JP2018030338A - Laminate - Google Patents

Abstract

【Task】
Molecular weight in a severe high-temperature and high-humidity environment of 1000 hours under a temperature of 85 ° C. and a humidity of 85% RH in relation to a laminate including a front plate having a layer mainly composed of a polycarbonate-based resin and an adhesive layer Is provided, and a new laminate that maintains the mechanical strength is provided.
[Solution]
A laminate comprising a front plate (X) having a polycarbonate resin layer (A layer) and an adhesive layer (Y), wherein the laminate is 1000 hours under an environment of temperature 85 ° C. and humidity 85% RH. The laminate, wherein the rate of decrease in weight average molecular weight of the front plate (X) after standing is 15% or less.
[Selection figure] None

Description

  The present invention relates to a laminate excellent in durability under a high temperature and high humidity environment. Specifically, it is used as a substrate material and a protective material, for example, a surface protection panel of an image display device, a cover material for a mobile phone, a smartphone, a tablet device, a wearable terminal, etc., and generally more severe than these applications. The present invention relates to a laminate that can be suitably used as various substrate materials and protective materials as constituent materials of in-vehicle displays such as car navigation and automobile meters, which require durability under a high temperature and high humidity environment.

  Conventionally, glass has been mainly used as a front plate of an image display device. The front plate is used as a surface protection panel or a cover material of an image display device by being bonded to a display constituent member such as a liquid crystal module, a polarizing plate, or a glass substrate via an adhesive layer, for example.

  However, since the front plate made of glass is easily broken by an impact and is heavy, substitution with a resin material has been studied.

The resin material as such a glass substitute material is mainly required to have impact resistance, surface hardness, and shape stability in a high temperature and high humidity environment.
Polycarbonate resin plates have transparency and are excellent in impact resistance and heat resistance, and thus are used for soundproof partitions, carports, signboards, glazing materials, lighting fixtures, and the like. However, since the surface hardness is low, it has a drawback of being easily scratched.

  In order to improve this defect, for example, Patent Document 1 discloses a resin laminate in which a laminate obtained by coextruding a polycarbonate resin and an acrylic resin is subjected to a hard coat treatment.

  On the other hand, an adhesive force and a cohesive force are required for the adhesive layer that bonds the front plate and the display constituent member. In order to impart these basic physical properties, it is a common practice to introduce a highly polar component such as a carboxylic acid group into the adhesive layer as a copolymer component and an additive. However, since such highly polar components have an oxidizing action, the adhesive layer easily oxidizes and deteriorates, such as an ITO film or an IGZO film, under an environment such as high temperature and high humidity or long-term storage. It may cause deterioration.

  For example, Patent Document 2 discloses a configuration of an adhesive sheet that bonds a display front member such as a glass front plate and a liquid crystal module.

JP 2006-103169 A JP 2012-246407 A

  In using the front plate provided with a layer mainly composed of the polycarbonate-based resin disclosed in Patent Document 1 as a surface protection panel or a cover material of an image display device, the adhesive layer disclosed in Patent Document 2 is used. And can be bonded to a display component such as a liquid crystal module.

  However, when the laminate having such a structure is exposed to a severe high temperature and high humidity environment of, for example, a temperature of 85 ° C. and a humidity of 85% RH for a long time of 500 to 1000 hours or more, the acid component derived from the adhesive layer is polycarbonate. The inventors of the present invention have found a problem of shifting to a front plate having a layer containing a main component resin as a main component, promoting a decrease in molecular weight due to hydrolysis of the polycarbonate resin, and significantly reducing the mechanical strength of the front plate.

  Among various image display devices, for example, as a protective material for image display devices such as mobile phone terminals, smart phones, portable electronic playground equipment, portable information terminals, tablet devices, mobile personal computers, wearable terminals, etc., generally, an acceleration test In general, it is required to have durability in a high-temperature and high-humidity environment of about 120 hours under a temperature of 85 ° C. and a humidity of 85% RH, but it is a protective material for in-vehicle displays such as car navigation and automobile meters. When used as a battery, from the viewpoint of safety, actual use conditions, durability, etc., durability in a severer high temperature and high humidity environment of about 500 to 1000 hours in a temperature 85 ° C. and humidity 85% RH environment May be required.

  According to the study by the present inventors, under a temperature of 85 ° C. and a humidity of 85% RH, under a high-temperature and high-humidity environment of about 120 hours, water is reduced due to a decrease in molecular weight of the front plate having a layer mainly composed of a polycarbonate-based resin. Although the problem of decomposition is small enough that it does not become a problem, the mechanical strength is lowered to an extent that is practically unacceptable in a severe environment of high temperature and high humidity of 500 hours or more in an environment of temperature 85 ° C. and humidity 85% RH. Was confirmed.

  The present invention relates to a laminate including a front plate having a layer mainly composed of a polycarbonate-based resin and an adhesive layer, and a severe high temperature and high humidity for 1000 hours in a temperature 85 ° C. and humidity 85% RH environment. It is intended to provide a new laminate that suppresses the decrease in molecular weight under the environment and maintains the mechanical strength.

  In the present invention, the laminate includes a front plate (X) having a polycarbonate-based resin layer (A layer) and an adhesive layer (Y), and the laminate is an environment having a temperature of 85 ° C. and a humidity of 85% RH. A laminate is proposed in which the rate of decrease in the weight average molecular weight of the front plate (X) after standing for 1000 hours is 15% or less.

  The laminate proposed by the present invention is capable of suppressing the decrease in molecular weight and maintaining the mechanical strength even in a severe high temperature and high humidity environment of 1000 hours in a temperature 85 ° C. and humidity 85% RH environment. . Therefore, this laminated body is bonded to display constituent members such as a liquid crystal module, a polarizing plate, and a glass substrate for various uses, for example, a mobile phone terminal, a smartphone, a portable electronic play equipment, a tablet device, a mobile personal computer, In addition to image display devices such as wearable devices, various substrate materials and protective materials as constituent materials for liquid crystal televisions, liquid crystal monitors, desktop PCs, etc. It can also be suitably used as various substrate materials and protective materials as constituent materials for in-vehicle displays such as car navigation systems and automobile meters that require durability.

  Hereinafter, an example of an embodiment of the present invention will be described in detail.

In the present specification, “the“ main component ”for each layer” means a resin component having the highest content (mass%) in the resin composition forming each layer. Although not specified, as a guideline, a resin that occupies 50% by mass or more, particularly 80% by mass or more, particularly 90% by mass (including 100% by mass) of the resin contained in the resin composition forming each layer. In addition, when there are two or more types of main components, the total amount thereof corresponds to the content.
Further, “the“ main component ”of the polymer and its derivative” means a monomer having the highest ratio among the monomer units constituting the polymer and its derivative.

<This laminate>
A laminate according to an example of an embodiment of the present invention (hereinafter also referred to as “the present laminate”) is a laminate including a front plate (X) having a polycarbonate resin layer and an adhesive layer (Y). The laminate is characterized in that it can suppress a decrease in molecular weight and maintain mechanical strength even under a severe high temperature and high humidity environment of 1000 hours under a temperature of 85 ° C. and a humidity of 85% RH. .

  In the present laminate, as a means for reducing the molecular weight decrease of the front plate (X) to 15% or less when the laminate is exposed for 1000 hours in an environment of temperature 85 ° C. and humidity 85% RH, First, it is important to reduce the amount of the acid component eluted from the adhesive layer (Y) in a high temperature and high humidity environment. By this, it can prevent that the acid component of an adhesive bond layer transfers to the said front board (X), and can reduce the molecular weight fall of a front board (X) to 15% or less as a result. The amount of the acid component can be obtained by measuring the amount of acidic ions contained in the adhesive layer (Y). A method for measuring acidic ions will be described later.

  Further, as a means for reducing the decrease in molecular weight of the front plate (X) to 15% or less, the content of the phosphorus antioxidant in the front plate (X) having the polycarbonate resin layer is set within a certain range. It is preferable.

  The phosphorus-based antioxidant may be hydrolyzed under an environment of a temperature of 85 ° C. and a humidity of 85% RH to generate an acid component such as phosphorous acid, and may promote the hydrolysis of the front plate (X). From the viewpoint of suppressing this, the content of the phosphorus-based antioxidant is preferably 0.04 parts by mass or less, and preferably 0.03 parts by mass or less with respect to 100 parts by mass of the polycarbonate-based resin of the A layer. 0.02 parts by mass or less is more preferable. On the other hand, in order to suppress oxidative degradation during polymer polymerization, the lower limit is preferably 0.01 parts by mass or more.

When the laminate is exposed to a temperature of 85 ° C. and a humidity of 85% RH for 1000 hours, the molecular weight reduction rate of the front plate (X) is preferably 15% or less, and preferably 13% or less. Is preferable, and it is further more preferable that it is 11%. When the molecular weight reduction rate is 15% or less, the strength reduction due to the molecular weight reduction in a high temperature and high humidity environment is sufficiently small that it does not cause a practical problem, and can be suitably used even in a severe environment. The molecular weight reduction rate can be calculated as follows.
(Molecular weight reduction rate:%)
= {(Weight average molecular weight before exposure for 1000 hours in an environment of temperature 85 ° C. and humidity 85% RH) − (weight average molecular weight after exposure for 1000 hours in an environment of temperature 85 ° C. and humidity 85% RH}} / (temperature 85 (Weight average molecular weight before exposure for 1000 hours in an environment of 85 ° C. and humidity of 85% RH) × 100

  The mechanical strength of the front plate (X) when the laminate is exposed for 1000 hours in an environment of temperature 85 ° C. and humidity 85% RH is, for example, the tensile strength measured according to JIS-K7127 as an index. be able to. When the laminate is exposed to a temperature of 85 ° C. and a humidity of 85% RH for 1000 hours, if the tensile strength of the front plate (X) is 40 N or more, it is sufficiently durable as a protective material for in-vehicle displays. It can be said that it has. From this point of view, the mechanical strength of the front plate (X) when the laminate is exposed for 1000 hours in an environment of temperature 85 ° C. and humidity 85% RH is more preferably 50 N or more, and 60 N or more. More preferably it is.

<Adhesive layer (Y)>
The composition of the adhesive layer (Y) used in the laminate is not particularly limited. However, from the viewpoint of tackiness, transparency, weather resistance, etc., it is preferable to use an adhesive layer (Y) obtained by crosslinking a pressure-sensitive adhesive composition containing an acrylic resin as a main component resin.

(Adhesive composition)
The pressure-sensitive adhesive composition preferably contains an acrylic resin, a crosslinking monomer, and, if necessary, a crosslinking initiator, a reaction catalyst, and the like.

As the acrylic resin as the main component resin, an acrylate polymer (including a copolymer) is preferable.
Acrylic acid ester polymers (including copolymers) have properties such as glass transition temperature (Tg) depending on the types and composition ratios of acrylic monomers and methacrylic monomers used to polymerize them, and polymerization conditions. It is possible to adjust appropriately.

  Examples of the acrylic monomer and methacrylic monomer used for polymerizing the acrylate polymer include 2-ethylhexyl acrylate, n-octyl acrylate, n-butyl acrylate, ethyl acrylate, methyl methacrylate, and the like. Vinyl acetate, hydroxyethyl acrylate, acrylic acid, glycidyl acrylate, acrylamide, acrylonitrile, methacrylonitrile, fluorine acrylate, silicone acrylate, etc., which are copolymerized with a hydrophilic group or an organic functional group, can also be used.

Among the acrylic ester polymers, (meth) acrylic acid alkyl ester copolymers are particularly preferable.
The (meth) acrylate used for forming the (meth) acrylic acid alkyl ester copolymer, that is, as the alkyl acrylate or alkyl methacrylate component, the alkyl group is n-octyl, isooctyl, 2-ethylhexyl, n-butyl, One of alkyl acrylate or alkyl methacrylate which is any one of isobutyl, methyl, ethyl and isopropyl, or a mixture of two or more selected from these is preferable.

As other components, an acrylate or methacrylate having an organic functional group such as a carboxyl group, a hydroxyl group, or a glycidyl group may be copolymerized. By including these highly polar functional groups, adhesive force and cohesive force can be imparted. Specifically, a monomer component obtained by appropriately and selectively combining the alkyl (meth) acrylate component and the (meth) acrylate component having an organic functional group as a starting material is subjected to heat polymerization to form a (meth) acrylate ester copolymer. A polymer polymer can be obtained.
Among them, preferably, an alkyl acrylate such as iso-octyl acrylate, n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture of two or more selected from these, or iso-octyl acrylate, Examples thereof include those obtained by copolymerizing at least one kind of n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like with acrylic acid.

  On the other hand, when the content of the organic functional group having acidity including a carboxyl group is high, the adhesive layer (Y) is subjected to a severe temperature of 500 to 1000 hours in a temperature 85 ° C. and humidity 85% RH environment. When the acid or acidic functional group-containing monomer itself is contained as a free acid when it is placed in a high humidity environment, the elution occurs, and hydrolysis of peripheral members such as the front plate occurs. Cause.

The magnitude of the adverse effect of the adhesive layer (Y) on the above-mentioned problem is that the adhesive layer (Y) is 85 as a measure of the amount of the acid component eluted from the adhesive layer (Y) in a high temperature and high humidity environment. The amount of the acid component eluted from the adhesive layer (Y) into the hot water when immersed in hot water at 0 ° C. for 45 minutes can be used as an index. In the present invention, the total amount of acidic ions was obtained by immersing an adhesive layer test piece having a thickness of 150 μm, a width of 5 cm and a length of 5 cm (exposed area of the adhesive surface: 25 cm ² ) in hot water at 85 ° C. for 45 minutes. It is obtained by quantifying the total amount of acidic ions eluted at the time using an ion chromatography method.

As a preferable range of the total amount of acidic ions eluted from the above-mentioned adhesive layer (Y) into hot water, the acid component of the adhesive layer is prevented from moving to the front plate (X). From the viewpoint that the molecular weight reduction of the face plate (X) can be reduced to 15% or less, it is preferably 9000 (ng / cm ² ) or less, more preferably 5000 (ng / cm ² ) or less, More preferably, it is 1000 (ng / cm ² ) or less, and particularly preferably 500 (ng / cm ² ) or less.

  The acidic ions eluted from the above-mentioned adhesive layer (Y) into hot water are acidic functional groups including carboxyl groups contained in the terminal groups and side chains of the polymer constituting the adhesive layer (Y). Although it depends on the type, for example, acetate ion, acrylate ion, methacrylate ion, maleate ion and the like can be mentioned.

In addition, the total amount of acidic ions eluted under wet heat conditions is affected by the composition ratio of the acidic functional group copolymerization component contained in the adhesive layer and the amount of free acid such as acidic functional group-containing monomers, and is mainly a carboxyl group. It can be adjusted by changing the composition ratio of the acidic functional group copolymerization component such as. Examples of the acidic functional group include a sulfonic acid group and a phosphoric acid group in addition to the carboxyl group.
In the present invention, the content of the acidic functional group contained in the adhesive layer (Y) is 20 mol% or less from the viewpoint of preventing the acid component of the adhesive layer from moving to the front plate (X). Preferably, it is 15 mol% or less, more preferably 10 mol% or less. On the other hand, as long as it functions as an adhesive layer (Y), the adhesive layer (Y) may contain no acidic functional groups, and the lower limit of the content of acidic functional groups. Is 0 mol%.

Examples of crosslinking monomers (also referred to as “crosslinking agents”) include organic compounds such as polyfunctional (meth) acrylates having two or more (meth) acryloyl groups, isocyanate groups, epoxy groups, melamine groups, glycol groups, siloxane groups, and amino groups. A polyfunctional organic functional group resin having two or more functional groups, an organometallic compound having a metal complex such as zinc, aluminum, sodium, zirconium, or calcium can be used.
Examples of the above polyfunctional (meth) acrylates include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, trimethylolpropane triacrylate, and the like. be able to.

  The content of the crosslinking monomer may be adjusted in combination with other factors so as to obtain a desired holding power, but generally 0.01 to 40.0 parts by mass, preferably 100 parts by mass with respect to 100 parts by mass of the main component resin. Is preferably adjusted within a range of 0.1 to 30.0 parts by mass, particularly 0.5 to 30.0 parts by mass. However, this range may be exceeded in balance with other elements.

  When crosslinking acrylic resins, it is effective to add crosslinking initiators (peroxidation initiators, photoinitiators) and reaction catalysts (tertiary amine compounds, quaternary ammonium compounds, tin laurate compounds, etc.) as appropriate. Is.

When the adhesive layer (Y) of the present invention is subjected to ultraviolet irradiation crosslinking (also referred to as “UV crosslinking”), it is preferable to incorporate a photoinitiator.
As the photoinitiator, either a cleavage type photoinitiator or a hydrogen abstraction type photoinitiator may be used, but both may be used in combination.
Examples of the cleavage type photoinitiator include benzoin butyl ether, benzyl dimethyl ketal, and hydroxyacetophenone.
On the other hand, examples of the hydrogen abstraction type photoinitiator include benzophenone, Michler's ketone, dibenzosuberone, 2-ethylanthraquinone, and isobutylthioxanthone.
However, it is not limited to the substances listed above.

  Although the addition amount of a photoinitiator should just be adjusted suitably, generally in the range of the ratio of 0.05-5.0 mass parts with respect to 100 mass parts of main component resin of an adhesive bond layer (Y). It is good to adjust, and it is good to use hydrogen abstraction type and cleavage type photoinitiators in a ratio of 1: 1. However, this range may be exceeded in balance with other elements.

(Other additives)
In addition to the above components, pigments such as pigments and dyes having near-infrared absorption characteristics, tackifiers, antioxidants, antioxidants, hygroscopic agents, ultraviolet absorbers, silane coupling agents, natural products, Various additives such as synthetic resins, glass fibers and glass beads can be appropriately blended.

  The above-mentioned adhesive layer (Y) is, for example, an acrylic resin as a main component resin and, if necessary, a cross-linking agent and a reaction initiator or a reaction catalyst, and the like are stirred and mixed, on the release film. The adhesive layer (Y) can be formed by forming a film so as to have a desired thickness and crosslinking by heat drying or ultraviolet irradiation.

(Thickness)
The thickness of the adhesive layer (Y) is preferably 10 μm to 300 μm, particularly from 30 μm to 250 μm, from the viewpoint of reducing the internal stress of the laminate and increasing the shape stability in a high temperature and high humidity environment. Of these, 50 μm or more or 200 μm or less is particularly preferable.

(Tensile modulus)
The tensile elastic modulus of the adhesive layer (Y) is preferably 0.001 MPa or more from the viewpoint of enhancing shape stability in a high temperature and high humidity environment. From this viewpoint, the pressure is more preferably 0.005 MPa or more, and further preferably 0.01 MPa or more.
Further, from the viewpoint of enhancing tackiness, the elastic modulus is 30 MPa or less, preferably 20 MPa or less, more preferably 10 MPa or less.
The tensile elastic modulus of the adhesive layer (Y) is to perform a tensile test at a test speed of 300 mm / min and a temperature of 23 ° C. in the length direction of the adhesive layer (Y) cut out using a tensile tester. Can be measured by.

(Tg)
The Tg of the adhesive layer (Y) affects the flexibility of the pressure-sensitive adhesive resin composition at room temperature and the wettability of the pressure-sensitive adhesive resin composition to the adherend, that is, the adhesion. In order for the pressure-sensitive adhesive resin composition to have appropriate adhesiveness (tackiness) at room temperature, the Tg is preferably −70 ° C. to 10 ° C., more preferably −65 ° C. or more and 0 ° C. or less. The temperature is particularly preferably −60 ° C. or higher and −10 ° C. or lower.
The Tg of the adhesive layer (Y) was measured using a rheometer (“MARS” manufactured by Eihiro Seiki Co., Ltd.), adhesive jig: Φ25 mm parallel plate, strain: 0.5%, frequency: 1 Hz, temperature: −50 to It can be measured by a loss tangent (tan δ) of dynamic viscoelasticity measurement by a shear method at 200 ° C. and a heating rate of 3 ° C./min.

<Front plate (X)>
The laminate includes a front plate (X) having a polycarbonate resin layer (A layer). In order to provide other functions to the front plate (X), a thermoplastic resin layer (B layer) different from the A layer may be formed on one side or both sides of the polycarbonate resin layer (A layer).

<Polycarbonate resin layer (A layer)>
Examples of the polycarbonate resin (a1) that is a main component of the polycarbonate resin layer (A layer) include aliphatic polycarbonate, alicyclic polycarbonate, and aromatic polycarbonate containing bisphenol C.

The polycarbonate-based resin (a1) may be used alone, or various modifiers (a2) described later can be mixed and used.
Moreover, it is preferable that polycarbonate-type resin (a1) contains antioxidant (a3) for thermal degradation at the time of superposition | polymerization and a sheet shaping | molding, and oxidation degradation suppression.

(Polycarbonate resin (a1))
Examples of the polycarbonate resin (a1) include aromatic polycarbonate resins and aliphatic polycarbonate resins.
The polycarbonate resin (a1) may be a homopolymer or a copolymer with another copolymerizable monomer.
Further, the structure of the polycarbonate resin (a1) may be a branched structure, a linear structure, or a mixture of a branched structure and a linear structure.
The polycarbonate resin (a1) may be obtained by any known production method such as a phosgene method, a transesterification method, or a pyridine method.

The weight average molecular weight of the polycarbonate-based resin (a1) may be 10,000 to 100,000, particularly 16,000 or more or 40,000 or less, and more preferably 18,000 or more or 28,000 or less. Further preferred.
As the polycarbonate resin (a1), only one kind can be used alone, or two or more kinds having different weight average molecular weights can be used in combination.
If the weight average molecular weight of polycarbonate-type resin (a1) exists in the said range, since impact resistance is ensured and extrusion moldability is also favorable, it is preferable.

(Modifier (a2))
In order to adjust the melt viscosity of the polycarbonate resin layer (A layer) and improve the hardness, it is preferable to mix the polycarbonate resin (a1) and the modifier (a2) and use them for forming the A layer.

  A specific acrylic resin (a2-1) can be illustrated as a modifier (a2).

(Acrylic resin (a2-1))
The acrylic resin (a2) is preferably an acrylic copolymer composed of 5 to 80% by mass of aromatic (meth) acrylate monomer units and 95 to 20% by mass of methyl methacrylate monomer units.
In the acrylic resin (a2-1), if the content ratio of the aromatic (meth) acrylate monomer unit and the methyl methacrylate monomer unit is within the above range, the compatibility with the polycarbonate resin (a1) It is preferable because the effect of improving the surface hardness can be exhibited.
From this viewpoint, the aromatic (meth) acrylate monomer unit is more preferably 10 to 70% by mass and the methyl methacrylate monomer unit 90 to 30% by mass, and the aromatic (meth) acrylate monomer unit 25 to 25%. More preferably, it is 60 mass% and methyl methacrylate monomer unit 75-40 mass%.

Examples of the aromatic (meth) acrylate monomer unit include phenyl (meth) acrylate and benzyl (meth) acrylate. These can be used alone or in combination of two or more.
Of these, phenyl methacrylate and benzyl methacrylate are preferable, and phenyl methacrylate is more preferable in view of compatibility with the polycarbonate resin (a1).

In the acrylic resin (a2-1), if necessary, other copolymerizable monomer units other than the aromatic (meth) acrylate monomer unit and the methyl methacrylate monomer unit can be contained. .
When other monomer units are contained, the content is preferably 0.1 to 10% by mass in the acrylic resin (a2-1).

The acrylic resin (a2-1) preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 5,000 to 30,000 as measured by gel permeation chromatography (GPC).
When the weight average molecular weight (Mw) of the acrylic resin (a2-1) is in the above range, the compatibility with the polycarbonate resin (a1) is good, and the moldability and surface hardness improving effect of the resulting A layer and It is preferable because of its excellent appearance.
From this viewpoint, it is more preferable that the range of the weight average molecular weight (Mw) of the acrylic resin (a2-1) is 10,000 to 28,000.

The mixing mass ratio of the polycarbonate resin (a1) and the acrylic resin (a2-1) is not particularly limited, and is (a1) / (a2-1) = 99 to 65/1 to 35. Is preferred. It is preferable if the mixing ratio of the two is in the above range because the A layer obtained is excellent in formability, surface hardness improvement effect and appearance.
From this viewpoint, it is more preferable that (a1) / (a2-1) = 95 to 70/5 to 30.

(Antioxidant (a3))
Phosphorous antioxidants and phenolic antioxidants are added as antioxidants (a3) added to suppress oxidative deterioration during polymerization of the polycarbonate resin (a1) and during molding of the polycarbonate resin layer (A layer). Etc. In particular, it is preferable to add a phosphorus-based antioxidant from the viewpoint of preventing yellowing during sheet molding.

On the other hand, phosphorus antioxidants may hydrolyze and generate acids such as phosphorous acid when exposed to harsh high temperature and high humidity environments such as a temperature of 85 ° C. and a humidity of 85% RH. As is known, depending on the amount of acid generated, metal corrosion of a molding machine or the like is accelerated, and when added to a thermoplastic resin such as polycarbonate, hydrolysis of the thermoplastic resin is promoted.
Therefore, it is necessary to set the concentration of the phosphorus-based antioxidant to an appropriate range in order to suppress oxidative degradation during polymerization and sheet molding. A preferable concentration range of the phosphorus-based antioxidant to be added is as described above.

  As the phosphorus-based antioxidant, distearyl-pentaerythritol-diphosphite (manufactured by ADEKA Co., Ltd.) is considered in view of the fact that it can be used even at a general processing temperature of 250 to 300 ° C. for polycarbonate resins. , Trade name “ADK STAB PEP-8”), bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite (manufactured by ADEKA, trade name “ADK STAB PEP-36”) and bis (2,6 -Di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite bis (2,6-cy-t-butyl-4-n-octadecyloxycarbonylethyl-phenyl) pentaerythritol-diphosphite can do.

  When a phenolic antioxidant is used as the antioxidant, examples of the phenolic antioxidant include 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methyl]. Phenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane (for example, “ADEKA STAB AO-80” manufactured by ADEKA, Sumitomo Chemical) Product name “Sumilyzer GA-80”, etc., ethylene bis (oxyethylene) bis [3- (5-t-butyl-hydroxy-m-tolyl) propionate] (for example, product manufactured by Ciba Specialty Chemicals, Inc. Name “IRGANOX 245”), triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propiyl Sulfonate (for example, ADEKA Corporation, trade name "ADK STAB AO-70"), and the like.

(Other ingredients)
The layer A can contain various functional additives in addition to the modifier (a2) and the antioxidant (a3) as long as the effects of the present invention are not impaired.
Examples of the additive include an ultraviolet absorber, a light stabilizer, a lubricant, a flame retardant, a colorant, and a hydrolysis inhibitor.

<B layer>
Here, a thermoplastic resin layer different from the polycarbonate resin that is the main component of the A layer on one surface or both surfaces of the A layer in that the surface hardness or scratch resistance of the polycarbonate resin layer (A layer) is supplemented. (B layer) is preferably laminated.

  The thermoplastic resin as the main component of the B layer is, for example, an aromatic polyester such as polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, and polylactic acid-based heavy polymer. Polyester resins typified by aliphatic polyesters such as coalescence, polyolefin resins such as polyethylene, polypropylene and cycloolefin resins, polycarbonate resins, acrylic resins, polystyrene resins, polyamide resins, polyether resins, polyurethane resins Resin, polyphenylene sulfide resin, polyesteramide resin, polyetherester resin, vinyl chloride resin, acrylonitrile-styrene copolymer, acrylonitrile Butadiene-styrene copolymer, modified polyphenylene ether resin, polyarylate resin, polysulfone resin, polyetherimide resin, polyamideimide resin, polyimide resin, and copolymers containing these as main components, or these resins And the like. These may be one kind or a mixture of two or more kinds.

<Preferable specific configuration example of layer B>
As an example of the thermoplastic resin as a main component of the B layer, a layer containing an acrylic resin (b1) as a main component resin can be exemplified. Preferably, the layer B comprises an acrylic resin (b1), a copolymer having an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic acid anhydride monomer unit ( b2).
As another preferred example of the B layer, a layer containing a polycarbonate resin (b3) containing a structural unit derived from a dihydroxy compound in a part of the structure as a main component resin can also be mentioned.
Next, each of these component resins (b1) to (b3) will be described.

(Acrylic resin (b1))
The acrylic resin (b1) is a (co) polymer obtained by polymerizing a (meth) acrylic acid ester monomer unit as a main component and a derivative thereof.

  Here, the term “(meth) acrylic acid ester monomer unit” is intended to include an acrylic acid ester monomer unit or a methacrylic acid ester monomer unit.

  Examples of the (meth) acrylic acid ester monomer unit include methyl methacrylate, methacrylic acid, acrylic acid, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo Ntanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate , 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (Meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. can be mentioned. These can be used alone or in combination of two or more. Examples of other monomer units that can be polymerized with these acrylic monomer units include olefin monomer units and vinyl monomer units.

  Among them, the acrylic resin (b1) is composed of a methyl methacrylate monomer, a methacrylic acid monomer, an acrylic acid monomer, and a maleic anhydride monomer from the viewpoint of improving heat resistance and reducing water absorption. A copolymer with any one or more of aromatic vinyl monomer and vinyl cyanide monomer can be suitably used.

  There is no restriction | limiting in particular about the stereoregularity of acrylic resin (b1). However, the three-dimensional structure of the (meth) acrylic acid ester monomer unit is preferred because the higher the proportion of the syndiotactic structure, the higher the glass transition temperature and the better the heat resistance. From this viewpoint, among the triad fractions of mm, mr, and rr, those having a three-dimensional structure having the highest molar ratio of rr can be preferably used. This triad fraction can be measured by a known method using a nuclear magnetic resonance measuring apparatus (1H-NMR).

(Copolymer (b2))
As described above, the B layer is preferably a layer containing the acrylic resin (b1) and the copolymer (b2) from the viewpoint of improving heat resistance and reducing water absorption.

  The copolymer (b2) is a copolymer having an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic anhydride monomer unit.

Examples of the “aromatic vinyl monomer unit” include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α- Examples include units derived from styrene monomers such as methylstyrene and α-methyl-p-methylstyrene. These aromatic vinyl monomer units can be used alone or in combination of two or more.
Of these, styrene units and α-methylstyrene units are preferred. Styrene monomer units are preferred because they are easily available industrially and are economical, and α-methylstyrene monomer units are preferred because they can improve the glass transition temperature.

Examples of the “(meth) acrylic acid ester monomer unit” include each methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, dicyclopentanyl methacrylate, and isobornyl methacrylate. Examples include units derived from ester monomers and acrylic ester monomers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, and decyl acrylate. These (meth) acrylic acid ester monomer units can be used alone or in combination of two or more.
Among these, a methyl methacrylate monomer unit is preferable from the viewpoint of compatibility with the acrylic resin (b1) and appearance.

Examples of the “unsaturated dicarboxylic acid anhydride monomer unit” include units derived from respective anhydride monomers such as maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, aconitic acid anhydride and the like. be able to. These unsaturated dicarboxylic acid anhydride monomer units can be used alone or in combination of two or more.
Among these, a maleic anhydride monomer unit is preferable from the viewpoint of compatibility with the acrylic resin (b1) and transparency.

The constituent unit of the copolymer (b2) is preferably 45 to 85% by mass of an aromatic vinyl monomer unit, 4 to 45% by mass of a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic acid anhydride unit. 8 to 20% by mass of a monomer unit, more preferably 55 to 85% by mass of an aromatic vinyl monomer unit, 5 to 30% by mass of a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic acid anhydride unit. It is the range of 10-18 mass% of monomer units.
The structural unit of the copolymer (b2) can be qualitatively and quantitatively analyzed by a known method, for example, a nuclear magnetic resonance (NMR) measuring device or other instrumental analyzer.

If the aromatic vinyl monomer unit occupies 45% by mass or more, particularly 55% by mass or more among all the structural units of the copolymer (b2), the thermal stability is improved, and the acrylic resin (b1) and When mixed, a good appearance can be obtained, and water absorption can be reduced, which is preferable.
Moreover, if a (meth) acrylic acid ester monomer unit occupies 4 mass% or more among all the structural units of a copolymer (b2), especially 5 mass% or more, it will be a phase with acrylic resin (b1). It is preferable because the solubility is improved and the transparency is improved.
Moreover, if unsaturated dicarboxylic anhydride monomer unit occupies 8 mass% or more among all the structural units of a copolymer (b2), especially 10 mass% or more, it is a phase with acrylic resin (b1). It is preferable because the solubility is improved and the transparency and heat resistance are improved.

On the other hand, if the ratio of the aromatic vinyl monomer unit is 85% by mass or less in the total constituent units of the copolymer (b2), the heat resistance is maintained while maintaining the miscibility with the acrylic resin (b1). This is preferable because it can improve water resistance and reduce water absorption.
Moreover, if the ratio of a (meth) acrylic acid ester monomer unit is 45 mass% or less among all the structural units of a copolymer (b2), especially 30 mass% or less, with acrylic resin (b1) It is preferable because water absorption can be suppressed while ensuring compatibility.
Moreover, if the ratio of unsaturated dicarboxylic acid anhydride unit is 20 mass% or less among all the structural units of a copolymer (b2), especially 18 mass% or less, compatibility with acrylic resin (b1) will be shown. While ensuring, improvement in thermal stability and water absorption can be suppressed, which is preferable.

The copolymer (b2) includes the above three monomer units, that is, an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic anhydride monomer unit. Other copolymerizable units "may be contained. However, the content is preferably 5% by mass or less.
Examples of the “other copolymerizable units” include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, N-methylmaleimide, and N-ethyl. N-alkylmaleimide monomers such as maleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-arylmaleimide monomers such as N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, etc. Mention may be made of units derived from a monomer. These copolymerizable units can be used alone or in combination of two or more.

  The copolymer (b2) preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 100,000 to 200,000 as measured by gel permeation chromatography (GPC). Here, it is preferable that the weight average molecular weight (Mw) is in this range because the B layer obtained by mixing with the acrylic resin (b1) is excellent in moldability and appearance. From this viewpoint, a more preferable range of weight average molecular weight (Mw) is 110,000 to 180,000.

  The method for producing the copolymer (b2) can be produced by a known polymerization method and is not particularly limited. For example, solution polymerization, bulk polymerization, and the like can be applied, and batch, semi-batch, and continuous methods can be appropriately employed as the polymerization process. In this laminate, there are few by-products, and it is easy to control molecular weight adjustment and transparency, so that a batch polymerization process can be suitably used in solution polymerization.

((B1) / (b2))
In the B layer, the mixing mass ratio of the acrylic resin (b1) and the copolymer (b2) is preferably (b1) / (b2) = 80/20 to 20/80.
If the mixing ratio of the acrylic resin (b1) and the copolymer (b2) is within the above range, the interlayer adhesion with the B layer is excellent, while maintaining the surface hardness and transparency that are the characteristics of the acrylic resin. It is preferable because heat resistance and water absorption are suppressed.

  In order to reduce the internal stress generated in the high temperature and high humidity environment of the present laminate, it is preferable that (b1) / (b2) = 70/30 to 40/60, and in particular, 70/30 to 60 / More preferably, it is 40.

(Polycarbonate resin (b3))
As described above, it is also preferable that the B layer contains a polycarbonate resin (b3) having a specific structure as a main component. Thereby, a high surface hardness can be imparted to the laminate.

Here, the polycarbonate resin (b3) is a polycarbonate resin including a structural unit derived from a dihydroxy compound represented by the following (Chemical Formula 1) in a part of the structure.

  Examples of the dihydroxy compound represented by the above (Chemical Formula 1) include isosorbide, isomannide and isoide which are in a stereoisomeric relationship. These may be used alone or in combination of two or more.

  The dihydroxy compound represented by the above (Chemical Formula 1) is an ether diol that can be produced from a saccharide using a biogenic material as a raw material. In particular, isosorbide can be produced at low cost by hydrogenating and dehydrating D-glucose obtained from starch, and can be obtained in abundant resources. For these reasons, isosorbide is most preferred.

  In the polycarbonate resin (b3) as the main component of the B layer, the content ratio of the structural unit derived from the dihydroxy compound represented by (Chemical Formula 1) is preferably 50 mol% or more, and 60 mol% or more. More preferably, it is preferably 90 mol% or less, and more preferably 80 mol% or less.

In the polycarbonate resin (b3) as the main component of the B layer, the content ratio of the structural unit derived from the dihydroxy compound represented by the above (Chemical Formula 1) is in the above range, so that the hardness of the polycarbonate resin (b3) is The intermediate value between the aromatic polycarbonate resin and the acrylic resin is taken, and the punching workability is dramatically improved as compared with the display front plate in which the acrylic resin layer is arranged on the surface layer.
More specifically, since the content ratio of the structural unit is 90 mol% or less, the surface hardness and heat resistance are excellent, and the impact resistance and the decrease in interlayer adhesion with the A layer can be suppressed. It is possible to prevent various problems such as a decrease in yield at the time of punching and breakage when handling a product as a display front plate.
On the other hand, when the content ratio is 50 mol% or more, impact resistance and punching workability are excellent, and a decrease in surface hardness and heat resistance can be suppressed. Moreover, this laminated body can obtain further sufficient surface hardness by disposing a hard coat layer on at least one surface, and is suitable for any use of a display front plate and a transparent building material.

  The polycarbonate resin (b3) may have a structural unit other than the structural unit. For example, a structural unit derived from an aliphatic dihydroxy compound described in International Publication No. 2004/111106 pamphlet, The structural unit derived from the alicyclic dihydroxy compound as described in 2007/148604 pamphlet can be mentioned.

  Among structural units derived from the above aliphatic dihydroxy compounds, selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol It is preferable to have a structural unit derived from at least one dihydroxy compound.

  Among the structural units derived from the alicyclic dihydroxy compound, those containing a 5-membered ring structure or a 6-membered ring structure are preferable. The six-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. By including a structural unit derived from an alicyclic dihydroxy compound having a 5-membered ring structure or a 6-membered ring structure, the heat resistance of the obtained polycarbonate can be increased. The number of carbon atoms contained in the alicyclic dihydroxy compound is usually preferably 70 or less, more preferably 50 or less, and further preferably 30 or less.

Examples of the alicyclic dihydroxy compound containing the 5-membered ring structure or the 6-membered ring structure include those described in the above-mentioned International Publication No. 2007/148604. Among these, cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol and pentacyclopentadecanedimethanol can be preferably exemplified.
From the viewpoint of industrial availability, cyclohexanedimethanol is preferably selected, and 1,4-cyclohexanedimethanol is particularly preferable. On the other hand, when importance is attached to heat resistance and interlayer adhesion with the A layer, it is preferable to select tricyclododecanedimethanol.

  The polycarbonate resin (b3) used for the B layer can be produced by a generally used polymerization method, and may be either a phosgene method or a transesterification method in which it is reacted with a carbonic acid diester. Among them, in the presence of a polymerization catalyst, a dihydroxy compound represented by the above formula (1) in a part of the structure, an aliphatic and / or alicyclic hydroxy compound, and other dihydroxy compounds used as necessary And a transesterification method in which carbonic acid diester is reacted.

  The transesterification method includes a dihydroxy compound represented by the above formula (1) as a part of the structure, an aliphatic and / or alicyclic hydroxy compound, other dihydroxy compounds used as necessary, and a carbonic acid diester. Is a basic catalyst, and further, an acidic substance that neutralizes the basic catalyst is added to perform a transesterification reaction.

  Representative examples of carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Is mentioned. Of these, diphenyl carbonate is particularly preferably used.

The molecular weight of the polycarbonate resin (b3) can be represented by a reduced viscosity. The lower limit of the reduced viscosity is preferably 0.20 dL / g or more, more preferably 0.30 dL / g or more, and 0.35 dL / g or more. The upper limit of the reduced viscosity is preferably 1.20 dL / g or less, more preferably 1.00 dL / g or less, and even more preferably 0.80 dL / g or less.
If the reduced viscosity of the polycarbonate resin is too low, the mechanical strength of the molded product may be small. If it is too large, the fluidity at the time of molding tends to decrease, and the productivity and moldability tend to decrease.

(Other ingredients)
The layer B can appropriately contain various additives, modifiers and the like as long as the effects of the present invention are not impaired. Here, examples of the additive include an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a flame retardant, and a colorant. Examples of the modifier include impact resistance improvers, compatibilizers and antistatic agents.

<Hard coat layer (C layer)>
The front plate (X) may further include a hard coat layer (C layer) as an outermost surface layer on one side or both sides. However, the hard coat layer (C layer) may not be provided.
The hard coat layer (C layer) is a layer that imparts excellent surface hardness and scratch resistance to the front plate (X).

The hard coat layer (C layer) is preferably formed of a curable resin. For example, is it possible to cure the curable resin composition for forming the C layer by irradiating energy rays such as electron beams, radiation, and ultraviolet rays? Alternatively, it can be formed by curing the C layer forming curable resin composition by heating.
Among these, from the viewpoint of molding time and productivity, it is preferable to form a hard coat layer (C layer) by irradiating ultraviolet rays to cure the C layer forming curable resin composition.

  The curable resin composition for C layer formation for forming a hard-coat layer (C layer) should just be a resin composition containing curable resin C1. As described above, when the C layer forming curable resin composition is cured by irradiating ultraviolet rays, the C layer forming curable resin composition starts photopolymerization in addition to the curable resin C1. A resin composition containing an agent is preferred.

Specific examples of the curable resin C1 include, for example, acrylate compounds, urethane acrylate compounds, epoxy acrylate compounds, carboxyl group-modified epoxy acrylate compounds, polyester acrylate compounds, copolymer acrylates, alicyclic epoxy resins, glycidyl ether epoxy resins. , Vinyl ether compounds, oxetane compounds and the like. These curable resins can be used alone or in combination of two or more.
As the curable resin C1 that imparts more excellent surface hardness, a polyfunctional acrylate compound, a polyfunctional urethane acrylate compound, a polyfunctional epoxy acrylate compound, or the like, a radical polymerization curable compound, an alkoxysilane, an alkylalkoxysilane, etc. A thermopolymerizable curable compound can be mentioned, and further, an organic / inorganic composite curable resin composition obtained by adding an inorganic component to the curable resin may be used.

An organic / inorganic hybrid curable resin composition may be mentioned as a curable resin composition for forming a C layer that gives particularly excellent surface hardness. Examples of the organic / inorganic hybrid curable resin composition include those composed of a curable resin composition containing an inorganic component having a reactive functional group in the curable resin.
Utilizing such an inorganic component having a reactive functional group, for example, an organic / inorganic composite in which this inorganic component is copolymerized and crosslinked with a radical polymerizable monomer, so that the organic binder simply contains the inorganic component. Compared to the system curable resin composition, it is preferable because curing shrinkage hardly occurs and high surface hardness can be expressed. Furthermore, from the viewpoint of reducing curing shrinkage, an organic / inorganic hybrid curable resin composition containing ultraviolet-reactive colloidal silica as an inorganic component having a reactive functional group can be mentioned as a more preferable example.

In order to give a particularly excellent surface hardness to the hard coat layer (C layer), it is preferable to adjust the concentration of the inorganic component contained in the hard coat layer (C layer), particularly the inorganic component having a reactive functional group.
From this viewpoint, it is preferable that the concentration of the inorganic component contained in the hard coat layer (C layer), particularly the inorganic component having a reactive functional group, is 10 to 65% by mass. If the said density | concentration is 10 mass% or more, since the effect which provides the surface hardness excellent in the hard-coat layer (C layer) is acquired, it is preferable. On the other hand, if the concentration is 65% by mass or less, the hard coat layer (C layer) can be filled with an inorganic component, particularly an inorganic component having a reactive functional group, with excellent surface hardness. Can be effectively imparted.
From this viewpoint, the concentration is preferably 10 to 65 mass%, more preferably 20 mass% or more or 60 mass% or less, and particularly preferably 40 mass% or more or 55 mass% or less.

  The main component resin of the hard coat layer (C layer) from the viewpoint of improving the adhesiveness to the adhesive layer (Y) described later and reducing internal stress generated in the high temperature and high humidity environment of the laminate. Is preferably the same resin as the main component resin of the adhesive layer (Y). For example, when the main component resin of the adhesive layer (Y) is an acrylic resin, the main component resin of the hard coat layer (C layer) is also preferably an acrylic resin.

The curable resin composition for forming the C layer contains a photopolymerization initiator, and the photopolymerization initiator absorbs ultraviolet rays to be excited and activated to cause a polymerization reaction, thereby curing the ultraviolet curable resin. Those where the reaction takes place are preferred.
Examples of the photopolymerization initiator include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyldimethyl ketals, α-hydroxyalkylphenones, α-hydroxyacetophenones, hydroxyketones, aminoalkylphenones, acylphosphine oxides. And so on. Among these, α-hydroxyalkylphenones are preferable because they hardly cause yellowing during curing and a transparent cured product is obtained. In addition, aminoalkylphenones are preferable because they have very high reactivity and a cured product having excellent hardness can be obtained. The said photoinitiator can be used individually by 1 type or in combination of 2 or more types.
As for the addition amount of a photoinitiator, it is preferable to add 0.1-5 mass parts with respect to 100 mass parts of curable resin.

The curable resin composition for forming a C layer can contain a leveling agent as a surface adjustment component.
Examples of the leveling agent include silicone leveling agents and acrylic leveling agents. In particular, those having a reactive functional group at the terminal are preferable, and those having a reactive functional group having two or more functionalities are more preferable. preferable.
Specific examples include polyether-modified polydimethylsiloxane having an acrylic group having double bonds at both ends, and a polyester-modified polydimethylsiloxane having acrylic groups having two double bonds at the ends. be able to.
Among these, polyester-modified polydimethylsiloxane having an acrylic group that has a stable haze value and contributes to improvement of scratch resistance is particularly preferable.

  In addition to the curable resin component, the curable resin composition for forming the C layer includes, for example, a lubricant such as a silicon compound, a fluorine compound, or a mixed compound thereof, an antioxidant, an ultraviolet absorber, and an antistatic agent. In addition, various additives such as a flame retardant such as a silicone compound, a filler, glass fiber, and an impact modifier can be contained within a range that does not impair the effects of the present invention.

The thickness of the hard coat layer (C layer) is not particularly limited. For example, the thickness is preferably 1 μm to 30 μm, more preferably 3 μm or more and 25 μm or less, particularly preferably 5 μm or more and 20 μm or less, and particularly preferably 7 μm or more or 15 μm or less.
Here, if the thickness of the hard coat layer (C layer) is in the above range, scratch resistance can be imparted and cracks due to stress are unlikely to occur, which is preferable.

  Moreover, when it has a hard-coat layer (C layer) on both surfaces, the thickness of each hard-coat layer may be the same and may differ. Especially, it is preferable that the thickness of each hard-coat layer is the range of 7 micrometers-15 micrometers.

<Laminated structure of front plate (X)>
The front plate (X) only needs to include a polycarbonate-based resin layer (A layer). As an example, a thermoplastic resin resin layer (B layer) different from the A layer is provided on one side or both sides of the A layer. The front plate (X) of the structure formed may be mentioned.
Further, for example, as described above, a hard coat layer (C layer) may be provided on the single-sided outermost surface or the double-sided outermost surface.

As the layer structure of the front plate (X), (B) / (A), (B) / (A) / (B), (C) / (B) / (A), (C) / (B) / (A) / (B), (C) / (B) / (A) / (C), and (C) / (B) / (A) / (B) / (C) etc. Can do.
Here, when two or more of the same classification layers are included in the layer structure, the layers may have the same composition or different compositions.
Among these, (B) / (A), (B) / (A) / (B), (C) / (B) / (A), (C) / (B) / (A) / (C ), (C) / (B) / (A) / (B) / (C).

<Thickness of front plate (X)>
The thickness of the front plate (X) is not particularly limited, and is preferably 0.1 mm to 3.0 mm, for example, and is preferably 1.5 mm or less, more preferably 0.15 mm or more or 1.2 mm or less. Is more preferable.

  Moreover, the thickness of the front plate (X) has a preferable range depending on the application of the laminate. For example, when applied to the front cover material of various image display devices, it is preferably 0.1 to 2.0 mm, 0.15 mm or more or 1.5 mm or less, 0.2 mm or more or 0.8 mm or less, More preferably, it is 0.2 mm or more or 0.7 mm or less. If it is in this range, it is preferable because it is excellent in lightness and rigidity and shape stability in a high temperature and high humidity environment.

<Glass transition temperature of front plate (X)>
The glass transition temperature of the front plate (X) is preferably 100 ° C. or higher from the viewpoint of ensuring heat resistance, particularly 110 ° C. or higher, particularly 115 ° C. or higher, and more preferably 120 ° C. or higher. preferable. When the front plate (X) has a plurality of layers, it is preferable that all the layers have a glass transition temperature in the above range.

In the front plate (X) having a polycarbonate resin layer (A layer), a thermoplastic resin resin layer (B layer) different from the polycarbonate resin that is the main component of the A layer is provided on one side or both sides of the A layer. From the viewpoint of suppressing warpage of the front plate (X) in a high temperature and high humidity environment, the absolute value of the difference between the glass transition temperature of the A layer and the glass transition temperature of the B layer is 30 ° C. or less. preferable. From such a viewpoint, the absolute value of the difference is preferably 30 ° C. or less, more preferably 20 ° C. or less, more preferably 10 ° C. or less, and particularly preferably 5 ° C. or less. More preferably.
This is because, in a high temperature and high humidity environment, the B layer is susceptible to various strain relaxation phenomena due to a decrease in softening temperature due to water absorption, but if the absolute value of the difference is within the above range, This is because the dimensional change behaviors of both layers are close to each other, and as a result, warpage is considered to be suppressed.
The glass transition temperature is a value obtained by measuring at a heating rate of 10 ° C./min according to JIS K7121 using a differential scanning calorimeter. However, the glass transition temperature can also be measured by other known instrument analyzers such as a dynamic viscoelastic device.

<Elastic modulus of front plate (X)>
The elastic modulus of the front plate (X) is preferably 1500 to 4500 (MPa) from the viewpoint of enhancing mechanical strength and shape stability against stress, and more preferably 1800 or more and 4000 (MPa) or less, and 2000 of these. More preferably, it is 3500 (MPa) or less.

<War amount of front plate (X)>
In the front plate (X) having a polycarbonate resin layer (A layer), a thermoplastic resin resin layer (B layer) different from the polycarbonate resin that is the main component of the A layer is provided on one side or both sides of the A layer. When exposed to high temperature and high humidity environment, the front plate (X) is warped due to the effects of the thermal expansion coefficient between the (A layer) and (B layer), the difference in the coefficient of humidity expansion, and distortion during molding. May occur. When warping occurs on the front plate (X), internal stress is generated at the interface between the front plate (X) and the adhesive layer (Y), causing the front plate (X) and the adhesive layer (Y) to peel off. It becomes. From the viewpoint of suppressing this, as a guideline of the range of allowable warpage when the front plate (X) is exposed to a high temperature and high humidity environment, the front plate (X) has a temperature of 85 ° C. and a humidity of 85% RH. It is preferable that the average value of the amount of warping at the four corners after being left to stand for 120 hours and then left in an environment of temperature 23 ° C. and humidity 50% RH for 4 hours is 1.5 mm or less. In particular, the thickness is particularly preferably 0.3 mm or less.

<Method for manufacturing front plate (X)>
As a method for forming the front plate (X), a known method can be employed. For example, an extrusion casting method using a T-die having a melt mixing facility such as a single-screw extruder, a multi-screw extruder, a Banbury mixer, a kneader, etc. can be suitably used from the viewpoints of handling properties and productivity.

As a laminating method in the case of laminating the A layer and the B layer, a method of coextrusion molding a melt-kneaded resin with a T die having a feed block or a multi manifold can be suitably used.
In order to improve the appearance of the laminate, it is preferable to use a forming roll (such as a metal elastic roll or a polishing roll) whose surface is mirror-finished.
The molding temperature in the extrusion casting method using a T die is appropriately adjusted depending on the flow characteristics and film-forming properties of the resin composition to be used, but is generally 300 ° C. or lower, preferably 230 to 260 ° C. The molding roll temperature is generally 90 to 160 ° C, preferably 95 to 150 ° C.

  Moreover, when each layer is extruded, a single screw extruder or a multi-screw extruder can be suitably used, and the extruder of each layer preferably has a vent function and a filter function. The vent function is preferable because it can be used for drying the resin composition used for each layer, removing a small amount of volatile components, and the like, and a laminate having few defects such as bubbles can be obtained. In addition, there are various types of filter functions, and specific examples include a leaf disk filter, a back disk filter, a cone filter, a candle filter, and a cylindrical filter. Among them, a leaf disk filter that can easily secure an effective filtration area is preferable. The filter function can remove foreign matters, minute gels, and the like, and a laminated body with few appearance defects can be obtained.

In addition, the resin composition for forming each layer may be used by mixing each component in advance with a mixer such as a tumbler, V-type blender, Banbury mixer, extruder, etc. The components may be supplied directly, or the components weighed separately may be supplied to each supply port of an extruder having two or more supply ports.
Furthermore, the mixing method of various additives can use a well-known method. For example, (a) a master batch in which various additives are mixed in a suitable base resin at a high concentration (typically about 3 to 60% by mass) is prepared separately, and the concentration is added to the resin used. And (b) a method of directly mixing various additives into the resin to be used.

  When the hard coat layer (C layer) is laminated on the surface of the layer A or B layer (also referred to as “resin layer surface”) laminated as described above, the above-described curable resin composition for forming the C layer is an organic solvent. A method of laminating by coating on the surface of the resin layer by forming a cured film after coating as a paint dissolved or dispersed in can be mentioned. However, it is not limited to this method.

As a method of laminating the C layer on the surface of the resin layer, a known method can be used. For example, laminating method using cover film, dip coating method, natural coating method, reverse coating method, comma coater method, roll coating method, spin coating method, wire bar method, extrusion method, curtain coating method, spray coating method, The gravure coat method etc. are mentioned. In addition, for example, a method of using a transfer sheet in which a hard coat layer (C layer) is formed on a release layer and laminating the hard coat layer (C layer) on the surface of the resin layer may be employed.
Moreover, for the purpose of improving the adhesion between the hard coat layer (C layer) and the resin layer surface, various surface treatments such as corona treatment, plasma treatment and primer treatment can be performed on the resin layer surface.

And after laminating the curable resin composition for forming the C layer on the surface of the resin layer, for example, the curable resin composition is cured by irradiating energy rays such as electron beam, radiation, and ultraviolet rays, or The curable resin composition is preferably cured by heating. Among these, from the viewpoint of molding time and productivity, curing by ultraviolet irradiation is preferable.
Here, as the light source that emits ultraviolet rays, for example, an electrodeless high-pressure mercury lamp, an electroded high-pressure mercury lamp, an electrodeless metal halide lamp, an electroded metal halide lamp, a xenon lamp, an ultrahigh-pressure mercury lamp, or a mercury xenon lamp can be used. Among these, an electrodeless high-pressure mercury lamp is preferable because it is easy to obtain ultraviolet rays with high illuminance and is advantageous for curing an ultraviolet curable resin.

  When the C-layer-forming curable resin composition is made of an ultraviolet curable resin and cured by irradiating with ultraviolet rays, since the transparency to the ultraviolet rays is high, the internal curing of the curable resin composition proceeds quickly. In some cases, the curing of the surface of the curable resin composition is delayed due to the inhibition effect of oxygen (referred to as oxygen damage). For this oxygen disorder, it is preferable to irradiate the resin composition with a nitrogen gas atmosphere by supplying nitrogen gas and then irradiate with ultraviolet rays, since the curing of the surface can proceed rapidly together with the inside of the resin composition. .

After the thermoplastic resin layer (B layer) is laminated on one side or both sides of the polycarbonate resin layer (A layer) to form a resin laminate, the resin laminate may be heat treated.
As the heat treatment conditions, the resin laminate is heat-treated in a temperature range lower by 5 ° C. to 30 ° C. than the glass transition temperature of the B layer, in particular, in a temperature range lower by 5 ° C. to 25 ° C., in particular in a temperature range lower by 5 ° C. to 20 ° C. Is preferred.

Further, the outermost surface on one side or both sides of the front plate (X) is subjected to any one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment. Can do.
Each processing method is not particularly limited, and a known method can be used. For example, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be exemplified.

<Features of this laminate>
As described above, the laminate is capable of suppressing the decrease in molecular weight even under a severe high temperature and high humidity environment of 1000 hours under a temperature of 85 ° C. and a humidity of 85% RH, maintaining mechanical strength, transparency, It is also possible to increase impact resistance, surface hardness, and the like. Therefore, this laminated body can be suitably used as various substrate materials, protective materials, and the like by bonding them to various applications, for example, a base material. For example, image display devices such as mobile phone terminals, smart phones, portable electronic playground equipment, portable information terminals, tablet devices, mobile personal computers, wearable terminals, various substrate materials and protection materials as constituent materials for liquid crystal televisions, liquid crystal monitors, desktop personal computers, etc. In addition to materials, various substrate materials and protections that are generally used as constituent materials for in-vehicle displays such as car navigation and automotive instruments, which are required to have durability in high-temperature and high-humidity environments that are more severe than those described above. It can also be suitably used as a material.

  The laminate can also be given a shape by various processing methods. For example, in addition to the method of heating and pressurizing using a mold, a pressure forming method, a vacuum forming method, a roll homing method and the like can be exemplified as the forming method. By imparting a shape to the laminate, it can be used for an image display device having a curved surface and various flexible devices.

<Explanation of phrases>
“Sheet” generally refers to a product that is thin by definition in JIS and has a thickness that is small and flat for the length and width. In general, “film” is thicker than the length and width. A thin flat product with an extremely small thickness and an arbitrarily limited maximum thickness, usually supplied in the form of a roll (Japanese Industrial Standard JISK6900). However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.
In addition, the expression “panel” such as an image display panel and a protection panel includes a plate, a sheet and a film, or a laminate thereof.

In the present specification, when “X to Y” (X and Y are arbitrary numbers) is described, it means “preferably greater than X” or “preferably,” with the meaning of “X to Y” unless otherwise specified. The meaning of “smaller than Y” is also included.
Further, when described as “X or more” (X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and described as “Y or less” (Y is an arbitrary number). In the case, unless otherwise specified, the meaning of “preferably smaller than Y” is included.

Examples will be described in more detail below. However, the present invention is not limited to the examples described below.
Various measured values and evaluations displayed in this specification were performed as follows.

(1) Thickness It measured using the commercially available thickness measuring device (made by MITUTOYO).

(2) Amount of acidic ions eluted when the adhesive layer (Y) is immersed in hot water (ion chromatography method)
The adhesive layer used in Examples and Comparative Examples was cut into a test piece size: thickness 150 μm, width 5 cm × length 5 cm (exposed area of the adhesive surface in the test piece: 25 cm ² ), and then pasted on both sides in advance. Of the two polyethylene terephthalate films, one side of the film was peeled off, and the side where the adhesive layer was exposed by peeling was immersed in 85 ° C. hot water (50 ml) for 45 minutes. After immersion, the total elution amount was quantitatively analyzed by ion chromatography for the acidic ions eluted in the solution, and the total acidic ion amount (ng / cm ² ) eluted from the unit area of the adhesive layer was calculated. Since it was acetate ion, acrylic acid ion, and methacrylic acid ion that were detected as acidic ion species, the total amount of these ions was defined as the acidic ion amount.
Table 1 shows the total amount (ng / cm ² ) of detected acidic ions for the adhesive layers obtained in Examples and Comparative Examples.
[Measurement conditions for ion chromatography]
Analyzer: ICS-2000, manufactured by DIONEX
Separation column: Ion Pac AS11-HC (4 mm × 250 mm)
Guard column: Ion Pac AG11-HC (4 mm x 50 mm)
Removal system (subrest mode): External mode, 120 mA
Detector: Electrical conductivity detector Eluent: 1.5 mM KOH (0-7 minutes)
20.0 mM KOH (7-15 minutes)
40.0 mM KOH (15-20 min) Eluent flow rate using eluent generator: 1.5 ml / min Sample injection volume: 50 μl

(3) Long-term wet heat exposure test The front plate (X) / adhesive layer (Y) laminate obtained in the examples and comparative examples was stuck on a glass plate, and the temperature was set to 85 ° C. and the humidity was set to 85% RH. Were left in a constant temperature and humidity chamber for 120 hours, 500 hours, and 1000 hours, respectively.

(4) Weight average molecular weight From the front plate (X) / adhesive layer (Y) laminate after the long-term wet heat exposure test, only the front plate (X) was peeled from the adhesive layer (Y) with a cutter, After the adhesive layer (Y) component was wiped off with ethanol, the weight average molecular weight of the front plate (X) was measured by gel permeation chromatography.
[Measurement conditions for gel permeation chromatography]
Measuring instrument: HLC-8120GPC manufactured by Tosoh Corporation
Column: Showa Denko Co., Ltd. KD-80M, KD-803, 2 connected in series Sample: 20 mg
Solvent: 4 ml of chloroform
Solution injection volume: 10 μl
Solvent flow rate: 1.0 ml / min Standard polymer: Polystyrene

(5) Molecular weight reduction rate The molecular weight reduction rate (%) was calculated based on the following formula.
= {(Weight average molecular weight before exposure in an environment of temperature 85 ° C., humidity 85% RH) − (weight average molecular weight after exposure in an environment of temperature 85 ° C., humidity 85% RH)} / (temperature 85 ° C., (Weight average molecular weight before exposure under humidity of 85% RH)
× 100

(6) Phosphorus antioxidant concentration The analytical sample is cut out from the polycarbonate resin layer of the front plate (X) obtained by the method described in the Examples and Comparative Examples, and the phosphorus antioxidant component is added by dissolution reprecipitation. After extraction, quantitative analysis was performed by gas chromatography (hydrogen flame ionization detector) and the absolute calibration curve method.

(7) Tensile strength Tensile strength is obtained by peeling only the front plate (X) from the adhesive layer (Y) with a cutter from the laminate of the front plate (X) / adhesive layer (Y) described later. After wiping off the component (Y) with ethanol, only the front plate (X) was separated and subjected to the test. The tester used Toyo Seiki Tensilon type II and measured according to JIS-K7127. When the mechanical strength of the front plate (X) decreased significantly, and it was difficult to handle the test piece, the test could not be carried out.

<Examples and comparative examples>
The main raw materials and materials used in Examples and Comparative Examples will be described.

(Front plate (X))
The front plate (X) was prepared using the following raw materials.

(Polycarbonate resin (a1))
Product name: Caliber 301-15, density: 1.20 g / cm ³ , Tg: 149 ° C., MFR (temperature: 300 ° C., load: 11.8 N): 15.0 g / 10 min, manufactured by Sumika Stylon Polycarbonate Co., Ltd. )

(Thermoplastic resin (b3))
The molar ratio of the monomer unit derived from isosorbide, which is a dihydroxy compound, and the monomer unit derived from tricyclodecane dimethanol, obtained by a method according to Japanese Patent Application Laid-Open No. 2008-024919, is isosorbide / tricyclode Polycarbonate copolymer with candimethanol = 70/30 mol% (density: 1.36 g / cm ³ , Tg: 128 ° C., MFR (temperature: 230 ° C., load: 37.3 N): 9.6 g / 10 min)

(Curable resin composition (c))
(C-1) (Product name “UVHC7800G” manufactured by MOMENTIVE)
(C-2) (Product name “XR39-C6210” manufactured by MOMENTIVE)

(Adhesive layer (Y))
As the adhesive layer (Y), a pressure-sensitive adhesive resin composition comprising an acrylic ester copolymer, a crosslinking agent and a photopolymerization initiator was shaped into a sheet shape having a thickness of 150 μm, and then polyethylene on both sides. What stuck the release film made from a terephthalate film was used.
(Adhesive layer Y1)
Amount of acidic ions eluted in hot water: 216 (ng / cm ² )
Tensile modulus: 0.01 (MPa)
Tg: -10 (° C)
(Adhesive layer Y2)
Amount of acidic ions eluted in hot water: 433 (ng / cm ² )
Tensile modulus: 0.08 (MPa)
Tg: 8 (° C)
(Adhesive layer Y3)
Amount of acidic ions eluted in hot water: 9200 (ng / cm ² )
Tensile modulus: 0.27 (MPa)
Tg: -12 (° C)

<Example 1>
Polycarbonate-based resin (a1) is previously kneaded at 260 ° C. with a phosphorus-based antioxidant (trade name “ADEKA STAB PEP-36”, manufactured by ADEKA) at a temperature of 260 ° C. so as to have the content shown in Table 1. A system resin layer material was obtained.
100 parts by mass of the thermoplastic resin (b3) and 100 parts by mass of the polycarbonate resin (a1) are supplied to separate extruders having a vent function and a filter function, and are melt-kneaded at a resin temperature of 240 to 265 ° C. After co-extrusion with a T die at 240 ° C. so that it becomes a laminated structure of two types and three layers of (Bf layer) / (A layer) / (Bb layer) with a T die having a multi-manifold, The first cooling roll set, the second cooling roll set to 110 ° C., and the third cooling roll set to 120 ° C. are sequentially passed through and cooled, the total thickness is 0.275 mm, and each layer thickness is (Bf layer) / (A Layer) / (Bb layer) = 0.075 mm / 0.125 mm / 0.075 mm was obtained. At this time, the weight average molecular weight of the front plate (X1) before exposure to wet heat was 53,000.

Next, the curable resin composition (cf) consisting of 60 parts by mass of the curable resin composition (c-1) and 40 parts by mass of the curable resin composition (c-2) is obtained using the bar coater. It is applied to the surface of the thermoplastic resin layer (Bf layer) of the face plate (X1), dried in this state at 90 ° C. for 1 minute, and then exposed to ultraviolet rays at an exposure amount of 700 mJ / cm ² to be curable resin composition. (C) was cured to form a hard coat layer (Cf).
Next, the curable resin composition (cb) composed of 60 parts by mass of the curable resin composition (c-2) and 40 parts by mass of the curable resin composition (c-3) is replaced with the resin by using a bar coater. It was applied to the surface of the thermoplastic resin layer (Bb layer) of the laminate, dried in this state at 90 ° C. for 1 minute, and then exposed to ultraviolet light at an exposure amount of 700 mJ / cm ² to obtain a curable resin composition (c ) Was cured to form a hard coat layer (Cb) having a thickness of 12 μm after curing to produce a front plate (X).

Next, the adhesive surface exposed by peeling off one release film of the adhesive layer (Y1) was laminated on the surface of the hard coat layer (Cb) of the front plate (X) and adhered with a hand roller. Next, autoclaving (50 ° C., 0.2 MPa, 20 minutes) was performed to produce a laminate. Further, the laminated body was irradiated with ultraviolet rays so that 365 nm ultraviolet rays reached 2000 mJ / cm ^{2 with} a high-pressure mercury lamp to cure the adhesive layer (Y1), and the front plate (X) / viscous A laminate of the adhesive layer (Y1) was produced. The evaluation results are shown in Table 1.

<Example 2>
Except for changing the adhesive layer to the adhesive layer (Y2), the laminate of the front plate (X) and the front plate (X) / adhesive layer (Y2) was made in the same manner as in Example 1. Produced. The evaluation results are shown in Table 1.

<Comparative Examples 1, 2, 3>
As shown in Table 1, the front plate (X) and the front plate (X) / adhesive layer (as in Example 1) except that the phosphorous antioxidant content of the polycarbonate resin layer was changed. A laminate of Y1) was produced. The evaluation results are shown in Table 1.

<Comparative Example 4>
The front plate (X) and the front plate (X) / adhesive layer (Y3) were the same as in Example 1 except that the adhesive layer (Y1) was changed to the adhesive layer (Y3). A laminate was prepared. The evaluation results are shown in Table 1.

  As shown in Table 1, the higher the concentration of the phosphorus-based antioxidant in the polycarbonate resin layer of the front plate (X), the more severe the heat and humidity exposure test of 500 hours or more in a temperature 85 ° C. and humidity 85% RH environment. It was confirmed that the hydrolysis of the polycarbonate resin was promoted when it was used. (Comparative Examples 1-3)

  In addition, when the amount of acidic ions eluted from the unit area of the adhesive layer (Y) is large, when subjected to a severe wet heat exposure test for 500 hours or more in a temperature 85 ° C. and humidity 85% RH environment, It was confirmed that hydrolysis of the face plate (X) was promoted. (Comparative Example 4)

  On the other hand, the laminates of Example 1 and Example 2 can suppress the molecular weight decrease to 15% or less even when subjected to a severe wet heat exposure test for 1000 hours in a temperature 85 ° C. and humidity 85% RH environment. It was confirmed that it can be used practically without any problem.

Claims (12)

  A laminate comprising a front plate (X) having a polycarbonate resin layer (A layer) and an adhesive layer (Y), wherein the laminate is 1000 hours under an environment of temperature 85 ° C. and humidity 85% RH. A laminate having a reduction rate of polystyrene-equivalent weight average molecular weight determined by gel permeation chromatography measurement of the front plate (X) after standing still is 15% or less.   The polycarbonate resin layer (A layer) contains a phosphorous antioxidant, and the content of the antioxidant is 0.04 with respect to 100 parts by mass of the polycarbonate resin constituting the polycarbonate resin layer (A layer). It is below a mass part, The laminated body of Claim 1 characterized by the above-mentioned. The total amount of acidic ions measured by ion chromatography, which is eluted when the adhesive layer (Y) is immersed in hot water at 85 ° C. for 45 minutes, is 9000 (ng / cm ² ) or less. The laminate according to claim 1 or 2, wherein:   The said front board (X) forms the thermoplastic resin layer (B layer) different from A layer in the single side | surface side or both surface side of a polycarbonate-type resin layer (A layer), The 1-3 characterized by the above-mentioned. The laminate according to any one of the above.   The layered product according to claim 4, wherein said B layer is a layer which makes acrylic resin (b1) a main ingredient resin.   The acrylic resin (b1) is a methyl methacrylate monomer, a methacrylic acid monomer, an acrylic acid monomer, a maleic anhydride monomer, an aromatic vinyl monomer, or a vinyl cyanide monomer. It consists of a copolymer with any 1 or more types among these, The laminated body of Claim 5 characterized by the above-mentioned.   The copolymer (b2) in which the B layer has the acrylic resin (b1), an aromatic vinyl monomer unit, a (meth) acrylic acid ester monomer unit, and an unsaturated dicarboxylic anhydride monomer. The layered product according to claim 5 or 6 characterized by things. 5. The B layer is a layer containing, as a main component resin, a polycarbonate resin (b3) containing a structural unit derived from a dihydroxy compound represented by the following (Chemical Formula 1) as a part of the structure. The laminated body as described in.

  The laminate according to any one of claims 1 to 8, wherein the adhesive layer (Y) has a tensile elastic modulus of 0.001 to 30 MPa.   The laminate according to any one of claims 1 to 9, wherein the front plate (X) includes a hard coat layer (C layer) as an outermost surface layer on one side or both sides.   11. The laminate according to claim 10, wherein the main component resin of the hard coat layer (C layer) is the same resin as the main component resin of the adhesive layer (Y).   The image display apparatus provided with the laminated body as described in any one of Claims 1-11.