JP2020122146A - Fluidity improver, aromatic polycarbonate-based resin composition and molded article of the same - Google Patents

Abstract

To provide a fluidity improver for improving fluidity during molding processing without deteriorating impact resistance which is an original characteristic of a PC resin composition, a PC resin composition excellent in fluidity containing the fluidity improver and a molded article.SOLUTION: There are provided: a fluidity improver which comprises 0.5 pts.mass or more and 99.5 pts.mass or less of a polymer (A) obtained by polymerizing a monomer mixture (a) containing 0.5 mass% or more and 99 mass% or less of an aromatic vinyl monomer (a1), 0.5 mass% or more and 99 mass% or less of a (meth)acrylate ester (a2) and 0.5 mass% or more and 5 mass% or less of a vinyl monomer (a3) having an epoxy group and 0.5 pt.mass or more and 99.5 pts.mass or less of a polymer (B) obtained by polymerizing a monomer mixture (b) containing a (meth)acrylic ester and a compound having a carboxyl group, wherein the amount of a methyl methacrylate monomer is 20 mass% or more and 80 mass% or less based on the total 100 mass% of the polymer (A) and the polymer (B); and a resin composition and a molded article containing the same.SELECTED DRAWING: None

Description

The present invention is a fluidity improver for improving fluidity at the time of molding without impairing impact resistance, which is an inherent characteristic of aromatic polycarbonate resins, and an aroma excellent in fluidity containing the fluidity improver. Group Polycarbonate-based resin compositions and molded articles.

Aromatic polycarbonate resin (hereinafter referred to as "PC resin") is excellent in mechanical strength, heat resistance, electric characteristics, dimensional stability, etc., and therefore, OA (office automation) equipment, information/communication equipment, electronic equipment It is used in a wide range of fields such as electric appliances, home appliances, automobile parts, and building materials. However, since the PC resin is usually amorphous, it has a problem that the molding temperature is high and the melt fluidity is poor.
In recent years, in these applications, moldings have become larger, thinner, and complicated in shape, and PC resins are required to have improved melt fluidity during molding.

As a method for improving melt flowability during molding without impairing the excellent properties of PC resin, aromatic vinyl monomer, phenyl (meth)acrylate monomer, and monomer polymer having epoxy group And a polymer containing a carboxyl group as a fluidity improver, a method of melt-kneading with a PC resin has been proposed (Patent Document 1).
However, this method has a problem that it cannot be applied to applications requiring impact resistance because the impact resistance is lowered.

International publication number WO2008/081791

The object of the present invention is a fluidity improver for improving the fluidity at the time of molding without impairing the impact resistance which is the original property of PC resin, and a PC having excellent fluidity containing the fluidity improver. It is to provide a resin composition and a molded article.

As a result of intensive studies by the present inventors, as a fluidity improver comprising a polymer having an epoxy group and a polymer having a carboxyl group, the ratio of methyl methacrylate monomer in the total amount is 20 to 80% by mass. It was found that, by melt-kneading the fluidity improver with the PC resin, the fluidity at the time of molding can be improved without impairing the impact resistance, which is a characteristic of the PC resin body.

That is, the above object is achieved by the following inventions [1] to [13].
[1] A vinyl vinyl monomer having an aromatic vinyl monomer (a1) of 0.5% by mass or more and 99% by mass or less, a (meth)acrylic acid ester (a2) of 0.5% by mass or more and 99% by mass or less, and an epoxy group. Polymer (A) obtained by polymerizing the monomer mixture (a) containing 0.5% by mass or more and 5% by mass or less of the monomer (a3) 0.5 part by mass or more and 99.5 parts by mass or less,
A monomer mixture (b) containing a (meth)acrylic ester and 0.5 to 99.5 parts by mass of a polymer (B) obtained by polymerizing using a compound having a carboxyl group. A fluidity improver which is contained, and the amount of the methyl methacrylate monomer is 20% by mass or more and 80% by mass or less based on 100% by mass of the total of the polymer (A) and the polymer (B).
[2] Further, a monomer mixture (c2) containing 30% by mass or more and 90% by mass or less of the aromatic vinyl monomer (c1) and 10% by mass or more and 70% by mass or less of the (meth)acrylic acid ester is polymerized. The polymer (C) obtained by containing 10 parts by mass or more and 80 parts by mass or less, the total of the polymer (A), the polymer (B) and the polymer (C), based on 100 mass%, The fluidity improver according to [1], wherein the amount of the methyl methacrylate monomer is 20% by mass or more and 80% by mass or less.
[3] The fluidity improver according to any of [1] or [2], which is obtained by reacting the epoxy group of the polymer (A) with the carboxyl group of the polymer (B).
[4] Contains 70% by mass or more and 99.9% by mass or less of an aromatic polycarbonate resin, and 0.1% by mass or more and 30% by mass or less of the fluidity improver according to any one of [1] to [3]. Aromatic polycarbonate resin composition.
[5] The fluidity improver is such that the amount of the methyl methacrylate monomer is 24% by mass or more and 60% by mass or less based on 100% by mass of the total of the polymer (A) and the polymer (B). The aromatic polycarbonate resin composition according to [4], which is a fluidity improver.
[6] The polymer (A) contained in the fluidity improver contains 59.5% by mass or more and 74.5% by mass or less of an aromatic vinyl monomer (a1), a (meth)acrylic acid ester (a2). Polymer obtained by polymerizing a monomer mixture (a) containing 25% by mass or more and 40% by mass or less and 0.5% by mass or more and 5% by mass or less of a vinyl monomer (a3) having an epoxy group ( The aromatic polycarbonate resin composition according to [5], which is A).
[7] 70% by mass or more and 99.9% by mass or less of the aromatic polycarbonate resin composition according to any one of [5] and [6], and 0.1% by mass or more and 30% by mass or less of a light diffusing agent. An aromatic polycarbonate resin composition containing:
[8] A molded product obtained by molding the aromatic polycarbonate resin composition according to any one of [4] to [7].
[9] A hard coat product having a hard coat layer on the surface of the molded product according to [8].
[10] A glazing material using the molded product according to [8] or the hard coat product according to [9].
[11] A light diffusion plate formed by molding the aromatic polycarbonate resin composition according to any one of [4] to [7].
[12] An optical disk substrate formed by molding the aromatic polycarbonate resin composition according to any one of [4] to [7].
[13] A light guide plate formed by molding the aromatic polycarbonate resin composition according to any one of [4] to [7].

According to the fluidity improver of the present invention, it is possible to improve fluidity at the time of molding without impairing the impact resistance, which is a characteristic of the PC resin body.
According to the PC resin composition of the present invention, a molded product can be obtained with good fluidity at the time of molding, and has excellent performance as a hard coat product, a glazing agent, a light diffusion plate, an optical disk substrate, and a light guide plate.
The molded product of the present invention has the original characteristics of PC resin and is useful as a hard coat product, a glazing material, a light diffusion plate, an optical disk substrate, and a light guide plate.

The polymer (A) of the present invention is a monomer mixture containing an aromatic vinyl monomer (a1), a (meth)acrylic acid ester (a2), and a vinyl monomer (a3) having an epoxy group ( Obtained by polymerizing a).

Examples of the aromatic vinyl monomer (a1) include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, and the like. Examples include chlorostyrene, bromostyrene, vinyltoluene, vinylnaphthalene, and vinylanthracene. These monomers may be used alone or in combination of two or more.
Among these, styrene, α-methylstyrene, and pt-butylstyrene are preferable, since the polymer (A) has a refractive index close to that of the aromatic polycarbonate resin and the glass transition temperature is high, and styrene and α are preferable. -It is more preferable to use methyl styrene together.

When the aromatic vinyl monomer (a1) is a combination of styrene and α-methylstyrene, the content of α-methylstyrene in the aromatic vinyl monomer (a1) is 10% by mass or more and 70% by mass or less. Is preferred.
When the content of α-methylstyrene in the aromatic vinyl monomer (a1) is 10% by mass or more, the glass transition temperature of the obtained polymer becomes high and the transparency at high temperature becomes good. It is more preferably 15% by mass or more, and further preferably 25% by mass or more.
When the content of α-methylstyrene in the aromatic vinyl monomer (a1) is 70% by mass or less, the copolymerizability does not deteriorate and the polymerization rate of the obtained polymer increases. It is more preferably 60% by mass or less, and further preferably 50% by mass or less.

Examples of the (meth)acrylic ester (a2) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, and (meth)acrylic. Acid n-butyl, (meth)acrylic acid iso-butyl, (meth)acrylic acid t-butyl, (meth)acrylic acid n-pentyl, (meth)acrylic acid n-hexyl, (meth)acrylic acid 2-ethylhexyl, Lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth ) Phenyl acrylate, 4-t-butylphenyl (meth)acrylate, bromophenyl (meth)acrylate, dibromophenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, (meth ) Monochlorophenyl acrylate, dichlorophenyl (meth)acrylate, trichlorophenyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, allyl (meth)acrylate, di(meth)acrylic Acid 1,3-butylene and the like can be mentioned. These monomers may be used alone or in combination of two or more.
Among these, phenyl (meth)acrylate or methyl (meth)acrylate is preferable because of high compatibility with the aromatic polycarbonate resin and good impact resistance of the molded product.
In addition, in this application, (meth)acryl means acryl or methacryl.

Examples of the vinyl monomer (a3) containing an epoxy group include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl methacrylate glycidyl ether, allyl glycidyl ether, manufactured by Daicel Chemical Industries, Ltd. Examples thereof include "CYCLOMER M-100", "CYCLOMER A-200", "M-GMA", and a partial (meth)acrylated compound of a polyfunctional epoxy compound. Glycidyl (meth)acrylate is preferred from the viewpoint of not impairing the heat resistance of the molded product.

The content of the aromatic vinyl monomer (a1) in the monomer mixture (a) is 0.5% by mass or more and 99% by mass or less, and the content of the (meth)acrylic acid ester (a2) is 0.5% by mass. The content of the vinyl monomer (a3) containing an epoxy group is 0.5% by mass or more and 5% by mass or less.

When the content of the aromatic vinyl monomer (a1) in the monomer mixture (a) (100% by mass) is 0.5% by mass or more, it becomes incompatible with the aromatic polycarbonate resin, The fluidity during molding can be improved. It is preferably 40% by mass or more, and more preferably 59.5% by mass or more.
If the content of the aromatic vinyl monomer (a1) in the monomer mixture (a) (100% by mass) is 99% by mass or less, the mechanical properties of the molded product will not be impaired. It is preferably 95% by mass or less, and more preferably 74.5% by mass or less.

If the content of the (meth)acrylic acid ester (a2) in the monomer mixture (a) (100% by mass) is 0.5% by mass or more, the surface layer peeling resistance of the molded product and the mechanical properties Is not damaged. It is preferably 5% by mass or more, and more preferably 25% by mass or more.
If the content of the (meth)acrylic acid ester (a2) in the monomer mixture (a) (100% by mass) is 99% by mass or less, it becomes incompatible with the aromatic polycarbonate resin, and the molding process is performed. Improve the fluidity of time. It is preferably 60% by mass or less, and more preferably 40% by mass or less.

When the content of the vinyl monomer (a3) having an epoxy group in the monomer mixture (a) (100% by mass) is 0.5% by mass or more, decomposition occurs during melt kneading with the aromatic polycarbonate resin. To improve fluidity without causing
If the content of the vinyl monomer (a3) having an epoxy group in the monomer mixture (a) (100% by mass) is 5% by mass or less, deterioration due to retention during melt-kneading with the aromatic polycarbonate resin To improve fluidity. It is preferably 2.5 mass% or less.

The monomer mixture (a) may optionally contain another monomer (a4) copolymerizable with the monomers (a1) to (a3).
Examples of the other monomer (a4) include vinyl benzoate; vinyl acetate; maleic anhydride; maleimide compounds such as N-phenylmaleimide and cyclohexylmaleimide; and ethylenically unsaturated monomers having a piperidyl group. .. These may be used alone or in combination of two or more.

The content of the other monomer (a4) in the monomer mixture (a) (100% by mass) is 0% by mass or more and 40% by mass or less.
When the content of the other monomer (a4) in the monomer mixture (a) (100% by mass) is 40% by mass or less, the fluidity during molding is improved, and the impact resistance of the molded product is improved. The sex is not lost.

The contents of the monomers (a1) to (a3) in the fluidity improver of the present invention are the same as those of the polymer (A), the polymer (B) and the polymer (C) in the fluidity improver. It can be measured by sampling and analyzing the composition. The method of preparative collection is not particularly limited, but a general method can be used, and for example, chromatography such as gas chromatography or liquid chromatography can be used. The method for composition analysis is not particularly limited, but a general method can be used, and for example, methods such as nuclear magnetic resonance spectrum measurement, mass spectrometry, and elemental analysis can be used.

Examples of the polymerization method for obtaining the polymer (A) of the present invention include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method. The turbid polymerization method and the emulsion polymerization method are preferable. However, in the case of the emulsion polymerization method, since the salts remaining in the polymer (A) may cause the decomposition of the aromatic polycarbonate resin, the polymer is recovered by acid coagulation using a carboxylic acid emulsifier. Alternatively, it is preferable to salt-coagulate with calcium acetate or the like using a nonionic anionic emulsifier such as phosphate ester.
Examples of the polymerization initiator include a redox type initiator composed of an organic peroxide, a persulfate salt, an organic peroxide or a combination of a persulfate salt and a reducing agent, and an azo compound.

The amount of the epoxy groups of the polymer (A) is 0.01 mmol/g or more and 0.2 mmol/g or less, preferably 0.03 mmol/g or more and 0.1 mmol/g or less.
When the amount of the epoxy group of the polymer (A) is 0.01 mmol/g or more, the reactivity with the polymer (B) becomes sufficient, and the surface layer peeling resistance and mechanical properties of the molded product are not impaired. ..
When the amount of the epoxy groups of the polymer (A) is 0.2 mmol/g or less, deterioration due to retention does not occur during melt kneading with the aromatic polycarbonate resin, and the fluidity is improved.
The amount of epoxy groups in the polymer (A) can be measured by titration operation. The titration operation is not particularly limited. For example, a method in which the polymer (A) is dissolved in a hydrochloric acid-containing organic solvent having a defined concentration and titrated with a potassium hydroxide solution using phenolphthalein as an indicator can be used.

The weight average molecular weight of the polymer (A) is 5,000 or more, preferably 10,000 or more, more preferably 15,000 or more, further preferably 30,000 or more, particularly preferably 40,000 or more. Further, the mass average molecular weight of the polymer (A) is 200,000 or less, preferably 170,000 or less, more preferably 150,000 or less, further preferably 120,000 or less, particularly preferably 100,000 or less.

When the mass average molecular weight of the polymer (A) is 5,000 or more, the number of relatively low molecular weight substances is relatively small, and the heat resistance and the like of the molded product are not impaired. In addition, the appearance of the molded product does not deteriorate due to smoke generation during melt-kneading. When a molded article having good transparency at high temperature (a molded article having a low temperature dependency of transparency) is required, the mass average molecular weight of the polymer is preferably high.
When the mass average molecular weight of the polymer (A) is 200,000 or less, the melt viscosity of the aromatic polycarbonate-based resin composition does not increase, and a sufficient effect of improving melt fluidity can be obtained.

The polymer (B) of the present invention is obtained by polymerizing a monomer mixture (b) containing a (meth)acrylic acid ester (b1) and a compound having a carboxyl group capable of reacting with an epoxy group. ..

As the (meth)acrylic acid ester (b1), the same as the above-mentioned monomer (a2) can be used. As the (meth)acrylic acid ester (b1), one type may be used alone, or two or more types may be used in combination.
Among these, phenyl (meth)acrylate or methyl (meth)acrylate is preferable because it has high compatibility with the aromatic polycarbonate resin and does not impair the impact resistance of the molded product.

The content of the (meth)acrylic acid ester (b1) in the monomer mixture (b) (100% by mass) is 0.5% by mass or more and 100% by mass or less.
When the content of the (meth)acrylic acid ester (b1) in the monomer mixture (b) (100% by mass) is 0.5% by mass or more, the mechanical properties of the molded product are not impaired. It is preferably 25% by mass or more, and more preferably 60% by mass or more.

The monomer mixture (b) may optionally contain another monomer (b2) copolymerizable with the monomer (b1).
Examples of other monomers include aromatic vinyl monomers such as styrene and α-methylstyrene; polyfunctional monomers such as divinylbenzene; vinyl benzoate; vinyl acetate; maleic anhydride; N-phenylmaleimide. , A maleimide compound such as cyclohexylmaleimide, a polycaprolactone macromonomer, an ethylenically unsaturated monomer having a piperidyl group, and the like. These may be used alone or in combination of two or more.

The content of the other monomer (b2) in the monomer mixture (b) (100% by mass) is 0% by mass or more and 99.5% by mass or less.
When the content of the other monomer (b2) in the monomer mixture (b) (100% by mass) is 99.5% by mass or less, the fluidity during molding can be improved. It is preferably 75% by mass or less, and more preferably 40% by mass or less.

The polymer (B) is obtained by polymerizing the monomer mixture (b) and a compound having a carboxyl group.
Examples of the compound having a carboxyl group include a monomer having a carboxyl group such as (meth)acrylic acid, a chain transfer agent having a carboxyl group such as 3-mercaptopropionic acid, and 4,4′-azobis(4-cyano). (Valeric acid), 2,2′ azobis[N-(2-carboxyethyl)-2-methyl-propionamidine] and other polymerization initiators having a carboxyl group. These compounds may be used alone or in combination of two or more.
Among these, a chain transfer agent having a carboxyl group and a polymerization initiator having a carboxyl group are preferable because a carboxyl group can be efficiently introduced into the terminal of the polymer (B).

As the polymer (B), a methacrylic acid ester polymer using 3-mercaptopropionic acid as a chain transfer agent is preferable.

As the polymerization method for obtaining the polymer (B) of the present invention, the same polymerization method as that for the polymer (A) can be used.

The amount of the carboxyl group of the polymer (B) is 0.02 mmol/g or more and 0.6 mmol/g or less, preferably 0.05 mmol/g or more and 0.4 mmol/g or less.
When the amount of the carboxyl group of the polymer (B) is 0.02 mmol/g or more, the reactivity with the polymer (A) becomes sufficient, and the finely divided polymer domain is present in the matrix of the aromatic polycarbonate resin. The formed article has a high degree of transparency.
When the amount of the carboxyl group of the polymer (B) is 0.6 mmol/g or less, hydrolysis and thermal decomposition do not occur during melt kneading.

The weight average molecular weight of the polymer (B) is 5,000 or more, preferably 10,000 or more. The mass average molecular weight of the polymer (B) is 200,000 or less, preferably 120,000 or less, more preferably 100,000 or less, and further preferably 50,000 or less.

When the mass average molecular weight of the polymer (B) is 5,000 or more, the number of relatively low molecular weight substances is relatively small, and the heat resistance and the like of the molded product are not impaired. In addition, the appearance of the molded product does not deteriorate due to smoke generation during melt-kneading.
When the mass average molecular weight of the polymer (B) is 200,000 or less, the compatibility with the aromatic polycarbonate resin does not decrease and the appearance of the molded product becomes good.

The content of the polymer (A) in the fluidity improver is 0.5 parts by mass or more and 99.5 parts by mass or less, and preferably 30 parts by mass or more and 70 parts by mass or less. The content of the polymer (B) in the fluidity improver is 0.5 parts by mass or more and 99.5 parts by mass or less, and preferably 30 parts by mass or more and 70 parts by mass or less. However, the total amount of the polymer (A) and the polymer (B) is 100 parts by mass.
The amount of epoxy groups in the fluidity improver is preferably lower than the amount of carboxyl groups in the fluidity improver. Improves fluidity without causing deterioration due to retention during melt-kneading with an aromatic polycarbonate resin.

The amount of the methyl methacrylate monomer is 20% by mass or more and 80% by mass or less based on 100% by mass of the total of the polymer (A) and the polymer (B) in the fluidity improver. It is preferably 24% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 60% by mass or less.
When the amount of the methyl methacrylate monomer is 20% by mass or more based on 100% by mass of the polymer (A) and the polymer (B) in the fluidity improver, the compatibility with the aromatic polycarbonate resin is high. Good and impact resistance of the molded product is good. If it is 80% by mass or less, it becomes incompatible with the aromatic polycarbonate resin, and the fluidity during molding can be improved.

The polymer (C) of the present invention is obtained by polymerizing a monomer mixture (c) containing an aromatic vinyl monomer (c1) and a (meth)acrylic acid ester (c2).

As the aromatic vinyl monomer (c1), the same aromatic vinyl monomer (a1) as described above can be used. As the aromatic vinyl monomer (c1), one type may be used alone, or two or more types may be used in combination.
Among these, styrene, α-methylstyrene and pt-butylstyrene are preferable, since the polymer (C) has a refractive index close to that of the aromatic polycarbonate resin and the glass transition temperature is high, and styrene and α are preferable. -It is more preferable to use methyl styrene together.

When the aromatic vinyl monomer (c1) is a combination of styrene and α-methylstyrene, the content of α-methylstyrene in the aromatic vinyl monomer (c1) is 10% by mass or more and 70% by mass or less. Preferably.
When the content of α-methylstyrene in the aromatic vinyl monomer (c1) is 10% by mass or more, the glass transition temperature of the obtained polymer becomes high and the transparency at high temperature becomes good. It is more preferably 20% by mass or more, and further preferably 30% by mass or more.
When the content of α-methylstyrene in the aromatic vinyl monomer (c1) is 70% by mass or less, the copolymerizability does not deteriorate and the polymerization rate of the obtained polymer increases. It is more preferably 60% by mass or less, and further preferably 50% by mass or less.

As the (meth)acrylic acid ester (c2), the same as the above-mentioned monomer (a2) can be used. As the (meth)acrylic acid ester (c2), one type may be used alone, or two or more types may be used in combination.
Among these, phenyl (meth)acrylate or methyl (meth)acrylate is preferable because it has high compatibility with the aromatic polycarbonate resin and does not impair the surface layer peeling resistance of the molded product.

The content of the aromatic vinyl monomer (c1) in the monomer mixture (c) (100% by mass) is 0.5% by mass or more and 99.5% by mass or less, (meth)acrylic acid ester (c2). Is 0.5% by mass or more and 99.5% by mass or less.

When the content of the aromatic vinyl monomer (c1) in the monomer mixture (c) (100% by mass) is 0.5% by mass or more, it becomes incompatible with the aromatic polycarbonate resin, Improves fluidity during molding and does not impair the chemical resistance of molded products. It is preferably 30% by mass or more, and more preferably 40% by mass or more.
When the content of the aromatic vinyl monomer (c1) in the monomer mixture (c) (100% by mass) is 99.5% by mass or less, the surface layer peeling resistance of the molded product and the mechanical properties Is not damaged. It is preferably 95% by mass or less.

When the content of the (meth)acrylic acid ester (c2) in the monomer mixture (c) (100% by mass) is 0.5% by mass or more, the surface layer peeling resistance of the molded product and the mechanical properties Is not damaged. It is preferably at least 5% by mass.
If the content of the (meth)acrylic acid ester (c2) in the monomer mixture (c) (100% by mass) is 99.5% by mass or less, it becomes incompatible with the aromatic polycarbonate resin, Improves fluidity during molding and does not impair the chemical resistance of molded products. It is preferably 60% by mass or less, and more preferably 40% by mass or less.

The monomer mixture (c) may optionally contain another monomer (c3) copolymerizable with the monomers (c1) and (c2).
As the other monomer (c3), the same as the above-mentioned monomer (a4) can be used. As the other monomer (c3), one type may be used alone, or two or more types may be used in combination.

The content of the other monomer (c3) in the monomer mixture (c) (100% by mass) is 0% by mass or more and 40% by mass or less.
When the content of the other monomer (c3) in the monomer mixture (c) (100% by mass) is 40% by mass or less, the fluidity at the time of molding is improved, and the chemical resistance of the molded product is improved. The sex is not lost.

The polymer (C) is incompatible with the aromatic polycarbonate resin and preferably has a refractive index close to that of the aromatic polycarbonate resin.
That is, the volume average domain diameter (dv) of the polymer domain dispersed in the aromatic polycarbonate resin matrix is confirmed as phase separation of 0.05 μm or more.

As the polymerization method for obtaining the polymer (C) of the present invention, the same polymerization method as that for the polymer (A) may be used.

The mass average molecular weight of the polymer (C) is 5,000 or more, preferably 10,000 or more, and more preferably 15,000 or more. The mass average molecular weight of the polymer (C) is 200,000 or less, preferably 120,000 or less, more preferably 100,000 or less.

When the mass average molecular weight of the polymer (C) is 5,000 or more, the number of relatively low molecular weight substances is relatively small, and the heat resistance and the like of the molded product are not impaired. In addition, the appearance of the molded product does not deteriorate due to smoke generation during melt-kneading.
When the mass average molecular weight of the polymer (C) is 200,000 or less, the melt viscosity of the aromatic polycarbonate resin-based composition does not increase, and the effect of improving melt fluidity can be obtained.

The fluidity improver of the present invention may contain the polymer (C).
When the polymer (C) is contained, when the total amount of the polymer (A), the polymer (B) and the polymer (C) is 100 parts by mass, the content of the polymer (A) in the fluidity improver. The amount is 10 parts by mass or more and 45 parts by mass or less, the content of the polymer (B) is 10 parts by mass or more and 45 parts by mass or less, and the content of the polymer (C) is 10 parts by mass or more and 80 parts by mass or less. Is.

When the content of the polymer (C) in the fluidity improver (100 parts by mass) is 45 parts by mass or less, further improving the fluidity during molding without impairing the transparency of the molded product. You can

The amount of the methyl methacrylate monomer is 20% by mass or more and 80% by mass with respect to 100% by mass of the total of the polymer (A), the polymer (B) and the polymer (C) in the fluidity improver. It is the following. It is preferably 25% by mass or more and 75% by mass or less, and more preferably 30% by mass or more and 70% by mass or less.
If the amount of the methyl methacrylate monomer is 20% by mass or more based on 100% by mass of the total of the polymer (A), the polymer (B) and the polymer (C) in the fluidity improver, Good compatibility with aromatic polycarbonate resins and good impact resistance of molded products. If it is 80% by mass or less, it becomes incompatible with the aromatic polycarbonate resin, and the fluidity during molding can be improved.

When the fluidity improver of the present invention is blended with an aromatic polycarbonate resin and melt-kneaded, the epoxy group of the polymer (A) and the carboxyl group of the polymer (B) react with each other. Due to the reaction between the epoxy group and the carboxyl group, the fluidity improver exhibits phase separation behavior with respect to the aromatic polycarbonate resin, and exhibits an effect of improving the fluidity during molding.
After the molding process, the domains of the fluidity improver that have been made fine are formed in the matrix of the aromatic polycarbonate resin. This makes it possible to improve fluidity during molding without impairing the original properties of the aromatic polycarbonate resin (transparency, resistance to surface layer peeling, heat resistance, impact resistance, and chemical resistance).

In order to mix the fluidity improver of the present invention with an aromatic polycarbonate resin, the following method (I), (II) or (III) can be used.
(I): A polymer (A), a polymer (B), and, if necessary, a fluidity improver containing the polymer (C) is blended with an aromatic polycarbonate resin and melt-kneaded.
(II): The polymer (A), the polymer (B), and, if necessary, the fluidity improver containing the polymer (C) are melt-kneaded to react the epoxy group and the carboxyl group with each other. This is blended with an aromatic polycarbonate resin and further melt-kneaded.
(III) The polymer (A), the polymer (B), and the fluidity improver containing the polymer (C), if necessary, are melt-kneaded to allow the epoxy group and the carboxyl group to react with each other. Aromatic polycarbonate resin is blended and further melt-kneaded.

Further, a method in which the polymer (A) is blended with an aromatic polycarbonate resin and melt-kneaded, and then the polymer (B) is blended and further melt-kneaded, or a masterbatch of a fluidity improver and an aromatic polycarbonate resin It is also possible to use a method in which after preparing the above, the aromatic polycarbonate resin is blended and melt-kneaded.

The aromatic polycarbonate resin used in the present invention may be one produced by a known method.
When the aromatic polycarbonate resin is 2,2-bis(4-hydroxyphenyl)propane-based polycarbonate, the production method thereof is, for example, using 2,2-bis(4-hydroxyphenyl)propane as a raw material and alkali Examples thereof include a method of blowing phosgene in the presence of an aqueous solution and a solvent to cause a reaction; a method of transesterifying 2,2-bis(4-hydroxyphenyl)propane and a carbonic acid diester in the presence of a catalyst.

The viscosity average molecular weight of the aromatic polycarbonate resin is not particularly limited, but is preferably 21,000 or more and 28,000 or less. The viscosity average molecular weight is defined in JIS K7252-2 and is obtained by capillary viscosity measurement. Generally, when the viscosity average molecular weight is high, the impact resistance and heat resistance are improved, but the compatibility when adding another resin is decreased, and the mechanical properties tend to be decreased. When the viscosity average molecular weight is in this range, the balance between mechanical properties, heat resistance and fluidity when the fluidity improver of the present invention is added is excellent. It is preferably 21,000 or more and 26,000 or less, and more preferably 21,000 or more and 24,000 or less.

When the viscosity average molecular weight of the aromatic polycarbonate resin is 21,000 or more and 28,000 or less, the total amount of the polymer (A) and the polymer (B) in the fluidity improver is 100% by mass, and The amount of the acid methyl monomer is preferably 24% by mass or more and 60% by mass or less, more preferably 30% by mass or more and 50% by mass or less.
If the amount of the methyl methacrylate monomer is 24% by mass or more based on 100% by mass of the total of the polymer (A) and the polymer (B) in the fluidity improver, the viscosity average of the aromatic polycarbonate resin is obtained. Even if the molecular weight is in the range of 21,000 or more and 28,000 or less, the compatibility is good and the impact resistance of the molded product is good. When it is 60% by mass or less, it becomes incompatible with the aromatic polycarbonate resin having a large viscosity average molecular weight, and the fluidity during molding can be improved.

When the viscosity average molecular weight of the aromatic polycarbonate resin is 21,000 or more and 28,000 or less, the total amount of the polymer (A), the polymer (B) and the polymer (C) in the fluidity improver, 100 mass. %, the amount of the methyl methacrylate monomer is 24% by mass or more and 70% by mass or less. It is preferably 35% by mass or more and 65% by mass or less.
When the viscosity average molecular weight of the aromatic polycarbonate resin is 21,000 or more and 28,000 or less, the total amount of the polymer (A), the polymer (B) and the polymer (C) in the fluidity improver, 100 mass. %, the compatibility with aromatic polycarbonate resin having a large viscosity average molecular weight is good, and the impact resistance of the molded product is good. When it is 70% by mass or less, it becomes incompatible with the aromatic polycarbonate resin having a large viscosity average molecular weight, and the fluidity during molding can be improved.

When the viscosity average molecular weight of the aromatic polycarbonate resin is 21,000 or more and 28,000 or less, the content of the aromatic vinyl monomer (a1) in the monomer mixture (a) is 59.5% by mass. Or more to 74.5 mass% or less, the content of the (meth)acrylic acid ester (a2) is 25 mass% or more to 40 mass% or less, and the content of the epoxy group-containing vinyl monomer (a3) is 0. It is preferably 5% by mass or more and 5% by mass or less.

When the viscosity average molecular weight of the aromatic polycarbonate resin is 21,000 or more and 28,000 or less, the content of the aromatic vinyl monomer (a1) in the monomer mixture (a) (100% by mass) is When it is 59.5% by mass or more, it becomes incompatible with the aromatic polycarbonate resin having a large viscosity average molecular weight, and the fluidity during molding can be improved.
When the content of the aromatic vinyl monomer (a1) in the monomer mixture (a) (100% by mass) is 74.5% by mass or less, the mechanical properties of the molded product are not impaired.

When the viscosity average molecular weight of the aromatic polycarbonate resin is 21,000 or more and 28,000 or less, the content of the (meth)acrylic acid ester (a2) in the monomer mixture (a) (100% by mass) is When it is 25% by mass or more, the surface layer peeling resistance and mechanical properties of the molded product are not impaired.
When the content of the (meth)acrylic acid ester (a2) in the monomer mixture (a) (100% by mass) is 40% by mass or less, it is incompatible with the aromatic polycarbonate resin having a large viscosity average molecular weight. It melts and improves the fluidity during molding.

When the viscosity average molecular weight of the aromatic polycarbonate resin is 21,000 or more and 28,000 or less, the content of the epoxy group-containing vinyl monomer (a3) in the monomer mixture (a) (100% by mass). When the ratio is 0.5% by mass or more, the fluidity is improved without causing decomposition during melt-kneading with the aromatic polycarbonate resin.
If the content of the vinyl monomer (a3) having an epoxy group in the monomer mixture (a) (100% by mass) is 5% by mass or less, melting with an aromatic polycarbonate resin having a large viscosity average molecular weight Improves fluidity without deterioration due to retention during kneading. It is preferably 2.5 mass% or less.

The aromatic polycarbonate resin composition (100% by mass) of the present invention comprises 70% by mass or more and 99.9% by mass or less of the aromatic polycarbonate resin, and 0.1% by mass or more and 30% by mass or less of the fluidity improver of the present invention. Contains and.
The content of the fluidity improver in the aromatic polycarbonate resin composition (100% by mass) is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more. The content of the fluidity improver in the aromatic polycarbonate resin composition (100% by mass) is preferably 20% by mass or less.

When the content of the fluidity improver in the aromatic polycarbonate resin composition (100% by mass) is 0.1% by mass or more, the fluidity during molding is sufficiently improved.
When the content of the fluidity improver in the aromatic polycarbonate resin composition (100% by mass) is 30% by mass or less, the mechanical properties of the aromatic polycarbonate resin are not impaired.

The aromatic polycarbonate resin composition of the present invention may contain a light diffusing agent.
Examples of the light diffusing agent include inorganic fine particles such as glass filler, calcium carbonate, barium sulfate, silica, talc, mica, wollastonite, and titanium oxide; obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer. Amorphous heat-resistant polymer particles such as organic cross-linked particles, silicone-based cross-linked particles and polyether sulfone particles, epoxy resin particles, urethane resin particles, melamine resin particles, benzoguanamine resin particles, and polymer fine particles such as phenol resin particles. ..

As the light diffusing agent, polymer fine particles are preferable to inorganic fine particles. By using polymer fine particles, both light diffusivity and total light transmittance can be realized at a higher level.
The refractive index of the polymer fine particles is usually about 1.33 or more and 1.7 or less. When the refractive index of the polymer fine particles is within this range, a sufficient light diffusing function is exhibited in the state of being blended with the resin composition.

The average particle diameter of the light diffusing agent is preferably 0.01 μm or more and 50 μm or less, more preferably 0.1 μm or more and 10 μm or less, and further preferably 0.1 μm or more and 8 μm or less. The average particle size is represented by 50% (D50) of the cumulative distribution of particle size obtained by the laser light scattering method.
The light diffusing agent preferably has a narrow particle size distribution, and more preferably has a distribution such that the fine particles having an average particle size of ±2 μm account for 70% by mass or more of the whole.

The absolute value of the difference between the refractive index of the light diffusing agent and the refractive index of the aromatic polycarbonate resin is preferably 0.02 or more and 0.2 or less. When the difference in refractive index is within this range, it is possible to achieve both high light diffusivity and high total light transmittance. The refractive index of the light diffusing agent is more preferably lower than that of the aromatic polycarbonate resin.

When it contains a light diffusing agent, the aromatic polycarbonate resin composition (100% by mass) of the present invention contains 69.9% by mass or more and 99.8% by mass or less of the aromatic polycarbonate resin, and the fluidity improver of the present invention. 0.1 mass% or more and 30 mass% or less and a light diffusing agent 0.1 mass% or more and 30 mass% or less are contained.
When the content of the light diffusing agent in the aromatic polycarbonate resin composition (100% by mass) is 0.1% by mass or more and 30% by mass or less, a sufficient light diffusing function is exhibited.

In the aromatic polycarbonate resin composition of the present invention, known stabilizers, coloring materials, antistatic agents, hydrolysis improvers, heat ray absorbers, mold release agents, reinforcing agents, impact resistance modifiers are added, if necessary. You may mix additives, such as a quality agent and a flame retardant. As the stabilizer, for example, a phosphorus-based stabilizer, a hindered phenol-based stabilizer, an ultraviolet absorber, and a light stabilizer may be contained in order to stabilize the molecular weight and the hue during molding. As the coloring material, for example, a bluing agent, a fluorescent dye or the like can be contained. Examples of the antistatic agent include organic sulfones such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. Acid alkali (earth) metal salts are mentioned. Examples of the releasing agent include fatty acid ester, polyolefin wax, silicone compound, fluorine compound, paraffin wax, beeswax, and the like, and by containing them, defective releasing can be prevented. Glass fibers, carbon fibers, potassium titanate fibers and the like may be contained in order to improve the strength, rigidity and flame retardancy of the molded product. Further, other engineering plastic compositions such as polyethylene terephthalate for improving chemical resistance, and rubber-like elastic bodies for improving impact resistance may be added.

Further, various dyes and pigments, inorganic fillers, antibacterial agents, photocatalytic antifouling agents and the like can be added to the aromatic polycarbonate resin composition of the present invention.

The aromatic polycarbonate-based resin composition of the present invention can be used, for example, with a Henschel mixer, a Banbury mixer, a simple screw extruder, a twin screw extruder, a twin roll, a kneader, and a Brabender to obtain a fluidity improver and an aromatic compound. It is prepared by a known method in which a polycarbonate resin and, if necessary, a light diffusing agent and the like are mixed and kneaded.

The molded article of the present invention is obtained by molding the aromatic polycarbonate resin composition of the present invention by a known method such as an injection molding method, an extrusion molding method, a compression molding method, a blow molding method, or a cast molding method. To be The aromatic polycarbonate resin composition of the present invention is particularly useful as a raw material for injection molded articles.

The molded product of the present invention includes a hard coat product, a glazing material, a light diffusing plate, an optical disk substrate, a light guide plate, a building, a building material, an agricultural material, a marine material, an electric/electronic device, a machine, a medical material, a vehicle member, and a miscellaneous item. It can be used in a wide range of applications such as.

Next, the hard coat product of the present invention will be described.
The hard coat product of the present invention has a hard coat layer provided on the surface of a molded product obtained by molding the above aromatic polycarbonate resin composition.
The hard coat layer is formed by applying a hard coat agent to the surface of a molded product obtained by molding the aromatic polycarbonate resin composition and curing the hard coat agent.
Examples of the hard coating agent include silicone resin-based hard coating agents and other organic resin-based hard coating agents.

The silicone resin-based hard coating agent forms a cured resin layer having a siloxane bond. As the silicone resin-based hard coating agent, for example, a partially hydrolyzed condensate of a compound containing a compound corresponding to a trifunctional siloxane unit (such as a trialkoxysilane compound) as a main component and a compound corresponding to a trifunctional siloxane unit and a tetrafunctional compound Examples thereof include partial hydrolysis-condensation products of compounds containing compounds corresponding to siloxane units (tetraalkoxysilane compounds, etc.), and partial hydrolysis-condensation products obtained by filling these partial hydrolysis condensation products with metal oxide fine particles such as colloidal silica. ..

Examples of other organic resin-based hard coating agents include melamine resins, urethane resins, alkyd resins, acrylic resins, and polyfunctional acrylic resins. Of these, monofunctional compounds such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, organic-inorganic hybrid (meth)acrylate obtained by condensing colloidal silica and (meth)acryloylalkoxysilane ( Monomers or oligomers such as (meth)acrylates or polyfunctional (meth)acrylates; organic-inorganic hybrid vinyl compounds are preferred.

The hard coat agent is applied to the molded article by a known coating method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method and a roller coating method. The coating method can be selected appropriately. Among these, the dip coating method, the flow coating method, and the spray coating method are preferable because they can easily cope with complicated shapes and can easily control the film thickness.
The hard coat agent can be cured by volatilizing the organic solvent when an organic solvent is used, and then irradiating and/or heating with active energy rays such as ultraviolet rays and electron rays.

The hard coat product described above is an aromatic aromatic resin having high melt fluidity without impairing the original properties of the aromatic polycarbonate resin (transparency, surface layer peeling resistance, heat resistance, impact resistance, and chemical resistance). Since it is composed of a polycarbonate resin composition, it has excellent moldability.
Since the hard coat product of the present invention is excellent in transparency, heat resistance, impact resistance and appearance, it is used in various electronic/electrical devices, OA equipment, vehicle parts, machine parts, agricultural materials, fishery materials, transport containers, packaging containers. It is useful for various purposes such as, playground equipment and sundries. In addition, because it can be made larger, lighter and thinner, more complex in shape, and have higher performance, it is possible to use front door windows (windshield), rear door windows, quarter windows, back windows, back door windows, sunroofs, roof panels, It is suitable for glazing materials for buildings and vehicles such as window materials.

Next, the light diffusion plate of the present invention will be described.
The light diffusing plate of the present invention is usually produced from the above-mentioned resin composition by a known injection molding method.
The aromatic polycarbonate resin composition of the present invention is particularly suitable for producing a large-sized and thin light diffusion plate (particularly, a light diffusion plate for an image display device). According to the aromatic polycarbonate resin composition of the present invention, the light diffusing plate obtained surface area of 500 cm ² or more 50,000 cm ² or less. The surface area of the light diffusing plate is preferably 1,000 cm ² or more and 25,000 cm ² or less, and the thickness thereof is preferably 0.3 mm or more and 3 mm or less. As described above, according to the aromatic polycarbonate resin composition of the present invention, it is possible to manufacture a light diffusion plate that is large in size, has high dimensional stability, and is thin (light weight).

The light diffusion plate may be a single layer plate having a surface shape such as Fresnel lens shape or cylindrical lens shape, or another material having a surface shape such as Fresnel lens shape or cylindrical lens shape is laminated on the light diffusion plate. It may be a laminated plate.

The light diffusing plate described above is an aromatic aromatic resin having a high melt fluidity without impairing the original properties of the aromatic polycarbonate resin (transparency, surface peeling resistance, heat resistance, impact resistance, and chemical resistance). Since it is composed of a polycarbonate resin composition, it has excellent moldability.
Further, since the light diffusing plate of the present invention is excellent in chemical resistance, it can be surface-modified and, as a result, can be provided with other functions. "Surface modification" means a new layer on the surface of a light diffusive molded product by vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dip plating, etc.), painting, coating, printing, etc. Is provided.

Next, the optical disk substrate of the present invention will be described.
The optical disk substrate of the present invention is usually manufactured by melt molding such as a known injection molding method (including an injection compression molding method) from the above resin composition, and in particular, the above resin composition. Has a high melt flowability and is excellent in moldability such as transferability. Therefore, the optical disk substrate of the present invention has grooves or pits transferred to one side or both sides by an injection molding method using a stamper. It is suitable for a wide range of applications, from ordinary recording density to high recording density.

The injection molding machine and stamper to be used may be general ones, but the cylinder and screw of the injection molding machine may suppress the generation of carbides derived from the resin composition and increase the reliability of the optical disk substrate. It is preferable to use a material that has low adhesion to the resin composition and is made of a material having corrosion resistance and abrasion resistance.
The environment of the molding step is preferably as clean as possible in view of the purpose of the present invention. Furthermore, before molding, the resin composition is sufficiently dried to remove water, and the resin composition. It is also important to consider that the product does not stay in the molding machine and melt and decompose.

The optical disc is not particularly limited in its specific laminated structure as long as it has an optical disc substrate made of the above-mentioned resin composition, and a reflecting film, a recording layer, a light transmitting layer may be provided on one side or both sides of the optical disc substrate. An example is a form in which the above are laminated as necessary.

The optical disk substrate described above is an aromatic polycarbonate having high melt flowability without impairing the original properties of the aromatic polycarbonate resin (transparency, surface layer peeling resistance, heat resistance, impact resistance, and chemical resistance). Since it is made of a resin composition, molding processability such as transferability is good, and the birefringence of the molded product is improved. Therefore, such an optical disk substrate is applicable to audio CDs (recording density of about 650 MB per disk having a diameter of 12 cm) to high density disks.

Next, the light guide plate of the present invention will be described.
The light guide plate of the present invention is usually manufactured by a known injection molding method from the above resin composition. Although the specific shape of the light guide plate is not particularly limited, the above resin composition has high melt fluidity and can satisfactorily transfer fine irregularities formed in the cavity of the injection molding die. Therefore, a light guide plate having a wedge-shaped cross section in which one surface is an inclined surface having a uniform inclination, and a continuous prism-shaped concavo-convex pattern is applied to the inclined surface to form an irregular reflection portion can be preferably exemplified. Such a light guide plate can be manufactured by using an injection molding die having a cavity having an uneven portion and performing injection molding while transferring the uneven portion. As a method for providing the uneven portion in the cavity of the injection molding die, a method of forming the uneven portion in the insert is simple and preferable.

By including at least such a light guide plate and a light source that emits light toward the light guide plate, a mobile phone, a mobile terminal, a camera, a clock, a laptop computer, a display, lighting, a signal, a tail lamp of an automobile, electromagnetic cooking It is possible to configure an edge-type surface light source used for displaying the heat power of a container. As the light source, a self-luminous body such as a cold cathode tube, an LED, an organic EL, etc. can be used in addition to the fluorescent lamp.

The light guide plate described above is an aromatic polycarbonate having high melt flowability without impairing the original properties of the aromatic polycarbonate resin (transparency, surface layer peeling resistance, heat resistance, impact resistance, and chemical resistance). Since it is made of a resin composition, it can be used in a wide range of applications without restrictions on the environment in which it is used, and the fine irregularities formed in the cavity of the injection molding die are sufficiently transferred to achieve good molding and brightness. The problems such as a decrease in power consumption are suppressed. Therefore, by using such a light guide plate, it is possible to provide a surface light source body having high performance and high industrial value.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
"Parts" and "%" in the examples mean "parts by mass" and "mass %", respectively.

(Measurement of polymerization rate)
The polymerization rate of the polymer was measured by the following procedure.
1) Measure the mass of the aluminum dish to the nearest 0.1 mg. (A)
2) About 1 g of the polymer is placed in an aluminum dish, and the mass is measured to the unit of 0.1 mg. (B)
3) Place the aluminum dish containing the polymer in a dryer at 180° C. and heat for 45 minutes.
4) The aluminum dish containing the polymer is taken out from the dryer, cooled to 24° C. in a desiccator, and then the mass is measured to the unit of 0.1 mg. (C)
5) The solid content of the polymer is calculated by the following formula.
(C-A)/(B-A) x 100 [%]
6) The calculated solid content is divided by the solid content at the time of charging to calculate the polymerization rate of the polymer.

(Measurement of mass average molecular weight (Mw) and number average molecular weight (Mn))
The (Mw) and (Mn) of the polymer were measured by the following procedure.
It was determined from a calibration curve using standard polystyrene using gel permeation chromatography. The measurement conditions are as follows.
Column: TSK-GEL SUPER HM-H (manufactured by Tosoh Corporation)
Measurement temperature: 40℃
Eluent: Tetrahydrofuran Eluent rate: 0.6 ml/min Detector: RI

(Measurement of epoxy group amount)
The amount of epoxy groups in the polymer (A) was measured by the following procedure.
1) Measurement of blank 1-1) 10 ml of the following solution A is sampled with a whole pipette and put in a 100 ml Erlenmeyer flask with a stopper.
Solution A: 0.1 N hydrochloric acid (tetrahydrofuran/ethanol=1/1) solution 1-2) The sampled solution A is titrated with the following solution B using phenolphthalein as an indicator. The point where the slight red color continues for 30 seconds is the end point of the titration, and the titer of the solution B at this time is X (ml).
Solution B: 0.1 N potassium hydroxide (alcoholic) solution

2) Measurement of polymer (A) 2-1) In a 100 ml Erlenmeyer flask with a stopper, W (g) of polymer (A) is taken in the range of 4 to 7 g. Tetrahydrofuran (THF) (30 ml) is added to dissolve the polymer (A).
2-2) To the Erlenmeyer flask containing the solution of the polymer (A), 10 ml of the solution A is sampled with a whole pipette and added.
2-3) Attach a cooling tube to the Erlenmeyer flask and heat at 60° C. for 5 minutes.
2-4) After cooling the Erlenmeyer flask, titrate with Solution B using phenolphthalein as an indicator. The point where the slight red color continues for 30 seconds is the end point of the titration, and the titer of the solution B at this time is Y (ml).
2-5) The amount of epoxy groups of the polymer (A) is calculated to the first decimal place by the following formula (f in the formula indicates the titer of the solution B).
Epoxy group amount=f×0.1×((X−Y)/1000)/W×1000 (mmol/g)

<Production Example 1>
Production of Polymer (A-1) In a separable flask equipped with a thermometer, a nitrogen introducing tube, a cooling tube and a stirrer, the following emulsifier mixture was charged and stirred, and the internal temperature was increased to 60°C under a nitrogen atmosphere. Heated.
Emulsifier mixture:
Phosphanol RS-610Na 1.0 part (manufactured by Kao Corporation, anionic emulsifier)
Deionized water 293 parts

Then, the following reducing agent mixture was put into a separable flask.
Reductant mixture:
Ferrous sulfate 0.0001 part Ethylenediaminetetraacetic acid disodium salt 0.0003 part Rongalit 0.3 part Deionized water 5 parts

The following monomer mixture was added dropwise into the separable flask over 360 minutes and then stirred for 60 minutes to complete the polymerization, to obtain a polymer (A-1) latex.
Monomer mixture:
Styrene 47.5 parts α-Methylstyrene 24.0 parts Phenyl methacrylate 27.5 parts Glycidyl methacrylate 1.0 parts n-Octanethiol 0.5 parts t-Butyl hydroperoxide 0.2 parts

625 parts of an aqueous solution in which 5 parts of calcium acetate was dissolved was heated to 90° C. and stirred. The obtained polymer (A-1) latex was gradually added dropwise thereto. Then, the temperature was raised to 94° C. and maintained for 5 minutes to coagulate the latex. The coagulated product was separated and washed, and then dried at 80° C. for 24 hours to obtain a polymer (A-1).
The polymerization rate of the polymer (A-1) was 95%, (Mw) was 40,000, and (Mn) was 21,000.

<Production Example 2>
Production of Polymer (A-2) A polymer (A-2) was obtained in the same manner as in Production Example 1, except that the composition of the monomer mixture was changed to the following.
Monomer mixture:
Styrene 47.5 parts α-Methylstyrene 24.0 parts Methyl methacrylate 27.5 parts Glycidyl methacrylate 1.0 parts n-Octanethiol 0.5 parts t-Butyl hydroperoxide 0.2 parts

The polymerization rate of the polymer (A-2) was 95%, (Mw) was 43,000, and (Mn) was 22,000.

<Production Example 3>
Production of Polymer (A-3) A polymer (A-3) was obtained in the same manner as in Production Example 1 except that the composition of the monomer mixture was changed to the following.
Monomer mixture:
Styrene 55.0 parts α-methylstyrene 24.0 parts Phenyl methacrylate 20.5 parts Glycidyl methacrylate 1.0 parts n-Octanethiol 0.5 parts t-Butyl hydroperoxide 0.2 parts

The polymerization rate of the polymer (A-3) was 95%, (Mw) was 43,000, and (Mn) was 22,000.

Table 1 shows the compositions of the polymers (A-1) to (A-3).

<Production Example 4>
Production of polymer (B-1) In a separable flask equipped with a thermometer, a nitrogen introducing tube, a cooling tube and a stirrer, the following emulsifier mixture was charged and stirred, and the internal temperature was increased to 60°C under a nitrogen atmosphere. Heated.
Emulsifier mixture:
Perex SS-L 3.0 parts (Kao Corporation anionic emulsifier)
Deionized water 291 parts

Then, the following reducing agent mixture was put into a separable flask.
Reductant mixture:
Ferrous sulfate 0.0001 part Ethylenediaminetetraacetic acid disodium salt 0.0003 part Rongalit 0.3 part Deionized water 5 parts

The following monomer mixture was added dropwise into the separable flask over 180 minutes, and then the mixture was stirred for 60 minutes to complete the polymerization to obtain a polymer (B-1) latex.
Monomer mixture:
Phenyl methacrylate 25.0 parts Methyl methacrylate 75.0 parts 3-Mercaptopropionic acid 3.0 parts t-Butyl hydroperoxide 0.2 parts

625 parts of an aqueous solution in which 5 parts of calcium acetate was dissolved was heated to 90° C. and stirred. The obtained polymer (B-1) latex was gradually added dropwise thereto. Then, the temperature was raised to 94° C. and maintained for 5 minutes to coagulate the latex. After the coagulated product was separated and washed, it was dried at 80° C. for 24 hours to obtain a polymer (B-1).
The polymerization rate of the polymer (B-1) was 96%, (Mw) was 15,000, and (Mn) was 4,000.

<Production Example 5>
Production of Polymer (B-2) A polymer (B-2) was obtained in the same manner as in Production Example 3, except that the composition of the monomer mixture was changed to the following.
Monomer mixture:
Methyl methacrylate 100.0 parts 3-mercaptopropionic acid 3.0 parts t-butyl hydroperoxide 0.2 parts

The polymerization rate of the polymer (B-2) was 96%, (Mw) was 11,000, and (Mn) was 5,000.

<Production Example 6>
Production of Polymer (B-3) A polymer (B-3) was obtained in the same manner as in Production Example 3, except that the composition of the monomer mixture was changed to the following.
Monomer mixture:
Phenylmethacrylate 100.0 parts 3-Mercaptopropionic acid 3.0 parts t-Butyl hydroperoxide 0.2 parts

The polymerization rate of the polymer (B-3) was 96%, (Mw) was 15,000, and (Mn) was 4,000.

<Production Example 7>
Production of Polymer (B-4) A polymer (B-4) was obtained in the same manner as in Production Example 3, except that the composition of the monomer mixture was changed to the following.
Monomer mixture:
Phenyl methacrylate 75.0 parts Methyl methacrylate 25.0 parts 3-Mercaptopropionic acid 3.0 parts t-Butyl hydroperoxide 0.2 parts

The polymerization rate of the polymer (B-4) was 99%, (Mw) was 15,000, and (Mn) was 4,000.

<Production Example 8>
Production of Polymer (C-1) In a separable flask equipped with a thermometer, a nitrogen introducing tube, a cooling tube and a stirrer, the following emulsifier mixture was charged and stirred, and the internal temperature was increased to 60°C under a nitrogen atmosphere. Heated.
Emulsifier mixture:
Phosphanol RS-610Na 1.0 part (manufactured by Kao Corporation, anionic emulsifier)
Deionized water 293 parts

Then, the following reducing agent mixture was put into a separable flask.
Reductant mixture:
Ferrous sulfate 0.0001 part Ethylenediaminetetraacetic acid disodium salt 0.0003 part Rongalit 0.3 part Deionized water 5 parts

The following monomer mixture was added dropwise into the separable flask over 360 minutes and then stirred for 60 minutes to complete the polymerization, to obtain a polymer (C-1) latex.
Monomer mixture:
Styrene 48.5 parts α-Methylstyrene 24.0 parts Methyl methacrylate 27.5 parts n-Octanethiol 0.55 parts t-Butyl hydroperoxide 0.2 parts

625 parts of an aqueous solution in which 5 parts of calcium acetate was dissolved was heated to 90° C. and stirred. The obtained polymer (C-1) latex was gradually added dropwise thereto. Then, the temperature was raised to 94° C. and maintained for 5 minutes to coagulate the latex. After the coagulated product was separated and washed, it was dried at 80° C. for 24 hours to obtain a polymer (C-1).
The polymerization rate of the polymer (C-1) was 95%, (Mw) was 40,000, and (Mn) was 21,000.

<Production Example 9>
Production of Polymer (C-2) A polymer (C-2) was obtained in the same manner as in Production Example 8 except that the composition of the monomer mixture was changed to the following.
Monomer mixture:
Styrene 48.5 parts α-methylstyrene 24.0 parts Phenyl methacrylate 27.5 parts n-Octanethiol 0.55 parts t-Butyl hydroperoxide 0.2 parts

The polymerization rate of the polymer (C-2) was 95%, (Mw) was 38,000, and (Mn) was 21,000.

Polymer (A), polymer (B), and polymer (C) were mixed in the proportions shown in Table 2 to prepare fluidity improvers (1) to (8).

<Examples 1 to 10 and Comparative Examples 1 to 8>
Aromatic polycarbonate resin (Upilon S-2000F, manufactured by Mitsubishi Chemical Engineering Plastics Co., Ltd., viscosity average molecular weight 22,000, abbreviated as PC1), aromatic polycarbonate resin P2 (Upilon S-3000F, Mitsubishi Chemical Engineering Plastics Co., Ltd.) Manufactured, viscosity average molecular weight 20,500, abbreviated as PC2), and fluidity improvers (1) to (8) were mixed in the proportions shown in Table 3, and a twin-screw extruder (TEM-35, manufactured by Toshiba Machine Co., Ltd.) ) And melt-kneaded at 280° C. to obtain an aromatic polycarbonate resin composition.
The method (I) was used to mix the fluidity improver with the aromatic polycarbonate resin.

The following evaluations were performed using the aromatic polycarbonate resin compositions obtained in Examples 1-10 and Comparative Examples 1-8.

(DuPont impact test)
The impact resistance of the molded product was evaluated by the DuPont impact test.
A resin composition is molded using an injection molding machine (IS-100, manufactured by Toshiba Machine Co., Ltd.) (molding temperature 280° C., mold temperature 60° C.) to obtain a molded product having a length of 150 mm×width of 150 mm×thickness of 2 mm. Obtained.
In the DuPont impact test, according to ASTM D2794, it was measured whether the test piece was penetrated by dropping a weight on the test piece. The measurement is performed using a 1/2 inch diameter shot type and a pedestal with a diameter of 3 cm. There are two conditions: a 1 kg weight is dropped from a height of 500 mm and a 5 kg weight is dropped from a height of 300 mm. The measurement was carried out at two locations, the center of the test piece and the vicinity of the gate during molding. The evaluation results are shown in Table 2. The case of not penetrating was evaluated as “◯”, and the case of penetrating was evaluated as “x”.

(Melt flowability)
The spiral flow length of the resin composition was evaluated using an injection molding machine (IS-100, manufactured by Toshiba Machine Co., Ltd.).
The molding temperature was 280° C., the mold temperature was 60° C., the injection pressure was 22 MPa, and the thickness of the molded product was 2 mm and the width was 15 mm. The evaluation results are shown in Table 3.

As is apparent from Table 3, the molded articles of the aromatic polycarbonate resin compositions obtained in Examples 1 to 10 were not significantly damaged during the molding process without significantly impairing the impact resistance which is the original characteristic of the aromatic polycarbonate resin. Has improved liquidity. It is considered that this is because the compatibility with the aromatic polycarbonate resin is good by containing a predetermined proportion of the methyl methacrylate monomer.

Even when a polycarbonate resin having a high viscosity average molecular weight such as PC1 is used, the fluidity improver of the present invention has good compatibility and does not significantly impair impact resistance.

Further, as in Examples 1 to 3 and 6 to 8, when the mass composition in the polymer (A) is within a predetermined range, good impact resistance is obtained both in the center of the test piece and in the vicinity of the gate. showed that.

In Comparative Examples 1 to 3 and 5 to 7 which did not contain a predetermined proportion of methyl methacrylate monomer, the impact resistance, which is a characteristic of the polycarbonate resin main body, was significantly impaired.
In Comparative Examples 4 and 8 in which the fluidity improver of the present invention was not blended, the fluidity was lower than in Examples 1-10.

According to the fluidity improver of the present invention, the fluidity at the time of molding processing is not impaired without impairing the original properties of the aromatic polycarbonate resin (transparency, surface layer peeling resistance, heat resistance, impact resistance, and chemical resistance). Can be improved. Therefore, the aromatic polycarbonate resin composition of the present invention realizes molding of a molded product having a large size, a thin wall, and a complicated shape, and a hard coat product, a glazing material, a light diffusing plate, an optical disk substrate, a light guide plate, and a building. It is preferably used for a wide range of applications such as goods, construction materials, agricultural materials, marine materials, electric/electronic devices, machines, medical materials, vehicle members, and miscellaneous goods.

Claims (13)

Aromatic vinyl monomer (a1) 0.5 mass% or more and 99 mass% or less, (meth)acrylic acid ester (a2) 0.5 mass% or more and 99 mass% or less, and an epoxy group-containing vinyl monomer ( a3) 0.5 to 99.5 parts by mass of a polymer (A) obtained by polymerizing a monomer mixture (a) containing 0.5 to 5% by mass,
A monomer mixture (b) containing a (meth)acrylic ester and 0.5 to 99.5 parts by mass of a polymer (B) obtained by polymerizing using a compound having a carboxyl group. A fluidity improver which is contained, and the amount of the methyl methacrylate monomer is 20% by mass or more and 80% by mass or less based on 100% by mass of the total of the polymer (A) and the polymer (B). Further, it is obtained by polymerizing a monomer mixture (c2) containing 30% by mass or more and 90% by mass or less of the aromatic vinyl monomer (c1) and 10% by mass or more and 70% by mass or less of the (meth)acrylic acid ester. Methyl methacrylate containing 10 parts by mass or more and 80 parts by mass or less of the polymer (C), based on 100% by mass of the total of the polymer (A), the polymer (B) and the polymer (C). The fluidity improver according to claim 1, wherein the amount of the monomer is 20% by mass or more and 80% by mass or less. The fluidity improver according to claim 1, which is obtained by reacting the epoxy group of the polymer (A) with the carboxyl group of the polymer (B). An aromatic polycarbonate resin containing 70% by mass or more and 99.9% by mass or less of the aromatic polycarbonate resin and 0.1% by mass or more and 30% by mass or less of the fluidity improver according to claim 1. Composition. Flow in which the fluidity improver is such that the amount of the methyl methacrylate monomer is 24% by mass or more and 60% by mass or less based on 100% by mass of the total amount of the polymer (A) and the polymer (B). The aromatic polycarbonate resin composition according to claim 4, which is a property improver. The polymer (A) contained in the fluidity improver contains 59.5% by mass or more and 74.5% by mass or less of the aromatic vinyl monomer (a1) and 25% by mass of the (meth)acrylic acid ester (a2). A polymer (A) obtained by polymerizing a monomer mixture (a) containing not less than 40% by mass and not less than 0.5% by mass and not more than 5% by mass of a vinyl monomer (a3) having an epoxy group. The aromatic polycarbonate resin composition according to claim 5, which is present. 70 mass% or more and 99.9 mass% or less of the aromatic polycarbonate resin composition according to any one of claims 5 and 6, and 0.1 mass% or more and 30 mass% or less of a light diffusing agent. Aromatic polycarbonate resin composition. A molded product obtained by molding the aromatic polycarbonate resin composition according to any one of claims 4 to 7. A hard coat product having a hard coat layer on the surface of the molded product according to claim 8. A glazing material using the molded product according to claim 8 or the hard coat product according to claim 9. A light diffusing plate obtained by molding the aromatic polycarbonate resin composition according to any one of claims 4 to 7. An optical disk substrate formed by molding the aromatic polycarbonate resin composition according to any one of claims 4 to 7. A light guide plate obtained by molding the aromatic polycarbonate resin composition according to any one of claims 4 to 7.