JP7000236B2 - Polycarbonate resin laminate - Google Patents

Description

The present invention relates to a polycarbonate resin laminate. More specifically, the present invention relates to a polycarbonate resin laminate containing a film layer containing a polycarbonate resin (A) containing a specific structural unit and a substrate containing a polycarbonate resin (B) different from the polycarbonate resin (A).

Polycarbonate resin is used in a wide range of fields because of its excellent transparency, impact resistance, heat resistance, and dimensional stability. On the other hand, the polycarbonate resin has a pencil hardness of 2B measured in accordance with the general paint test method described in JIS K5600-5-4-Part 5: Mechanical properties of the coating film-Section 4: Scratch hardness (pencil method). It is known that the surface of the resin is easily scratched. Therefore, for the purpose of increasing the added value of the product, improvement by a multilayer structure in which a separately molded molded product is laminated on the main body of the polycarbonate resin molded product has been proposed.

As a method for forming such a multilayer structure, printing or hard coating is applied to the surface of the thermoplastic resin film, the film is inserted into the mold cavity surface or the core surface, and the thermoplastic resin is placed in the mold cavity. An insert molding method is generally used in which a film and a molded product are integrated by filling by an injection molding method to add value to a surface portion.

Therefore, it has been proposed to laminate a hard-coated polycarbonate resin film, but there have been problems that cracks occur in the hard coat layer due to heat shrinkage during insert molding and that optical strain becomes large.

In order to solve such a problem, a method of laminating an acrylic resin (for example, Patent Document 1) is known, but the glass transition temperature difference from the polycarbonate resin as a substrate is large, so that the moldability is inferior and the moldability is poor. Since acrylic resin is inferior in impact resistance, there is a problem that cracks are likely to occur.

Further, a method of laminating a high surface hardness polycarbonate resin (for example, Patent Documents 2 and 3) is known, but although the surface hardness is improved, optical strain occurs due to heat shrinkage during insert molding, so that the interior of an automobile is used. It was insufficient as a laminated film used for various display devices used in, for example, a display panel front plate of a car navigation system.

Therefore, there is not yet a polycarbonate resin laminate having excellent scratch resistance, heat resistance, and impact resistance and having little optical distortion.

JP-A-2007-160892 Japanese Patent No. 5468896 Japanese Patent No. 5872058

An object of the present invention is to solve the above-mentioned conventional problems and to provide a polycarbonate resin laminate having excellent surface hardness, heat resistance, and impact resistance and having less optical strain.

As a result of diligent research to solve the above problems, the present inventors have obtained a film layer containing a polycarbonate resin (A) containing a specific structural unit and a polycarbonate resin (B) different from the polycarbonate resin (A). It has been found that the above-mentioned object can be achieved by preparing a polycarbonate resin laminate containing a substrate containing. As a result of further studies based on such findings, the present invention has been completed.
That is, according to the present invention, the following (configuration 1) to (configuration 7) are provided.

（式（１）中、Ｒ^１～Ｒ^２は夫々独立して水素原子、炭素原子数１～６のアルキル基である。）
で表される構成単位（ａ）、
下記式（２）

（式（２）中、Ｒ^３～Ｒ^４は夫々独立して炭素原子数１～６のアルキル基であり、Ｘは単結合、置換もしくは無置換の炭素原子数１～１０のアルキレン基、置換もしくは無置換の炭素原子数１～１０のアルキリデン基である。）
で表される構成単位（ｂ）、および
下記式（３）

（式（３）中、Ｗは単結合、置換もしくは無置換の炭素原子数１～１０のアルキレン基、置換もしくは無置換の炭素原子数１～１０のアルキリデン基である。）
で表される構成単位（ｃ）から構成される共重合ポリカーボネートであること
（ＩＩ）フィルム層の厚さが０．０５～０．５ｍｍであり、積層体の合計厚みが０．８～５．０ｍｍであること
（ＩＩＩ）ポリカーボネート樹脂（Ａ）のガラス転移温度が１４０℃以上であり、ポリカーボネート樹脂（Ｂ）のガラス転移温度との温度差が１０℃以下であること
（ＩＶ）フィルム層のＪＩＳ Ｋ５６００に準拠して測定した鉛筆硬度が、基体の鉛筆硬度よりも高く、且つ積層体表層の鉛筆硬度がＨ以上であること
（構成２）
前記ポリカーボネート樹脂（Ａ）の全構成単位における構成単位（ａ）の割合が５～１５モル％、構成単位（ｂ）の割合が２０～６０モル％、構成単位（ｃ）の割合が２５～７５モル％であるポリカーボネート共重合体であることを特徴とする構成１記載のポリカーボネート樹脂積層体。
（構成３）
前記ポリカーボネート樹脂（Ａ）の粘度平均分子量が１５，０００～４０，０００であり、前記ポリカーボネート樹脂（Ｂ）の粘度平均分子量が１０，０００～３０，０００であることを特徴とする構成１～２のいずれか１項に記載のポリカーボネート樹脂積層体。
（構成４）
前記ポリカーボネート樹脂（Ｂ）が下記式（４）で表される構成単位を少なくとも含むポリカーボネート樹脂であることを特徴とする構成１～３のいずれか１項に記載のポリカーボネート樹脂積層体。

（構成５）
前記フィルム層の光弾性係数が７０×１０^－１２ｍ^２／Ｎ以下であることを特徴とする構成１～４のいずれか１項に記載のポリカーボネート樹脂積層体。
（構成６）
前記フィルム層の複屈折が２０×１０^－３以下であることを特徴とする構成１～５のいずれか１項に記載のポリカーボネート樹脂積層体。
（構成７）
前記ポリカーボネート樹脂（Ａ）を含有するフィルム層を金型に設置し、次いで前記ポリカーボネート樹脂（Ｂ）を射出成形することで形成されることを特徴とする構成１～６のいずれか１項に記載のポリカーボネート樹脂積層体の製造方法。 (Structure 1)
A polycarbonate resin laminate containing at least a film layer containing a polycarbonate resin (A) and a substrate containing a polycarbonate resin (B) different from the polycarbonate resin (A), wherein the film layer is a surface layer of the polycarbonate resin laminate. A polycarbonate resin laminate characterized by satisfying the following conditions (I) to (IV).
(I) The following formula (1) is used as the main constituent unit of the polycarbonate resin constituting the film layer.

(In the formula (1), R ¹ to R ² are independent hydrogen atoms and alkyl groups having 1 to 6 carbon atoms, respectively.)
The structural unit (a) represented by
The following formula (2)

(In the formula (2), R ³ to R ⁴ are independently alkyl groups having 1 to 6 carbon atoms, and X is a single bond, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, substituted. Alternatively, it is an unsubstituted alkylidene group having 1 to 10 carbon atoms.)
The structural unit (b) represented by and the following formula (3)

(In the formula (3), W is a single-bonded, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and substituted or unsubstituted an alkylidene group having 1 to 10 carbon atoms.)
(II) The thickness of the film layer is 0.05 to 0.5 mm, and the total thickness of the laminated body is 0.8 to 5. 0 mm (III) The glass transition temperature of the polycarbonate resin (A) is 140 ° C. or higher, and the temperature difference from the glass transition temperature of the polycarbonate resin (B) is 10 ° C. or lower (IV) JIS of the film layer. The pencil hardness measured according to K5600 is higher than the pencil hardness of the substrate, and the pencil hardness of the surface layer of the laminated body is H or more (Structure 2).
The proportion of the constituent unit (a) in all the constituent units of the polycarbonate resin (A) is 5 to 15 mol%, the proportion of the constituent unit (b) is 20 to 60 mol%, and the proportion of the constituent unit (c) is 25 to 75. The polycarbonate resin laminate according to Configuration 1, which is a polycarbonate copolymer having a molar percentage.
(Structure 3)
The configurations 1 to 2 characterized in that the viscosity average molecular weight of the polycarbonate resin (A) is 15,000 to 40,000 and the viscosity average molecular weight of the polycarbonate resin (B) is 10,000 to 30,000. The polycarbonate resin laminate according to any one of the above items.
(Structure 4)
The polycarbonate resin laminate according to any one of configurations 1 to 3, wherein the polycarbonate resin (B) is a polycarbonate resin containing at least a structural unit represented by the following formula (4).

(Structure 5)
The polycarbonate resin laminate according to any one of configurations 1 to 4, wherein the film layer has a photoelastic coefficient of 70 × ^10-12 m ² / N or less.
(Structure 6)
The polycarbonate resin laminate according to any one of configurations 1 to 5, wherein the film layer has a birefringence of 20 × 10 ^-3 or less.
(Structure 7)
The item according to any one of the configurations 1 to 6, wherein the film layer containing the polycarbonate resin (A) is placed in a mold and then the polycarbonate resin (B) is injection-molded to form the film layer. Method for manufacturing a polycarbonate resin laminate.

The polycarbonate resin laminate of the present invention is excellent in surface hardness, heat resistance, and impact resistance, and has little optical distortion, so that it is suitably used for various display devices of automobile interior parts. Therefore, the industrial effect it produces is exceptional.

It is a schematic diagram which showed an example of the apparatus used when manufacturing the film layer in this invention.

Hereinafter, the details of the present invention will be described.

The polycarbonate resin laminate of the present invention contains at least a film layer containing a polycarbonate resin (A) and a substrate containing a polycarbonate resin (B) different from the polycarbonate resin (A), and the film layer is used as a surface layer. A polycarbonate resin molded body.

<Polycarbonate resin (A)>
The polycarbonate resin (A) of the present invention has the following formula (1) as a main constituent unit.

（式（１）中、Ｒ^１～Ｒ^２は夫々独立して水素原子、炭素原子数１～６のアルキル基である。）
で表される構成単位（ａ）、
下記式（２）、および

(In the formula (1), R ¹ to R ² are independent hydrogen atoms and alkyl groups having 1 to 6 carbon atoms, respectively.)
The structural unit (a) represented by
The following formula (2) and

（式（２）中、Ｒ^３～Ｒ^４は夫々独立して炭素原子数１～６のアルキル基であり、Ｘは単結合、置換もしくは無置換の炭素原子数１～１０のアルキレン基、置換もしくは無置換の炭素原子数１～１０のアルキリデン基である。）
で表される構成単位（ｂ）、および
下記式（３）

(In the formula (2), R ³ to R ⁴ are independently alkyl groups having 1 to 6 carbon atoms, and X is a single bond, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, substituted. Alternatively, it is an unsubstituted alkylidene group having 1 to 10 carbon atoms.)
The structural unit (b) represented by and the following formula (3)

（式（３）中、Ｗは単結合、置換もしくは無置換の炭素原子数１～１０のアルキレン基、置換もしくは無置換の炭素原子数１～１０のアルキリデン基である。）
で表される構成単位（ｃ）から構成される共重合ポリカーボネートである。

(In the formula (3), W is a single-bonded, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and substituted or unsubstituted an alkylidene group having 1 to 10 carbon atoms.)
It is a copolymerized polycarbonate composed of the structural unit (c) represented by.

Here, the "main" is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 95 mol% in 100 mol% of the total carbonate constituent units excluding the terminal. The above shows that the ratio is most preferably 100 mol%.

In the structural unit (A) represented by the formula (1), it is preferable that R ¹ and R ² are independently hydrogen atoms and alkyl groups having 1 to 4 carbon atoms, respectively.

Examples of the divalent phenol that induces the structural unit (a) include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. The most suitable divalent phenol is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.

In the polycarbonate resin (A) of the present invention, the ratio of the constituent unit (a) to all the constituent units is preferably 5 to 15 mol%. When the ratio of the structural unit (a) exceeds 15 mol%, the heat resistance is improved, but the impact resistance may be inferior. If the proportion of the structural unit (a) is less than 5 mol%, the heat resistance may be inferior.

In the structural unit (b) represented by the formula (2), it is preferable that R ³ to R ⁴ are independently alkyl groups having 1 to 4 carbon atoms, and X is a single bond, substituted or unsubstituted. It is preferable that the alkylene group has 1 to 5 carbon atoms, and the substituted or unsubstituted alkylidene group has 1 to 5 carbon atoms.

Examples of the dihydric phenol that induces the structural unit (b) include 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter referred to as bisphenol C) and 2,2-bis (4-hydroxy-3). -Isopropylphenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane and the like can be mentioned. The most suitable divalent phenol is bisphenol C.

In the polycarbonate resin (A) of the present invention, the ratio of the constituent unit (b) to all the constituent units is preferably 20 to 60 mol%, more preferably 30 to 50 mol%. If the proportion of the structural unit (b) exceeds 60 mol%, the impact resistance and heat resistance may be inferior. If the proportion of the structural unit (b) is less than 20 mol%, the surface hardness may be inferior.

In the structural unit (c) represented by the formula (3), W is a single-bonded, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkylated group having 1 to 10 carbon atoms. Is preferable.

Examples of the divalent phenol that induces the structural unit (c) include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 4,4'-dihydroxy-1,1-biphenyl, 4, 4'-Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylthioether, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfooxide, 4,4'-dihydroxydiphenylsulfide, 1,1-bis (4-) Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4-bis (4,4-bis) Examples thereof include 4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, and 1,1-bis (4-hydroxyphenyl) decane. The most suitable divalent phenol is bisphenol A.

In the polycarbonate resin (A) of the present invention, the ratio of the constituent unit (c) to all the constituent units is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, still more preferably 35 to 65 mol%. %, Especially preferably 40 to 60 mol%. If the proportion of the structural unit (c) exceeds 75 mol%, scratch resistance and amine resistance are inferior, which is not preferable. If the ratio of the structural unit (c) is less than 25 mol%, the impact resistance is inferior, which is not preferable.

Further, as the divalent phenol for inducing a structural unit other than the structural units (a), (b) and (c), 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, and an alkyl group having 1 to 3 carbon atoms are preferable. Resolsinol substituted with, 3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5-ol, 1- (4-hydroxyphenyl) -1,3,3-trimethylindan-5-ol, 6,6'-Dihydroxy-3,3,3', 3'-Tetramethylspirindan, 1-methyl-1,3-bis (4-hydroxyphenyl) -3-isopropylcyclohexane, 1-methyl-2- ( Examples thereof include 4-hydroxyphenyl) -3- [1- (4-hydroxyphenyl) isopropyl] cyclohexane, 1,6-bis (4-hydroxyphenyl) -1,6-hexanedione and the like. Other details of such polycarbonate are described in, for example, WO03 / 080728 pamphlet, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, JP-A-2002-117580 and the like. Has been done.

The polycarbonate resin (A) of the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of the reaction method include an interfacial transesterification method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a terminal terminator of monohydric phenols is usually used. Further, it may be a branched polycarbonate obtained by polymerizing a trifunctional component, or may be a copolymerized polycarbonate obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a vinyl-based monomer.

In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used to promote the reaction. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

The transesterification reaction using, for example, a carbonic acid diester as a carbonic acid precursor is carried out by a method of distilling off the produced alcohol or phenol by stirring a predetermined ratio of aromatic dihydroxy components with the carbonic acid diester while heating them in an inert gas atmosphere. It is. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed by distilling off the produced alcohols or phenols under reduced pressure from the initial stage. It is also possible to use a catalyst usually used for transesterification reaction to promote the reaction. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable.

Monofunctional phenols commonly used as terminal inhibitors can be used. Especially in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminal terminator for molecular weight regulation, and the obtained polycarbonate resin is based on monofunctional phenols at the end. Since it is sealed by a group, it has better thermal stability than those that do not. Specific examples of the monofunctional phenols include, for example, phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, and the like. Examples thereof include p-cumylphenol, isooctylphenol, and p-long-chain alkylphenol.

The polycarbonate resin (A) of the present invention can be copolymerized with a fatty acid, if necessary. For example, 1,10-dodecandionic acid (DDDA), adipic acid, hexanedioic acid, isophthalic acid, 1,3-benzenedicarboxylic acid, terephthalic acid, 1,4-benzenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Examples thereof include 3-hydroxybenzoic acid (mHBA) and 4-hydroxybenzoic acid (pHBA).

The polycarbonate resin (A) of the present invention contains a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosandioic acid, and cyclohexanedicarboxylic acid. An alicyclic dicarboxylic acid such as an acid is preferably used. These carboxylic acids may be copolymerized as long as they do not impair the purpose. The polycarbonate resin of the present invention can also be copolymerized with a structural unit containing a polyorganosiloxane unit, if necessary.

If necessary, the polycarbonate resin (A) of the present invention may be copolymerized with a structural unit containing a trifunctional or higher polyfunctional aromatic compound to obtain a branched polycarbonate. Trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonate include 4,6-dimethyl-2,4,6-tris (4-hydrochidiphenyl) heptene-2, 2,4,6-trimethyl-. 2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1 -Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4- {4- [1,1-bis (1,1-bis) 4-Hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols are preferably exemplified. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane is preferable. The structural unit derived from such a polyfunctional aromatic compound is preferably 0.03 to 1.5 mol%, more preferably 0.1, based on 100 mol% in total including the structural unit from other divalent components. It is about 1.2 mol%, particularly preferably 0.2 to 1.0 mol%.

Further, the branched structural unit is not only derived from the polyfunctional aromatic compound, but also derived without using the polyfunctional aromatic compound such as a side reaction generated during the polymerization reaction by the molten ester exchange method. You may. The ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

The polycarbonate resin (A) of the present invention has a viscosity average molecular weight (Mv) of preferably 15,000 to 40,000, more preferably 16,000 to 30,000, and even more preferably 18,000. It is ~ 28,000. A polycarbonate resin having an Mv of less than 15,000 may not have sufficient toughness and crack resistance for practical use. On the other hand, a polycarbonate resin having an Mv of more than 40,000 is inferior in versatility because it requires a high molding temperature or a special molding method, and further, due to an increase in melt viscosity, the optics of the molded product Distortion tends to be large, and the yield may decrease due to poor appearance or the like.

For the Mv of the polycarbonate resin (A) in the present invention, first, an Ostwald viscometer was used from a solution in which 0.7 g of the polycarbonate resin was dissolved in 100 ml of methylene chloride at 20 ° C. for the specific viscosity (η _SP ) calculated by the following formula. Ask,
Specific viscosity (η _SP ) = (tt ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]
The viscosity average molecular weight Mv was calculated from the obtained specific viscosity (η _SP ) by the following formula.
η _SP / c = [η] +0.45 × [η] ² c (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 Mv ^0.83
c = 0.7

The glass transition temperature of the polycarbonate resin (A) of the present invention is 140 ° C. or higher, preferably 140 to 160 ° C., more preferably 140 to 155 ° C., and even more preferably 140 to 150 ° C. .. When the glass transition temperature is 140 ° C. or higher, the heat resistance becomes sufficient. Further, when the glass transition temperature is 160 ° C. or lower, it is not necessary to raise the molding processing temperature to a high temperature, and molding becomes easy.

<Polycarbonate resin (B)>
The polycarbonate resin (B) used as the substrate of the polycarbonate resin laminate of the present invention is different from the polycarbonate resin (A) used for the film layer. The polycarbonate resin (B) is preferably an aromatic polycarbonate resin obtained by reacting a divalent phenol with a carbonate precursor. In particular, a polycarbonate resin containing at least a carbonate constituent unit derived from bisphenol A is preferable.

Examples of the reaction method include an interfacial transesterification method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. The polycarbonate resin may be produced by any production method, and in the case of interfacial polycondensation, a terminal terminator of monohydric phenols is usually used. The polycarbonate resin may be a branched polycarbonate obtained by polymerizing a trifunctional or higher functional component in addition to the divalent phenol or the bifunctional alcohol. Further, it may be a branched polycarbonate resin obtained by polymerizing polyfunctional phenols such as trifunctional phenols, and further polymerized with an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a polyorganosiloxane component, and a vinyl-based monomer. It may be a copolymerized polycarbonate. As the carbonate precursor, the terminal terminator, the trifunctional or higher functional component, and the dicarboxylic acid component, the same substances as those described in the paragraph of <Polycarbonate resin (A)> can be used.

Typical examples of divalent phenols are 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl). ) Cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) sulfide, Examples thereof include bis (4-hydroxyphenyl) sulfone. Preferred divalent phenols are bis (4-hydroxyphenyl) alkanes, with bisphenol A being particularly preferred.

The viscosity average molecular weight of the polycarbonate resin (B) is preferably 10,000 to 30,000, more preferably 15,000 to 28,000, and even more preferably 18,000 to 25,000. Within the range of the viscosity average molecular weight, practically sufficient mechanical properties can be obtained, and the molding processability is also excellent.

The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (η _sp ) obtained from a solution of 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C into the following equation.
η _sp / c = [η] +0.45 × [η] ² c (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 M ^0.83
c = 0.7

The glass transition temperature of the polycarbonate resin (B) in the present invention is preferably 140 to 160 ° C, more preferably 140 to 155 ° C, and even more preferably 140 to 150 ° C. The temperature difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the polycarbonate resin (B) is 10 ° C. or lower, preferably 8 ° C. or lower, and more preferably 6 ° C. or lower. When the glass transition temperature of the polycarbonate resin (B) is 140 ° C. or higher, the heat resistance is sufficient, and when it is 160 ° C. or lower, it is not necessary to raise the molding processing temperature to a high temperature, and molding becomes easy. Further, if the temperature difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the polycarbonate resin (B) exceeds the above upper limit, optical strain becomes large due to thermal shrinkage during insert molding, which is not preferable.

The polycarbonate resin (B) of the present invention may appropriately contain a resin other than the polycarbonate resin as long as the effects of the present invention are not significantly impaired. As the other resin, one type may be contained, or two or more types may be contained in any combination and ratio. Examples of other resins include thermoplastic polyester resins such as polyethylene tephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin); polystyrene resin (PS resin) and high impact. Polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene rubber -A styrene resin such as a styrene copolymer (AES resin); a polyethylene resin (PE resin), a polypropylene resin (PP resin), a cyclic cycloolefin resin (COP resin), a cyclic cycloolefin copolymer (COP) resin, etc. Polyolefin resin; Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone Examples thereof include a resin (PSU resin); a polymethacrylate resin (PMMA resin); and the like.

<Ingredients other than polycarbonate resin>
In the present invention, the polycarbonate resin (A) and / or the polycarbonate resin (B) may be used as a mold release agent, a heat stabilizer, an ultraviolet absorber, a flow modifier, an antistatic agent, etc., as long as the effects of the present invention are not impaired. It can contain a functional agent known per se.

The method for blending the additive with the polycarbonate resin used in the present invention is not particularly limited, and a known method can be used. The most commonly used method is to premix the polycarbonate resin and additives, then put them in an extruder for melt kneading, cool the extruded threads, and cut them with a pelletizer to produce pellet-shaped molding materials. There is a way to do it.

As the extruder in the above method, either a single-screw extruder or a twin-screw extruder can be used, but a twin-screw extruder is preferable from the viewpoint of productivity and kneadability. As a typical example of such a twin-screw extruder, ZSK (manufactured by Werner & Pfreederer, trade name) can be mentioned. Specific examples of the same type include TEX (manufactured by Japan Steel Works, Ltd., product name), TEM (manufactured by Toshiba Machine Co., Ltd., product name), KTX (manufactured by Kobe Steel, Ltd., product name), etc. Can be mentioned. As the extruder, one having a vent capable of degassing the moisture in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent to efficiently discharge the generated water and volatile gas to the outside of the extruder. It is also possible to install a screen for removing foreign matter and the like mixed in the extruded raw material in the zone in front of the die portion of the extruder to remove the foreign matter from the resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (disc filter, etc.) and the like.

Further, although the additive can be independently supplied to the extruder, it is preferable to premix it with the resin raw material as described above. Examples of such premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. A more preferred method is, for example, to prepare a master agent by mixing a part of the raw material resin and the additive with a high-speed stirrer such as a Henschel mixer, and then leaving the remaining master agent as a total amount of the resin raw material and a Nauter mixer. It is a method of mixing with a non-high speed stirrer.

The resin extruded from the extruder is directly cut and pelletized, or after forming the strands, the strands are cut with a pelletizer and pelletized. When it is necessary to reduce the influence of external dust and the like, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical discs are used to narrow the shape distribution of pellets, further reduce miscuts, and generate fine powder during transportation or transportation. It is preferable to further reduce the amount of bubbles (vacuum bubbles) generated inside the strands and pellets. To reduce miscuts, measures such as controlling the temperature of threads during cutting with a pelletizer, blowing ion air during cutting, optimizing the rake angle of the pelletizer, and properly formulating a release agent, as well as cutting were performed. Examples thereof include a method of filtering a mixture of pellets and water to separate the pellets from water and miscut. An example of the measuring method is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-200421. With these formulations, it is possible to increase the cycle of molding and reduce the rate of defects such as silver.

The amount of miscut in the molding material (pellet) is preferably 10 ppm or less, more preferably 5 ppm or less. Here, the miscut means a powder or granular material finer than a pellet of a desired size that passes through a JIS standard sieve having an opening of 1.0 mm. The shape of the pellet can be a general shape such as a cylinder, a prism, and a sphere, but more preferably a cylinder (including an elliptical pillar), and the diameter of the cylinder is preferably 1.5 to 4 mm, more preferably. Is 2 to 3.5 mm. In the elliptical column, the ratio of the minor axis to the major axis is preferably 60% or more, more preferably 65% or more. On the other hand, the length of the cylinder is preferably 2 to 4 mm, more preferably 2.5 to 3.5 mm.

<Film layer>
As a method for producing the film layer constituting the polycarbonate resin laminate of the present invention, the molten polycarbonate resin (A) extruded from the T-die is cooled by sandwiching pressure or a plurality of mirror surface cooling rolls of a single-sided touch method. The method of forming the film into a film is preferably adopted. By such a method, a polycarbonate resin film having a thickness of 0.05 to 0.5 mm can be produced. The device used at this time does not have to be a special device, and a device used for manufacturing a film or a sheet is arbitrarily adopted. The method for producing the film layer in the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing an example of a film manufacturing apparatus suitable for carrying out film manufacturing in the present invention. In the figure, 1 is a T die, 2 is a first cooling roll, 3 is a second cooling roll, 4 is a third cooling roll, and 5 is a pair of take-up rolls. Has a mirror finish, and a heat medium circulates inside it so that the temperature can be controlled.

First, the molten polycarbonate resin (A) is extruded from the T die 1 into a film. The melt extrusion at this time does not require any special conditions, and the melt extrusion conditions of a normal polycarbonate resin film are arbitrarily adopted. Next, the extruded film-like material is rolled by the two rolls or brought into close contact with the central second cooling roll 3 while being supplied between the first cooling roll 2 and the second cooling roll 3 as it is. After being inherited by the third roll 4 at the other end, it is picked up by a pair of pick-up rolls 5.

At this time, it is preferable to increase the rotation speed of the third cooling roll 4 with respect to the second cooling roll 3 by 1.001 to 1.015 times. If the rotation speed of the third cooling roll 4 with respect to the second cooling roll 3 is made smaller than 1.001 times, cooling proceeds slowly, but the speed is slow and good seating may not be possible. Since the take-up speed is high, the seating is good, but since the polycarbonate resin film has a stretching action in the extrusion direction, the heating expansion and contraction in the extrusion direction becomes large, and the heating expansion and contraction in the width direction and the balance are lost, making it difficult to put into practical use. There is.

Further, it is preferable to set the temperature of the first cooling roll 2 to 130 to 145 ° C, the temperature of the second cooling roll 3 to 135 to 150 ° C, and the temperature of the third cooling roll 4 to 145 to 155 ° C. The polycarbonate resin (A) is normally extruded at 260 to 280 ° C., whereas if the temperature of each cooling roll 2 to 4 is less than the lower limit, the cooling is too fast and the heat shrinkage becomes large, and the temperature of each cooling roll If the temperature exceeds the upper limit, it may not be sufficiently cooled and may be taken by a cooling roll to prevent seating. The temperature of the first to third cooling rolls 2 to 4 can be easily controlled by the conventional roll temperature control means.

The thickness of the film layer is 0.05 to 0.5 mm, preferably 0.05 to 0.3 mm, and more preferably 0.06 to 0.2 mm. If the thickness of the film layer is thinner than 0.05 m, the pencil hardness of the surface of the laminate is inferior, which is not preferable. On the other hand, if it is thicker than 0.5 mm, the optical strain during insert molding becomes large, which is not preferable. Even when a plurality of film layers are used, the thickness of the above-mentioned film layer means the thickness of each (single layer) film layer.

The pencil hardness measured according to JIS K5600 of the film layer is preferably H or more, and preferably 2H or more. When the pencil hardness satisfies the above range, the surface of the laminated body is less likely to be scratched, which is preferable.

The photoelastic coefficient of the film layer is preferably 70 × ^10-12 m ² / N or less, more preferably 65 × ^10-12 m ² / N or less, and even more preferably 60 × ^10-12 m ² / N or less. If it is smaller than the above upper limit, the optical strain during insert molding becomes small, which is preferable.

The birefringence of the film layer is preferably 20 × 10 ^-3 or less, more preferably 15 × 10 ^-3 or less. If it is smaller than the above upper limit, the optical strain during insert molding becomes small, which is preferable.

<Polycarbonate resin laminate>
The film layer made of the polycarbonate resin (A) used in the present invention can be suitably used as a film to be inserted into a mold at the time of insert molding. Such a film can be used with at least one side surface-treated. Examples of this surface treatment include hard coat processing, anti-fog processing, antistatic processing, non-reflective processing, primer processing, printing, stamping, thin film deposition, sputtering, and the like. There may be. The thickness of these layers other than vapor deposition and sputtering is preferably 0.1 to 20 μm. In the case of a film with one side processed, the processed side (desired side in the case of double-sided processing) is set to the mold surface side, and the film is set. Next, the polycarbonate resin (B) is injected and molded.

An injection molding method is usually used to produce the polycarbonate resin laminate of the present invention. Specifically, the polycarbonate resin laminate of the present invention can be obtained by inserting a film layer into a mold, closing the mold, and injection molding the raw material of the substrate containing the polycarbonate resin (B). can.

The polycarbonate resin laminate thus obtained contains a film layer containing the polycarbonate resin (A) and a substrate containing the polycarbonate resin (B), and has a structure in which the film layer is used as a surface layer. Here, the "structure with the film layer as the surface layer" means a structure in which the film layer is present in the uppermost layer and / or the lowermost layer of the laminated body.

The mold temperature at the time of molding the polycarbonate resin laminate of the present invention is not particularly limited, but is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 100 ° C. or lower. If the mold temperature is too high, it is necessary to lengthen the cooling time during molding, which may lengthen the manufacturing cycle of the molded product and reduce productivity. Further, if the mold temperature is too low, the melt viscosity of the resin constituting the substrate becomes too high, and a uniform molded body may not be obtained or the surface of the molded body may be uneven. 30 ° C. or higher is preferable, and 50 ° C. or higher is particularly preferable.

The injection speed when molding the polycarbonate resin laminate of the present invention is not particularly limited, but
It is preferably 200 mm / sec or less, more preferably 150 mm / sec or less, and most preferably 100 mm / sec or less. Further, 1 mm / sec or more is preferable, 5 mm / sec or more is more preferable, and 10 mm / sec or more is most preferable. If the injection speed is too high, the film may tear during injection molding. On the other hand, if the injection speed is too low, the molded product may have a short shot.

The total thickness of the laminate is 0.8 to 5 mm, preferably 1 to 4.5 mm, more preferably 1.5 to 4 mm, still more preferably 2 to 3.5 mm. If the thickness of the laminate is thinner than 0.8 mm, the mechanical strength of the laminate is inferior, which is not preferable. On the other hand, if it is thicker than 5 mm, optical strain increases during molding, which is not preferable.

The pencil hardness measured according to JIS K5600 of the laminated body is H or more, preferably 2H or more. When the pencil hardness satisfies the above range, the surface of the laminated body is less likely to be scratched, which is preferable.

The polycarbonate resin laminate of the present invention not only has high surface hardness, but also has excellent impact resistance and heat resistance, and has little optical distortion. Therefore, in addition to buildings such as roofing materials, wall materials, and window materials, vehicle windows Materials, head lamp materials, meter covers, car navigation systems, head-up displays and other vehicle components, mobile phone buttons and keyboards, housings, LED lighting components, display front panels and other electrical and electronic equipment components, game components , Can be used in various fields such as eyeglass members and lens members.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the measurement method of each characteristic is as follows.
(1) Viscosity average molecular weight Mv of the polycarbonate resin was measured by the following method. From a solution of 0.7 g of polycarbonate resin in 100 ml of methylene chloride, the specific viscosity (η _sp ) of the solution at 20 ° C. was measured. Then, Mv calculated by the following formula was used as the viscosity average molecular weight.
η _sp / c = [η] +0.45 × [η] ² c
[Η] = 1.23 × 10 ^-4 Mv ^0.83
η _sp : Specific viscosity η: Extreme viscosity c: Constant (= 0.7)
Mv: viscosity average molecular weight (2) composition ratio 40 mg of polycarbonate resin was dissolved in 0.6 ml deuterated chloroform solution, and ^{1 1} H-NMR was measured by JNM-AL400 (resonance frequency 400 MHz) manufactured by JEOL Ltd. The composition ratio of the polycarbonate resin was calculated from the characteristic spectral peak area ratio.
(3) Glass transition temperature Measured under the conditions of nitrogen atmosphere (nitrogen flow rate: 40 ml / min) and temperature rise rate: 20 ° C / min according to JIS K7121 using the thermal analysis system DSC-2910 manufactured by TA Instruments. did.
(4) High-speed surface impact test Using Hydroshot HTM-1 manufactured by Shimadzu Corporation, the impact energy of the laminate was measured at a test speed of 7 m / sec and an impact core radius of 6.4 mm, and the fracture morphology was visually observed. ..
(5) Pencil hardness The pencil hardness of the film, the substrate, and the laminate was measured according to JIS K5600.
(6) Film Thickness The film thickness was measured using a continuous thickness meter (Film Thick Nestester manufactured by Anritsu Co., Ltd., model KG601A).
(7) Transparency The total light transmittance and haze value of the laminated body were measured according to JIS K 7631-1 and JIS K 7136.
(8) Photoelasticity coefficient A film having a length of 50 mm and a width of 20 mm was dried at 60 ° C. for 2 hours, and then measured using an ellipsometer (model: M-220) manufactured by JASCO Corporation. As the measurement conditions, a load of 1 N or less was applied to the film, the phase difference at each load was measured, and the photoelastic coefficient was calculated by the following formula.
Re = F × c × d
Re: Phase difference [nm]
F: Stress [N / m ² ]
c: Photoelastic constant [m ² / N]
d: Thickness [nm]
(9) Birefringence index (phase difference expression)
The film is cut into a shape with a width of 10 mm and a length of 100 mm, dried at 120 ° C. for 2 hours, uniaxially stretched in the length direction at a predetermined stretching temperature (glass transition temperature + 10 ° C.) at a stretching speed of 15 mm / min, and lengthened. A 200 mm double stretched film was obtained. The film was observed with a polarizing plate, and after confirming that the film was uniformly stretched, the phase difference was measured with an ellipsometer (model: M-220) manufactured by JASCO Corporation. From the obtained phase difference, the phase difference expression was calculated by the following formula.
Δn (× ^10-3 ) = Ret / d
Δn; Phase difference expression Ret; Phase difference [nm]
d; Film thickness [μm]
(10) Observation of cross Nicol A polarizing plate with a phase difference of 90 ° is placed on a laminate having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm, and white light is incident from one of the polarizing plates to cause interference that appears in the laminate. The degree of birefringence was evaluated by visually observing the colors. The evaluation was performed with ◯: 0 to 1 interference fringe pattern and ×: 2 or more interference fringes.

[Example 1]
A reactor equipped with a thermometer, agitator and a reflux cooler was charged with 4,555 parts of a 48% sodium hydroxide aqueous solution and 22,730 parts of ion-exchanged water, which was charged with 9,9-bis (4-hydroxyphenyl). Fluoren (manufactured by Honshu Chemical Co., Ltd., hereinafter abbreviated as BCF) 596 parts, Bisphenol C (manufactured by Honshu Chemical Co., Ltd., hereinafter abbreviated as BPC) 1,213 parts, Bisphenol A (manufactured by Nippon Steel Chemical Co., Ltd., hereinafter abbreviated as BPA) 2,159 parts, After dissolving 7.94 parts of hydrosphenol (manufactured by Wako Pure Chemical Industries, Ltd.), 13,415 parts of methylene chloride was added, and 2,000 parts of phosgen was blown at 15 to 25 ° C. over about 70 minutes with stirring. After the injection of phosgene was completed, 650 parts of 48% sodium hydroxide aqueous solution and 89.9 parts of p-tert-butylphenol (hereinafter, PTBP) were added, stirring was restarted, and after emulsification, 3.94 parts of triethylamine was added, and further 28 to 35. The reaction was terminated with stirring at ° C. for 1 hour.

After completion of the reaction, the product is diluted with methylene chloride and washed with water, then hydrochloric acid is added to make it acidic and washed with water, and then water washing is repeated until the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water. A methylene solution was obtained. Next, this solution was passed through a filter with an opening of 0.3 μm, and further dropped onto warm water in a kneader with an isolation chamber having a foreign matter take-out port on the bearing portion to flake the polycarbonate resin while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder.

Then, with respect to 100 parts by weight of the powder, 0.05 part by weight of ADEKA ADEKA STAB PEP-36 (bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite) was added to BASF. Irganox 1076 (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate stearyl) was added in an amount of 0.07 parts by weight, mixed uniformly, and then the obtained powder was added. It was put into a heating hopper of a melt extruder heated to 110 ° C. and melt-extruded at 280 ° C. In order to remove foreign matter from the molten polymer, a disc-shaped filter made of stainless non-woven fabric having an average opening of 10 μm was used.

The molten resin after filtration was extruded onto a rotating cooling roll surface having a diameter of 800 mm and a roll surface length of 1800 mm by a die set at 290 ° C. The lip width of the extrusion die was 1500 mm, and the lip gap was about 2 mm. In order to uniformly cool and take over the film, the entire width of the film was brought into close contact with the cooling roll surface by the electrostatic close contact method. A cleanly polished stainless steel piano wire was used as the electrode for electrostatic adhesion. The positive electrode of the DC power supply was connected to this piano wire, and the cooling drum side was grounded. The applied voltage was 7 KV. Thus, a film having a thickness of 100 μm was taken up via a take-off roll at a cooling roll rotation speed of 10 m / min.

Subsequently, the film was passed through a roll suspension type heat treatment machine for heat treatment. Rolls of 100 mmφ were alternately arranged vertically in the roll suspension type heat treatment machine. The distance between the upper and lower rolls was 1.6 m, and the distance from the adjacent roll placed one was 100 mmφ, which is the same as the roll diameter. Then, the film to be treated was prepared so that the length of the film staying in the oven in the roll suspension type heat treatment machine was about 50 m (residence time 60 seconds). The temperature of the hot air in the oven in the heat treatment machine was 145 ° C., and the film tension at the outlet of the oven was 3.0 kg / (thickness 100 μm × total film width 1440 mm) (2.1 kg / square centimeter per cross-sectional load). After leaving the oven, the film was cooled to 60 ° C. or lower in the same manner with a roll suspension type processing machine, and then taken out to room temperature. Both ends of the heat-treated film were cut off by 70 mm to obtain a film having a width of 1300 mm. The results of evaluation using the film are shown in Table 1.

Polycarbonate resin (Teijin Panlite L-1225Y, polycarbonate resin made from BPA) as a substrate is dried at 120 ° C. for 5 hours using a hot air dryer, and then injection compression molding equipped with an injection device having a cylinder inner diameter of 45 mmφ. Molding was performed using a machine (ULTRA220NIV · A manufactured by Sumitomo Heavy Industries, Ltd.). For molding, the film cut out to have substantially the same length and width as the main body of the molded product was mounted on the surface of the mold cavity using static electricity in the mold. As molding conditions, the polycarbonate resin was filled in the mold cavity at a cylinder temperature of 280 ° C. and an injection speed of 50 mm / sec. After cooling, the molded product was taken out from the mold to obtain a polycarbonate resin laminate. The laminated body was a plate-shaped molded product having a main body length of 100 mm, a width of 100 mm, and a thickness of 3 mm. The gate had a film-shaped gate (thickness of the gate portion was 1.5 mm), and the mold temperature was maintained at 100 ° C. using a mold temperature controller. The obtained molded product was evaluated as shown above, and the evaluation results are shown in Table 1.

[Example 2]
A polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that the BPC was 1,618 parts, the BPA was 1,799 parts, and the PTBP was 87.6 parts. The results of various evaluations are shown in Table 1.

[Example 3]
A polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that the BPC was 2,023 parts, the BPA was 1,440 parts, and the PTBP was 82.8 parts. The results of various evaluations are shown in Table 1.

[Example 4]
A polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that 298 parts of BCF, 1,820 parts of BPC, 1,799 parts of BPA, and 71.0 parts of PTBP were used. The results of various evaluations are shown in Table 1.

[Example 5]
A polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that BCF894 parts, BPC1,213 parts, BPA1,979 parts, and PTBP106.5 parts were used. The results of various evaluations are shown in Table 1.

[Comparative Example 1]
A polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that 179 parts of BCF, 2,023 parts of BPC, 1,691 parts of BPA, and 92.3 parts of PTBP were used. The results of various evaluations are shown in Table 1.

[Comparative Example 2]
A polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that the BCF was 1,193 parts, the BPC was 1,618 parts, the BPA was 1,439 parts, and the PTBP was 92.3 parts. The results of various evaluations are shown in Table 1.

[Comparative Example 3]
A polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that 566 parts of BCF, 3,452 parts of BPC, and 80.1 parts of PTBP were used without using BPA. The results of various evaluations are shown in Table 1.

[Comparative Example 4]
A polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that 596 parts of BCF, 3,238 parts of BPA, and 71.0 parts of PTBP were used without using BPC. The results of various evaluations are shown in Table 1.

[Comparative Example 5]
A polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that BPC was 2,023 parts, BPA 1,799 parts, and PTBP 87.6 parts without using BCF. The results of various evaluations are shown in Table 1.

[Comparative Example 6]
A polycarbonate resin film and a laminate were obtained using Teijin's polycarbonate resin Panlite L-1225Y (polycarbonate resin made from BPA). The results of various evaluations are shown in Table 1.

[Comparative Example 7]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 5,126 parts of a 48% sodium hydroxide aqueous solution and 22,377 parts of ion-exchanged water, which were charged with 2,349 parts of BCF and 2,125 parts of BPA. After dissolving 8.95 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.), 13,209 parts of methylene chloride was added, and 2,000 parts of phosgen was blown at 15 to 25 ° C. over about 70 minutes with stirring. After the injection of phosgene was completed, 640 parts of 48% sodium hydroxide aqueous solution and 116.6 parts of PTBP were added, stirring was restarted, 3.94 parts of triethylamine was added after emulsification, and the reaction was further stirred at 28 to 35 ° C. for 1 hour to complete the reaction. did.

After completion of the reaction, the product is diluted with methylene chloride and washed with water, then hydrochloric acid is added to make it acidic and washed with water, and then water washing is repeated until the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water. A methylene solution was obtained. Next, this solution was passed through a filter with a mesh opening of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet in the bearing portion, and the polycarbonate resin was flaked while distilling off methylene chloride, and then the solution was continued. The liquid-containing flakes were crushed and dried to obtain a powder.

Then, with respect to 100 parts by weight of the powder, 0.05 part by weight of Irgafos 168 (manufactured by Ciba Specialty Chemicals), 0.1 part by weight of S-100A (manufactured by Riken Vitamin), and 0.3 parts by weight of Chemisorb 79 (Cemipro). After addition and uniform mixing, a polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that the powder was used. The results of various evaluations are shown in Table 1.

[Comparative Example 8]
In a reactor equipped with a stirrer and a distillation column, 56.3 parts (0.22 mol) of BPC, 49.2 parts (0.23 mol) of diphenyl carbonate, 0.000005 parts of sodium hydroxide as a catalyst and tetramethylammonium hydroxide 0.0016 parts were charged and replaced with nitrogen. The mixture was dissolved while heating to 180 ° C. Then, the stirrer was rotated to keep the internal temperature of the reactor at 220 ° C. The pressure in the reactor was reduced from 101.3 kPa to 13.3 kPa over 40 minutes while distilling off the by-produced phenol. Subsequently, the transesterification reaction was carried out for 80 minutes while maintaining the pressure in the responder at 13.3 kPa and further distilling off phenol.

The internal pressure was reduced from 13.3 kPa to 2 kPa in absolute pressure, and the temperature was further raised to 260 ° C. to remove distilling phenol from the system. Further, the temperature was continuously raised, and after the inside of the reactor reached 0.3 Pa or less, the internal pressure was maintained and the polycondensation reaction was carried out. The final internal temperature in the reactor was 295 ° C. The polycondensation reaction was terminated when the stirrer of the reactor became a predetermined stirring power. The polymerization reaction time in the reactor was 140 minutes. Next, in the molten state, 0.0023 parts (4 × ^10-5 mol / 1 mol of bisphenol) of dodecylbenzene sulfonic acid tetrabutylphosphonium salt was added as a catalyst neutralizer, and the reaction was carried out at 295 ° C. and 10 Torr or less for 10 minutes. The obtained polymer was sent to a vent type twin-screw extruder [KTX-46 manufactured by Kobe Steel, Ltd.] by a gear pump. In the middle of the extruder, tris (2,4-di-tert-butylphenyl) phosphite and phosphite are added, the inlet barrel temperature is 230 ° C, the outlet barrel temperature is 270 ° C, the polycarbonate resin outlet temperature is 285 ° C, and the temperature is removed. It was melt-kneaded and extruded while being mindful, extruded into strands from the outlet of the twin-screw extruder, cooled and solidified with water, and then pelletized with a rotary cutter to obtain polycarbonate resin pellets. A polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that the pellets were used. The results of various evaluations are shown in Table 1.

[Comparative Example 9]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 4,555 parts of a 48% sodium hydroxide aqueous solution and 22,730 parts of ion-exchanged water, which were charged with 2,023 parts of BPC and 1,799 parts of BPA. After dissolving 7.94 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.), 13,415 parts of methylene chloride was added, and 2,000 parts of phosgen was blown at 15 to 25 ° C. over about 70 minutes with stirring. After the injection of phosgene was completed, 650 parts of a 48% aqueous sodium hydroxide solution and 89.9 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 3.94 parts of triethylamine was added, and the mixture was further stirred at 28 to 35 ° C. for 1 hour. And the reaction was finished.

After completion of the reaction, the product is diluted with methylene chloride and washed with water, then hydrochloric acid is added to make it acidic and washed with water, and then water washing is repeated until the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water. A methylene solution was obtained. Next, this solution was passed through a filter with a mesh opening of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet in the bearing portion, and the polycarbonate resin was flaked while distilling off methylene chloride, and then the solution was continued. The liquid-containing flakes were pulverized and dried to obtain a powder (A).

A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 4,936 parts of a 48% sodium hydroxide aqueous solution and 21,550 parts of ion-exchanged water, which were charged with 1,696 parts of BCF and 2,388 parts of BPA. After dissolving 8.17 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.), 19,080 parts of methylene chloride was added, and 2,000 parts of phosgen was blown at 15 to 25 ° C. over about 70 minutes with stirring. After the injection of phosgene was completed, 617 parts of a 48% aqueous sodium hydroxide solution and 85.3 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 3.94 parts of triethylamine was added, and the mixture was further stirred at 28 to 35 ° C. for 1 hour. And the reaction was finished.

After completion of the reaction, the product is diluted with methylene chloride and washed with water, then hydrochloric acid is added to make it acidic and washed with water, and then water washing is repeated until the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water. A methylene solution was obtained. Next, this solution was passed through a filter with a mesh opening of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter take-out port on the bearing portion, and the polycarbonate resin was flaked while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder (B).

90 parts by weight of powder (A), 10 parts by weight of powder (B), 0.05 parts by weight of Irgafos 168 (manufactured by Chivas Specialty Chemicals), 0.1 parts by weight of S-100A (manufactured by RIKEN Vitamin), Chemisorb 790. 3 parts by weight (manufactured by Chemipro Kasei) was added and mixed uniformly. A polycarbonate resin film and a laminate were obtained by the same method as in Example 1 except that such a powder was used. The results of various evaluations are shown in Table 1.

The polycarbonate resin laminate of the present invention has excellent scratch resistance, heat resistance, impact resistance, and low optical distortion. Therefore, for example, resin molded products for optical applications such as liquid crystal displays, head-up displays, and car navigation front plates. It can be used for various display devices such as, protective parts, and automobile interior parts such as translucent parts.

1 T die 2 1st cooling roll 3 2nd cooling roll 4 3rd roll 5 Pair of pick-up rolls

Claims (7)

A polycarbonate resin laminate containing at least a film layer containing a polycarbonate resin (A) and a substrate containing a polycarbonate resin (B) different from the polycarbonate resin (A), wherein the film layer is a surface layer of the polycarbonate resin laminate. A polycarbonate resin laminate characterized by satisfying the following conditions (I) to (IV).
(I) The following formula (1) is used as the main constituent unit of the polycarbonate resin constituting the film layer.

(In the formula (1), R ¹ to R ² are independent hydrogen atoms and alkyl groups having 1 to 6 carbon atoms, respectively.)
The structural unit (a) represented by
The following formula (2)

(In the formula (2), R ³ to R ⁴ are independently alkyl groups having 1 to 6 carbon atoms, and X is a single bond, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, substituted. Alternatively, it is an unsubstituted alkylidene group having 1 to 10 carbon atoms.)
The structural unit (b) represented by and the following formula (3)

(In the formula (3), W is a single-bonded, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and substituted or unsubstituted an alkylidene group having 1 to 10 carbon atoms.)
(II) The thickness of the film layer is 0.05 to 0.5 mm, and the total thickness of the laminated body is 0.8 to 5. 0 mm (III) The glass transition temperature of the polycarbonate resin (A) is 140 ° C. or higher, and the temperature difference from the glass transition temperature of the polycarbonate resin (B) is 10 ° C. or lower (IV) JIS of the film layer. The pencil hardness measured according to K5600 is higher than the pencil hardness of the substrate, and the pencil hardness of the surface layer of the laminated body is H or more. The proportion of the constituent unit (a) in all the constituent units of the polycarbonate resin (A) is 5 to 15 mol%, the proportion of the constituent unit (b) is 20 to 60 mol%, and the proportion of the constituent unit (c) is 25 to 75. The polycarbonate resin laminate according to claim 1, wherein the polycarbonate copolymer is in mol%. Claims 1 to 40, wherein the polycarbonate resin (A) has a viscosity average molecular weight of 15,000 to 40,000, and the polycarbonate resin (B) has a viscosity average molecular weight of 10,000 to 30,000. 2. The polycarbonate resin laminate according to any one of 2. The polycarbonate resin laminate according to any one of claims 1 to 3, wherein the polycarbonate resin (B) is a polycarbonate resin containing at least a structural unit represented by the following formula (4).

The polycarbonate resin laminate according to any one of claims 1 to 4, wherein the film layer has a photoelastic coefficient of 70 × ^10-12 m ² / N or less. The polycarbonate resin laminate according to any one of claims 1 to 5, wherein the film layer has a birefringence of 20 × 10 ^-3 or less. The invention according to any one of claims 1 to 6, wherein the film layer containing the polycarbonate resin (A) is placed in a mold and then the polycarbonate resin (B) is injection-molded. The method for producing a polycarbonate resin laminate according to the above method.

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