JP6055655B2 - Polycarbonate resin molded product - Google Patents

Description

  The present invention relates to a polycarbonate resin molded product, and more particularly to a polycarbonate resin molded product having both high surface hardness and excellent surface impact strength.

  Polycarbonate resin is a thermoplastic resin with excellent impact resistance, heat resistance, and transparency, and is used in a wide range of applications such as automotive interior panels, automotive headlamp lenses, mobile phones and personal digital assistants, LCD TVs, and personal computer housings. Furthermore, since it is lighter and more productive than inorganic glass, it is also used for automobile windows.

  However, the polycarbonate resin using 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), which is widely used at present, has excellent mechanical properties, but has a pencil hardness. The representative surface hardness (2B for polycarbonate resin using bisphenol A) is low.

In order to improve the surface hardness of the polycarbonate resin, many polycarbonate resins or polycarbonate resin compositions have been proposed so far.
For example, in Patent Document 1, it is reported that a copolymer polycarbonate of dimethyl bisphenol cyclohexane and bisphenol A has a high surface hardness of 2H pencil hardness.
In Patent Document 2, the aromatic polycarbonate resin contains a specific amount of a specific (meth) acrylic copolymer, a phosphorus stabilizer, and an ester of an aliphatic alcohol and an aliphatic carboxylic acid. It has been reported that a composition having a high surface hardness can be obtained while maintaining the pencil hardness H and transparency.

  However, in the case of these polycarbonate resins, the surface hardness is certainly improved, but it is still insufficient when a higher surface hardness, a higher impact strength, particularly a high-speed surface impact strength is required.

Special table 2009-500195 gazette JP 2012-025790 A

  In view of the above problems, an object of the present invention is to obtain a polycarbonate resin molded article having high surface hardness and transparency and having excellent surface impact strength without losing the excellent mechanical properties of the polycarbonate resin.

As a result of intensive studies to achieve the above-mentioned problems, the present inventor is a molded product obtained by molding a polycarbonate resin, preferably a polycarbonate resin having a specific structural unit, and has a pencil hardness of HB or more, and A molded product in which the energy at a puncture point in a high-speed surface impact test is a specific value or more and the surface thereof is coated with a cured layer of an energy ray-curable acrylic resin composition The present inventors have found a solution and have completed the present invention.
The present invention provides the following polycarbonate resin molded articles.

[1] The surface of a polycarbonate resin molded article having a pencil hardness according to JIS K5600 of HB or higher and an energy at a puncture point in a high-speed surface impact test according to JIS K7211 of 50 J or higher is an energy ray-curable acrylic resin. A polycarbonate resin molded article coated with a cured product layer of the composition.
[2] The polycarbonate resin molded product according to the above [1], wherein the molded product coated with the cured product layer has an energy at a puncture point in a high-speed surface impact test according to JIS K7211 of 8 J or more.

[3] The polycarbonate resin is a polycarbonate resin composition containing at least a polycarbonate resin (i) and a polycarbonate resin (ii), wherein the mass ratio of the polycarbonate resin (i) and the polycarbonate resin (ii) is 80/20 to The polycarbonate resin molded article according to the above [1] or [2], which is 20/80.
(I) A polycarbonate resin having a structural unit represented by the following general formula (1) and having a viscosity average molecular weight (Mv) of 20,000 to 35,000
(In the general formula (1), R ¹ represents a methyl group, R ² and R ³ each independently represents a hydrogen atom or a methyl group, and X represents
R ⁴ and R ⁵ each independently represents a hydrogen atom or a methyl group, and Z represents an alicyclic carbon hydrogen having 6 to 12 carbon atoms and optionally having a substituent by bonding to C. The group to be formed is shown. )
(Ii) A polycarbonate resin having a structural unit represented by the following general formula (2) and having a viscosity average molecular weight (Mv) of 16,000 to 28,000
(X in the general formula (2) has the same meaning as the general formula (1).)

[4] The polycarbonate resin molded article according to the above [3], wherein R ² and R ³ in the general formula (1) are hydrogen atoms and X is an isopropylidene group.
[5] The polycarbonate resin molded article according to the above [3] or [4], wherein X in the general formula (2) is an isopropylidene group.
[6] The molded product according to any one of [1] to [5], wherein the molded product is any one of an automobile interior panel, an automobile lamp lens, a window, or a housing.

  According to the polycarbonate resin molded product of the present invention, a polycarbonate resin molded product having both high surface hardness and excellent surface impact strength can be provided. In particular, both the surface hardness and the surface impact strength after forming the cured product layer can be improved in a balanced manner.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples.
In addition, in this-application specification, unless there is particular notice, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

[Overview]
As described above, the polycarbonate resin molded product of the present invention is a polycarbonate resin molded product having a pencil hardness according to JIS K5600 of HB or higher and an energy at a puncture point in a high-speed surface impact test according to JIS K7211 of 50 J or higher. It is a polycarbonate resin molded article whose surface is coated with a cured product layer of an energy ray curable acrylic resin composition.
Hereinafter, each component used for the polycarbonate resin molded product of the present invention, a method for producing the molded product, and the like will be described in detail.

[Polycarbonate resin]
As the polycarbonate resin used for the polycarbonate resin molded product of the present invention, those having a pencil hardness of JIS K5600 or higher are used. Examples of the polycarbonate resin include an aliphatic polycarbonate resin and an aromatic-aliphatic polycarbonate resin. In the present invention, an aromatic polycarbonate resin is preferably used. Specifically, an aromatic dihydroxy compound is converted to phosgene or a diester of carbonic acid. A thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting is used.

The pencil hardness of the polycarbonate resin used has a hardness equal to or higher than HB. Here, the pencil hardness is measured in accordance with JIS K5600-5-4.
If the pencil hardness is lower than HB, the surface hardness of the molded product molded from this is low, and the effect of improving the surface hardness of the molded product whose surface is coated with a cured product layer of an energy ray-curable acrylic resin composition is small. The surface becomes easily damaged during use. The pencil hardness of the polycarbonate resin is preferably F or higher, particularly H or higher.

  The polycarbonate resin having such pencil hardness is represented by the following polycarbonate resin (i) having at least a structural unit represented by the following general formula (1) in the molecule and the following general formula (2). A polycarbonate resin composition comprising a polycarbonate resin (ii) having a structural unit is preferred.

[Polycarbonate resin (i)]
Preferable examples of the polycarbonate resin (i) include a polycarbonate resin (i) having at least a structural unit represented by the following general formula (1) in the molecule.
(In the general formula (1), R ¹ represents a methyl group, R ² and R ³ each independently represents a hydrogen atom or a methyl group, and X represents
R ⁴ and R ⁵ each independently represents a hydrogen atom or a methyl group, and Z represents an alicyclic carbon hydrogen having 6 to 12 carbon atoms and optionally having a substituent by bonding to C. The group to be formed is shown. )

In the general formula (1), R ¹ is a methyl group, and R ² and R ³ are each independently a hydrogen atom or a methyl group, but R ² and R ³ are particularly preferably a hydrogen atom.

X is
Is preferably an isopropylidene group in which both R ⁴ and R ⁵ are methyl groups, and X is
In this case, Z is bonded to carbon C bonded to the two phenyl groups in the above formula (1) to form a bivalent alicyclic hydrocarbon group having 6 to 12 carbon atoms. Examples of the alicyclic carbon hydrogen group include a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, a cyclododecylidene group, and the like. Examples of the substituted ones include those having these methyl substituents and ethyl substituents. Among these, a cyclohexylidene group, a methyl-substituted cyclohexylidene group (preferably 3,3,5-trimethyl-substituted), and a cyclododecylidene group are preferable.

Preferable specific examples of the polycarbonate resin (i) used in the present invention include the following polycarbonate resins (a) to (d).
A) having a 2,2-bis (3-methyl-4-hydroxyphenyl) propane structural unit, that is, a structural unit in which R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, and X is an isopropylidene group What you have,
B) a 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane structural unit, that is, a structural unit in which R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, and X is a cyclododecylidene group. What you have.
C) 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane structural unit, that is, a structural unit in which R ¹ is a methyl group, R ² and R ³ are methyl groups, and X is an isopropylidene group thing,
D) 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane structural unit, that is, having a structural unit in which R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, and X is a cyclohexylidene group ,
Among these, the polycarbonate resin of the above a), b) or c), more preferably the above b) or b), and particularly b) above is preferred.

  These polycarbonate resins (i) are respectively 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane, and 2,2-bis. (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane can be used as the dihydroxy compound.

  The polycarbonate resin (i) may have a carbonate structural unit other than the structural unit represented by the general formula (1). For example, the structural unit represented by the general formula (2) (for example, derived from bisphenol-A) (Structural unit) or a structural unit derived from another dihydroxy compound as described later. The copolymerization amount of structural units other than the structural unit represented by the general formula (1) is usually 60 mol% or less, preferably 50 mol% or less, more preferably 40 mol% or less, and further 30 mol% or less. Is most preferred.

The viscosity average molecular weight (Mv) of the polycarbonate resin (i) preferably used in the present invention is preferably 20,000 to 35,000. When the viscosity average molecular weight is within this range, a molded article having good moldability and high mechanical strength can be obtained. When the viscosity average molecular weight is less than 20,000, the surface impact resistance is deteriorated, which causes a problem in practical use. If it exceeds 000, the melt viscosity increases, and it tends to be difficult to perform injection molding or extrusion molding. The lower limit of the molecular weight of the polycarbonate resin (i) is more preferably 22,000, more preferably 23,000, particularly preferably 24,000, and the upper limit is more preferably 33,000, still more preferably 32,500. It is.
Here, the viscosity average molecular weight (Mv) is determined using the Schnell viscosity equation, using dichloromethane as a solvent, using an Ubbelohde viscometer, and determining the intrinsic viscosity ([η]) (unit dl / g) at a temperature of 20 ° C. : Means a value calculated from the equation of η = 1.23 × 10 ⁻⁴ M ^0.83 .

  The polycarbonate resin (i) may be used singly or in combination of two or more, and may be adjusted to the viscosity average molecular weight by mixing two or more types of polycarbonate resins having different viscosity average molecular weights. Moreover, you may mix and use the polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

<Polycarbonate resin (ii)>
The polycarbonate resin (ii) used in combination with the polycarbonate resin (i) is a polycarbonate resin having a structural unit represented by the following general formula (2).
(X in the general formula (2) has the same meaning as the general formula (1).)

A preferable specific example of the polycarbonate structural unit represented by the general formula (2) is 2,2-bis (4-hydroxyphenyl) propane, that is, a carbonate structural unit derived from bisphenol-A.
The polycarbonate resin (ii) may have a carbonate structural unit other than the structural unit represented by the general formula (2), and may have a carbonate structural unit derived from another dihydroxy compound. The copolymerization amount of structural units other than the structural unit represented by the general formula (2) is usually preferably less than 50 mol%, more preferably 40 mol% or less, further 30 mol% or less, and particularly 20 mol% or less. 10 mol% or less, and most preferably 5 mol% or less.

Examples of other dihydroxy compounds include the following aromatic dihydroxy compounds.
Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-) (1-methylethyl) phenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3- (1-methylpropyl) phenyl) propane 2,2-bis (4-hydroxy-3-cyclohexylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) Phenylmethane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3) -(1-methylethyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) Cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, 1,1- (4-hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) -1- Phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclopent Tan, 1,1-bis (4-hydroxyphenyl) cyclooctane, 4,4 ′-(1,3-phenylenediisopropylidene) bisphenol, 4,4 ′-(1,4-phenylenediisopropylidene) bisphenol, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxyphenyl ether, 4,4 '-Dihydroxybiphenyl, 1,1-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane, 1,1-bis (4-hydroxy-6-methyl-3-tert-butylphenyl) butane, etc. Can be mentioned.

The viscosity average molecular weight (Mv) of the polycarbonate resin (ii) is preferably 16,000 to 28,000. When the viscosity average molecular weight is within this range, a molded product having good moldability and high mechanical strength can be obtained. When the viscosity average molecular weight is less than 16,000, the surface impact resistance is remarkably lowered, and thus it is difficult to use. If it exceeds 28,000, the melt viscosity increases and injection molding or extrusion tends to be difficult. The minimum of the more preferable molecular weight of polycarbonate resin (ii) is 17,000, More preferably, it is 18,000, The upper limit is more preferably 27,000.
The definition of the viscosity average molecular weight (Mv) is as described above.

  The polycarbonate resin (ii) may be used singly or in combination of two or more, and may be adjusted to the above viscosity average molecular weight by mixing two or more types of polycarbonate resins having different viscosity average molecular weights. Moreover, you may mix and use the polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

<Production method of polycarbonate resin>
The method for producing the polycarbonate resin used in the present invention is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, a particularly preferable one of these methods will be specifically described.

-Interfacial polymerization method First, the case where a polycarbonate resin is manufactured by the interfacial polymerization method will be described.
In the interfacial polymerization method, in the presence of an organic solvent inert to the reaction and an alkaline aqueous solution, the pH is usually kept at 9 or more, and each dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted, followed by polymerization. A polycarbonate resin is obtained by performing interfacial polymerization in the presence of a catalyst. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present if necessary, and an antioxidant may be present for the purpose of preventing oxidation of the dihydroxy compound.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate. Among them, sodium hydroxide and Potassium hydroxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. In particular, it is preferably set to 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the molecular weight regulator include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, and the like. Among them, aromatic phenols are preferable.
Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-oxinebenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a polycarbonate resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt transesterification method Next, the case where polycarbonate resin is manufactured by the melt transesterification method is demonstrated. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. It is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, a polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among these, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the conditions in this range while removing by-products such as hydroxy compounds.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. In the case of a batch system, the order of mixing the reaction substrate, reaction medium, catalyst, additive, etc. is arbitrary as long as the desired polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. However, in view of the stability of the polycarbonate resin and the polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 mass ppm or more normally with respect to polycarbonate resin, and is 100 mass ppm or less normally, Preferably it is 20 mass ppm or less.

<Ratio of polycarbonate resin (i) and (ii)>
The mixing ratio of the polycarbonate resin (i) and the polycarbonate resin (ii) preferably used as the polycarbonate resin used in the present invention is a mass ratio of both, and the polycarbonate resin (i) / polycarbonate resin (ii) = 80/20 to 20 / 80 is preferable. By using it in such a mixing ratio, it becomes possible to achieve high surface hardness, surface impact resistance, and further high transparency. When the mass ratio of the polycarbonate resin (i) is less than 20, the surface hardness of the molded product is lowered, and the surface is likely to be damaged when it is made into an actual product, and when it exceeds 80, the surface impact resistance of the molded product is increased. Decreases, and it becomes easy to break when made into a real product.
A preferable mixing ratio is polycarbonate resin (i) / polycarbonate resin (ii) = 80/20 to 30/70.

Moreover, 10 mass% or more of polycarbonate resin (i) and polycarbonate resin (ii) may be used as flaky powder in 100 mass% in total of polycarbonate resin (i) and polycarbonate resin (ii). The content ratio of the flaky powder is preferably 15% by mass or more, more preferably 20% by mass or more. By including the flaky powder at such a ratio, the additive components are prevented from being classified during the production of the composition when additives are added as necessary, as described below. It tends to be easy to obtain a molded product that suppresses agglomeration and the like and is excellent in flame retardancy, surface impact resistance, and transparency. The average particle size of the flaky powder is preferably 2 mm or less, and more preferably 1.5 mm or less.
The polycarbonate resin other than the flaky powder is preferably a pellet. The pellet length is preferably 1 to 5 mm, more preferably 2 to 4 mm. When the cross section is elliptical, the major axis is 2 to 3.5 mm, the minor axis is 1 to 2.5 mm, and the section is circular. Those having a diameter of 2 to 3 mm are preferred. The length and cross-sectional shape of the pellet can be adjusted by the number of rotations of the blade of the strand cutter during the production of the polycarbonate resin, the winding speed, the discharge amount of the extruder, and the like.

[Other ingredients]
The polycarbonate resin composition may contain other components other than those described above as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer ( AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin), styrene-based acrylonitrile-butadiene-styrene copolymer (ABS resin), etc. Resins; Polyolefin resins such as polyethylene resins and polypropylene resins; Polyamide resins; Polyimide resins; Polyetherimide resins; Polyurethane resins; Polyphenylene ether resins; Rensulfide resin; polysulfone resin; (meth) acrylate copolymer and the like.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.
When it contains other resins, it is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less, based on a total of 100% by mass of the polycarbonate resin and other resins. More preferably. When other resin is used more than the above range, surface hardness, surface impact strength, and transparency may be lowered.

-Resin additives Examples of resin additives include heat stabilizers, antioxidants, mold release agents, UV absorbers, flame retardants, dyes and pigments, antistatic agents, antifogging agents, lubricants, antiblocking agents, and fluidity. Examples include improvers, plasticizers, dispersants, and antibacterial agents. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
Hereinafter, the example of an additive suitable for the polycarbonate resin composition used for this invention is demonstrated concretely.

.. Heat stabilizer Examples of the heat stabilizer include phosphorus compounds. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
Specific examples of such organic phosphite compounds include, for example, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 "," JP-3CP "," Irgaphos 168 "manufactured by Ciba Specialty Chemicals, and the like.
In addition, 1 type may contain the heat stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the heat stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, based on 100 parts by mass of the polycarbonate resin. It is not more than part by mass, preferably not more than 0.7 part by mass, more preferably not more than 0.5 part by mass. If the heat stabilizer content is less than or equal to the lower limit of the range, the heat stability effect may be insufficient, and if the heat stabilizer content exceeds the upper limit value of the range, the effect reaches a peak. And may become less economical.

.. Antioxidants Examples of antioxidants include hindered phenol antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-te t- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such phenolic antioxidants include “Irganox 1010” and “Irganox 1076” manufactured by Ciba Specialty Chemicals, “Adekastab AO-50” and “Adekastab AO” manufactured by ADEKA. -60 "and the like.
In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the antioxidant is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 part by mass with respect to 100 parts by mass of the polycarbonate resin. Or less. When the content of the antioxidant is less than or equal to the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

.. Release agent Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oil, and the like. Can be mentioned.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an aliphatic includes an alicyclic compound here.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

In addition, 1 type may contain the mold release agent mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.
The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass or less with respect to 100 parts by mass of the polycarbonate resin. It is. When the content of the release agent is not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

..Ultraviolet absorbers Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, Examples include organic ultraviolet absorbers such as hindered amine compounds. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorbent, the transparency and mechanical properties of the polycarbonate resin composition are improved.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, among others, 2- (2′- Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] And 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferable.

  Specific examples of such benzotriazole compounds include “Seesorb 701”, “Seesorb 702”, “Seesorb 703”, “Seesorb 704”, and “Seesorb 705” manufactured by Sipro Kasei Co., Ltd. (trade names, the same applies hereinafter). , “Seasorb 709”, “Biosorb 520”, “Biosorb 580”, “Biosorb 582”, “Biosorb 583” manufactured by Kyodo Yakuhin Co., Ltd. UV5411, ADEKA "LA-32", "LA-38", "LA-36", "LA-34", "LA-31", Ciba Specialty Chemicals "Tinubin P", "Tinubin" 234 "," Tinuvin 326 "," Tinubin 327 "," Chinubi 328 ", and the like.

The content of the ultraviolet absorber is usually 0.001 parts by mass or more, preferably 0.1 parts by mass or more, and usually 1 part by mass or less, preferably 0.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin. Or less. When the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance is poor, and when the content of the UV absorber exceeds the upper limit of the above range, mold deposits and the like occur and mold contamination Easy to cause.
In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

[Production Method of Polycarbonate Resin Composition]
There is no limitation on the production method of the polycarbonate resin composition for molding the molded product of the polycarbonate resin, and the production method of the known polycarbonate resin composition can be widely adopted, and the polycarbonate resin and other components blended as necessary For example, after mixing in advance using various mixers such as a tumbler and a Henschel mixer, a method of melt kneading with a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. It is done. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[Molding]
The obtained polycarbonate resin composition is formed into a molded product by molding pellets obtained by pelletizing the above-described polycarbonate resin composition by various molding methods. Further, the resin melt-kneaded by an extruder can be directly molded into a molded product without going through the pellets.
The shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. For example, a plate shape, a plate shape, a rod shape, a sheet shape, a film shape, a cylindrical shape, an annular shape, Circular, elliptical, polygonal, irregular, hollow, frame, box, panel, etc. Specific examples include automobile interior panels, automobile (two-wheeler) headlamps, etc. Examples include various shapes such as lenses, windows, housings, and special shapes. Further, for example, the surface may be uneven or may have a three-dimensional curved surface. Moreover, when using as a sheet | seat, a film, plate shape, etc., the laminated body of the multilayer structure laminated | stacked with the other resin sheet may be sufficient.

  The method for molding a molded product is not particularly limited, and a conventionally known molding method can be employed.For example, an injection molding method, an injection compression molding method, an extrusion molding method, a profile extrusion method, a transfer molding method, a hollow molding method, Gas assisted hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotational molding method, multilayer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method And a pressure molding method.

The molded product thus obtained has a pencil hardness according to JIS K5600 of HB or higher and an energy at a puncture point in a high-speed surface impact test according to JIS K7211 of 50 J or higher. When the pencil hardness is lower than HB, even when a cured product layer is formed on the molded product, the surface hardness of the molded product is low, and when the product is used as an actual product, the surface is easily damaged. The pencil hardness is preferably F or higher, particularly H or higher. In addition, when the energy at the puncture point is less than 50 J, the surface impact strength is low even when a cured product layer is formed on the molded product, and there are problems such as cracking and chipping in the market when making an actual product. There is a very high risk of causing
The energy at the puncture point in the high-speed surface impact test of the molded product before the cured product layer is formed conforms to JIS K7211-2, striker diameter 20 mm, sample support 40 mm, punching test speed 4.4 m / Measured under the conditions of sec and temperature of 23 ° C.

[Hardened material layer]
In the present invention, the surface of the polycarbonate resin molded article is covered with a cured product layer of an energy ray curable acrylic resin composition. Examples of energy rays include radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays, and ultraviolet ray curable types are preferable from the viewpoints of practicality, workability, working environment, and the like.
As the energy ray curable acrylic resin composition, a resin composition containing an acrylic photopolymerizable prepolymer or a photopolymerizable monomer as a main component and a photopolymerization initiator added thereto can be used. .

Examples of the acrylic photopolymerizable prepolymer include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and melamine (meth) acrylate.
Examples of the acrylic photopolymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-e Xoxyethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Mention of methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, etc. Can do.
Moreover, you may use these individually or in mixture of 2 or more types.

Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2 -Hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc. Acetophenones; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthioxanthone, 2-isopropyl Thioxanthones such as thioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide and 4,4′-bismethylaminobenzophenone; And phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
Moreover, you may use these individually or in mixture of 2 or more types.

  Various additions such as light stabilizers, UV absorbers, antioxidants, antifoaming agents, viscosity modifiers, anti-sagging agents, flame retardants, pigments / dyes, antistatic agents, etc. to energy ray curable acrylic resin compositions An agent or additive aid may be added.

The energy ray-curable acrylic resin composition as described above is coated on the surface of the polycarbonate resin molded article to form a cured product layer.
Coating can be performed by appropriately selecting a coating method according to the shape of the molded product from known coating methods, such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, and a spin coating method. Method, roller coating method and the like.

The atmosphere for irradiating active energy rays is usually preferably an inert gas atmosphere such as nitrogen gas or carbon dioxide gas, but depending on the type of acrylic resin composition, it can be sufficiently cured even when the oxygen content in the atmosphere is high to some extent. It is also possible to form a physical layer.
The thickness of the cured product layer is preferably about 1 to 30 μm, more preferably 5 μm or more, and the upper limit is more preferably 25 μm or less.

[Molded product with cured product layer]
The molded article on which the cured product layer obtained in this way is formed has a very high effect of improving the pencil hardness by forming the cured product layer. The molded article on which the cured product layer is formed preferably has a pencil hardness according to JIS K5600 of 3H or more, and more preferably 4H or more. Further, the resin molded product of the present invention maintains a good energy at the puncture point in the high-speed surface impact test according to JIS K7211, even when a cured product layer is formed, and the energy at the puncture point is preferably Is 8 J or more, more preferably 10 J or more. When the energy at the puncture point when this cured product layer is formed is less than 8 J, the molded product on which the cured product layer is formed is very brittle, and independent sharp debris is formed by breakage due to impact. . For example, when such a molded product is used for an automobile window, the sharp fragments are not preferable because they are very dangerous for passengers.

  In addition, the energy at the puncture point in the high-speed surface impact test of the molded product on which the cured product layer is formed conforms to JIS K7211-2, the striker diameter is 5/8 inch (about 15.9 mm), the sample support is 40 mm, It is measured by punching from the cured product layer side at a punching test speed of 4.4 m / sec and a temperature of 23 ° C.

The molded product of the present invention having a cured product layer formed thereon has excellent mechanical properties, high surface hardness and surface impact resistance, and can be preferably applied to the following, for example.
・ Window glass of buildings (buildings, houses, greenhouses, etc.); window glass of cars, airplanes, construction machinery; roofs of garages, arcades, etc .; sunroofs, roof panels, awnings;
・ Lighting lenses, traffic light lenses, optical equipment lenses; lens covers; mirrors, glasses, goggles, motorcycle windshields; solar cell covers; protective covers;
・ Various lamp covers for automobiles such as headlamps, inner lenses, and rear lamps; automotive interior panels;
・ Display device covers, display panel members, parts for gaming machines (pachinko, etc.);
・ Various portable terminals, cameras, game machines, etc., electrical and electronic equipment and OA equipment enclosures; helmets;
-Film (sheet) and its laminated body.
It is particularly suitable for automobile interior panels, automobile lamp lenses, windows, housings, and the like.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
The raw materials used in the following examples and comparative examples are as follows.

[Polycarbonate resin]
As a polycarbonate resin corresponding to the above-described polycarbonate resin (i), a polycarbonate resin (hereinafter “PC-1”) according to the following production example was used.
(1) Production of polycarbonate resin (PC-1):
2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter referred to as “BPC”) 26.14 mol (6.75 kg) and diphenyl carbonate 26.66 mol (5.71 kg) The reactor was placed in a SUS reactor (with an internal volume of 40 liters) equipped with a stirrer and a distillation condenser, and after the inside of the reactor was replaced with nitrogen gas, the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction liquid in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is used as a transesterification reaction catalyst in the molten reaction liquid so that it becomes 1.5 × 10 ⁻⁶ mol per 1 mol of BPC. In addition, the reaction solution was stirred and brewed at 220 ° C. for 30 minutes in a nitrogen gas atmosphere. Next, under the same temperature, the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further performed for 100 minutes to distill phenol.

Next, the temperature in the reactor was raised to 280 ° C. over 60 minutes and the pressure was reduced to 3 Torr to distill phenol corresponding to almost the entire distillation theoretical amount. Next, the pressure in the reactor was kept below 1 Torr under the same temperature, and the reaction was further continued for 80 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rotations / minute, the reaction liquid temperature immediately before the completion of the reaction was 300 ° C., and the stirring power was 1.40 kW.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4-fold molar amount of butyl p-toluenesulfonate is supplied from the first supply port of the twin screw extruder with respect to cesium carbonate, After kneading with the reaction solution, the reaction solution was extruded into a strand through a die of a twin-screw extruder and cut with a cutter to obtain carbonate resin (PC-1) pellets.

The physical properties of the obtained polycarbonate resin (PC-1) were as follows.
Pencil hardness: 2H
Viscosity average molecular weight (Mv): 32,000

Moreover, the following polycarbonate resin (PC-3) was used as polycarbonate resin (Mv = 17,100) which does not correspond to above-mentioned polycarbonate resin (i).
Further, as a polycarbonate resin corresponding to the above-described polycarbonate resin (ii), a polycarbonate resin (hereinafter referred to as “PC-2” and “PC-4”) is replaced with a polycarbonate resin (Mv = 15) not corresponding to the polycarbonate resin (ii). , 000), the following polycarbonate resin (PC-5) was used.
(2) PC-2
Polycarbonate resin by melting method using bisphenol-A as a starting material Mitsubishi Engineering Plastics Co., Ltd. Trade name “NOVAREX M7027BF”
Pencil hardness 2B
Viscosity average molecular weight (Mv) 26,000
(3) PC-3
Polycarbonate resin starting from 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane, manufactured by SABIC, trade name “Lexan DMX2415”
Pencil hardness 2H
Viscosity average molecular weight (Mv) 17,100
(4) PC-4
Polycarbonate resin by the interfacial method using bisphenol-A as a starting material. Product name “Iupilon S-3000” manufactured by Mitsubishi Engineering Plastics.
Pencil hardness 2B
Viscosity average molecular weight (Mv) 21,000
(5) PC-5
Polycarbonate resin by the interfacial method using bisphenol-A as a starting material Product name “Iupilon H-4000” (flaked powder) manufactured by Mitsubishi Engineering Plastics
Pencil hardness 2B
Viscosity average molecular weight (Mv) 15,000

The viscosity average molecular weight (Mv) of the polycarbonate resin was determined by dissolving the polycarbonate resin in dichloromethane (concentration 6.0 g / L) and measuring the specific viscosity (η _sp ) at 20 ° C. using an Ubbelohde viscosity tube. The viscosity average molecular weight (Mv) was calculated from the formula.
η _sp /C=[η](1+0.28η _sp)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
In addition, the pencil hardness of the polycarbonate resin is a multi-purpose injection molded in accordance with JIS K7152, using an injection molding machine (J55AD manufactured by Nippon Steel Works) under conditions of a barrel temperature of 280 ° C. and a mold temperature of 80 ° C. The surface hardness of the test piece was determined in accordance with JIS K5600-5-4, and the pencil hardness measured at a load of 750 g using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) was obtained.

[Energy ray curable acrylic resin composition]
The following acrylic ultraviolet curable resin composition was used.
Product name "Diabeam UL-1167" manufactured by Mitsubishi Rayon Co., Ltd.

(Examples 1-2, Comparative Examples 1-3)
[Production of polycarbonate resin composition pellets]
Each component described above was blended in the proportions (parts by mass) shown in Table 1, mixed for 20 minutes with a tumbler, and then a single screw extruder with a vent with a screw diameter of 40 mm (“VS-40” manufactured by Tanabe Plastic Machinery Co., Ltd.). ) Was melt-kneaded at a cylinder temperature of 280 ° C., and pellets were obtained by strand cutting.

[Create specimen]
The obtained pellets were subjected to a resin temperature of 300 ° C., a mold temperature of 80 ° C., an injection time of 1.8 sec, an injection pressure of 140 MPa, a holding pressure of 65 MPa, and a holding time by using an injection molding machine (J220) manufactured by Nippon Steel Works. A flat test piece of 100 mm × 100 mm × 4 mmt was molded under the conditions of 10 sec and cooling time 20 sec.

[Formation of cured product layer]
Next, the acrylic ultraviolet curable resin composition is applied onto a flat test piece, and then the solvent is blown off in an infrared drying oven at 60 ° C. for 90 seconds, and ultraviolet rays are integrated with a high-pressure mercury lamp to 1000 mJ / cm ^2. Irradiation was performed to obtain a test piece on which a cured product layer having a thickness of 10 μm was formed.
The following evaluation and measurement were performed on the obtained test pieces.

[Measurement of pencil hardness]
About the flat test piece before and after the cured product layer formation, the pencil hardness measured at a load of 750 g was obtained using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.) in accordance with JIS K5600-5-4. . In addition, about the flat test piece after hardened | cured material layer formation, the pencil hardness of the hardened | cured material layer side was measured.

[High-speed surface impact test]
In accordance with JIS K7211-2, using a high-speed puncture impact tester “Hydroshot HITS-P10” manufactured by Shimadzu Corporation, a flat test piece before forming a cured product layer has a striker diameter of 20 mm, a sample support of 40 mm, As for the flat test piece after measurement at a punching test speed of 4.4 m / sec and a temperature of 23 ° C. and forming a cured product layer, the striker diameter is 5/8 inch (about 15.9 mm), the sample support is 40 mm, the punching test speed. It measured by punching from the hardened | cured material layer side at 4.4 m / sec and the temperature of 23 degreeC (unit: J).
The above evaluation results are shown in Table 1 below.

As is apparent from Table 1, the molded articles of the examples have remarkably high hardness with pencil hardness F of 3H and H of 4H before and after the formation of the cured product layer. Further, the molded product before the formation of the cured product layer has a very high surface impact strength of 66 J and 75 J, and it can be seen that even when the cured product layer is formed, the surface impact strength can be maintained well. On the other hand, in Comparative Examples 1-2, the hardness originally high as 2H is 4H-5H, and the improvement width of the hardness is small and the surface impact strength is remarkably bad. In Comparative Example 3, the pencil hardness is increased only to H. It is shown that.
Therefore, it can be seen that the object of the present invention to provide a polycarbonate resin molded article having high surface hardness and surface impact resistance is achieved only when all the requirements of the present invention are satisfied.

  The polycarbonate resin molded product of the present invention has excellent mechanical properties and has high surface hardness and surface impact resistance, so it can be suitably used in a wide range of fields such as automobiles, electrical / electronic devices, and houses, Industrial applicability is very high.

Claims (3)

The surface of a polycarbonate resin molded article having a pencil hardness according to JIS K5600 of HB or higher and an energy at a puncture point in a high-speed surface impact test according to JIS K7211 of 50 J or higher is made of an energy ray curable acrylic resin composition. A polycarbonate resin molded article coated with a cured product layer ,
The polycarbonate resin is a polycarbonate resin composition containing at least a polycarbonate resin (i) and a polycarbonate resin (ii), wherein the mass ratio of the polycarbonate resin (i) and the polycarbonate resin (ii) is 80/20 to 20/80. A polycarbonate resin molded product characterized by
(I) A polycarbonate resin having a structural unit represented by the following general formula (1) and having a viscosity average molecular weight (Mv) of 20,000 to 35,000
(In general formula (1), R ¹ is a methyl group, R ² and R ³ are hydrogen atoms, and X is an isopropylidene group.)
(Ii) A polycarbonate resin having a structural unit represented by the following general formula (2) and having a viscosity average molecular weight (Mv) of 16,000 to 28,000
(X in the general formula (2) is an isopropylidene group.)
A molded polycarbonate resin product.   2. The polycarbonate resin molded product according to claim 1, wherein the molded product coated with the cured product layer has an energy at a puncture point of 8 J or more in a high-speed surface impact test according to JIS K7211. The molded article according to claim 1 or 2 , wherein the molded article is any one of an automobile interior panel, an automobile lamp lens, a window, and a casing.