JP7803680B2 - Laminate - Google Patents

Description

The present invention relates to a laminate that has excellent transparency, chemical resistance, heat resistance, adhesion, and scratch resistance.

Conventionally, known transparent resins include methacrylic resin and polycarbonate resin made from bisphenol A (hereinafter sometimes referred to as PC-A), which are used in a wide range of fields, including electrical and electronic components, optical components, automotive components, and mechanical components, in the form of molded products and films.

In recent years, concerns about the depletion of petroleum resources and the problem of increasing atmospheric carbon dioxide, which contributes to global warming, have led to significant attention being paid to biomass resources, which do not rely on petroleum as a raw material and are carbon-neutral, meaning that combustion does not increase carbon dioxide emissions. In the field of polymers, bioplastics produced from biomass resources have also been actively developed. In particular, polycarbonates made primarily from isosorbide as a monomer offer excellent heat resistance, weather resistance, surface hardness, and chemical resistance, and have attracted attention for their distinct characteristics from PC-A, leading to extensive research. While these isosorbide-based polycarbonates offer excellent heat resistance, impact resistance, weather resistance, and chemical resistance, they exhibit extremely poor adhesion to other resins, such as PC-A and acrylic resins, making it generally difficult to form laminates with them.

In addition, as a way to combat VOCs, attention is being paid to decorative methods that replace painting and plating, but there are issues with moldability due to the glass transition temperature of typical polycarbonate, such as low-temperature preforming, vacuum molding, and injection molding.

Patent Document 1 describes a structure that improves processability by laminating a polycarbonate resin containing a thermoplastic elastomer with an acrylic resin, but because the surface layer is made of acrylic resin, it is difficult to achieve chemical resistance.

Patent Document 2 describes using an acrylic resin to laminate with PC-A, but there was an issue with the inclusion of acrylic components in the structure, which meant that the inherent chemical resistance of the material could not be fully utilized.

Patent Documents 3 to 6 describe laminates in which an isosorbide-based polycarbonate resin is used to adhere to PC-A resin, but no proposals have been made regarding structures with polycarbonate containing a thermoplastic elastomer.

Patent No. 5639837 International Publication No. 2018/143194 Patent No. 6068538 Patent No. 5718679 Patent No. 6200002 Patent No. 6775610

The object of the present invention is to provide a laminate that has excellent transparency, chemical resistance, heat resistance, adhesion, and scratch resistance.

As a result of extensive research, the present inventors have discovered that by forming a laminate using a polycarbonate resin (A) containing a thermoplastic elastomer and a polycarbonate resin (B) containing carbonate units derived from isosorbide, a laminate having excellent transparency, chemical resistance, and moldability, improved adhesion without the need for an adhesive layer, and excellent scratch resistance can be obtained, leading to the completion of the present invention.
That is, according to the present invention, the object of the invention is achieved by the following items 1 to 9.

1. A laminate having a layer (layer A) formed from a polycarbonate resin composition containing polycarbonate resin (A) and a thermoplastic elastomer, and a layer (layer B) formed from polycarbonate resin (B) containing units (b) represented by the following formula (B):

2. The laminate according to the above item 1, wherein the polycarbonate resin (A) used in the layer A contains 50 mol % or more of carbonate units derived from aromatic dihydroxy units.
3. The laminate according to item 1 or 2 above, wherein the thermoplastic elastomer used in layer A is a thermoplastic elastomer constituted of hard segments composed of polybutylene terephthalate units and soft segments composed of polyester units having an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid as the dicarboxylic acid component and a diol having 5 to 15 carbon atoms as the diol component.

4. The laminate according to any one of items 1 to 3 above, wherein the content of the thermoplastic elastomer in layer A is 3 to 50 parts by weight per 100 parts by weight of the polycarbonate resin (A).
5. The laminate according to any one of items 1 to 4 above, wherein the polycarbonate resin (B) used in layer B contains 30 to 100 mol % of the unit (b) represented by formula (B).
6. The laminate according to any one of items 1 to 5 above, wherein the polycarbonate resin (B) used in layer B further contains 5 to 70 mol % of units (c) represented by the following formula (C-1):

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, R represents a branched or straight-chain alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, and m represents an integer between 0 and 10.)

7. The laminate according to any one of items 1 to 6 above, wherein the thickness of the laminate is 0.05 to 10.0 mm.
8. The laminate according to any one of items 1 to 7 above, wherein the laminate has a visible light transmittance of 85% or more.
9. The laminate according to any one of items 1 to 8 above, wherein the laminate is produced by a melt extrusion method.

The present invention uses a polycarbonate resin (A) containing a thermoplastic elastomer and a polycarbonate resin (B) containing carbonate units derived from isosorbide. This laminate, which has a layer formed from the resin (A) and a layer formed from the resin (B), exhibits excellent transparency, chemical resistance, heat resistance, adhesion, and scratch resistance. Therefore, it is useful as transparent sheets for building materials, interior parts, display covers, etc., sheets for resin-coated metal plates, sheets for molding (vacuum/pressure molding, hot press molding, etc.), colored plates, transparent plates, shrink films, shrink labels, shrink tubes, automotive interior materials, resin glazing, home appliance components, and office equipment components. Therefore, the industrial effects it achieves are exceptional.

The present invention is described in detail below.

The present invention relates to a laminate having a layer (layer A) formed from a polycarbonate resin composition containing a polycarbonate resin (A) and a thermoplastic elastomer, and a layer (layer B) formed from a polycarbonate resin (B) containing a unit (b) represented by the following formula (B):

(About Layer A)
In the present invention, the layer A is a layer formed from a polycarbonate resin composition containing a polycarbonate resin (A) and a thermoplastic elastomer.

(Polycarbonate resin (A))
The polycarbonate resin (A) used in the present invention is a polymer in which dihydroxy compounds are bonded by carbonate ester bonds, and although there are no particular limitations, it is usually obtained by reacting a dihydroxy component with a carbonate precursor by interfacial polymerization or melt polymerization.

The polycarbonate resin (A) is preferably an aromatic polycarbonate resin in which, of all dihydroxy components, bisphenol components account for preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more. In other words, the polycarbonate resin (A) used in Layer A preferably contains carbonate units derived from aromatic dihydroxy units for 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more.

Typical examples of dihydroxy components include 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1, Examples include 1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane, 9,9-bis{(4-hydroxy-3-methyl)phenyl}fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene, isosorbide, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. These may be homopolymers using a single one of these, or copolymers of two or more types. Among these, bisphenol A is preferred from the viewpoints of physical properties and cost. In particular, it is preferable for bisphenol A to account for 50 mol% or more of the bisphenol component, more preferably 60 mol% or more, even more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more.

Specific examples of polycarbonate resin (A) include a homopolymer of bisphenol A, a copolymer of bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and a copolymer of bisphenol A and 9,9-bis{(4-hydroxy-3-methyl)phenyl}fluorene, with a homopolymer of bisphenol A being the most preferred.

The glass transition temperature of the polycarbonate resin (A) is preferably in the range of 100 to 200°C, more preferably 120 to 180°C. A glass transition temperature below the upper limit is preferred because the resin composition with the thermoplastic elastomer has good melt viscosity, facilitating melt film formation, and the resulting laminate has sufficient heat resistance.

Carbonate precursors include carbonyl halides, carbonate esters, and haloformates, such as phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

When producing a polycarbonate resin by reacting the above dihydroxy compound with a carbonate precursor via interfacial polymerization or melt polymerization, a catalyst, a terminal terminator, an antioxidant, etc. may be used as needed. Furthermore, the polycarbonate resin (A) may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, or a mixture of two or more of the resulting polycarbonate resins.

The molecular weight of the polycarbonate resin (A) in the present invention is preferably in the range of 13,000 to 40,000, expressed as a viscosity average molecular weight. A viscosity average molecular weight within this range is preferred because it reduces the brittleness of the laminate and reduces the likelihood of cracking or burrs during hot bending. It is also preferred because the resin composition with a thermoplastic elastomer exhibits good melt viscosity, facilitating melt film formation. The viscosity average molecular weight is more preferably in the range of 15,000 to 35,000, even more preferably in the range of 20,000 to 32,000, and particularly preferably in the range of 22,000 to 28,000. When the polycarbonate resin (A) is a mixture of two or more types, the molecular weight refers to the molecular weight of the entire mixture. Here, the viscosity average molecular weight is determined by measuring the specific viscosity (η _sp ) at 20°C of a solution in which 0.7 g of polycarbonate is dissolved in 100 mL of methylene chloride, and calculating the viscosity average molecular weight M using the following formula:
η _sp /c=[η]+0.45×[η] ² c
[η]=1.23× ^10-4 M ^0.83
(where c = 0.7 g/dL, [η] is the intrinsic viscosity)

Polycarbonate resin (A) may contain various additives commonly used in polycarbonate resins. Examples include heat stabilizers, antioxidants, mold release agents, UV absorbers, antistatic agents, light stabilizers, flame retardants, impact modifiers, colorants, and dyes, as described below. It may also contain reinforcing fillers such as glass fibers, provided that the effects of the present invention are not impaired.

<Thermoplastic elastomer>
The thermoplastic elastomer used in the present invention is preferably a polyester-based thermoplastic elastomer, which is preferably composed of a hard segment composed of a polybutylene terephthalate unit and a soft segment composed of a polyester unit having an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid as the dicarboxylic acid component and a diol having 5 to 15 carbon atoms as the diol component.

(Hardware segment)
The hard segment is preferably a polyester segment, the melting point of the polymer comprising the segment being preferably 150° C. or higher.

The hard segments are composed of polybutylene terephthalate units. Polybutylene terephthalate has excellent compatibility with polycarbonate resins and is preferable in terms of transparency and thermoformability, and also has good properties in terms of strength, etc. Polybutylene terephthalate may contain other components as copolymerization components as long as the effects of the present invention are not impaired. The proportion of such copolymerization components is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, of the total 100 mol% of both the dicarboxylic acid component and the diol component.

(Software segment)
The soft segment refers to a segment in which the melting point of the polymer formed from the segment is preferably 100°C or lower, or which is liquid and amorphous at 100°C.

The soft segment is preferably a polyester composed of an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and a diol having 5 to 15 carbon atoms (hereinafter sometimes referred to as "SS-1"). SS-1 is preferred because it provides extremely good transparency.

In order to obtain better transparency, the soft segment SS-1 preferably contains 60 to 99 mol% aromatic dicarboxylic acid and 1 to 40 mol% aliphatic dicarboxylic acid out of a total of 100 mol% of dicarboxylic acid components. It is more preferable that the aromatic dicarboxylic acid content be 70 to 95 mol% and the aliphatic dicarboxylic acid content be 5 to 30 mol%. It is even more preferable that the aromatic dicarboxylic acid content be 85 to 93 mol% and the aliphatic dicarboxylic acid content be 7 to 15 mol%. It is particularly preferable that the aromatic dicarboxylic acid content be 89 to 92 mol% and the aliphatic dicarboxylic acid content be 8 to 11 mol%.

As the aromatic dicarboxylic acid for SS-1, terephthalic acid and isophthalic acid are preferred, with isophthalic acid being particularly preferred in terms of reducing crystallinity. As the aliphatic dicarboxylic acid for SS-1, linear aliphatic dicarboxylic acids having 6 to 12 carbon atoms, such as succinic acid, adipic acid, and sebacic acid, are preferred, with sebacic acid being particularly preferred.

Preferred diol components of SS-1 having 5 to 15 carbon atoms are linear aliphatic diols having 6 to 12 carbon atoms, such as hexamethylene glycol, decamethylene glycol, 3-methylpentanediol, and 2-methyloctamethylenediol. Hexamethylene glycol is particularly preferred.

SS-1 is particularly preferred because it has high compatibility with polycarbonate resins, allowing for highly transparent laminates to be obtained, and also because it has good surface properties and transparency after thermoforming. More specifically, SS-1 is preferably a polyester composed of isophthalic acid and sebacic acid components and hexamethylene glycol.

In addition, the ratio of hard segments to soft segments in polyester-based thermoplastic elastomers is preferably 20 to 70% by weight of hard segments and 80 to 30% by weight of soft segments, and more preferably 20 to 40% by weight of hard segments and 80 to 60% by weight of soft segments, based on 100% by weight of elastomer. The intrinsic viscosity of the polyester-based thermoplastic elastomer (measured in o-chlorophenol at 35°C) is preferably 0.6 or higher, more preferably in the range of 0.8 to 1.5, and even more preferably in the range of 0.8 to 1.2. An intrinsic viscosity within the above range is preferred, as it provides sufficient strength for the laminate.

Polyester-based thermoplastic elastomers can be obtained by melt-kneading the aforementioned hard and soft segments to react them and form a multi-block copolymer.

The intrinsic viscosity of the polymer that becomes the hard segment is preferably in the range of 0.2 to 2.0, more preferably 0.5 to 1.5. The intrinsic viscosity of the polymer that becomes the soft segment is preferably in the range of 0.2 to 2.0, more preferably 0.5 to 1.5.
The reaction is preferably carried out at a temperature in the range of 200 to 300°C, more preferably 220 to 260°C.

The number average molecular weight of the above multi-blocked hard and soft segments is preferably in the range of 500 to 7,000, and more preferably in the range of 800 to 5,000.

In the present invention, the content of thermoplastic elastomer in Layer A is preferably 3 to 50 parts by weight, more preferably 4 to 30 parts by weight, and even more preferably 5 to 25 parts by weight, per 100 parts by weight of polycarbonate resin (A). A content above the lower limit is preferred because the addition of the thermoplastic elastomer provides an excellent effect in improving thermoformability. A content below the upper limit is preferred because the resin composition has a good heat distortion temperature, resulting in excellent heat resistance for the laminate.

(About Layer B)
In the present invention, the layer B is a layer formed from a polycarbonate resin (B) containing a unit (b) represented by the following formula (B).

(Polycarbonate resin (B))
The polycarbonate resin (B) is a polycarbonate containing a plant-derived ether diol residue and contains the unit (b) represented by the above formula (B). The unit (b) accounts for preferably 30 mol% or more, more preferably 50 mol% or more, even more preferably 60 mol% or more, particularly preferably 65 mol% or more, and most preferably 70 mol% or more of the total carbonate units. When the repeating unit (b) is at least the above lower limit based on the total carbonate units, this is preferred because the chemical resistance is improved.

(Unit (b))
The unit (b) constituting the polycarbonate resin (B) is derived from an aliphatic diol having an ether group, as shown in the formula (B) above. The formula (B) is preferably a diol having an ether bond among biomass resources, and is a material with high heat resistance and pencil hardness. Examples of the formula (B) include units (b1), (b2), and (b3) represented by the following formulas (B1), (B2), and (B3), which are stereoisomers.

These are ether diols derived from carbohydrates, and can also be obtained from natural biomass, making them one of the renewable resources. Units (b1), (b2), and (b3) are derived from ether diols called isosorbide, isomannide, and isoidide, respectively. Isosorbide is obtained by hydrogenating D-glucose obtained from starch, followed by dehydration. Other ether diols can also be obtained by similar reactions, except for the starting material.

Among isosorbide, isomannide, and isoidide, units (b1) derived from isosorbide (1,4;3,6-dianhydro-D-sorbitol) are particularly preferred due to their ease of production and excellent heat resistance.

(Other units (c))
The polycarbonate resin (B) preferably contains the above-mentioned unit (b) and further contains unit (c) derived from one or more compounds selected from the group consisting of an aliphatic diol compound, an alicyclic diol compound, and an aromatic dihydroxy compound, and is particularly preferably a copolymer polycarbonate resin thereof.

The total of units (b) and units (c) is preferably 70 mol% or more of all carbonate units, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more.

Repeating unit (c) is preferably a repeating unit derived from at least one compound selected from the group consisting of aliphatic diol compounds and alicyclic diol compounds. The aliphatic diol compound is preferably a straight-chain aliphatic diol compound. A straight-chain aliphatic diol compound having 4 to 24 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 8 to 12 carbon atoms, is preferably used. The alicyclic diol compound is preferably an alicyclic diol compound having 6 to 24 carbon atoms, more preferably 6 to 20 carbon atoms.

Specific examples of aliphatic diol compounds 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, and hydrogenated dioleyl glycol. Of these, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred, with 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol being particularly preferred.

Specific examples of alicyclic diol compounds include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol; cyclohexanedimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; norbornanedimethanols such as 2,3-norbornanedimethanol and 2,5-norbornanedimethanol; tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 1,3-adamantanediol, 2,2-adamantanediol, decalindimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane. Of these, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane are preferred.

These aliphatic diol compounds and alicyclic diol compounds may be used alone or in combination of two or more. Furthermore, it is preferable that polycarbonate resin (B) contains the above-mentioned unit (b) and one or more alicyclic diol compounds and/or aliphatic diol compounds.

Further examples of aromatic dihydroxy compounds 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, bisphenol A, 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.

(composition)
In the polycarbonate resin (B), the molar ratio (b)/(c) of the units (b) to the units (c) is preferably 30/70 to 99/1, more preferably 50/50 to 95/5, even more preferably 60/40 to 92/8, and particularly preferably 65/35 to 90/10. When the molar ratio (b)/(c) is within the above range, the resin has excellent chemical resistance and heat resistance, and further has an appropriate melt viscosity and good moldability, resulting in excellent impact resistance. The molar ratio of the units (b) to the units (c) can be measured and calculated using a proton NMR spectrometer, JNM-AL400, manufactured by JEOL Ltd.

It is also preferable that the polycarbonate resin (B) contains the above unit (b) and a unit (c-1) represented by the following formula (C-1):

(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, R represents a branched or straight-chain alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, and m represents an integer between 0 and 10.)

The polycarbonate resin (B) preferably contains 5 to 70 mol %, more preferably 10 to 40 mol %, and even more preferably 15 to 30 mol % of units (c-1) represented by the above formula (C-1). By containing units (c-1) within the above range, the transparency and adhesion to layer A are superior.

(Method for producing polycarbonate resin (B))
The polycarbonate resin (B) can be produced by a reaction method known per se, for example, by reacting a diol component with a carbonate precursor such as a carbonic acid diester. The basic means for these production methods will now be briefly described.

Transesterification reactions using a carbonate diester as a carbonate precursor are carried out by heating and stirring a specified proportion of diol components with the carbonate diester under an inert gas atmosphere, and then distilling off the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is usually in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning and distilling off the resulting alcohol or phenol. If necessary, a terminal capping agent, antioxidant, etc. may also be added.

The carbonate diester used in the transesterification reaction includes esters of optionally substituted aryl groups and aralkyl groups having 6 to 12 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, per 1 mol of the total dihydroxy compounds.

In addition, in melt polymerization methods, a polymerization catalyst can be used to increase the polymerization rate. Examples of such polymerization catalysts include alkali metal compounds, alkaline earth metal compounds, basic phosphorus compounds, and metal compounds. Among these, alkali metals or alkaline earth metals are preferred as polymerization catalysts. Among alkali metal compounds, sodium hydroxide and sodium bicarbonate are particularly preferred. Furthermore, among alkaline earth metal compounds, calcium carbonate and barium stearate are particularly preferred.

The amount of these polymerization catalysts used is selected from the range of preferably 1×10 ⁻⁹ to 1×10 ⁻² equivalents, preferably 1×10 ⁻⁸ to 1×10 ⁻⁵ equivalents, more preferably 1×10 ⁻⁷ to 1×10 ⁻³ equivalents per mole of the diol component.

A catalyst deactivator can also be added in the later stages of the reaction. Known catalyst deactivators are effectively used, but ammonium and phosphonium salts of sulfonic acid are preferred. Salts of dodecylbenzenesulfonic acid, such as tetrabutylphosphonium dodecylbenzenesulfonate, and salts of paratoluenesulfonic acid, such as tetrabutylammonium paratoluenesulfonate, are particularly preferred. Furthermore, preferred sulfonic acid esters include methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, octyl paratoluenesulfonate, and phenyl paratoluenesulfonate.

Of these, tetrabutylphosphonium dodecylbenzenesulfonate is most preferably used.

When at least one polymerization catalyst selected from alkali metal compounds and/or alkaline earth metal compounds is used, the amount of these catalyst deactivators used is preferably 0.5 to 50 moles per mole of the catalyst, more preferably 0.5 to 10 moles, and even more preferably 0.8 to 5 moles.

(Specific viscosity: _ηSP )
The specific viscosity (η _SP ) of the polycarbonate resin (B) is preferably 0.2 to 0.5, more preferably 0.22 to 0.49, and even more preferably 0.24 to 0.48. When the specific viscosity of the polycarbonate resin (B) is within the above range, the strength is sufficient and the moldability is good.

The specific viscosity of the polycarbonate resin in the present invention can be determined by dissolving 0.7 g of the resin in 100 ml of methylene chloride at 20° C. using an Ostwald viscometer.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]
The specific viscosity can be measured as follows: First, polycarbonate resin is dissolved in methylene chloride in an amount 20 to 30 times its weight, and the soluble matter is collected by filtration through Celite. The solution is then removed and the mixture is thoroughly dried to obtain a solid soluble in methylene chloride. 0.7 g of this solid is dissolved in 100 ml of methylene chloride, and the specific viscosity at 20°C is determined using an Ostwald viscometer.

(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the polycarbonate resin (B) is preferably 80 to 150° C., more preferably 90 to 140° C., and even more preferably 100 to 130° C. If the Tg is within the above range, the heat resistance and moldability are good, which is preferable.

The glass transition temperature (Tg) is measured using a 2910 DSC manufactured by TA Instruments Japan Co., Ltd. in accordance with JIS K7121 at a heating rate of 20°C/min.

(Pencil hardness)
The polycarbonate resin (B) preferably has a pencil hardness of HB or higher, more preferably F or higher. From the viewpoint of excellent scratch resistance, a pencil hardness of H or higher is even more preferable. A pencil hardness of 4H or lower provides sufficient functionality. Pencil hardness can be increased by increasing the weight ratio of the acrylic resin. Pencil hardness refers to the hardness at which no scratches remain when the resin of the present invention is rubbed with a pencil having a specific pencil hardness. It is preferable to use the pencil hardness used in the surface hardness test of a coating film, which can be measured according to JIS K-5600, as an index. Pencil hardness increases in the following order: 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, and 6B, with the hardest being 9H and the softest being 6B.

(Additives)
The polycarbonate resin (B) may be blended with additives such as other thermoplastic resins, heat stabilizers, plasticizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, mold release agents, colorants, and impact modifiers, depending on the application and as needed.

(Heat stabilizer)
The polycarbonate resin (A) and polycarbonate resin (B) used in the present invention preferably contain a heat stabilizer in order to suppress a decrease in molecular weight and deterioration in color during extrusion and molding. Examples of heat stabilizers include phosphorus-based heat stabilizers, phenol-based heat stabilizers, and sulfur-based heat stabilizers, and these can be used alone or in combination of two or more. In particular, it is preferable to contain a phosphorus-based heat stabilizer. As the phosphorus-based stabilizer, it is preferable to blend a phosphite compound. Examples of phosphite compounds include pentaerythritol-type phosphite compounds, phosphite compounds that react with dihydric phenols to have a cyclic structure, and phosphite compounds with other structures.

Specific examples of the pentaerythritol-type phosphite compounds include distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite. Of these, distearyl pentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite are particularly preferred.

Examples of phosphite compounds that react with the above dihydric phenols and have a cyclic structure include 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, Examples of suitable phosphates include 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylene-bis-(4,6-di-t-butylphenyl)octylphosphite, and 6-tert-butyl-4-[3-[(2,4,8,10)-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]-2-methylphenol.

Examples of phosphite compounds having the above other structures include triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl) phosphite, tris(di-isopropylphenyl) phosphite, tris(di-n-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and tris(2,6-di-tert-butylphenyl) phosphite.

In addition to various phosphite compounds, examples include phosphate compounds, phosphonite compounds, and phosphonate compounds.

Examples of phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, with triphenyl phosphate and trimethyl phosphate being preferred.

Phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis Examples of suitable phosphonite compounds include (2,4-di-tert-butylphenyl)-3-phenyl-phenyl phosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenyl phosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenyl phosphonite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenyl phosphonite. Preferred are tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenyl phosphonite, with tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenyl phosphonite being more preferred. Such phosphonite compounds can be used in combination with the above-mentioned phosphite compounds having an aryl group substituted with two or more alkyl groups, which is preferred.

Examples of phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Of the above phosphorus-based heat stabilizers, trisnonylphenyl phosphite, trimethyl phosphate, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite are preferably used.

The above phosphorus-based heat stabilizers can be used alone or in combination of two or more types. The phosphorus-based heat stabilizer is preferably blended in an amount of 0.001 to 1 part by weight, more preferably 0.01 to 0.5 parts by weight, and even more preferably 0.01 to 0.3 parts by weight per 100 parts by weight of polycarbonate resin.

The polycarbonate resin (A) and polycarbonate resin (B) used in the present invention may contain a heat stabilizer, such as a hindered phenol-based heat stabilizer or a sulfur-based heat stabilizer, in combination with a phosphorus-based heat stabilizer, to suppress a decrease in molecular weight and deterioration in color during extrusion and molding.

Hindered phenol-based heat stabilizers are not particularly limited as long as they have antioxidant properties, but examples include n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, tetrakis{methylene-3-(3',5'-di-t-butyl-4-hydroxyphenyl)propionate}methane, distearyl(4-hydroxy-3-methyl-5-t-butylbenzyl)malonate, triethyleneglycol-bis{3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate}, 1,6-hexanediol-bis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, pentaerythrityl-tetrakis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, 2,2-thiazolinone ... diethylene bis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, 2,2-thiobis(4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,4-bis{(octylthio) (e)methyl)}-o-cresol, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,5,7,8-tetramethyl-2(4',8',12'-trimethyltridecyl)chroman-6-ol, 3,3',3",5,5',5"-hexa-t-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, etc.

Of these, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, pentaerythrityl-tetrakis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, 3,3',3",5,5',5"-hexa-t-butyl-a,a',a'-(mesitylene-2,4,6-triyl)tri-p-cresol, 2,2-thiodiethylenebis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, etc. are preferred.

These hindered phenol-based heat stabilizers may be used alone or in combination of two or more.

The hindered phenol-based heat stabilizer is preferably blended in an amount of 0.001 to 1 part by weight, more preferably 0.01 to 0.5 parts by weight, and even more preferably 0.01 to 0.3 parts by weight per 100 parts by weight of polycarbonate resin.

Sulfur-based heat stabilizers include, for example, dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetrakis(3-laurylthiopropionate), bis[2-methyl-4-(3-laurylthiopropionyloxy)-5-tert-butylphenyl]sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, and 1,1'-thiobis(2-naphthol). Of the above, pentaerythritol tetrakis(3-laurylthiopropionate) is preferred.

These sulfur-based heat stabilizers may be used alone or in combination of two or more.

The sulfur-based heat stabilizer is preferably blended in an amount of 0.001 to 1 part by weight, more preferably 0.01 to 0.5 parts by weight, and even more preferably 0.01 to 0.3 parts by weight per 100 parts by weight of polycarbonate resin.

When using a phosphite-based heat stabilizer, a phenol-based heat stabilizer, or a sulfur-based heat stabilizer in combination, the total amount of these is preferably 0.001 to 1 part by weight, and more preferably 0.01 to 0.3 parts by weight, per 100 parts by weight of polycarbonate resin.

(Release agent)
The polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention may contain a mold release agent in order to further improve the releasability from a mold during melt molding, within a range that does not impair the object of the present invention.

Such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefin-based waxes, olefin-based waxes containing carboxyl groups and/or carboxylic anhydride groups, silicone oils, organopolysiloxanes, etc.

Preferred higher fatty acid esters are partial or full esters of monohydric or polyhydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms. Examples of such partial or full esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearate monosorbitate, stearyl stearate, behenic acid monoglyceride, behenyl behenate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, and 2-ethylhexyl stearate.

Among these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

Higher fatty acids are preferably saturated fatty acids having 10 to 30 carbon atoms. Examples of such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.

These release agents may be used alone or in combination of two or more. The amount of such release agent added is preferably 0.01 to 5 parts by weight per 100 parts by weight of polycarbonate resin.

(ultraviolet absorber)
The polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention may contain an ultraviolet absorber, such as a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, a cyclic iminoester-based ultraviolet absorber, or a cyanoacrylate-based ultraviolet absorber, with benzotriazole-based ultraviolet absorbers being preferred.

Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-3'-dodecyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-bis(α,α'-dimethylbenzyl)phenylbenzotriazole, 2-[2'-hydroxy Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], and methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenylpropionate-polyethylene glycol condensate.

The blending ratio of such UV absorbers is preferably 0.03 to 2.5 parts by weight, more preferably 0.1 to 2 parts by weight, and even more preferably 0.2 to 1.5 parts by weight per 100 parts by weight of polycarbonate resin.

(Light stabilizer)
The polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention may contain a light stabilizer, which has the advantages of improving weather resistance and making molded articles less susceptible to cracking.

Examples of light stabilizers include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, didecanoic acid bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidinyl) ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) tetramethylpiperidin-2-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)carbonate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethyl- 4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)diphenylmethane-p,p'-dicarbamate, bis(2,2,6,6-tetramethyl-4-piperidyl)benzene-1,3-disulfonate, bis(2,2,6,6-tetramethyl-4-piperidyl)phenylphosphite, etc. Examples of suitable light stabilizers include hindered amines, nickel bis(octylphenyl sulfide), nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, and nickel complexes such as nickel dibutyldithiocarbamate. These light stabilizers may be used alone or in combination. The amount of light stabilizer contained is preferably 0.001 to 1 part by weight, and more preferably 0.01 to 0.5 parts by weight, per 100 parts by weight of polycarbonate resin.

(epoxy stabilizer)
In order to improve hydrolysis resistance, the polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention may contain an epoxy compound within a range that does not impair the object of the present invention.

Epoxy stabilizers include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3',4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 4-(3,4-epoxy-5-methylcyclohexyl)butyl-3',4'-epoxycyclohexyl carboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylcyclohexylcarboxylate, bisphenol A diglycidyl ether, tetrabromobisphenol A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxydicyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetrafluoroethylene glycol, bis-epoxycyclohexyl methyl ester, bisphenol A diglycidyl ether, bis-epoxycyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetrafluoroethylene glycol, bis-epoxycyclohexyl methyl ester, bisphenol A diglycidyl ether, bis-epoxycyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate, butadiene diepoxide, tetrafluoroethylene glycol, bis-epoxycyclohexyl methyl ester, bisphenol A diglycidyl ether, bis-epoxycyclohexyl methyl ester ... Phenylethylene epoxide, octyl epoxy thalate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexyl Examples of epoxy esters include octadecyl-3,4-epoxycyclohexyl carboxylate, 2-ethylhexyl-3',4'-epoxycyclohexyl carboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3',4'-epoxycyclohexyl carboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, and di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate. Bisphenol A diglycidyl ether is preferred from the standpoint of compatibility, etc.

Such epoxy-based stabilizers are preferably blended in an amount of 0.0001 to 5 parts by weight, more preferably 0.001 to 1 part by weight, and even more preferably 0.005 to 0.5 parts by weight per 100 parts by weight of polycarbonate resin.

(Bluing agent)
The polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention can be blended with a bluing agent to counteract the yellow color of the lens due to the polymer or ultraviolet absorber. Any bluing agent that is used for polycarbonate can be used without any particular problems. Generally, anthraquinone dyes are easily available and are therefore preferred.

Specific examples of bluing agents include Solvent Violet 13 [CA. No. (Color Index No.) 60725], Solvent Violet 31 [CA. No. 68210], Solvent Violet 33 [CA. No. 60725], Solvent Blue 94 [CA. No. 61500], Solvent Violet 36 [CA. No. 68210], Solvent Blue 97 [Bayer's "Macrolex Violet RR"], and Solvent Blue 45 [CA. No. 61110].

These bluing agents may be used alone or in combination of two or more. These bluing agents are preferably blended in a ratio of 0.1×10 ⁻⁴ to 2×10 ⁻⁴ parts by weight per 100 parts by weight of polycarbonate resin.

(Flame retardant)
The polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention can also be blended with a flame retardant. Examples of the flame retardant include halogen-based flame retardants such as brominated epoxy resin, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, and chlorinated polyethylene, phosphate ester-based flame retardants such as monophosphate compounds and phosphate oligomer compounds, organic phosphorus-based flame retardants other than phosphate ester-based flame retardants such as phosphinate compounds, phosphonate compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds, organic metal salt-based flame retardants such as organic alkali (earth) metal sulfonates, metal borate-based flame retardants, and metal stannate-based flame retardants, as well as silicone-based flame retardants, ammonium polyphosphate-based flame retardants, and triazine-based flame retardants. Additionally, a flame retardant auxiliary (for example, sodium antimonate, antimony trioxide, etc.) or an anti-dripping agent (for example, fibril-forming polytetrafluoroethylene, etc.) may be blended and used in combination with the flame retardant.

Among the flame retardants mentioned above, compounds that do not contain chlorine or bromine atoms reduce factors that make them undesirable when incinerated or thermally recycled, making them more suitable as flame retardants for the molded articles of the present invention, which are also characterized by their reduced environmental impact.

When a flame retardant is added, the amount is preferably in the range of 0.05 to 50 parts by weight per 100 parts by weight of polycarbonate resin. At 0.05 parts by weight or more, sufficient flame retardancy is achieved, while at 50 parts by weight or less, the molded product will have excellent strength and heat resistance.

(elastic polymer)
For the polycarbonate resin (A) and polycarbonate resin (B) used in the present invention, elastic polymers other than the above-mentioned thermoplastic elastomers can be used as impact improvers, and examples of elastic polymers include natural rubber or graft copolymers in which a rubber component having a glass transition temperature of 10°C or less is copolymerized with one or more monomers selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and vinyl compounds copolymerizable therewith. More preferred elastic polymers are core-shell graft copolymers in which a shell of one or more of the above monomers is graft copolymerized onto a core of the rubber component.

Also included are block copolymers of such rubber components and the above-mentioned monomers. Specific examples of such block copolymers include thermoplastic elastomers such as styrene-ethylene-propylene-styrene elastomer (hydrogenated styrene-isoprene-styrene elastomer) and hydrogenated styrene-butadiene-styrene elastomer. Furthermore, various elastic polymers known as thermoplastic elastomers, such as polyurethane elastomers, polyester elastomers, and polyetheramide elastomers, can also be used.

A more suitable impact modifier is a core-shell graft copolymer. In a core-shell graft copolymer, the core preferably has a weight average particle diameter of 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and even more preferably 0.1 to 0.5 μm. A particle diameter in the range of 0.05 to 0.8 μm achieves better flex resistance. The elastomeric polymer preferably contains 40% or more of a rubber component, and even more preferably 60% or more.

Rubber components include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those with hydrogen added to the unsaturated bonds. However, due to concerns about the generation of hazardous substances during combustion, rubber components that do not contain halogen atoms are preferred in terms of environmental impact.

The glass transition temperature of the rubber component is preferably -10°C or below, more preferably -30°C or below. Particularly preferred rubber components are butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, and acrylic-silicone composite rubber. Composite rubber refers to rubber obtained by copolymerizing two types of rubber components, or rubber polymerized to form an IPN structure in which the components are inseparably intertwined.

Aromatic vinyl compounds in the vinyl compounds copolymerized with the rubber component include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene, with styrene being particularly preferred. Examples of acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate. Examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and octyl methacrylate, with methyl methacrylate being particularly preferred. Among these, it is preferable to include methacrylic esters such as methyl methacrylate as an essential component. More specifically, the methacrylic ester content is preferably 10% by weight or more, and more preferably 15% by weight or more, based on 100% by weight of the graft component (or 100% by weight of the shell in the case of a core-shell polymer).

Elastic polymers containing a rubber component with a glass transition temperature of 10°C or lower may be produced by any of the following polymerization methods: bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The copolymerization method may be either single-stage or multi-stage grafting. They may also be a mixture with a copolymer of only the graft component, a by-product of production. Polymerization methods include standard emulsion polymerization, soap-free polymerization using an initiator such as potassium persulfate, seed polymerization, and two-stage swelling polymerization. In suspension polymerization, the aqueous phase and monomer phase are kept separate and precisely fed into a continuous disperser, with the particle size controlled by the disperser's rotation speed. In continuous production, particle size can also be controlled by feeding the monomer phase into an aqueous liquid with dispersibility through a small orifice or porous filter with a diameter of several to several tens of micrometers. In the case of core-shell graft polymers, the reaction for both the core and shell may be single-stage or multi-stage.

Such elastic polymers are commercially available and easily available. For example, rubber components primarily made of butadiene rubber, acrylic rubber, or butadiene-acrylic composite rubber include Kane Ace B series (e.g., B-56) from Kanegafuchi Chemical Industry Co., Ltd., Metablen C series (e.g., C-223A) and W series (e.g., W-450A) from Mitsubishi Rayon Co., Ltd., Paraloid EXL series (e.g., EXL-2602), HIA series (e.g., HIA-15), BTA series (e.g., BTA-III), and KCA series from Kureha Chemical Industry Co., Ltd., Paraloid EXL series and KM series (e.g., KM-336P, KM-357P) from Rohm and Haas, and UCL Modifier Resin series from Ube Cycon Co., Ltd. (UMG from UMG ABS Co., Ltd.). Examples include the AXS Resin series, and products with an acrylic-silicone composite rubber as the main rubber component include those sold by Mitsubishi Rayon Co., Ltd. under the trade names Metablen S-2001 or SRK-200.

The composition ratio of the impact modifier is preferably 0.2 to 50 parts by weight, more preferably 1 to 30 parts by weight, and even more preferably 1.5 to 20 parts by weight per 100 parts by weight of polycarbonate resin. This composition range can impart good flex resistance to the composition while suppressing a decrease in rigidity.

(Carbodiimide)
The polycarbonate resin (A) and the polycarbonate resin (B) used in the present invention preferably contain a carbodiimide in order to suppress deterioration of color in a humid and hot environment. The carbodiimide is not particularly limited as long as it is a compound having an "-N=C=N-" structure in the molecule. Examples of carbodiimide compounds include monocarbodiimide compounds, polycarbodiimide compounds, and cyclic carbodiimide compounds, and these are widely known, and any of them can be used. Examples of carbodiimide compounds are described in, for example, JP-A-9-309871, JP-A-9-249801, JP-A-9-208649, JP-A-9-296097, JP-A-8-81,533, JP-A-8-27092, JP-A-9-136869, JP-A-9-124582, JP-A-9-188807, and JP-A-2005-82642. , JP 2005-53870, JP 2012-36392, JP 2010-163203, JP 2011-174094, WO 2008/072514, WO 2010/071211, JP 2012-81759, JP 2012-52014, JP 2012-7079, etc.

The molecular weight of the carbodiimide is preferably 150 or more, more preferably 185 or more, and even more preferably 200 or more. Within this range, good storage stability is achieved in addition to improved moisture resistance. Furthermore, the molecular weight of the carbodiimide is preferably 13,000 or less, more preferably 8,000 or less, and even more preferably 4,000 or less. A molecular weight within this range is preferred because it provides excellent compatibility with polycarbonate resins and acrylic resins and excellent transparency when molded into a molded product.

In this specification, when the carbodiimide is a polymer, the molecular weight of the carbodiimide refers to the "mass average molecular weight." Here, the mass average molecular weight of the carbodiimide is the polystyrene-equivalent mass average molecular weight measured by gel permeation chromatography (GPC). Specifically, the polystyrene-equivalent mass average molecular weight of the carbodiimide can be measured using a Shimadzu Corporation LC-9A/RID-6A measuring device, a Showa Denko Corporation Shodex K-800P/K-804L/K-804L column, and chloroform or the like as the mobile phase at a column temperature of 40°C, and calculated using a calibration curve for standard polystyrene.

As carbodiimides, monocarbodiimides, polycarbodiimides, and cyclic carbodiimides can all be used, but cyclic carbodiimides and polycarbodiimides are more preferred.

Commercially available polycarbodiimides may be used, such as aliphatic polycarbodiimides ("HMV-8CA" and "LA-1" manufactured by Nisshinbo Chemical Inc.) and carbodiimide-modified isocyanates ("Carbodilite V-05" manufactured by Nisshinbo Chemical Inc.). Of these, aliphatic polycarbodiimides ("HMV-8CA" and "LA-1" manufactured by Nisshinbo Chemical Inc.) are preferred.

(Method for manufacturing laminate)
The laminate of the present invention can be produced by known methods such as coextrusion, extrusion lamination, thermal lamination, dry lamination, etc. Among these, the coextrusion method is particularly preferred.

In the case of co-extrusion, the resins and additives that make up each layer of the laminate are fed into multiple extruders through a feed block or multi-manifold die, where the resins are joined to form the laminate. To further improve the strength and impact resistance of the laminate, the laminate obtained in this process can be stretched uniaxially or biaxially using a roll method, tenter method, tubular method, etc.

(Properties and uses of laminate)
The thickness of the laminate of the present invention is preferably in the range of 0.05 to 10.0 mm, more preferably in the range of 0.1 to 5.0 mm, even more preferably in the range of 0.15 to 3.0 mm, particularly preferably in the range of 0.2 to 2.0 mm, and most preferably in the range of 0.25 to 1.0 mm.

In the laminate of the present invention, the thickness of Layer B is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more. The thickness of Layer B is preferably 500 μm or less, more preferably 300 μm or less, even more preferably 200 μm or less, particularly preferably 100 μm or less, and most preferably 80 μm or less. When the thickness of Layer B is within the above range, the laminate will have excellent heat resistance, as well as excellent flexibility, chemical resistance, and scratch resistance.

The laminate of the present invention also has excellent transparency, with a visible light transmittance of preferably 85% or more, more preferably 87% or more, even more preferably 88% or more, particularly preferably 89% or more, and most preferably 90% or more. Furthermore, the haze of the laminate is preferably 2.0% or less, more preferably 1.5% or less, even more preferably 1.0% or less, and particularly preferably 0.5% or less.

(Surface treatment)
The laminate of the present invention can be subjected to various surface treatments. Surface treatments referred to here are those that form a new layer on the surface of a resin molded product, such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, and printing, and commonly used methods can be applied. Specific examples of surface treatments include hard coating, water-repellent/oil-repellent coating, ultraviolet-absorbing coating, infrared-absorbing coating, and metallizing (vapor deposition, etc.). Hard coating is a particularly preferred and necessary surface treatment.

The laminate of the present invention has excellent transparency, chemical resistance, surface hardness, flexibility, and adhesion. Therefore, the uses of the laminate of the present invention are not particularly limited, but can be used, for example, as transparent sheets for building materials, interior parts, display covers, etc., sheets for resin-coated metal plates, sheets for molding (vacuum/pressure molding, hot press molding, etc.), colored plates, transparent plates, shrink films, shrink labels, shrink tubes, automotive interior materials, resin glazing, home appliance components, and office equipment components.

The present invention will be described in detail below using examples, but the present invention is not limited to these. In the examples, "parts" means "parts by weight." The resins and evaluation methods used in the examples are as follows:

1. Polymer composition ratio (NMR)
Each repeating unit was measured by proton NMR using JNM-AL400 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated.

2. Specific Viscosity: Measured using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20°C.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]

3. Heat resistance (glass transition temperature)
The measurement was carried out using a DSC (model DSC2910) manufactured by TA Instruments, with approximately 10 mg of pellets being heated at a temperature increase rate of 20° C./min.

4. Scratch resistance (gloss)
A rubbing test was carried out using steel wool (#0000) with a load of 1 kg and 20 strokes back and forth using a rubbing tester IMC-1507 manufactured by Imoto Manufacturing Co., Ltd. After the test, the reflectance at 20° was evaluated using a handy gloss meter manufactured by Nippon Denshoku Industries Co., Ltd.
◎: The change in reflectance is 70% or less. ○: The change in reflectance is more than 70% but not more than 90%. △: The change in reflectance is more than 90% but not more than 120%. ×: The change in reflectance is more than 120%.

5. Chemical Resistance A sheet sample was cut into a size of 50 x 50 mm, and a commonly available suntan cream (Neutrogena) was uniformly applied to the surface of the film and sheet (film layer side) sample. After heat treatment at 80°C for 4 hours, the surface was washed with a neutral detergent and wiped with a cloth. The haze of the film surface appearance was then measured and evaluated using a haze meter SH-7000 manufactured by Nippon Denshoku Industries Co., Ltd. under conditions of a D65 light source and an angle of 10°.
◎: Haze change is 20% or less. ○: Haze change is more than 20% but not more than 35%. △: Haze change is more than 35% but not more than 45%. ×: Haze change is more than 45%.

6. Adhesion A melt-coextruded sheet sample was cut into a size of 50 x 50 mm, and 100 squares of 1 mm width were scratched using the cross-cut method from the surface of the sheet (on the film layer side) to the interface layer, and tape was attached to the squares and peeled off.
○: No peeling in all 100 squares ×: Peeling occurred in one or more squares

7. Transparency A sheet sample was cut into a size of 50 x 50 mm, and the transmittance was measured and evaluated using a haze meter SH-7000 manufactured by Nippon Denshoku Industries Co., Ltd. under conditions of a D65 light source and an angle of 10°.

8. Flexibility Samples of the film and the melt-co-extruded sheet were cut into 50 x 50 mm pieces, and folded at 180° so that both ends met, and the change in the bent portion was observed.
〇: Does not break ×: Breaks

[Polycarbonate resin (A)]
(Example):
PC/Elastomer 1:
Polycarbonate resin pellets (Panlite L-1250 manufactured by Teijin Limited) and a polyester-based thermoplastic elastomer were each pre-dried in advance, and mixed in a V-type blender so that the polycarbonate resin/polyester-based thermoplastic elastomer ratio was 90/10 (by weight), and then extruded into pellets using a twin-screw extruder at a cylinder temperature of 260°C.

PC/Elastomer 2:
Polycarbonate resin pellets (Panlite L-1250 manufactured by Teijin Limited) and a polyester-based thermoplastic elastomer were each pre-dried in advance, and mixed in a V-type blender so that the polycarbonate resin/polyester-based thermoplastic elastomer ratio was 80/20 (wt %). The mixture was then extruded into pellets using a twin-screw extruder at a cylinder temperature of 260°C.

PC/Elastomer 3:
Polycarbonate resin pellets (Panlite L-1250 manufactured by Teijin Limited) and a polyester-based thermoplastic elastomer were each pre-dried in advance, and mixed in a V-type blender so that the polycarbonate resin/polyester-based thermoplastic elastomer ratio was 95/5 (wt %). The mixture was then extruded into pellets using a twin-screw extruder at a cylinder temperature of 260°C.

[Polycarbonate resin (B)]
(Example)
ISS-PC1:
Structural units derived from isosorbide (hereinafter referred to as ISS)/structural units derived from 1,9-nonanediol (hereinafter referred to as ND)=88/12 (mol %), specific viscosity 0.366
(Manufacturing method)
ISS 445 parts, ND 67 parts, diphenyl carbonate (hereinafter abbreviated as DPC) 750 parts, and 0.0025 parts of barium stearate as a catalyst were heated to 120 ° C. under a nitrogen atmosphere and melted. Then, the mixture was sent to a reaction vessel, the heat medium temperature of the condenser was adjusted to 40 ° C., the internal resin temperature was adjusted to 170 ° C., and the vacuum was adjusted to 13.4 kPa over 30 minutes. Then, the vacuum was adjusted to 3.4 kPa over 20 minutes and maintained at that temperature for 10 minutes. The vacuum was further reduced to 0.9 kPa over 30 minutes, the internal resin temperature was adjusted to 180 ° C., and maintained at that temperature for 10 minutes, after which the vacuum was reduced to 0.2 kPa, and the resin temperature was increased from 180 ° C. to 240 ° C. over 30 minutes, and after reaching the specified viscosity, the mixture was discharged under nitrogen pressure from the bottom of the reaction vessel, and cooled in a water bath, and cut with a pelletizer to obtain pellets.

ISS-PC2:
Structural units derived from ISS/structural units derived from 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane (hereinafter referred to as SPG) = 80/20 (mol %), specific viscosity 0.344
(Manufacturing method)
The same procedure as in Example 1 was carried out, except that 405 parts of ISS, 211 parts of SPG, and 750 parts of DPC were used as raw materials.

ISS-PC3:
Structural units derived from ISS/structural units derived from SPG/structural units derived from ND=75/15/10 (mol %), specific viscosity 0.361
(Manufacturing method)
The same procedure as in Example 1 was carried out, except that 380 parts of ISS, 158 parts of SPG, 55 parts of ND, and 750 parts of DPC were used as raw materials.

ISS-PC4:
Structural units derived from ISS/structural units derived from 1,4-cyclohexanedimethanol (hereinafter referred to as CHDM)=70/30 (mol %), specific viscosity 0.301
(Manufacturing method)
The same procedure as in Example 1 was carried out except that 354 parts of ISS, 150 parts of CHDM and 750 parts of DPC were used as raw materials.

ISS-PC5:
Structural units derived from ISS/structural units derived from SPG/structural units derived from ND=65/35/5 (mol %), specific viscosity 0.312
(Manufacturing method)
The same procedure as in Example 1 was carried out, except that 329 parts of ISS, 369 parts of SPG, 28 parts of ND, and 750 parts of DPC were used as raw materials.

ISS-PC6:
Structural units derived from ISS/structural units derived from 1,4-cyclohexanedimethanol (hereinafter referred to as CHDM)=50/50 (mol %), specific viscosity 0.376
(Manufacturing method)
The same procedure as in Example 1 was carried out except that 253 parts of ISS, 250 parts of CHDM and 750 parts of DPC were used as raw materials.

[Example 1]
<Production of Laminate>
The (PC/Elastomer 1) obtained by the above-described production of polycarbonate resin (A) was melted in a single-screw extruder with a screw diameter of 65 mm set at 260°C, the extrusion rate per hour was adjusted to a thickness of 240 μm, and the resulting mixture was supplied to a multi-manifold T-die. Furthermore, the (ISS-PC1) obtained by the production of polycarbonate resin (B) was melted in a single-screw extruder with a screw diameter of 40 mm set at 230°C, the extrusion rate per hour was adjusted to a thickness of 60 μm, and the resulting mixture was supplied to a multi-manifold T-die. The laminate extruded from the T-die was cooled with a mirror-finished roll to obtain a laminate with a total thickness of 300 μm. The various evaluation results of the resulting laminate are shown in Table 1.

[Example 2]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Example 1, except that (PC/Elastomer 2) was used as the polycarbonate resin (A). The various evaluation results of the obtained laminate are shown in Table 1.

[Example 3]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Example 1, except that (PC/Elastomer 3) was used as the polycarbonate resin (A). The various evaluation results of the obtained laminate are shown in Table 1.

[Example 4]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Example 1, except that the thickness of the polycarbonate resin (A) was adjusted to 260 μm and the thickness of the polycarbonate (B) was adjusted to 40 μm. The various evaluation results of the obtained laminate are shown in Table 1.

[Example 5]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Example 1, except that the thickness of the polycarbonate resin (A) was adjusted to 280 μm and the thickness of the polycarbonate (B) was adjusted to 20 μm. The various evaluation results of the obtained laminate are shown in Table 1.

[Example 6]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Example 1, except that (ISS-PC2) was used as the polycarbonate resin (B). Various evaluation results of the obtained laminate are shown in Table 1.

[Example 7]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Example 1, except that (ISS-PC3) was used as the polycarbonate resin (B). Various evaluation results of the obtained laminate are shown in Table 1.

[Example 8]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Example 7, except that the thickness of the polycarbonate resin (A) was adjusted to 260 μm and the thickness of the polycarbonate (B) was adjusted to 40 μm. The various evaluation results of the obtained laminate are shown in Table 1.

[Example 9]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Example 7, except that the thickness of the polycarbonate resin (A) was adjusted to 280 μm and the thickness of the polycarbonate (B) was adjusted to 20 μm. The various evaluation results of the obtained laminate are shown in Table 1.

[Example 10]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Example 1, except that (ISS-PC4) was used as the polycarbonate resin (B). The various evaluation results of the obtained laminate are shown in Table 1.

[Example 11]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Example 1, except that ISS-PC5 was used as the polycarbonate resin (B). The various evaluation results of the obtained laminate are shown in Table 1.

[Comparative Example 1]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Example 1, except that polycarbonate resin (A) was Panlite L-1250 (a polycarbonate resin obtained using bisphenol A) manufactured by Teijin Limited, melted in a single-screw extruder having a screw diameter of 65 mm set at 280° C., the extrusion rate per hour was adjusted to a thickness of 240 μm, and the resin was supplied to a multi-manifold T-die. Various evaluation results of the obtained laminate are shown in Table 2.

[Comparative Example 2]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Comparative Example 1, except that ISS-PC5 was used as the polycarbonate resin (B). The various evaluation results of the obtained laminate are shown in Table 2.

[Comparative Example 3]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Comparative Example 1, except that ISS-PC4 was used as the polycarbonate resin (B). The various evaluation results of the obtained laminate are shown in Table 2.

[Comparative Example 4]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Comparative Example 1, except that ISS-PC6 was used as the polycarbonate resin (B). The various evaluation results of the obtained laminate are shown in Table 2.

[Comparative Example 5]
A laminate having a total thickness of 300 μm was obtained in the same manner as in Comparative Example 1, except that ACRYPET VH001 manufactured by Mitsubishi Chemical Corporation was used instead of polycarbonate resin (B) and the temperature was set to 250° C. The various evaluation results of the obtained laminate are shown in Table 2.

The sheets or films and laminates of the present invention have excellent transparency, chemical resistance, formability, adhesion, and scratch resistance, and are useful as transparent sheets for building materials, interior parts, display covers, etc., sheets for resin-coated metal plates, sheets for molding (vacuum/pressure molding, hot press molding, etc.), colored plates, transparent plates, shrink films, shrink labels, shrink tubes, automotive interior materials, resin glazing, home appliance components, and office equipment components.

Claims (8)

A laminate having a layer (A layer) formed from a polycarbonate resin composition containing a polycarbonate resin (A) and a thermoplastic elastomer, and a layer (B layer) formed from a polycarbonate resin (B) containing 30 mol % or more of a unit (b) represented by the following formula (B) and 5 to 70 mol % of a unit (c) represented by the following formula (C-1):
(In the formula, W represents an alkylene group having 1 to 20 carbon atoms or a cycloalkylene group having 6 to 20 carbon atoms, R represents a branched or linear alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, and m represents an integer of 0 to 10.) The laminate according to claim 1, wherein the polycarbonate resin (A) used in layer A contains 50 mol % or more of carbonate units derived from aromatic dihydroxy units. The laminate according to claim 1 or 2, wherein the thermoplastic elastomer used in layer A is a thermoplastic elastomer composed of hard segments consisting of polybutylene terephthalate units and soft segments consisting of polyester units having an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid as the dicarboxylic acid component and a diol having 5 to 15 carbon atoms as the diol component. The laminate according to any one of claims 1 to 3, wherein the content of the thermoplastic elastomer in Layer A is 3 to 50 parts by weight per 100 parts by weight of the polycarbonate resin (A). 5. The laminate according to claim 1, wherein the polycarbonate resin (B) used in the layer B contains 30 to 95 mol % of the unit (b) represented by the formula (B). The laminate according to any one of claims 1 to 5, wherein the thickness of the laminate is 0.05 to 10.0 mm. The laminate described in any one of claims 1 to 6, wherein the visible light transmittance of the laminate is 85% or more. The laminate according to any one of claims 1 to 7, wherein the laminate is produced by a melt extrusion method.