JP2015178545A - Light diffusing polycarbonate resin composition, molding and cover for led illumination - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light diffusing polycarbonate resin composition which does not cause blue retina injury by LED illumination and lowers less in brightness, its molding and a cover for LED illumination free of problems of blue retina injury.SOLUTION: A polycarbonate resin composition comprises (A) 100 pts.mass of a polycarbonate resin and (B) 0.1-10 pts.mass of a light diffusing fine particle and has a total luminous flux retention with a thickness of 1 mm of 40% or higher and an exposure allowable time index of 30 or greater.

Description

  The present invention relates to a light diffusing polycarbonate resin composition, a molded product thereof, and a cover for LED lighting, and more specifically, a light diffusing polycarbonate resin composition that has no problem of blue retinal damage in LED lighting and has little reduction in brightness. And its molded product and LED illumination cover.

  In recent years, the performance of LEDs has increased, and conventional lighting devices (instruments) have been replaced with those using LEDs for reasons such as long life and low power consumption. Among them, white LED is an effective technique for illumination. There are several ways to achieve white light with an LED, but the one that achieves pseudo white light by combining a phosphor with a blue LED near the wavelength of 450 nm is the mainstream, and the yellow color is above the blue LED. A white LED of a type in which a phosphor is installed is widely used.

However, the illumination device that combines the blue LED and the yellow phosphor is excited by the blue LED, and therefore has a large blue component in the intensity spectrum. I don't get it.
In recent years, in the health of living organisms, blue light has a risk of causing injury due to its strong energy, and there is a concern that it may cause damage to the retina and the like, and it is desirable to reduce the risk of retinal injury due to blue light as much as possible. In December 2013, a safety standard for retinal damage caused by blue light was established in JIS C7550. Even in LED lighting fixtures, it is required that repeated exposure does not affect health.

In addition, it is necessary for the optical cover of the LED lighting device (equipment) to achieve bright illumination that emits the amount of light emitted from the LED light source to the outside of the cover without losing as much as possible.
Furthermore, it is necessary to provide a light diffusing function in the cover or the like depending on the use and purpose of LED lighting. The light diffusion manifestation methods are (1) a method of devising the product shape, such as applying a crease on the cover surface, (2) a method of installing a light diffusion layer on the surface layer by coating or attaching a film, (3) a polycarbonate resin For example, there is a technique in which particles having a refractive index different from that of the base material are present in the cover base material.
As the method (3), specifically, a polycarbonate resin composition containing an inorganic filler such as titanium oxide or calcium carbonate or organic crosslinked particles as a light diffusing agent is known (for example, Patent Document 1). reference). However, the inclusion of the light diffusing agent leads to a decrease in the amount of light emitted from the LED light source, although the light diffusibility is improved.

JP2012-251108A

  In view of the above situation, an object of the present invention is to provide a light diffusing polycarbonate resin composition, a molded article thereof, and a cover for LED lighting that do not have a problem of blue retinal damage in LED lighting and have little reduction in brightness. It is in.

In order to solve the above problems, the present inventors have made extensive studies, and as a result, a polycarbonate resin composition containing a specific amount of light diffusing fine particles in a polycarbonate resin, comprising a specific total luminous flux retention rate and a specific The present inventors have found that a polycarbonate resin composition having an exposure allowance time index becomes a light diffusive polycarbonate resin composition with less problems of blue retinal damage in LED lighting and less reduction in brightness.
The present invention provides the following light-diffusing polycarbonate resin composition, molded article, and LED illumination cover.

[1] A polycarbonate resin composition containing 0.1 to 10 parts by mass of (B) light diffusing fine particles with respect to 100 parts by mass of (A) polycarbonate resin,
A light diffusing polycarbonate resin composition having a total luminous flux retention ratio of 40% or more and an exposure allowable time index of 30 or more at a thickness of 1 mm.
[2] The method according to [1], further including (C) a blue light-cutting dye capable of achieving a light transmittance at a wavelength of 450 nm of 50% with a content of 0.02% by mass or less based on the polycarbonate resin. A light diffusing polycarbonate resin composition.
[3] The light diffusing polycarbonate resin composition according to the above [2], wherein the content of the (C) blue light cut dye is 0.0001 to 0.01 parts by mass with respect to 100 parts by mass of the (A) polycarbonate resin. object.
[4] Furthermore, (D) The organic sulfonic acid alkali metal salt is contained in 0.01 to 1 part by mass with respect to 100 parts by mass of the (A) polycarbonate resin. A light diffusing polycarbonate resin composition.
[5] The light diffusibility according to any one of [1] to [4], further comprising 0.01 to 1 part by mass of (E) a fluorine-based resin with respect to 100 parts by mass of the (A) polycarbonate resin. Polycarbonate resin composition.

[6] The light diffusibility according to any one of [1] to [5] above, further containing 0.01 to 5 parts by mass of (F) an organosilicon compound with respect to 100 parts by mass of (A) the polycarbonate resin. Polycarbonate resin composition.
[7] The light diffusing polycarbonate resin according to any one of the above [1] to [6], wherein the (A) polycarbonate resin contains 30% by mass or more of a polycarbonate resin (A1) having a structural viscosity index of 1.2 or more. Composition.
[8] The light-diffusing polycarbonate resin according to any one of [1] to [7], wherein the (A) polycarbonate resin contains 5% by mass or more of a polycarbonate resin (A2) having a viscosity average molecular weight of 38,000 or more. Composition.
[9] A molded article comprising the light diffusing polycarbonate resin composition according to any one of [1] to [8].
[10] A cover for LED lighting comprising the light diffusing polycarbonate resin composition according to any one of [1] to [8].

  According to the light diffusing polycarbonate resin composition of the present invention, it is possible to provide a light diffusing polycarbonate resin composition having no problem of blue retinal damage in LED lighting and having little reduction in brightness. It can be suitably used as an optical member of an instrument), particularly as a cover for LED lighting.

It is a block diagram of the LED straight tube type illuminating lamp using the illumination cover concerning one Embodiment of this invention.

Hereinafter, although an embodiment, an example thing, etc. are shown and explained in detail about the present invention, the present invention is limited to an embodiment, an example, etc. shown below and is not interpreted.
In the present specification, unless otherwise specified, “to” is used in a sense that includes numerical values described before and after it as a lower limit value and an upper limit value. Further, “part” means a part by mass based on the mass standard unless otherwise specified.

In the polycarbonate resin composition containing 0.1 to 10 parts by mass of (B) light diffusing fine particles with respect to 100 parts by mass of (A) polycarbonate resin, the present invention has a total luminous flux retention of 40% or more at a thickness of 1 mm. And an exposure allowance index of 30 or more has been found to be a light-diffusible polycarbonate resin composition with no problem of blue retinal damage in LED lighting and little reduction in brightness. . Moreover, this invention contains the (C) blue light cut dye which can achieve 50% of the light transmittance in wavelength 450nm by content below 0.02 mass% with respect to polycarbonate resin as the preferable aspect. A light diffusing polycarbonate resin composition is provided.
The method of controlling the diffusion using fine particles has been conventionally applied. In the present invention, (B) light diffusing fine particles are blended in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) polycarbonate resin. The exposure allowable time index is set to 30 or more after setting the total luminous flux retention rate to 40% or more.

  Here, the total luminous flux retention is measured with a test piece having a thickness of 1 mm in accordance with CIE127: 2007. A specific method for measuring the total luminous flux retention is as described in detail in the examples.

式（１）中、Ｌ_Ｂは、青色光による網膜傷害の実行放射輝度（Ｗ・ｍ^−２・ｓｒ^−１）である。 Further, the exposure allowable time index (T _B ) is determined as follows in accordance with JIS C75550: 2011, and is a value indicating the difficulty of retinal damage caused by blue light.
According to JIS C75550: 2011, the exposure allowable time t _{max for} retinal damage caused by blue light is obtained by the following equation (1).

In formula (1), L _B is the effective radiance (W · m ⁻² · sr ⁻¹ ) of retinal injury caused by blue light.

式（２）中、Ｌ（λ）は分光放射輝度（Ｗ・ｍ^−２・ｓｒ^−１・ｎｍ^−１）、Ｂ（λ）は青色光傷害作用関数、Δλは波長幅（ｎｍ）である。 Then, the L _B is defined as given by the following equation (2).

In formula (2), L (λ) is the spectral radiance (W · m ⁻² · sr ⁻¹ · nm ⁻¹ ), B (λ) is the blue light damage function, and Δλ is the wavelength width (nm). .

式（３）中、ＬＩ（λ）は全光束測定で得られる分光放射強度（Ｗ・ｎｍ^−１）、Ｂ（λ）はＪＩＳ Ｃ７５５０に記載の青色光傷害作用関数、Δλは波長幅５ｎｍである。なお、ＬＥＤは３５０ｎｍ未満の波長は発しないので下限は３５０ｎｍとした。 Here, the spectral radiance L (λ) is the luminance per unit solid angle. In the present invention, the total value in all directions is used, and the spectral radiance obtained when measuring the total luminous flux retention rate. The intensity (LI) is used as the blue retinal injury radiation intensity index (LI _B ).
The blue retinal injury radiation intensity index (LI _B ) is obtained by the following formula (3).

In the formula (3), LI (λ) is a spectral radiation intensity (W · nm ⁻¹ ) obtained by total luminous flux measurement, B (λ) is a blue light damage action function described in JIS C7550, and Δλ is a wavelength width of 5 nm. is there. Since the LED does not emit a wavelength less than 350 nm, the lower limit is set to 350 nm.

Further, the exposure allowable time is indexed with reference to the formula (1), and the exposure allowable time index (T _B ) represented by the following formula (4) is obtained.

The exposure permissible time index (T _B ) indicates that the larger the numerical value, the less likely to cause blue retinal damage. In the present invention, the exposure permissible time index (T _B ) is 30 or more and the total luminous flux retention is It needs to be 40% or more. The exposure allowable time index (T _B ) is preferably 35 or more, more preferably 40 or more, and further preferably 40 or more. The upper limit is not limited, but is preferably 100 or less, more preferably 90 or less. More preferably, it is 85 or less. The total luminous flux retention is preferably 45% or more, more preferably 50% or more, further preferably 55% or more, particularly preferably 60% or more, preferably 95% or less, more preferably 93% or less, Preferably it is 91% or less.
Hereinafter, each component contained in the polycarbonate resin composition of the present invention will be described.

[(A) Polycarbonate resin]
There is no restriction | limiting in the kind of (A) polycarbonate resin used for the polycarbonate resin composition of this invention. Moreover, (A) polycarbonate resin may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.
The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by a general formula: — (— O—X—O—C (═O) —) —. In the formula, X is generally a hydrocarbon group, but for imparting various properties, X introduced with a hetero atom or a hetero bond may be used.
The polycarbonate resin can be classified into an aromatic polycarbonate resin in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon, and an aliphatic polycarbonate resin in which the carbon is an aliphatic carbon. From the viewpoint of electrical characteristics and the like, it is preferable to use an aromatic polycarbonate resin.

Although there is no restriction | limiting in the specific kind of aromatic polycarbonate resin, For example, the polycarbonate resin formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used.
The aromatic polycarbonate resin may be linear or branched. Furthermore, the aromatic polycarbonate resin may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

Among monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include:
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;
2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxy diaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

Dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

Dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (ie, from the viewpoint of impact resistance and heat resistance). Bisphenol A) is preferred.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  Among the monomers used as the raw material for the aromatic polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.

  Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

-Manufacturing method of polycarbonate resin The manufacturing method of polycarbonate resin is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, a particularly preferable one of these methods will be specifically described.

.. Interfacial polymerization method First, the case where a polycarbonate resin is produced by the interfacial polymerization method will be described. In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

  The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.

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

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

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

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

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

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

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

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

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

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

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

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

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.

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

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

-(A) Other matters regarding polycarbonate resin (A) The polycarbonate resin preferably contains a certain percentage or more of a polycarbonate resin having a structural viscosity index N in a predetermined range.
The structural viscosity index N is an index for evaluating the flow characteristics of a melt as described in detail in the document “Rheology for chemists” (Chemical Doujin, 1982, pp. 15-16). . Usually, the melting characteristics of polycarbonate resin can be expressed by the formula: γ = a · σ ^N. In the above formula, γ: shear rate, a: constant, σ: stress, N: structural viscosity index.

  In the above formula, when N = 1, Newtonian fluidity is exhibited, and the non-Newtonian fluidity increases as the value of N increases. That is, the flow characteristics of the melt are evaluated by the magnitude of the structural viscosity index N. In general, a polycarbonate resin having a large structural viscosity index N tends to have a high melt viscosity in a low shear region. For this reason, when polycarbonate resin with a large structural viscosity index N is mixed with another polycarbonate resin, dripping at the time of combustion of the molded product obtained can be suppressed, and a flame retardance can be improved. However, in order to maintain the moldability of the obtained polycarbonate resin composition in a favorable range, the structural viscosity index N of the polycarbonate resin is preferably not excessively large.

In the polycarbonate resin composition of the present invention, the (A) polycarbonate resin preferably contains a polycarbonate resin (A1) having a structural viscosity index N of preferably 1.2 or more. The structural viscosity index N of the polycarbonate resin (A1) is more preferably 1.25 or more, further preferably 1.28 or more, particularly preferably 1.30 or more, and usually 1.8 or less, preferably 1. 7 or less.
Thus, the high structural viscosity index N means that the polycarbonate resin has a branched structure. By containing the polycarbonate resin having a high structural viscosity index N in this way, dripping at the time of burning of the polycarbonate resin molded product Can be suppressed and flame retardancy can be improved.

The structural viscosity index N can also be expressed by Log η _a = [(1-N) / N] × Log γ + C, which is derived from the above equation, as described in, for example, JP-A-2005-232442. Is possible. In the above formula, N: structural viscosity index, γ: shear rate, C: constant, η _a : apparent viscosity. As can be seen from this equation, the N value can also be evaluated from γ and ηa in _a low shear region in which the viscosity behavior is greatly different. For example, the N value can be determined from η _a at γ = 12.16 sec ⁻¹ and γ = 24.32 sec ⁻¹ .

  A polycarbonate resin having a structural viscosity index N of 1.2 or more is obtained by, for example, aromatic dihydroxy by a melting method (transesterification method) as described in JP-A-8-259687 and JP-A-8-245782. When reacting a compound with a carbonic acid diester, an aromatic polycarbonate resin having a high structural viscosity index and excellent hydrolytic stability can be obtained without adding a branching agent by selecting the catalyst conditions or production conditions. it can.

In addition, a polycarbonate resin having a structural viscosity index N of 1.2 or more can be produced by a method using a branching agent when produced by a phosgene method or a melting method (a transesterification method) according to a conventional method.
Specific examples of the branching agent include phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris (4-hydroxy). Phenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenylheptene-3,1,3,5-tris (4-hydroxyphenyl) ethane and the like, and 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichloroisatin bisphenol, 5-bromoisatin bisphenol and the like.
The amount to be used is preferably in the range of 0.01 to 10 mol%, particularly preferably in the range of 0.1 to 3 mol%, based on the aromatic dihydroxy compound.

In the polycarbonate resin composition of the present invention, (A) the polycarbonate resin is the above-described polycarbonate resin (A1) having a structural viscosity index N of 1.2 or more, preferably 30% by mass or more, more preferably in the polycarbonate resin. It is desirable to contain 40% by mass or more, more preferably 50% by mass or more, and most preferably 60% by mass or more. By combining with the polycarbonate resin (A1) in this way, the torque during extrusion is not increased more than necessary, so that the productivity is hardly lowered. That is, both formability and productivity can be exhibited remarkably.
In addition, there is no restriction | limiting in the upper limit of content of polycarbonate resin (A1) in (A) polycarbonate resin, Usually, it is 100 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less. It is. Moreover, 1 type may be used for polycarbonate resin (A1) and it may use 2 or more types together by arbitrary combinations and a ratio.

  Moreover, (A) polycarbonate resin may contain the polycarbonate resin whose structural viscosity index | exponent N is outside said predetermined range other than the polycarbonate resin (A1) mentioned above. Although there is no restriction | limiting in the kind, A linear polycarbonate resin is preferable especially. By combining the polycarbonate resin (A1) and the linear polycarbonate resin, there is an advantage that it is easy to balance the flame retardancy (anti-dripping property) and moldability (fluidity) of the obtained polycarbonate resin composition. From this viewpoint, it is particularly preferable that the (A) polycarbonate resin is composed of the polycarbonate resin (A1) and the linear polycarbonate resin. In addition, the structural viscosity index N of this linear polycarbonate resin is usually about 1-1.15.

  (A) The molecular weight of the polycarbonate resin may be appropriately selected and determined, but is usually 15,000 or more, preferably 19,000 or more, more preferably 21,000 in terms of viscosity average molecular weight [Mv] converted from the solution viscosity. 3,000 or more, particularly 23,000 or more, and usually 36,000 or less, preferably 34,000 or less, more preferably 32,000 or less, still more preferably 30,000 or less, particularly preferably 29,000 or less. It is. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is less than the upper limit of the above range, the fluidity of the polycarbonate resin composition of the present invention can be suppressed and improved, and the molding processability can be improved and the molding process can be easily performed.

The (A) polycarbonate resin may be used by mixing two or more kinds of polycarbonate resins having different viscosity average molecular weights. In this case, the polycarbonate resin having a viscosity average molecular weight outside the above preferred range is mixed. May be.
When mixed and used, it is preferable to use a polycarbonate resin (A2) having a large Mv mixed with a polycarbonate resin having a relatively small viscosity average molecular weight (Mv). In this case, a polycarbonate having a small Mv is used. The resin is selected from the range of less than 38,000, preferably 10,000 to 30,000, more preferably 12,000 to 20,000, and the Mv of the polycarbonate resin (A2) having a large Mv is 38,000 or more, preferably It is preferable to use a combination of 50,000 to 90,000, more preferably 60,000 to 85,000.
In this case, the proportion of the polycarbonate resin (A2) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more in 100% by mass of the total polycarbonate resin. In particular, it is preferably 20% by mass or more, and usually 50% by mass or less. Moreover, 1 type may be used for polycarbonate resin (A2) and it may use 2 or more types together by arbitrary combinations and a ratio.

  Moreover, it is also preferable that (A) polycarbonate resin contains both above-mentioned polycarbonate resin (A1) and polycarbonate resin (A2).

In the present invention, the viscosity average molecular weight [Mv] refers to the intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. using a Ubbelohde viscometer using methylene chloride as a solvent. It means a value calculated from the viscosity formula, that is, η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

(A) The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1,500 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of the polycarbonate resin composition of the present invention can be further improved. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the polycarbonate resin composition of this invention can be improved more.
In addition, the unit of a terminal hydroxyl group density | concentration represents the mass of the terminal hydroxyl group with respect to the mass of polycarbonate resin in ppm. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

  (A) The polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and includes, for example, an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. It may be used in the sense) or may be used in combination with an alloy (mixture) of a polycarbonate resin and another thermoplastic resin. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  Moreover, in order to improve the appearance of the molded product and the fluidity, (A) the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, (A) the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include optical recording media such as optical discs; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include building materials such as windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resins contained in the polycarbonate resin composition of the present invention. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[(B) Light diffusing fine particles]
The polycarbonate resin composition of the present invention contains (B) light diffusing fine particles in a range of 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) polycarbonate resin.
(B) The light diffusing fine particles are fine particle inorganic or organic particles, and examples thereof include organic fine particles such as glass fine particles, polystyrene resin, (meth) acrylic resin, and silicone resin. Organic fine particles are preferable, and light diffusing effect. From this point, the fine particles are preferably spherical.

  (B) The average particle diameter of the light diffusing fine particles is usually 0.1 to 50 μm, preferably 0.5 μm or more, more preferably 1.0 μm or more, preferably 30 μm or less, more preferably 20 μm or less. More preferably, it is 10 μm or less, and most preferably 6 μm or less. When the average particle size is less than 0.1 μm, the light diffusibility of the obtained polycarbonate resin composition is difficult to improve, while the brightness tends to be lowered. On the other hand, if it exceeds 50 μm, the light diffusing effect tends to decrease and the luminance tends to decrease.

  As described above, the content of the (B) light diffusing fine particles is 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) polycarbonate resin, preferably 0.2 parts by mass or more, and more preferably. Is 0.3 parts by mass or more, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less, and particularly preferably 1.5 parts by mass or less. If the content is less than 0.1 parts by mass, the light diffusibility is insufficient and the high-brightness LED light source is easily seen through, and the dazzling reduction effect becomes insufficient, and if it exceeds 10 parts by mass, the necessary illumination is required. The brightness cannot be obtained.

  (B) As the light diffusing fine particles, crosslinked organic fine particles that are not substantially melted in the polycarbonate resin even when heated to the molding temperature of the polycarbonate resin are preferable. Specifically, crosslinked acrylic polymer fine particles, crosslinked Siloxane polymer fine particles are particularly preferred.

Crosslinked acrylic polymer fine particles As the crosslinked acrylic polymer fine particles, preferred are crosslinked acrylic resin fine particles produced by a non-crosslinkable acrylic monomer and a crosslinkable monomer, preferably by suspension polymerization.
As the non-crosslinkable acrylic monomer, an acrylic monomer alone or a combination of acrylic monomers is used. As acrylic monomers, acrylic acid esters such as methyl acrylate, n-butyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl-hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate Preferred examples thereof include methacrylic acid esters, and these can be used alone or in combination of two or more. Of these, methyl methacrylate is preferably used.
The monomer may be added with a monomer copolymerizable with a (meth) acrylic acid ester monomer. Examples of such a monomer include styrene, α-methylstyrene, Examples thereof include monomers having a vinyl group such as vinyl acetate.

  On the other hand, as the crosslinkable monomer, a compound having two or more unsaturated bonds in the molecule is preferably used. For example, trimethylolpropane tri (meth) acrylate, allyl methacrylate, triallyl cyanurate, triallyl isocyanate, ethylene glycol dimethacrylate, propylene glycol diallyl ether, divinylbenzene, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, etc. Can be mentioned. Of these, trimethylolpropane tri (meth) acrylate is preferable.

  The crosslinked acrylic polymer fine particles can be produced by suspension polymerization of a non-crosslinkable acrylic monomer and a crosslinkable monomer. For example, both monomers can be polymerized by suspending them using polyvinyl alcohol as a dispersant, followed by filtration, washing, sieving and drying. The proportion of both monomers used is preferably 90 to 99% by mass of the non-crosslinkable acrylic monomer and 10 to 1% by mass of the crosslinkable monomer. If the amount of the crosslinkable monomer is too small, the dispersibility of the obtained bead-shaped crosslinked acrylic polymer fine particles in the polycarbonate resin tends to be poor, and conversely, if the blending ratio of the crosslinkable monomer is large, The coalesced fine particles become too hard and the impact strength tends to decrease, which is not preferable.

  In the present invention, the particle size and particle size distribution are measured on a number basis by the Coulter counter method. In the Cole Counter method, an electrolyte in which sample particles are suspended is passed through pores (apertures), and changes in voltage pulses generated in proportion to the volume of the particles at that time are read to quantify the particle diameter. In addition, the volume distribution histogram of the sample particles can be obtained by measuring the voltage pulse height one by one. Such particle size or particle size distribution measurement by the call counter method is most frequently used as a particle size distribution measuring apparatus.

  The average particle diameter of the crosslinked acrylic polymer fine particles is preferably 1.5 to 5 μm. When the average particle diameter is in this range, the light diffusivity and the degree of dispersion are further increased. The average particle size is preferably 1 to 3 μm, more preferably 1.5 to 3 μm.

  The crosslinked acrylic polymer fine particles preferably have a 5% thermal weight loss temperature of 280 ° C. or higher, more preferably 295 ° C. or higher. When the temperature is less than 280 ° C., the resin composition of the present invention is not preferable because the particle shape cannot be maintained and the desired transmittance and light diffusibility cannot be obtained when the resin composition is produced by melt kneading.

  The content of the crosslinked acrylic polymer fine particles is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, and still more preferably 0.00 with respect to 100 parts by mass of the (A) polycarbonate resin. 3 to 1.5 parts by mass. When the amount is less than 0.1 parts by mass, the effect of improving the transmittance and light diffusibility of the polycarbonate resin is difficult to obtain sufficiently, and when it exceeds 5 parts by mass, the impact resistance of the polycarbonate resin tends to decrease. This is not preferable.

The method for producing the crosslinked acrylic polymer fine particles is known and is not particularly limited, but it is also preferable to directly polymerize and produce the particles by an emulsion polymerization method or a suspension polymerization method. When the crosslinked acrylic polymer fine particles are produced directly by polymerization, the particle diameter can be controlled by the polymerization conditions. For example, a polymer having a broad distribution can be obtained by using a homogenizer so that the particle diameter is a predetermined one and the particle diameter distribution is not loaded with an excessive shearing force.
In addition, the acrylic resin obtained in a solid state is pulverized by a pulverizer such as a jet airflow pulverizer, a mechanical collision pulverizer, a roll mill, a hammer mill, an impeller breaker, etc., and the pulverized product obtained is classified into an air classifier and a sieve classification. The particle size of the particles may be controlled by being introduced into a classification device such as a device for classification.

-Crosslinked siloxane polymer fine particles Polyorganosiloxane constituting the crosslinked siloxane polymer fine particles includes phenyl group, diphenyl group, vinyl group or alkoxy group (for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group). , N-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, etc.), polyorganosiloxane having phenyl group and diphenyl group, polyorganosiloxane having vinyl group and alkoxy group, phenyl group And polyorganosiloxane having an alkoxy group and a vinyl group are preferred.

Polyorganosilsesquioxane is preferred as the polyorganosiloxane. The polyorganosilsesquioxane is a polyorganosiloxane having a trifunctional siloxane unit represented by R—SiO _1.5 (R is a monovalent organic group) (hereinafter sometimes referred to as “T unit”). That is, 50 mol% or more of the total 100 mol% of all siloxane units. The proportion of T units is more preferably 80 mol% or more, still more preferably 90 mol%, particularly 95 mol%.

  Examples of the organic group R bonded to the polyorganosilsesquioxane include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a dodecyl group, an octadecyl group, etc., a C1-C20 alkyl group, a cyclohexyl group Preferred examples include cyclic alkyl groups such as phenyl groups, tolyl groups, and aryl groups such as xylyl groups, and aralkyl groups such as phenylethyl groups and phenylpropyl groups. As the polyorganosilsesquioxane, polyalkylsilsesquioxanes are preferable, and polymethylsilsesquioxane is particularly preferable.

  The crosslinked siloxane-based polymer fine particles preferably have an average particle size of 1.5 to 5 μm. If the average particle size is less than 1.5 μm, the resulting polycarbonate resin composition has little effect of improving the light diffusibility, while lowering the luminance. If it exceeds 5 μm, the light diffusion effect also decreases and the luminance tends to decrease.

  The content of the crosslinked siloxane-based polymer fine particles is preferably 0.35 to 3 parts by mass with respect to 100 parts by mass of the (A) polycarbonate resin. By blending such cross-linked siloxane polymer fine particles in such an amount, the excellent light diffusibility and light transmittance of the polycarbonate resin composition of the present invention can be achieved.

  A method for producing the preferred crosslinked siloxane-based polymer fine particles as described above is known. For example, as described in JP-A-01-217039, organotrialkoxysilane is hydrolyzed under acidic conditions. Then, an alkaline aqueous solution is added to and mixed with the water / alcohol solution of the organosilane triol, and the organosilane triol is polycondensed in a stationary state.

  The particle size can be adjusted mainly by adjusting the pH of the aqueous alkali solution. If small particles are to be obtained, the pH is increased, and if large particles are to be obtained, the pH is decreased to reduce the particle size. The condensation reaction is usually carried out in the range of 0.5 to 10 hours, preferably 0.5 to 5 hours after alkali addition, and the condensate is aged, but the stirring during the aging is weakened. By preventing the association of particles, the particle size and particle size distribution can be adjusted. Further, the obtained crosslinked siloxane polymer particles may be further pulverized to adjust the particle size. The crosslinked siloxane polymer fine particles can also be obtained by specifying the specifications of the desired particle size and distribution to the manufacturer.

[(C) Blue light cut dye]
The polycarbonate resin composition of the present invention preferably contains (C) a blue light cut dye capable of achieving 50% light transmittance at a wavelength of 450 nm with a content of 0.02% by mass or less with respect to the polycarbonate resin. .
Blue light absorbers for synthetic resins include indigo dyes, quinophthalone dyes, quinone dyes, coumarin dyes, chlorophyll dyes, diphenylmethane dyes, spiropyran dyes, thiazine dyes, and triphenylmethane dyes. However, in the present invention, among these, (C) a blue light cut dye that absorbs blue light capable of achieving 50% light transmittance at a wavelength of 450 nm with a content of 0.02% by mass or less with respect to the polycarbonate resin. contains.

  Here, as a polycarbonate resin used for determining whether the light transmittance at a wavelength of 450 nm can be achieved with a content of 0.02% by mass or less, a light transmittance of the commercially available general-purpose polycarbonate resin can be obtained. Therefore, it can be measured sufficiently with a commercially available polycarbonate resin. If the light transmittance is delicate at around 50%, “Iupilon (registered trademark) S-3000” (viscosity average molecular weight Mv: 21,000) manufactured by Mitsubishi Engineering Plastics Co., Ltd. is used as a standard polycarbonate resin. Use and measure the thickness of the test piece as 1 mm. A specific method for measuring the light transmittance will be described in detail in Examples.

  As such (C) blue light cut dye, for example, yellow dyes such as anthraquinone, azo, nitro, methine, and phthalocyanine can be used. Specifically, for example, “KP PLAST Yellow HK” manufactured by Kiwa Chemical Industry Co., Ltd., “MACROLEX Yellow 6G” manufactured by LANXESS, “Sumiplast Olive MR” manufactured by Sumika Chemtex, and the like can be exemplified.

  (C) 0.0001-0.01 mass part is preferable with respect to 100 mass parts of (A) polycarbonate resin, and, as for content of (C) blue light cut dye, More preferably, it is 0.001 mass part or more, Preferably 0.005 parts by mass or less. (C) If the content of the blue light-cutting dye is too small, the total luminous flux retention of the polycarbonate resin composition will be small, and the exposure allowable time index will be low. As a result, the appearance of the molded product is deteriorated and the mechanical strength is lowered.

[(D) Alkali metal salt of organic sulfonic acid]
The polycarbonate resin composition of the present invention preferably contains (D) an alkali metal sulfonic acid alkali metal salt. By containing the organic metal sulfonic acid alkali metal salt, the flame retardancy of the polycarbonate resin composition of the present invention can be improved.

  Examples of the alkali metal that the organic sulfonic acid alkali metal salt has include alkali metals such as lithium, sodium, potassium, rubidium, and cesium. Among them, sodium, potassium, and cesium are preferable, and potassium and sodium are particularly preferable. .

Examples of preferred organic sulfonic acid alkali metal salts include alkali metal salts of fluorine-containing aliphatic sulfonic acids, alkali metal salts of fluorine-containing organic sulfonic acids such as alkali metal salts of fluorine-containing aliphatic sulfonic acid imides, aromatic An alkali metal salt of an aromatic sulfonic acid and an alkali metal salt of an aromatic sulfonamide.
Among them, specific examples of preferable ones include potassium perfluorobutanesulfonate, lithium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, Alkali metal salts of fluorine-containing aliphatic sulfonic acids having at least one C—F bond in the molecule, such as potassium trifluoromethanesulfonate, potassium perfluoroethanesulfonate, potassium perfluoropropanesulfonate;

  Disodium perfluoromethane disulfonate, dipotassium perfluoromethane disulfonate, sodium perfluoroethane disulfonate, dipotassium perfluoroethane disulfonate, dipotassium perfluoropropane disulfonate, dipotassium perfluoroisopropane disulfonate, dipotassium perfluorobutane disulfonate Fluorine-containing aliphatic sulfonic acid such as sodium, alkali metal salt of fluorine-containing aliphatic disulfonic acid having at least one C—F bond in the molecule, such as dipotassium perfluorobutane disulfonate and dipotassium perfluorooctane disulfonate; Metal salt,

  Bis (perfluoropropanesulfonyl) imide lithium, bis (perfluoropropanesulfonyl) imide sodium, bis (perfluoropropanesulfonyl) imide potassium, bis (perfluorobutanesulfonyl) imide lithium, bis (perfluorobutanesulfonyl) imide sodium, In the molecule, such as potassium bis (perfluorobutanesulfonyl) imide, potassium trifluoromethane (pentafluoroethane) sulfonylimide, sodium trifluoromethane (nonafluorobutane) sulfonylimide, potassium trifluoromethane (nonafluorobutane) sulfonylimide, trifluoromethane, etc. An alkali metal salt of a fluorine-containing aliphatic disulfonic imide having at least one C—F bond;

  Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide sodium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide potassium An alkali metal salt of a cyclic fluorinated aliphatic sulfonimide having at least one C—F bond in the molecule; an alkali metal salt of a fluorinated aliphatic sulfonic imide, such as

  Diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, sodium (branched) dodecylbenzenesulfonate, tri Sodium chlorobenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, potassium (branched) dodecylbenzenesulfonate, potassium trichlorobenzenesulfonate, cesium benzenesulfonate, ( Poly) cesium styrene sulfonate, cesium p-toluenesulfonate, cesium (branched) dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate Etc., alkali metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule;

  Sodium salt of saccharin, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfimide, potassium salt of N- (N′-benzylaminocarbonyl) sulfanilimide, potassium of N- (phenylcarboxyl) -sulfanilimide Examples thereof include metal salts of aromatic sulfonamides such as alkali metal salts of aromatic sulfonamides having at least one aromatic group in the molecule, such as salts.

Among the above-described examples, alkali metal salts of fluorine-containing organic sulfonic acids, particularly fluorine-containing aliphatic sulfonic acid alkali metal salts and aromatic sulfonic acid metal salts are more preferable, and fluorine-containing aliphatic sulfonic acid metal salts are particularly preferable. .
The fluorine-containing aliphatic sulfonic acid metal salt is more preferably a fluorine-containing aliphatic sulfonic acid alkali metal salt having at least one C—F bond in the molecule, particularly preferably an alkali metal salt of perfluoroalkanesulfonic acid, Specifically, potassium perfluorobutane sulfonate and sodium perfluoroethane sulfonate are preferable.
The alkali metal salt of aromatic sulfonic acid is more preferably an alkali metal salt of aromatic sulfonic acid, an alkali of diphenyl sulfone-sulfonic acid such as dipotassium diphenylsulfone-3,3′-disulfonic acid dipotassium or diphenylsulfone-3-sulfonic acid potassium. Metal salts; sodium paratoluenesulfonate, and alkali metal salts of paratoluenesulfonic acid such as potassium paratoluenesulfonate and cesium paratoluenesulfonate are particularly preferable, and alkali metal salts of paratoluenesulfonic acid are more preferable.
In addition, (D) organic sulfonic acid alkali metal salt may use 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

The purity of the organic sulfonic acid alkali metal salt is preferably 99% or more. If the purity is lower than this, the composition is discolored or the thermal stability is deteriorated.
Specific examples of such alkali metal sulfonic acid alkali metal salts include, for example, “Megafac F114P” manufactured by DIC, “Biowet C4” manufactured by LANXESS, and “IHT-FR21” manufactured by Insight High Technology. Is done.

  The content of the (D) organic sulfonic acid alkali metal salt in the polycarbonate resin composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0.02 with respect to 100 parts by mass of the (A) polycarbonate resin. Part by mass or more, more preferably 0.04 part by mass or more, particularly preferably 0.05 part by mass or more, preferably 1 part by mass or less, more preferably 0.7 part by mass or less, further preferably 0.5 part by mass. Part or less, particularly preferably 0.3 part by weight or less. (D) If the content of the organic metal sulfonic acid alkali metal salt is too small, the flame retardancy of the obtained polycarbonate resin composition tends to be insufficient, and conversely if too large, the thermal stability of the polycarbonate resin is lowered and molded. Deterioration of the appearance of the product and reduction in mechanical strength are likely to occur.

[(E) Fluororesin]
The polycarbonate resin composition of the present invention preferably contains 0.01 to 1 part by mass of (E) a fluororesin as an anti-dripping agent with respect to 100 parts by mass of (A) the polycarbonate resin. By containing the fluororesin in this way, the melting characteristics of the resin composition can be improved, and the dripping prevention property during combustion can be improved.

  (E) If the content of the fluororesin is less than 0.01 parts by mass, the effect of improving the flame retardancy by the fluororesin tends to be insufficient. The mechanical strength is likely to decrease. The lower limit of the content is more preferably 0.05 parts by mass, still more preferably 0.1 parts by mass, and particularly preferably 0.2 parts by mass, and the upper limit of the content is more preferably 0.75 parts by mass. Parts, more preferably 0.6 parts by mass, particularly preferably 0.5 parts by mass.

(E) Among the fluororesins, fluoroolefin resins are preferred. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, Of these, tetrafluoroethylene resin is preferred.
Moreover, as this fluororesin, what has a fibril formation ability is preferable, and specifically, the fluoro olefin resin which has a fibril formation ability is mentioned. Thus, it has the tendency to improve dripping prevention property at the time of combustion by having fibril formation ability.

  Examples of the fluoroolefin resin having a fibril forming ability include “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon (registered trademark) F201L” and “Polyflon (registered trademark) F103” manufactured by Daikin Industries , “Polyflon (registered trademark) FA500” and the like. Furthermore, as commercially available products of aqueous dispersions of fluoroolefin resins, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon ( Registered trademark) D-1 "and the like.

  Furthermore, an organic polymer-coated fluoroolefin resin can also be suitably used. By using the organic polymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and the surface foreign matter can be suppressed. The organic polymer-coated fluoroolefin resin can be produced by various known methods. For example, (1) a polyfluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and powdered by coagulation or spray drying. (2) A method of polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then pulverizing or producing the powder by solidification or spray drying. 3) After emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, a powder is obtained by coagulation or spray drying. For example, a method for producing the same is mentioned.

The organic polymer for coating the fluoroolefin resin is not particularly limited, and specific examples of monomers for producing such an organic polymer include styrene, α-methylstyrene, p. -Methylstyrene, o-methylstyrene, tert-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4- Aromatic vinyl monomers such as dimethylstyrene;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, (Meth) acrylic acid ester monomers such as tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate;

Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile;
Α, β-unsaturated carboxylic acids such as maleic anhydride; maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide;
Glycidyl group-containing monomers such as glycidyl methacrylate;
Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate;
Olefinic monomers such as ethylene, propylene, isobutylene;
Examples thereof include diene monomers such as butadiene, isoprene and dimethylbutadiene. In addition, these monomers can be used individually or in mixture of 2 or more types.

  Among them, as a monomer for producing an organic polymer that coats a fluoroolefin resin, those having high affinity with the polycarbonate resin are preferable from the viewpoint of dispersibility when blended with the polycarbonate resin, and aromatic monomers are preferable. A vinyl monomer, a (meth) acrylic acid ester monomer, and a vinyl cyanide monomer are more preferable.

  The content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is usually 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more. Usually, it is 95 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, Most preferably, it is 75 mass% or less. It is preferable that the content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is in the above-described range because the balance between the flame retardancy and the appearance of the molded product tends to be excellent.

Specific examples of such an organic polymer-coated fluoroolefin resin include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., “Blendex 449” manufactured by GE Specialty Chemical, “Poly TS AD001” manufactured by PIC, and the like. Can be mentioned.
In addition, (E) fluorine-type resin may contain 1 type, and 2 or more types may contain it by arbitrary combinations and a ratio.

[(F) Organosilicon compound]
The polycarbonate resin composition of the present invention preferably contains (F) an organosilicon compound, can improve flame retardancy, and may be contained together with the (D) alkali metal sulfonate.

  (F) As the organosilicon compound, any organosilicon compound containing silicon (Si) atoms in the molecule may be used, but it is relatively inexpensive and easily available in the market. Polyorganosiloxane is preferable from the viewpoint of excellent thermal stability. Especially, as polyorganosiloxane, what has aromatic groups, such as a phenyl group, in a molecule | numerator is preferable. Examples of such a polyorganosiloxane include polydiphenylsiloxane, polymethylphenylsiloxane, phenyl group-containing cyclic siloxane, and phenyl group-containing silane monomer.

  As commercially available products of such polyorganosiloxane, for example, “X-40-9805”, “X-40-9243”, “X40-9244” manufactured by Shin-Etsu Chemical Co., Ltd., “SILRES SY430” manufactured by Asahi Kasei Wacker Silicone, Examples include “217FLAKE” and “SH-6018” manufactured by Toray Dow Corning.

  Furthermore, the polyorganosiloxane may contain a functional group such as a silanol group, an epoxy group, an alkoxy group, a hydrosilyl (SiH) group, or a vinyl group in addition to the organic group described above in the molecule. By containing these special functional groups, the compatibility between the polyorganosiloxane and the polycarbonate resin may be improved, or the reactivity during combustion may be improved, thereby increasing the flame retardancy.

  Furthermore, the content of silanol groups in the polyorganosiloxane is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, particularly preferably 4% by mass or more, and usually 10% by mass or less. Preferably it is 9 mass% or less, More preferably, it is 8 mass% or less, Most preferably, it is 7.5 mass% or less. By setting the silanol group content in the above range, a high flame retardancy effect tends to be obtained. Moreover, when there is too much silanol group content, the heat stability and wet heat stability of a polycarbonate resin composition may fall remarkably.

  The average molecular weight (weight average molecular weight) of the polyorganosiloxane is not particularly limited and may be appropriately selected and used. Usually, 450 or more, preferably 1,000 or more, more preferably 1,500 or more, and particularly preferably 1, It is 700 or more, usually 300,000 or less, preferably 100,000 or less, more preferably 20,000 or less, and particularly preferably 15,000 or less. Those having a weight average molecular weight of less than the lower limit of the above range are difficult to produce, and the heat resistance of the polyorganosiloxane may be extremely reduced. Moreover, when the weight average molecular weight exceeds the upper limit of the above range, the dispersibility is poor or the flame retardancy tends to be reduced, and the mechanical properties of the polycarbonate resin composition tend to be lowered. The weight average molecular weight is usually measured by GPC (gel permeation chromatograph).

  Moreover, as the (F) organosilicon compound, an aryl group-containing polysilane is also preferable. In particular, the flame retardancy of the polycarbonate resin composition can be remarkably improved by containing the aryl group-containing polysilane simultaneously with the (D) alkali metal sulfonate. Although the details of the reason for the synergistic effect of the remarkable flame retardancy improvement with this metal salt compound are not known, the catalytic action of the metal salt compound partially cleaves the Si-Si bond of polysilane at the temperature during combustion. This can be attributed to the efficient formation of a composite of polycarbonate resin and polysilane. Moreover, when the aryl group is contained, the heat resistance of the polysilane itself is increased, and the compatibility and dispersibility in the polycarbonate resin are improved, whereby a polycarbonate resin composition having excellent transparency and impact resistance can be obtained. Conceivable.

  Examples of such aryl group-containing polysilanes include polyalkylaryl silanes such as polymethylphenylsilane and methylphenylsilane-phenylhexylsilane copolymers; polydiarylsilanes such as polydiphenylsilane; dimethylsilane-methylphenylsilane copolymers. , Dimethylsilane-phenylhexylsilane copolymer, dialkylsilane-alkylarylsilane copolymer such as dimethylsilane-methylnaphthylsilane copolymer; linear or branched, network-like, aryl group-containing polysilane such as And cyclic aryl group-containing polysilanes such as cyclic alkylarylsilanes such as methylphenylcyclosilane, cyclic arylsilanes such as diphenylcyclosilane;

  These (F) organosilicon compounds may be used alone or in a combination of two or more.

  (F) As for content in the case of containing an organosilicon compound, 0.01-5 mass parts is preferable with respect to 100 mass parts of (A) polycarbonate resin, More preferably, it is 0.1 mass part or more, More preferably, it is 0. .3 parts by mass or more, particularly 0.4 parts by mass or more, more preferably 3 parts by mass or less, further preferably 2 parts by mass or less, and particularly preferably 0.4 to 1.5 parts by mass or less. If the content is less than the above lower limit value, the effect of improving flame retardancy due to the blending cannot be sufficiently obtained, and if it is more than the above upper limit value, the heat resistance may be lowered.

[Other additives]
The polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Such additives include heat stabilizers, antioxidants, mold release agents, UV absorbers, dyes and pigments, fluorescent whitening agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers. , Plasticizers, dispersants, antibacterial agents and the like.

-Heat stabilizer As a heat stabilizer, a phosphorus compound is mentioned, for example. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Examples thereof include phosphates of Group 1 or Group 10 metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

  Among them, triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, Dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) ) Organic phosphites such as octyl phosphite are preferred.

  The content of the heat stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more with respect to 100 parts by mass of the (A) polycarbonate resin. Usually, it is 1 part by mass or less, preferably 0.7 part by mass or less, more preferably 0.5 part by mass or less. If the amount of the heat stabilizer is too small, the heat stabilization effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.

-Antioxidant As an antioxidant, a hindered phenolic antioxidant is mentioned, for example. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(me Citylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

  Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable.

  Content of antioxidant is 0.001 mass part or more normally with respect to 100 mass parts of (A) polycarbonate resin, Preferably it is 0.01 mass part or more, and is 1 mass part or less normally, Preferably it is 0. .5 parts by mass or less. When the content of the antioxidant is less than the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

-Release agent Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils. It is done.

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

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

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

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

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons.
Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.

  The content of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 1 with respect to 100 parts by mass of the (A) polycarbonate resin. It is below mass parts. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding may occur.

UV absorbers Examples of UV absorbers include inorganic UV absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, hindered amines Examples include organic ultraviolet absorbers such as compounds. Of these, organic ultraviolet absorbers are preferred, and benzotriazole compounds are more preferred. By selecting the organic ultraviolet absorber, the polycarbonate resin composition of the present invention has good transparency and mechanical properties.

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

  Specific examples of such a benzotriazole compound include “Seesorb 701”, “Seesorb 702”, “Seesorb 703”, “Seesorb 704”, “Seesorb 705”, and “Seesorb 709” manufactured by Sipro Kasei Co., Ltd. “Biosorb 520”, “Biosorb 580”, “Biosorb 582”, “Biosorb 583”, Chemipro Kasei “Chemsorb 71”, “Chemisorb 72”, Cytec Industries “Siasorb UV5411”, ADEKA “ “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “TINUVIN P”, “TINUVIN 234”, “TINUVIN 326”, “TINUVIN 327” manufactured by BASF ”,“ Tinuvin 328 ”and the like.

  The content of the ultraviolet absorber is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the (A) polycarbonate resin, and the upper limit thereof is preferably 1 part by mass. Part or less, more preferably 0.5 part by weight or less. If the content of the ultraviolet absorber is less than the lower limit of the range, the effect of improving the weather resistance may be insufficient, and if the content of the ultraviolet absorber exceeds the upper limit of the range, the mold Debogit etc. may occur and cause mold contamination. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

[Production Method of Polycarbonate Resin Composition]
There is no restriction on the production method of the polycarbonate resin composition, and a known production method of the polycarbonate resin composition can be widely adopted. (A) Polycarbonate resin, (B) Light diffusing fine particles, and blended as necessary. Other components are mixed in advance using various mixers such as tumblers and Henschel mixers, and then melt-kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader. The method of doing is mentioned. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[Molding]
The polycarbonate resin composition of the present invention is suitably molded for an LED lighting member.
In particular, the polycarbonate resin composition of the present invention is suitable as a light diffusing member such as a light diffusing cover for white LED illumination, and can be particularly suitably used as a white LED bulb cover or a white LED straight tube illumination cover.

  There is no restriction | limiting in the shape and manufacturing method of an LED lighting member, The molded article can be manufactured by shape | molding the pellet which pelletized the above-mentioned polycarbonate resin composition by various shaping | molding methods. Further, the resin melt-kneaded by an extruder can be directly molded into a molded product without going through the pellets. The molding method is preferably a molding method such as an injection molding method, an extrusion molding method, a hollow molding method, an injection compression molding method, or a transfer molding method. Of these, the injection molding method is particularly preferable.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.

(Examples 1-20)
Each component described in Table 1 below was mixed in the amount (all parts by mass) described in Table 3 and below for 20 minutes with a tumbler, and then a twin screw extruder (TEX30XCT manufactured by Nippon Steel Works) equipped with 1 vent. ), Kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 290 ° C., the molten resin composition extruded in a strand shape is rapidly cooled in a water tank, and pelletized using a pelletizer, A pellet of a polycarbonate resin composition was obtained.

In Table 1 above, (C) the measurement of the amount of addition of blue light-cutting dye that achieves a light transmittance of 50% at a wavelength of 450 nm was carried out by using a polycarbonate resin “Iupilon (registered trademark)” manufactured by Mitsubishi Engineering Plastics Co., Ltd. as a polycarbonate resin. ) S-3000 "(viscosity average molecular weight Mv: 21,000) and obtained by kneading with a Tanabe Plastics Machinery 40mm single screw extruder at a temperature of 280 ° C and a discharge rate of 20 kg / h to obtain resin pellets. The obtained pellets were dried at 120 ° C. for 5 hours, and then injection-molded at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using a J55AD type injection molding machine manufactured by Nippon Steel Co., Ltd. 3 mm-2 mm-1 mm three-stage thickness) was produced.
The light transmittance is measured in accordance with JIS K7105 using a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation for the 1 mm thick part of the above-mentioned three-stage plate, in accordance with JIS K0115, with a light transmittance at a wavelength of 450 nm ( Unit:%) was measured.

The following measurements and evaluations were performed using the polycarbonate resin composition pellets obtained above.
[Total light transmittance (unit:%)]
The polycarbonate resin composition pellets obtained above were injection molded under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine J55AD manufactured by Nippon Steel, Ltd., and a three-stage plate (thickness 3 mm) -2mm-1mm three-stage thickness) was used as a test piece, and a 1 mm-thick portion of the three-stage plate was measured with a NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K7105.

[Light diffusion dispersion (unit: °)]
Using the three-stage plate test piece obtained above, using GP-5 GONIOPHOTOMETER made by MURAKAMI COLOR RESEARCH LABORATORY, incident light: 0 °, tilt angle: 0 °, light receiving range: 0 ° to 90 °, luminous flux The brightness of the 1 mm thick part of the three-stage plate was measured under the conditions of aperture: 2.0, light receiving aperture: 3.0, and the angle at which the brightness was reduced by half with respect to the brightness of 0 ° was determined as the degree of dispersion (°). .
The higher the degree of dispersion, the higher the light diffusibility, and it is preferable because it has the effect of further diffusing the light from the light source, maintaining the illuminance in a wider range, and lowering the light source visibility.

[Total luminous flux retention (unit:%)]
The total luminous flux retention was evaluated according to CIE 127: 2007.
Specifically, the resin composition pellets obtained above are injection molded under the conditions of a set temperature of 280 ° C. and a mold temperature of 80 ° C., and a hemispherical molded product having a radius of 25.5 mm and a thickness of 1 mm. Got.
Remove the illumination cover of a commercially available LED bulb ("EVERLEDS LDA7-G" manufactured by PANASONIC), attach the above hemispherical molded product, and the total luminous flux (TLFw) and hemispherical shape with the hemispherical molded product attached to the LED bulb The total luminous flux without a molded product (TLFw / o) was measured by a total luminous flux spectrometry system CSLMS-2021 (integral sphere 20 inches, spectrometer CDS-2100) manufactured by Labsphere.
The total luminous flux retention rate (unit:%) is defined as [TLFw / TLFw / o] * 100%. The higher the total luminous flux retention rate, the smaller the luminous flux loss due to the illumination cover, indicating brighter illumination.

[Blue Retina Injury Radiation Intensity Index LI _B ]
Using the spectral radiant intensity for each wavelength (every 5 nm) obtained by the measurement of the luminous flux measuring device using an integrating sphere, which was obtained in the measurement of the total luminous flux retention rate, the above-mentioned formula based on JIS C7550 (2011) according (3) to obtain the blue retinal injury radiation strength index LI _B.
The greater the blue retinal injury radiant intensity index, the more blue light there is and the higher the risk of retinal injury.

[Exposure Allowable Time Index T _B ]
Blue retinal injury radiation strength index LI _B obtained above was determined exposure allowable time index T _B by Equation (4) described above.
The greater the exposure latitude the time index T _B, even if prolonged exposure to illumination indicates that less likely to retinal injury.

[Exposure allowable time index magnification]
The exposure allowable time T _B divided by the exposure time allowed T _B0 of composition not blended only the blue light cut dye, was determined T B _/ T _B0 as the exposure time allowed exponential factor.
The larger the exposure allowable time index magnification, the greater the degree of extension of the exposure allowable time due to the inclusion of the blue light cut dye, indicating that it is safer.

[Flame Retardancy Evaluation (UL)]
The resin composition pellets obtained above were injection molded under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine J55AD manufactured by Nippon Steel, Ltd., and had a length of 127 mm and a width of 12.7 mm. The test pieces for UL test having thicknesses of 1.0 mm, 1.2 mm, and 1.5 mm were obtained.
The obtained test specimen for UL test was conditioned for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity, and the UL94 test (plastic for equipment parts) defined by US Underwriters Laboratories (UL). (Combustion test of material). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 2 below.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied. In the table, “combustibility” is indicated.

(Comparative Examples 1-4)
Except having used the component described in following Table 3 or less, it carried out similarly to Example 1, and obtained the pellet of the polycarbonate resin composition.
Various evaluations were performed in the same manner as in Example 1.
The above results are shown in Tables 3 to 6 below.

(Example 21)
Production and evaluation of LED straight tube lighting cover:
Using the pellets of the resin composition obtained in Example 17, a pipe-shaped extruded product having an outer diameter of 30 mm and a wall thickness of 1 mm was prepared using the following profile extrusion molding machine and conditions. A pipe-shaped molded article having a good appearance was obtained without any problem in the profile extrusion molding.
Extruder: 40 mm single screw extruder Barrel temperature: 280 ° C., screw rotation speed: 15 rpm, discharge rate: 5 kg / h
Single-layer hollow die: outer diameter 45mm, inner diameter 42.5mm
Water-cooled vacuum sizing equipment: sizing die length 160mm, cooling water temperature 25 ° C
Belt-type take-up device: take-up speed 0.8 m / min

Next, using this pipe-shaped molded product as an illumination cover, an LED straight tube type illumination lamp was produced. In FIG. 1, 1 is a long substrate on which LEDs are mounted, 2 is an LED, 3 is a base, 4 is a terminal, and 5 is an illumination cover made of a pipe-shaped molded product.
When this straight tube type illuminating lamp was attached to a lighting device for LED straight tube and turned on, the glare caused by blue light was reduced, and even when working for a long time under the illumination, eye fatigue was good. .

  Since the light diffusing polycarbonate resin composition of the present invention is a light diffusing resin material that does not cause blue retinal damage in LED lighting and has little reduction in brightness, various optical members of various LED lighting devices, particularly LED lighting. There are some which are very suitable for industrial covers and have very high industrial applicability.

Claims (10)

(A) A polycarbonate resin composition containing 0.1 to 10 parts by mass of light diffusing fine particles with respect to 100 parts by mass of a polycarbonate resin,
A light diffusing polycarbonate resin composition having a total luminous flux retention ratio of 40% or more and an exposure allowable time index of 30 or more at a thickness of 1 mm.   The light-diffusing polycarbonate according to claim 1, further comprising (C) a blue light-cutting dye capable of achieving a light transmittance at a wavelength of 450 nm of 50% with a content of 0.02% by mass or less based on the polycarbonate resin. Resin composition.   The light-diffusing polycarbonate resin composition according to claim 2, wherein the content of (C) the blue light cut dye is 0.0001 to 0.01 parts by mass with respect to 100 parts by mass of (A) the polycarbonate resin.   The light-diffusing polycarbonate according to any one of claims 1 to 3, further comprising (D) an organic sulfonic acid alkali metal salt in an amount of 0.01 to 1 part by mass with respect to 100 parts by mass of the (A) polycarbonate resin. Resin composition.   The light-diffusing polycarbonate resin composition according to any one of claims 1 to 4, further comprising (E) 0.01 to 1 part by mass of a fluorine-based resin with respect to 100 parts by mass of the (A) polycarbonate resin. .   The light-diffusing polycarbonate resin composition according to any one of claims 1 to 5, further comprising 0.01 to 5 parts by mass of (F) an organosilicon compound with respect to 100 parts by mass of (A) the polycarbonate resin. .   The light diffusing polycarbonate resin composition according to any one of claims 1 to 6, wherein the (A) polycarbonate resin contains 30% by mass or more of a polycarbonate resin (A1) having a structural viscosity index of 1.2 or more.   The light-diffusing polycarbonate resin composition according to any one of claims 1 to 7, wherein (A) the polycarbonate resin contains 5% by mass or more of a polycarbonate resin (A2) having a viscosity average molecular weight of 38,000 or more.   A molded article comprising the light diffusing polycarbonate resin composition according to any one of claims 1 to 8.   The cover for LED lighting which consists of a light diffusable polycarbonate resin composition of any one of Claims 1-8.

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