JP2015232076A - Thermoplastic resin material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin material having high optical transparency and no problem of coloring to an unintended dark color or poor appearance while containing an inorganic phosphor, and a molded article.SOLUTION: There are provided a thermoplastic resin material manufactured by externally adding (C-2) a mold release agent of 0.001 to 1 pts.mass relative to 100 pts.mass of (D) a resin pellet obtained by melting and mixing 0.1 to 20 pts.mass of (B) an inorganic phosphor and 0.01 to 3 pts.mass of (C-1) a mold release agent relative to 100 pts.mass of (A) a transparent thermoplastic resin, and a molded article by molding the same.

Description

  The present invention relates to a thermoplastic resin material, and more particularly, to an inorganic phosphor-containing thermoplastic resin material and a molded article excellent in hue.

  Transparent thermoplastic resins such as polycarbonate resins and acrylic resins are used in a wide range of fields such as electric / electronic, mechanical, automotive, optical and medical. For example, in optical applications, it is used for lighting cover members and the like by taking advantage of its excellent transparency. There are various types of lighting covers, such as a transparent cover and a milky white translucent cover with a light diffusion function.

  In recent years, special LED lighting called a remote phosphor system has been adopted. In this remote phosphor system, a resin cover containing a phosphor is installed so as to cover the LED element at a position separated from the LED element, and a part of the light emitted from the LED element is covered by the cover. This is a system that converts the wavelength and finally emits white light or the like (for example, Patent Document 1).

Examples of the inorganic phosphor used for the cover material for remote phosphor include phosphors of various oxides, nitrides, oxynitrides, sulfides, and oxysulfides, such as Y A YAG yellow phosphor having a garnet structure represented by ₃ Al ₅ O ₁₂ : Ce is used.
However, it has been found that when these inorganic phosphors are blended with a transparent thermoplastic resin, the color tends to be changed to a dark color by melt kneading or molding, and partial appearance defects such as black stripes are likely to occur. Such unintentional discoloration has been found to be a serious problem because it causes deterioration of light transmission, which is the most important characteristic in lighting cover applications.

JP2012-064345A

  In view of the above situation, the object of the present invention is to use a resin material containing an inorganic phosphor in a transparent thermoplastic resin, and to obtain a hue and light transmittance of a molded product obtained by melt kneading, molding processing, and the like. An object of the present invention is to provide a thermoplastic resin material that can improve the above.

As a result of intensive studies in order to solve the above problems, the present inventor has made unintentional discoloration of material pellets and molded articles composed of an inorganic phosphor and a transparent thermoplastic resin due to melt kneading for pellet production. At the time of plasticizing in the molding process for the production of molded products, and inferring that this may have occurred due to high friction and shear forces in the screw and cylinder. As a result of further studies with the aim of realizing friction reduction in each process, resin pellets obtained by blending a transparent thermoplastic resin, an inorganic phosphor and a release agent, and melt-kneading are further separated. It has been found that the hue and light transmission can be improved by externally adding the mold agent in a specific amount, and the present invention has been achieved.
The present invention provides the following thermoplastic resin materials and molded articles.

[1] (B) 0.1-20 parts by mass of inorganic phosphor and (C-1) 0.01-3 parts by weight of release agent are melt-kneaded with 100 parts by mass of (A) transparent thermoplastic resin. A thermoplastic resin obtained by further adding 0.001 to 1 part by mass of (C-2) a release agent to 100 parts by mass of (D) resin pellets to the obtained (D) resin pellets material.
[2] The thermoplastic resin material according to [1], wherein the transparent thermoplastic resin (A) is a polycarbonate resin.
[3] In the above [1] or [2], the (D) resin pellet further contains (E) a light diffusing agent in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the (A) transparent thermoplastic resin. The thermoplastic resin material described.
[4] The thermoplastic resin material according to any one of [1] to [3], wherein the (C-2) release agent is a fatty acid amide.
[5] The thermoplastic resin material according to [3] or [4], wherein (E) the light diffusing agent is organic crosslinked fine particles having an average particle diameter of 1 to 10 μm.
[6] (D) The resin pellet is further 0.01 to 1 part by mass of (F) ultraviolet absorber and (001) 0.001 of the thermal stabilizer with respect to 100 parts by mass of (A) transparent thermoplastic resin. The thermoplastic resin material according to any one of [1] to [5], which is contained in 1 part by mass.
[7] Any of the above [1] to [6], wherein (D) the resin pellet further contains (H) a flame retardant in an amount of 0.01 to 15 parts by mass with respect to 100 parts by mass of (A) the transparent thermoplastic resin. The thermoplastic resin material according to crab.
[8] The thermoplastic resin material according to any one of [1] to [7], wherein (C-2) the release agent has a melting point of 120 ° C. or higher.
[9] A molded product formed by molding the thermoplastic resin material according to any one of [1] to [8].
[10] The molded article according to [9], which is a lighting cover.
[11] The molded product according to [10], which is a light-transmitting cover for a remote phosphor type LED light-emitting device.

  According to the thermoplastic resin material of the present invention, a transparent thermoplastic resin contains an inorganic phosphor, has high light transmittance, and has no problem of appearance defects such as unintentional dark coloration or discoloration. Goods can be provided. In particular, it is possible to provide a resin material suitable for an illumination cover of an LED lighting device, a light-transmitting cover (glove, etc.) of a remote phosphor type LED light emitting device, and the like.

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

[Overview]
The thermoplastic resin material of the present invention comprises (A) 0.1 to 20 parts by mass of an inorganic phosphor and (C-1) 0.01 to 3 parts by weight of a release agent with respect to 100 parts by mass of (A) a transparent thermoplastic resin. (D) The resin pellet obtained by melt-kneading the part is further added with 0.001 to 1 part by mass of (C-2) a release agent with respect to 100 parts by mass of the (D) resin pellet. Features.
[(A) Transparent thermoplastic resin]
The transparent thermoplastic resin (A) which is the main component of the thermoplastic resin material of the present invention includes polycarbonate resin; acrylic resin such as polymethyl methacrylate and polymethacrylate; alicyclic ring such as alicyclic polyolefin resin containing norbornene and the like. Polyolefin resin: Ionomer resins such as copolymers of ethylene and methyl-, ethyl-, propyl-, butyl-acrylates or methacrylates, ethylene-acrylic acid copolymers; polystyrene resins, ABS resins, AS resins, AAS Styrenic resins such as resins, AES resins and MBS resins; Polyester resins such as polyethylene terephthalate resins and polybutylene terephthalate resins; Modified polyphenylene ether resins; Polyarylate resins; Polyetherimide resins; Etc. These one or more blends thereof.
Of these, polycarbonate resins, acrylic resins, and alicyclic polyolefin resins are preferable, and polycarbonate resins are more preferable in terms of impact resistance, heat resistance, and flame retardancy.

[(A1) Polycarbonate resin]
There is no restriction | limiting in the kind of (A1) polycarbonate resin used for the thermoplastic resin material of this invention. Moreover, (A1) polycarbonate resin may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.
The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by a general formula: — (— O—X—O—C (═O) —) —. In the formula, X is generally a hydrocarbon group, but for imparting various properties, X introduced with a hetero atom or a hetero bond may be used.
The polycarbonate resin can be classified into an aromatic polycarbonate resin in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon, and an aliphatic polycarbonate resin in which the carbon is an aliphatic carbon. From the viewpoint of electrical characteristics and the like, it is preferable to use an aromatic polycarbonate resin.

(A1) Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate resin formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used.
Moreover, (A1) polycarbonate resin may be linear or branched. Furthermore, the (A1) polycarbonate resin may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

(A1) Among the monomers used as the raw material for the polycarbonate resin, examples of the aromatic dihydroxy compound include:
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;
2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

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

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

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

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

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

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

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

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

  (A1) Among the monomers used as the raw material for the polycarbonate resin, carbonyl halides, carbonate esters, and the like are used as examples of carbonate precursors. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

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

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

  (A1) The manufacturing method of polycarbonate resin is not specifically limited, A well-known arbitrary method is employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

  (A1) The molecular weight of the polycarbonate resin may be appropriately selected and determined, but is usually 12,000 or more, preferably 15,000 or more, more preferably 17, in terms of viscosity average molecular weight [Mv] converted from the solution viscosity. 000 or more, particularly 20,000 or more, and usually 36,000 or less, preferably 34,000 or less, more preferably 32,000 or less, still more preferably 30,000 or less, particularly preferably 29,000 or less. It is. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the thermoplastic resin material can be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, by setting the viscosity average molecular weight to be equal to or less than the upper limit of the above range, it is possible to suppress and improve the fluidity drop of the thermoplastic resin material of the present invention, and to improve the molding processability and easily perform the molding process.

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

(A1) The polycarbonate resin is a polycarbonate resin alone (a polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and includes, for example, an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. It may be used in the sense) or may be used in combination with an alloy (mixture) of a polycarbonate resin and another thermoplastic resin. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy. Copolymer with monomer, oligomer or polymer having atoms; copolymer with monomer, oligomer or polymer having dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; polystyrene to improve optical properties, etc. A copolymer with an oligomer or polymer having an olefin structure of the above; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Also good.
Furthermore, it is also preferable to use a polycarbonate resin in which at least a part of the molecular chain is branched for the purpose of improving flame retardancy. Examples of such a polycarbonate resin having a branched chain include a polycarbonate resin produced by a melt transesterification method and a polycarbonate resin produced by an interfacial polymerization method by blending a branching agent.

Further, in order to improve the appearance of the molded product and the fluidity, (A1) the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).
The shape of the (A1) polycarbonate resin used in melt-kneading may be any, but it is usually in the form of pellets, granules, or powders.

[(A2) Acrylic resin]
As the (A2) acrylic resin, a (co) polymer containing a methyl methacrylate unit as a main component and containing 0 to 5% by mass of other acrylic ester units is preferable. The acrylic resin preferably has a mass average molecular weight in the range of 30,000 to 250,000. If a material having a mass average molecular weight lower than 30,000 is used, the resulting resin composition tends to have a low mechanical strength. Moreover, in the thing higher than 250,000, the fluidity | liquidity of a resin composition worsens and a moldability tends to deteriorate. In addition, a mass average molecular weight says the value of polystyrene conversion by a gel permeation chromatography (GPC) method.

  The acrylic ester units that can be copolymerized with methyl methacrylate units are specifically methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic acid-iso-butyl, acrylic acid-t-butyl. , Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl cyclohexyl acrylate, bornyl acrylate, isobornyl acrylate, adamantyl acrylate, cycloalkyl acrylates, phenyl acrylate, acrylic acid Acrylic acid aromatic esters such as benzyl, acrylic acid-substituted aromatic esters such as fluorophenyl acrylate, chlorophenyl acrylate, fluorobenzyl acrylate, chlorobenzyl acrylate, and fluoromethacrylate Acrylic acid alkyl halide esters such as acrylic acid fluoroethyl, hydroxy alkyl acrylate, glycidyl acrylate, ethylene glycol ester and acrylic acid polyethylene glycol esters. These acrylic acid ester units can use 1 type (s) or 2 or more types. Of these, methyl acrylate is preferred.

[(A3) Alicyclic polyolefin resin]
(A3) The alicyclic polyolefin resin is a polyolefin resin containing an alicyclic structure in the main chain, and the alicyclic structure includes a saturated alicyclic hydrocarbon (cycloalkane) structure, an unsaturated alicyclic hydrocarbon. (Cycloalkene) structure and the like can be mentioned. From the viewpoints of mechanical strength and heat resistance, a cycloalkane structure and a cycloalkene structure are preferable, and a cycloalkane structure is most preferable. Although there is no special restriction | limiting in the number of carbon atoms which comprises an alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is the range of 5-15 pieces.
The proportion of the repeating unit containing the alicyclic structure in the alicyclic polyolefin resin may be appropriately selected according to the purpose of use, but is preferably 55% by mass or more, more preferably 70% by mass or more, particularly Preferably it is 90 mass% or more. When the ratio of the repeating unit having an alicyclic structure in the alicyclic polyolefin resin is within this range, the transparency and heat resistance of the thermoplastic resin material of the present invention are improved.

  Examples of (A3) alicyclic polyolefin resins include norbornene resins, monocyclic olefin resins, cyclic conjugated diene resins, vinyl alicyclic hydrocarbon resins, and hydrides thereof. . Among these, norbornene-based resins can be suitably used because of their good transparency and moldability.

  Examples of the norbornene-based resin include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening polymer of a monomer having a norbornene structure and another monomer, a hydride thereof, or a norbornene structure. Examples thereof include addition polymers of monomers, addition polymers of monomers having a norbornene structure and other monomers, and hydrides thereof.

Examples of monomers having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene. (Common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0. 1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene), and derivatives of these compounds (for example, those having a substituent in the ring).

Other monomers capable of ring-opening copolymerization with monomers having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene; Derivatives thereof; and the like.
A ring-opening polymer of a monomer having a norbornene structure and a ring-opening copolymer of a monomer having a norbornene structure and another monomer copolymerizable with the monomer have a known ring-opening polymerization catalyst. It can be obtained by (co) polymerization in the presence.

Examples of other monomers that can be addition copolymerized with a monomer having a norbornene structure include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, and 1-butene, and derivatives thereof; cyclobutene, cyclopentene, And cycloolefins such as cyclohexene and derivatives thereof; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and the like. These monomers can be used alone or in combination of two or more. Among these, α-olefin is preferable and ethylene is more preferable.
An addition polymer of a monomer having a norbornene structure and an addition copolymer of a monomer having a norbornene structure with another monomer copolymerizable with a monomer having a norbornene structure are prepared in the presence of a known addition polymerization catalyst. It can be obtained by polymerization.

  A hydrogenated product of a ring-opening polymer of a monomer having a norbornene structure, a hydrogenated product of a ring-opening copolymer of a monomer having a norbornene structure and another monomer capable of ring-opening copolymerization thereof, Hydrogenated products of addition polymers of monomers having a norbornene structure and hydrogenated products of addition polymers of monomers having a norbornene structure and other monomers copolymerizable therewith are not A known hydrogenation catalyst containing a transition metal such as nickel or palladium is added to the combined solution, and the carbon-carbon unsaturated bond is preferably hydrogenated by 90% or more.

  (A3) The molecular weight of the alicyclic polyolefin resin is appropriately selected according to the purpose of use, but is usually a polyisoprene-converted mass average molecular weight (Mw) measured by gel permeation chromatography using cyclohexane as a solvent. It is 10,000 to 100,000, preferably 15,000 to 80,000, more preferably 20,000 to 50,000.

[(B) Inorganic phosphor]
As the (B) inorganic phosphor used in the thermoplastic resin material of the present invention, various inorganic phosphors can be used, and various phosphors such as red (orange), green, blue, and yellow can be used.
Examples of red phosphors include CaAlSiN ₃ : Eu (abbreviated as “CASN”), (Sr, Ca) AlSiN ₃ : Eu (abbreviated as “SCASN”), and Ca _1-x Al _{1 1−. x Si 1 + x N 3-} x O x: Eu, CaAlSiN 3: Eu, (Sr, Ba, Ca) 3 SiO 5: Eu , and the like preferably.
Examples of the green phosphor include (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu, Si _6-z Al _z N _{8 -z} O _z : Eu, and M ₃ Si ₆ O ₁₂ N ₂ : Eu (M Is preferably an alkaline earth metal element).
As the blue phosphor, (Sr, Ca, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ and BaMgAl ₁₀ O ₁₇ : Eu can be preferably used.
As the yellow phosphor, a garnet phosphor is preferably used, and in particular, Y ₃ Al ₅ O ₁₂ : Ce (also referred to as “YAG”) is preferably used.
These inorganic phosphors may be used alone or in combination of two or more at any ratio.

  (B) Although the magnitude | size of an inorganic fluorescent substance does not have limitation in particular, Usually, it exists in the range of 0.1-100 micrometers by an average particle diameter, Preferably it is 1-50 micrometers. If the average particle size is less than 0.1 μm, the wavelength conversion efficiency tends to be insufficient. On the other hand, if it exceeds 100 μm, it is difficult to obtain the hue improving effect of the present invention, and the mechanical strength of the resulting thermoplastic resin material may be lowered, which is not preferable. (B) The shape of the inorganic phosphor is not particularly limited, but is usually indefinite.

The Mohs hardness of (B) the inorganic phosphor is usually 6 or more, preferably 7 or more, more preferably 8 or more. Since inorganic phosphors with higher Mohs hardness are more likely to cause discoloration problems, it is considered that the effect of improving hue by adding the release agents (C-1) and (C-2) is greater.
Note that the Mohs hardness is an index obtained by quantifying the hardness of a substance, but in the present invention, an index classified into 10 levels is used.

These (B) inorganic phosphors were treated with various surface treatment agents such as inorganic acids, organic acids, silane coupling agents, titanate coupling agents, methyl hydrogen polysiloxanes, silicone oils, and fatty acid-containing hydrocarbon compounds. It may be a thing. Among these, in particular, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, alkyltrimethoxysilane such as dodecyltrimethoxysilane, methyl having a kinematic viscosity in the range of 5 to 10,000 mm ² / s at 25 ° C. hydrogen polysiloxane, dimethyl silicone oil or methylphenyl silicone oil 5-10000 ^mm 2 / s at a kinematic viscosity of 25 ° C. are preferred, kinematic viscosity at 25 ° C. of 10~1,000mm ² / s methylhydrogenpolysiloxane Polysiloxane is more preferred.
The amount of the surface treatment agent is preferably in the range of 0.001 to 10 parts by mass, more preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the (B) inorganic phosphor. A known method can be arbitrarily used for the surface treatment.

  (B) Content of inorganic fluorescent substance is 0.1-20 mass parts with respect to 100 mass parts of (A) transparent thermoplastic resin, Preferably it is 0.5 mass part or more, More preferably, it is 1 mass part or more. And preferably 15 parts by mass or less, more preferably 10 parts by mass or less. If the content is less than 0.1 parts by mass, the wavelength conversion efficiency of light is insufficient. If the content is more than 20 parts by mass, the mechanical strength of the resulting thermoplastic resin material is greatly reduced.

[(C-1) mold release agent]
The (C-1) release agent used for the thermoplastic resin material of the present invention usually refers to various known release agents that can be used for the (A) transparent thermoplastic resin. (C-1) A mold release agent may be used individually by 1 type, and may be used together with multiple types.
(C-1) When the release agent has a melting point, the melting point by a differential scanning calorimeter (DSC) is preferably 40 to 260 ° C, more preferably 100 to 230 ° C, and 120 to 200. More preferably, the temperature is C. When the melting point is less than 40 ° C., the handling during the production of the thermoplastic resin material tends to be difficult, and when it exceeds 260 ° C., the friction reducing effect tends to be small, and the hue improving effect of the present invention is reduced. There is.
In the present specification, the melting point of the release agent refers to the melting point by differential scanning calorimetry (DSC) and refers to the peak temperature (° C.) of the main peak of melting. Specifically, it refers to the peak top temperature (° C.) of the exothermic main peak detected when the temperature is raised from 30 ° C. to the expected melting point + 40 ° C. at 20 ° C./min in a nitrogen atmosphere.

  In addition, when the release agent (C-1) is liquid at room temperature, (D) in the raw material mixing stage before melt-kneading the resin pellets, a case where a partial lump in which the raw materials are aggregated is formed or mixed. When feeding the raw material into the extruder, caution is required such that the mixed raw material tends to adhere to the extruder inlet. From the above, the (C-1) release agent is more preferably a solid at room temperature.

  Examples of (C-1) mold release agents include fatty acids, esters of aliphatic carboxylic acids and alcohols, fatty acid amides, fatty acid metal salts, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxanes. Examples include silicone oil. Among these, from the viewpoint of the effect of improving hue and the stability of residence heat, it is selected from fatty acids, esters of aliphatic carboxylic acids and alcohols, and aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000. preferable.

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

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

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

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

The fatty acid amide is a fatty acid amide or a fatty acid bisamide, and is preferably a compound obtained by a dehydration reaction between a fatty acid and / or a polybasic acid and a diamine.
The fatty acid is preferably a saturated aliphatic monocarboxylic acid having 16 or more carbon atoms, more preferably 16 to 30 carbon atoms. Specific examples include palmitic acid, stearic acid, behenic acid, and montanic acid.
The polybasic acid is a carboxylic acid of dibasic acid or more, for example, aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid, azelaic acid, and aromatics such as phthalic acid and terephthalic acid. Examples thereof include dicarboxylic acids and alicyclic dicarboxylic acids such as cyclohexyl dicarboxylic acid and cyclohexyl succinic acid.
Examples of the amine include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine and the like.
Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, and isophoronediamine. Among these, a linear saturated aliphatic diamine having 2 to 20 carbon atoms is preferable.

  Specifically, the fatty acid amide preferably includes stearic acid amide, behenic acid amide, montanic acid amide, and the like, and the fatty acid bisamide includes the above fatty acid and carbon number of 1 to 10, preferably carbon number. And fatty acid bisamides obtained by reaction with 1 to 6 aliphatic diamines, specifically, methylene bis stearic acid amide, ethylene bis stearic acid amide, ethylene bis behenic acid amide, ethylene bis palmitic acid amide, Examples thereof include ethylene bis (12-hydroxystearic acid amide) and hexamethylene bis (12-hydroxystearic acid amide). Of these, stearamide and ethylene bis stearamide are preferable.

  Preferred examples of the fatty acid metal salt include calcium stearate, zinc stearate, magnesium stearate, lead stearate, aluminum stearate, sodium montanate and the like.

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

  The content of the (C-1) release agent is 0.01 to 3 parts by mass, preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the (A) transparent thermoplastic resin. Preferably it is 2 mass parts or less, More preferably, it is 1 mass part or less. (C-1) When the content of the release agent is less than the lower limit of the range, the effect of improving the hue is insufficient, and when the content of the release agent exceeds the upper limit of the range, heating is performed. There is a possibility that the generated gas increases or mold contamination due to mold deposits occurs.

[(C-2) mold release agent]
The (C-2) release agent externally added to the (D) resin pellet of the present invention usually refers to various known release agents that can be used for the (A) transparent thermoplastic resin. (C-2) A mold release agent may be used individually by 1 type, and may use multiple types together.
(C-2) As the mold release agent, those exemplified in the description of the above (C-1) mold release agent can be used, and (C-1) the same kind as the mold release agent is different. It may be of a kind.

(C-2) The mold release agent is selected from those which do not melt at the preliminary drying temperature of the pellets before molding the thermoplastic resin material of the present invention, but melt at the temperature at the time of molding, It is preferable from the viewpoint of handleability and hue improvement effect.
For example, when (A) the transparent thermoplastic resin is a polycarbonate resin, the preliminary drying temperature before molding is at least 80 ° C. or higher, and usually 100 ° C. or higher. Therefore, the melting point of (C-2) the release agent is 80 It is preferable that the temperature is at least 100 ° C, more preferably at least 100 ° C, especially at least 120 ° C. Further, it is particularly preferable that the resin has a melting point of 260 ° C. or lower which is the lower limit of the substantial molding temperature of the polycarbonate resin.

  Examples of such preferable release agents include fatty acid amides such as ethylene bis stearamide and stearamide, polyethylene wax having a relatively high molecular weight, calcium stearate, and the like. In particular, ethylene bis stearamide is preferable.

  In addition, when (C-2) the release agent is solid at room temperature, (D) in order to suppress the release of (C-2) release agent from the resin pellet, It is also preferable to spread various oils or the like on (D) resin pellets in advance and then add (C-2) a release agent to the outside.

  (C-2) A mold release agent is externally added in an amount of 0.001 to 1 part by mass with respect to 100 parts by mass of (D) resin pellets. The minimum with the preferable amount of external addition is 0.005 mass part, More preferably, it is 0.01 mass part. The upper limit with the preferable amount of external addition is 0.5 mass part, More preferably, it is 0.3 mass part. (C-2) When the external addition amount of the release agent is less than the lower limit value of the above range, sufficient hue improvement effect cannot be obtained, and when the external addition amount exceeds the upper limit value of the above range, heating is generated. In addition to gas contamination and mold contamination due to mold deposits, the release agent is detached from the material pellets and classified to contaminate material drying equipment, molding machine hoppers, etc., and transportation piping when materials are transported pneumatically Problems such as clogging are likely to occur.

  In this invention, (A) 0.1-20 mass parts of (B) inorganic fluorescent substance and (C-1) mold release agent 0.01-3 mass parts are mix | blended with respect to 100 mass parts of transparent thermoplastic resins. Then, this is melt-kneaded to obtain (D) resin pellets, which will be described later, but the (D) resin pellets of the present invention preferably further contain (E) a light diffusing agent. (E) By containing a light diffusing agent, not only can the light diffusibility and the glare reduction function be used in applications such as illumination covers, but also (B) the wavelength conversion efficiency of the inorganic phosphor is increased. It is preferable because the content of the inorganic phosphor can be reduced. Further, the reduction of the inorganic phosphor is preferable because it leads to suppression of unintentional dark coloring associated with the blending of the inorganic phosphor.

(E) The light diffusing agent includes fine inorganic or organic particles, for example, inorganic particles such as calcium carbonate fine particles and glass fine particles, organic materials such as polystyrene resins, (meth) acrylic resins, and silicone resins. Fine particles are mentioned. Among these, transparent organic fine particles are preferable. Further, the fine particles are preferably spherical in terms of light transmittance and light diffusion effect.
The average particle diameter of the fine particle light diffusing agent is preferably 0.1 to 50 μm, more preferably 0.5 to 30 μm, and further preferably 1 to 10 μm.

As such organic fine particles, crosslinked organic crosslinked fine particles that do not melt in the resin even when heated to the molding temperature of the transparent thermoplastic resin are preferable. Specifically, crosslinked (meth) acrylic resins, silicone-based fine particles are preferable. Organic crosslinked fine particles of resin. Specific examples include partially cross-linked polymethyl methacrylate polymer fine particles, cross-linked silicone resin particles, silicone rubber powder obtained by coating a silicone rubber with a silicone resin, and the like.
Among these, silicone resin organic fine particles are preferable, polyorganosilsesquioxane particles are more preferable, and polymethylsilsesquioxane particles are particularly preferable from the viewpoint of excellent thermal stability.

  (E) 0.01-10 mass parts is preferable with respect to 100 mass parts of (A) transparent thermoplastic resin in (D) resin pellet, and, as for content of a light diffusing agent, 0.1-5 mass parts is more. preferable. When the content ratio of the light diffusing agent is less than 0.01 parts by mass, the light diffusibility is insufficient, the high-brightness LED light source is easily seen through, and the effect of reducing glare is insufficient, and (B) inorganic phosphor However, it is difficult to obtain the effect of blending the light diffusing agent. On the other hand, when there is too much content of a light-diffusion agent, transparency and a fluid fall may be caused, and it is unpreferable. In addition, 1 type may contain the light-diffusion agent and 2 or more types may contain it by arbitrary combinations and a ratio.

  Furthermore, the thermoplastic resin material of the present invention can also contain (F) an ultraviolet absorber, (G) a thermal stabilizer, and (H) a flame retardant in (D) resin pellets.

(F) Ultraviolet Absorber In the present invention, blending (F) an ultraviolet absorber is preferable because discoloration under an ultraviolet irradiation environment such as outdoors can be suppressed.
Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; organics such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds Examples include ultraviolet absorbers. Of these, organic ultraviolet absorbers are preferred, and benzotriazole compounds are more preferred.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3' , 5′-di-tert-amyl) -benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2 , 2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], among others, 2- (2′-hydroxy- 5′-tert-octylphenyl) benzotriazole and 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] are preferred. In particular, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is preferred. In particular, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] has low volatility during molding, and gold This is preferable because there is little mold contamination.

  (F) As for content of a ultraviolet absorber, 0.01-1 mass part is preferable with respect to 100 mass parts of (A) transparent thermoplastic resin in (D) resin pellet, 0.05-0.7 mass. Part is more preferable, and 0.1 to 0.5 part by mass is further preferable. When the content of the ultraviolet absorber is less than 0.01 parts by mass, the improvement effect may be insufficient. When the content is more than 1 part by mass, the problem of mold contamination during molding tends to occur. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

(G) Heat Stabilizer In the present invention, it is preferable to add a heat stabilizer because the hue and heat aging resistance can be improved. Examples of the heat stabilizer include phenolic antioxidants and phosphorus heat stabilizers. One type of heat stabilizer may be used alone, or a plurality of combined systems may be used.

(G-1) Phenol-based antioxidant As the phenol-based antioxidant, a phenol compound having a specific structure in the molecule is preferable. Specifically, for example, 2,2′-methylenebis (4-methyl-6-tert- Butylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3,9 -Bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5. 5] Undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6- Xanthdiolbis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], pentaerythritol-tetrakis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] , Octadecyl [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, etc. Is mentioned.

  Among these, when (A) the transparent thermoplastic resin is a polycarbonate resin, 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy) -5-tert-butylphenyl) butane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2 , 4,8,10-tetraoxaspiro [5.5] undecane, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane are preferred, especially 1,1 , 3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3,9-bis [2- {3- (3-tert-butyl- -Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, tetrakis [methylene-3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate] methane is preferred because of its high thermal stability improving effect.

  (G-1) The content of the phenolic antioxidant is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the (A) transparent thermoplastic resin in the (D) resin pellet, and 0.01 to 0.5 mass part is more preferable, and 0.03-0.2 mass part is further more preferable. If the content of the phenolic antioxidant is too small, the effect may be insufficient. On the other hand, if the content is too large, the molecular weight of the polycarbonate resin may be lowered or the hue may be lowered.

(G-2) Phosphorus-based heat stabilizer Examples of the phosphorous-based stabilizer include phosphorous acid, phosphoric acid, phosphorous acid ester, phosphoric acid ester, etc. Among them, trivalent phosphorus is included, and a discoloration suppressing effect is exhibited. From the standpoint of ease, phosphites such as phosphites and phosphonites are preferred.

  Specific examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, and tris. (Tridecyl) phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetra Phosphite, hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-t rt-butylphenyldi (tridecyl) phosphite) tetra (tridecyl) 4,4'-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilauryl Pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Polymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphos Aito, 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

  Examples of phosphonites include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6- -Tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, and tetrakis (2,6-di-) tert-butylphenyl) -3,3′-biphenylenediphosphonite.

  Examples of the acid phosphate include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, and lauryl phosphate. Phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid Sulfate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phenyl Acid phosphate, bisnonylphenyl acid phosphate, etc. are mentioned.

  Among the phosphites, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Erythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferable, and heat resistance is good. Tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred in that it is difficult to hydrolyze.

  (G-2) The content of the phosphorus-based heat stabilizer is preferably 0.001 to 1 part by mass, and 0.005 to 100 parts by mass of (A) the transparent thermoplastic resin in (D) resin pellets. 0.5 parts by mass is more preferable, and 0.01 to 0.2 parts by mass is even more preferable. If the content of the heat stabilizer is too small, the heat stabilizing effect tends to be insufficient, and conversely if too large, the molecular weight may be lowered or the hue may be lowered.

(H) Flame Retardant The thermoplastic resin material of the present invention may contain a flame retardant, and (D) the resin pellet preferably includes (H) a flame retardant.
Examples of the flame retardant include halogen-based, phosphorus-based, silicone-based, nitrogen-based, metal salt-based flame retardant, and the like, and a known one can be arbitrarily mixed in a necessary amount.
For example, when a polycarbonate resin is used as the transparent thermoplastic resin, a condensed phosphate ester, a cyclic or chain phenoxyphosphazene compound, a silicone compound, a sulfonate metal salt such as potassium perfluorobutanesulfonate, a powder or a day super A polytetrafluoroethylene coated with a john, acrylic resin or the like is preferably used. The thermoplastic resin material which has desired flame retardance can be obtained by using these individually or in combination of multiple types.

(H) It is preferable that content of a flame retardant is 0.01-15 mass parts with respect to 100 mass parts of (A) transparent thermoplastic resin in (D) resin pellet. When the content is less than 0.01 parts by mass, a sufficient flame retardant effect may not be obtained. When the content is more than 15 parts by mass, it is difficult to obtain a good hue, and mechanical properties and the like are liable to deteriorate.
In particular, when the flame retardant is a sulfonic acid metal salt, a silicone compound, or polytetrafluoroethylene, the content is preferably 0.01 parts by mass or more with respect to 100 parts by mass of (A) the transparent thermoplastic resin. Preferably it is 0.03 mass part or more, Moreover, the upper limit becomes like this. Preferably it is 5 mass parts, More preferably, it is 2 mass parts. When the flame retardant is a condensed phosphate ester or phosphazene, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and the upper limit is preferably 100 parts by mass of the transparent thermoplastic resin (A). Is 10 parts by mass. When the flame retardant content is less than the lower limit of the above range, it is difficult to obtain an effect of improving flame retardancy, and when it exceeds the upper limit, mechanical strength, heat and humidity resistance, thermal stability, etc. may be reduced. is there. In addition, 1 type may be contained for a flame retardant, and 2 or more types may be contained by arbitrary combinations and ratios.

  When (A) the transparent thermoplastic resin is a polycarbonate resin, a part or all of the polycarbonate resin is a polycarbonate resin having a branched structure, a silicone copolymer polycarbonate resin, or a polycarbonate resin having a viscosity average molecular weight of 30,000 or more. It is preferable because the flame retardancy is further improved.

[Other additives]
In addition, the thermoplastic resin material of the present invention may contain (A) a thermoplastic resin other than the transparent thermoplastic resin, and various additives as long as the effects of the present invention are not impaired. Examples of such additives include dyes and pigments, optical brighteners, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, reinforcing fillers, elastomers, etc. Is mentioned.

[(D) Production of resin pellets]
In this invention, (A) 0.1-20 mass parts of (B) inorganic fluorescent substance and (C-1) mold release agent 0.01-3 mass parts with respect to 100 mass parts of transparent thermoplastic resin, Furthermore, if necessary, (E) a light diffusing agent, (F) an ultraviolet absorber, (G) a heat stabilizer, (H) a flame retardant and other additives are blended and melt-kneaded (D ) Obtain resin pellets. There is no restriction on the method for producing (D) resin pellets by melt-kneading, and a wide variety of known methods for producing thermoplastic resin composition pellets can be adopted. For example, after premixing using various mixers such as a tumbler or Henschel mixer And a melt kneading method using a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader. Among them, it is preferable to use a single-screw kneading extruder and a twin-screw kneading extruder because of excellent productivity. The material and structure of the screw or cylinder can be selected as appropriate, but the screw and cylinder are preferably excellent in corrosion resistance and wear resistance. The raw materials may be charged from the root of the kneading extruder or a part or all of the raw materials may be charged from the middle of the kneading extruder. The temperature of melt kneading is not particularly limited, but in the case of polycarbonate resin, it is usually in the range of 240 to 320 ° C.
In melt-kneading, it is preferable to melt so that excessive shearing force is not applied as much as possible, and therefore, it is preferable to select an apparatus and conditions. Excessive shearing load is not preferable because the resin composition may be changed to a dark color.

The (D) resin pellet obtained in this way may have any shape or size, but usually the minor axis and the major axis are both in the range of 0.1 to 10 mm, particularly 1 to 5 mm. The range is preferable from the viewpoint of improving the bite into the screw and reducing the shear friction in the heating cylinder.
The cross section of the resin pellet may be circular, elliptical, rectangular, oval, or flat.

[(C-2) External addition of release agent]
The (D) resin pellet produced as described above is externally added with (C-2) a release agent in an amount of 0.001 to 1 part by mass with respect to 100 parts by mass of the (D) resin pellet. .
The method of external addition is not particularly limited. For example, before (D) resin pellets are put into a hopper of a molding machine, (D) resin pellets and (C-2) release agent are blended with a blender mixer, Examples of the method include mixing with a tumbler mixer or the like, or charging (D) resin pellets and (C-2) a release agent directly into a molding machine hopper with separate raw material input devices.

  (C-2) When a release agent is externally added to (D) resin pellets, (C-2) the release agent melts earlier than (D) resin pellets in the plasticizing step, and the cylinder inner wall and screw surface of the molding machine It is considered that this contributes to friction reduction when plasticizing the resin pellet (D) and suppresses discoloration.

[Molding]
The obtained thermoplastic resin material of the present invention is made into various molded products by applying various molding methods. The molding method is preferably a molding method such as an injection molding method, a blow molding method, an extrusion molding method, a hollow molding method, an injection compression molding method, or a transfer molding method. Of these, the injection molding method and the extrusion molding method are particularly preferable. In the molding process, it is preferable to melt so as not to apply an excessive shearing force as much as possible. For this purpose, it is preferable to select an apparatus and conditions. Excessive shearing force loading is not preferable because it may cause the molded product to discolor to a dark color system.

  As the molding machine, for example, a method of adopting a screw of a type in which the screw configuration is more slowly compressed so as not to apply abrupt shear to the unmelted resin can be preferably used. Moreover, it is preferable that a cylinder and a screw are excellent in corrosion resistance and abrasion resistance.

In adjusting the molding conditions, it is particularly preferable to avoid plasticization at a high shear rate. As plasticization and measurement conditions in the case of injection molding, it is preferable to adjust, for example, cylinder temperature, back pressure, screw rotation speed, and the like. Although it is necessary to adjust suitably according to the kind of (A) transparent thermoplastic resin to be used, for example, when (A) transparent thermoplastic resin is a polycarbonate resin, it is preferable to employ the following conditions. .
The cylinder temperature is preferably set to 240 to 320 ° C, more preferably 260 to 300 ° C. When adjusting the back pressure is preferably 0.5 to 20 / cm ^2, more preferably set to 1~15kg / cm ^2. When adjusting a screw rotation speed, Preferably it sets to 30-200 rpm, More preferably, it sets to 50-150 rpm.

  By adjusting any of the molding conditions such as molding machine conditions, cylinder temperature, back pressure, screw rotation speed, etc. within the above preferred range, or by combining two or more conditions within these preferred ranges, It becomes easier to obtain a molded article having excellent appearance and free from problems of coloring and discoloration. In the present invention, among these conditions, the method of adjusting the back pressure is particularly preferable.

  The molded product thus obtained can be applied to various applications, such as electric / electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods and miscellaneous goods. It can be applied to parts such as lighting equipment. Among these, it is suitable for parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment, and in particular, a light-transmitting cover (globe) that covers LED elements in remote phosphor lighting equipment. It is suitable for.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
The raw material components used in the following examples and comparative examples are as shown in Table 1 below.

(Examples 1-8 and Comparative Examples 1-3)
1. Blend for melt-kneading Among the components described in Table 1 above, each component other than the release agent (C-2) added externally is weighed in a predetermined amount (parts by mass) described in Table 2 below. Mix with a tumbler mixer.

2. Melt kneading ((D) Pellet production conditions)
The mixture obtained by the above method 1 is supplied from the root of a single-screw extruder “VS40” (screw pattern: full flight) manufactured by Isuzu Machine, and kneaded at a screw rotation speed of 75 rpm and a melt-kneading temperature of 280 ° C. The molten resin composition extruded in a strand shape was quenched in a water bath and pelletized using a pelletizer to obtain a polycarbonate resin composition (D) resin pellet.

3. (D) External Addition of (C-2) Release Agent to Pellets In Examples 1 to 8, (D) Resin pellets obtained by the above method 2 were used for external addition described in Table 1 (C -2) The release agent was blended in the proportions shown in Table 2 and mixed with a tumbler mixer. In Comparative Examples 1 to 3, as shown in Table 2, the (C-2) release agent for external addition was not blended.

4). Material Drying Before Molding The thermoplastic resin material obtained through the above methods 1 to 3 was put into a stainless steel vat and dried at 120 ° C. for 5 hours with a shelf-type hot air dryer.

5). Injection Molding The thermoplastic resin material obtained through the above methods 1 to 4 was injection molded under the following conditions to produce the following flat plate-shaped molded product.
・ Molding machine: Nissei Plastic Industry's injection molding machine "NS40"
Molded product: 1 mm thickness x 30 mm length x 50 mm width flat plate shaped product Molding temperature: 280 ° C
・ Mold temperature: 80 ℃
-Screw rotation speed: 120rpm
・ Back pressure (gauge pressure): 5 kg / cm ²
・ Injection time: 12 sec
・ Cooling time: 15 sec

6). Characteristic Evaluation The obtained thermoplastic resin material and molded article were measured or evaluated for total light transmittance, appearance (hue) and material dry vat contamination by the following methods.
・ Total light transmittance:
The total light transmittance (unit:%) was measured with a D65 light source using a Nippon Denshoku HAZE meter “NDH-4000”.
・ Hue:
The hue of the molded product was visually evaluated, and whether or not the hue was dark was determined, and the vividness of the hue was determined and evaluated according to the following criteria.
Judgment criteria:
A: The hue is not dark and vivid.
○: The hue is not dark.
X: It is quite dark and dark.
・ Assessment of material dry vat contamination:
After the material 4 was dried, the material was taken out and the bat was contaminated after the bat was cooled to room temperature, and visually evaluated according to the following criteria.
A: There is no fused material.
◯: There is a slight amount of melted material, but it can be easily removed.
The above evaluation results are shown in Table 2 below.

From the results in Table 2, it can be seen that the molded products obtained from the thermoplastic resin material of the present invention have no darkness, all have improved hue, excellent appearance, and high total light transmittance ( Examples 1-8).
Moreover, about Examples 1-3, 6, and 8, the melted material derived from the (C-2) mold release agent is not observed at all in the material drying bat, and it is understood that the workability is excellent. In the materials of Examples 4, 5 and 7, a slight amount of fused material was observed, but it was easily removed and the workability was not significantly reduced. In particular, it can be seen that (C-2) the materials of Examples 1 to 3 blended with ethylenebisstearic acid amide as a release agent are excellent in all light transmittance, appearance, and contamination of the dry vat. .
On the other hand, in Comparative Example 1 in which the externally added (C-2) release agent was not blended, it was found that the obtained molded product was dark and the total light transmittance was low. Comparative Example 2 shows the case where the (C-1) release agent for internal addition was not blended. In this case, the color changed to a significantly dark color at the stage of (D) resin pellets after melt-kneading. Therefore, subsequent molding evaluation was not performed. Comparative Example 3 shows a case where the amount of (C-1) release agent for internal addition was increased and (C-2) release agent for external addition was not blended, but (C- 1) It can be seen that even if the amount of the release agent is increased, the obtained molded product has a dark taste, and the total light transmittance is also lower than in the examples.

  Since the thermoplastic resin material of the present invention is a thermoplastic resin material that contains an inorganic phosphor and has no problem of coloring or discoloration, electrical / electronic equipment, OA equipment, information terminal equipment, mechanical parts, home appliances, Suitable for use in vehicle parts, building materials, various containers, leisure goods / miscellaneous goods, lighting equipment, etc., especially for light covers for LED lighting devices and translucent covers (gloves, etc.) for remote phosphor type LED light-emitting devices And industrial applicability is very high.

Claims (11)

  (A) It is obtained by melting and kneading 0.1 to 20 parts by weight of an inorganic phosphor and (C-1) 0.01 to 3 parts by weight of a release agent with respect to 100 parts by weight of a transparent thermoplastic resin ( D) A thermoplastic resin material obtained by further adding 0.001 to 1 part by mass of (C-2) a release agent to 100 parts by mass of (D) resin pellets.   (A) The thermoplastic resin material according to claim 1, wherein the transparent thermoplastic resin is a polycarbonate resin.   The thermoplastic resin material according to claim 1 or 2, wherein (D) the resin pellet further contains (E) a light diffusing agent in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of (A) the transparent thermoplastic resin. .   (C-2) A mold release agent is fatty acid amide, The thermoplastic resin material of any one of Claims 1-3.   The thermoplastic resin material according to claim 3 or 4, wherein (E) the light diffusing agent is organic crosslinked fine particles having an average particle diameter of 1 to 10 µm.   (D) The resin pellets are further 0.01 to 1 part by mass of (F) UV absorber and (G) 0.001 to 1 part by mass of thermal stabilizer with respect to 100 parts by mass of (A) transparent thermoplastic resin. The thermoplastic resin material according to any one of claims 1 to 5, which is contained in a part.   The resin pellet according to any one of claims 1 to 6, wherein the resin pellet further contains (H) a flame retardant in an amount of 0.01 to 15 parts by mass with respect to 100 parts by mass of the (A) transparent thermoplastic resin. Thermoplastic resin material.   (C-2) Melting | fusing point of a mold release agent is 120 degreeC or more, The thermoplastic resin material of any one of Claims 1-7.   The molded article formed by shape | molding the thermoplastic resin material of any one of Claims 1-8.   The molded article according to claim 9, which is a lighting cover.   The molded article according to claim 10, which is a light-transmitting cover of a remote phosphor type LED light-emitting device.