JP2012111881A - Light-diffusible resin composition and light-diffusing member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-diffusible resin composition that has high light resistance, has high total light transmittance and high haze, has no glare, and can provide a molded article excellent in visibility, and in which bleed-out is prevented from occurring; and to provide a light-diffusing member that consists of the light-diffusible resin composition.SOLUTION: The light-diffusible resin composition comprises: a compound (an ultraviolet absorber) that has a predetermined configuration; a predetermined light diffusion agent; and an aromatic polycarbonate resin. The light-diffusing member consists of the light-diffusible resin composition.

Description

  The present invention relates to a light diffusing resin composition and a light diffusing member.

  A molded article having a light diffusing function in which a light diffusing agent comprising inorganic fine particles or polymer fine particles is blended with polycarbonate resin is, for example, various illumination device covers such as lamp covers, housings, meters, signboards (especially internal illumination type). ), Resin window glass, image reading device, light diffusion plate for display device (for example, light diffusion plate used for backlight module such as liquid crystal display device, light diffusion used for screen of projection display device such as projector TV) It is used in a wide range of fields such as plates, buttons of various devices, and switches). Such a molded body is advantageous in that it has excellent heat resistance, dimensional stability, and impact resistance as compared with conventional acrylic resins.

  For example, Patent Document 1 discloses an excellent machine possessed by an aromatic polycarbonate resin by blending an aromatic polycarbonate resin with a light diffusing agent, an organometallic salt compound, and a silicone resin having a specific structure in a predetermined ratio. It discloses that excellent light diffusibility, flame retardancy and fluidity can be imparted without impairing physical properties, thermophysical properties, electrical properties and the like. Patent Document 2 discloses light transmittance without impairing the original properties of polycarbonate by blending acrylic-styrene copolymer fine particles having a specific refractive index and a specific particle diameter into polycarbonate at a specific ratio. The present invention discloses a light diffusing resin composition that is excellent in light diffusibility and effective in obtaining a molded article that does not have glare when an LED is used as a light source. Furthermore, Patent Document 3 discloses that a light diffusing polycarbonate resin composition comprising a polycarbonate resin, a polymer fine particle light diffusing agent, and a triazine ultraviolet absorber having a specific structure is suitable for light transmittance storage stability and color tone suitable for liquid crystal panels and the like. It discloses that it exhibits excellent light resistance in terms of stability. However, the molded body made of the light diffusing resin composition of Patent Documents 1 to 3 has low or insufficient light resistance, and its improvement has been demanded.

JP 2010-65164 A JP 2005-247999 A JP 2006-45389 A

  An object of the present invention is a light diffusion that has high light resistance, suppresses bleeding out, has high total light transmittance and haze, is free from glare, and can provide a molded article having excellent visibility. It is in providing a conductive resin composition. Another object of the present invention is to provide a light diffusing member comprising the light diffusing resin composition.

As a result of examining the above-mentioned problems in detail, the present inventors have shown that triazine-based compounds having a shielding effect up to the UV-A region and having unprecedented light resistance can be used together with a specific light diffusing agent and an aromatic polycarbonate resin. It came to complete this invention by making it contain in a diffusible resin composition.
That is, the subject of this invention was achieved by the following means.

［Ｒ^１ａ、Ｒ^１ｂ、Ｒ^１ｃ、Ｒ^１ｄ及びＲ^１ｅは、互いに独立して、水素原子又はヒドロキシ基を除く１価の置換基を表し、置換基のうち少なくとも１つは、ハメット則のσｐ値が正である置換基を表す。また置換基同士で結合して環を形成しても良い。Ｒ^１ｇ、Ｒ^１ｈ、Ｒ^１ｉ、Ｒ^１ｊ、Ｒ^１ｋ、Ｒ^１ｍ、Ｒ^１ｎ及びＲ^１ｐは、互いに独立して、水素原子又は１価の置換基を表す。また置換基同士で結合して環を形成しても良い。］
〔２〕
前記１価の置換基が、ハロゲン原子、置換又は無置換の炭素数１〜２０のアルキル基、シアノ基、カルボキシル基、置換又は無置換のアルコキシカルボニル基、置換又は無置換のカルバモイル基、置換又は無置換のアルキルカルボニル基、ニトロ基、置換又は無置換のアミノ基、ヒドロキシ基、置換又は無置換の炭素数１〜２０のアルコキシ基、置換又は無置換のアリールオキシ基、置換又は無置換のスルファモイル基、チオシアネート基、又は置換又は無置換のアルキルスルホニル基であり、前記１価の置換基が置換基を有する場合の置換基がハロゲン原子、炭素数１〜２０のアルキル基、シアノ基、カルボキシル基、アルコキシカルボニル基、カルバモイル基、アルキルカルボニル基、ニトロ基、アミノ基、ヒドロキシ基、炭素数１〜２０のアルコキシ基、アリールオキシ基、スルファモイル基、チオシアネート基又はアルキルスルホニル基である、上記〔１〕に記載の光拡散性樹脂組成物。
〔３〕
前記Ｒ^１ｂ、Ｒ^１ｃ及びＲ^１ｄの少なくとも一つがハメット則のσｐ値が正である置換基である、上記〔１〕又は〔２〕に記載の光拡散性樹脂組成物。
〔４〕
前記ハメット則のσｐ値が正である置換基が、ＣＯＯＲ^ｒ、ＣＯＮＲ^ｓ _２、シアノ基、トリフルオロメチル基、ハロゲン原子、ニトロ基及びＳＯ_３Ｍからなる群より選択される基である、上記〔１〕〜〔３〕のいずれか１項に記載の光拡散性樹脂組成物。ここで、Ｒ^ｒ及びＲ^ｓは、互いに独立して、水素原子又は１価の置換基を表す。Ｍは、水素原子又はアルカリ金属を表す。
〔５〕
前記ハメット則のσｐ値が正である置換基がＣＯＯＲ^ｒである、上記〔１〕〜〔４〕のいずれか１項に記載の光拡散性樹脂組成物。ここで、Ｒ^ｒは、水素原子又は１価の置換基を表す。
〔６〕
前記Ｒ^１ｇ、Ｒ^１ｈ、Ｒ^１ｉ、Ｒ^１ｊ、Ｒ^１ｋ、Ｒ^１ｍ、Ｒ^１ｎ及びＲ^１ｐが、水素原子である、上記〔１〕〜〔５〕のいずれか１項に記載の光拡散性樹脂組成物。
〔７〕
更に、リン系安定剤を含有する、上記〔１〕〜〔６〕のいずれか１項に記載の光拡散性樹脂組成物。
〔８〕
前記芳香族ポリカーボネート樹脂１００質量部に対し、前記一般式（１）で表される化合物０．０５〜３質量部、前記光拡散剤０．１〜１０質量部、前記リン系安定剤０．０００５〜０．３質量部である、上記〔７〕に記載の光拡散性樹脂組成物。
〔９〕
更にヒンダードフェノール系安定剤を含有する、上記〔１〕〜〔８〕のいずれか１項に記載の光拡散性樹脂組成物。
〔１０〕
前記芳香族ポリカーボネート樹脂の粘度平均分子量が１０，０００〜５０，０００の範囲である、上記〔１〕〜〔９〕のいずれか１項に記載の光拡散性樹脂組成物。
〔１１〕
更に、有機金属塩化合物を含有する、上記〔１〕〜〔１０〕のいずれか１項に記載の光拡散性樹脂組成物。
〔１２〕
更に、フルオロポリマーを含有する、上記〔１〕〜〔１１〕のいずれか１項に記載の光拡散性樹脂組成物。
〔１３〕
前記一般式（１）で表される化合物のｐＫａが−５．０〜−７．０の範囲である、上記〔１〕〜〔１２〕のいずれか１項に記載の光拡散性樹脂組成物。
〔１４〕
上記〔１〕〜〔１３〕のいずれか１項に記載の光拡散性樹脂組成物からなる光拡散性部材。
〔１５〕
ＬＥＤ用である、上記〔１４〕に記載の光拡散性部材。 [1]
It contains a compound represented by the following general formula (1), a light diffusing agent, and an aromatic polycarbonate resin, and the light diffusing agent is one of acrylic fine particles, silicone fine particles, and acrylic-styrene copolymer fine particles. A light diffusing resin composition.

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or a hydroxy group, and at least one of the substituents is a Hammett's σp Represents a substituent whose value is positive. Moreover, you may combine with substituents and may form a ring. R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p each independently represent a hydrogen atom or a monovalent substituent. Moreover, you may combine with substituents and may form a ring. ]
[2]
The monovalent substituent is a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, substituted or Unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group, substituted or unsubstituted sulfamoyl Group, thiocyanate group, or substituted or unsubstituted alkylsulfonyl group, and when the monovalent substituent has a substituent, the substituent is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group , Alkoxycarbonyl group, carbamoyl group, alkylcarbonyl group, nitro group, amino group, hydroxy group, 1 to 2 carbon atoms An alkoxy group, an aryloxy group, a sulfamoyl group, a thiocyanate group or an alkylsulfonyl group, the light-diffusing resin composition according to [1].
[3]
The light diffusing resin composition according to the above [1] or [2], wherein at least one of R ^1b , R ^1c and R ^1d is a substituent having a positive Hammett's σp value.
[4]
The substituent having a positive σp value according to the Hammett rule is a group selected from the group consisting of COOR ^r , CONR ^s ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, and SO ₃ M, [1] The light diffusing resin composition according to any one of [3]. Here, R ^r and R ^s each independently represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal.
[5]
The light diffusing resin composition according to any one of [1] to [4] above, wherein the substituent having a positive Hammett's σp value is COOR ^r . Here, R ^r represents a hydrogen atom or a monovalent substituent.
[6]
The light diffusibility according to any one of the above [1] to [5], wherein the R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p are hydrogen atoms. Resin composition.
[7]
Furthermore, the light diffusable resin composition of any one of said [1]-[6] containing a phosphorus stabilizer.
[8]
0.05 to 3 parts by mass of the compound represented by the general formula (1), 0.1 to 10 parts by mass of the light diffusing agent, and 0.0005 of the phosphorus stabilizer with respect to 100 parts by mass of the aromatic polycarbonate resin. The light diffusing resin composition according to the above [7], which is ˜0.3 parts by mass.
[9]
Furthermore, the light diffusable resin composition of any one of said [1]-[8] containing a hindered phenol type stabilizer.
[10]
The light diffusing resin composition according to any one of [1] to [9], wherein the aromatic polycarbonate resin has a viscosity average molecular weight in the range of 10,000 to 50,000.
[11]
Furthermore, the light diffusable resin composition of any one of said [1]-[10] containing an organometallic salt compound.
[12]
Furthermore, the light diffusable resin composition of any one of said [1]-[11] containing a fluoropolymer.
[13]
The light diffusing resin composition according to any one of [1] to [12], wherein the pKa of the compound represented by the general formula (1) is in the range of -5.0 to -7.0. .
[14]
A light diffusing member comprising the light diffusing resin composition according to any one of [1] to [13].
[15]
The light diffusing member according to [14], which is for LEDs.

  The light diffusing resin composition of the present invention exhibits an ultraviolet shielding effect even in a long wavelength region, and a compound represented by the general formula (1) having light resistance, together with a specific light diffusing agent and an aromatic polycarbonate resin. By containing, it was possible to provide a molded article having high light resistance, suppressing bleeding out, having high total light transmittance and haze, no glare, and excellent visibility.

Hereinafter, the present invention will be described in detail.
(Light diffusing resin composition)
The light diffusing resin composition of the present invention contains a compound represented by the following general formula (1), a specific light diffusing agent described later, and an aromatic polycarbonate resin. The light diffusing resin composition of the present invention contains a compound represented by the general formula (1) having an ultraviolet shielding effect even in a long wavelength region and having light resistance together with a specific light diffusing agent and an aromatic polycarbonate resin. The reason why it is possible to provide a molded article having high light resistance, suppression of bleeding out, high total light transmittance and haze, no glare, and excellent visibility. However, it is estimated as follows.
The compound represented by the general formula (1) exhibits an ultraviolet shielding effect even in a long wavelength region and has light resistance. In addition, since the specific light diffusing agent of the present invention is not an inorganic fine particle but an organic fine particle having a reactive group, it reacts by being contained together with the compound represented by the general formula (1), resulting in high light resistance. It is considered that it is possible to provide a molded article having excellent visibility, bleeding out being suppressed, high total light transmittance and haze, and no glare. The light diffusing resin composition of the present invention is preferably for LEDs, and more preferably for a light diffusing plate.
First, the compound represented by the following general formula (1) will be described.

  [1] Compound represented by general formula (1)

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or a hydroxy group, and at least one of the substituents is a Hammett's σp Represents a substituent whose value is positive. Moreover, you may combine with substituents and may form a ring. R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p each independently represent a hydrogen atom or a monovalent substituent. Moreover, you may combine with substituents and may form a ring. ]

R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or a hydroxy group, and at least one of the substituents has a Hammett's σp value Represents a substituent which is positive.
Among the substituents represented by R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e , it is preferable that 1 to 3 represent a substituent having a positive Hammett's σp value, and 1 to 2 represent a Hammett rule. More preferably, it represents a substituent having a positive σp value.
Further, it is preferable from the viewpoint of light resistance that at least one of R ^1b , R ^1c and R ^1d is a substituent having a positive Hammett's σp value.
Specific examples and preferred ranges of the substituent having a positive Hammett's σp value are the same as those described in the first embodiment described later.

Examples of the monovalent substituent (hereinafter referred to as A) in the general formula (1) include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group having 1 to 20 carbon atoms (for example, Methyl, ethyl), an aryl group having 6 to 20 carbon atoms (eg, phenyl, naphthyl), cyano group, carboxyl group, alkoxycarbonyl group (eg, methoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), substituted or unsubstituted Carbamoyl groups (eg carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl groups (eg acetyl), arylcarbonyl groups (eg benzoyl), nitro groups, substituted or unsubstituted amino groups (eg amino, dimethyl) Amino, anilino, substituted sulfoamino groups , Acylamino groups (eg acetamide, ethoxycarbonylamino), sulfonamido groups (eg methanesulfonamide), imide groups (eg succinimide, phthalimide), imino groups (eg benzylideneamino), hydroxy groups, alkoxy groups having 1 to 20 carbon atoms (Eg methoxy), aryloxy groups (eg phenoxy), acyloxy groups (eg acetoxy), alkylsulfonyloxy groups (eg methanesulfonyloxy), arylsulfonyloxy groups (eg benzenesulfonyloxy), sulfo groups, substituted or unsubstituted Sulfamoyl group (for example, sulfamoyl, N-phenylsulfamoyl), alkylthio group (for example, methylthio), arylthio group (for example, phenylthio), thiocyanate group, alkylsulfonyl (E.g. methanesulfonyl), an arylsulfonyl group (e.g., benzenesulfonyl), and the like Hajime Tamaki having 6 to 20 carbon atoms (e.g. pyridyl, morpholino).
Further, the substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. In that case, the above-mentioned monovalent substituent A can be mentioned as an example of a substituent. Moreover, you may combine with substituents and may form a ring.

  Rings formed by bonding between substituents include benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, oxadiazole And a ring, a thiazole ring, a thiadiazole ring, a furan ring, a thiophene ring, a selenophene ring, a silole ring, a gelmol ring, and a phosphole ring.

Examples of the monovalent substituent in the general formula (1) include a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted. Substituted carbamoyl group, substituted or unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group A substituted or unsubstituted sulfamoyl group, a thiocyanate group, or a substituted or unsubstituted alkylsulfonyl group, where the monovalent substituent has a substituent, the substituent is a halogen atom, and an alkyl having 1 to 20 carbon atoms. Group, cyano group, carboxyl group, alkoxycarbonyl group, carbamoyl group, alkylcarbonyl group, nitro group, amino group, Dorokishi group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, a sulfamoyl group, be a thiocyanate group or an alkylsulfonyl group preferably, OR u ^{(R u} represents a hydrogen atom or a monovalent substituent.) , An alkyl group and an amide group are more preferable, and OR ^u and an alkyl group are more preferable.
R ^u represents a hydrogen atom or a monovalent substituent, and examples of the monovalent substituent include the substituent A. Among them, it is preferable to represent a linear or branched alkyl group having 1 to 20 carbon atoms. A linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, and examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, i-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, t-hexyl group A methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.

As a preferred first embodiment of the present invention, an embodiment in which at least one of R ^1a , R ^1c and R ^1e represents a substituent having a positive Hammett's σp value can be mentioned. More preferably, R ^1c represents a substituent having a positive Hammett's σp value.
More preferably, R ^1c is a substituent having a positive Hammett's σp value, and R ^1a , R ^1b , R ^1d , and R ^1e represent a hydrogen atom.
When R ^1c represents a substituent having a positive Hammett's σp value, LUMO is stabilized by the electron-attracting group, which is preferable because the excitation lifetime is shortened and the light resistance is improved.

In a preferred second embodiment, R ^1a , R ^1c and R ^1e each represents a hydrogen atom, and R ^1b and R ^1d are each independently a hydrogen atom or a substituent having a positive Hammett σp value. Wherein at least one of the substituents has a positive Hammett σp value. Thereby, the compound represented by the general formula (1) is particularly excellent in solvent solubility and compatibility with the aromatic polycarbonate resin, and the light diffusing resin composition containing the compound is excellent in visibility and light resistance. Has the effect of forming a light diffusing resin composition having excellent properties.
Solvent solubility means solubility in organic solvents such as ethyl acetate, methyl ethyl ketone, and toluene. In terms of compatibility with aromatic polycarbonate resin, when using a solvent, It is preferable to dissolve 10% by mass or more, and more preferable to dissolve 30% by mass or more.

<Preferred first embodiment>
In a first aspect, the substituent σp value is a positive Hammett equation in formula (1), preferably, sigma _p value is an electron withdrawing group 0.1-1.2, More preferably, it is an electron withdrawing group having a σ _p value of 0.3 to 1.2. Specific examples of the electron withdrawing group having a σ _p value of 0.1 or more include COOR ^r (R ^r represents a hydrogen atom or a monovalent substituent, and includes a hydrogen atom and an alkyl group, preferably hydrogen CONR ^s ₂ (R ^s represents a hydrogen atom or a monovalent substituent), a cyano group, a halogen atom, a nitro group, or SO ₃ M (M represents a hydrogen atom or an alkali metal). .), Acyl group, formyl group, acyloxy group, acylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, dialkylphosphono group, diarylphosphono group, dialkylphosphinyl group, diarylphosphinyl group, phosphoryl group, Alkylsulfinyl group, arylsulfinyl group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, imino group, N atom A substituted imino group, a carboxy group (or a salt thereof), an alkyl group substituted with at least two or more halogen atoms (for example, a trifluoromethyl group), an alkoxy group substituted with at least two or more halogen atoms, at least 2 An aryloxy group substituted with one or more halogen atoms, an acylamino group, an alkylamino group substituted with at least two or more halogen atoms, an alkylthio group substituted with at least two or more halogen atoms, and a σ _p value of 0 And aryl groups, heterocyclic groups, halogen atoms, azo groups, and selenocyanate groups substituted with two or more other electron-withdrawing groups. For Hammett σp values, see Hansch, C .; Leo, A .; Taft, R .; W. Chem. Rev. 1991, 91, 165-195.

The substituent having a positive Hammett's σp value in the general formula (1) is more preferably COOR ^r , CONR ^s ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, or SO ₃ M. [R ^r and R ^s each independently represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal]. Among these, COOR ^r or a cyano group is more preferable, and COOR ^r is more preferable. This is because it has excellent light resistance, solvent solubility and compatibility.

R ^r and R ^s represent a hydrogen atom or a monovalent substituent, and examples of the monovalent substituent include the substituent A. Of these, a linear or branched alkyl group is preferable, a linear or branched alkyl group having 1 to 20 carbon atoms is more preferable, and a linear or branched alkyl group having 5 to 20 carbon atoms is still more preferable. Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl. Group, n-pentyl group, i-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, t-hexyl group, n-octyl group, t-octyl group, i-octyl group, 2-ethylhexyl Group, [7-methyl-2- (3-methylbutyl)] octyl group, 2-hexyldecyl group, [8-methyl-2- (4-methylhexyl)] decyl group, [5,7,7-trimethyl- 2- (1,3,3-trimethylbutyl)] octyl group, 2-heptylundecyl group, [5,9-dimethyl-2- (1,5-dimethylhexyl)] decyl group, 3,5,5- List trimethyl-1-hexyl groups Methyl group, ethyl group, 2-ethylhexyl group, [7-methyl-2- (3-methylbutyl)] octyl group, 2-hexyldecyl group, [8-methyl-2- (4-methylhexyl)] decyl Group, [5,7,7-trimethyl-2- (1,3,3-trimethylbutyl)] octyl group, 2-heptylundecyl group, [5,9-dimethyl-2- (1,5-dimethylhexyl) )] Decyl group, 3,5,5-trimethyl-1-hexyl group is preferred, methyl group, 2-ethylhexyl group, [7-methyl-2- (3-methylbutyl)] octyl group, 2-hexyldecyl group, [8-methyl-2- (4-methylhexyl)] decyl group, [5,7,7-trimethyl-2- (1,3,3-trimethylbutyl)] octyl group, 2-heptylundecyl group, [ 5,9-Dime Le-2- (1,5-dimethyl-hexyl)] decyl group, 3,5,5-trimethyl-1-hexyl group are particularly preferred.

In the compound represented by the general formula (1), R ^1c is COOR ^r , CONR ^s ₂ , cyano group, trifluoromethyl group, halogen atom, nitro group, SO ₃ M (M is a hydrogen atom or an alkali metal) represented.) is preferably one of, more preferably COOR ^r or cyano group, from the viewpoint of improving the light fastness and bleed-out of the suppression, COOR ^r is more preferred.

In the present invention, when R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p represent a monovalent substituent, R ^1g , R ^1h , R ¹ⁱ , R More preferably, at least one of ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p represents a substituent having a positive Hammett's σp value, and R ^1g , R ^1h , R ¹ⁱ and R ^1j More preferably, at least one of them represents a substituent having a positive Hammett σp value (preferably 0.1 to 1.2, more preferably 0.3 to 1.2), and R ^1h is More preferably, it represents a substituent having a positive Hammett's σp value. It is particularly preferred that R ^1c and R ^1h represent a substituent having a positive Hammett σp value (preferably 0.1 to 1.2, more preferably 0.3 to 1.2). This is because it has excellent light resistance.
In the present invention, R ^1h or R ¹ⁿ each independently represents a hydrogen atom, COOR ^r , CONR ^s ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, SO ₃ M (M represents a hydrogen atom or an alkali metal). R ^1h or R ¹ⁿ is more preferably a hydrogen atom, R ^1h and R ¹ⁿ are more preferably a hydrogen atom, R ^1g , R ^1h , R ^1i. , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p particularly preferably represent a hydrogen atom. It is for showing the outstanding light resistance.

In the compound represented by the general formula (1), R ^1c is a substituent having a positive Hammett's σp value (preferably 0.1 to 1.2, more preferably 0.3 to 1.2). R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p preferably represent a hydrogen atom, and R ^1c is COOR ^r , CONR ^s ₂ , cyano group, trifluoro Any one of a methyl group, a halogen atom, a nitro group, and SO ₃ M (M represents a hydrogen atom or an alkali metal), and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p are more preferably a hydrogen atom. It is for showing the outstanding light resistance.

  The compound represented by the general formula (1) preferably has a pKa in the range of -5.0 to -7.0. Further, it is more preferably in the range of -5.2 to -6.5, particularly preferably in the range of -5.4 to -6.0.

<Preferred second embodiment>
In a preferred second embodiment, R ^1a , R ^1c and R ^1e represent a hydrogen atom, and R ^1b and R ^1d each independently represent a hydrogen atom or a substituent having a positive Hammett's σp value. , At least one of the embodiments may be a substituent having a positive Hammett's σp value. Specific examples and preferred ranges of the substituent having a positive Hammett's σp value are the same as those described in the first embodiment.
R ^1a , R ^1c and R ^1e represent a hydrogen atom, R ^1b and R ^1d each independently represent a hydrogen atom or a substituent having a positive Hammett's σp value, and at least one is a Hammett In the second aspect in which the σp value of the rule is positive, the substituent having a positive Hammett's σp value in the general formula (1) is more preferably COOR ^r , CONR ^s ₂ , A cyano group, a trifluoromethyl group, a halogen atom, a nitro group, or SO ₃ M [R ^r and R ^s each independently represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal].
^{Examples of} the monovalent substituent for R ^r and R ^s include the substituent A as described above.
The substituent having a positive Hammett's σp value in the general formula (1) is more preferably a COOR ^r or cyano group, and further preferably COOR ^r . This is because when the substituent having a positive Hammett's σp value is a cyano group, excellent light resistance is exhibited. In addition, when the substituent having a positive Hammett's σp value is COOR ^r , excellent solvent solubility and compatibility are exhibited.
R ^r preferably represents a hydrogen atom or an alkyl group, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and still more preferably a linear or branched alkyl group having 1 to 15 carbon atoms.

R ^r is more preferably a branched alkyl group having 5 to 20 carbon atoms from the viewpoint of solubility in a solvent and compatibility with an aromatic polycarbonate resin.
The branched alkyl group has a secondary carbon atom or a tertiary carbon atom, preferably contains 1 to 5 secondary carbon atoms or tertiary carbon atoms, preferably contains 1 to 3, preferably 1 or 2 It is preferable to contain it, and it is more preferable to contain 1 or 2 secondary carbon atoms and tertiary carbon atoms. Moreover, it is preferable that 1-3 asymmetric carbons are included.
From the viewpoint of solubility in a solvent and compatibility with an aromatic polycarbonate resin, R ^r contains 1 or 2 secondary carbon atoms and tertiary carbon atoms and 5 carbon atoms containing 1 or 2 asymmetric carbon atoms. Particularly preferred is a -20 branched alkyl group. This is because the symmetry of the compound structure is broken and the solubility in the solvent and the compatibility are improved.

On the other hand, from the viewpoint of ultraviolet absorbing ability, a linear or branched alkyl group having 1 to 20 carbon atoms is more preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is still more preferable.
Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl. Group, n-pentyl group, i-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, t-hexyl group, n-octyl group, t-octyl group, i-octyl group, 2-ethylhexyl , [7-methyl-2- (3-methylbutyl)] octyl group, 2-hexyldecyl, [8-methyl-2- (4-methylhexyl)] decyl group, [5,7,7-trimethyl-2- (1,3,3-trimethylbutyl)] octyl group, 2-heptylundecyl group, [5,9-dimethyl-2- (1,5-dimethylhexyl)] decyl group, 7-methyloctyl group, 3, 5,5-trimethyl-1-hex Methyl group, ethyl group, 2-ethylhexyl, [7-methyl-2- (3-methylbutyl)] octyl group, 2-hexyldecyl group, [8-methyl-2- (4- Methylhexyl)] decyl group, [5,7,7-trimethyl-2- (1,3,3-trimethylbutyl)] octyl group, 2-heptylundecyl group, [5,9-dimethyl-2- (1) , 5-dimethylhexyl)] decyl group, 7-methyloctyl group, 3,5,5-trimethyl-1-hexyl group, methyl group, 2-ethylhexyl group, [7-methyl-2- (3-methylbutyl) )] Octyl group, 2-hexyldecyl group, [8-methyl-2- (4-methylhexyl)] decyl group, [5,7,7-trimethyl-2- (1,3,3-trimethylbutyl)] Octyl group, 2 Heptylundecyl group, [5,9-dimethyl-2- (1,5-dimethyl-hexyl)] decyl group, 7-methyl-octyl group, 3,5,5-trimethyl-1-hexyl group are particularly preferred.

In the present invention, when R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p represent a monovalent substituent, R ^1g , R ^1h , R ¹ⁱ , R More preferably, at least one of ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p represents a substituent having a positive Hammett's σp value, and R ^1g , R ^1h , R ¹ⁱ and R ^1j More preferably, at least one of them represents a substituent having a positive Hammett σp value (preferably 0.1 to 1.2, more preferably 0.3 to 1.2), and R ^1h is More preferably, it represents a substituent having a positive Hammett's σp value. It is particularly preferred that R ^1b or R ^1d and R ^1h represent a substituent having a positive (preferably 0.1 to 1.2, more preferably 0.3 to 1.2) σp value according to the Hammett rule. . This is because it has excellent light resistance.
In the present invention, R ^1h or R ¹ⁿ each independently represents a hydrogen atom, COOR ^r , CONR ^s ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, SO ₃ M (M represents a hydrogen atom or an alkali metal). R ^1h or R ¹ⁿ is more preferably a hydrogen atom, R ^1h and R ¹ⁿ are more preferably a hydrogen atom, R ^1g , R ^1h , R ^1i. , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p particularly preferably represent a hydrogen atom. It is for showing the outstanding light resistance.

In the compound represented by the general formula (1), R ^1b or R ^1d has a positive Hammett's σp value (preferably 0.1 to 1.2, more preferably 0.3 to 1.2). It is a certain substituent, and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p preferably represent a hydrogen atom, and R ^1b or R ^1d is COOR ^r , CONR ^{any one of s} ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, and SO ₃ M (M represents a hydrogen atom or an alkali metal), and R ^1g , R ^1h , R ¹ⁱ , R More preferably, ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p are hydrogen atoms. It is for showing the outstanding light resistance.

  The compound represented by the general formula (1) preferably has a pKa in the range of -5.0 to -7.0. Further, it is more preferably in the range of -5.2 to -6.5, particularly preferably in the range of -5.4 to -6.0.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.
In the following specific examples, Me represents a methyl group, Et represents an ethyl group, ^t Bu represents a tert-butyl group, Ph represents a phenyl group, and —C ₆ H ₁₃ represents n-hexyl.

  The compound represented by the general formula (1) can take a tautomer depending on the structure and the environment in which the compound is placed. Although the present invention is described in one of the representative forms, tautomers different from those described in the present invention are also included in the compounds of the present invention.

The compound represented by the general formula (1) may contain an isotope (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O, ¹⁸ O, etc.).

The compound represented by the general formula (1) can be synthesized by any method.
For example, known patent documents and non-patent documents, for example, Japanese Patent Laid-Open No. 7-188190, Japanese Patent Laid-Open No. 11-315072, Japanese Patent Laid-Open No. 2001-220385, “Dye and Drug”, Vol. 40 No. 12 (1995), 325 It can be synthesized with reference to page 339. Specifically, exemplary compound (16) can be synthesized by reacting salicylamide, 3,5-bis (trifluoromethyl) benzoyl chloride and 2-hydroxybenzamidine hydrochloride. It can also be synthesized by reacting salicylamide, salicylic acid and 3,5-bis (trifluoromethyl) benzamidine hydrochloride.

The compound represented by the general formula (1) according to the present invention is characterized by excellent solubility in an organic solvent and compatibility with an aromatic polycarbonate resin. In addition, since it has a substituent with a positive Hammett's σp value at a specific position, LUMO is stabilized by an electron-attracting group, so that the excitation life is shortened and it has excellent light resistance. Have. Even when used as a UV absorber, known triazine compounds, when used at a high concentration, are not sufficiently transparent, exhibiting deterioration such as degradation of the resin, decomposition and yellowing. On the other hand, the compound represented by the general formula (1) according to the present invention has excellent solvent solubility, compatibility and light resistance, so that even when used at a high concentration, it is excellent in transparency and deteriorates the resin. It is possible to form a light diffusing resin composition that is suppressed and excellent in light resistance. Moreover, even if it uses for a long time, the effect that it does not decompose and does not yellow will be acquired.
In the light diffusing resin composition of the present invention, the compound represented by the general formula (1) may be used alone or in combination of two or more having different structures.

  The compounds according to the invention are particularly suitable for stabilizing organic materials against damage by light, oxygen or heat. Among these, the compound represented by the general formula (1) can be suitably used as an ultraviolet absorber.

  Although the maximum absorption wavelength of the compound represented by the general formula (1) is not particularly limited, it is preferably 250 to 400 nm, more preferably 280 to 380 nm. The full width at half maximum is preferably 20 to 100 nm, more preferably 40 to 80 nm.

  Those skilled in the art can easily measure the maximum absorption wavelength and the half-value width defined in the present invention. The measurement method is described in, for example, “The Fourth Edition Experimental Chemistry Course 7 Spectroscopy II” (Maruzen, 1992), pages 180-186, edited by the Chemical Society of Japan. Specifically, the sample is dissolved in a suitable solvent, and measurement is performed by a spectrophotometer using a cell made of quartz or glass and using two cells for sample and control. The solvent to be used is required to have no absorption in the measurement wavelength region, have a small interaction with the solute molecule, and have a very low volatility in addition to the solubility of the sample. Any solvent that satisfies the above conditions can be selected. In the present invention, measurement is performed using ethyl acetate (EtOAc) as a solvent.

In the present invention, the maximum absorption wavelength and the half-value width of the compound were measured using a quartz cell having an optical path length of 10 mm by preparing a solution having a concentration of about 5 × 10 ⁻⁵ mol · dm ^{−3 using} ethyl acetate as a solvent. Use the value.

  The half width of the spectrum is described in, for example, “The Fourth Edition Experimental Chemistry Course 3 Basic Operation III” (Maruzen, 1991), page 154, edited by the Chemical Society of Japan. In the above-mentioned book, the half-value width is explained with an example in which the horizontal axis is taken on the wave number scale, but the half-value width in the present invention is the value when the axis is taken on the wavelength scale, The unit is nm. Specifically, it represents the width of the absorption band that is half the absorbance at the maximum absorption wavelength, and is used as a value that represents the shape of the absorption spectrum. A spectrum with a small half-value width is a sharp spectrum, and a spectrum with a large half-value width is a broad spectrum. The UV-absorbing compound that gives a broad spectrum has absorption in a wide region from the maximum absorption wavelength to the long wave side. Therefore, in order to effectively block the long wave UV region without yellowing, a spectrum with a small half-value width is used. The ultraviolet absorbing compound having is preferable.

  As described in Sumida Tokita "Chemistry Seminar 9 Color Chemistry" (Maruzen, 1982), pages 154-155, the intensity of light absorption, that is, the oscillator strength, is proportional to the integral of the molar extinction coefficient, and the absorption spectrum. When the symmetry is good, the oscillator strength is proportional to the product of the absorbance at the maximum absorption wavelength and the full width at half maximum (however, the full width at half maximum is a value obtained by taking an axis on the wavelength scale). This means that when the transition moment values are the same, a compound having a spectrum with a small half width has a large absorbance at the maximum absorption wavelength. Such UV-absorbing compounds have the advantage of being able to effectively shield the area around the maximum absorption wavelength with a small amount of use, but since the absorbance decreases sharply when the wavelength is slightly away from the maximum absorption wavelength, a wide range of areas can be used. It cannot be shielded.

  The compound represented by the general formula (1) preferably has a molar extinction coefficient at the maximum absorption wavelength of 20000 or more, more preferably 30000 or more, and particularly preferably 50000 or more. If it is 20000 or more, the absorption efficiency per mass of the compound represented by the general formula (1) can be sufficiently obtained, so that the compound represented by the general formula (1) for completely absorbing the ultraviolet region can be obtained. The amount used can be reduced. This is preferable from the viewpoint of preventing skin irritation and accumulation in the living body, and being able to form a molded article that is excellent in transparency, suppresses deterioration of the resin, and is excellent in light resistance. The molar extinction coefficient is based on the definition described in, for example, “New Edition Experimental Chemistry Lecture 9 Analytical Chemistry [II]” (Maruzen, 1977), page 244, edited by the Chemical Society of Japan. It can be determined together with the absorption wavelength and the half width.

  The light diffusing resin composition of the present invention can contain the compound represented by the general formula (1) in any amount necessary for imparting desired performance. These differ depending on the light diffusing agent and aromatic polycarbonate resin to be used, but the content can be appropriately determined. The content of the compound represented by the general formula (1) is preferably 0.01 to 5 parts by mass, and 0.05 to 4 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. Is more preferable, and it is still more preferable that it is 0.1-3 mass parts. If the content is in the above range, an ultraviolet shielding effect can be obtained, and the hue change and deterioration of the molded product can be more effectively suppressed, which is preferable.

[2] Resin The light diffusing resin composition of the present invention contains at least an aromatic polycarbonate resin (hereinafter also simply referred to as “polycarbonate”) as a resin component.
The resin component such as an aromatic polycarbonate resin contained in the light diffusing resin composition of the present invention will be described.
Polycarbonate is a polymer compound containing a carbonate type structure obtained by transesterification of a disubstituted carbonate and a diol or a reaction of phosgene and a diol as a structural unit in the main chain. Examples of the polycarbonate include linear polycarbonate, branched polycarbonate, and a composite containing linear polycarbonate and branched polycarbonate. This linear polycarbonate or branched polycarbonate is obtained by copolymerizing a diol with a disubstituted carbonate or phosgene in the absence or presence of a branching agent and, if necessary, a terminal stopper. Can do.

Examples of the diol include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, and bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane. , Bis (3,5-dichloro-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis ( 4-hydroxyphenyl) propane [common name: bisphenol A], 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2 -Bis (4-hydroxyphenyl) ethane, 2-methyl-1,1-bis (4-hydroxyphene) ) Propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5- Dichloro-4-hydroxyphenyl) propane, 2,
2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,4-bis ( 4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4-methyl-2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) nonane, 1,10-bis (4-hydroxyphenyl) L) Dihydroxydiarylalkanes such as decane; 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (4- Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane 1,1-bis (4-hydroxyphenyl) ) Dihydroxydiarylcycloalkanes such as cyclodecane; dihydroxydiaryls such as bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone Sulfones; bis (4-hydroxyphenyl) ether, bis ( , 5-dimethyl-4-hydroxyphenyl) ether; dihydroxydiaryl ethers such as 4,4′-dihydroxybenzophenone and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone Ketones; dihydroxydiaryl sulfides such as bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide; Dihydroxydiaryl sulfoxides such as hydroxyphenyl) sulfoxide; dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl; dihydroxyaryl fluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene. In addition to the diol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 4,4′-dihydroxyethoxyphenylmethane; hydroquinone, It may contain dihydroxybenzenes such as resorcinol and methylhydroquinone; dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene. These diols may be used alone or in combination of two or more. Among these, 2,2-bis (4-hydroxyphenyl) propane is typical.

  Examples of the di-substituted carbonate compound include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. These disubstituted carbonate compounds may be used alone or in combination of two or more.

  As the branching agent, a compound having three or more functional groups can be used, and is not particularly limited. Specific examples of this branching agent include phloroglucin, meritic acid, trimellitic acid, trimellitic chloride, trimellitic anhydride, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-resorcinic acid, β-resorcinic acid, Resorcinaldehyde, trimethyl chloride, isatin bis (o-cresol), trimethyltrichloride, 4-chloroformylphthalic anhydride, benzophenonetetracarboxylic acid, 2,4,4'-trihydroxybenzophenone, 2,2 ', 4,4 '-Tetrahydroxybenzophenone, 2,4,4'-trihydroxyphenyl ether, 2,2', 4,4'-tetrahydroxyphenyl ether, 2,4,4'-trihydroxydiphenyl-2-propane, 2, 2'-bis (2,4-dihydroxy) propane, 2 , 2 ′, 4,4′-tetrahydroxydiphenylmethane, 2,4,4′-trihydroxydiphenylmethane, 1- [α-methyl-α- (4′-dihydroxyphenyl) ethyl] -3- [α ′, α '-Bis (4' '-hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (4'-dihydroxyphenyl) ethyl] -4- [α', α'-bis (4 ''-hydroxy Phenyl) ethyl] benzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 2,6-bis (2-hydroxy-5′-methylbenzyl)- 4-methylphenol, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptene, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) − 2-heptane, 1,3,5-tris (4′-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2-bis [4,4-bis (4′- Hydroxyphenyl) cyclohexyl] propane, 2,6-bis (2′-hydroxy-5′-isopropylbenzyl) -4-isopropylphenol, bis [2-hydroxy-3- (2′-hydroxy-5′-methylbenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2'-hydroxy-5'-isopropylbenzyl) -5-methylphenyl] methane, tetrakis (4-hydroxyphenyl) methane, tris (4-hydroxy Phenyl) phenylmethane, 2 ′, 4 ′, 7-trihydroxyflavan, 2,4,4-trimethyl-2 ′, 4 ′, 7- Polyhydroxy flavan, 1,3-bis (2 ', 4'-dihydroxyphenyl) benzene, tris (4'-hydroxyphenyl) - amyl -s- triazine. These branching agents may be used alone or in combination of two or more.

  As the terminal terminator, monohydric phenol can be used, and its structure is not particularly limited. Examples of the monohydric phenol include p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-tert-amylphenol, p-nonylphenol, p-cresol, 2,4,6-tribromo. Phenol, p-bromophenol, 4-hydroxybenzophenone, phenol and the like are used. These terminal terminators may be used alone or in combination of two or more.

  As the polymerization method, an interfacial method or a transesterification method is used. For example, when the diol and phosgene are polymerized by the interfacial method, a branching agent or a terminal terminator may be reacted in the presence of phosgene, or after reacting the diol and phosgene to obtain a polycarbonate oligomer, A branching agent or a terminal terminator may be reacted in the absence of. In the case of the transesterification method, a branched polycarbonate resin can be obtained by adding a branching agent or a terminal terminator to the transesterification reaction between the diol and the disubstituted carbonate compound.

  The linear polycarbonate is usually obtained by polymerizing a diol and phosgene or a di-substituted carbonate compound in the presence of a terminal stopper as required. That is, it is the same as the branched polycarbonate resin except that no branching agent is used.

  Among the polycarbonates obtained by polymerizing the diol and phosgene or a disubstituted carbonate compound, 2,2-bis (4-hydroxyphenyl) propane and diphenyl carbonate from the viewpoint of the balance between mechanical strength and moldability. A polycarbonate obtained by reacting 2,2-bis (4-hydroxyphenyl) propane and dimethyl carbonate, a polycarbonate obtained by reacting 2,2-bis (4-hydroxyphenyl) propane and diethyl carbonate. Polycarbonate obtained by reacting, polycarbonate obtained by reacting bis (4-hydroxyphenyl) methane and diphenyl carbonate, polycarbonate obtained by reacting bis (4-hydroxyphenyl) phenylmethane and diphenyl carbonate Over door, such as is desirable.

  In the present invention, a polycarbonate-polyorganosiloxane copolymer containing a polycarbonate structural unit and a polyorganosiloxane structural unit may be used as the polycarbonate. In addition, as an acid component, terephthalic acid, isophthalic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, adipic acid and other aromatic or aliphatic dibasic acids or esters thereof are included as copolymerization components. In this case, in addition to the carbonate type structure, a carboxylic acid ester structure is partially introduced into the main chain.

  In the present invention, the polycarbonate obtained by using the diol and the disubstituted carbonate or phosgene or, if necessary, other components can be used alone or in combination of two or more.

  Although there is no restriction | limiting in the specific kind of aromatic polycarbonate resin, For example, the aromatic polycarbonate polymer formed by making an aromatic dihydroxy compound and a carbonate precursor react is mentioned. In this case, the aromatic polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. Usually, such an aromatic polycarbonate polymer becomes a thermoplastic resin.

The polymer chain of the aromatic polycarbonate resin may be linear or branched. Therefore, the light diffusing resin composition may contain a linear aromatic polycarbonate resin (A-1) as an aromatic polycarbonate resin, or a branched aromatic polycarbonate resin (A-2). It is also possible to include both in combination. The linear aromatic polycarbonate resin is a linear aromatic polycarbonate resin having a high molecular structure as can be seen from its name, and usually has a structural viscosity index N of less than 1.2. Further, the branched aromatic polycarbonate resin is an aromatic polycarbonate resin having a branch in its polymer structure, and generally has a high structural viscosity index N of 1.2 or more. Here, the structural viscosity index N is a value described in, for example, “Shigeharu Onoki,“ Rheology for chemists ”, pages 15-16.
Especially, it is preferable that a light diffusable resin composition contains at least a linear aromatic polycarbonate resin as an aromatic polycarbonate resin.

・ Linear aromatic polycarbonate resin (A-1)
Examples of aromatic dihydroxy compounds among monomers used as raw materials for linear aromatic polycarbonate resins include 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A), 2,2-bis ( 3,5-dibromo-4-hydroxyphenyl) propane (ie, tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4 -Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4- Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis ( -Bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2- Bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1 Bis (hydroxyaryl) alkanes such as 1,1,3,3,3-hexafluoropropane;

  Bis such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Hydroxyaryl) cycloalkanes;

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

  Dihydroxy diaryl ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether;

  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, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;

  Hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like can be mentioned.

Among these, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A) is particularly preferable from the viewpoint of impact resistance.
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.

Of the monomers used as the raw material for the linear aromatic polycarbonate resin, carbonyl halides, carbonate esters, haloformates, and the like are used as examples of carbonate precursors. Specific examples include phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; and dihaloformates of dihydric phenols.
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.

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

.. Interfacial polymerization method First, the case of producing a linear aromatic polycarbonate resin by the interfacial polymerization method will be described. In the interfacial polymerization method, in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, the pH is usually kept at 9 or higher, and an aromatic dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted and then polymerized. A linear aromatic polycarbonate resin is obtained by interfacial polymerization in the presence of a catalyst. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present if necessary, and an antioxidant may be present for preventing the oxidation of the aromatic dihydroxy compound.

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

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

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. In addition, 1 type may be used for an alkali compound and it may use 2 or more types together by arbitrary combinations and a ratio.

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

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

  Examples of the polymerization catalyst include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine; quaternary such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride. Ammonium salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group. Specific examples include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

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

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

.. Melt transesterification method Next, a case where a linear aromatic polycarbonate resin is produced by a melt transesterification method will be described. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound is performed.

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

  The ratio of the aromatic dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired linear aromatic polycarbonate resin can be obtained, but the molar amount of the carbonic acid diester should be used in an equimolar amount or more with respect to 1 mol of the aromatic dihydroxy compound. Among them, it is more preferable to use 1.01 mol or more. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

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

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

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

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

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing in a batch system, the order of mixing the reaction substrate, reaction medium, catalyst, additive, etc. is arbitrary as long as the desired linear aromatic polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. . However, among them, the melt polycondensation reaction is preferably performed in a continuous manner in consideration of the stability of the linear aromatic polycarbonate resin and the light diffusing resin composition.

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

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

・ Branched aromatic polycarbonate resin (A-2)
The light diffusing resin composition of the present invention may contain a branched aromatic polycarbonate resin. The branched aromatic polycarbonate resin functions as an anti-dripping agent and can suppress dripping of the resin that has been ignited and melted during the burning of the light diffusing resin composition of the present invention.

As the monomer of the branched aromatic polycarbonate resin, for example, those described in the section of the linear aromatic polycarbonate resin (A-1) can be used similarly.
Moreover, there is no restriction | limiting in particular in the manufacturing method of branched aromatic polycarbonate resin, A well-known arbitrary manufacturing method can be used. Specific examples include the methods described in JP-A-8-259687, JP-A-8-245782, and the like. In the methods described in these documents, when the aromatic dihydroxy compound and the carbonic acid diester are reacted by the melt transesterification method, the structural viscosity is selected without using a branching agent by selecting the catalyst conditions or production conditions. A branched aromatic polycarbonate resin having a high index N and excellent hydrolytic stability can be obtained.

  As another method, in addition to the above-mentioned aromatic dihydroxy compound and carbonate precursor, a trifunctional or higher polyfunctional aromatic compound is used, and these are copolymerized by the above-described interfacial polymerization method or melt transesterification method. The method of doing is mentioned.

  Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4, 6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, Polyhydroxy compounds such as 1,1,1-tri (4-hydroxyphenyl) ethane;

3,3-bis (4-hydroxyaryl) oxindole (that is, isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred.
In addition, a polyfunctional aromatic compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  A polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound. The amount of the polyfunctional aromatic compound used is usually 0.01 mol% or more, preferably 0.1 mol% or more, and usually 10 mol% or less, preferably 3 mol% or less, based on the aromatic dihydroxy compound. It is.

Examples of the branched structure contained in the branched aromatic polycarbonate resin obtained by the melt transesterification method include structures of the following formulas (P-1) to (P-4). In the following formulas (P-1) to (P-4), X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, or a cycloalkylene group having 5 to 15 carbon atoms. , cycloalkylidene group having 5 to 15 carbon atoms, or, -O -, - S -, - CO -, - SO -, - SO 2 - a divalent group selected from the group consisting of groups represented by.

  As described above, the branched aromatic polycarbonate resin according to the present invention usually has a structural viscosity index N of 1.2 or more. It is preferable to use a branched aromatic polycarbonate resin having a high structural viscosity index N in this manner because the dripping prevention effect (an effect of preventing dripping of a molten resin ignited during combustion) is increased.

In addition, the branched aromatic polycarbonate resin according to the present invention is usually the same as the linear aromatic polycarbonate resin in matters other than those described above.
For example, the branched aromatic polycarbonate resin may be either monopolymerization or copolymerization, and is usually a thermoplastic resin.

  The branched aromatic polycarbonate resin according to the present invention may be contained only in the branched aromatic polycarbonate resin in the light diffusing resin composition of the present invention, but in combination with the linear aromatic polycarbonate resin of the present invention. It is preferable to make it contain in a light diffusable resin composition. When contained in combination, the content of the linear aromatic polycarbonate resin is usually 80% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, based on 100% by mass of the entire aromatic polycarbonate resin. In addition, it is usually 10% by mass or more, preferably 15% by mass or more. On the other hand, the content of the branched aromatic polycarbonate resin is usually 20% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and usually 90% by mass or less, preferably 85% by mass or less. . If the amount of the branched aromatic polycarbonate resin is too small, it is difficult to obtain the dripping prevention effect. Conversely, if the amount is too large, the fluidity of the light diffusing resin composition tends to extremely decrease.

  The aromatic polycarbonate resin preferably has a viscosity average molecular weight in the range of 10,000 to 50,000, more preferably in the range of 13,000 to 40,000, and in the range of 20,000 to 30,000. Are more preferred. When the viscosity average molecular weight is in the above range, the obtained molded product is robust and does not require a high molding temperature. The viscosity average molecular weight of the aromatic polycarbonate can be measured in terms of the specific viscosity at 20 ° C. obtained from a solution obtained by dissolving the aromatic polycarbonate resin in methylene chloride.

  In addition to the aromatic polycarbonate resin, the light diffusing resin composition of the present invention can contain other resin components in combination. The resin component that can be used in combination may be either a natural or synthetic polymer. For example, polyolefin (for example, polyethylene, polypropylene, polyisobutylene, poly (1-butene), poly-4-methylpentene, polyvinylcyclohexane, polystyrene, poly (p-methylstyrene), poly (α-methylstyrene), polyisoprene, Polybutadiene, polycyclopentene, polynorbornene, etc.), copolymers of vinyl monomers (eg ethylene / propylene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / vinylcyclohexane copolymer, ethylene / cycloolefin copolymer (eg ethylene / propylene copolymer) Cycloolefin copolymers such as norbornene (COC), propylene / butadiene copolymers, Isobutylene / isoprene copolymer, ethylene / vinyl cyclohexene copolymer, ethylene / alkyl acrylate copolymer, ethylene / alkyl methacrylate copolymer, etc.), acrylic polymer (eg, polymethacrylate, polyacrylate, polyacrylamide, polyacrylonitrile, etc.), polyvinyl chloride, poly Vinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride / vinyl acetate copolymer, polyether (eg, polyalkylene glycol, polyethylene oxide, polypropylene oxide, etc.), polyacetal (eg, polyoxymethylene), polyamide, polyimide, polyurethane, Polyurea, polyester (for example, polyethylene terephthalate, polyethylene naphthalate, etc. , Polyketone, polysulfone polyetherketone, phenolic resin, melamine resin, cellulose ester (eg diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polysiloxane, natural polymer ( Examples thereof include cellulose, rubber, gelatin, and the like.

The resin component that can be used in combination is preferably a synthetic polymer, more preferably a polyolefin, an acrylic polymer, a polyester, or a cellulose ester. Among these, polyethylene, polypropylene, poly (4-methylpentene), polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and triacetyl cellulose are particularly preferable. The resin component that can be used in combination is preferably a thermoplastic resin.
When the light diffusing resin composition of the present invention contains a resin component other than the aromatic polycarbonate resin, the content of the resin component other than the aromatic polycarbonate resin is 20 with respect to 100 parts by mass of the aromatic polycarbonate resin. It is preferable that it is -80 mass parts, It is more preferable that it is 30-70 mass parts, It is still more preferable that it is 40-50 mass parts. If the content is in the above range, it is preferable because it is easier to process and form.

  Examples of the aromatic polycarbonate resin according to the present invention include Iupilon (registered trademark) S-3000N (aromatic polycarbonate resin, viscosity average molecular weight: 21000, manufactured by Mitsubishi Engineering Plastics), Iupilon (registered trademark) S-3000F (aromatic). Group polycarbonate resin viscosity average molecular weight: 21,000 manufactured by Mitsubishi Engineering Plastics Co., Ltd., Panlite L-1250WP (aromatic polycarbonate resin viscosity average molecular weight: 24000 manufactured by Teijin Chemicals Ltd.), Gulliver (registered trademark) 200-3 (aromatic polycarbonate resin, viscosity average molecular weight: 28000, manufactured by Sumitomo Dow Co., Ltd.), and the like. From the viewpoint of optical properties, Iupilon S-3000N, Iupilon S-3000F, and Panlite L-1250WP are preferred. From the viewpoint of dimensional stability, Panlite L-1250WP is more preferable.

[3] Light Diffusing Agent The light diffusing resin composition of the present invention contains at least one of acrylic fine particles, silicone fine particles, and acrylic-styrene copolymer fine particles as a light diffusing agent. By containing the light diffusing agent as described above, the light diffusibility of the molded product such as the light diffusing resin composition of the present invention and the light diffusing member made of the light diffusing resin composition can be enhanced.

  As the acrylic fine particles and the silicone fine particles, acrylic fine particles and silicone fine particles having a crosslinked structure in which main chains constituting the polymer are crosslinked are preferable. Especially, what can maintain a fine particle state without deform | transforming practically in the process of the light diffusable resin composition of this invention, for example at the time of injection molding, is preferable.

  From the above viewpoint, the acrylic fine particles and the silicone fine particles, which are light diffusing agents, are aromatic even when heated to the molding temperature (for example, 350 ° C.) of the relatively low molecular weight aromatic polycarbonate resin used in the present invention. Fine particles that do not substantially melt in the polycarbonate resin are preferred. Examples of such fine particles include crosslinked acrylic resin fine particles (crosslinked acrylic fine particles) and silicone resin fine particles (crosslinked silicone fine particles). In particular, polymer microparticles based on partially cross-linked methyl methacrylate and having a poly (butyl acrylate) core and a poly (methyl methacrylate) shell, or a rubbery vinyl polymer core Polymer fine particles having a core / shell monoholgy including a shell and a shell are preferred.

  In addition, the acrylic fine particles and silicone fine particles which are light diffusing agents are preferably those having a refractive index difference (Δn) of 0.01 or more from the aromatic polycarbonate resin from the viewpoint of light diffusibility. In addition, acrylic fine particles are used to sufficiently exhibit light diffusibility, for example, to suppress problems such as the light source behind the molded body (light diffusing plate, etc.) being seen through, and to exhibit sufficient luminance. Further, the difference in refractive index between the silicone fine particles and the aromatic polycarbonate resin is more preferably 0.05 or more, and particularly preferably 0.07 or more.

  The aromatic polycarbonate resin used in the present invention is more preferably, for example, an aromatic polycarbonate resin using bisphenol A as a raw material, and the refractive index in that case is usually 1.58. Therefore, as the light diffusing agent, it is preferable to use a light diffusing agent having a refractive index difference equal to or more than the above range.

  Here, the refractive index is a value for the d-line (587.562 nm, He) at a temperature of 25 ° C. The actual measurement is performed as follows. That is, the refractive index (npc) of the aromatic polycarbonate resin is measured by the V-block method (manufactured by Kalnew Optical Co., Ltd., type KPR). (Comparison with standard solution)

  Furthermore, the acrylic fine particles and the silicone fine particles which are light diffusing agents are preferably incompatible with the aromatic polycarbonate resin from the viewpoint of light diffusibility.

  The weight average particle size of the acrylic fine particles and the silicone fine particles as the light diffusing agent is usually 0.7 μm or more, preferably 1 μm or more, more preferably 2 μm or more, and usually 30 μm or less, preferably 20 μm or less. Preferably it is 10 micrometers or less. If the weight average particle size is too small, the light diffusing resin composition obtained is inferior in light diffusibility, and when used as a luminaire member, diffusion plate, etc., the light source tends to be seen through, or the visibility tends to be inferior. Yes, if too large, the diffusion effect on the content may be low

  Acrylic-styrene copolymer fine particles are fine particles obtained by copolymerizing an acrylic monomer and a styrene monomer, for example, fine particles obtained by polymerizing an acrylic monomer and a styrene monomer by a suspension polymerization method or the like. It is preferable that it is crosslinked using a crosslinking agent. As acrylic monomers, for example, methacrylate monomers such as methyl methacrylate and ethyl methacrylate, acrylate monomers such as methyl acrylate and ethyl acrylate, acrylamide, and the like can be exemplified as typical examples. Examples of styrene monomers include styrene and α-methyl. Styrene, vinyltoluene and the like can be exemplified as typical examples. In the copolymerization of these monomers, these monomers may be used as the main components, and other monomers may be copolymerized as necessary. Examples of the crosslinking agent include commonly used ones such as ethylene glycol dimethacrylate, divinylbenzene, 1,6-hexanediol, trimethylpropane trimethacrylate, trimethylpropane trimethacrylate, and trimethylpropane triacrylate. Functional monomers can be used.

The weight average particle diameter of the acrylic-styrene copolymer fine particles is 0.5 to 30 μm, preferably 1.0 to 20 μm. When the particle diameter is 0.5 μm or more, the light diffusibility is sufficient and the light source is prevented from being seen through, and when it is 30 μm or less, the diffusion effect with respect to the addition amount is good, and when an LED light source is used Furthermore, glare is prevented and visibility is excellent.
Further, the refractive index of the acrylic-styrene copolymer fine particles is changed from 1.493 to 1.99 by changing the copolymerization ratio of the acrylic monomer and the styrene monomer in the range of 99: 1 to 1:99. Adjustment can be made within a range of 590. However, if the copolymerization ratio of the styrene monomer is too high, the light resistance is lowered and yellowish, and conversely if the copolymerization ratio of the acrylic monomer is too high, the fine particles and the aromatic polycarbonate The difference in refractive index is too wide, the glare of the LED light source is conspicuous, and the visibility is low. Therefore, the refractive index of the acrylic-styrene copolymer fine particles is preferably 1.505 to 1.575, more preferably 1.510 to 1.570, and still more preferably 1.515 to 1.565. Use one. In order to obtain fine particles having such a refractive index, it is necessary to adjust the copolymerization ratio of the acrylic monomer and the styrene monomer. Although the adjustment ratio varies depending on the monomer used, the refractive index becomes lower when a large amount of acrylic monomer is used, and the refractive index becomes higher when a large amount of styrene monomer is used. For example, when methyl methacrylate is used as an acrylic monomer and styrene is used as a styrene monomer, the ratio of acrylic monomer to styrene monomer is about 7: 3 when the refractive index is adjusted to about 1.52. When the ratio is adjusted to about 1.56, it is about 3: 7, and usually it should be adjusted before and after this.

The structure of the acrylic-styrene copolymer fine particles is not particularly limited, but the hollow one is easily deformed when mixed with the aromatic polycarbonate resin or when the resin composition is molded, and the appearance of the molded article becomes poor. In many cases, the balance between light diffusibility and light transmittance is often not good, which is not preferable. A porous material is excellent in light diffusibility even in a small amount, but is not preferred because the transmittance tends to decrease. In the case of fine particles having a two-layer structure of a core part and a shell part, the shell part is an acrylic-styrene copolymer fine particle, and the particle diameter and refractive index satisfy the scope of the present invention. Can be used. In that case, a core having a refractive index lower than that of the shell portion such as polymethyl methacrylate or silicone is preferable. However, in the case of such multi-layer structured fine particles, the cost may increase, and in the present invention, solid fine particles of an acrylic-styrene cross-linked copolymer are preferable.
As the acrylic-styrene copolymer fine particles usable in the present invention, those available from the market may be used. As an example of such a commercial product, for example, from the GBS series or GSM series marketed by Gantz Kasei Co., Ltd. under the trade name Gantzpearl or Staphyloid, it conforms to the physical properties defined in the present invention. To do.

  In addition, 1 type may be used for a light-diffusion agent and it may use 2 or more types together by arbitrary combinations and a ratio.

  The content of the light diffusing agent in the light diffusing resin composition of the present invention is preferably 0.1 to 50 parts by mass, and 0.25 to 10 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. It is more preferable, and it is still more preferable that it is 0.5-3 mass parts. When the content of the light diffusing agent is 0.1 parts by mass or more with respect to 100 parts by mass of the aromatic polycarbonate resin, a molded product such as a light diffusing member made of the light diffusing resin composition has sufficient light diffusibility. And the possibility that the light source can be seen through is suppressed when used as a lighting fixture member, a diffusion plate, or the like. Moreover, when the content of the light diffusing agent is 50 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin, the molded article such as the light diffusing member of the present invention has an appropriate light transmittance, and illumination. When used as an instrument member, a diffusion plate or the like, the possibility of excessively low luminance is suppressed.

The acrylic fine particles, silicone fine particles, and acrylic-styrene copolymer fine particles as the light diffusing agent can be synthesized by an emulsion polymerization method, and commercially available products can also be used.
Specific examples of the acrylic fine particles as the light diffusing agent include Gantz Pearl GM-0632F, GM-0630H (Bridged Acrylic Fine Particles manufactured by Ganz Kasei Co., Ltd.), Paraloid EXL-5136 (weight distribution average particle size 5 μm) (acrylic) Fine particles manufactured by Rohm and Haas Co., Ltd.), Tuftic AR650S (acrylic fine particles manufactured by Toyobo Co., Ltd.) and the like, and from the viewpoint of haze and transparency, Gantz Pearl GM-0632F, GM-0630H, Paraloid EXL-5136 Are preferable, and Ganzpearl GM-0632F and GM-0630H are more preferable.
Specific examples of the silicone-based fine particles as the light diffusing agent include KMP-590 (manufactured by Shin-Etsu Chemical Co., Ltd.), MSP-S020 (manufactured by Nikko Rica Co., Ltd.), Trefill E (Toray Dow Corning Co., Ltd.) From the viewpoint of heat resistance, KMP-590 and MSP-S020 are preferable, and KMP-590 is more preferable.
Specific examples of the acrylic-styrene copolymer fine particles as the light diffusing agent include Gantz Pearl GSM-1261, GSM-1841, GSM-0561 (manufactured by Ganz Kasei Co., Ltd.), and Staphyloid (manufactured by Ganz Kasei Co., Ltd.). From the viewpoint of suppressing variation in haze, Gantz Pearl GSM-1261, GSM-1841, and GSM-0561 are preferable.

[4] Silicone Resin The light diffusing resin composition of the present invention may contain a desired amount of silicone resin. This silicone resin acts as a fluidizing agent, and acts as a flame retardant that imparts a high degree of flame retardancy to the light diffusing resin composition when used in combination with an organometallic salt compound described below. is there. The flame retardant mechanism is that when a silicone resin and an organometallic salt compound are contained in a light diffusing resin composition, the silicone resin is vaporized and a large number of fine bubbles are generated in the light diffusing resin composition by foaming. It is presumed that the light diffusing resin composition is difficult to burn.

However, usually, the amount of the silicone resin in the light diffusing resin composition is suppressed to a very small amount. This is considered to be because when the amount of the silicone resin increases, the vaporized silicone resin itself burns, and rather reduces the flame retardancy.
However, when the amount of the silicone resin falls within a certain low concentration range, the flame retardancy decreases as the amount of the silicone resin increases as described above, but more silicone resin is included than the range. In that case, the flame retardancy is unexpectedly improved. This is presumably because the vaporization action of the silicone resin and the surface hardening action due to the Si—C formation reaction were significantly accelerated. Therefore, a light diffusing resin composition containing a larger amount of silicone resin than before can exhibit a high degree of flame retardancy.

The silicone resin according to the present invention has a T unit represented by RSiO _1.5 as an essential component, and (i) the T unit is an entire siloxane unit (R _0-3 SiO _{2.0-0. 5} ), the aryl group occupies a predetermined concentration or more of the total hydrocarbon group (R) contained in (ii) at least a predetermined concentration. In addition to the T unit, the silicone resin according to the present invention includes an M unit represented by R ₃ SiO _0.5 , a D unit represented by R ₂ SiO _1.0 , and SiO _2.0 . Containing the Q unit represented may be used as long as the object of the present invention is not impaired.
Hereinafter, the configuration of the silicone resin will be described in detail.

  Silicone (polyorganosiloxane) has the following four units (namely, M unit represented by formula (S-1), D unit represented by formula (S-2), and formula (S-3). It is comprised from 1 or more types of repeating units chosen from the group which consists of T unit represented, and Q unit represented by Formula (S-4). Among these, silicone resins generally indicate those containing T units and / or Q units.

In the above formulas (S-1) to (S-4), R represents a monovalent hydrocarbon group having 1 to 12 carbon atoms. Each R may be the same or different.
Among them, the R is at least one selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. The hydrocarbon group is preferably. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, hexyl group, octyl group, dodecyl group, and the like. Particularly preferred. Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl group, butenyl group, allyl group and the like. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and the like. Among these, a phenyl group is particularly preferable from the viewpoint of safety and industrial availability.

  The silicone resin according to the present invention is usually at least 50 mol%, preferably 60 mol, of the total hydrocarbon groups (that is, R) of each repeating unit such as M unit, D unit, T unit and Q unit described above. % Or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 100 mol% is occupied by the aryl group. This is because when the content of the aryl group is less than the above range, the compatibility of the silicone resin with the aromatic polycarbonate resin is lowered and the flame retardancy may be inferior. Especially, it is more preferable that a phenyl group is included in the said ratio as said aryl group.

Further, silicone resin according to the present invention, the T-unit, with respect to the total siloxane units _{(R 0~3 SiO 2.0~0.5),} usually 50 mol% or more, preferably 60 mol% or more More preferably, it contains 80 mol% or more, and 100 mol% is particularly preferable. This means that the proportion of the T units in the repeating units such as M units, D units, T units, and Q units constituting the silicone resin is equal to or higher than a predetermined concentration. When the content of the T unit is less than the predetermined range, the heat resistance of the silicone resin itself is extremely lowered, and further, the dispersibility in the aromatic polycarbonate resin is inferior, so that high flame retardancy tends to be hardly obtained. .

The silicone resin according to the present invention may contain a silanol group or an alkoxy group in the side chain and / or the terminal. The content thereof is arbitrary and may be appropriately selected and determined, but is usually 1.0 part by mass or more, preferably 3.5 parts by mass or more, more preferably 5 parts by mass or more, and usually 10 parts by mass or less. , Preferably 9 parts by mass or less, more preferably 8 parts by mass or less. Thereby, a flame retardance may be able to be improved.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a phenoxy group, and among them, a methoxy group is preferable.

  The weight average molecular weight of the silicone resin according to the present invention is arbitrary and may be appropriately selected and determined, but is usually 500 or more, preferably 750 or more, more preferably 1000 or more, further preferably 1500 or more, and usually 500,000. In the following, it is preferably 300,000 or less, more preferably 100,000 or less, still more preferably 20000 or less, and particularly preferably 10,000 or less. When the weight average molecular weight is equal to or greater than the lower limit of the above range, the heat resistance of the silicone resin itself is good, so that it is easy to obtain a flame retardant effect. The possibility of causing mold contamination and mold contamination is suppressed. Further, when the weight average molecular weight is not more than the upper limit of the above range, the melt viscosity of the silicone resin is not too high, good kneadability with the aromatic polycarbonate resin is maintained, causing poor dispersion, and flame retardant The possibility of extremely reducing the properties and mechanical properties is suppressed. Moreover, it exists in the tendency which the fluidity | liquidity of the aromatic polycarbonate resin composition obtained improves by making a weight average molecular weight into the said range. The weight average molecular weight is usually measured by GPC (gel permeation chromatograph).

  In addition, 1 type may be used for a silicone resin and it may use 2 or more types together by arbitrary combinations and a ratio.

  When the light diffusing resin composition of the present invention contains a silicone resin, the content of the silicone resin in the light diffusing resin composition of the present invention is usually 1.8 masses per 100 mass parts of the aromatic polycarbonate resin. Part or more, preferably 1.9 parts by weight or more, more preferably 2 parts by weight or more, and usually 7.5 parts by weight or less, preferably 5 parts by weight or less, more preferably 4.5 parts by weight or less. By including a large amount of the silicone resin in this way, it is possible to further improve the flame retardancy and improve the fluidity of the light diffusing resin composition of the present invention as described above. In addition, if the content of the silicone resin is too small, the flame retardant property of the light diffusing resin composition of the present invention may be insufficient. The mechanical strength and thermal stability may be reduced.

Various commercially available products can be used for the silicone resin according to the present invention.
Examples of the silicone resin according to the present invention include 217 FLAKE (manufactured by Toray Dow Corning Silicone Co., Ltd.) and TSR116 (manufactured by GE Toshiba Silicone Co., Ltd.), and 217 FLAKE is preferred from the viewpoint of heat resistance.

[5] Organometallic salt compound The light diffusing resin composition of the present invention may contain an organometallic salt compound. Here, the organic metal salt compound is a metal salt compound of an organic acid. Thus, the flame retardance of the light diffusable resin composition of this invention can be improved by containing an organometallic salt compound.
As a kind of metal which an organometallic salt compound has, it is preferable that they are an alkali gold electrode or an alkaline-earth metal. The light diffusing resin composition of the present invention can promote carbonization at the time of combustion to further enhance flame retardancy, and mechanical properties such as impact resistance, heat resistance, electrical characteristics, etc. possessed by the aromatic polycarbonate resin. This is because the properties of can be maintained well. Accordingly, the organometallic salt compound according to the present invention is preferably at least one organometallic salt compound selected from the group consisting of alkali metal salts and alkaline earth metal salts, and more preferably alkali metal salts.

  Examples of the organic metal salt compound include an organic sulfonic acid metal salt compound, an organic carboxylic acid metal salt compound, an organic boric acid metal salt compound, and an organic phosphoric acid metal salt compound. Of these, organic sulfonic acid metal salts are preferred from the viewpoint of thermal stability when mixed with an aromatic polycarbonate resin.

  Examples of organic sulfonic acid metal salt compounds include organic lithium sulfonate (Li) salt compounds, organic sodium sulfonate (Na) salt compounds, organic potassium sulfonate (K) salt compounds, and organic sulfonic acids. Rubidium (Rb) salt compound, organic cesium sulfonate (Cs) salt compound, organic magnesium sulfonate (Mg) salt compound, organic calcium sulfonate (Ca) salt compound, organic strontium sulfonate (Sr) salt compound And organic barium sulfonate (Ba) salt compounds. Of these, organic sodium sulfonate (Na) salt compounds, organic potassium sulfonate (K) salt compounds, organic cesium (Cs) salt compounds, and the like are particularly preferable.

  Specific examples of the organic metal salt compound include diphenylsulfone-3,3′-disulfonic acid, diphenylsulfone-3-sulfonic acid, benzenesulfonic acid, (poly) styrenesulfonic acid, paratoluenesulfonic acid, and (branched) dodecyl. Aromatic sulfonic acid such as benzene sulfonic acid and trichlorobenzene sulfonic acid; hydrogen atom of alkyl sulfonic acid such as trifluoromethane sulfonic acid, perfluoroethane sulfonic acid, perfluoropropane sulfonic acid, perfluorobutane sulfonic acid is replaced with fluorine atom And alkali and / or alkaline earth metal salts such as fluorine-containing alkylsulfonic acid having the above structure.

Among them, diphenylsulfone-3,3′-disulfonate potassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, (branched) dodecylbenzene Sodium sulfonate, sodium trichlorobenzenesulfonate, sodium perfluorobutanesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, (branched) potassium dodecylbenzenesulfonate, Potassium trichlorobenzenesulfonate, potassium perfluorobutanesulfonate, cesium benzenesulfonate, cesium (poly) styrenesulfonate, paratoluenesulfo Examples include cesium acid, cesium (branched) dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate, cesium perfluorobutane sulfonate, and the like.
Among these, diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium paratoluenesulfonate, potassium paratoluenesulfonate, and potassium perfluorobutanesulfonate are particularly preferable.
In addition, 1 type may contain the organometallic salt compound, and 2 or more types may contain it by arbitrary combinations and a ratio.

  When the light diffusing resin composition of the present invention contains an organometallic salt compound, the content of the organometallic salt compound in the light diffusing resin composition of the present invention is usually based on 100 parts by mass of the aromatic polycarbonate resin. 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.075 parts by mass or more, particularly preferably 0.1 parts by mass or more, usually 1 part by mass or less, preferably 0.75 parts by mass. Parts or less, more preferably 0.5 parts by mass or less, particularly preferably 0.4 parts by mass or less. If the amount of the organometallic salt compound is too small, the flame retardancy may be insufficient. If the amount is too large, the appearance of the molded article of the light diffusing resin composition may be poor and the mechanical strength may be decreased.

[6] Fluoropolymer The light diffusing resin composition of the present invention preferably contains a fluoropolymer. The fluoropolymer functions as an anti-dripping agent. By containing the fluoropolymer in this manner, it is possible to suppress dripping of the resin that has been ignited and melted during combustion of the light diffusing resin composition of the present invention.

As the fluoropolymer, a known polymer having fluorine can be arbitrarily selected and used, and among these, a fluoroolefin resin is preferable.
As fluoroolefin resin, the polymer and copolymer containing a fluoroethylene structure are mentioned, for example. Specific examples thereof include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. As this fluoroethylene resin, a fluoroethylene resin having a fibril forming ability is preferable.

Examples of the fluoroethylene resin having a fibril-forming ability include Teflon (registered trademark) 6J manufactured by Mitsui / Dupont Fluorochemicals, Polyflon F201L, Polyflon F103 manufactured by Daikin Chemical Industries, and the like.
Examples of the aqueous dispersion of fluoroethylene resin include Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and Fullon D-1 manufactured by Daikin Chemical Industries, Ltd.
Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used as the fluoropolymer. Specific examples thereof include METABRENE A-3800 manufactured by Mitsubishi Rayon Co., Ltd.

  When the light diffusing resin composition of the present invention contains a fluoropolymer, the content of the fluoropolymer in the light diffusing resin composition of the present invention can provide sufficient flame retardancy (anti-drip performance) and light. It is a range in which diffusibility and fluidity are not extremely lowered. Although there is no restriction | limiting in specific fluoropolymer content, Usually 0.01 weight part or more with respect to 100 weight part of aromatic polycarbonate resin, Preferably it is 0.05 weight part or more, More preferably, it is 0.075 weight part. Above, particularly preferably 0.1 parts by weight or more, usually 1 part by weight or less, preferably 0.75 parts by weight or less, more preferably 0.5 parts by weight or less, particularly preferably 0.4 parts by weight or less. . If the content of the fluoropolymer is too small, it is difficult to obtain the dripping prevention effect. Conversely, if the content is too large, the appearance of the molded article of the present invention may be deteriorated or the mechanical properties may be lowered.

  By the way, when the aromatic polycarbonate resin mentioned above has a fluorine, the said aromatic polycarbonate resin functions not only as an aromatic polycarbonate resin based on this invention but as a fluoropolymer. In this case, the aromatic polycarbonate resin having fluorine is handled as an aromatic polycarbonate resin and a fluoropolymer in the calculation of the content of the fluoropolymer described above.

In addition, 1 type may be used for a fluoropolymer and it may use 2 or more types together by arbitrary combinations and a ratio.
Further, the light diffusing resin composition of the present invention may contain a component that acts as an anti-dripping agent in addition to the fluoropolymer. When the example is given, a thermosetting resin etc. will be mentioned.

[7] Additives The light diffusing resin composition of the present invention appropriately contains optional additives such as antioxidants, light stabilizers, processing stabilizers, anti-aging agents, and compatibilizers as necessary. Also good.

  As the antioxidant, it is preferable that the light diffusing resin composition of the present invention further contains a phosphorus-based stabilizer from the viewpoint that the thermal stability can be improved. Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphorous acid ester, phosphoric acid ester, etc. Among them, phosphoric acid stabilizers include trivalent phosphorous and easily exhibit a discoloration suppressing effect. Phosphites such as phosphites and phosphonites are preferred.

  Examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl) phosphite. Phyto, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, water Bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butyl) Ruphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4'-isopropylidene diphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilaurylpentaerythritol diphosphite Phosphite, 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 diphosphite 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, etc., among which hydrolytic resistance viewpoint To tris (2,4-di-tert-butylphenyl) phosphite and tris (4-tert-butylphenyl) phosphite are preferred, and tris (2,4-di-tert-butylphenyl) phosphite is more preferred. preferable.

  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 and the like. Among these, from the viewpoint of hydrolysis resistance and volatilization resistance, tetrakis (2,6-di-tert-butylphenyl) -3, 3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4 ′ -Biphenylenediphosphonite is preferred, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphospho Honaito, tetrakis (2,6-di -tert- butylphenyl) 4,3'-biphenylene phosphonite preferred.

  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.

Two or more types of phosphorus stabilizers used in the present invention can be mixed and contained. When the light diffusing resin composition of the present invention contains a phosphorus stabilizer, the total content of the phosphorus stabilizer is 0.0005 to 0.3 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. It is preferable that it is 0.001 to 0.1 parts by mass. If it is said range, the effect as a stabilizer is enough, and the fall of the molecular weight at the time of shaping | molding and a hue deterioration do not occur easily.
In particular, in the present invention, 0.05 to 3 parts by mass of the compound represented by the general formula (1), 0.1 to 10 parts by mass of the light diffusing agent, and 0 to phosphorus stabilizer with respect to 100 parts by mass of the aromatic polycarbonate resin. It is preferable to contain 0.0005-0.3 mass part.

As an antioxidant, the light diffusing resin composition of the present invention further contains a hindered phenol-based stabilizer to stabilize the compound represented by the general formula (1), and thereby the light diffusing resin composition. It is preferable in that the light stability can be improved.
Examples of the hindered phenol stabilizer include, for example, a substituent other than at least one hydrogen atom at the ortho position of the phenolic hydroxyl group (for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, And compounds having an aryloxy group, a substituted amino group, etc.).
The hindered phenol-based stabilizer is a compound known as an antioxidant and may be a commercially available one. For example, 2,6-di-t-butyl-4-methylphenol, BASF Japan Ltd. Irganox series antioxidants manufactured and the like can be mentioned. Among these, Irganox 1010, Irganox 245, and Irganox 1076 are preferable, and Irganox 1010 and Irganox 1076 are more preferable from the viewpoint of low volatility.
Two or more types of hindered phenol stabilizers used in the present invention can be mixed and contained. When the light diffusing resin composition of the present invention contains a hindered phenol stabilizer, the total content of the hindered phenol stabilizer is 0.0001 to 1 mass relative to 100 parts by mass of the aromatic polycarbonate resin. Part is preferable, and 0.001 to 0.1 part by mass is more preferable.

[8] Method for adjusting light diffusing resin composition The compound represented by the general formula (1), the light diffusing agent, and an aromatic polycarbonate resin are mixed, and the light diffusing resin composition of the present invention is mixed. There is no particular limitation on the preparation method.
When the compound represented by the general formula (1) and the light diffusing agent are compatible with the aromatic polycarbonate resin, the compound represented by the general formula (1) and the light diffusing agent are used as the aromatic polycarbonate resin. Can be added directly. Moreover, the method of pelletizing with melt kneading | mixing machine represented by a vent type twin-screw extruder and apparatuses, such as a pelletizer, is mentioned.
The compound represented by the general formula (1) and the light diffusing agent may be dissolved in an auxiliary solvent having compatibility with the aromatic polycarbonate resin, and the solution may be added to the aromatic polycarbonate resin. The compound represented by the general formula (1) and the light diffusing agent may be dispersed in a high-boiling organic solvent or polymer, and the dispersion may be added to the aromatic polycarbonate resin.
The timing of addition and mixing may be before the aromatic polycarbonate resin is formed by polymerization or after it is formed by polymerization.
The light diffusing resin composition of the present invention may be formed by dissolving an aromatic polycarbonate resin in an arbitrary solvent.

Examples of the high boiling point organic solvent include phosphate ester, phosphonate ester, benzoate ester, phthalate ester, fatty acid ester, carbonate ester, amide, ether, halogenated hydrocarbon, alcohol and paraffin. Phosphate esters, phosphonate esters, phthalate esters, benzoate esters and fatty acid esters are preferred.
Regarding the method for preparing the light diffusing resin composition of the present invention, JP-A-58-209735, JP-A-63-264748, JP-A-4-191851, JP-A-8-272058 and British Patent No. 2016017A. You can refer to the specification.

[9] Molded body The above-described light diffusing resin composition of the present invention is usually molded into some shape and used as a molded body (aromatic polycarbonate resin composition molded body). There is no restriction | limiting in the shape, pattern, color, dimension, etc. of this molded object, What is necessary is just to set arbitrarily according to the use of the molded object.

  Examples of molded products include electrical and electronic equipment and parts, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building components, various containers, leisure goods and miscellaneous goods, lighting devices, liquid crystal televisions, etc. Various uses such as a direct type backlight unit and an edge light unit. Among them, it is particularly suitable for use in electrical / electronic equipment, OA equipment, information terminal equipment, housings for home appliances, cover members, vehicle exterior / skin parts, and interior parts.

Examples of the electrical / electronic devices, OA devices, information terminal devices, housings for home appliances, and cover members include display devices such as personal computers, game machines, and televisions, printers, copiers, scanners, fax machines, electronic notebooks, and PDAs. , Electronic desk calculators, electronic dictionaries, cameras, video cameras, mobile phones, battery packs, drive and readers for recording media, mice, numeric keys, CD players, MD players, portable radio / audio player housings, covers, keyboards , Buttons, switch members, and the like.
Among these members, in particular, when applied to a member having a light source behind and covering the light source, it is difficult to see through the light source, and it is possible to ensure luminance that can provide visibility, so that it is preferably used. Can do.

[10] Light diffusing member The light diffusing member of the present invention comprises the light diffusing resin composition of the present invention.
Applications of the light diffusing member of the present invention include light diffusing molding equipment, such as covers and lenses for various display devices using LEDs (light emitting diode elements), for example, LED signal lamp lenses or lens covers, and OA equipment. And a display such as a television, a light diffusion sheet of a liquid crystal display device, a light guide plate, a cover of a lighting device or a lighting fixture, a lighting signboard, a transmission screen, and the like. In the present invention, the light source is particularly effective when used as a cover or a lens of a lighting fixture or a display fixture using an LED having a low luminous flux and high directivity. That is, the light diffusing member of the present invention is preferably used for LEDs.
Examples of the shape of the light diffusing member of the present invention include a plate shape, a film shape, a sheet shape, and a paste shape. From the viewpoint of strength, the shape is preferably a plate shape, a film shape, and a sheet shape, and more preferably a plate shape. It is in the form of a sheet.

  The method for producing a molded body such as a light diffusing member is not particularly limited, and for example, a molding method generally used for thermoplastic resins can be arbitrarily adopted. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, etc. Is mentioned. A molding method using a hot runner method can also be used.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.
(Synthesis example)
Synthesis Example 1 (Preparation of Exemplified Compound (1))
To 160.0 g of salicylamide, 600 mL of acetonitrile and 356.2 g of DBU (1,8-diazabiccyclo [5.4.0] undec-7-ene) were added and dissolved. To this solution, 231.7 g of methyl 4- (chloroformyl) benzoate was added and stirred at room temperature for 24 hours. 1800 mL of water and 170 mL of 35% hydrochloric acid were added to the reaction solution, and the resulting solid was filtered and washed with water to obtain 343.0 g of synthetic intermediate A (yield 98%).

  To 200.0 g of the synthetic intermediate A, 1200 mL of acetonitrile and 98.1 g of sulfuric acid were added and stirred at 90 ° C. for 4 hours. To this reaction solution, 600 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 182.3 g of synthetic intermediate B (yield 97%).

(Synthesis of X-2)
A three-necked flask was charged with 39.5 g (1.1 molar equivalent) of acetoxime, 600 mL of DMF (N, N-dimethylformamide), 60.6 g (1.1 molar equivalent) of potassium tert-butoxide at room temperature. Stir for minutes. Thereafter, the internal temperature was set to 0 ° C., and 60 g (1.0 molar equivalent) of the compound (X-1) was slowly added dropwise thereto. After the dropwise addition, the internal temperature was raised to 25 ° C. and stirred at that temperature for 1 hour.
The reaction mixture was extracted and separated with an aqueous ammonium chloride solution and ethyl acetate, and the resulting organic phase was washed with saturated brine and separated. The organic phase thus obtained was concentrated by a rotary evaporator to obtain a residue obtained as a crude product of compound (X-2).

(Synthesis of X-3)
In a three-necked flask, put the entire amount of the crude product of the compound (X-2) obtained above, add 700 mL of ethanol and 500 mL of 1 mol / l hydrochloric acid water, and raise the reaction mixture to an internal temperature of 80 ° C. The mixture was stirred at that temperature for 3 hours.
The reaction mixture was cooled to an internal temperature of 25 ° C., extracted and separated with a saturated aqueous sodium hydrogen carbonate solution and ethyl acetate, and saturated brine was added to the obtained organic phase to wash and separate the layers. The organic phase thus obtained was concentrated by a rotary evaporator to obtain a residue obtained as a crude product of compound (X-3).

(Synthesis of X-4)
After filling the flask with nitrogen gas, 6.5 g of 10% Pd-C (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the three-necked flask, and ethanol (2,000 mL) was added to the compound (X- The whole amount of the crude product of 3) was added and heated and refluxed. Thereto was slowly added 55 mL (3 molar equivalents) of formic acid, and the mixture was stirred at this temperature for 5 hours. Thereafter, the reaction mixture was cooled to an internal temperature of 25 ° C., 105 g of 1,5-naphthalenedisulfonic acid was added to the mother liquor filtered through celite and separated by furnace, the internal temperature was raised to 70 ° C., and the mixture was stirred for 30 minutes. Then, it cooled gradually to room temperature, the crystal | crystallization was separated by filtration, and 100g of compounds (X-4) were obtained. The yield was 72% starting from compound (X-1). The obtained crystal was light brown. ¹ H NMR (deuterated DMSO): δ 6.95-6.98 (1H), δ 7.02-7.04 (1H), δ 7.40-7.51 (3H), δ 7.90-7.95 (1H ), Δ 8.75 (1H), δ 8.85-8.88 (2H), δ 9.03 (2H), δ 10.89 (1H)

50 mL of methanol and 3.8 g of 28% sodium methoxide methanol solution were added to 5.5 g of compound (X-4). To this solution, 5.0 g of synthetic intermediate B was added and stirred at 60 ° C. for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.8 g of Exemplified Compound (1) (yield 95%).
MS: m / z 400 (M +) ¹ H NMR (CDCl ₃ ): δ 7.04-7.12 (4H), δ 7.53-7.57 (2H), δ 8.24-8.27 (2H), δ 8.51-8.53 (4H), δ 12.91 (2H) λmax = 353 nm (EtOAc)

Synthesis Example 2 (Preparation of Exemplified Compound (2))
To 160.0 g of salicylamide, 600 mL of acetonitrile and 355.2 g of DBU were added and dissolved. To this solution, 193.2 g of 4-cyanobenzoyl chloride was added and stirred at room temperature for 24 hours. To this reaction solution, 1200 mL of water and 150 mL of hydrochloric acid were added, and the resulting solid was filtered and washed with water to obtain 292.8 g of synthetic intermediate C (yield 94%).

  To 200.0 g of the synthetic intermediate C, 1200 mL of acetonitrile and 110.5 g of sulfuric acid were added and stirred at 90 ° C. for 4 hours. To this reaction solution, 600 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 177.2 g of synthetic intermediate D (yield 95%).

50 mL of methanol and 4.3 g of 28% sodium methoxide methanol solution were added to 6.2 g of compound (X-4). Synthetic intermediate D5.0g was added to this solution, and it stirred at 60 degreeC for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 7.1 g of Compound (2) (yield 96%).
MS: m / z 367 (M +) ¹ H NMR (CDCl ₃ ): δ 7.01-7.13 (4H), δ 7.56-7.59 (2H), δ 7.91-7.93 (2H), δ 8.52-8.54 (2H), δ 8.58-8.60 (2H), δ 12.77 (2H) λmax = 355 nm (EtOAc)

Synthesis Example 3 (Preparation of Exemplified Compound (4))
To 200.0 g of salicylamide, 800 mL of acetonitrile and 444.0 g of DBU were added and dissolved. To this solution, 255.0 g of 4-chlorobenzoyl chloride was added and stirred at room temperature for 24 hours. To this reaction solution, 2000 mL of water and 200 mL of hydrochloric acid were added, and the resulting solid was filtered and washed with water to obtain 389.9 g of synthetic intermediate E (yield 97%).

  Acetonitrile 240mL and sulfuric acid 20.2g were added to the synthetic intermediate E38.0g, and it stirred at 90 degreeC for 4 hours. To this reaction solution, 150 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 30.8 g of synthetic intermediate F (yield 94%).

50 mL of methanol and 4.1 g of 28% sodium methoxide methanol solution were added to 6.0 g of compound (X-4). The synthetic intermediate F5.0g was added to this solution, and it stirred at 60 degreeC for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.8 g of Exemplified Compound (4) (yield 93%).
MS: m / z 376 (M +) ¹ H NMR (CDCl ₃ ): δ 7.04-7.12 (4H), δ 7.53-7.60 (4H), δ 8.41-8.43 (2H), δ 8.53-8.55 (2H), δ 12.96 (2H) λ max = 352 nm (EtOAc)

Synthesis Example 4 (Preparation of Exemplified Compound (104))
To 20.0 g of 4-methoxysalicylamide, 80 mL of acetonitrile and 36.4 g of DBU were added and dissolved. To this solution, 23.8 g of methyl 4- (chloroformyl) benzoate was added and stirred at room temperature for 24 hours. 100 mL of water and 20 mL of hydrochloric acid were added to the reaction solution, and the resulting solid was filtered and washed with water to obtain 36.0 g of synthetic intermediate G (yield 91%).

  200 mL of acetonitrile and 8.9 g of sulfuric acid were added to 20.0 g of the synthetic intermediate G, and the mixture was stirred at 90 ° C. for 4 hours. To this reaction solution, 80 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 17.1 g of synthetic intermediate H (yield 90%).

50 mL of methanol and 3.4 g of 28% sodium methoxide methanol solution were added to 5.5 g of compound (X-4). To this solution, 5.0 g of synthetic intermediate H was added and stirred at 60 ° C. for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.3 g of Compound (104) (yield 91%). MS: m / z 430 (M +) ¹ H NMR (CDCl ₃ ): δ 6.54-6.55 (1H), δ 6.63-6.64 (1H), δ 7.02-7.10 (2H), δ7.51-7.55 (1H), δ8.23-8.25 (2H), δ8.48-8.50 (3H), δ13.02 (1H), δ13.17 (1H) λmax = 352 nm ( EtOAc)

Synthesis Example 5 (Preparation of Exemplified Compound (3))
To 200.0 g of salicylamide, 800 mL of acetonitrile and 444.0 g of DBU were added and dissolved. To this solution, 303.9 g of 4- (trifluoromethyl) benzoyl chloride was added and stirred at room temperature for 24 hours. To this reaction solution, 2000 mL of water and 200 mL of hydrochloric acid were added, and the resulting solid was filtered and washed with water to obtain 428.3 g of synthetic intermediate I (yield 95%).

  Acetonitrile 240mL and sulfuric acid 20.2g were added to the synthetic intermediate I34.0g, and it stirred at 90 degreeC for 4 hours. To this reaction solution, 150 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 34.8 g of synthetic intermediate J (yield 94%).

  50 mL of methanol and 4.6 g of 28% sodium methoxide methanol solution were added to 6.8 g of compound (X-4). Synthetic intermediate J5.0g was added to this solution, and it stirred at 60 degreeC for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.7 g of Exemplified Compound (3) (yield 95%). MS: m / z 409 (M +)

Synthesis Example 6 (Preparation of Exemplified Compound (m-1))
To 160.0 g of salicylamide, 600 mL of acetonitrile and 356.2 g of DBU were added and dissolved. To this solution, 231.7 g of methyl 3- (chloroformyl) benzoate was added and stirred at room temperature for 24 hours. 1800 mL of water and 170 mL of 35% hydrochloric acid were added to the reaction solution, and the obtained solid was filtered and washed with water to obtain 329.0 g of synthetic intermediate K (yield 94%).

  Acetonitrile 1200mL and sulfuric acid 98.1g were added to the synthetic intermediate K200.0g, and it stirred at 90 degreeC for 4 hours. To this reaction solution, 600 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 178.5 g of synthetic intermediate L (yield 95%).

  50 mL of methanol and 3.8 g of 28% sodium methoxide methanol solution were added to 5.5 g of compound (X-4). To this solution, 5.0 g of synthetic intermediate L was added and stirred at 60 ° C. for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.9 g of exemplary compound (m-1) (yield 96%). MS: m / z 400 (M +)

Synthesis Example 7 (Preparation of exemplary compound (m-2))
To 160.0 g of salicylamide, 600 mL of acetonitrile and 355.2 g of DBU were added and dissolved. To this solution, 193.2 g of 3-cyanobenzoyl chloride was added and stirred at room temperature for 24 hours. 1200 mL of water and 150 mL of hydrochloric acid were added to this reaction solution, and the resulting solid was filtered and washed with water to obtain 296.0 g of synthetic intermediate M (yield 95%).

  Acetonitrile 1200mL and sulfuric acid 110.5g were added to the synthetic intermediate M200.0g, and it stirred at 90 degreeC for 4 hours. To this reaction solution, 600 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 177.3 g of synthetic intermediate N (yield 95%).

  50 mL of methanol and 4.3 g of 28% sodium methoxide methanol solution were added to 6.2 g of compound (X-4). The synthetic intermediate N5.0g was added to this solution, and it stirred at 60 degreeC for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.9 g of exemplary compound (m-2) (yield 93%). MS: m / z 367 (M +)

Synthesis Example 8 (Preparation of Exemplified Compound (21))
To 10 g of the exemplified compound (1), 31.6 g of 2-ethylhexanol, 0.13 g of NaOMe and 100 mL of xylene were added, followed by stirring at 90 ° C. for 6 hours under reduced pressure. Water and ethyl acetate were added to the reaction solution and stirred, and the separated organic phase was concentrated. The obtained residue was crystallized from hexane / isopropyl alcohol (volume ratio 1:10) to obtain 11.7 g of Exemplified Compound (21) (yield 95%). MS: m / z 498 (M +)

Synthesis Example 9 (Preparation of Exemplified Compound (24))
To 10 g of the exemplified compound (1), 9.8 g of fine oxocol 180N (manufactured by Nissan Chemical Industries), 0.13 g of NaOMe and 100 mL of xylene were added and stirred at 90 ° C. for 6 hours under reduced pressure. Water and ethyl acetate were added to the reaction solution and stirred, and the separated organic phase was concentrated. The obtained residue was crystallized from hexane / isopropyl alcohol (volume ratio 1:10) to obtain 14.5 g of Exemplified Compound (24) (yield 92%). MS: m / z 638 (M +)

Synthesis Example 10 (Preparation of Exemplified Compound (72))
To 20.0 g of 2-hydroxy-4- (trifluoromethyl) benzamide, 80 mL of acetonitrile and 29.7 g of DBU were added and dissolved. To this solution, 19.4 g of methyl 4- (chloroformyl) benzoate was added and stirred at room temperature for 24 hours. 100 mL of water and 20 mL of 35% hydrochloric acid were added to the reaction solution, and the obtained solid was filtered and washed with water to obtain 34.1 g of synthetic intermediate O (yield 95%).

  Acetonitrile 200mL and sulfuric acid 6.9g were added to the synthetic intermediate O20.0g, and it stirred at 90 degreeC for 4 hours. To this reaction solution, 80 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 18.4 g of synthetic intermediate P (yield 97%).

  100 mL of methanol and 3.4 g of 28% sodium methoxide methanol solution were added to 5.5 g of compound (X-4). The synthetic intermediate P5.0g was added to this solution, and it stirred at 60 degreeC for 3 hours. After cooling this reaction liquid to room temperature, 0.2 mL of 35% hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 5.9 g of Compound (72) (yield 91%). MS: m / z 467 (M +)

Synthesis Example 11 (Preparation of Exemplified Compound (81))
To 20.0 g of 2-hydroxy-5-methoxybenzamide, 80 mL of acetonitrile and 36.4 g of DBU were added and dissolved. To this solution, 23.8 g of methyl 4- (chloroformyl) benzoate was added and stirred at room temperature for 24 hours. 100 mL of water and 20 mL of 35% hydrochloric acid were added to the reaction solution, and the resulting solid was filtered and washed with water to obtain 38.0 g of synthetic intermediate Q (yield 96%).

  200 mL of acetonitrile and 8.9 g of sulfuric acid were added to 20.0 g of the synthetic intermediate Q, and the mixture was stirred at 90 ° C. for 4 hours. To this reaction solution, 80 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 18.1 g of synthetic intermediate R (yield 96%).

  50 mL of methanol and 3.4 g of 28% sodium methoxide methanol solution were added to 5.5 g of compound (X-4). Synthetic intermediate R5.0g was added to this solution, and it stirred at 60 degreeC for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.3 g of Compound (81) (yield 91%). MS: m / z 430 (M +)

Synthesis Example 12 (Preparation of Exemplified Compound (84))
To 20.0 g of 2-hydroxy-5-chlorobenzamide, 80 mL of acetonitrile and 35.4 g of DBU were added and dissolved. To this solution, 23.1 g of methyl 4- (chloroformyl) benzoate was added and stirred at room temperature for 24 hours. 100 mL of water and 20 mL of 35% hydrochloric acid were added to the reaction solution, and the obtained solid was filtered and washed with water to obtain 38.1 g of synthetic intermediate S (yield 98%).

  Acetonitrile 200mL and sulfuric acid 9.0g were added to synthetic intermediate S20.0g, and it stirred at 90 degreeC for 4 hours. To this reaction solution, 80 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 18.3 g of synthetic intermediate T (yield 97%).

  100 mL of methanol and 3.3 g of 28% sodium methoxide methanol solution were added to 5.5 g of compound (X-4). To this solution, 5.0 g of synthetic intermediate T was added and stirred at 60 ° C. for 3 hours. After cooling this reaction liquid to room temperature, 0.2 mL of 35% hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.1 g of Compound (84) (yield 92%). MS: m / z 434 (M +)

Synthesis Example 13 (Preparation of Exemplified Compound (98))
To 20.0 g of 3-hydroxy-2-naphthamide, 80 mL of acetonitrile and 32.4 g of DBU were added and dissolved. To this solution was added 21.2 g of methyl 4- (chloroformyl) benzoate and stirred at room temperature for 24 hours. 100 mL of water and 20 mL of 35% hydrochloric acid were added to the reaction solution, and the obtained solid was filtered and washed with water to obtain 35.1 g of synthetic intermediate U (yield 94%).

  Acetonitrile 200mL and sulfuric acid 9.1g were added to the synthetic intermediate U20.0g, and it stirred at 90 degreeC for 4 hours. To this reaction solution, 80 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 17.9 g of synthetic intermediate V (yield 94%).

  100 g of methanol and 3.0 g of 28% sodium methoxide methanol solution were added to 5.5 g of compound (X-4). The synthetic intermediate V5.0g was added to this solution, and it stirred at 60 degreeC for 3 hours. After cooling this reaction liquid to room temperature, 0.2 mL of 35% hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.1 g of Compound (98) (yield 94%). MS: m / z 449 (M +)

Synthesis Example 14
(Preparation of exemplary compound (m-21))
To 25 g of the exemplified compound (m-2), 250 mL of 3,5,5-trimethylhexanol and 13 g of sulfuric acid were added and stirred at 150 ° C. for 10 hours. After cooling this reaction liquid to 50 degreeC, 100 mL of toluene and 100 mL of water were added and stirred, and then the aqueous layer was removed. 850 mL of methanol was added, and the obtained solid was filtered and washed with water and methanol to obtain 31.4 g of the exemplary compound (m-21) (yield 90%) MS: m / z 512 (M +) ¹ 1 H NMR (CDCl ₃ ): δ 0.88-0.93 (9H), δ 1.07-1.08 (3H), δ 1.14-1.92 (1H), δ 1.32-1.37 (1H) , Δ 1.67-1.88 (3H), δ 4.40-4.45 (2H), δ 6.99-7.06 (4H), δ 7.48-7.53 (2H), δ 7.64-7. .68 (1H), δ 8.29-8.32 (1H), δ 8.46-8.57 (3H), δ 9.08 (1H), δ 12.86 (2H) λmax = 354 nm (EtOAc)

Synthesis Example 15
(Preparation of exemplary compound (120))
To 25 g of exemplary compound (1), 250 mL of 3,5,5-trimethylhexanol and 13 g of sulfuric acid were added and stirred at 150 ° C. for 10 hours. After cooling this reaction liquid to 50 degreeC, 100 mL of toluene and 100 mL of water were added and stirred, and then the aqueous layer was removed. 850 mL of methanol was added, and the obtained solid was filtered, washed with water and methanol to obtain 31.4 g of the exemplary compound (120) (yield 90%) MS: m / z 512 (M +) ¹ H NMR (CDCl ₃ ): δ0.94 (9H), δ1.03-1.05 (3H), δ1.14-1.19 (1H), δ1.31-1.35 (1H), δ1.62-1 .88 (3H), δ 4.41-4.44 (2H), δ 7.05-7.13 (4H), δ 7.54-7.58 (2H), δ 8.24-8.27 (2H), δ 8.53-8.57 (4H), δ 12.93 (2H) λmax = 354 nm (EtOAc)

  In addition, exemplary compound (m-45) is the same except that methyl 4- (chloroformyl) benzoate in the preparation of exemplary compound (1) is changed to methyl 3- (chloroformyl) -5-trifluoromethylbenzoate. Can be synthesized. Exemplified compounds (5) and (10) can also be synthesized in the same manner except that methyl 4- (chloroformyl) benzoate in the preparation of exemplified compound (1) is changed to an acid chloride corresponding to each compound. The exemplified compound (98) can be synthesized in the same manner except that salicylamide in the preparation of the exemplified compound (1) is changed to 3-hydroxy-2-naphthalenecarboxamide. Exemplified compound (8) can be synthesized in the same manner except that salicylamide in the preparation of exemplified compound (1) is changed to 4-methoxysalicylamide and methyl 4- (chloroformyl) benzoate is converted to the corresponding acid chloride. It is.

<Measurement method of pKa>
Exemplified compound (1) was dissolved in acetonitrile so that the absorbance was 1, and 70% perchloric acid (acetic acid solvent) was added dropwise to this solution to change the pH. The solution absorption spectrum at that time was measured, and the ratio between the triazine free form and the proton adduct at each pH was calculated from the absorbance at λmax. The pKa value was determined from the point at which the values became equal. Here, the triazine-free form represents the exemplified compound (1) itself, and the proton adduct represents a compound in which a proton is added to the nitrogen atom of the triazine ring of the exemplified compound (1). Similarly, the values of pKa were determined for the compounds of the present invention, comparative compound A and comparative compound B described in the following table. The absorption spectrum was measured using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation. The pH was measured using a pH meter meter HM60G (trade name) manufactured by Toa Denpa Kogyo. The absorbance is a value measured at the maximum absorption wavelength of each compound. The results are shown in the table below. Here, since Comparative Compound C has no dissociation property, pKa cannot be described.

(Examples 1-42 and Comparative Examples 1-33)
[Production of resin pellets]
As Examples 1-42 and Comparative Examples 1-33, using the ultraviolet absorbers described in Table 9, prescriptions specified later in Table 9, each component and ratio described in Tables 1 to 8 ( (Mass ratio), and mixed for 20 minutes with a tumbler, then supplied to Nippon Steel Works (TEX30HSST) equipped with 1 vent, screw rotation speed 200rpm, discharge rate 15kg / hour, barrel temperature 280 ℃ The molten resin that was kneaded and extruded in a strand shape was quenched in a water bath and pelletized using a pelletizer to obtain pellets of an aromatic polycarbonate resin composition.

[Square plate forming]
The pellets obtained by the above production method were dried in a hot air circulation dryer at 120 ° C. for 5 hours, and then a cylinder temperature of 290 ° C. and gold using a J50-EP type injection molding machine manufactured by Nippon Steel. Injection molding was carried out under conditions of a mold temperature of 80 ° C. and a molding cycle of 30 seconds to form a 50 mm square plate having a thickness of 2 mm.

<Evaluation>
[Hue change (light resistance) and bleed out]
The obtained molded plate was irradiated with a metal halide lamp (cut about 290 nm or less) (trade name: iSuper UV Tester, manufactured by Iwasaki Electric Co., Ltd.) under conditions of illuminance of 90 mW / cm ² , temperature of 63 ° C. and humidity of 50% for 1000 hours. Table 9 shows the hue change before and after light irradiation and the presence or absence of bleed-out when irradiated.
Regarding the change in hue, ◎ indicates no hue change, ◯ indicates almost no hue change, Δ indicates slight coloration, and x indicates large coloration.
Regarding bleed-out, ◎ is not present at all, ○ indicates visually, but no bleed-out adheres to the hand even when touched by hand, and x indicates adherence of bleed-out by hand.

As the ultraviolet absorber according to the present invention, the compound represented by the above general formula (1) was used. The numbers of the ultraviolet absorbers listed in Table 9 correspond to the numbers of the specific example compounds.
Moreover, the following comparative compounds AD were used as a comparative ultraviolet absorber. In addition, the compound which has the same structure as the following comparison compound B is marketed also as Seesorve 709 (made by Dipro Kasei Co., Ltd.).
Comparative compound A: TINUVIN1577FF (manufactured by BASF)
Comparative compound B: TINUVIN329 (manufactured by BASF)
Comparative compound C: Pionein ZA-101 (manufactured by Takemoto Yushi Co., Ltd.)
Comparative compound D: Compound having the following structure (manufactured by ADEKA)

  As is clear from the results in Table 9, the light diffusing resin composition of the examples containing the compound represented by the general formula (1), the light diffusing agent according to the present invention, and the aromatic polycarbonate resin has the general formula Compared with the light diffusing resin compositions of Comparative Examples 1 to 33 that do not contain the compound represented by (1), the hue of the molded product was small and excellent in suppression of bleeding out.

(Examples 43 to 73 and Comparative Examples 34 to 38)
Aromatic polycarbonate resin (trade name: Iupilon (registered trademark) S-3000F viscosity average molecular weight: 21,000) manufactured by Mitsubishi Engineering Plastics Co., Ltd., 100 parts by mass as exemplified compounds (1) to (4 ), (21) to (27), (104), (114) to (120), (m-1), (m-2), (m-21), (m-31), comparative compound A to Acrylic-styrene copolymer fine particles A having 0.2 parts by mass of D, manufactured by Asahi Denka Kogyo Co., Ltd. as a heat stabilizer, 0.05 parts by mass of Adeka Stub 2112 and a table as a light diffusing agent (Gantz Kasei Co., Ltd., trade name: Gantz Pearl GSM-1261), B (Gantz Kasei Co., Ltd., trade name: Gantz Pearl GSM-1841) or C (Gantz Kasei Co., Ltd., trade name: Gantz) Pearl GSM-0561) (hereinafter may be abbreviated as “copolymerized fine particles A, B, or C”) in the ratio shown in Table 10, single screw extruder having a screw diameter of 40 mm and a cylinder set temperature of 260 ° C. Pellets were prepared, test pieces were molded under the following conditions, evaluated, and the results are shown in Table 10. Table 10 also shows the weight average particle diameter and refractive index of “copolymerized fine particles A, B, or C”.
Evaluation methods and molding conditions of test pieces in Examples and Comparative Examples of the light diffusing resin composition of the present invention are as follows. In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.

1) Total light transmittance and haze: A test piece having a thickness of 3 mm was measured using NDH-2000 manufactured by Nippon Denshoku in accordance with JIS K7105.
2) Visibility (diffusibility): 10 x 0.6 candela LEDs (Light Emitting Diodes) are placed 10 cm away from the back side of the 2 × 300 × 600 mm sheet-shaped molded body, and 30 cm away from the surface side of the sheet-shaped molded body. The glare and brightness of the LED from the spot were visually observed. The case where there was a slight glare was rated as x, the case where there was almost no glare, and the case where there was no glare as ◯.
3) Regarding bleed-out, ◎ was completely absent, ○ was visually confirmed, but even if touched by hand, no bleed-out was attached to the hand, and × was touched by hand, and bleed-out was attached.
4) Molding conditions of test piece: The pellets pre-dried at 120 ° C. for 4 hours were molded with a 150M3 type injection molding machine manufactured by Meiki Seisakusho at a cylinder temperature of 280 ° C., a molding cycle of 50 seconds, and a mold temperature of 80 ° C.

  From Table 10, the test piece of the present invention molded from the light diffusing resin composition containing the compound represented by the general formula (1), the light diffusing agent according to the present invention, and the aromatic polycarbonate resin is totally transmissive. The light diffusing resin composition of Comparative Examples 34 to 38 which does not contain the compound represented by the general formula (1), while being excellent in rate, haze, suppression of bleed-out, and visibility (inhibition of LED glare) In the test piece of the comparative example molded from the product, the balance of properties was poor, and there was no satisfactory light diffusing resin composition.

Claims (15)

It contains a compound represented by the following general formula (1), a light diffusing agent, and an aromatic polycarbonate resin, and the light diffusing agent is one of acrylic fine particles, silicone fine particles, and acrylic-styrene copolymer fine particles. A light diffusing resin composition.

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or a hydroxy group, and at least one of the substituents is a Hammett's σp Represents a substituent whose value is positive. Moreover, you may combine with substituents and may form a ring. R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p each independently represent a hydrogen atom or a monovalent substituent. Moreover, you may combine with substituents and may form a ring. ]   The monovalent substituent is a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, substituted or Unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group, substituted or unsubstituted sulfamoyl Group, thiocyanate group, or substituted or unsubstituted alkylsulfonyl group, and when the monovalent substituent has a substituent, the substituent is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group , Alkoxycarbonyl group, carbamoyl group, alkylcarbonyl group, nitro group, amino group, hydroxy group, 1 to 2 carbon atoms An alkoxy group, an aryloxy group, a sulfamoyl group, a thiocyanate group or an alkylsulfonyl group, the light-diffusing resin composition according to claim 1. 3. The light diffusing resin composition according to claim 1, wherein at least one of R ^1b , R ^1c, and R ^1d is a substituent having a positive Hammett σp value. The substituent having a positive Hammett's σp value is a group selected from the group consisting of COOR ^r , CONR ^s ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, and SO ₃ M. Item 4. The light diffusing resin composition according to any one of Items 1 to 3. Here, R ^r and R ^s each independently represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal. The light diffusing resin composition according to any one of claims 1 to 4, wherein the substituent having a positive Hammett's σp value is COOR ^r . Here, R ^r represents a hydrogen atom or a monovalent substituent. The light diffusing resin composition according to claim ¹ , wherein R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p are hydrogen atoms. .   Furthermore, the light diffusable resin composition of any one of Claims 1-6 containing a phosphorus stabilizer.   0.05 to 3 parts by mass of the compound represented by the general formula (1), 0.1 to 10 parts by mass of the light diffusing agent, and 0.0005 of the phosphorus stabilizer with respect to 100 parts by mass of the aromatic polycarbonate resin. The light diffusable resin composition of Claim 7 which is -0.3 mass part.   Furthermore, the light diffusable resin composition of any one of Claims 1-8 containing a hindered phenol type stabilizer.   The light-diffusing resin composition according to any one of claims 1 to 9, wherein the aromatic polycarbonate resin has a viscosity average molecular weight in the range of 10,000 to 50,000.   Furthermore, the light diffusable resin composition of any one of Claims 1-10 containing an organometallic salt compound.   Furthermore, the light diffusable resin composition of any one of Claims 1-11 containing a fluoropolymer.   The light diffusing resin composition according to claim 1, wherein the compound represented by the general formula (1) has a pKa in the range of −5.0 to −7.0.   A light diffusing member comprising the light diffusing resin composition according to claim 1.   The light diffusing member according to claim 14, which is for an LED.