JP2021088651A - Polycarbonate resin composition and molded article - Google Patents

Abstract

To provide a polycarbonate resin composition excellent in balance of various characteristics such as transparency, impact resistance, heat resistance, scratch resistance and optical characteristics, and a molded article using the composition.SOLUTION: The polycarbonate resin composition contains: a polycarbonate resin containing a specific oxygen-containing heterocyclic structural unit; a first acrylic resin containing 5-50 wt.% of a structural unit of formula (2) and 50-95 wt.% of a methyl methacrylate structural unit; and a second acrylic resin containing 90 wt.% or more of a methyl methacrylate structural unit and containing no structural unit of formula (2).SELECTED DRAWING: None

Description

The present invention relates to a polycarbonate resin composition having excellent transparency, impact resistance, heat resistance, scratch resistance, optical properties, etc., and a molded product using the same.

Conventionally, glass plates have been used for front plate applications for protecting the display surface of liquid crystal televisions and the like, and for glazing applications for automobiles, from the viewpoints of transparency, heat resistance, weather resistance, scratch resistance, and the like. In recent years, in the above applications, there is an increasing demand for weight reduction of members and improvement of design such as curved surface shape. Acrylic resins, polycarbonate resins, etc., which are lightweight, have excellent transparency, and can be molded into any shape, are being studied as resin glasses, but acrylic resins have the drawback of brittleness, and polycarbonate resins also have weather resistance. It has drawbacks such as scratch resistance and double refraction.

On the other hand, since there is concern about global warming due to the depletion of petroleum resources and the increase in carbon dioxide emissions, the development of plastics made from plant-derived monomers has been required in recent years. Polycarbonate resins manufactured using a certain isosorbide (hereinafter, may be referred to as "ISB") have been developed and have begun to be used for automobile parts applications, optical applications, and glass substitute applications (for example, Patent Document 1, Patent Document 1, 2).

Polycarbonate resins obtained from ISBs are not only excellent in optical properties, but also excellent in weather resistance and surface hardness as compared with conventional general-purpose aromatic polycarbonate resins, and are therefore being studied for display front panel applications. (For example, Patent Document 3).

International Publication No. 2004/111106 Pamphlet International Publication No. 2007/148604 Pamphlet Japanese Unexamined Patent Publication No. 2014-174271

No material has yet been found that can meet all of the characteristics required for display front panel applications and automobile glazing applications, and the market demands resin materials that maintain high transparency and further improve other characteristics. Has been done. Especially when compared with glass, it is necessary to improve scratch resistance and optical characteristics (low birefringence).

As a result of diligent studies to solve the above problems, the present inventors have found that a polycarbonate resin composition containing two kinds of acrylic resins has transparency, impact resistance, heat resistance, scratch resistance, optical properties, and the like. It was found that the balance of various characteristics is excellent. That is, the gist of the present invention is as follows.

[1] A polycarbonate resin containing a structural unit represented by the following formula (1) and
A first acrylic resin containing 5% by weight or more and 50% by weight or less of the structural unit represented by the following formula (2) and 50% by weight or more and 95% by weight or less of the methyl methacrylate structural unit.
A polycarbonate resin composition containing a second acrylic resin containing 90% by weight or more of a methyl methacrylate structural unit and not containing a structural unit represented by the following formula (2).

(In the formula (2), R ¹ is a hydrogen atom and an alkyl group having 1 to 10 carbon atoms which may ^{have a substituent. R 2} is an aryl group and a substituent which may have a substituent. It is an aralkyl group that may have.)
[2] The glass transition temperature of the polycarbonate resin is 90 ° C. or higher and 150 ° C. or lower.
The polycarbonate resin composition according to [1].
[3] The polycarbonate resin composition according to [1] or [2], wherein the polycarbonate resin contains a structural unit derived from an aliphatic dihydroxy compound or an alicyclic dihydroxy compound.
[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the structural unit represented by the formula (1) in the polycarbonate resin is 30% by weight or more and 90% by weight or less.
[5] The structural unit represented by the formula (2) is a phenyl methacrylate structural unit, [1]
] To [4]. The polycarbonate resin composition according to any one of the items.
[6] The polycarbonate resin is contained in an amount of 50% by weight or more and 95% by weight or less, [1] to
The polycarbonate resin composition according to any one of [5].
[7] The refractive index of the first acrylic resin and the refractive index of the second acrylic resin are different, [1]
The polycarbonate resin composition according to any one of [6].
[8] The polycarbonate according to any one of [1] to [7], wherein the refractive index of the polycarbonate resin is smaller than the refractive index of the first acrylic resin and larger than the refractive index of the second acrylic resin. Resin composition.
[9] A molded product obtained by injection molding the polycarbonate resin composition according to any one of [1] to [8].

The polycarbonate resin composition of the present invention has an excellent balance of various properties such as transparency, impact resistance, heat resistance, scratch resistance, and optical properties, and is a molded product that requires scratch resistance and low birefringence. Can be used for. In particular, it can be suitably used for a display front plate formed by injection molding.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and carried out without departing from the gist of the present invention.

In the present specification, when "~" is used and a numerical value or a physical property value is inserted before and after the "~"
It shall be used as including the values before and after that.

As used herein, the term "repeating structural unit" means a structural unit in which the same structure repeatedly appears in a resin, and the structural units are connected to each other to form the resin. For example, in the case of a polycarbonate resin, it is called a repeating structural unit including a carbonyl group. Further, the "structural unit" means a partial structure constituting the resin and a specific partial structure included in the repeating structural unit. For example, it refers to a partial structure sandwiched between adjacent linking groups in a resin, or a partial structure sandwiched between a polymerization reactive group existing at a terminal portion of a polymer and a linking group adjacent to the polymerizable reactive group. .. More specifically, in the case of a polycarbonate resin, a partial structure in which a carbonyl group is a linking group and is sandwiched between adjacent carbonyl groups is called a structural unit.

The polycarbonate resin composition of the present invention contains a polycarbonate resin containing a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) in an amount of 5% by weight or more and 50% by weight.
The first acrylic resin containing the following, containing 50% by weight or more and 95% by weight or less of the methyl methacrylate structural unit, and 90% by weight or more of the methyl methacrylate structural unit are contained in the following formula (
It is composed of a second acrylic resin that does not contain the structural unit represented by 2). Hereinafter, the above formula (1)
) May be referred to as a “structural unit (1)”, and the structural unit represented by the above formula (2) may be referred to as a “structural unit (2)”.

In the formula (2), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent. R ² is an aryl group which may have a substituent and an aralkyl group which may have a substituent.

[Polycarbonate resin]
Examples of the dihydroxy compound forming the structural unit (1) include isosorbide (ISB), isomannide, and isoidet, which are in a stereoisomeric relationship. These may be used individually by 1 type, and may be used in combination of 2 or more type. Among them, isosorbide obtained by dehydration condensation of sorbitol, which is abundantly abundant as a plant-derived resource and is produced from various readily available starches, is available, is easy to produce, and has characteristics of the obtained molded product (for example,). , Heat resistance, impact resistance, surface hardness, carbon neutral) are most preferable.

The weight ratio of the structural unit (1) in the polycarbonate resin is not particularly limited, but is preferably 30% by weight or more and 90% by weight or less. The lower limit is more preferably 35% by weight or more, and particularly preferably 40% by weight or more. The upper limit is more preferably 80% by weight or less, further preferably 70% by weight or less, and particularly preferably 60% by weight or less. Within the above range, high impact resistance and surface hardness can be obtained while having practical heat resistance.

The polycarbonate resin of the present invention may contain a structural unit other than the structural unit (1). Hereinafter, structural units other than the structural unit (1) may be referred to as "other structural units". Examples of the compound forming other structural units include an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, an ether-containing dihydroxy compound, an acetal-containing dihydroxy compound, an aromatic-containing dihydroxy compound, and a diester compound. A polycarbonate resin partially incorporating a structural unit derived from a diester compound is called a polyester carbonate resin. In the present specification, the polycarbonate resin includes a polyester carbonate resin.

Examples of the aliphatic dihydroxy compound include the following dihydroxy compounds. Ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4
Linear aliphatic dihydroxy compounds such as −butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol; 1,3 An aliphatic dihydroxy compound having a branched chain such as −butanediol, 1,2-butanediol, neopentyl glycol, hexylene glycol and the like.

Examples of the alicyclic dihydroxy compound include the following dihydroxy compounds. 1,2-Cyclohexanedimethanol, 1,3-Cyclohexanedimethanol, 1,4
-Cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-decalin dimethanol, 2
, 3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantan dimethanol, dihydroxy compounds derived from terpene compounds such as limonene, and the like. Dihydroxy compound which is a primary alcohol of the formula hydrocarbon; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantandiol, hydrogenated bisphenol A, 2,2,4,4-tetramethyl-1 , 3-Cyclobutanediol and the like, for example, a secondary alcohol of an alicyclic hydrocarbon or a dihydroxy compound which is a tertiary alcohol.

Examples of the ether-containing dihydroxy compound include oxyalkylene glycols and a dihydroxy compound containing an acetal ring. As the oxyalkylene glycols, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like can be used.

Examples of the acetal-containing dihydroxy compound include spiroglycol (also known as 3,
9-bis (1,1-dimethyl-2-hydroxyethyl-2,4,8,10-tetraoxaspiro [5,5] undecane) and dioxane glycol (also known as 2- (1,1-dimethyl-2-) Hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane)
Etc. can be used.

As the aromatic-containing dihydroxy compound, for example, the following dihydroxy compounds can be used. 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3-phenyl) phenyl) propane, 2
, 2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) methane, 1, 1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 1,1
-Bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 1,1-bis (4-hydroxyphenyl) ) Decane, bis (4-hydroxy-3-nitrophenyl) methane, 3,3-bis (4-hydroxyphenyl) pentane, 1,3-bis (
2- (4-Hydroxyphenyl) -2-propyl) benzene, 1,3-bis (2- (4- (4-4-hydroxyphenyl) -2-propyl) benzene
Hydroxyphenyl) -2-propyl) benzene, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4 '-Dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4-hydroxyphenyl) disulfide, 4,4'-dihydroxydiphenyl ether, 4,4'- Aromatic bisphenol compounds such as dihydroxy-3,3'-dichlorodiphenyl ether; 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, 2,2-bis (4- (2-hydroxypropoxy) phenyl) Bonded to aromatic groups such as propane, 1,3-bis (2-hydroxyethoxy) benzene, 4,4'-bis (2-hydroxyethoxy) biphenyl, bis (4- (2-hydroxyethoxy) phenyl) sulfone, etc. Dihydroxy compounds with ether groups; 9,9-bis (4-)
(2-Hydroxyethoxy) phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene,
9,9-bis (4- (2-hydroxypropoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (
4- (2-Hydroxypropoxy) -3-methylphenyl) fluorene, 9,9-bis (
4- (2-Hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-
Bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene,
9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis ( 4- (2-Hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6
A dihydroxy compound having a fluorene ring such as −methylphenyl) fluorene and 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene.

Examples of the diester compound include the dicarboxylic acids shown below. Telephthalic acid, phthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 4,4'-diphenoxyetanedicarboxylic acid, 4,4 Aromatic dicarboxylic acids such as'-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid; 1,2-cyclohexanedicarboxylic acid,
Alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; aliphatics such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Dicarboxylic acid. These dicarboxylic acid components can be used as a raw material for a polyester carbonate resin as the dicarboxylic acid itself, but depending on the production method, a dicarboxylic acid ester such as a methyl ester or a phenyl ester or a dicarboxylic acid such as a dicarboxylic acid halide may be used. An acid derivative can also be used as a raw material.

Among the above other structural units, an aliphatic dihydroxy compound and an alicyclic dihydroxy compound are preferable from the viewpoint of improving mechanical properties and fluidity during melt molding. Of these, 1,4-cyclohexanedimethanol and tricyclodecanedimethanol are preferable, and 1,4-cyclohexanedimethanol is particularly preferable.

The content ratio of other structural units in the polycarbonate resin of the present invention is preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more. Also, 7
0% by weight or less is preferable, 65% by weight or less is more preferable, and 60% by weight or less is particularly preferable. Within the above range, the balance of other physical properties can be improved without significantly impairing the excellent properties of the structural unit (1).

By using an aromatic-containing dihydroxy compound such as a bisphenol compound or a diester compound as a copolymerization component, the heat resistance of the polycarbonate resin may be improved, but on the other hand, the polycarbonate resin contains a large amount of aromatic structure. And the weather resistance tends to decrease. Further, since there is a large difference in the polymerization reactivity between the bisphenol compound and the diester compound and the dihydroxy compound forming the structural unit (1), the bisphenol compound and the diester compound remain in the terminal group, and the polycarbonate having a high molecular weight. It becomes difficult to obtain a resin, and mechanical properties such as impact resistance tend to deteriorate. When the reaction temperature is raised in an attempt to promote the reaction, the structural unit (1) is thermally decomposed and the obtained polycarbonate resin tends to be colored. For these reasons, the content ratio of the structural unit derived from the aromatic-containing dihydroxy compound or diester compound is preferably 20% by weight or less, preferably 10% by weight.
The following is more preferable.

[Manufacturing method of polycarbonate resin]
The polycarbonate resin can be synthesized by polycondensing the above-mentioned dihydroxy compound and carbonic acid diester by a transesterification reaction. More specifically, it can be obtained by removing a monohydroxy compound or the like produced as a by-product in the transesterification reaction from the system together with polycondensation.

The transesterification reaction proceeds in the presence of a transesterification reaction catalyst (hereinafter, the transesterification reaction catalyst is referred to as a "polymerization catalyst"). The type of polymerization catalyst is the reaction rate of the transesterification reaction,
And can have a very large effect on the quality of the resulting polycarbonate resin.

As the polymerization catalyst, the transparency, color tone, heat resistance, and weather resistance of the obtained polycarbonate resin,
And there is no particular limitation as long as it can satisfy the mechanical properties. As a polymerization catalyst, for example
Group I or Group II (hereinafter simply referred to as "Group 1" and "Group 2") metal compounds in the long periodic table, as well as basic boron compounds, basic phosphorus compounds, and basic ammonium. Basic compounds such as compounds and amine compounds can be used, with Group 1 metal compounds and / or Group 2 metal compounds being preferred.

Examples of Group 1 metal compounds include the following compounds. Sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, Lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium hydride, sodium phenylated, boron phenylated Potassium, lithium boron phenylated, cesium boron phenylated, sodium borohydride, potassium benzoate,
Lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, Dipotassium phenylphosphate, sodium, potassium, lithium, alcoholate of cesium, phenolate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, dicesium salt and the like. As the Group 1 metal compound, a lithium compound is preferable from the viewpoint of polymerization activity and the color tone of the obtained polycarbonate resin.

Examples of the group 2 metal compound include the following compounds. Calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, strontium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, Magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc. As the group 2 metal compound, a magnesium compound, a calcium compound or a barium compound is preferable, a magnesium compound and / or a calcium compound is more preferable, and a calcium compound is most preferable from the viewpoint of polymerization activity and the color tone of the obtained polycarbonate resin.

It is also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the above-mentioned Group 1 metal compound and / or Group 2 metal compound. Although there are, it is more preferable to use only group 1 metal compounds and / or group 2 metal compounds. From the viewpoint of the color tone of the obtained polycarbonate resin, it is most preferable that only the Group 2 metal compound is used.

The amount of the polymerization catalyst used is 1 μm per 1 mol of the total dihydroxy compound used in the reaction.
It is preferably ol or more, more preferably 3 μmol or more, and particularly preferably 5 μmol or more. The amount of the polymerization catalyst used is 10 per 1 mol of the total dihydroxy compound used in the reaction.
It is preferably 0 μmol or less, more preferably 70 μmol or less, and particularly preferably 50 μmol or less.

By adjusting the amount of the polymerization catalyst used to the above range, the polymerization rate can be increased, so that a polycarbonate resin having a desired molecular weight can be obtained without necessarily raising the polymerization temperature. It is possible to suppress the deterioration of the color tone of.
Further, since it is possible to prevent the unreacted raw material from volatilizing during the polymerization and the molar ratio of the dihydroxy compound and the carbonic acid diester from collapsing, it is possible to more reliably obtain a resin having a desired molecular weight and a copolymerization ratio. it can. Furthermore, since it is possible to suppress the occurrence of side reactions, it is possible to further prevent deterioration of the color tone of the polycarbonate resin or coloring during molding.

Considering the adverse effects of sodium, potassium, and cesium on the color tone of the polycarbonate resin and the adverse effects of iron on the color tone of the polycarbonate resin among the Group 1 metals, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin is 1, 1 weight pp
It is preferably m or less. In this case, deterioration of the color tone of the polycarbonate resin can be further prevented, and the color tone of the polycarbonate resin can be further improved. From the same viewpoint, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin is more preferably 0.5 ppm by weight or less. In addition, these metals may be mixed not only from the catalyst used but also from the raw material and the reaction apparatus. Regardless of the source, the total amount of compounds of these metals in the polycarbonate resin is preferably in the above range as the total content of sodium, potassium, cesium and iron.

The method of polycondensing a dihydroxy compound and a carbonic acid diester is carried out in multiple steps using a plurality of reactors in the presence of the above-mentioned catalyst. The reaction type can be a batch type, a continuous type, or a combination of a batch type and a continuous type, but it is possible to adopt a continuous type in which a polycarbonate resin can be obtained with a smaller thermal history and excellent productivity. preferable.

From the viewpoint of controlling the polymerization rate and the quality of the obtained polycarbonate resin, it is important to appropriately select the jacket temperature, the internal temperature, and the pressure in the reaction system according to the reaction stage. Specifically, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the initial stage of the polycondensation reaction, and to raise the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the latter stage of the reaction.
In this case, the distillation of the unreacted monomer is suppressed, and the molar ratio of the dihydroxy compound and the carbonic acid diester can be easily adjusted to a desired ratio. As a result, a decrease in the polymerization rate can be suppressed. In addition, it becomes possible to more reliably obtain a polymer having a desired molecular weight and terminal group.

By adjusting the temperature of the polycondensation reaction, it is possible to improve productivity and avoid an increase in thermal history of the product. Further, it becomes possible to further prevent the volatilization of the monomer and the decomposition and coloring of the polycarbonate resin. Specifically, the following conditions can be adopted as the reaction conditions in the first stage reaction. That is, the maximum internal temperature of the polymerization reactor is usually 16.
It is set in the range of 0 to 230 ° C., preferably 170 to 220 ° C., and more preferably 180 to 210 ° C. The pressure of the polymerization reactor (hereinafter, pressure means absolute pressure) is usually 1 to 11.
It is set in the range of 0 kPa, preferably 5 to 50 kPa, and more preferably 7 to 30 kPa. The reaction time is usually set in the range of 0.1 to 10 hours, preferably 1 to 5 hours. The first-stage reaction is preferably carried out while distilling off the generated monohydroxy compound to the outside of the reaction system.

From the second stage onward, the pressure of the reaction system is gradually lowered from the pressure of the first stage, and the pressure (absolute pressure) of the reaction system is finally reduced while removing the continuously generated monohydroxy compound to the outside of the reaction system. 1
It is preferably kPa or less. The maximum internal temperature of the polymerization reactor is usually 200 to 200.
It is set in the range of 260 ° C., preferably 210-240 ° C., particularly preferably 215-230 ° C. The reaction time is usually set in the range of 0.1 to 10 hours, preferably 0.5 to 5 hours, and particularly preferably 1 to 3 hours.

After confirming that the predetermined melt viscosity (molecular weight) has been reached using stirring power as an index, polymerize by introducing nitrogen into the reactor to return the pressure to normal pressure or by extracting the molten resin from the reactor. Stop the reaction. The molten resin is discharged from the die head in the form of strands.
It is cooled and solidified, and pelletized with a rotary cutter or the like. If necessary, steps of extrusion devolatilization, extrusion kneading, and extrusion filtration may be added before pelletization. In this step, additives are mixed with the resin, low molecular weight components are devolatile with a vacuum vent, and foreign matter is removed using a polymer filter.

[Characteristics of polycarbonate resin]
-Molecular weight The molecular weight of the polycarbonate resin can be expressed by the reduced viscosity, the number average molecular weight measured by ^{1 H-NMR, or the like.} The values obtained by these measurement methods indicate that the higher the numerical value, the larger the molecular weight. The number average molecular weight of the polycarbonate resin is 8000 or more and 3000
0 or less is preferable. The lower limit is more preferably 9000 or more, and particularly preferably 10000 or more. The upper limit is more preferably 25,000 or less, and particularly preferably 20,000 or less. Within the above range, sufficient mechanical strength can be obtained, and the fluidity during melt molding can be adjusted to a preferable range.

-Glass transition temperature The glass transition temperature of the polycarbonate resin is preferably 40 ° C. or higher, and preferably 2
It is 20 ° C. or lower. The glass transition temperature of the first polycarbonate resin is 80 ° C or higher and 160 ° C.
The following is preferable. The lower limit is more preferably 90 ° C. or higher, and particularly preferably 95 ° C. or higher. The upper limit is more preferably 155 ° C. or lower, and particularly preferably 150 ° C. or lower. When it is within the above range, it has sufficient heat resistance and the molding process becomes easy.

-Melting viscosity The melt viscosity of the polycarbonate resin is 800 Pa · s or more and 3000 at 240 ° C.
Pa · s or less is preferable. The lower limit is more preferably 1000 Pa · s or more, 1200 Pa · s.
s or more is particularly preferable. The upper limit is more preferably 2500 Pa · s or less, and 2000 Pa · s.
The following are particularly preferred. Within the above range, sufficient mechanical strength can be obtained, and fluidity during melt molding can be ensured. Further, in this case, coloring and foaming due to an increase in the resin temperature due to shear heat generation can be further prevented. In the present specification, the melt viscosity means the melt viscosity at a temperature of 240 ° C. and a shear rate of 91.2 sec ^-1 as measured by using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.). Details of the method for measuring the melt viscosity will be described later.

-Refractive index The refractive index of the polycarbonate resin is preferably 1.490 or more and 1.530 or less. The upper limit is preferably 1.520 or less, and particularly preferably 1.510 or less. Within the above range, the refractive indexes of the polycarbonate resin phase and the acrylic resin phase in the resin composition can be strictly matched by using the first acrylic resin and the second acrylic resin described later in combination.
The transparency of the resin composition can be improved.

[Additive]
Polycarbonate resin is an antioxidant, a heat stabilizer, as long as the effect of the present invention is not impaired.
Light stabilizers, UV absorbers, fillers such as fillers, neutralizers, lubricants, antifogging agents, anti-blocking agents, slip agents, dispersants, colorants, flame retardants, antistatic agents, conductivity-imparting agents, cross-linking Agent,
Crosslinking aids, metal inactivating agents, molecular weight modifiers, fungicides, fungicides, optical brighteners, organic diffusers,
An inorganic diffusing agent or the like can be used as an additive.

The polycarbonate resin preferably contains a catalytic deactivator. The catalyst deactivating agent is not particularly limited as long as it is an acidic substance and has a deactivating function of the polymerization catalyst, but among them, a phosphorus-based acidic compound is excellent in the effect of catalyst deactivating and color suppression. , Phosphonate (
Phosphorous acid) and phosphonic acid ester are more preferable, and phosphonic acid (phosphorous acid) is particularly preferable.

By adjusting the content of the phosphorus-based acidic compound according to the amount of the polymerization catalyst, the effect of catalyst deactivation and color suppression can be obtained more reliably. The content of the phosphorus-based acidic compound is preferably 0.5 times mol or more, more preferably 0.7 times mol or more, and 0.8 times or more as the amount of phosphorus atoms with respect to 1 mol of the metal atom of the polymerization catalyst. The above is more preferable. Also, 5 times m
It is preferably ol or less, more preferably 3 times mol or less, and even more preferably 1.5 times mol or less.

[1st acrylic resin]
The polycarbonate resin composition of the present invention contains 5% by weight of the structural unit represented by the formula (2).
As described above, it contains an acrylic resin containing 50% by weight or less and containing 50% by weight or more and 95% by weight or less of methyl methacrylate structural units. Hereinafter, this acrylic resin may be referred to as "first acrylic resin".

The first acrylic resin is preferably compatible with the second acrylic resin described later, and from that viewpoint, in the above formula (2), R ¹ is preferably a hydrogen atom or a methyl group, and R ² is a phenyl group. , Or a benzyl group is preferable. That is, as the vinyl compound forming the structural unit (2), phenyl acrylate, phenyl methacrylate, benzyl acrylate, and benzyl methacrylate are preferable. Of these, phenyl acrylate and phenyl methacrylate are preferable, and phenyl acrylate is particularly preferable.

The lower limit of the content of the structural unit (2) in the first acrylic resin is more preferably 10% by weight or more, and particularly preferably 15% by weight or more. The upper limit is more preferably 45% by weight or less, and particularly preferably 40% by weight or less. Further, the lower limit of the content of the methyl methacrylate structural unit in the first acrylic resin is more preferably 55% by weight or more, and particularly preferably 60% by weight or more. The upper limit is more preferably 90% by weight or less, and particularly preferably 85% by weight or less. Within the above range, compatibility with the second acrylic resin described later can be obtained, and the refractive index can be adjusted to a desired range.

The first acrylic resin may contain a structural unit other than the structural unit (2) and the methyl methacrylate structural unit. Examples of vinyl compounds forming other structural units include methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, acrylonitrile, styrene, and α-. Methylstyrene, butadiene and the like can be used. Of these, methyl acrylate and n-butyl acrylate are preferable from the viewpoint of improving thermal stability and mechanical properties. The content of the structural unit other than the structural unit (2) and the methyl methacrylate structural unit is preferably relatively small in order to reduce the compatibility with the first polycarbonate resin, and the content in the first acrylic resin. Is preferably 1
It is 0% by weight or less, particularly preferably 5% by weight or less.

The first acrylic resin plays a role of adjusting the refractive index of the acrylic resin phase in the resin composition by combining with the second acrylic resin described later. Since high transparency can be obtained by making the refractive index of the acrylic resin phase and the polycarbonate resin phase in the resin composition as close as possible, the refractive index of each resin is as follows: 2nd acrylic resin <polycarbonate resin <1st acrylic resin. It is preferable to do so.

The refractive index of the first acrylic resin is preferably 1.502 or more and 1.600 or less. The lower limit is more preferably 1.504 or more, and particularly preferably 1.506 or more. The upper limit is 1.580
The following is preferable, and 1.560 or less is particularly preferable. Within the above range, by blending the first acrylic resin and the second acrylic resin, the desired refractive index can be adjusted, and the compatibility between the two resins can be ensured.

[Second acrylic resin]
The polycarbonate resin composition of the present invention contains 90% by weight of a methyl methacrylate structural unit.
It further contains an acrylic resin containing the above and does not contain the structural unit represented by the formula (2). Hereinafter, this acrylic resin may be referred to as a "second acrylic resin".
The second acrylic resin plays a role of imparting properties such as high surface hardness and low birefringence of the methyl methacrylate structural unit to the polycarbonate resin composition, and from that viewpoint, the second acrylic resin is used.
The content of the methyl methacrylate structural unit in the acrylic resin is more preferably 93% by weight or more, further preferably 95% by weight or more.

The refractive index of the second acrylic resin is preferably 1.470 or more and 1.500 or less. The lower limit is more preferably 1.480 or more, and particularly preferably 1.490 or more. Within the above range, by blending the first acrylic resin and the second acrylic resin, the desired refractive index can be adjusted, and the compatibility between the two resins can be ensured.
The difference (absolute value) between the refractive index of the first acrylic resin and the refractive index of the second acrylic resin is 0.01.
It is preferably 0 or more and 0.060 or less. The lower limit is more preferably 0.015 or more. The upper limit is 0.
050 or less is more preferable, and 0.040 or less is particularly preferable. If it is within the above range, the first
The refractive index can be adjusted in a wide range while ensuring the compatibility between the acrylic resin and the second acrylic resin.

In the resin composition of the present invention, two kinds of acrylic resins having different refractive indexes are used. Even when only one type of acrylic resin is used, it is possible to adjust it to the refractive index of the polycarbonate resin by adjusting the copolymerization component, but since it is usually necessary to optimize the physical properties of the resin material for each application. It is not realistic to produce resins having different copolymerization compositions as many as the number of uses. If you have two types of acrylic resin, you can change the composition as appropriate at the stage of manufacturing the resin composition, so it is possible to speed up material development. In addition, it is easy to adjust the quality of the product (resin composition).

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention contains 50% by weight or more and 95% by weight or less of the polycarbonate resin containing the structural unit (1). The lower limit of the content of the polycarbonate resin is more preferably 60% by weight or more, and particularly preferably 70% by weight or more. The upper limit is particularly preferably 90% by weight or less. Within the above range, the excellent mechanical strength of the polycarbonate resin and the high hardness and optical properties (low birefringence) of the acrylic resin can be balanced at a high level.

The polycarbonate resin composition of the present invention includes a polycarbonate resin, a first acrylic resin, and the like.
In addition to the second acrylic resin, other components such as additives may be contained. Further, as long as the effects of the present invention are not impaired, for example, aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, amorphous polyolefin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile- Synthetic resins such as styrene copolymer (AS resin); acrylic rubber, butadiene rubber,
Elastomers such as silicone rubber; one or more resins such as biodegradable resins such as polylactic acid and polybutylene succinate may be further contained.

[Manufacturing method of resin composition]
The resin composition can be produced, for example, by a method of mechanically melting and kneading each of the above-mentioned components constituting the resin composition. As the melt kneader, for example, a single-screw extruder, a twin-screw extruder, a lavender, a Banbury mixer, a kneader blender, a roll mill, or the like can be used. In kneading, each component may be kneaded all at once, or a multi-stage split kneading method may be used in which any component is kneaded and then the other remaining components are added and kneaded. Above all, a method of continuously charging each component using a twin-screw extruder equipped with a vacuum vent to continuously obtain a resin composition is preferable from the viewpoint of productivity and quality uniformity. The lower limit of the kneading temperature is usually 150 ° C. or higher, preferably 180 ° C. or higher, and more preferably 200 ° C. or higher. The upper limit of the kneading temperature is usually 2
80 ° C or lower, preferably 260 ° C or lower, more preferably 250 ° C or lower, particularly preferably 2
It is 40 ° C. or lower. Within this range, productivity (kneading processing speed) can be increased while suppressing thermal deterioration due to heating by the kneading machine and heat generation from shearing.

[Characteristics of Polycarbonate Resin Composition]
-The transparent resin composition preferably has a haze value of 10% or less as measured by the method described later. 5% or less is more preferable, 3% or less is further preferable, and 1% or less is particularly preferable. Within the above range, it can be applied to members that require extremely high transparency, such as display front plate applications and automobile glazing applications.

-The heat-resistant resin composition preferably has a deflection temperature under load measured by a method described later at 80 ° C. or higher and 150 ° C. or lower. The upper limit is more preferably 140 ° C. or lower, further preferably 130 ° C. or lower, 1
20 ° C. or lower is particularly preferable. Within the above range, it is excellent in mechanical properties such as impact resistance and melt processability while having practical heat resistance.

-Impact strength The resin composition preferably satisfies the following three conditions at the same time. The Charpy impact value measured by the method described later is 5 J / m ² or more, the brittle fracture rate of the surface impact test is 50% or less, and the tensile elongation at break is 10% or more. The brittle fracture rate in the surface impact test is more preferably 30% or less, and particularly preferably 10% or less. The tensile elongation at break is more preferably 20% or more, and 40.
% Or more is particularly preferable. If the above characteristics are satisfied, it can be applied to applications requiring impact resistance such as interior members of automobiles.

-Pencil hardness The resin composition preferably has a pencil hardness (surface hardness) of HB or higher, and more preferably F or higher, as measured by a method described later. In this case, it is suitably used for applications where scratch resistance is required, such as a display front plate and an automobile interior / exterior. If a higher surface hardness is required, it is possible to further hard coat the surface of the molded product of the resin composition.

-Photoelastic modulus The photoelastic coefficient of the resin composition is preferably ^{20 × 10 -12} Pa ^{-1 or less as an absolute value.}
In this case, the birefringence generated by the stress associated with bending or the like can be sufficiently reduced.

[Molding]
The resin composition is, for example, injection molding (insert molding method, two-color molding method, sandwich molding method, gas injection molding method, etc.), extrusion molding method, inflation molding method, T-die film molding method, laminate molding method, blow molding method. , Hollow molding method, compression molding method, calendar molding method and other molding methods can be used to process various molded products. Of these, the injection molding method is preferable in terms of productivity and the degree of freedom in designing the molded product. There are no particular restrictions on the shape of the molded product.
Sheets, films, plates, particles, lumps, fibers, rods, porous bodies, foams, etc. may be mentioned.
Sheets, films, and plate-like products are preferable, and plate-shaped molded products are preferable because they are compatible with the characteristics of the resin composition of the present invention. The molded film can also be uniaxially or biaxially stretched. Examples of the stretching method include a roll method, a tenter method, a tubular method and the like. Further, surface treatments such as corona discharge treatment, flame treatment, plasma treatment, and ozone treatment, which are usually used industrially, can be applied.

The phase difference of the molded product of the present invention is usually 300 nm or less, preferably 200 nm or less, and particularly preferably 100 nm or less. If the above range is satisfied, it can be applied to an optical application such as a front plate of a display and automobile glazing.
The scratch resistance of the molded product of the present invention shall be such that the following two tests are performed, and the plate after the test is visually observed under illumination, and no scratches or slight scratches are observed. Is preferable.
The scratch resistance test is evaluated by a Gakushin type friction tester (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.). The test will be conducted under the following two conditions.

(1) Attach a tissue (Scotty Flower Box, manufactured by Nippon Paper Crecia) to the tip of the wearer, and rub the surface of the plate under the conditions of a load of 1 kg, a stroke of 3 cm, a speed of 50 times / min, and 100 times.
(2) With double-sided tape attached to the tip of the wearer and glass beads (glass beads for blasting J-54, manufactured by Potters Barotini) attached, the load is 500 g, the stroke is 3 cm, and the speed is 50 times / min. , The surface of the plate is rubbed under the condition of 50 times.

[Use]
The use of the molded product is not particularly limited, but since the polycarbonate resin composition of the present invention is excellent in weather resistance and optical properties in addition to mechanical properties, it is used as an interior / exterior member of an automobile or a building material used outdoors. (Lighting cover, carport, highway sound insulation wall, etc.), front plate of display, housing of electrical and electronic equipment, etc. are preferably used.

The molded product of the polycarbonate resin composition of the present invention has excellent scratch resistance by itself, but in the case of applications requiring particularly high scratch resistance such as display covers for mobile phones and touch panels, the molded product The surface can be hard coated.

The hard coat layer can be composed of an acrylic resin, a urethane resin, a melamine resin, an organic silicate compound, a silicone resin, a metal oxide, or the like. From the viewpoint of excellent hardness and durability, the hard coat layer is preferably composed of a silicone resin or an acrylic resin. From the viewpoint of not only excellent hardness and durability but also excellent curability, flexibility, and productivity, it is more preferable that the hard coat layer is composed of an acrylic resin, and an active ray-curable acrylic resin. , It is more preferable that it is composed of a thermosetting acrylic resin.

Various additives can be further added to the hard coat layer, if necessary, as long as the effects of the present disclosure are not impaired. As the additive, for example, an antioxidant, a light stabilizer, a stabilizer such as an ultraviolet absorber, a surfactant, a leveling agent, an antistatic agent and the like can be used.

In addition to the hard coat layer, a decorative layer, an adhesive layer, an antireflection layer, an antifouling layer, and the like can be formed on the surface of the molded product as long as the effects of the present invention are not impaired. In order to improve the adhesion between these layers and the laminate, the surface of the laminate can be pretreated. As the pretreatment, corona discharge treatment, UV treatment, application of an anchor coating agent and the like are used. As the anchor coating agent, for example, at least one resin selected from the group consisting of polyester resin, acrylic resin, acrylic modified polyester resin, polyurethane resin, polysiloxane, and epoxy resin is preferably used.

By providing an antireflection layer or an antifouling layer on the surface of the molded product, it becomes particularly suitable for the display front plate of an image display device used outdoors. In this case, the visibility of the image can be further improved. As the antireflection layer and the antifouling layer, layers having each function may be laminated on the laminated body, or layers having both functions may be laminated.
A decorative layer can be formed on the surface of the molded product. As the decorative layer, for example, a printing layer and a thin-film deposition layer can be formed. As the decorative layer, a colored resin layer formed on the base film may be used.

As the binder resin material of the printing layer, polyurethane resin, vinyl resin, polyamide resin, polyester resin, acrylic resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin, thermoplastic elastomer resin and the like are preferable. Among these, a resin having a flexible coating is more preferable. It is preferable to mix a colored ink of a desired color in the binder resin. Coloring inks contain, for example, pigments or dyes as colorants.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

[Measuring method]
Various physical properties were measured according to the following methods.

-Reduction Viscosity A polycarbonate resin sample was dissolved in methylene chloride to prepare a resin solution having a concentration of 0.6 g / dL. Using an Ubbelohde viscous tube (manufactured by Moritomo Rika Kogyo Co., Ltd.), 20.0 ° C ± 0.1
At a temperature of ° C., the solvent transit time t ₀ and the solution transit time t were measured. The obtained t ₀ and t
Obtains the relative viscosity eta _rel by the following equation (i) using a value, further, the resulting relative viscosity eta _{re
The specific viscosity η sp} was determined by the following equation (ii) using l.
η _rel = t / t ₀ ... (i)
η _sp = (η − η ₀ ) / η ₀ = η _rel -1 ・ ・ ・ (ii)
Then, the obtained specific viscosity η _sp was divided by the concentration c [g / dL] to obtain the reduced viscosity η _sp / c. The higher this value, the larger the molecular weight.

^{-Number average molecular weight by 1 1} H-NMR A polycarbonate resin sample of about 15 mg was weighed, dissolved in about 0.7 mL of deuterated chloroform, placed in an NMR tube having an inner diameter of 5 mm, and ¹ H-NMR spectrum was measured. The number average molecular weight was calculated from the intensity ratio of the signal based on each repeating structural unit of the polycarbonate resin and the signal of various terminal groups. The equipment and conditions used are as follows.
・ Equipment: JNM-ECZ400S (manufactured by JEOL Ltd.)
・ Measurement temperature: 30 ℃
・ Relaxation time: 6 seconds ・ Cumulative number: 64 times

^{For example, 1} H-NMR analysis of a copolymerized polycarbonate resin of ISB and CHDM is performed as follows. The ISB double bond end and the CHDM double bond end are terminal group structures generated by a thermal decomposition reaction during the polymerization reaction.

[Range to calculate the integrated value]
(A): 5.6-4.4 ppm: Derived from all ISB repeating structural units (proton number: 4, molecular weight: 172.14)
(B): 2.2-0.5 ppm: Derived from all CHDM repeating structural units (proton number: 10,
Molecular weight: 170.21)
(C): 4.4 ppm: Derived from the hydroxy end group of ISB (proton number: 1)
(D): 3.6-3.5 ppm: derived from ISB hydroxy end group (proton number: 1) and CH
Derived from DM hydroxy end group (proton number: 2)
(E): 3.5-3.4 ppm: derived from CHDM hydroxy end group (proton number: 2) and I
Derived from SB double bond end group (proton number: 1)
(F): 2.6 ppm: derived from ISB hydroxy end group (proton number: 1)
(G): 6.7-6.5 ppm: Derived from ISB double bond end group (proton number: 1)
(H): 2.3 ppm: Derived from CHDM double bond end group (proton number: 2)
(I): 7.4 ppm: Derived from DPC terminal group (proton number: 2, molecular weight: 93.10)

[Calculation of values corresponding to the number of moles of each structure]
-All ISB repeating structural units (a'): (a) Integral value / 4
-All CHDM repeating structural units (b'): (b) Integral value / 10
-ISB hydroxy end group (c'): (c) Integral value + (f) Integral value-CHDM Hydroxy end group (d'): {(d) Integral value- (f) Integral value} / 2 + {(e)
Integral value- (g) Integral value} / 2
-ISB double bond end group (e'): (g) integral value-CHDM double bond end group (f'): (h) integral value / 2
DPC end group (i'): (i) Integral value / 2

[Calculation of number average molecular weight]
(A'x172.14 + b'x170.21 + i'x93.10) / {(c'+ d'+ e
´ ＋ f´ ＋ i´) / 2}

-Melting viscosity The resin sample was vacuum dried at 90 ° C. for 5 hours or more. Next, the melt viscosity of the pellets was measured with a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.). The measurement temperature was 240 ° C. and the shear rate was in the range ^{of 6.08 to 1824 sec -1.} The value at a shear rate of 91.2 sec ^-1 was used as the melt viscosity of the resin to be measured. The orifice used was 1 mmφ × 10 mmL.

-Glass transition temperature The glass transition temperature was measured using a differential scanning calorimeter DSC6220 (manufactured by SII Nanotechnology). Approximately 10 mg of resin is placed in the aluminum pan made by the same company, sealed, and 50 m.
The measurement was started at 200 ° C. under a nitrogen stream of L / min and cooled to 30 ° C. at a rate of 20 ° C./min. The temperature was maintained at 30 ° C. for 3 minutes, and the temperature was raised again to 200 ° C. at a rate of 20 ° C./min. DS at the time of temperature rise
From the C data, it is the temperature of the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the curve of the stepwise change part of the glass transition is maximized. The glass transition start temperature was determined and used as the glass transition temperature.

-Refractive index A film was formed from a resin sample using a heat press. Approximately 5 g of resin sample, 14 cm in length
Place it inside a SUS spacer with a width of 14 cm and a thickness of 0.1 mm, spread polyimide films on the top and bottom of the sample, preheat it at a temperature of 190 to 210 ° C. for 3 minutes, pressurize it at a pressure of 7 MPa for 5 minutes, and then use the spacer. The whole film was taken out and cooled to prepare a film. From this film
A rectangular test piece having a length of 40 mm and a width of 8 mm was cut out and used as a measurement sample. 589 nm (D
Using an interference filter of the line), a refractive index was measured _{n D} by a multi-wavelength Abbe refractometer DR-M4 / 1550 (manufactured by Atago). The measurement was carried out using monobromonaphthalene as the interface liquid and the temperature was 20 ° C.

-The haze resin sample was vacuum dried at 90 ° C. for 5 hours or more, and then a plate having a length of 60 mm, a width of 60 mm, and a thickness of 3 mm was molded using an injection molding machine EC-75 (manufactured by Toshiba Machine Co., Ltd.). The cylinder temperature of the injection molding machine was 240 ° C., and the molding cycle was 25 seconds. The haze of the plate molded product was measured with a D65 light source using a haze meter NDH2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS K7136.

Deflection temperature under load (HDT)
Using the injection molding machine EC-75 (manufactured by Toshiba Machine Co., Ltd.) described above, ISO test pieces for mechanical properties were obtained. Next, a strip-shaped test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was cut out from the ISO test piece. After that, using a thermal deformation tester (manufactured by Toyo Seiki Co., Ltd.), JIS K7191
According to -1, the deflection temperature under load of the strip-shaped test piece was determined by the flatwise method and the bending stress of 1.8 MPa.

-Charpy impact An ISO test piece for mechanical properties was molded using the above-mentioned injection molding machine EC-75 (manufactured by Toshiba Machine Co., Ltd.), and a notched Charpy impact test was carried out in accordance with ISO179. The tip radius of the notch was 0.25 mm.

-Tension fracture elongation The above-mentioned injection molding machine EC-75 (manufactured by Toshiba Machine Co., Ltd.) was used to mold an ISO test piece for mechanical properties, and the tensile elongation at break was measured in accordance with ISO527.

-Surface impact test A sheet was formed by using the above-mentioned heat press machine using spacers having a length of 70 mm, a width of 70 mm, and a thickness of 0.5 mm. Using a DuPont impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), a weight was dropped on this sheet, and the brittle fracture rate was measured in 10 measurements. The test conditions were as follows. Cradle: Inner diameter 30 mm, Outer diameter 50 mm, Strike radius: 1/4 inch, Temperature: 23
℃, mass of weight: 100 g, drop height: 50 cm.

-Pencil hardness Using the injection-molded plate described above, the pencil hardness was measured by the method described in JIS K5600-5-4 using a pencil scratch coating hardness tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.).

-Phase difference measurement of plate molded products Using the injection-molded plate described above, using the phase difference measuring device KOBRA-WPR (manufactured by Oji Measuring Instruments Co., Ltd.), at a wavelength of 585.9 nm, the length and width of the plate surface are 50 mm. The phase difference distribution was measured at intervals of 10 mm in 50 mm. The average value of the obtained 36 points was taken as the phase difference value of the plate molded product.

-Photoelastic coefficient Measured using a device that combines a birefringence measuring device consisting of a He-Ne laser, a polarizer, a compensator, an analyzer, and a photodetector and a vibrating viscoelasticity measuring device (DVE-3 manufactured by Rheology). did. For details, see the Journal of the Society of Rheology, Vol. 19, p. See 93-97 (1991). A sample having a width of 5 mm and a length of 20 mm was cut out from the film produced by the above-mentioned hot press, fixed to a viscoelasticity measuring device, and the storage elastic modulus E'was measured at a room temperature of 25 ° C. at a frequency of 96 Hz.
At the same time, the emitted laser light is passed through the polarizer, the sample, the compensator, and the analyzer in that order, and the photodetector (
It was picked up by a photodiode), and the phase difference between the amplitude and distortion of the waveform with an angular frequency ω or 2ω was obtained through a lock-in amplifier, and the strain optical coefficient O'was obtained. At this time,
The directions of the absorption axes of the polarizer and the analyzer are orthogonal to each other, and π / 4 with respect to the elongation direction of the sample, respectively.
Adjusted to form the angle of. The photoelastic coefficient C was obtained from the following equation using the storage elastic modulus E'and the strain optical coefficient O'.
C = O'/ E'

-Scratch resistance Using the injection molded plate mentioned above, the scratch resistance was evaluated with a Gakushin type friction tester (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.). The test was carried out under the following two conditions.
(1) A tissue (Scotty Flower Box, manufactured by Nippon Paper Crecia) was attached to the tip of the wearer, and the surface of the plate was rubbed under the conditions of a load of 1 kg, a stroke of 3 cm, a speed of 50 times / min, and 100 times.
(2) With double-sided tape attached to the tip of the wearer and glass beads (glass beads for blasting J-54, manufactured by Potters Barotini) attached, the load is 500 g, the stroke is 3 cm, and the speed is 50 times / min. The surface of the plate was rubbed under the condition of 50 times.
The plate after the test is visually observed under illumination, and those with no scratches are indicated by "+++", those with slight scratches are indicated by "++", and those with obvious scratches are indicated by "+". It was.

(Raw materials used)
The abbreviations and manufacturers of the compounds used in the following examples and production examples are as follows.

[Dihydroxy compound]
・ ISB: Isosorbide (manufactured by Rocket Foil)
-CHDM: 1,4-Cyclohexanedimethanol (manufactured by SK Chemical)
[Carbonate diester]
・ DPC: Diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation)
[Catalyst deactivator]
・ Phosphonate (manufactured by Tokyo Chemical Industry Co., Ltd.)
[Heat stabilizer (antioxidant)]
Irganox 1010: Pentaerythritol-Tetrakis (3- (3,5-di-t)
ert-Butyl-4-hydroxyphenyl) propionate] (manufactured by BASF)
AS2112: Tris (2,4-di-tert-butylphenyl) phosphite (AD)
EKA)
[Release agent]
-E-275: Ethylene glycol distearate (manufactured by NOF CORPORATION)
[UV absorber]
SEESORB709: 2- (2-Hydroxy-5-tert-octylphenyl)-
2H-benzotriazole (manufactured by Cipro Chemical Co., Ltd.)

(Manufacturing Example 1 / Reference Example 1) PC-1
The polycarbonate resin was polymerized using a continuous polymerization facility consisting of three vertical stirring reactors, one horizontal stirring reactor, and a twin-screw extruder. ISB, CHDM, and DPC are melted in tanks, respectively, and ISB 29.8 kg / hr, CHDM 12.6 kg / hr, and DPC.
62.9 kg / hr (ISB / CHDM / DPC = 0.700 / 0.300 / in molar ratio)
It was continuously supplied to the first vertical stirring reactor at a flow rate of 1.008). At the same time, an aqueous solution of calcium acetate monohydrate as a polymerization catalyst was supplied to the first vertical stirring reactor in an amount of 1.5 μmol of calcium acetate monohydrate with respect to 1 mol of the total dihydroxy compound. The internal temperature, internal pressure, and residence time of each reactor are the first vertical stirring reactor: 190 ° C., 25 kPa, respectively.
120 minutes, 2nd vertical stirring reactor: 195 ° C, 10kPa, 90 minutes, 3rd vertical stirring reactor:
205 ° C, 4 kPa, 45 minutes, 4th horizontal stirring reactor: 220 ° C, 0.1 to 1.0 kPa,
It was set to 120 minutes. The operation was performed while finely adjusting the internal pressure of the fourth horizontal stirring reactor so that the number average molecular weight of the obtained polycarbonate resin was 8000 to 9000. Vent type twin-screw extruder TEX with the polycarbonate resin extracted from the 4th horizontal stirring reactor in a molten state.
It was supplied to 30α [manufactured by Japan Steel Works, Ltd.]. The extruder has three vacuum vent ports, where the residual low molecular weight components in the resin are volatilized and removed, and phosphonic acid is applied as a catalyst deactivator to the polycarbonate resin before the first vent. Add 0.64 wt ppm and before the 3rd vent, Irganox1010, AS2112, Resinob709, E-275.
1000 wt ppm and 500 wt ppm, respectively, with respect to the polycarbonate resin. 2
00 ppm by weight and 3000 ppm by weight were added. The polycarbonate resin that has passed through the extruder is still in a molten state, and the Ultipleated candle filter with an opening of 10 μm [
Foreign matter was filtered through PALL]. Then, the polycarbonate resin was extruded from the die into a strand shape, water-cooled and solidified, and then pelletized by cutting with a rotary cutter. The polycarbonate resin thus obtained is referred to as "PC-1".
The analysis results of this polycarbonate resin are shown in Table 1 as Reference Example 1.

(Manufacturing Example 2 / Reference Example 2) PC-2
Raw material preparation is ISB 21.3kg / hr, CHDM 21.1kg / hr, DPC
62.9 kg / hr (ISB / CHDM / DPC = 0.500 / 0.500 / in molar ratio)
The same procedure as in Production Example 1 was carried out except that the flow rate was set to 1.005).

(Manufacturing Example 3 / Reference Example 3) PMMA-1
A copolymerized acrylic resin having a methyl methacrylate / methyl acrylate / phenyl methacrylate = 78.5 / 1.5 / 20.0% by weight was synthesized according to the method described in JP-A-2010-116501. This acrylic resin is referred to as "PMMA-1". The analysis results are shown in Table 1 as Reference Example 3.

(Manufacturing Example 4 / Reference Example 4) PMMA-2
A copolymerized acrylic resin having methyl methacrylate / methyl acrylate = 97/3% by weight was synthesized in the same manner as in Production Example 4. This acrylic resin is referred to as "PMMA-2".
The analysis results are shown in Table 1 as Reference Example 4.

(Example 1)
After blending 80.0 parts by weight of PC-1, 12.9 parts by weight of PMMA-1, and 7.1 parts by weight of PMMA-2, a twin-screw extruder TEX30HSS [manufactured by Japan Steel Works] equipped with a vacuum vent is used. Then, extrusion kneading was performed at a cylinder temperature of 240 ° C. and an extrusion rate of 12 kg / hr.
Pellets of the polycarbonate resin composition were obtained. The obtained polycarbonate resin composition was evaluated in various ways as described above. The results are shown in Table 2.

(Example 2)
PC-2 70.0 parts by weight, PMMA-1 16.5 parts by weight, PMMA-2 13.5
The same procedure as in Example 1 was carried out except that the parts by weight were used. The results are shown in Table 2.

(Comparative Examples 1 to 3)
Each of PC-1, PC-2, and PMMA-2 was used alone to perform the above-mentioned various evaluations. The results are shown in Table 2.

(Comparative Examples 4 to 7)
The same procedure as in Example 1 was carried out except that the formulations shown in Table 2 were used. All of the obtained polycarbonate resin compositions were cloudy.

Claims (9)

A polycarbonate resin containing a structural unit represented by the following formula (1) and
A first acrylic resin containing 5% by weight or more and 50% by weight or less of the structural unit represented by the following formula (2) and 50% by weight or more and 95% by weight or less of the methyl methacrylate structural unit.
A polycarbonate resin composition containing a second acrylic resin containing 90% by weight or more of a methyl methacrylate structural unit and not containing a structural unit represented by the following formula (2).

(In the formula (2), R ¹ is a hydrogen atom and an alkyl group having 1 to 10 carbon atoms which may ^{have a substituent. R 2} is an aryl group and a substituent which may have a substituent. It is an aralkyl group that may have.) The polycarbonate resin composition according to claim 1, wherein the glass transition temperature of the polycarbonate resin is 90 ° C. or higher and 150 ° C. or lower. The polycarbonate resin composition according to claim 1 or 2, wherein the polycarbonate resin contains a structural unit derived from an aliphatic dihydroxy compound or an alicyclic dihydroxy compound. The structural unit represented by the formula (1) in the polycarbonate resin is 30% by weight or more, 9
The polycarbonate resin composition according to any one of claims 1 to 3, which is 0% by weight or less. Claim 1 in which the structural unit represented by the formula (2) is a phenyl methacrylate structural unit.
The polycarbonate resin composition according to any one of 4 to 4. Claims 1 to 5 containing the polycarbonate resin in an amount of 50% by weight or more and 95% by weight or less.
The polycarbonate resin composition according to any one of the above. Claims 1 to 2, wherein the refractive index of the first acrylic resin and the refractive index of the second acrylic resin are different.
6. The polycarbonate resin composition according to any one of 6. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the refractive index of the polycarbonate resin is smaller than the refractive index of the first acrylic resin and larger than the refractive index of the second acrylic resin. A molded product obtained by injection molding the polycarbonate resin composition according to any one of claims 1 to 8.