JP2014125597A - Thermoplastic resin composition, wavelength conversion member, light-emitting device, and led luminaire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for LED illumination which has sufficient weather resistance, causes little change in luminance and chromaticity, and is excellent in light-emitting efficiency, and to provide a wavelength conversion member, a light-emitting device, and a luminaire.SOLUTION: A thermoplastic resin composition contains a polycarbonate resin having at least a structural unit derived from a specific dihydroxy compound in a part of its structure. A content of a phosphor in the thermoplastic resin composition is 0.01 wt.% or more.

Description

  The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition that contains a phosphor and is preferably applied as a wavelength conversion member of a light emitting device or an LED lighting fixture.

Light-emitting devices using semiconductor light-emitting elements (hereinafter, also simply referred to as LED light-emitting devices) have increased presence as energy-saving light-emitting devices. The LED light-emitting device includes a phosphor that emits light of different wavelengths when excited by light emitted from the semiconductor light-emitting element, along with the semiconductor light-emitting element.
The phosphor included in the LED light-emitting device is, for example, formed into a slurry in which the phosphor is dispersed in a resin, and is included in the LED light-emitting device as a wavelength conversion member (see, for example, Patent Documents 1 and 2).

  As an LED light emitting device, a brighter one, that is, a high total luminous flux is required, and in order to emit more luminous flux from the LED light emitting device, a translucent material is used for the resin constituting the wavelength conversion member. It has been. For example, in Patent Document 2, a silicone resin is exemplified, but other epoxy resins and glass may be used.

JP 2007-95770 A JP 2011-159813 A

  However, an aromatic polycarbonate resin excellent in transparency, rigidity, and moldability is preferably used as the base material of the wavelength conversion member used in these LED lighting devices and light emitting devices, but it does not necessarily have sufficient weather resistance. The development of LED lighting resin compositions, wavelength conversion members, light-emitting devices, and lighting fixtures that have low luminance and chromaticity changes and excellent luminous efficiency even when used under harsh conditions for long periods of time is desired. It was rare. In addition, there has been a demand for the development of a wavelength conversion member that hardly deteriorates even when used outdoors with a lot of ultraviolet rays such as street lights and road signs, and that has excellent durability even when the wavelength of the semiconductor light emitting element is short.

The present inventors have repeatedly studied to solve the above problems, and by using a specific thermoplastic resin composition, the resin composition for LED having excellent durability, little change in luminance and chromaticity, and excellent luminous efficiency. The present invention has been completed by finding that the product can be provided.
The first aspect of the present invention is the following thermoplastic resin composition.
A thermoplastic resin composition comprising a polycarbonate resin having at least a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) as a part of the structure (hereinafter referred to as “specific dihydroxy compound”). And
The thermoplastic resin composition, wherein the content of the phosphor in the thermoplastic resin composition is 0.01% by weight or more.

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)
Furthermore, the phosphor content in the thermoplastic resin composition is preferably 0.2 wt% or more and 50 wt% or less.
Moreover, it is preferable that content of the said polycarbonate resin with respect to the total amount of the thermoplastic resin contained in the said thermoplastic resin composition is 50 to 100 weight%.

  Moreover, it is preferable that a specific dihydroxy compound is a compound represented by following General formula (2).

Moreover, it is preferable that the polycarbonate resin further includes a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound.
Furthermore, the polycarbonate resin preferably contains 90 mol% or less of structural units derived from the specific dihydroxy compound with respect to the structural units derived from all the dihydroxy compounds constituting the polycarbonate resin.

On the other hand, the phosphor is preferably an inorganic compound.
The phosphor is preferably a short afterglow phosphor.
Furthermore, it is preferable to blend a transmittance adjusting agent.
Moreover, it is preferable that the total light transmittance of the 1.0 mm thickness plate of the said thermoplastic resin composition is 30 to 70%.

In addition, the second aspect of the present invention provides:
A wavelength conversion member that converts the wavelength of at least part of incident light and emits outgoing light having a wavelength different from that of the incident light;
The wavelength conversion member has a planar structure including a phosphor that absorbs at least a part of the incident light and emits an emitted light having a wavelength different from that of the incident light, and a thermoplastic resin that holds the phosphor. Having
The thermoplastic resin contains a polycarbonate resin having at least a structural unit derived from the specific dihydroxy compound,
At least a part of the planar structure is a wavelength conversion member having a total light transmittance of 30% or more and 70% or less.

Moreover, the aspect of 3rd invention of this invention is a light-emitting device provided with the wavelength conversion member which concerns on a 2nd aspect, The aspect of 4th invention of this invention is provided with the light-emitting device which concerns on 3rd aspect. LED lighting fixture.

  Provided are a resin composition for LED lighting, a wavelength conversion member, a light emitting device, and an LED lighting fixture that have excellent durability, little change in luminance and chromaticity, and excellent light emission efficiency. In addition, the present invention provides a wavelength conversion member, a light emitting device, and an LED lighting device that are less likely to deteriorate even when used outdoors with a lot of ultraviolet rays. Furthermore, the present invention provides a wavelength conversion member, a light emitting device, and an LED lighting fixture that are excellent in durability even when the light emitting wavelength of the semiconductor light emitting element is a short wavelength.

It is a schematic diagram which shows the structural example of the semiconductor light-emitting device which concerns on the embodiment of this invention. It is a schematic diagram which shows the structural example of the semiconductor light-emitting device which concerns on the embodiment of this invention.

<1. Thermoplastic resin composition>
A first aspect of the present invention is a polycarbonate resin having at least a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure (hereinafter referred to as “specific dihydroxy compound”). And a phosphor content in the thermoplastic resin composition is 0.01 wt% or more.

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)
It is preferable that content of the said polycarbonate resin with respect to the total amount of the thermoplastic resin contained in the said thermoplastic resin composition is 50 to 100 weight%. If the content of the polycarbonate resin is small, it may be difficult to maintain the characteristics of the polycarbonate resin, such as insufficient weather resistance.

<1-1. Polycarbonate resin>
The polycarbonate resin used in the present invention is a polycarbonate resin containing at least a structural unit derived from a specific dihydroxy compound.

(However, the site represented by the above formula (1) unless a portion constituting a part of _-CH 2 -OH.)
[Production method of polycarbonate resin]
Hereinafter, the method for producing the polycarbonate resin of the present invention will be described in detail.

<Raw material>
(Dihydroxy compound)
The polycarbonate resin of the present invention contains at least a structural unit derived from a specific dihydroxy compound. That is, the specific dihydroxy compound refers to a compound containing at least two hydroxyl groups and a structural unit represented by the following formula (1).

(However, the site represented by the above formula (1) unless a portion constituting a part of _-CH 2 -OH.)
Specific examples of the specific dihydroxy compound include oxyalkylene glycols, dihydroxy compounds having an ether group bonded to an aromatic group in the main chain, and dihydroxy compounds having a cyclic ether structure. These dihydroxy compounds are preferable in that they have good polymerization reactivity and are excellent in mechanical properties, heat resistance, optical properties, and the like of the obtained polycarbonate resin.

Examples of the oxyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol.
Examples of the dihydroxy compound having an ether group bonded to an aromatic group in the main chain include 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2 -Hydroxypropoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] Fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-isopropylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-isobutylphenyl] fluorene, 9,9- Bis [4- (2-hydroxyethoxy) -3-tert-butylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethyl) Xyl) -3-cyclohexylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5 -Dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl] fluorene, 9,9-bis [4- (3-hydroxy-2,2 -Dimethylpropoxy) phenyl] fluorene, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, 2,2-bis [4- (2-hydroxypropoxy) phenyl] propane, 1,3-bis ( 2-hydroxyethoxy) benzene, 4,4′-bis (2-hydroxyethoxy) biphenyl and bis [4- (2-hydroxyethoxy) Phenyl] sulfone, and the like.

  Examples of the dihydroxy compound having a cyclic ether structure include a dihydroxy compound represented by the following formula (2), a spiro glycol represented by the following formula (4) and the following formula (5). The “cyclic ether structure” of the “dihydroxy compound having a cyclic ether structure” includes an ether group in the cyclic structure and a structure in which the carbon atoms constituting the cyclic chain are aliphatic carbon atoms. Means.

Examples of the dihydroxy compound represented by the formula (2) include isosorbide (ISB), isomannide and isoide which are in a stereoisomeric relationship. These may be used individually by 1 type and may be used in combination of 2 or more type.
Among these specific dihydroxy compounds, dihydroxy compounds represented by the above formula (2), (4) or (5) from the viewpoint of easy availability, handling, reactivity during polymerization, and hue of the obtained polycarbonate resin. A dihydroxy compound having a cyclic ether structure represented by a compound is preferable, and a dihydroxy compound having two cyclic ether structures such as a dihydroxy compound represented by the formula (2) or a spiroglycol represented by the formula (5) Is more preferable, and in particular, anhydrosugars such as dihydroxy compounds represented by the above formula (2) obtained by dehydration condensation of sorbitol produced from various starches that are abundant as plant-derived resources Alcohol is easy to obtain and manufacture, weather resistance, optical properties, moldability, heat resistance and carbon The most preferable from the viewpoint of Toraru.

  These specific dihydroxy compounds may be used alone or in combination of two or more depending on the required performance of the polycarbonate resin to be obtained. The polycarbonate resin of the present invention preferably contains 25% by weight or more of a structure derived from a specific dihydroxy compound in consideration of the balance of heat resistance, mechanical properties, optical properties, etc., and particularly 30% by weight or more and 80% by weight. % Or less, in particular 35% by weight or more and 75% by weight or less is preferable.

  The polycarbonate resin of the present invention may contain a structural unit derived from a dihydroxy compound other than the specific dihydroxy compound (hereinafter sometimes referred to as “other dihydroxy compound”). Examples of the other dihydroxy compounds include aliphatic dihydroxy compounds (straight chain aliphatic hydrocarbon dihydroxy compounds, branched straight chain aliphatic hydrocarbon dihydroxy compounds), alicyclic hydrocarbon dihydroxy compounds, and aromatic compounds. Examples thereof include bisphenols.

Examples of the straight-chain aliphatic hydrocarbon dihydroxy compounds include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2 -Butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol and the like.

Examples of the branched straight chain aliphatic hydrocarbon dihydroxy compound include neopentyl glycol and hexylene glycol.
Examples of the alicyclic hydrocarbon dihydroxy compound include 1,2-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and tricyclodecanedi. Methanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1, Examples thereof include dihydroxy compounds derived from terpene compounds such as 3-adamantane dimethanol and limonene.

  Examples of the aromatic bisphenols include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2, 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3, 5-Dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4′-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexa 1,1-bis (4-hydroxyphenyl) decane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 2,2-bis (4-hydroxyphenyl) octane, 2, 2-bis (4-hydroxyphenyl) nonane, 2,2-bis (4-hydroxyphenyl) decane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, Bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 4,4′-dihydroxy-2,5-diethoxydiphenyl ether, 9,9-bis ( -Hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, (4-hydroxy-3-n-propyl) Phenyl) fluorene, 9,9-bis (4-hydroxy-3-isopropylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-butylphenyl) fluorene, 9,9-bis (4-hydroxy-) 3-sec-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-tert-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene and the like.

  Among the above-mentioned other dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) or the following formula (3) is preferred from the viewpoint of optical properties, heat resistance and mechanical properties of the obtained polycarbonate resin. It is preferable to use the dihydroxy compound represented by these. From the viewpoint of availability and production and the aforementioned performance, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 9,9-bis [4- (2-hydroxyethoxy) is particularly preferable. ) Phenyl] fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.

(In the general formula (3), R ^{1 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein X ¹ and X ² are each independently a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon number; A cycloalkylene group having 6 to 20 or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, m and n are each independently an integer of 0 to 5)
In the polycarbonate resin of the present invention, in order to satisfy desired optical properties and mechanical properties such as retardation wavelength dispersion and heat resistance, 25 structural units derived from the dihydroxy compound represented by the formula (3) are used. It is preferably contained in an amount of not less than 75% by weight and not more than 75% by weight, and more preferably not less than 30% by weight and not more than 70% by weight.

  These other dihydroxy compounds may be used alone or in combination with the specific dihydroxy compound depending on the required performance of the obtained polycarbonate resin, or may be used in combination with the specific dihydroxy compound after combining two or more kinds. Good. Among them, from the viewpoint of the color tone, weather resistance, and optical properties of the polycarbonate resin, a dihydroxy compound having no aromatic ring structure in the molecular structure, that is, a dihydroxy compound of an aliphatic hydrocarbon or a dihydroxy compound of an alicyclic hydrocarbon is preferable. These may be used in combination.

Among the above, the aliphatic hydrocarbon dihydroxy compounds are particularly those having 3 to 6 carbon atoms such as 1,3-propanediol, 1,4-butanediol, 1,5-heptanediol or 1,6-hexanediol. A straight-chain aliphatic hydrocarbon dihydroxy compound having hydroxy groups at both ends is preferred.
As the alicyclic hydrocarbon dihydroxy compound, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or tricyclodecane dimethanol is preferable, and 1,2 cyclohexanedimethanol is more preferable. -Dihydroxy compounds having a cyclohexane structure such as cyclohexanedimethanol, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol, and most preferred is 1,4-cyclohexanedimethanol.

  By using these other dihydroxy compounds in combination with the specific dihydroxy compound, it is possible to obtain effects such as improvement in flexibility and mechanical properties of the polycarbonate resin and improvement in moldability. However, if the content ratio of the structural unit derived from the other dihydroxy compound in the polycarbonate resin is too large, it may cause a decrease in mechanical properties or a decrease in heat resistance. The proportion of structural units derived from the dihydroxy compound is preferably 70% by weight or less, more preferably 65% by weight or less, and particularly preferably 60% by weight or less. On the other hand, it is preferably 10% by weight or more, more preferably 15% by weight or more, and particularly preferably 20% by weight or more.

Further, in order to effectively obtain the above-described effects by the combined use of other dihydroxy compounds and specific dihydroxy compounds, the proportion of structural units derived from the specific dihydroxy compounds in the structural units derived from all dihydroxy compounds in the polycarbonate resin is In terms of ratio, when the structural unit derived from all dihydroxy compounds is 1, it is preferably 0.1 or more and 0.95 or less, particularly preferably 0.2 or more and 0.9 or less.

  Moreover, when using together the dihydroxy compound represented by said Formula (2) and the dihydroxy compound represented by said Formula (3) as a specific dihydroxy compound, it is preferable to use oxyalkylene glycol together, and in this case A structural unit derived from the dihydroxy compound represented by the formula (2) occupying in a structural unit derived from all dihydroxy compounds in the polycarbonate resin, a structural unit derived from the dihydroxy compound represented by the formula (3), The proportion of structural units derived from oxyalkylene glycols is a molar ratio of the structural units derived from all dihydroxy compounds as 1, and the structural units derived from the dihydroxy compounds represented by the formula (2) are 0. .1 to 0.7, structural units derived from the dihydroxy compound represented by the formula (3) .1～0.5, it is preferable to 0.001 to 0.3 structural units derived from oxyalkylene glycol.

All dihydroxy compounds used in the production of the polycarbonate resin of the present invention contain stabilizers such as reducing agents, antioxidants, oxygen scavengers, light stabilizers, antacids, pH stabilizers or heat stabilizers. May be. In particular, since the specific dihydroxy compound of the present invention is easily altered under acidic conditions, it is preferable to include a basic stabilizer.
Examples of the basic stabilizer include hydroxides, carbonates, phosphates, phosphites, hypophosphites of group 1 or group 2 metals in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Acid salts, borates and fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium Basic ammonium compounds such as dimethyl hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide and butyltriphenylammonium hydroxide, diethylamine, di Butylamine, triethylamine, morpholine, N-methylmorpholine, pyrrolidine, piperidine, 3-amino-1-propanol, ethylenediamine, N-methyldiethanolamine, diethylethanolamine, 4-aminopyridine, 2-aminopyridine, N, N-dimethyl- 4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypi Amine compounds such as lysine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole and aminoquinoline, and di- (tert-butyl) amine and 2, Examples include hindered amine compounds such as 2,6,6-tetramethylpiperidine. Among these stabilizers, tetramethylammonium hydroxide, imidazole or hindered amine compounds are preferable from the viewpoint of stabilization effect.

The content of these basic stabilizers in all the dihydroxy compounds used in the present invention is not particularly limited, but the specific dihydroxy compounds used in the present invention are unstable in an acidic state. It is preferable to add a stabilizer so that the pH of the aqueous solution containing the specific dihydroxy compound is around 7.
If the amount of the stabilizer is too small, the effect of preventing the alteration of the specific dihydroxy compound may not be obtained. If the amount is too large, the specific dihydroxy compound may be modified. On the other hand, it is preferably 0.0001% by weight to 1% by weight, and more preferably 0.001% by weight to 0.1% by weight.

When these basic stabilizers are included in the dihydroxy compound used in the present invention and used as a raw material for the production of polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, and it becomes difficult to control the polymerization rate or quality. The hue will be deteriorated.
Therefore, for specific dihydroxy compounds or other dihydroxy compounds containing a basic stabilizer, the basic stabilizer should be removed by ion exchange resin or distillation before using it as a raw material for producing polycarbonate resin. Is preferred.

  In addition, since the specific dihydroxy compound used in the present invention is gradually oxidized by oxygen, in order to prevent decomposition due to oxygen during storage or handling during manufacture, water should not be mixed and deoxygenated. It is preferable to use an agent or to put it in a nitrogen atmosphere.

(Carbonated diester)
The polycarbonate resin of the present invention can be obtained by polycondensation by a transesterification reaction using a dihydroxy compound containing the above-mentioned specific dihydroxy compound and a carbonic acid diester as raw materials. As a carbonic acid diester used, what is normally represented by following formula (6) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

In the above formula (6), A ¹ and A ² are each a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group, and A ¹ and A ² May be the same or different. A preferable example of A ¹ and A ² is a substituted or unsubstituted aromatic hydrocarbon group, and a more preferable example is an unsubstituted aromatic hydrocarbon group.

  Examples of the carbonic acid diester represented by the formula (6) include substituted diphenyl carbonates such as diphenyl carbonate (DPC) and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Among them, preferred is diphenyl carbonate or substituted diphenyl carbonate, and particularly preferred is diphenyl carbonate.

In addition, carbonic acid diester may contain impurities such as chloride ions, and the impurities may hinder the polymerization reaction or deteriorate the hue of the resulting polycarbonate resin. It is preferable to use a product purified by the above.
<Transesterification reaction catalyst>
The polycarbonate resin of the present invention is produced by transesterification of the above-described dihydroxy compound and carbonic acid diester. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system.

In the transesterification reaction, polycondensation is performed in the presence of a transesterification reaction catalyst. The transesterification reaction catalyst (hereinafter simply referred to as a catalyst or a polymerization catalyst) that can be used in the production of the polycarbonate resin of the present invention may be used. ) Can greatly affect the reaction rate or the quality of the polycarbonate resin obtained by polycondensation.
The catalyst used is not limited as long as it can satisfy the transparency, hue, heat resistance, weather resistance, and mechanical strength of the produced polycarbonate resin. For example, metal compounds of Group 1 or Group 2 (hereinafter simply referred to as “Group 1” or “Group 2”) in the long-period periodic table, as well as basic boron compounds, basic phosphorus compounds, and basic ammonium compounds And basic compounds such as amine compounds. Preferably, Group 1 metal compounds and / or Group 2 metal compounds are used.

  Examples of the Group 1 metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, and carbonic acid. Lithium, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, hydrogenated Cesium boron, sodium phenide boron, potassium phenide boron, lithium phenide boron, cesium phenide boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, hydrogen phosphate 2 Thorium, 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, Examples include cesium alcoholate, phenolate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, and dicesium salt. Among these, lithium compounds are preferable from the viewpoint of polymerization activity and the hue of the obtained polycarbonate resin.

  Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, carbonic acid. Examples thereof include magnesium, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate. Among these, a magnesium compound, a calcium compound or a barium compound is preferable, and a magnesium compound and / or a calcium compound is more preferable, and a calcium compound is most preferable from the viewpoint of polymerization activity and the hue of the obtained polycarbonate resin.

In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound can be used in combination with the above-mentioned Group 1 metal compound and / or Group 2 metal compound. However, it is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.
Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide. Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium Dorokishido and butyl triphenyl ammonium hydroxide, and the like.

  Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, and 4-methoxypyridine. 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, guanidine and the like.

The amount of the polymerization catalyst used is preferably 0.1 μmol to 300 μmol, more preferably 0.5 μmol to 100 μmol, and particularly preferably 1 μmol to 50 μmol per 1 mol of all dihydroxy compounds used in the polymerization.
In particular, when using a compound containing at least one metal selected from the group consisting of Group 2 and lithium in the long-period periodic table, particularly when using a magnesium compound and / or a calcium compound, the amount of metal is The amount is preferably 0.1 μmol or more, more preferably 0.3 μmol or more, and particularly preferably 0.5 μmol or more per 1 mol of the dihydroxy compound. Moreover, as an upper limit, 20 micromol or less is preferable, More preferably, it is 10 micromol or less, More preferably, it is 5 micromol or less, Most preferably, it is 3 micromol or less.

  If the amount of the catalyst is too small, the polymerization rate is slowed down. Therefore, in order to obtain a polycarbonate resin having a desired molecular weight, the polymerization temperature must be increased accordingly. Therefore, there is a high possibility that the hue of the obtained polycarbonate resin is deteriorated, and the unreacted raw material volatilizes during the polymerization, and the molar ratio of the dihydroxy compound and the carbonic acid diester collapses, and the desired molecular weight may not be reached. There is sex. On the other hand, if the amount of the polymerization catalyst used is too large, undesirable side reactions may occur, and the resulting polycarbonate resin may be deteriorated in hue or colored during molding.

  However, if a large amount of sodium, potassium or cesium is included in the polycarbonate resin, the hue may be adversely affected. And these metals may mix not only from the catalyst to be used but from a raw material or a reaction apparatus. Regardless of the source, the total amount of the compounds of these metals in the polycarbonate resin is preferably 1 ppm by weight or less, more preferably 0.5 ppm by weight or less as the amount of metal.

<Production method of polycarbonate resin>
The polycarbonate resin of the present invention can be obtained by polycondensing a dihydroxy compound containing a specific dihydroxy compound and a carbonic acid diester by a transesterification reaction.
The raw material dihydroxy compound and carbonic acid diester are preferably mixed uniformly before the transesterification reaction. The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often causing problems such as solidification, and if the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated. May adversely affect the hue and thermal stability of the polycarbonate resin obtained.

The operation of mixing the dihydroxy compound containing the specific dihydroxy compound which is the raw material of the polycarbonate resin of the present invention and the carbonic acid diester is an oxygen concentration of 10 vol% or less, further 0.0001 vol% to 10 vol%, and more preferably 0.0001 vol% to 5 vol%. It is particularly preferable to carry out in an atmosphere of 0.0001 vol% to 1 vol% from the viewpoint of preventing hue deterioration.

  In order to obtain the polycarbonate resin of the present invention, it is preferable to use a carbonic acid diester in a molar ratio of 0.90 to 1.20, more preferably 0 to all dihydroxy compounds including the specific dihydroxy compound used in the reaction. A molar ratio of .95 to 1.10. When this molar ratio is decreased, the terminal hydroxyl group of the produced polycarbonate resin is increased, the thermal stability of the polymer is deteriorated, coloring occurs during molding, the rate of transesterification reaction is reduced, and the desired high molecular weight. The body may not be obtained.

  Moreover, when this molar ratio becomes large, the rate of transesterification may decrease, or it may be difficult to produce a polycarbonate resin having a desired molecular weight. The decrease in the transesterification reaction rate may increase the heat history during the polymerization reaction, and may deteriorate the hue and weather resistance of the resulting polycarbonate resin. Furthermore, when the molar ratio of the carbonic acid diester is increased with respect to all the dihydroxy compounds including the specific dihydroxy compound, the amount of residual carbonic acid diester in the obtained polycarbonate resin is increased, which may cause problems of dirt and odor during molding. Yes, not preferred.

In the present invention, the method of polycondensing a dihydroxy compound and a carbonic acid diester is usually carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. The type of reaction may be any of a batch method, a continuous method, or a combination of a batch method and a continuous method, but a continuous method is preferred, in which a polycarbonate resin can be obtained with less heat history and excellent productivity.
In the initial stage of polymerization, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum, and in the latter stage of polymerization, it is preferable to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum, but the jacket temperature at each molecular weight stage. Appropriate selection of the internal temperature and pressure in the reaction system is important from the viewpoint of controlling the polymerization rate and the quality of the polycarbonate resin obtained. For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer will be distilled, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a decrease in the polymerization rate. Or a polymer having a predetermined molecular weight or terminal group cannot be obtained, and as a result, the object of the present invention may not be achieved.

  Furthermore, it is effective to use a reflux condenser for the polymerization reactor in order to suppress the amount of the monomer to be distilled off, and the effect is particularly great in a reactor at the initial stage of polymerization where there are many unreacted monomer components. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected according to the monomer used, but the temperature of the refrigerant introduced into the reflux condenser is usually 45 to 180 ° C. at the inlet of the reflux condenser. Yes, preferably 80 to 150 ° C, particularly preferably 100 to 130 ° C. If the temperature of the refrigerant is too high, the amount of reflux decreases and the effect is reduced. On the other hand, if the temperature is too low, the distillation efficiency of the monohydroxy compound that should be distilled off tends to decrease. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

  In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer while not impairing the hue of the final polycarbonate resin, it is important to select the kind and amount of the catalyst described above. The polycarbonate resin of the present invention is preferably produced by polymerizing in a multistage using a plurality of reactors using a catalyst, but the reason for carrying out the polymerization in a plurality of reactors is that at the initial stage of the polymerization reaction, Since there are many monomers contained in the reaction solution, it is important to suppress the volatilization of the monomers while maintaining the necessary polymerization rate. In the late stage of the polymerization reaction, in order to shift the equilibrium to the polymerization side, This is because it is important to sufficiently distill off the produced monohydroxy compound. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polymerization reactors arranged in series.

As described above, the number of reactors used in the production of the polycarbonate resin of the present invention may be at least two. However, from the viewpoint of production efficiency, three or more, preferably 3 to 5, particularly preferably. There are four. In the present invention, if there are two or more reactors, a plurality of reaction stages having different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed.

In the present invention, the polymerization catalyst can be added to the raw material preparation tank, the raw material storage tank, or can be added directly to the polymerization tank. From the viewpoint of supply stability and polymerization control, the polymerization catalyst is supplied to the polymerization tank. A catalyst supply line is installed in the middle of the raw material line before being fed, and preferably supplied as an aqueous solution.
If the temperature of the polymerization reaction is too low, the productivity is lowered and the thermal history of the product is increased. If it is too high, not only the monomer is volatilized but also decomposition and coloring of the polycarbonate resin may be promoted. Specifically, the first stage reaction is carried out at 130 to 250 ° C., preferably 150 to 240 ° C., more preferably 170 to 230 ° C., and preferably 110 to 110 kPa, as the maximum internal temperature of the polymerization reactor. Is carried out at a pressure of 5 to 70 kPa, more preferably 7 to 30 kPa (absolute pressure) for 0.1 to 10 hours, preferably 0.5 to 3 hours, while distilling off the generated monohydroxy compound out of the reaction system. Is done.

  In the second and subsequent stages, the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system. The pressure is 200 Pa or less, and the maximum internal temperature is 210 to 270 ° C., preferably 220 to 250 ° C., and usually 0.1 to 10 hours, preferably 1 to 6 hours, particularly preferably 0.5 to 3 hours.

  In order to obtain a polycarbonate resin having a predetermined molecular weight, if the polymerization temperature is high and the polymerization time is too long, the color tone tends to deteriorate. In particular, in order to suppress the coloring and thermal deterioration of the polycarbonate resin and obtain a polycarbonate resin having a good hue, it is preferable that the maximum internal temperature in all reaction stages is less than 250 ° C, particularly 220 to 245 ° C. In order to suppress the decrease in the polymerization rate in the latter half of the polymerization reaction and minimize degradation due to thermal history, it is necessary to use a horizontal reactor with excellent plug flow and interface renewability at the final stage of polymerization. preferable.

The monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.
The polycarbonate resin of the present invention is usually cooled and solidified after polycondensation as described above, and pelletized with a rotary cutter or the like. The method of pelletization is not limited, but it is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and pelletized, or from the final polymerization reactor in a molten state, uniaxial or biaxial extrusion. The resin is supplied to the machine, melt-extruded, cooled and solidified into pellets, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, once pelletized, and then uniaxially again Alternatively, a method may be mentioned in which resin is supplied to a biaxial extruder, melt-extruded, cooled and solidified, and pelletized.

When an extruder is used, in the extruder, the residual monomer is devolatilized under reduced pressure, and generally known thermal stabilizers, neutralizers, UV absorbers, light stabilizers, mold release agents, colorants, antistatic agents Further, a lubricant, a lubricant, a plasticizer, a compatibilizer, a flame retardant and the like can be added and kneaded.
The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin, but is usually 200 to 300 ° C, preferably 210 to 280 ° C, and more preferably 220 to 270 ° C. When the melt kneading temperature is lower than 200 ° C., the melt viscosity of the polycarbonate resin is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the polycarbonate resin is severely deteriorated by heat, resulting in a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.

The molecular weight of the polycarbonate resin of the present invention thus obtained can be expressed by a reduced viscosity, and the reduced viscosity is usually 0.30 dL / g or more, preferably 0.35 dL / g or more, The upper limit is more preferably 1.20 dL / g or less and 1.00 dL / g or less, and still more preferably 0.80 dL / g or less. If the reduced viscosity of the polycarbonate resin is too low, the mechanical strength of the molded product may be small. If it is too large, the fluidity at the time of molding tends to decrease, and the productivity and moldability tend to decrease. The reduced viscosity of the polycarbonate resin was measured using a Ubbelohde viscosity tube at a temperature of 20.0 ° C. ± 0.1 ° C., using methylene chloride as a solvent and adjusting the polycarbonate resin concentration to 0.6 g / dL precisely. The Details of the method for measuring the reduced viscosity are described in the Examples section.

[Polycarbonate resin additive]
<Phosphorus compounds>
The polycarbonate resin of the present invention preferably contains a phosphorus compound added to deactivate the polymerization catalyst and further suppress coloring of the polycarbonate resin at high temperatures. The phosphorus compound is at least one selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid ester, acidic phosphoric acid ester, and aliphatic cyclic phosphite ester. Is preferably used. Among them, phosphorous acid, phosphonic acid, and phosphonic acid ester are more excellent in catalyst deactivation and coloring suppression effects, and phosphonic acid ester is particularly preferable.

  Examples of phosphonic acid include phosphonic acid (phosphorous acid), methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylenediphosphonic acid, 1-hydroxyethane- Examples include 1,1-diphosphonic acid, 4-methoxyphenylphosphonic acid, nitrilotris (methylenephosphonic acid), and propylphosphonic anhydride.

  Examples of phosphonic acid esters include dimethyl phosphonate, diethyl phosphonate, bis (2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, dimethyl methylphosphonate, diphenyl methylphosphonate, and ethylphosphonic acid. Diethyl, diethyl benzylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, diethyl (methoxymethyl) phosphonate, diethyl vinylphosphonate, diethyl hydroxymethylphosphonate, dimethyl (2-hydroxyethyl) phosphonate, p-methylbenzylphosphonate diethyl, diethylphosphonoacetic acid, diethylphosphonoacetic acid ethyl, diethylphosphonoacetic acid tert-butyl, (Robenzyl) diethyl phosphonate, diethyl cyanophosphonate, diethyl cyanomethylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethylphosphonoacetaldehyde diethyl acetal, diethyl (methylthiomethyl) phosphonate Can be mentioned.

  Acid phosphate esters include dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis (butoxyethyl) phosphate, bis (2-ethylhexyl) phosphate, diisotridecyl phosphate, phosphate Examples include phosphoric acid diesters such as dioleyl, distearyl phosphate, diphenyl phosphate, and dibenzyl phosphate, or mixtures of diesters and monoesters, diethyl chlorophosphate, and zinc stearyl phosphate.

An aliphatic cyclic phosphite is defined as a phosphite compound that does not contain an aromatic group in a cyclic structure containing a phosphorus atom. For example, bis (decyl) pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,6-tert-butylphenyl) pentaerythritol diphosphite, bis (nonyl) Phenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Examples thereof include a polymer type compound composed of a dihydroxy compound such as hydrogenated bisphenol A / pentaerythritol phosphite polymer and pentaerythritol diphosphite.

These may be used alone or in a combination of two or more in any combination and ratio.
If the content of the phosphorus compound in the polycarbonate resin is too small, the effect of catalyst deactivation and coloring suppression is insufficient, and if it is too much, the polycarbonate resin is colored instead. The phosphorus atom content in the polycarbonate resin is 1 to 8 ppm by weight, preferably 1.2 to 7 ppm, more preferably 1.5 to 6 ppm. preferable.

  Since the phosphorus compound is usually phosphorus trichloride as a starting material, unreacted substances and chlorine-containing components derived from detached hydrochloric acid may remain, but the chlorine atom contained in the phosphorus compound may remain. The amount is preferably 5% by weight or less. When the residual amount of chlorine atoms is large, there is a concern that the metal part of the production facility to which the phosphorus compound is added is corroded, the thermal stability of the polycarbonate resin is lowered, and the molecular weight reduction due to coloring or thermal deterioration is promoted.

  As described above, the phosphorus compound is preferably added and kneaded to the polycarbonate resin using an extruder. In particular, it is most effective to supply the polycarbonate resin to the extruder in a molten state after polymerization and immediately add the phosphorus compound to the resin. Further, when the catalyst is deactivated and devolatilization is performed by a vacuum vent with an extruder, low molecular components can be efficiently devolatilized.

<Hindered phenol compounds>
The polycarbonate resin of the present invention can be expected to further improve the color tone of the polycarbonate resin by containing a hindered phenol compound in addition to the phosphorus compound.
Specific examples of hindered phenol compounds include 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, and 2-tert-butyl- 4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,5-di-tert-butylhydroquinone, n- Octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 2-t
ert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,2′-methylene-bis- (4-methyl-6-tert- Butylphenol), 2,2'-methylene-bis- (6-cyclohexyl-4-methylphenol), 2,2'-ethylidene-bis- (2,4-di-tert-butylphenol), tetrakis- [methylene-3 -(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] -methane, n-octadecyl-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) Propionate 1,3
, 5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, triethylene glycol-bis [3- (3-tert-butyl-5-methyl- 4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate] and the like.

These may be used alone or in a combination of two or more in any combination and ratio.
The content of the hindered phenol compound in the polycarbonate resin of the present invention is preferably 0.001 to 1 part by weight, and 0.005 to 0.5 part by weight when the polycarbonate resin is 100 parts by weight. Part is more preferable, and 0.01 part by weight to 0.3 part by weight is even more preferable.
In addition, it is preferable that a hindered phenol compound and the following antioxidants are added and kneaded to the polycarbonate resin using an extruder, similarly to the phosphorus compound.

<Antioxidant>
For the purpose of antioxidation, a generally known antioxidant can be added to the polycarbonate resin of the present invention.

  Specific examples of the antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, Trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4 6-di-tert-butylphenyl) octyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, trimethyl phosphate Phenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), pentaerythritol tetrakis (3-mercaptopropio Nate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, N, N-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinna Mido), tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl) 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxa Examples include spiro (5, 5) undecane.

These antioxidants may be used alone or in combination of two or more.
The blending amount of these antioxidants is preferably 0.0001 parts by weight to 0.1 parts by weight, more preferably 0.0005 parts by weight to 0.08 parts by weight, when the polycarbonate resin is 100 parts by weight. More preferred is 0.001 to 0.05 parts by weight.

[Physical properties of polycarbonate resin]
The preferred physical properties of the polycarbonate resin of the present invention will be described below.
<Amount of double bond end group derived from specific dihydroxy compound>
When the polycarbonate resin of the present invention includes a structural unit derived from the specific dihydroxy compound represented by the above formula (2), the following is given to the entire structural unit derived from the specific dihydroxy compound represented by the above formula (2). The content of the double bond end groups represented by the formulas (2A) and (2B) is preferably 0.4 mol% or less, and more preferably 0.3 mol% or less. The double bond end groups represented by the following formulas (2A) and (2B) are structures generated by thermal decomposition, and serve as an index representing the thermal history received by the polycarbonate resin. When the amount of the double bond terminal group is larger than the above upper limit, an excessive heat history is applied during the polymerization or molding process, and the color tone and weather resistance of the resin tend to deteriorate.

<Melt viscosity>
The melt viscosity of the polycarbonate resin of the present invention is preferably 400 Pa · s or more and 4000 Pa · s or less, more preferably 450 Pa · s or more and 3700 Pa · s or less, and particularly preferably 500 Pa · s or more and 3500 Pa · s or less. When the melt viscosity of the polycarbonate resin is lower than the above range, the polycarbonate resin becomes brittle and does not become a material having sufficient mechanical properties. On the other hand, if the melt viscosity is higher than the above range, the fluidity is insufficient at the time of molding, and the appearance of the molded product is impaired or the dimensional accuracy is deteriorated. Further, there is a concern that the resin temperature rises due to shear heat generation, and the resin is colored or foamed. In the present specification, the melt viscosity indicates a melt viscosity at a measurement temperature of 240 ° C. and a shear rate of 91.2 sec ⁻¹ using a capillary rheometer [manufactured by Toyo Seiki Co., Ltd.].

<Glass transition temperature>
The glass transition temperature of the polycarbonate resin of the present invention is preferably 80 ° C. or higher and 180 ° C. or lower, more preferably 90 ° C. or higher and 160 ° C. or lower, and particularly preferably 95 ° C. or higher and 140 ° C. or lower. If the glass transition temperature of the polycarbonate resin is too low, the molded product may be deformed at high temperature or high humidity, and heat resistance that can withstand use cannot be satisfied. On the other hand, if the glass transition temperature of the polycarbonate resin is excessively high, the temperature must be increased during the molding process, resulting in a decrease in the molecular weight of the polycarbonate resin, thermal degradation such as coloring, and the generation of gas. There is a risk of damaging the appearance. In addition, the glass transition temperature of polycarbonate resin is measured using a differential scanning calorimeter (DSC).

<Remaining amount of carbonic acid diester>
As described above, the polycarbonate resin of the present invention is usually obtained by polycondensing a dihydroxy compound, a carbonic acid diester, and a catalyst under melting. At this time, if the residual amount of carbonic acid diester in the obtained polycarbonate resin is large, it causes contamination and odor problems of the apparatus during molding, so the residual amount of carbonic acid diester in the polycarbonate resin of the present invention is 150 ppm by weight or less Furthermore, it is preferably 100 ppm by weight or less, and particularly preferably 80 ppm by weight or less. Actually, the polycarbonate resin may contain an unreacted carbonic acid diester, and the lower limit of the carbonic acid diester content is usually 1 ppm by weight.

<Remaining amount of monohydroxy compound>
The polycarbonate resin of the present invention is usually obtained by polycondensation of a dihydroxy compound, a carbonic acid diester and a catalyst under melting as described later. In this polycondensation reaction, a monohydroxy compound is produced as a leaving component from the carbonic acid diester. For example, when diphenyl carbonate is used as the carbonic acid diester, the monohydroxy compound produced is phenol. At this time, if the residual amount of the monohydroxy compound in the obtained polycarbonate resin is large, there may be a problem of contamination of the apparatus and odor during molding. The residual amount of the monohydroxy compound in the polycarbonate resin of the present invention is 700 ppm by weight or less, more preferably 500 ppm by weight or less, and particularly preferably 300 ppm by weight or less. During the production of polycarbonate resin, the appropriate amount of the specific phosphorus compound used as the catalyst deactivator described above is used, and further sufficient devolatilization treatment is performed to reduce the residual amount of the monohydroxy compound in the polycarbonate resin, and heating. Under generation can be suppressed.

<Increased amount of monohydroxy compound>
Monohydroxy compounds are generated not only during the polycondensation reaction, but also when the polycarbonate resin is heated to form or process it, so that the polymerization reaction and thermal decomposition progress and are therefore suppressed under heating conditions after polymerization. There is a need. Increase amount of monohydroxy compound after heating at 260 ° C. for 60 minutes, that is, monohydroxy compound generated by heating at 260 ° C. for 60 minutes is 700 ppm by weight or less, and further 400 ppm by weight or less. Particularly preferred is 200 ppm by weight or less.

<Color tone>
The difference between the yellow index (YI) values of the plates injection-molded under the two conditions described below is preferably 0.30 or less, more preferably 0.20 or less, and 0.10 or less. More preferably. When the difference in YI value becomes large, the polycarbonate resin is highly colored when performing melt processing such as injection molding or extrusion molding, and it becomes difficult to apply to applications where transparency, goodness, and hue are required.

  In the present invention, the color tone of the polycarbonate resin is evaluated as follows. Using an injection molding machine, the cylinder temperature is set to 250 ° C., the injection cycle is set so that the resin stays in the cylinder for 5 minutes or less, and a plate having a thickness of 3 mm is molded. Subsequently, the residence time is set to 20 minutes or longer, and a plate having a thickness of 3 mm is similarly formed. Using a color difference meter, the yellow index (YI) value in the transmitted light of the obtained plate is measured.

<Reduced viscosity retention>
The reduced viscosity retention after steaming at 120 ° C. and 2 atm for 24 hours using a pressure cooker is preferably 95% or more, and more preferably 96% or more. If this retention rate is low, the surface of the molded product may be cracked or the molded product may be deformed in accelerated weathering tests simulating rainfall conditions such as sunshine weather meters. It can be.
It is possible to improve the retention rate of reduced viscosity by neutralizing the basic component in the polycarbonate resin by using an appropriate amount of the specific phosphorus compound used as the catalyst deactivator during the production of the polycarbonate resin. Become.

<1-2. Phosphor>
The thermoplastic resin composition and wavelength conversion member used in the present invention contain a phosphor. The content of the phosphor in the thermoplastic resin composition is usually 0.01% by weight or more, and preferably 0.2% by weight or more and 50% by weight or less.

The phosphor used in the present invention is preferably a short afterglow phosphor. The short afterglow phosphor preferably has a short afterglow time in which the amount of light emitted from the phosphor when irradiated with excitation light is reduced to one-tenth. Preferably for display applications, it is preferably within 1/10 second.
The type of phosphor used in the present invention is selected as appropriate, but is preferably an inorganic phosphor, and the following are typical phosphors for red (orange), green, blue, and yellow phosphors. Can be mentioned.

  At this time, the phosphor may be used alone or in combination of two or more. By using two or more kinds of phosphors, the color temperature can be lowered or the color rendering properties can be improved.

<1-2-1. Red phosphor>
The emission peak wavelength of the red phosphor is usually in the wavelength range of 565 nm or more, preferably 575 nm or more, more preferably 580 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less. .
The full width at half maximum of the emission peak of the red phosphor is usually in the range of 1 nm to 120 nm. The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, usually 40 μm. Hereinafter, it is preferably 30 μm or less, more preferably 20 μm or less.

As such a red phosphor, for example, CaAlSiN ₃ : Eu described in JP-A-2006-008721 (also referred to as “CASN” in this specification), JP-A-2008-7751, for example. (Sr, Ca) AlSiN ₃ : Eu described in the publication No., and Ca _1−x Al _1−x Si _{1 + x} N _3−x O _x : Eu and the like described in JP 2007-231245 A Activated oxides, nitrides, oxynitride phosphors, and the like, and Japanese Patent Application Laid-Open No. 2008-38081 (Sr, Ba, Ca) ₃ SiO ₅ : Eu (hereinafter, abbreviated as “SBS phosphor”). ) Can also be used.

In addition, as red phosphors, Eu-activated alkaline earth silicon nitride phosphors such as (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu, (La, Y) ₂ O ₂ S: Eu Eu-activated oxysulfide phosphor such as (Y, La, Gd, Lu) ₂ O ₂ S: Eu, etc. Eu-activated rare earth oxychalcogenide-based phosphor, Y (V, P) O ₄ : Eu, Y Eu-activated oxide phosphor such as ₂ O ₃ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn, etc. Activated silicate phosphor, LiW ₂ O ₈ : Eu, LiW ₂ O ₈ : Eu, Sm, Eu ₂ W ₂ O ₉ , Eu ₂ W ₂ O ₉ : Nb, Eu ₂ W ₂ O ₉ : Em with Eu, etc. Activated tungstate phosphor, Eu-activated sulfide such as (Ca, Sr) S: Eu Light body, YAlO _3: Eu-activated aluminate phosphor such as _{Eu, Ca 2 Y 8 (SiO} 4) 6 O 2: Eu, LiY 9 (SiO 4) 6 O 2: Eu -activated silicate such as Eu Phosphor, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, (Tb, Gd) ₃ Al ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, (Mg, Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Mg, Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Mg, Ca, Sr, Ba) AlSi (N, O) ₃ : Eu such as Eu Activated oxide, nitride or oxynitride phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn activated halophosphate phosphor such as Eu, Mn, Ba _{3 MgSi 2 O 8: Eu, Mn} , (Ba, Sr, Ca, Mg) 3 (Zn, Mg) S ₂ O _8: Eu, Eu such as Mn, Mn-activated silicate _{phosphor, 3.5MgO · 0.5MgF 2 · GeO 2} : Mn activated germanate salt phosphors such as Mn, Eu-activated α sialon and the like Eu-activated oxynitride phosphor, (Gd, Y, Lu, La) ₂ O ₃ : Eu, Bi-activated oxide phosphor such as Eu, Bi, (Gd, Y, Lu, La) ₂ O ₂ S : Eu, Bi-activated oxysulfide phosphor such as Eu, Bi, (Gd, Y, Lu, La) VO ₄ : Eu, Bi-activated vanadate phosphor such as Eu, Bi, SrY ₂ S ₄ : Eu, Ce activated sulfide phosphors such as Eu and Ce, Ca activated sulfide phosphors such as CaLa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn activated phosphor phosphor such as Eu, Mn, Y, Lu) ₂ WO ₆ : Eu, Mo activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) _x Si _y N _z : Eu, Ce (where x, y, z are Represents an integer of 1 or more. Eu, Ce-activated nitride phosphors such as (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH): Eu, Mn-activated halophosphoric acid such as Eu, Mn Salt phosphor, ((Y, Lu, Gd, Tb
_{) 1-x-y Sc x} Ce y) 2 (Ca, Mg) 1-r (Mg, Zn) 2 + r Si z-q Ge q O 12 + δ can also be used Ce-activated silicate phosphor such as.

In addition, in order to improve the color rendering properties of the emitted light from the semiconductor light emitting device or to increase the light emission efficiency of the light emitting device, a red phosphor having a half-value width of the red emission spectrum of 20 nm or less (hereinafter referred to as “narrow”) as the red phosphor. May be used alone or in combination with other red phosphors, particularly red phosphors with a red emission spectrum having a half-value width of 50 nm or more. . As such a red phosphor, A _{2 + x} M _y Mn _z F _n (A is Na and / or K; M is Si and Al; −1 ≦ x ≦ 1 and 0.9 ≦ y + z ≦ 1.1 and 0) KSF, KSNAF, and solid solution of KSF and KSNAF represented by .001 ≦ z ≦ 0.4 and 5 ≦ n ≦ 7), (kx) MgO.xAF ₂ .GeO ₂ : yMn ⁴⁺ , K is a real number of 2.8-5, x is a real number of 0.1-0.7, y is a real number of 0.005-0.015, A is calcium (Ca), strontium ( Sr), barium (Ba), zinc (Zn), or a mixture thereof), which is represented by the chemical formula of 3.5MgO.0.5MgF ₂ .GeO ₂ : Mn and other deep red (600 nm to 670 nm) germanate phosphor, (La _{1-x-y, Eu x} , Ln y) 2 O 2 S (x and y represent the number of each satisfy 0.02 ≦ x ≦ 0.50 and 0 ≦ y ≦ 0.50, Ln is Y, A LOS phosphor represented by a chemical formula of at least one trivalent rare earth element of Gd, Lu, Sc, Sm, and Er.

Further, SrAlSi ₄ N ₇ described in International Publication WO 2008-096300 and Sr ₂ Al ₂ Si ₉ O ₂ N ₁₄ : Eu described in US Pat. No. 7,524,437 may be used.
Among these, as the red phosphor, CASN phosphor, SCASN phosphor, CASON phosphor, and SBS phosphor are preferable.
Any one of the red phosphors exemplified above may be used, or two or more may be used in any combination and ratio.

<1-2-2. Green phosphor>
The emission peak wavelength of the green phosphor is usually larger than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, particularly 540 nm or less, and further preferably 535 nm or less. If this emission peak wavelength is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and there is a possibility that the characteristics as green light will deteriorate.

The full width at half maximum of the emission peak of the green phosphor is usually in the range of 1 nm to 80 nm. The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, usually 40 μm. Hereinafter, it is preferably 30 μm or less, more preferably 20 μm or less.
As such a green phosphor, for example, (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu (hereinafter referred to as “BSS phosphor”) may be described in International Publication WO2007-091687. And Eu-activated alkaline earth silicate phosphors.

In addition, as the green phosphor, for example, Si _6-z Al _z N ₈ -z O _z : Eu (provided that 0 <z ≦ 4.2, which is described in Japanese Patent No. 3911545). Eu-activated oxynitride phosphor such as “β-SiAlON phosphor”), or M ₃ Si ₆ O ₁₂ N ₂ : Eu described in International Publication WO 2007-088966. (However, M represents an alkaline earth metal element. Hereinafter, it may be abbreviated as “BSON phosphor”.) Eu-activated oxynitride phosphor, and Japanese Patent Application Laid-Open No. 2008-274254. It is also possible to use a BaMgAl ₁₀ O ₁₇ : Eu, Mn activated aluminate phosphor (hereinafter sometimes abbreviated as “GBAM phosphor”).

Other green phosphors include Eu-activated alkaline earth silicon oxynitride phosphors such as (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu, Sr ₄ Al ₁₄ O ₂₅ : Eu, Eu-activated aluminate phosphors such as (Ba, Sr, Ca) Al ₂ O ₄ : Eu, (Sr, Ba) Al ₂ Si ₂ O ₈ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, ( Ba, Sr, Ca) ₂ (Mg, Zn) Si ₂ O ₇ : Eu, (Ba, Ca, Sr, Mg) ₉ (Sc, Y, Lu, Gd) ₂ (Si, Ge) ₆ O ₂₄ : Eu, etc. Eu-activated silicate _{phosphors, Y 2 SiO 5: Ce,} Ce and Tb such, Tb-activated silicate _{phosphor, Sr 2 P 2 O 7 -Sr} 2 B 2 O 5: Eu -activated borate such as Eu phosphate _{phosphor, Sr 2 Si 3 O 8 -2SrCl} 2: such as Eu u-activated halo silicate _phosphor, Zn 2 _SiO 4: Mn-activated silicate phosphors such as _{Mn, CeMgAl 11 O 19: Tb} , Y 3 Al 5 O 12: Tb -activated aluminate phosphors such as Tb , Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Tb, La ₃ Ga ₅ SiO ₁₄ : Tb-activated silicate phosphors such as Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb, Sm Eu, Tb, Sm activated thiogallate phosphor such as Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce-activated silicate fluorescence such as Ce body, CaSc ₂ O _4: Ce activated oxide such as Ce Phosphor, Eu Tsukekatsusan nitride phosphor such as Eu-activated β-sialon, SrAl ₂ O _4: Eu-activated aluminate phosphor such as _{Eu, (La, Gd, Y} ) 2 O 2 S: Tb , etc. Tb-activated oxysulfide phosphors, CePO4, Ceb-activated phosphate phosphors such as LaPO ₄ : Ce, Tb, sulfide phosphors such as ZnS: Cu, Al, ZnS: Cu, Au, Al, _{Y, Ga, Lu, Sc,} La) BO 3: Ce, Tb, Na 2 Gd 2 B 2 O 7: Ce, Tb, (Ba, Sr) 2 (Ca, Mg, Zn) B 2 O 6: K, Ce, Tb activated borate phosphor such as Ce, Tb, Eu, Mn activated halosilicate phosphor such as Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn, (Sr, Ca, Ba) ( _{al, Ga, in) 2 S} 4: Eu activated thioaluminate phosphors such as Eu or thiogallate Light _{body, (Ca, Sr) 8 (} Mg, Zn) (SiO 4) 4 Cl 2: Eu, Eu such as Mn, Mn-activated halo silicate _{phosphor, M 3 Si 6 O 9 N} 4: Eu-like Eu-activated oxynitride phosphors or the like can also be used.

Also, Sr ₅ Al ₅ Si ₂₁ O ₂ N ₃₅ : Eu described in International Publication WO2009-072043 and Sr ₃ Si ₁₃ Al ₃ N ₂₁ O ₂ described in International Publication WO2007-105631 are disclosed. : Eu can also be used.
Among these, as the green phosphor, BSS phosphor, β-SiAlON phosphor, and BSON phosphor are preferable.

Any one of the green phosphors exemplified above may be used, or two or more may be used in any combination and ratio.
In addition, in order to enhance the color rendering property of the emitted light from the semiconductor light emitting device or to increase the light emission efficiency of the light emitting device, a green phosphor having a half width of the green emission spectrum of 20 nm or less (hereinafter referred to as “narrow”) as the green phosphor. May be referred to as "band green phosphors") alone.

<1-2-3. Blue phosphor>
The emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, usually less than 500 nm, preferably 490 nm or less, more preferably 480 nm or less, still more preferably 470 nm or less, particularly preferably. The wavelength range is 460 nm or less.

The full width at half maximum of the emission peak of the blue phosphor is usually in the range of 10 nm to 100 nm. Also,
The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, usually 40 μm or less, Preferably it is 30 micrometers or less, More preferably, it is 20 micrometers or less.

As such a blue phosphor, for example, a europium activated calcium halophosphate phosphor represented by (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl: Eu, (Ca, Sr, Ba) ₂ B ₅ O Europium activated alkaline earth chloroborate phosphor represented by ₉ Cl: Eu, (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu And europium activated alkaline earth aluminate phosphors.

In addition, as the blue phosphor, Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, Sr ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, BaAl ₈ O ₁₃ : Eu-activated aluminate phosphors such as Eu, Ce-activated thiogallate phosphors such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Tb, Sm activated aluminate phosphor such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn activated aluminate phosphor such as Eu, Mn (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu, Mn, Sb, etc. Eu, b, Sm-activated halophosphate _{phosphor, BaAl 2 Si 2 O 8:} Eu, (Sr, Ba) 3 MgSi 2 O 8: Eu -activated silicate phosphors such as _{Eu, Sr 2 P 2 O 7} : Eu Eu-activated phosphate phosphors such as ZnS: Ag, ZnS: Ag, Al and other sulfide phosphors, Ce-activated silicate phosphors such as Y ₂ SiO ₅ : Ce, and tungstates such as CaWO ₄ Phosphor, (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ · nB ₂ O ₃ : Eu, 2SrO · 0.84P ₂ O ₅ · 0.16B ₂ O ₃ : Eu, Mn-activated borate phosphor phosphor such as Eu, Eu-activated halosilicate phosphor such as Sr ₂ Si ₃ O ₈ · 2SrCl ₂ : Eu, etc. can also be used.

Among these, (Sr, Ca, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ and BaMgAl ₁₀ O ₁₇ : Eu can be preferably used. _{Further, (Sr, Ca, Ba)} 10 (PO 4) 6 Cl 2: Among the phosphors represented by ^{_{Eu 2+, Sr a Ba b Eu}} x (PO 4) c Cl d (c, d and x are 2 0.7 ≦ c ≦ 3.3, 0.9 ≦ d ≦ 1.1, 0.3 ≦ x ≦ 1.2, and x is preferably 0.3 ≦ x ≦ 1.0 Furthermore, a and b satisfy the condition of a + b = 5-x and 0.05 ≦ b / (a + b) ≦ 0.6, and b / (a + b) is preferably 0.1 ≦ b / The phosphor represented by (a + b) ≦ 0.6 can be preferably used.

  In addition, in order to enhance the color rendering properties of the emitted light from the semiconductor light emitting device or to increase the light emission efficiency of the light emitting device, a blue phosphor having a half-value width of blue emission spectrum of 20 nm or less (hereinafter referred to as “narrow”) as the blue phosphor. May be referred to as "band blue phosphor") alone.

<1-2-4. Yellow phosphor>
The emission peak wavelength of the yellow phosphor is usually 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. The full width at half maximum of the emission peak of the yellow phosphor is usually in the range of 80 nm to 130 nm. The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, usually 40 μm. Hereinafter, it is preferably 30 μm or less, more preferably 20 μm or less.

Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors. In particular, RE ₃ M ₅ O ₁₂ : Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents Al, Ga, and Sc. And Ma ₃ Mb ₂ Mc ₃ O ₁₂ : Ce (where Ma is a divalent metal element, Mb is a trivalent metal element, and Mc is tetravalent). A garnet phosphor having a garnet structure represented by AE ₂ MdO ₄ : Eu (where AE is selected from the group consisting of Ba, Sr, Ca, Mg, and Zn). Represents at least one element, and Md represents Si and / or Ge.) Orthosilicate phosphors represented by the above, etc., and part of oxygen of the constituent elements of these phosphors is replaced with nitrogen Oxynitride phosphor, AE lSiN _3: Ce (., where, AE is, Ba, Sr, Ca, represents at least one element selected from the group consisting of Mg and Zn) nitride phosphor having a CaAlSiN ₃ structure, such as with Ce Examples include activated phosphors.

Among these, garnet-based phosphors are preferably used, and among them, Y ₃ Al ₅ O ₁₂ : Ce (sometimes described as “YAG” in the present specification) is particularly preferably used.
In addition, as yellow phosphors, sulfide-based fluorescence such as CaGa ₂ S ₄ : Eu, (Ca, Sr) Ga ₂ S ₄ : Eu, (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu, etc. _{body, Ca x (Si, Al)} 12 (O, N) 16: fluorescent material activated with Eu of oxynitride-based fluorescent material or the like having a SiAlON structure such as _{Eu, (M 1-a-} B Eu a Mn _{B) 2 (BO 3) 1} -P (PO 4) P X ( where, M represents Ca, Sr, and at least one element selected from the group consisting of Ba, X is F, Cl, and Represents one or more elements selected from the group consisting of Br. A, B, and P are 0.001 ≦ A ≦ 0.3, 0 ≦ B ≦ 0.3, and 0 ≦ P ≦ 0.2, respectively. Eu-activated or Eu / Mn co-activated halogenated borate phosphor, alkaline earth metal element It is also possible to use a Ce-activated nitride-based phosphor having a La ₃ Si ₆ N ₁₁ structure, which may contain bismuth. Note that a part of the Ce-activated nitride phosphor described above may be partially substituted with Ca or O.

  In the thermoplastic resin composition of the present invention, the phosphor content when the total weight of the thermoplastic resin composition is 100% by weight is usually 0.01% by weight or more, but 0.2% by weight or more. Is preferable, 0.5% by weight or more is more preferable, and 1% by weight or more is most preferable. On the other hand, the upper limit of the phosphor content is usually 50% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less. By setting it as this range, the thickness when the resin composition is used as the wavelength conversion member is likely to be in an appropriate range, and the strength reduction of the wavelength conversion member can be suppressed.

The average particle size of the phosphor is preferably 10 μm or more, and more preferably 15 μm or more. By setting it as this range, the fall of the wavelength conversion efficiency when it is set as a wavelength conversion member can be suppressed.
Here, the said average particle diameter is an average particle diameter of a primary particle, and is the value measured with the laser granulometer.

<1-3. Other Elements that Thermoplastic Resin Composition may Contain>
The thermoplastic resin of the present invention is 1-1. In addition to the polycarbonate resin described in the above, for example, aromatic polycarbonate resin, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS, AS, and other synthetic resins, polylactic acid, polybutylene sushi It can also be used as a polymer alloy by kneading with one or more of biodegradable resins such as nate and rubber.

The thermoplastic resin composition in the present embodiment preferably contains a diffusing agent. By containing the diffusing agent, it is possible to adjust the total light transmittance of the wavelength conversion member prepared from the thermoplastic resin composition.
Examples of the diffusing agent include inorganic light diffusing agents, organic light diffusing agents, and bubbles.
As the inorganic light diffusing agent, for example, an inorganic light diffusing agent containing an element such as silicon, aluminum, titanium, zirconium, calcium, magnesium, zinc and barium can be used, and silicon, aluminum, It is preferable to use an inorganic light diffusing agent containing at least one element of the group consisting of titanium and zirconium. As the organic light diffusing agent, it is possible to use acrylic, styrene, polyamide, or an organic light diffusing agent containing silicon or fluorine as an element. Among them, acrylic light diffusing agent or silicon as an element can be used. It is preferable to use an organic light diffusing agent.

  Specific examples of inorganic light diffusing agents include silicon dioxide (silica), white carbon, fused silica, talc, magnesium oxide, zinc oxide, titanium oxide, aluminum oxide, zirconium oxide, boron oxide, boron nitride, aluminum nitride, and nitride. Silicon, calcium carbonate, barium carbonate, magnesium carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, barium sulfate, calcium silicate, magnesium silicate, aluminum silicate, sodium silicate aluminide, zinc silicate, zinc sulfide, Examples of the material include glass particles, glass fibers, glass flakes, mica, wollastonite, zeolite, sepiolite, bentonite, montmorillonite, hydrotalcite, kaolin, and potassium titanate.

These inorganic diffusing agents may be treated with various surface treatment agents such as silane coupling agents, titanate coupling agents, methyl hydrogen polysiloxanes, fatty acid-containing hydrocarbon compounds, and the surface is inactive. It may be coated with an inorganic compound.
Examples of organic light diffusing agents include aromatic polycarbonates, aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, aliphatic polyesters, styrene (co) polymers such as AS, ABS, and SBS, and acrylic (co) polymers. , Siloxane (co) polymer, polyamide (co) polymer, rubber such as SBR, MBS, MES and the like. Some or all of these organic diffusing agent molecules may or may not be crosslinked. Here, “(co) polymer” means both “polymer” and “copolymer”.

The diffusing agent preferably includes at least one selected from the group consisting of silica, glass, calcium carbonate, and mica. Further, the average particle diameter is preferably 1 μm or more, and preferably 30 μm or less. The average particle size is a particle size measured with an integrated weight percentage, a particle size distribution meter or the like.
Further, as the diffusing agent, the Mohs hardness is preferably less than 8, and more preferably less than 7. By using a diffusing agent having such hardness, discoloration of the wavelength conversion member prepared from the thermoplastic resin composition is suppressed, and impurities are not mixed without damaging the container.

Moreover, as a spreading | diffusion agent, it is preferable that ratio L / D of the major axis L and the minor axis D is 200 or less. By using a diffusing agent in such a range, discoloration of the wavelength conversion member prepared from the thermoplastic resin composition is suppressed, and impurities are not mixed without damaging the container.
L / D is more preferably 50 or less.
In addition, when adjusting the transmittance of the wavelength conversion member prepared from the thermoplastic resin composition with a diffusing agent, for example, a diffusing agent having a small average particle diameter is added, and the refractive index difference from the thermoplastic resin composition is Adjustment can be performed by adding a large diffusing agent or decreasing the transmittance of the wavelength conversion member by increasing the amount of diffusing agent added.

  The diffusing agent can adjust the total light transmittance of the wavelength conversion member prepared from the thermoplastic resin composition, but in some cases, the thermoplastic resin composition may be discolored. Therefore, the difference ΔE between the hue of a 1 mm thick thermoplastic resin composition formed by containing a diffusing agent and the hue of a 1 mm thick thermoplastic resin composition formed without containing a diffusing agent is 10 or less. It is preferable to use what is. ΔE is more preferably 8 or less, and further preferably 6 or less. As described above, by selecting a diffusing agent with less discoloration when used as a wavelength conversion member, luminous efficiency is improved.

The hue can be measured using, for example, a colorimetric color difference meter manufactured by Nippon Denshoku Industries Co., Ltd.
When a diffusing agent is used in this embodiment, it is usually contained in the thermoplastic resin composition in an amount of 0.1% by weight or more, preferably 0.3% by weight or more. Further, it is usually contained in an amount of 40% by weight or less, preferably 30% by weight or less.

The diffusing agent is usually contained in an amount of 0.1% by weight or more, preferably 0.3% by weight or more with respect to the wavelength conversion member after molding. Further, it is usually contained in an amount of 40% by weight or less, preferably 30% by weight or less.
As other additives, the wavelength conversion member or the thermoplastic resin composition according to this embodiment may use an effective amount of an additive that can be usually used for the resin. Specifically, other thermoplastic resins, antioxidants, antiblocking agents, ultraviolet absorbers, light stabilizers, plasticizers, heat stabilizers, colorants, flame retardants, mold release agents, antistatic agents, antifogging Agents, surface wetting improvers, incineration aids, lubricants, flame retardants, crosslinking agents, dispersion aids and various surfactants, slip agents, hydrolysis inhibitors, neutralizers, reinforcing materials, heat conduction materials, etc. . These may be used alone or in combination of two or more.

  Specific examples of the antioxidant include 2,6-di-tert-butyl-4-hydroxytoluene, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pentaerythritol tetrakis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene- 2,4,6-triyl) tri-p-cresol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris [(4-tert-butyl -3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (3,5-di) -Tert Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, calcium diethylbis [[3,5-bis (1,1-dimethylethyl)- 4-hydroxyphenyl] methyl] phosphonate, bis (2,2′-dihydroxy-3,3′-di-tert-butyl-5,5′-dimethylphenyl) ethane, N, N′-hexane-1,6- Diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide) and other hindered phenol antioxidants, tridecyl phosphite, diphenyldecyl phosphite, tetrakis (2,4-di-tert -Butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, bis [2,4-bis (1,1-dimethyle) ) -6-methylphenyl] ethyl ester phosphorous acid, phosphorous antioxidants such as bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 3-hydroxy-5,7-di- Examples include lactone antioxidants such as a reaction product of tert-butyl-furan-2-one and xylene, sulfur antioxidants such as dilauryl thiodipropionate and distearyl thiodipropionate. An antioxidant may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Although the usage-amount of antioxidant is arbitrary unless the effect of this invention is impaired remarkably, it is normally 100 weight ppm or more and 50000 weight ppm or less with respect to resin. If the lower limit of this range is not reached, the effect of the antioxidant may be reduced, and if the upper limit is exceeded, the antioxidant may bleed out or cause coloring.
Examples of the light stabilizer include decanoic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (1,2,2 , 6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate , 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine -2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] Examples include hindered amine stabilizers.

A light stabilizer may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
Furthermore, the usage-amount of a light stabilizer is 0.1 to 5 mass parts normally with respect to 100 mass parts of resin.
Examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide. Among these, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine -4-one], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

  Specific examples of the benzotriazole compound include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methyl Ren-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H- Benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate.

A ultraviolet absorber may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
Moreover, the usage-amount of a ultraviolet absorber is 100 ppm or more and 5 mass% or less normally.
Examples of the flame retardant include organic flame retardants such as organic halogen compounds, antimony compounds, phosphorus compounds, nitrogen compounds, and inorganic flame retardants. Examples of the organic halogen compound include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, pentabromobenzyl polyacrylate, and the like. Examples of the antimony compound include antimony trioxide, antimony pentoxide, sodium antimonate, and the like. Examples of the phosphorus compound include phosphate esters, polyphosphoric acid, ammonium polyphosphate, red phosphorus, and phosphazene compounds such as phenoxyphosphazene and aminophosphazene having a bond of a phosphorus atom and a nitrogen atom in the main chain. Examples of the nitrogen-based compound include melamine, cyanuric acid, melamine cyanurate, and the like. Examples of the inorganic flame retardant include aluminum hydroxide, magnesium hydroxide, silicon compound, boron compound and the like.

  Specific examples of phosphate ester flame retardants include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), and 4,4′-biphenol bis. (Dixylenyl phosphate), bisphenol A bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4'-biphenol bis (Diphenyl phosphate), bisphenol A bis (diphenyl phosphate) and the like. Content of a flame retardant is 1-30 weight part normally with respect to 100 weight part of resin.

<2. Wavelength conversion member>
A second aspect of the present invention is a wavelength conversion member that wavelength-converts at least part of incident light and emits outgoing light having a wavelength different from that of the incident light, the wavelength conversion member including the incident light. Having a planar structure, including a phosphor that absorbs at least a part of the phosphor and emits outgoing light having a wavelength different from that of the incident light, and a thermoplastic resin that holds the phosphor. The resin contains a polycarbonate resin having at least a structural unit derived from a specific dihydroxy compound, and at least a part of the planar structure relates to a wavelength conversion member having a total light transmittance of 30% or more and 70% or less.

  The method for producing the wavelength conversion member according to this embodiment is not particularly limited, and may be produced according to a conventional method. For example, it is preferable to use the thermoplastic resin composition of the first aspect of the present invention, and produce a composition containing a thermoplastic resin and a phosphor, preferably a diffusing agent and other additives added as necessary. In order to do so, a single or twin screw extruder can be used as the kneader. Other additives including thermoplastic resin, phosphor, and diffusing agent may be supplied all at once from one place, or other compounding agents such as phosphor may be sequentially supplied after supplying thermoplastic resin. Also good. Moreover, you may mix and knead | mix beforehand 2 or more types of components chosen from each component. In particular, the phosphor is preferably supplied after mixing with other powder components. In addition, the extruder may be provided with a vent port that can volatilize volatile components. After kneading, the wavelength conversion member is manufactured by melt molding by a method such as press molding, injection molding, hollow molding, or extrusion molding.

  The wavelength conversion member may have any shape as long as it has a planar structure that can be a white light emitting surface in the white LED light emitting device, but generally the thickness of the planar structure is 0. 3 mm to 5 mm is common. In addition, the wavelength conversion member of the present invention may have a single-layer structure or a multi-layer structure having two or more layers as long as the total light transmittance is in the range of 30 to 70%. Further, the surface may be a mirror surface or may have a fine structure such as a texture, and the outer surface can be hard-coated or printed.

<2-1. Total light transmittance of wavelength conversion member>
As described above, the wavelength conversion member according to this embodiment is characterized in that at least a part of the planar structure has a total light transmittance of 30% or more and 70% or less. With such a range, the total luminous flux can be improved at a low color temperature when applied to a light emitting device.
The total light transmittance is preferably 35% or more, more preferably 40% or more, and further preferably 45% or more. On the other hand, it is preferably 65% or less, more preferably 60% or less, and further preferably 55% or less.

The total light transmittance can be measured according to JIS K7361. However, since it contains a phosphor, it becomes a colored wavelength conversion member with low transparency, so the entrance opening is 20 mmΦ, and a device using a halogen lamp as a light source. It is necessary to make a measurement.
Adjustment of the total light transmittance of the wavelength conversion member is possible, for example, by containing a diffusing agent (light diffusing agent) described later. Further, the total light transmittance can be adjusted by alloying the thermoplastic resin.

  Here, the wavelength conversion member according to the present embodiment has a planar structure. The planar structure is intended to be a light emitting surface portion in a light emitting device. For example, when a wavelength converting member is provided as a wavelength converting member in a light emitting device, it is combined with other members that are seen at an end portion thereof. It is not a part / joint / meshing part, but a part that is located near the center of the wavelength conversion member and that can mainly receive excitation light and emit light to the outside.

If it demonstrates using FIG. 1, all the dashed-dotted line parts in the wavelength conversion member 3 in FIG. 1 are planar structure parts. On the other hand, the portion near the wiring substrate 2 in the wavelength conversion member 3 is not a planar structure.
In the present embodiment, it is sufficient that at least a part of the planar structure of the wavelength conversion member satisfies the range of the total light transmittance, and the entire planar structure of the wavelength conversion member satisfies the range of the total light transmittance. More preferably. At least a part may be 10% or more normally, Preferably it is 30%, More preferably, it may be 50%.

  The thickness of the planar structure is preferably 0.3 mm or more, more preferably 0.5 mm or more, and further preferably 0.7 mm or more. Further, it is preferably 5 mm or less, more preferably 3 mm or less, and further preferably 2.5 mm or less. In the thermoplastic resin composition of the first embodiment of the present invention, a plate having a thickness of 1.0 mm is prepared and the total light transmittance of the thermoplastic resin composition is evaluated in the same manner as in the measurement method. be able to.

<3. Light emitting device>
3rd embodiment of this invention is a light-emitting device provided with the semiconductor light-emitting device and the wavelength conversion member which concerns on 2nd embodiment.
The light emitting device according to this embodiment includes at least a blue semiconductor light emitting element and a wavelength conversion member according to the second embodiment of the present invention which is a wavelength conversion member that converts the wavelength of blue light. The blue semiconductor light-emitting element and the wavelength conversion member according to the second embodiment of the present invention may be in close contact with each other, may be separated from each other, may be provided with a transparent resin therebetween, and have a space. Also good. As shown in a schematic diagram in FIG. 1, a structure having a space between the light emitting element and the wavelength conversion member is preferable.

Hereinafter, the configuration will be described with reference to FIGS.
FIG. 1 is a schematic view of a light emitting device according to a third embodiment of the present invention.
The light emitting device 10 includes at least a blue semiconductor light emitting element 1 and a wavelength conversion member 3 as its constituent members. The blue semiconductor light emitting element 1 emits excitation light for exciting the phosphor contained in the wavelength conversion member 3.

The blue semiconductor light-emitting element 1 usually emits excitation light having a peak wavelength of 425 nm to 475 nm,
Preferably, excitation light having a peak wavelength of 430 nm to 470 nm is emitted. The number of blue semiconductor light emitting elements 1 can be appropriately set depending on the intensity of excitation light required by the apparatus.
On the other hand, a purple semiconductor light emitting element can be used instead of the blue semiconductor light emitting element 1. The violet semiconductor light emitting device usually emits excitation light having a peak wavelength of 390 nm to 425 nm, and preferably emits excitation light having a peak wavelength of 395 to 415 nm.

The blue semiconductor light emitting element 1 is mounted on the chip mounting surface 2 a of the wiring board 2. A wiring pattern (not shown) for supplying electrodes to these blue semiconductor light emitting elements 1 is formed on the wiring substrate 2 to constitute an electric circuit. In FIG. 1, the wavelength conversion member 3 is displayed on the wiring substrate 2, but the present invention is not limited to this, and the wiring substrate 2 and the wavelength conversion member 3 may be arranged via other members.
For example, in FIG. 2, the wiring board 2 and the wavelength conversion member 3 are arranged via the frame body 4. The frame body 4 may have a tapered shape in order to give light directivity. The frame 4 may be a reflective material.

  The wiring board 2 is excellent in electrical insulation, has good heat dissipation, and preferably has a high reflectance, but on the surface where the blue semiconductor light emitting element 1 is not present on the chip mounting surface of the wiring board 2, Alternatively, a reflective plate having a high reflectance can be provided on at least a part of the inner surface of another member that connects the wiring substrate 2 and the wavelength conversion member 3. The reflectance of such a wiring board or reflector is preferably 80% or more. As such a wiring board, alumina ceramic, resin, glass epoxy, composite resin containing filler in resin, or the like can be used. Further, as the reflection plate placed on the chip mounting surface 2a of the wiring board 2, a resin containing a white pigment such as alumina powder, silica powder, magnesium oxide, titanium oxide, zirconium oxide, zinc oxide, zinc sulfide is used. it can. Preferred resins include silicone resin, polycarbonate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, fluorine-based resin and the like.

  The wavelength conversion member 3 converts the wavelength of a part of incident light emitted from the blue semiconductor light emitting element 1 and emits outgoing light having a wavelength different from that of the incident light. The wavelength conversion member 3 contains a resin and a phosphor. The type of phosphor (not shown) is not particularly limited, and if the light emitting device is a white light emitting device, the type of phosphor is appropriately adjusted to emit white light according to the type of excitation light of the semiconductor light emitting element. do it.

When the semiconductor light-emitting element is a blue semiconductor light-emitting element, a light-emitting device that emits white light can be obtained by using a yellow phosphor or a green phosphor and a red phosphor.
When the semiconductor light-emitting element is a violet semiconductor light-emitting element, a light-emitting device that emits white light can be obtained by using a blue phosphor, a green phosphor, and a red phosphor.
The wavelength conversion member 3 preferably contains a small amount of a transmittance adjusting agent together with the phosphor. Examples of the transmittance adjusting agent include an inorganic light transmittance adjusting agent, an organic light transmittance adjusting agent, and air bubbles. The transmittance adjusting agent preferably contains one or more selected from the group consisting of silica, glass, calcium carbonate, titanium oxide, silsesquioxane, and mica.

The wavelength conversion member 3 has a distance from the blue semiconductor light emitting element 1. A space may be provided between the wavelength conversion member 3 and the blue semiconductor light emitting element 1, and a transparent resin may be provided. Thus, by the aspect which has distance between the wavelength conversion member 3 and the blue semiconductor light-emitting device 1, deterioration of the phosphor contained in the wavelength conversion member 3 and the wavelength conversion member by the heat which the blue semiconductor light-emitting device 1 emits is suppressed. can do. The distance between the blue semiconductor light emitting element 1 and the wavelength conversion member 3 is preferably 10 μm or more, more preferably 100 μm or more, particularly preferably 1.0 mm or more, on the other hand, 1.0 m or less, more preferably 500 mm or less, 1
00 mm or less is particularly preferable.

The light emitting device according to the third embodiment of the present invention is preferably a light emitting device that emits white light. In the light emitting device that emits white light, the light emitted from the light emitting device has a deviation duv from a light-colored black body radiation locus of −0.0200 to 0.0200, and a color temperature of 1800 K or more and 7000 K or less. It is preferable that
The light emitting device according to the third embodiment can achieve a high luminous flux even when emitting light with a low color temperature. Therefore, it is particularly suitable when light having a low color temperature such as a color temperature of 5500K or less, 5000K or less, or 4500K or less is emitted.
Thus, the light-emitting device which radiate | emits white light is suitably provided in an illuminating device.

<4. LED lighting equipment>
4th embodiment of this invention is a lighting fixture provided with the light-emitting device which concerns on 3rd embodiment. As described above, a high total luminous flux is emitted from the light emitting device according to the third embodiment,
In addition, even a light-emitting device that emits white light with a low color temperature, at which the total luminous flux is likely to decrease, can achieve a high total luminous flux, so that a lighting fixture with a high total luminous flux can be obtained. It is preferable that the luminaire is provided with a diffusing member that covers the wavelength conversion member in the light-emitting device so that the color of the wavelength conversion member does not stand out when the light is turned off. The diffusing member is not particularly limited as long as the haze is 40% or more and the total light transmittance is 60% or more. If the diffusing member is arranged outside the wavelength conversion member, it can be used as a lighting fixture in the light emitting device. It may be built in. It is preferable that at least a part of other members in the space including both the diffusing member and the wavelength converting member is a reflecting plate having a high reflectance.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it cannot be overemphasized that this invention is not restricted only to the following embodiments.
<Raw material>
The following resin, phosphor and diffusing agent were prepared. Table 1 shows the physical properties of the diffusing agent.
(Thermoplastic resin)
PC1 Polycarbonate resin
PC2 Polycarbonate resin Iupilon S-3000RN manufactured by Mitsubishi Engineering Plastics
PMMA PMMA resin Mitsubishi Rayon Co., Ltd. Acryhet VH001

(Phosphor)
Phosphor 1 YAG product name manufactured by Mitsubishi Chemical Corporation Phosphor 2 treated with silicone oil treated by BY102D 2 CASN product name BR101A manufactured by Mitsubishi Chemical Corporation
(Transmittance adjuster)
Transmittance adjuster 1 Gantz Kasei Co., Ltd. Gantz Pearl SI-020 Material: Silicone Particle size = 2μm
Permeability adjuster 2 Titanium oxide CR60 Ishihara Sangyo Co., Ltd.

[Production Example of Polycarbonate Resin PC1]
Polycarbonate resin was polymerized using a continuous polymerization facility comprising three vertical stirring reactors, one horizontal stirring reactor, and a twin screw extruder. ISB, CHDM, and DPC were melted in tanks, ISB 25.6 kg / hr, CHDM 25.3 kg / hr, DPC 75.5 kg / hr (mole ratio ISB / CHDM / DPC = 0.500 / 0) .500 / 1.005) was continuously fed to the first vertical stirring reactor. At the same time, an aqueous solution of calcium acetate monohydrate as a catalyst was supplied to the first vertical stirring reactor so as to be 1.5 μmol with respect to 1 mol of all dihydroxy compounds. Average residence time in the first vertical stirring reactor is 90
The liquid level was kept constant while controlling the degree of opening of the valve provided in the transfer pipe at the bottom of the reactor. The reaction liquid discharged from the bottom of the reactor is successively successively supplied to the second vertical stirring reactor, the third vertical stirring reactor, and the fourth horizontal stirring reactor [2-axis glasses blade manufactured by Hitachi Plant Technologies, Ltd.]. Continuously supplied. The first vertical stirring reactor and the second vertical stirring reactor were equipped with a reflux condenser, and the distillation of unreacted dihydroxy compound and DPC was suppressed by adjusting the reflux ratio.

  The reaction temperature, internal pressure and residence time of each reactor are as follows: first vertical stirring reactor: 190 ° C., 25 kPa, 90 minutes, second vertical stirring reactor: 195 ° C., 10 kPa, 45 minutes, third vertical type Stirring reactor: 210 ° C., 3 kPa, 45 minutes, fourth horizontal stirring reactor: 225 ° C., 0.5 kPa, 90 minutes. The operation was carried out while finely adjusting the internal pressure of the fourth horizontal stirring reactor so that the reduced viscosity of the obtained polycarbonate resin was 0.61 dL / g to 0.64 dL / g.

  The polycarbonate resin was extracted from the fourth horizontal stirring reactor at an amount of 60 kg / hr, and then the resin was supplied in a molten state to a twin-screw extruder [TEX30α manufactured by Nippon Steel Works]. The extruder had three vacuum vents, and the remaining low molecular components in the resin were removed by devolatilization. Before the second vent, water was added in an amount of 2000 ppm by weight with respect to the resin, and water injection devolatilization was performed. The extruder was set to a cylinder temperature of 220 ° C. and a screw rotation speed of 230 rpm. The resin temperature at the exit of the extruder was 262 ° C.

After the polycarbonate resin that has passed through the extruder is continuously melted and filtered through the filter, the polycarbonate resin is discharged from the die into strands, cooled with water, solidified, pelletized with a rotary cutter, and ISB / CHDM = 50 / 50 mol% of polycarbonate resin PC1 was obtained.
The obtained polycarbonate resin PC1 had a melt viscosity of 1640 Pa · s and a glass transition temperature of 100 ° C. The total content of sodium, potassium and cesium in the resin was 0.1 ppm by weight. The amount of the double bond end group derived from ISB was 0.25 mol% with respect to the entire structural unit derived from ISB.

<Examples 1-5, Comparative Examples 1-3>
Each resin was dried at 80 to 120 ° C. for 4 hours and then kneaded under the composition and processing conditions shown in Table 1. Here, as the kneading conditions, a lab plast mill manufactured by Toyo Seiki Seisakusho Co., Ltd. was used, and kneading was performed at a screw rotation speed of 80 rpm and 240 to 280 ° C.
After kneading, a disk having a thickness of 1 mm and 45 mmΦ was formed by press molding.

  About the obtained molded body, total light transmittance measurement, initial characteristics (luminescence characteristics measurement, xy chromaticity coordinates, color temperature), characteristics after weathering test (luminescence characteristics measurement, xy chromaticity coordinates, relative color temperature (CCT) )) Was carried out by the following method. In addition, the result (light beam) of the light emission characteristic measurement is a relative value with the light beam of Example 1 as 100.

<Total light transmittance measurement>
Using a turbidimeter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd., measurement was performed in accordance with JIS K7361. The entrance opening of this apparatus was 20 mmΦ, and the light source was a halogen lamp.

<Measurement of luminous characteristics>
The molded product was held on an LED light emitting device emitting light at 450 nm, and the light intensity (Lumen), CIE chromaticity coordinates (x, y), and color temperature were measured as the characteristics of light that was transmitted through the molded product and converted in wavelength. . The light intensity was expressed in% as an intensity ratio based on the light intensity of the material at the left end of each table of the examples.

<Weather resistance test conditions>
Testing machine: Metal weather meter (Daipura: KU-R5N-W)
Sample surface irradiance: 900 W / m ² (wavelength range: 300-400 nm)
Black panel temperature: 63 ℃
Humidity: 50%
Operating conditions: Continuous irradiation (100hr)
Radiation exposure dose: 300 MJ / m ²
After measuring the light emission characteristics after the weather resistance test by the above method, the results were compared with the values before the weather resistance test, and the Lumen retention, chromaticity differences Δx, Δy, and color temperature difference (ΔCCT) were measured.

DESCRIPTION OF SYMBOLS 10 Light-emitting device 1 Semiconductor light-emitting element 2 Wiring board 2a Chip mounting surface 3 Wavelength conversion member 4 Frame

Claims (13)

A thermoplastic resin composition comprising a polycarbonate resin having at least a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) as a part of the structure (hereinafter referred to as “specific dihydroxy compound”). And
The thermoplastic resin composition, wherein the content of the phosphor in the thermoplastic resin composition is 0.01% by weight or more.

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)   2. The thermoplastic resin composition according to claim 1, wherein a content of the phosphor in the thermoplastic resin composition is 0.2 wt% or more and 50 wt% or less.   3. The heat according to claim 1, wherein a content of the polycarbonate resin with respect to a total amount of the thermoplastic resin contained in the thermoplastic resin composition is 50% by weight or more and 100% by weight or less. Plastic resin composition. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the specific dihydroxy compound is a compound represented by the following general formula (2).

  The polycarbonate resin further contains a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound and an alicyclic dihydroxy compound. The thermoplastic resin composition described in 1.   The polycarbonate resin contains 90 mol% or less of structural units derived from a specific dihydroxy compound with respect to structural units derived from all dihydroxy compounds constituting the polycarbonate resin. 2. The thermoplastic resin composition according to item 1.   The thermoplastic resin composition according to any one of claims 1 to 6, wherein the phosphor is an inorganic compound.   The thermoplastic resin composition according to claim 1, wherein the phosphor is a short afterglow phosphor.   Furthermore, the transmittance | permeability regulator is mix | blended, The thermoplastic resin composition of any one of Claims 1-8 characterized by the above-mentioned.   The thermoplastic resin composition according to any one of claims 1 to 9, wherein the total light transmittance of a 1.0 mm thick plate of the thermoplastic resin composition is 30 to 70%. A wavelength conversion member that converts the wavelength of at least part of incident light and emits outgoing light having a wavelength different from that of the incident light;
The wavelength conversion member has a planar structure including a phosphor that absorbs at least a part of the incident light and emits an emitted light having a wavelength different from that of the incident light, and a thermoplastic resin that holds the phosphor. Having
The thermoplastic resin contains a polycarbonate resin having at least a structural unit derived from the specific dihydroxy compound,
At least a part of the planar structure has a total light transmittance of 30% or more and 70% or less.   A light emitting device comprising the wavelength conversion member according to claim 11 and a semiconductor light emitting element.   The LED lighting fixture which has a light-emitting device of Claim 12.

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