is compatible with polycarbonate resin (B1). By using a compatible resin, it is possible to prevent a decrease in the transparency of the laminate.
The resin constituting the resin layer (b) may mainly contain polycarbonate resin (B1), and the amount of polycarbonate resin (B1) 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 contained in the resin layer (b).

Furthermore, resin layers (a) and (b) may each contain various additives in addition to those mentioned above, to the extent that they do not impair the properties of the resin, or to further improve physical properties other than those targeted by the present invention. Examples of additives include those commonly used in a wide range of resin materials, such as antioxidants, heat stabilizers, process stabilizers, UV absorbers, light stabilizers, matting agents, processing aids, metal deactivators, residual polymerization catalyst deactivators, antibacterial/antifungal agents, antiviral agents, antistatic agents, lubricants, flame retardants, fillers, pigments, dyes, and other colorants. For these as well, the amount typically used should be added according to the intended purpose. Additionally, resin layer (b) may contain the impact resistance improver mentioned above.

[Layer composition]
In this laminate, resin layer (a) may be provided on at least one side of resin layer (b), or it may be provided on both sides of resin layer (b). Therefore, examples of laminated structures of resin layer (a) and resin layer (b) include a two-layer configuration of resin layer (a)/resin layer (b) and a three-layer configuration of resin layer (a)/resin layer (b)/resin layer (a). It is preferable that resin layer (a) is provided on both sides of resin layer (b), and therefore, a layer configuration of resin layer (a)/resin layer (b)/resin layer (a) is preferred as the laminated structure. In this laminate, it is preferable that resin layer (a) is provided on at least one surface of the laminate, and more preferably on both sides.

By providing resin layer (a) on at least one side of resin layer (b), resin layer (a) protects resin layer (b), thereby improving the solvent resistance of at least one surface of the laminate while imparting low-temperature heat-sealability to the laminate. Furthermore, by providing resin layer (a) on both sides of resin layer (b), both surfaces of the laminate can be made to have good solvent resistance and low-temperature heat-sealability. In addition, resin layer (a) makes it easier to impart predetermined surface characteristics, described later, to one or both sides of the laminate.
Furthermore, when resin layers (a) are provided on both sides, another resin layer (for example, resin layer (c) described later) can be fused to one side of the laminate at a low temperature with high thermal press suitability, and the other side of the laminate can also impart predetermined surface properties to the surface of the final product.

The resin layer (a) is preferably laminated directly onto the resin layer (b), but other layers, such as an anchor coat layer, may be provided between the resin layer (a) and the resin layer (b) as needed. The functions of the anchor coat layer include solvent resistance, barrier properties, adhesive properties, whitening properties, opacity, cushioning properties, and antistatic properties.

The laminate of the present invention is preferably used as an oversheet. An oversheet is a sheet positioned outside the core sheet, laser marking sheet, etc., in a card or passport, and protects the inside of the card or passport. The oversheet is preferably provided on the outermost surface of the card or passport, but an image-receiving layer, such as a dye-sublimation thermal transfer image-receiving layer, may be provided on the outer surface of the oversheet. The image-receiving layer is used as an image-receiving layer when printing full-color images such as facial photographs. Furthermore, a printed layer may be formed on the outer surface of the oversheet by known printing methods.

(Biomass content)
The biomass content of this laminate is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and even more preferably 12% by mass or more. By setting the biomass content of the laminate to a certain value or higher, the biomass content of the final product such as a card or passport containing this laminate can also be increased, thereby reducing the environmental burden. From the viewpoint of reducing the environmental burden, the higher the biomass content, the better. However, from the viewpoint of using a specific resin for resin (B) and improving bending durability, it may be, for example, 50% by mass or less, 40% by mass or less, or 30% by mass or less.
The biomass content can be determined by calculating the proportion of plant-derived components from the raw materials used to obtain this laminate. The same method can be used to determine the biomass content of the composite laminate described later.

(Layer thickness)
In the laminate, the thickness of each resin layer (a) is preferably 3 μm or more. A thickness of 3 μm or more allows the resin layer (a) to fully perform its function, resulting in good performance in various aspects such as solvent resistance, low-temperature heat fusion properties, and suitability for hot pressing, and also makes it easier to impart predetermined surface characteristics. The thickness of each resin layer (a) is more preferably 5 μm or more, even more preferably 6 μm or more, and even more preferably 8 μm or more.
Furthermore, in the laminate, the thickness of each resin layer (a) is preferably 50 μm or less. By keeping the thickness of each resin layer (a) below the above upper limit, solvent resistance and low-temperature heat fusion properties can be improved without making the laminate unnecessarily thick, and a decrease in bending durability can also be prevented. The thickness of each resin layer (a) is more preferably 40 μm or less, even more preferably 30 μm or less, even more preferably 25 μm or less, and even more preferably 20 μm or less.

Furthermore, the thickness of the resin layer (b) is not particularly limited, but is preferably 6 μm or more. By setting the thickness to above the lower limit, it becomes easier to improve the mechanical strength of the laminate and the bending durability also tends to improve. In addition, if a laser coloring agent is included, the laser printability also tends to improve. The thickness of the resin layer (b) is more preferably 10 μm or more, even more preferably 20 μm or more, even more preferably 25 μm or more, and particularly preferably 30 μm or more.
Furthermore, the thickness of the resin layer (b) is not particularly limited, but is preferably 200 μm or less. By keeping the thickness of the resin layer (b) below the above upper limit, it becomes easier to improve various performances without making the laminate unnecessarily thick. It also prevents a decrease in bending characteristics, etc. The thickness of the resin layer (b) is more preferably 175 μm or less, even more preferably 150 μm or less, even more preferably 125 μm or less, even more preferably 100 μm or less, and particularly preferably 80 μm or less.

The laminate of the present invention is in the form of a sheet (i.e., a laminated sheet), and its total thickness is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 30 μm or more, preferably 300 μm or less, more preferably 250 μm or less, even more preferably 200 μm or less, even more preferably 150 μm or less, and even more preferably 120 μm or less.
In the laminate, the ratio (b/a) of the thickness of resin layer (b) to the thickness of each resin layer (a) is preferably 1 or more, more preferably 1.5 or more, even more preferably 2 or more, even more preferably 2.5 or more, particularly preferably 3 or more, and also preferably 10 or less, more preferably 9 or less, even more preferably 8 or less, even more preferably 7 or less, particularly preferably 6 or less.
By keeping the ratio of the thicknesses of resin layer (b) to resin layer (a) within the above range, it becomes easier to improve various properties such as solvent resistance, low-temperature fusion properties, bending durability, and, if laser colorants are included, laser printability, without unnecessarily increasing the thickness of the laminate.

(Surface properties)
The laminate preferably has surface characteristics in which at least one surface has a certain roughness, as described below. Specifically, at least one surface of the laminate preferably has a maximum height roughness (Rz) of 1 μm or more and 20 μm or less. Furthermore, at least one surface of the laminate preferably has an arithmetic mean roughness (Ra) of 0.1 μm or more and 5 μm or less.
When the maximum height roughness (Rz) or arithmetic mean roughness (Ra) of the laminate surface is equal to or greater than the lower limit mentioned above, the roughness becomes of an appropriate size, making it slippery and improving handling, for example, when manufacturing cards and passports. Furthermore, when stacking the laminates during storage after processing, the printed surface on the laminate surface is prevented from sticking to other materials (so-called blocking), making it less likely for defects such as peeling of the printed surface to occur.
On the other hand, if the maximum height roughness (Rz) or arithmetic mean roughness (Ra) of the laminate surface is below the above upper limit, the roughness is kept to a certain level, making it easier for printing to adhere to the laminate surface and improving printability on the laminate surface. In addition, the amount of crushing of surface irregularities when hot-pressed is suppressed, the amount of thickness reduction during hot-pressing is small, and the thickness design of the card structure becomes easier. Furthermore, it is more preferable that both Rz and Ra of at least one surface of the laminate are within the above range.

The above-mentioned maximum height roughness (Rz) is more preferably 3 μm or more, even more preferably 5 μm or more, even more preferably 7 μm or more, and more preferably 17 μm or less, even more preferably 15 μm or less, and even more preferably 13 μm or less.
Furthermore, the arithmetic mean roughness (Ra) is more preferably 0.3 μm or more, even more preferably 0.5 μm or more, even more preferably 0.7 μm or more, and more preferably 3.5 μm or less, even more preferably 2.5 μm or less, and even more preferably 2 μm or less.

Furthermore, it is preferable that at least one surface of the laminate has a crustosis (Rku) of 3.0 or less. Crustosis (Rku) represents the mean fourth power of Z(x) in a dimensionless reference length obtained by raising the root mean square height Rq to the fourth power, and represents the degree of sharpness, which is a measure of the sharpness of the surface. Therefore, a smaller crustosis (Rku) allows the print to adhere better to the laminate surface and to be more easily fixed. In addition, it is preferable that at least one surface of the laminate has a crustosis (Rku) of 3.0 or less, and that one of Rz and Ra is within the above range, and more preferably both Rz and Ra are within the above range.
On the other hand, the crustosis (Rku) is more preferably 2.9 or less, and even more preferably 2.8 or less. Furthermore, the crustosis (Rku) is not particularly limited in terms of its lower limit, but for example, it may be 1 or more, and preferably 1.2 or more.

In the present invention, it is preferable that at least one surface of the laminate has a root mean square height (Rq), maximum peak height (Rp), maximum valley depth (Rv), maximum cross-sectional height (Rt), or skewness (Rsk) within the following predetermined range. Having the following surface characteristics provides the laminate surface with appropriate slipperiness for good handling, facilitates the adhesion of prints to the laminate surface, and improves printability on the laminate surface.
Specifically, at least one surface of the laminate preferably has a root mean square height (Rq) of 0.1 μm or more, more preferably 0.6 μm or more, even more preferably 0.8 μm or more, and also preferably 6.5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less.
Furthermore, at least one surface of the laminate preferably has a maximum peak height (Rp) of 0.5 μm or more, more preferably 1 μm or more, even more preferably 1.5 μm or more, preferably 10 μm or less, more preferably 7.5 μm or less, and even more preferably 5 μm or less.
Furthermore, at least one surface of the laminate preferably has a maximum valley depth (Rv) of 0.5 μm or more, more preferably 1.5 μm or more, even more preferably 2.5 μm or more, preferably 10 μm or less, more preferably 8.5 μm or less, and even more preferably 7.5 μm or less.
Furthermore, at least one surface of the laminate preferably has a maximum cross-sectional height (Rt) of 1 μm or more, more preferably 3 μm or more, even more preferably 5 μm or more, preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less.

Furthermore, at least one surface of the laminate preferably has a skewness (Rsk) of -3 or higher, more preferably -2 or higher, even more preferably -1 or higher, and preferably 3 or lower, more preferably 2 or lower, and even more preferably 1 or lower.
Skewness (Rsk) represents the mean cube of Z(x) on a dimensionless reference length obtained by cube the root mean square height Rq, and represents the symmetry between the peaks and troughs when the mean line is centered, i.e., the degree of distortion.
In other words, Rsk is a parameter related to the height distribution. A positive value suggests that the height distribution is skewed downwards relative to the mean line, resulting in sharper peaks, while a negative value suggests that the height distribution is skewed upwards relative to the mean line, resulting in blunter peaks.

Furthermore, by constructing at least one surface of the laminate with a resin layer (a) containing the specific polycarbonate resin (A) as described above, it becomes easier to impart surface roughness through the surface processing described later, and thus easier to obtain the various surface properties described above. For example, it becomes easier to impart appropriate surface roughness even when processing at relatively low temperatures.

At least one surface of the laminate may be subjected to surface treatment such as matte finishing in order to obtain the above-mentioned surface characteristics. The method of surface treatment is not particularly limited, but a mirror-finish sheet may be formed and then matte finished on the surface separately using a matte roll or the like, or a casting roll described later may be made into a matte roll or a roll with appropriately adjusted surface roughness, and surface treatment such as matte finishing may be performed while forming the sheet. In addition, various methods such as transfer treatments such as embossing roll transfer, embossing belt transfer, and embossing film transfer, sandblasting, shot blasting, etching, engraving, and surface crystallization can be used.
In particular, a method of adjusting the surface roughness to the desired level by casting a film-like molten resin onto a roll such as a casting roll is preferred because it allows for continuous and uniform adjustment of the surface roughness while extruding the molten resin into a film. In this case, the surface roughness of the laminate can be adjusted by adjusting the surface roughness, such as the arithmetic mean roughness, of the casting roll.
The laminate may have one surface that possesses the specific surface properties described above, or both surfaces may possess the specific surface properties described above.

The coefficient of linear expansion of this laminate is preferably 5 × ^10⁻⁴ /°C or less, more preferably 3 × ^10⁻⁴ /°C or less, even more preferably 1 × ^10⁻⁴ /°C or less, and even more preferably 8 × ^10⁻⁵ /°C or less. A lower limit is preferable, but is usually 1 × ^10⁻⁶ /°C, and may also be 5 × ^10⁻⁶ /°C. When the coefficient of linear expansion is within this range, the heat resistance is good, which has the advantage of minimizing deformation of products such as cards even when heat is applied during processing such as sublimation transfer printing. Detailed measurement conditions should be carried out as described in the examples.

<Method for manufacturing laminates>
Methods for manufacturing laminates include, for example, a method of laminating each layer by melt extrusion molding to a desired thickness (co-extrusion method), a method of forming each layer into a film of a desired thickness and laminating it, or a method of forming one or more layers by melt extrusion and laminating them to a separately formed film. Among these, lamination by melt extrusion molding is preferred in terms of productivity and cost.

Specifically, the resins constituting each layer, or resin compositions containing resins and additives, are prepared separately, or, if necessary, formed into pellets, and then fed into each hopper of a multilayer T-die extruder with shared T-dies. Furthermore, the materials are melted at, for example, a temperature in the range of 200 to 300°C and subjected to multilayer T-die melt extrusion molding. Next, the materials are cooled and solidified using a cooling roll (casting roll) or the like. In this way, a laminate (laminated sheet) can be formed. Note that the method for manufacturing the laminate of the present invention is not limited to the above method, and any method may be used.

<Composite Laminate>
This laminate may be further laminated with another resin layer (c) to form a composite laminate (hereinafter sometimes referred to as "this composite laminate"). As described above, this laminate has good low-temperature fusion properties and suitability for hot pressing. Therefore, this laminate and another resin layer (c) can be fused at a relatively low temperature by incorporating a resin with a relatively low glass transition temperature, such as a plant-derived resin, into the resin layer (c). Furthermore, even when the resin layer (c) contains a resin with a relatively low glass transition temperature, such as a plant-derived resin, it is possible to prevent the resin constituting the resin layer (c) from flowing or shrinking when fusing the resin layer (c) and this laminate by hot pressing.

This composite laminate comprises the main laminate and a resin layer (c), wherein the resin layer (c) is preferably laminated on one surface of the main laminate, and the resin layer (c) is preferably laminated on the surface of the main laminate on which the resin layer (a) is provided. Therefore, the composite laminate preferably has either a laminated structure of resin layer (c)/resin layer (a)/resin layer (b) or a laminated structure of resin layer (c)/resin layer (a)/resin layer (b)/resin layer (a). Here, the resin layer (c) may be a single layer or a multilayer structure.

(Resin layer (c))
The following describes preferred embodiments of the resin layer (c). If the resin layer (c) has a multilayer structure, all resin layers (c) may have the configuration of the preferred embodiment of the resin layer (c) described below. However, it is not necessary for all resin layers (c) to have the following configuration; at least one resin layer (c) may have the following configuration. However, each of the one or more resin layers (c) arranged on the surface of the laminate may have at least the configuration of the preferred embodiment described below.

The resin layer (c) contains resin (C). It is preferable that resin (C) has a glass transition temperature close to that of the polycarbonate resin (A) used in resin layer (a). Here, resin layer (a) refers to the resin layer (a) positioned on the surface of the laminate on which resin layer (c) is laminated. Having similar glass transition temperatures for resin (A) and resin (C) prevents resin from flowing or shrinking in the resin layer (c) during hot press molding with the laminate. Furthermore, it facilitates proper heat fusion between the resin layer (c) and the laminate during hot press molding.
Specifically, the absolute value of the difference between the glass transition temperature of resin (C) and the glass transition temperature of the polycarbonate resin (A) used in the resin layer (a) is preferably 30°C or less, more preferably 20°C or less, even more preferably 10°C or less, and even more preferably 5°C or less. Furthermore, the closer the absolute value of the difference in glass transition temperatures is to 0°C, the better, and it may even be 0°C.

Here, it is preferable to use a polycarbonate resin containing the structural unit (A1) described above as resin (C). By using such a polycarbonate resin, the difference between the glass transition temperature of resin (C) and the glass transition temperature of the polycarbonate resin (A) used in resin layer (a) can be reduced, making it easier for resin layer (c) and resin layer (a) to be heat-fused. Therefore, during hot press molding, the resin layer (c) can be fused to the laminate with high adhesive strength without the resin flowing or shrinking. Furthermore, by using a polycarbonate resin containing the structural unit (A1), resin (C) can be manufactured from plant-derived raw materials, and the biomass content of the final product, such as cards and passports, containing this composite laminate can be improved.
The details of the polycarbonate resin containing structural unit (A1), which is used as resin (C) (hereinafter, for convenience, may be referred to as "polycarbonate resin (C1)"), are as explained in the section on polycarbonate resin (A), and therefore the explanation of polycarbonate resin (C1) will be omitted.
However, the polycarbonate resin (C1) used in the resin layer (c) may be the same type as the polycarbonate resin (A) used in the resin layer (a), or a different type may be used.

In the resin layer (c), the polycarbonate resin (C1) may be used alone as resin (C) or in combination with another resin.
In the resin layer (c), the polycarbonate resin (C1) is often the main component, and the amount of polycarbonate resin (C1) 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 contained in the resin layer (c).

In the resin layer (c), preferred alternative resins used in combination with the polycarbonate resin (C1) include polycarbonate resins other than those containing structural units (A1), and polyester resins.
The polycarbonate resin other than the polycarbonate resin containing structural unit (A1) is not particularly limited, but bisphenol-based polycarbonate is preferred. Bisphenol-based polycarbonate is as described above in the section on polycarbonate resin (B1), so its description will be omitted.

Polyester resins used as resin (C) include polyesters obtained by polycondensation of a dicarboxylic acid and a dihydroxy compound. Dicarboxylic acid derivatives such as esters and acid halides may also be used as the dicarboxylic acid in the synthesis of the polyester resin.
From the viewpoint of heat resistance, aromatic dicarboxylic acids are preferred as the dicarboxylic acids used to obtain polyester resins, and therefore, it is preferable that the polyester resin contains structural units derived from aromatic dicarboxylic acids.
There are no particular restrictions on the aromatic dicarboxylic acid, and examples include terephthalic acid, isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, anthracenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5-sulfoisophthalic acid, sodium 3-sulfoisophthalate, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, etc. Among these, terephthalic acid and isophthalic acid are preferred, and terephthalic acid is more preferred.
Aromatic dicarboxylic acids may be used individually or in combination of two or more.

It is even more preferable that the structural units derived from aromatic dicarboxylic acids are present in the polyester resin at a concentration of, for example, 60 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more. Furthermore, there is no particular upper limit, and it is acceptable as long as it is 100 mol% or less, but most preferably it is 100 mol%.
Furthermore, the polyester resin may contain a small amount of structural units derived from aliphatic dicarboxylic acids (usually 40 mol% or less, for example 30 mol% or less, preferably 20 mol% or less) in addition to structural units derived from aromatic dicarboxylic acids. There are no particular restrictions on the aliphatic dicarboxylic acids, and examples include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecanedionic acid, dimer acid, 1,3 or 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and 4,4'-dicyclohexyldicarboxylic acid. The aliphatic dicarboxylic acid may be used alone or in combination of two or more.

The polyester resin preferably contains structural units derived from chain-like dihydroxy compounds. The inclusion of these structural units in the polyester resin tends to result in good low-temperature fusion properties for the film.
The chain-like dihydroxy compounds used in polyester resins may be linear or have a branched structure. Specific examples of chain-like dihydroxy compounds include chain-like dihydroxy compounds with approximately 2 to 18 carbon atoms, such as ethylene glycol (EG), diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, triethylene glycol, 1,2-hexadecanediol, and 1,18-octadecanediol, as well as polyglycols such as polytetramethylene ether glycol, polypropylene glycol, and polyethylene glycol. Among these, chain-type dihydroxy compounds having 2 to 12 carbon atoms are preferred, and more preferably one or more selected from ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, with ethylene glycol (EG) being particularly preferred.
The chain-like dihydroxy compounds may be used individually or in combination of two or more.

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

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

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

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

(filling material)
The resin layer (c) preferably contains a filler. By containing a filler, the resin layer (c) has reduced light transmittance and can exhibit opacity. Therefore, this composite laminate can be suitably used as a core sheet when used in cards or passports.

The filler can be either an inorganic or organic filler, but examples include titanium dioxide, talc, mica, calcium carbonate, barium oxide, zinc oxide, carbon black, silica, lead titanate, potassium titanate, zircon oxide, zinc sulfide, antimony oxide, and zinc oxide. Among these, at least one filler 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 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 a filler with a refractive index of 2 or higher provides even better opacity. Furthermore, the film can be colored white. From these viewpoints, titanium dioxide is more preferred as the filler. Titanium dioxide is not particularly limited, but examples include rutile-type titanium dioxide and anatase-type titanium dioxide. The refractive index of the filler material can be measured using the Becke line method.

The average particle size of the filler is not particularly limited, but for example, it is 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.

The filler content in the resin layer (c) is preferably 1% by mass or more and 60% by mass or less. A filler content of 1% by mass or more reduces the transmittance of the resin layer (c), providing a certain degree of opacity and allowing it to be colored white or other colors. Furthermore, a filler content of 60% by mass or less makes it easier to maintain good mechanical properties such as bending durability.
From the viewpoint of improving opacity, the content of the filler is more preferably 3% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. Furthermore, from the viewpoint of improving mechanical properties such as bending durability, the content of the filler is more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, and even more preferably 25% by mass or less.

(Impact-resistant additive)
The resin layer (c) may also preferably contain an impact-resistant modifier. Even if the resin layer (c) contains a large amount of filler as described above, further inclusion of an impact-resistant modifier mitigates the effects of external impacts such as bending and impact during actual use, making it easier to maintain good bending durability. In addition, it helps to prevent a decrease in softening and fluidity during heating, which can occur due to the use of a specific resin such as polycarbonate resin or the inclusion of a large amount of filler, making it easier to maintain good processability. Details of the impact-resistant modifier are as described in the description of resin layer (a), and are omitted here.

The content of the impact-resistant modifier in the resin layer (c) is preferably 2% by mass or more and 40% by mass or less. A content of 2% by mass or more of the impact-resistant modifier moderately mitigates the effects of external impacts, making it easier to improve bending durability and other properties. Furthermore, it helps prevent a decrease in softening and fluidity during film heating, which can occur due to the type of resin used, thus maintaining good processability.
On the other hand, by limiting the content to 40% by mass or less, the effect commensurate with the content can be achieved. Furthermore, it is possible to prevent a decrease in various physical properties such as the heat resistance of the resin layer (c), a decrease in the biomass content of the composite laminate, and excessive fluidity of the resin layer (c) during processing.
From these viewpoints, the content of the impact-resistant modifier in the resin layer (c) is more preferably 4% by mass or more, even more preferably 6% by mass or more, even more preferably 8% by mass or more, even more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 13% by mass or less.

Furthermore, the resin layer (c) may contain various additives other than those mentioned above, to the extent that it does not impair its properties, or to further improve physical properties other than those targeted by the present invention. Examples of additives include antioxidants, heat stabilizers, process stabilizers, ultraviolet absorbers, light stabilizers, matting agents, processing aids, metal deactivators, residual polymerization catalyst deactivators, antibacterial/antifungal agents, antiviral agents, antistatic agents, lubricants, flame retardants, pigments, dyes and other colorants, laser colorants, and a wide range of other additives commonly used in resin materials. For these as well, the amount added should be the amount typically used, depending on the intended purpose.

The resin layer (c) may constitute a core sheet or a laser marking sheet in a card or passport, but it is preferable that it constitutes a core sheet. The core sheet or laser marking sheet may be formed by a single resin layer (c), or it may be a multilayer sheet formed by laminating multiple resin layers (c).
Furthermore, the composite laminate may have two or more of these laminates; for example, one or more resin layers (c) may be provided between two of these laminates.

The thickness of the resin layer (c) is not particularly limited, but for example, it may be 10 μm or more and 2000 μm or less, preferably 50 μm or more and 1000 μm or less, more preferably 70 μm or more and 600 μm or less, and even more preferably 100 μm or more and 500 μm or less. If the resin layer (c) has a multilayer structure, it is preferable that its total thickness be within the above range.
Furthermore, the composite laminate may be in sheet form, and its thickness is not particularly limited, but for example, it may be 100 μm or more and 3000 μm or less, preferably 150 μm or more and 2000 μm or less, and more preferably 200 μm or more and 1000 μm or less.

The composite laminate is preferably obtained by laminating the laminate onto another resin sheet (hereinafter also referred to as resin sheet (X)) by fusion. The resin sheet (X) consists of a single resin layer (c) or a multilayer resin layer (c).
Furthermore, multiple resin sheets (X) and the laminate may be fused together, or one or more resin sheets (X) and two or more laminates may be fused together. For example, when using two laminates, the laminate, one or more resin sheets (X), and the laminate may be stacked in that order, and these may be heat-fused by a hot press or the like to obtain a composite laminate.
In this composite laminate, it is preferable that the laminate is laminated onto the resin sheet (X) such that the side on which the resin layer (a) is provided is positioned on the side of the resin sheet (X).

The fusion process is preferably carried out by heat fusion, such as by hot pressing. The temperature during heat fusion should be, for example, 90°C to 150°C, preferably 100°C to 140°C, and more preferably 105°C to 135°C. By setting the heat fusion temperature below the above upper limit, it is possible to suppress the leakage of plant-derived resin during heat fusion, even if the laminate or resin sheet (X) contains plant-derived resin. Furthermore, by setting the heat fusion temperature below the above lower limit, the laminate can be fused to other resin sheets with appropriate adhesive strength.

As described above, it is preferable that this composite laminate has a biomass content of a certain level or higher by using plant-derived resins for the resin layer (c) and the resin layer (a).
From the viewpoint of reducing environmental impact, the biomass content of this composite laminate is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and even more preferably 30% by mass or more. The biomass content of this composite laminate is not particularly limited, but in order to impart various mechanical properties such as bending durability to the composite laminate, it may be, for example, 70% by mass or less, 50% by mass or less, or 45% by mass or less.
Furthermore, this composite laminate may constitute the data pages of a card or passport, as described later, and the resin sheet (X) is preferably a core sheet, laser marking sheet, or the like, as described later.

<Passport or card>
This laminate and composite laminate can be used in various types of cards, such as passports, IC cards, magnetic cards, driver's licenses, residence cards, qualification certificates, employee IDs, student IDs, My Number cards, seal registration certificates, vehicle registration certificates, tag cards, prepaid cards, cash cards, bank cards, credit cards, SIM cards, ETC cards, identification cards, information-carrying cards, smart cards, B-CAS cards, and memory cards. In various types of cards and passports, this laminate and composite laminate are used as recording layers on which various types of information are printed. In passports, this laminate and composite laminate are used for data pages.

A card or passport (more specifically, the data pages of a passport) typically comprises a core sheet and an oversheet. The card or passport may also further include a laser-marked sheet.
The card or passport of the present invention may be manufactured by layering multiple resin sheets, for example, one or more core sheets, one or more oversheets, and a laser marking sheet used as needed, pressing and heat-fusing them together, and then performing die-cutting or the like. Alternatively, instead of heat-fusing, adhesives or the like may be used to bond the sheets together as appropriate.
The card or passport of the present invention may include the laminate described above, and at least one of the resin sheets described above may be the laminate, and as described above, it is preferable to use the laminate as an oversheet.

A specific example of the card is shown in Figure 1. Preferably, the card is either card 20A, shown in Figure 1(a), consisting of an oversheet 4/core sheet 2/oversheet 4, or card 20B, shown in Figure 1(b), consisting of an oversheet 4/laser marking sheet 1/core sheet 2/laser marking sheet 1/oversheet 4. Of these, card 20A, consisting of an oversheet 4/core sheet 2/oversheet 4, is more preferable.

Here, although Figure 1 schematically shows a single core sheet 2, it is generally preferable to have two or more core sheets. Each core sheet may be a printing 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 concealing 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 with adhesive sheets. In addition, each core sheet may have a single-layer structure, or it may have a multi-layer structure of two or more layers.

The core sheet is preferably a resin sheet using polycarbonate resin, polyester resin, or a mixture thereof as the resin material, and for example, any of the resins listed above as resin (C) may be appropriately selected and used. Furthermore, as explained in resin layer (c), the sheet may contain additives such as fillers and impact modifiers.
Furthermore, as described above, since the oversheet 4 is preferably this laminate, in the structure of Figure 1(a), the core sheet is preferably made of the resin sheet (X) described above.

The laser marking sheet is preferably a resin sheet using polycarbonate resin, polyester resin, or a mixture thereof as the resin material, and for example, any of the resins listed above as resin (C) may be appropriately selected and used. In addition, the resin layer (c) may appropriately contain additives as described above.
Furthermore, the laser marking sheet 1 may have a resin layer containing a laser colorant, and may consist of a resin layer containing a laser colorant, or it may have a multilayer structure of a resin layer containing a laser colorant and a resin layer not containing a laser colorant.
Furthermore, the oversheet 4 is preferably the laminate as described above. In the structure of Figure 1(b), the oversheet can suppress so-called "blistering," which occurs when the laser-printed portion foams up due to laser irradiation, for example.

Furthermore, when using this laminate as an oversheet, the resin layer (b) may or may not contain a laser colorant. However, if the resin layer (b) contains a laser colorant, the card does not need to contain a laser marking sheet, as shown in Figure 1(a). By using a laminate having a resin layer (b) containing a laser colorant as an oversheet, it becomes possible to laser mark the card without providing a separate laser marking sheet.

(passport)
A passport, especially an electronic passport, may include a hinge sheet and core sheets provided on both sides of the hinge sheet, with an oversheet on the surface of the core sheet. Alternatively, a laser marking sheet may be included between the core sheet and the oversheet. Specifically, a passport 10A consisting of an oversheet 4/core sheet 2/hinge sheet 3/core sheet 2/oversheet 4, as shown in Figure 2(a), or a passport 10B consisting of an oversheet 4/laser marking sheet 1/core sheet 2/hinge sheet 3/core sheet 2/laser marking sheet 1/oversheet 4, as shown in Figure 2(b), is preferred.

The hinge sheet is a sheet that holds the oversheet, core sheet, etc., and plays the role of securely binding the passport cover to other visa sheets, etc., as a single unit. Therefore, it is preferable that the hinge sheet has strong heat-sealing properties, appropriate flexibility, and heat resistance during the heat-sealing process.
The hinge sheet can be 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. Furthermore, a detailed explanation of the core sheet, laser marking sheet, and oversheet in the passport is as explained on the card above and will therefore be omitted.

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

The evaluation and measurement methods are as follows:
The glass transition temperature was measured using a differential scanning calorimeter "Pyris1 DSC" (manufactured by PerkinElmer) in accordance with JIS K7121:2012. The temperature was increased from 30°C to 200°C at a rate of 20°C/min, then decreased to 30°C at a rate of 20°C/min, and then increased again to 200°C at a rate of 20°C/min. The glass transition temperature was determined using the midpoint glass transition temperature (Tmg).

Mass average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw/Mn)
The raw material resin pellets were measured using gel permeation chromatography "HLC-8320GPC" (manufactured by Tosoh Corporation) under the following conditions.
• Columns: Shim-Pack GPC-806 (30cm x 8.0mmφ) + Shim-Pack GPC-804C (30cm x 8.0mmφ) + Shim-Pack GPC-8025C (30cm x 8.0mmφ) + Shim-Pack GPC-801C (30cm x 8.0mmφ) (manufactured by Shimadzu Corporation)
• Eluent: Chloroform • Detector: Differential refractive index detector • Flow rate: 1.0 mL/min • Column temperature: 40°C
• Sample concentration: 5 mg/mL
Sample injection volume: 20 μL
Calibration curve: A first-order approximation curve using standard polystyrene (manufactured by Tosoh Corporation).

(3) Solvent resistance At room temperature, a sheet sample was immersed in a petri dish containing methyl ethyl ketone as a solvent for 1 minute, and its appearance was visually inspected and evaluated according to the following evaluation criteria.
A: There was no change, or whitening did not occur to the extent that the matte surface disappeared.
B: Whitening occurred.

(4) Coefficient of Linear Expansion The laminated sheets and single-layer sheets obtained in the examples and comparative examples were subjected to a thermomechanical analysis using a "TMA/SDTA841" (Mettler Toledo) in accordance with JIS K7197:2012. The sample length was measured at 20°C intervals while the temperature was increased from 20 to 200°C at a rate of 5°C/min under conditions of a test specimen width of 6 mm, a distance between measuring chucks of 10 mm, and tensile mode. The average coefficient of linear expansion was calculated by averaging the obtained measurement results. The measurement direction was MD.

(5) Biomass content In the examples and comparative examples, the biomass content of the following raw material ISP was calculated based on the mass percentage of structural units derived from isosorbide, a plant-derived component. Based on this biomass content, the biomass content of the entire laminate and the entire composite laminate was calculated. In the examples and comparative examples, no plant-derived raw materials other than ISP were used in the laminates and composite laminates.

(6) Surface Characteristics The surface characteristics of the laminated or single-layer sheets of each example and comparative example were measured using a surface roughness measuring device "Surfcom 130A" (manufactured by Tokyo Seimitsu Co., Ltd.) in accordance with ISO 1997, with a measurement speed of 0.6 mm/s, a measurement length of 5 mm, a cutoff value of 2.5 mm, and a Gaussian filter type. In each example and comparative example, the surface characteristics of both surfaces were measured, and the values were recorded as one being the front surface and the other the back surface.

(7) Amount of laser colorant per unit area The amount of laser colorant per unit area was calculated according to the following formula.
Amount of laser colorant per unit area (μg/ ^cm² ) = Specific gravity of laser colorant (μg/ ^cm³ ) × Mass ratio of laser colorant in the laser colorant-containing layer (resin layer (b)) (%) × Thickness of the laser colorant-containing layer (cm)
For example, in the case of Example 3, the calculation is as follows.
8.9 × ^10⁶ (specific gravity) × 0.001 (mass ratio) × 50 × (4 ÷ 6) × ^10⁻⁴ (thickness) = 30

(8) Dynamic bending durability The composite laminate sheets (composite laminates) obtained in the examples and comparative examples were tested according to the following procedure, referring to the dynamic bending force (bending characteristics) specified in 5.8 of "JIS X6305-1:2010", to evaluate their bending durability. The size of the composite laminate sheet used in the evaluation test was 54.0 mm × 85.6 mm.
The test apparatus used to apply dynamic bending force to the sheet during the test was the one specified in JIS X6305-1:2010, section 5.8.1.
The movable part of the test apparatus was a crank mechanism. The maximum deflection (hw) of the test apparatus was set by adjusting the stroke of the movable part. The minimum deflection (hv) was set by the starting position. Both hv and hw were measured on the underside of the composite laminated sheet. The inclination angle α of the meshing part of the movable part of the test apparatus was set to 30°.

The tests were conducted under the test conditions specified in JIS X6305-1:2010, section 4.1, following the procedure below. The test conditions specified in 4.1 are a temperature of 23°C ± 3°C and a relative humidity of 40-60%.
First, the composite laminated sheet was placed between the interlocking parts of the test apparatus. The interlocking parts were positioned so that the short side of the sheet curved along the direction of the sheet's short side during bending. The starting position of the apparatus was set so that the minimum deflection (hv) was 1.0 mm ± 0.5 mm, and the stroke of the apparatus was set so that the maximum deflection (hw) was between 10.0 mm and 9.0 mm. The movable part of the test apparatus was operated so that the bending force changed sinusoidally at a frequency of 0.5 Hz, and the number of cycles until cracking was observed was counted.

(9) Hot Press Processing Test Using the electric sealer "Impulse Sealer OPL-200-10" (manufactured by Fuji Impulse Co., Ltd.), the laminated sheets or single-layer sheets obtained in each example and comparative example were heat-sealed to the core sheet under the conditions of heating for 5 seconds, followed by cooling at 40°C for 5 seconds, resulting in a sheet width of 20 mm x length of 40 mm (heat-sealed length 10 mm, unheat-sealed length 30 mm). After that, a T-shaped peel test was performed by holding the unheat-sealed portion by hand to check whether the laminated sheet broke. The heating temperature was increased in 5°C increments, and the first temperature at which the material broke (material breakage temperature) is defined as the hot press temperature and is shown in Table 3. Note that the material breakage temperature (hot press temperature) is the temperature at which the laminated sheet fuses properly, and a lower temperature indicates better low-temperature heat fusion performance.
Furthermore, the suitability for heat pressing was evaluated according to the following criteria by observing the appearance after heat fusion at the above-mentioned heat pressing temperature.
A: A composite laminated sheet was obtained properly without resin leakage from the edges of the stacked sheets during heat pressing.
B: The edges of the overlapping sheets melted and spread, preventing the creation of a properly laminated composite sheet.

The raw materials used in the examples and comparative examples are as follows:
ISP: A polycarbonate resin obtained by melt polymerization using isosorbide and 1,4-cyclohexanedimethanol as dihydroxy compounds, such that the ratio of structural units derived from isosorbide to those derived from 1,4-cyclohexanedimethanol is 50:50 (mol%). Glass transition temperature: 98°C
PC1: Bisphenol A homopolycarbonate (interfacial polymerization method), Mw: 72000, Mn: 23900, Mw/Mn: 3.0, Melt flow rate (300°C, 1.2 kgf): 4 g/10 min, Glass transition temperature: 154°C
PC2: Bisphenol A homopolycarbonate (interfacial polymerization method), Mw: 53200, Mn: 18700, Mw/Mn: 2.8, Melt flow rate (300°C, 1.2 kgf): 15 g/10 min, Glass transition temperature: 149°C
Impact-resistant additive 1: Core-shell type elastomer, "Metablen E-870A" manufactured by Mitsubishi Chemical Corporation.
Impact-resistant additive 2: Core-shell type elastomer, "Metablen S-2001" manufactured by Mitsubishi Chemical Corporation.
Filler: Titanium oxide (rutile type, refractive index 2.7)
Antistatic agent: Ionic liquid; Laser colorant: Bismuth-neodymium metal oxide, average particle size 0.8 μm, specific gravity: 8.9 g/ ^cm³

<Laminate (Laminated Sheet)>
[Example 1]
ISP was kneaded using an extruder and extruded at 235°C as the first and third layers (both outer layers) from a two-type, three-layer multi-manifold die. PC1 was kneaded using an extruder as resin layer (b) and extruded at 260°C as the second layer (intermediate layer) from the same die. The extruded film was cooled on a casting roll set to 90°C to obtain a laminate (laminated sheet) consisting of resin layer (a)/resin layer (b)/resin layer (a) with a thickness ratio of 1/4/1 and a total thickness of 50 μm. The obtained laminate sheet was evaluated, and the evaluation results are shown in Table 1.

[Example 2]
The procedure was carried out in the same manner as in Example 1, except that the composition of the resin layer (a) was changed as shown in Table 1, dry-blended, and then fed into an extruder.

[Examples 3 and 4]
The procedure was carried out in the same manner as in Examples 1 and 2, except that the composition of the resin layer (b) was changed as shown in Table 1, dry-blended, and then fed into the extruder.

[Comparative Example 1]
Using an extruder, the ISP was kneaded and extruded at 230°C. The extruded film was cooled on a casting roll set to 95°C to obtain a single-layer sheet with a thickness of 50 μm. Evaluation tests were conducted on the obtained single-layer sheet. The evaluation results are shown in Table 1.

[Comparative Example 2]
The materials were dry-blended according to the predetermined formulation shown in Table 1, kneaded using an extruder, and extruded at 230°C. The extruded film was then cooled on a casting roll set to 90°C to obtain a single-layer sheet with a thickness of 120 μm. Evaluation tests were conducted on the obtained single-layer sheet. The evaluation results are shown in Table 1.

[Comparative Example 3]
The procedure was carried out in the same manner as in Example 1, except that the composition of the resin layer (a) was changed as shown in Table 1, dry blended, and fed into an extruder, and the extrusion temperature was changed to 280°C and the casting roll temperature to 120°C.

[Comparative Example 4]
The procedure was carried out in the same manner as in Example 1, except that the formulations in resin layers (a) and (b) were changed as shown in Table 1, dry blended, and fed into an extruder, and the extrusion temperature was changed to 240°C and the casting roll temperature to 120°C.

<Evaluation of composite laminates (composite laminated sheets)>
[Example 5]
(Fabrication of composite laminated sheets)
For the core sheet 1 to form the resin layer (c), the materials were dry-blended to the predetermined formulation shown in Table 2, kneaded using an extruder, and the film was extruded from the die at 230°C. The extruded film was rapidly cooled on a casting roll set to 95°C to obtain a single-layer core sheet 1 with a thickness of 310 μm.
The obtained core sheet 1 and the laminated sheet prepared in Example 1 were laminated in the order of Laminated sheet of Example 1 / Core sheet 1 / Laminated sheet of Example 1, and the above-described hot press processing test was performed to determine the material break temperature (hot press temperature). Based on the determined hot press temperature, a composite laminated sheet was prepared by laminating the core sheet 1 and the laminated sheet under the conditions of the above hot press processing test. The obtained composite laminated sheet was evaluated, and the results are shown in Table 3.

[Examples 6, 7, 8, Comparative Examples 5, 7]
The procedure was carried out in the same manner as in Example 5, except that the laminated sheets used were those listed in Table 3, either as the laminated sheets or single-layer sheets.

[Comparative Example 6]
The material was dry-blended to the predetermined composition shown in Table 2 for core sheet 2, and then kneaded using an extruder. The film was then extruded at 270°C as the first and third layers (both outer layers) from a two-type, three-layer multi-manifold die. The material was also dry-blended to the predetermined composition shown in Table 2, and then kneaded using an extruder. The film was then extruded at 270°C as the second layer (intermediate layer) from the same die. The extruded film was cooled on a casting roll set to 120°C to obtain a multilayer core sheet 2 consisting of the first, second, and third layers with a thickness ratio of 1/8/1 and a total thickness of 100 μm.
The obtained core sheet 2 and the laminated sheet prepared in Comparative Example 1 were subjected to the above-described hot press processing test to determine the material break temperature (hot press temperature). Based on the determined hot press temperature, the core sheet 2 and the laminated sheet were laminated under the conditions of the above-described hot press processing test to produce a composite laminated sheet. An evaluation test was conducted on the obtained composite laminated sheet, and the results are shown in Table 3.

[Comparative Example 8]
The procedure was carried out in the same manner as in Comparative Example 7, except that the laminated sheet used was the one listed in Table 3.

As shown in Examples 1 to 8 above, in the laminated sheet having resin layer (a) and resin layer (b), using polycarbonate resin (A) containing structural unit (A1) in resin layer (a) resulted in high solvent resistance and good low-temperature fusion properties. Therefore, as shown in Examples 5 to 8, even when fused with resin layer (c) formed from plant-derived resin, fusion was possible at low temperatures, and no resin leakage occurred during pressing. This allowed for increased biomass content of the composite laminate while maintaining good suitability for hot pressing. Furthermore, by using a resin (B) with a high mass-average molecular weight other than resin (A) in resin layer (b), the composite laminated sheet obtained by laminating this laminate onto a core sheet as an oversheet exhibited excellent bending durability, as shown in Examples 5 to 8.

In contrast, as shown in Comparative Examples 1 and 2, single-layer sheets containing polycarbonate resin (A) with structural unit (A1) exhibited high biomass content, good solvent resistance, and good low-temperature fusion properties. However, composite laminated sheets obtained by laminating these single-layer sheets onto a core sheet as an oversheet failed relatively early in dynamic bending durability tests and did not exhibit good bending durability (Comparative Example 5). On the other hand, single-layer sheets containing polycarbonate resin (A) with structural unit (A1) could not be fused to the core sheet at low temperatures when general polycarbonate resin was used for the core sheet. Furthermore, when heat-fused to the core sheet at high temperatures, resin leakage occurred during pressing, resulting in poor suitability for hot pressing (see Comparative Example 6).
Furthermore, as shown in Comparative Examples 3 and 4, when general polycarbonate resin was used for the resin layers (a) and (b), solvent resistance was low and good low-temperature fusion properties could not be achieved (see Comparative Examples 7 and 8). Moreover, when heat-sealed to the resin layer (c) formed from plant-derived resin, resin leakage occurred during pressing, resulting in poor suitability for hot pressing.

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

Claims (14)

A resin layer (a) containing a polycarbonate resin (A) which includes a structural unit (A1) derived from a dihydroxy compound represented by the following formula ( 2 ) in part of its structure , and a structural unit (A2) derived from at least one dihydroxy compound selected from aliphatic dihydroxy compounds and alicyclic dihydroxy compounds ,
A laminate comprising a resin layer (a) and a resin layer (b) containing a resin (B) other than the polycarbonate resin (A) contained in the aforementioned resin layer (a),
The resin layer (a) is directly provided on both sides of the resin layer (b),
The aliphatic dihydroxy compound is an aliphatic dihydroxy compound having 2 to 12 carbon atoms, and the alicyclic dihydroxy compound is an alicyclic dihydroxy compound having 5 to 70 carbon atoms, including at least one of a 5-membered ring structure or a 6-membered ring structure.
The resin (B) is a bisphenol-based polycarbonate resin other than the polycarbonate resin (A), and its mass-average molecular weight is 54,000 or more, and its glass transition temperature (Tg) is 132°C or more.
A laminate in which the glass transition temperature of the polycarbonate resin (A) is lower than that of the resin (B), and is between 80°C and 140°C.

However, this excludes cases where the portion represented by formula ( 2 ) is part of _-CH2 -O-H. The laminate according to claim 1, wherein the polycarbonate resin (A) contains 30 mol% or more of the structural unit (A1) derived from the dihydroxy compound. The laminate according to claim 1 or 2, wherein the polycarbonate resin (A) contains 75 mol% or less of the structural unit (A1) derived from the dihydroxy compound. The laminate according to any one of claims 1 to 3 , wherein the resin layer (a) contains an impact-resistant agent. The laminate according to any one of claims 1 to 4 , wherein the resin layer (b) contains a laser colorant. A laminate according to any one of claims 1 to 5 , to be used as an oversheet. A laminate according to any one of claims 1 to 6 , for use in a card. A laminate according to any one of claims 1 to 6 , for use in a passport. A composite laminate comprising a laminate according to any one of claims 1 to 5 and a resin layer (c). The composite laminate according to claim 9 , wherein the resin layer (c) contains a polycarbonate resin comprising the structural unit (A1). The composite laminate according to claim 9 or 10 , wherein the resin layer (c) contains a filler in an amount of 1% by mass or more and 60% by mass or less. A method for manufacturing a composite laminate according to any one of claims 9 to 11 ,
A method for manufacturing a composite laminate, comprising laminating the laminate by fusing it to a resin sheet made of the resin layer (c). A card comprising a laminate according to any one of claims 1 to 7 , or a composite laminate according to any one of claims 9 to 11 . A passport comprising a laminate according to any one of claims 1 to 6 and 8 , or a composite laminate according to any one of claims 9 to 11 .