JP5371869B2 - Cellulose ester resin composition and molded article thereof - Google Patents

Description

  The present invention relates to a cellulose ester resin composition containing a triazine compound and a cellulose ester resin, and a molded article thereof.

Conventionally, an ultraviolet absorber is commonly used for various resins and the like to impart ultraviolet absorptivity to a resin composition or a molded product thereof. Examples of the ultraviolet absorber include inorganic ultraviolet absorbers and organic ultraviolet absorbers.
Inorganic ultraviolet absorbers (see, for example, Patent Documents 1 to 3) are excellent in durability such as weather resistance and heat resistance, but are free to be selected because the absorption wavelength is determined by the band gap of the compound. Less degree. Inorganic ultraviolet absorbers that can absorb up to 400 nm in the long-wave ultraviolet (UV-A) region have absorption up to the visible region and are therefore colored, and there is no one that can absorb long-wave ultraviolet light without coloring.
On the other hand, since the organic ultraviolet absorber has a high degree of freedom in the structural design of the absorbent, it is possible to obtain various absorption wavelengths by devising the structure of the absorbent.

  So far, a system using various organic ultraviolet absorbers has been studied, and Patent Document 4 discloses a triazole ultraviolet absorber. Patent Document 5 describes a trisaryl-s-triazine having an alkoxy group and a hydroxy group at a specific position. However, these organic ultraviolet absorbers have a maximum absorption wavelength in the UV-A region, but those having such a maximum absorption wavelength in the long wave ultraviolet region have poor light resistance, and the ultraviolet absorption effect decreases with time. End up. Therefore, an ultraviolet absorber having absorption ability in the UV-A region and excellent light resistance has been desired.

JP-A-5-339033 JP-A-5-345639 JP-A-6-56466 Special Table 2002-524442 Japanese Patent No. 3965631

  Cellulose ester resins are used as various molded article materials as synthetic resins. For example, it has been used as a molding material for a protective film of a polarizing plate and a support for various optical films in an image display device such as a liquid crystal display device. In recent years, an image display device has been used as a liquid crystal display for mobile phones, electronic advertisements, etc. It is also increasingly used outdoors. It was inevitable that the property deteriorated by exposure to sunlight outdoors for a long time and exposure to ultraviolet rays over time. For this reason, there has been a demand for a cellulose-based resin composition containing an ultraviolet absorber having an ultraviolet shielding effect up to the UV-A region and having an excellent light resistance, and a molded product thereof.

  An object of the present invention is to provide a cellulose ester resin composition having a long wave ultraviolet ray shielding effect for a long time and having excellent light resistance, and a molded product thereof.

As a result of examining the above problems in detail, the present inventors have found a novel triazine-based compound that exhibits an ultraviolet shielding effect up to the UV-A region and has excellent light resistance, and contains this in a cellulose ester-based resin composition. Thus, the present invention has been completed.
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ＯＨを除く１価の置換基を表し、該置換基のうち少なくとも１つは、ハメット則のσｐ値が正の置換基であるＣＯＯＲ ^ｒ 又はＣＮ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、水素原子を表す。Ｒ ^ｒ は、水素原子又は１価の置換基を表す。］
＜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、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、置換基を有する場合の該置換基が、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ことを特徴とする、＜１＞に記載のセルロースエステル系樹脂組成物。
＜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値が正の置換基であるＣＯＯＲ ^ｒ （Ｒ ^ｒ は水素原子又は１価の置換基）又はＣＮであることを特徴とする＜１＞又は＜２＞に記載のセルロースエステル系樹脂組成物。
＜４＞
一般式（１）で表される化合物を０．１〜３０質量％含有することを特徴とする＜１＞〜＜３＞のいずれか１項に記載のセルロースエステル系樹脂組成物。
＜５＞
前記セルロースエステル系樹脂が、セルロースアセテート、セルロースアセテートプロピオネート及びセルロースアセテートブチレートからなる群より選ばれる少なくとも１つであることを特徴とする＜１＞〜＜４＞のいずれか１項に記載のセルロースエステル系樹脂組成物。
＜６＞
更に、紫外線吸収剤、光安定剤、酸化防止剤及び可塑剤からなる群より選ばれる少なくとも１つを含むことを特徴とする＜１＞〜＜５＞のいずれか１項に記載のセルロースエステル系樹脂組成物。
＜７＞
＜１＞〜＜６＞のいずれか１項に記載のセルロースエステル系樹脂組成物からなる成形品。
＜８＞
一般式（１）で表される化合物を０．１〜１０．０ｇ／ｍ ^２ 含むことを特徴とする＜７＞に記載の成形品。
＜９＞
厚さが２０μｍ〜１０００μｍであることを特徴とする＜７＞又は＜８＞に記載の成形品。
本発明は、上記＜１＞〜＜９＞に係る発明であるが、以下、それ以外の事項（例えば、下記１〜１２）についても記載している。
１．下記一般式（１）で表される化合物と、セルロースエステル系樹脂とを含有することを特徴とするセルロースエステル系樹脂組成物。
<1>
A cellulose ester resin composition comprising a compound represented by the following general formula (1) (excluding a compound having a sugar residue) and a cellulose ester resin.

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or OH, and at least one of the substituents is a Hammett's σp COOR ^r or CN whose value is a positive substituent . 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 represent a hydrogen atom. R ^r represents a hydrogen atom or a monovalent substituent. ]
<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, alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group, substituted or unsubstituted sulfamoyl group, thiocyanate group, Or a substituted or unsubstituted alkylsulfonyl group, and when having a substituent, the substituent is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylcarbonyl group Group, nitro group, amino group, hydroxy group, alkoxy group having 1 to 20 carbon atoms, aryloxy group Group, a sulfamoyl group, characterized in that it is a thiocyanate group, or an alkylsulfonyl group, a cellulose ester-based resin composition according to <1>.
<3>
At least one of R ^1b , R ^1c and R ^1d is COOR ^r (R ^r is a hydrogen atom or a monovalent substituent) or CN which is a substituent having a positive Hammett's σp value < The cellulose ester resin composition according to 1> or <2>.
<4>
The cellulose ester-based resin composition according to any one of <1> to <3>, comprising 0.1 to 30% by mass of the compound represented by the general formula (1).
<5>
<1>-<4>, wherein the cellulose ester-based resin is at least one selected from the group consisting of cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate. Cellulose ester-based resin composition.
<6>
The cellulose ester system according to any one of <1> to <5>, further comprising at least one selected from the group consisting of an ultraviolet absorber, a light stabilizer, an antioxidant, and a plasticizer. Resin composition.
<7>
<1>-<6> The molded article which consists of a cellulose-ester-type resin composition of any one of <6>.
<8>
<10> The molded article according to <7>, comprising 0.1 to 10.0 g / m ^{2 of the} compound represented by the general formula (1) .
<9>
The molded product according to <7> or <8>, wherein the thickness is 20 μm to 1000 μm.
Although this invention is invention which concerns on said <1>-<9>, hereafter, other matters (for example, the following 1-12) are also described.
1. A cellulose ester-based resin composition comprising a compound represented by the following general formula (1) and a cellulose ester-based resin.

  By containing the compound represented by the general formula (1), the cellulose ester resin composition of the present invention exhibits an ultraviolet shielding effect even in a long wavelength region and has excellent light resistance. In addition, by molding the cellulose ester resin composition of the present invention, a molded product such as a film having an ultraviolet absorption effect including a long wave ultraviolet region over a long period of time can be obtained.

Hereinafter, the present invention will be described in detail.
The cellulose ester resin composition of the present invention contains a compound represented by the following general formula (1) and a cellulose ester resin.
The compound represented by the general formula (1) is highly soluble in an organic solvent, exhibits an ultraviolet shielding effect even in a long wavelength region, and is excellent in light resistance. Therefore, when added to a cellulose ester-based resin as an ultraviolet absorber, the long wave ultraviolet shielding ability is maintained for a long period of time, and the light resistance of the resin is also improved.
First, the compound represented by the following general formula (1) will be described.

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or OH, 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 OH, 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.

Examples of the monovalent substituent (hereinafter referred to as “substituent A”) in the general formula (1) include, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a carbon number of 1 to 20 Alkyl group (for example, methyl, ethyl), aryl group having 6 to 20 carbon atoms (for example, phenyl, naphthyl), cyano group, carboxyl group, alkoxycarbonyl group (for example, methoxycarbonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), Substituted or unsubstituted carbamoyl group (for example, carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl group (for example, acetyl), arylcarbonyl group (for example, benzoyl), nitro group, substituted or unsubstituted amino group (Eg amino, dimethylamino, anilino, substituted Famino group), acylamino group (for example, acetamide, ethoxycarbonylamino), sulfonamide group (for example, methanesulfonamide), imide group (for example, succinimide, phthalimide), imino group (for example, benzylideneamino), hydroxy group, 1 to 20 carbon atoms An alkoxy group (for example, methoxy), an aryloxy group (for example, phenoxy), an acyloxy group (for example, acetoxy), an alkylsulfonyloxy group (for example, methanesulfonyloxy), an arylsulfonyloxy group (for example, benzenesulfonyloxy), a sulfo group, a substituted or Unsubstituted sulfamoyl groups (eg sulfamoyl, N-phenylsulfamoyl), alkylthio groups (eg methylthio), arylthio groups (eg phenylthio), thiocyanate groups, alkyl A sulfonyl group (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 is preferable. In the case where the group mentioned here is a substituted group, as the substituent, among the above-described monovalent substituent A, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, Carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, substituted or unsubstituted carbon number Examples thereof include 1 to 20 alkoxy groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted sulfamoyl groups, thiocyanate groups, and substituted or unsubstituted alkylsulfonyl groups.
As the monovalent substituent in the general formula (1), 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 Further preferred.
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, ethyl, n-propyl, i-propyl, n-butyl, i -Butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl, i-octyl Methyl or ethyl is preferred, and methyl 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.
R ^1c is preferable because LUMO is stabilized by a substituent having a positive Hammett's σp value and an electron-attracting group, so that the excitation life is shortened and the light resistance is improved.

In a preferred second embodiment, R ^1a , R ^1c and R ^1e each represent a hydrogen atom, and R ^1b and R ^1d are each independently a hydrogen atom or a substituent having a positive Hammett σp value. And at least one of R ^1b and R ^1d is a substituent having a positive Hammett's σp value. Thereby, since the compound represented by the general formula (1) is particularly excellent in solvent solubility, it is excellent in compatibility with the cellulose ester resin, and the cellulose ester resin composition containing the compound precipitates the compound. Or it has the effect of making it difficult to bleed out.
Solvent solubility means solubility in an organic solvent such as ethyl acetate, methyl ethyl ketone, and toluene. In terms of compatibility with a cellulose ester resin, the solvent solubility is 10% by mass or more based on the solvent used. Preferably, 20% by mass or more is more preferable, and 30% by mass or more is more preferable.

<Preferred first embodiment>
In a first embodiment, as a substituent σp value is a positive Hammett equation in formula 1, preferably, sigma electron withdrawing group _p value of 0.1 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, preferably a hydrogen atom or an alkyl group, more preferably hydrogen. CONR ^s ₂ (R ^s represents a hydrogen atom or a monovalent substituent), CN, halogen atom, NO ₂ , 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, alkyl Sulfinyl group, arylsulfinyl group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, imino group, N atom Conversion and imino group, a carboxy group (or a salt thereof), substituted with at least two or more halogen atoms an alkyl group (e.g. CF _3), substituted with at least two or more halogen atoms alkoxy groups, at least two An aryloxy group substituted with a halogen atom, 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 0.2 Examples thereof include aryl groups, heterocyclic groups, halogen atoms, azo groups, and selenocyanate groups substituted with 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 , CN, CF ₃ , a halogen atom, NO ₂ , or SO ₃ M [R ^r , R ^s each independently represents a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal]. Among these, COOR ^r or CN is more preferable, and COOR ^r is more preferable. This is because it has excellent light resistance and solvent solubility.

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 having 1 to 20 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i- Examples include pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl and i-octyl, preferably methyl or ethyl, and particularly preferably methyl.

In the compound represented by the general formula (1), R ^1c is preferably any one of COOR ^r , CONR ^s ₂ , CN, CF ₃ , a halogen atom, NO ₂ , SO ₃ M, and COOR ^r or CN CN is more preferable.

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 (preferably 0.1 to 1.2) σp value according to the Hammett rule, and R ^1h is a substituent having a positive σp value according to the Hammett rule. Is more preferable. It is particularly preferable that R ^1c and R ^1h represent a substituent having a positive (preferably 0.1 to 1.2) σp value according to the Hammett rule. This is because it has excellent light resistance.
In the present ^invention, it is preferable that ^{R 1h} or ^{R 1n} is either each independently a hydrogen _{^{atom, COOR r, CONR s 2,}} CN, CF 3, halogen _atom, NO 2, SO ₃ ^{M, R 1h} or R more preferably ¹ⁿ is a hydrogen ^atom, more preferably ^{R 1h} and ^{R 1n} is a hydrogen ^{atom, R 1g, R 1h, R} 1i, R 1j, R 1k, R 1m, R 1n and ^{R 1p} is It is particularly preferred that it represents 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), 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 ^1c is any of COOR ^r , CONR ^s ₂ , CN, CF ₃ , a halogen atom, NO ₂ , SO ₃ M More preferably, R ^1g , R ^1h , R ¹ⁱ , R ^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.

<Preferred second embodiment>
In a preferred second embodiment, R ^1a , R ^1c and R ^1e each represents a hydrogen atom, and R ^1b and R ^1d each independently represent a hydrogen atom or a substituent having a positive Hammett σp value. , At least one of the embodiments may be a substituent having a positive Hammett's σp value.
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 , CN, CF ₃ , halogen atom, NO ₂ , 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 is 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 15 carbon atoms from the viewpoint of solubility in a solvent.
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.
R ^r is a branched alkyl group having 5 to 15 carbon atoms containing 1 or 2 secondary carbon atoms and tertiary carbon atoms and 1 or 2 asymmetric carbons from the viewpoint of solubility in a solvent. It is particularly preferred.
This is because the symmetry of the compound structure is broken and the solubility is improved.

On the other hand, from the viewpoint of ultraviolet absorbing ability, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable.
Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i- Examples include pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl and i-octyl, preferably methyl or ethyl, and particularly preferably methyl.

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 (preferably 0.1 to 1.2) σp value according to the Hammett rule, and R ^1h is a substituent having a positive σp value according to the Hammett rule. Is more preferable. R ^1b or R ^1d and R ^1h particularly preferably represent a substituent having a positive (preferably 0.1 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 is preferably each independently a hydrogen atom, COOR ^r , CONR ^s ₂ , a cyano group, CF ₃ , a halogen atom, a nitro group, or SO ₃ M, and R ^1h or R ¹ⁿ is more preferably a hydrogen atom, R ^1h and R ¹ⁿ are more preferably hydrogen atoms, and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p Particularly preferably represents 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 is a substituent having a positive Hammett's σp value (preferably 0.1 to 1.2), and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p preferably represent a hydrogen atom [R ^r and R ^s each independently represent a hydrogen atom or a monovalent substituent. . M represents a hydrogen atom or an alkali metal], R ^1b or R ^1d is any one of COOR ^r , CONR ^s ₂ , a cyano group, CF ₃ , a halogen atom, a nitro group, and SO ₃ M, and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p are more preferably 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, 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.

Since the compound represented by the general formula (1) according to the present invention has a substituent having a positive Hammett's σp value at a specific position, LUMO is stabilized by the electron withdrawing group. It has the characteristics that the lifetime is shortened and it has excellent light resistance. Even when used as a UV absorber, the known triazine compounds have adverse effects such as decomposition and yellowing. On the other hand, the compounds represented by the general formula (1) according to the present invention are: Since it has excellent light resistance, the effect of not being decomposed and yellowing even when used for a long time can be obtained.
In the cellulose ester-based 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.

In the cellulose ester-based 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.
The compounds according to the invention are particularly suitable for stabilizing organic materials against damage by light, oxygen or heat. Among them, the compound represented by the general formula (1) can be suitably used as a light stabilizer, particularly 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 a living body and from the point that bleeding out hardly occurs. 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 cellulose ester-based resin composition of the present invention can contain the compound represented by the general formula (1) in any amount necessary for imparting desired performance. As content, it is preferable that it is 0.1-30 mass% in the cellulose-ester-type resin composition of this invention, It is more preferable that it is 0.1-15.0 mass%, 0.5-10. The content is more preferably 0% by mass, and still more preferably 1.0 to 4.0% by mass. If the content is in the above range, an ultraviolet shielding effect can be obtained and bleeding out can be effectively suppressed, which is preferable.

  The cellulose ester-based resin composition of the present invention may contain two or more types of compounds represented by the general formula (1) having different structures as the ultraviolet absorber as described above. Moreover, you may use together the compound represented with the said General formula (1), and 1 or more types of ultraviolet absorbers which have another structure. When two types (preferably three types) of ultraviolet absorbers having different basic skeleton structures are used in combination, ultraviolet rays in a wide wavelength region can be absorbed. Further, when two or more kinds of ultraviolet absorbers are used in combination, the dispersion state of the ultraviolet absorber is also stabilized. Any ultraviolet absorber having a structure other than the general formula (1) can be used. Triazine, benzotriazole, benzophenone, merocyanine, cyanine, dibenzoylmethane, cinnamic acid, cyano Examples include acrylate-based and benzoate-based compounds. For example, Fine Chemical, May 2004 issue, pages 28-38, published by Toray Research Center, Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999), pages 96-140, Junichi Okachi Examples include ultraviolet absorbers described in the supervision of “Development of polymer additives and environmental measures” (CMC Publishing Co., Ltd., 2003), pages 54 to 64.

  The ultraviolet absorber having a structure other than the general formula (1) is preferably a benzotriazole compound, a benzophenone compound, a salicylic acid compound, a benzoxazinone compound, a cyanoacrylate compound, a benzoxazole compound, or a merocyanine compound. , A triazine compound. More preferred are benzoxazinone compounds, benzotriazole compounds, benzophenone compounds, and triazine compounds. Particularly preferred are benzotriazole compounds. The ultraviolet absorber having a structure other than the general formula (1) is described in detail in paragraphs [0117] to [0121] of Japanese Patent Application No. 2008-273950, and the material described in the publication is the present invention. It can also be applied.

As described above, the cellulose ester resin composition of the present invention preferably contains a combination of the compound represented by the general formula (1) and the benzotriazole compound. Since the compound represented by the general formula (1) has excellent light resistance even in a long wavelength region, it has an effect of preventing deterioration of benzotriazole which can be shielded to a longer wavelength region, and is used together with a benzotriazole compound. Therefore, it is preferable because the shielding effect can be maintained for a long time up to a longer wavelength region.
It is preferable that the addition amount of ultraviolet absorbers other than the compound represented by General formula (1) is 0.1-30 mass% in a cellulose-ester-type resin composition, and is 0.5-10 mass%. It is still more preferable, and it is still more preferable that it is 1-4 mass%.

  Although the cellulose ester-based resin composition of the present invention can provide a practically sufficient ultraviolet shielding effect only by using the compound represented by the general formula (1) as an ultraviolet absorber, it requires further strictness. In this case, a white pigment having a strong hiding power, such as titanium oxide, may be used in combination. In addition, when the appearance and color tone become problems, or a small amount (0.05% by mass or less) of a colorant can be used in combination depending on the preference. For applications where transparency or white color is important, a fluorescent brightening agent may be used in combination. Examples of the fluorescent whitening agent include commercially available products, general formula [1] described in JP-A-2002-53824, and specific compound examples 1 to 35.

  Next, the cellulose ester resin component contained in the cellulose ester resin composition of the present invention will be described.

  The cellulose ester-based resin is a cellulose ester compound and a compound having an ester-substituted cellulose skeleton obtained by introducing a functional group biologically or chemically from cellulose as a raw material. For example, cellulose diacetate (DAC), Examples include cellulose triacetate (TAC), cellulose propionate, cellulose butyrate, cellulose acetate propionate, and nitrocellulose.

  The cellulose ester compound is an ester of cellulose and an acid, and the acid constituting the ester is preferably an organic acid, more preferably a carboxylic acid, still more preferably a fatty acid having 2 to 22 carbon atoms, and a carbon atom. Cellulose acylate, which is a lower fatty acid having 2 to 4 numbers, is most preferred.

Examples of the raw material cellulose include cotton linter and wood pulp (hardwood pulp, softwood pulp). Cellulose esters obtained from any raw material cellulose can be used, and two or more kinds may be mixed and used in some cases. Detailed descriptions of these raw material celluloses can be found in, for example, “Plastic Materials Course (17) Fibrous Resin” (Marusawa, Uda, Nikkan Kogyo Shimbun, published in 1970) and Invention Association Publication Technical Report 2001-1745 ( The cellulose described in pages 7 to 8) can be used, but is not particularly limited.
Next, the cellulose acylate suitable for the present invention produced from the above-mentioned cellulose will be described.

[Substitution degree of cellulose acylate]
The cellulose acylate used in the present invention is an acylated hydroxyl group of cellulose, and the substitution degree of cellulose acylate is present in the structural unit of cellulose (glucose having (β) 1,4-glycosidic bonds). It means the ratio of three hydroxyl groups being acylated. The degree of substitution (acylation degree) can be calculated by measuring the amount of bound fatty acid per unit mass of cellulose. The measuring method is carried out according to “ASTM D817-91”. The cellulose acylate used in the present invention is preferably cellulose acetate having an acetyl substitution degree of 2.50 to 3.00. The acetyl substitution degree is more preferably 2.70 to 2.97.

Among the acetic acid substituted for the hydroxyl group of cellulose and / or the fatty acid having 3 to 22 carbon atoms, the acyl group having 2 to 22 carbon atoms may be an aliphatic group or an allyl group, and is not particularly limited. A mixture of Examples of the cellulose ester in which the hydroxyl group is substituted with these acyl groups include cellulose alkylcarbonyl ester, alkenylcarbonyl ester, aromatic carbonyl ester, and aromatic alkylcarbonyl ester. You may have. Preferred examples of the acyl group having 2 to 22 carbon atoms include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, i-butanoyl, t -Butanoyl, cyclohexanecarbonyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl group and the like. Among these, acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like are preferable, and acetyl, propionyl and butanoyl are more preferable. The most preferred group is acetyl.
As the cellulose ester resin used in the present invention, cellulose acetate is particularly preferable for fatty acid esters, and cellulose acetate propionate and cellulose acetate butyrate are particularly preferable for mixed fatty acid esters.
In the present invention, the cellulose acylate can be used singly or as a mixture of two or more different types, particularly cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate alone or in combination of two or more thereof. It is preferable to use it.

[Degree of polymerization of cellulose acylate]
The degree of polymerization of cellulose acylate preferably used in the present invention is 180 to 700 in terms of viscosity average polymerization degree, and in cellulose acetate, 180 to 550 is more preferable, 180 to 400 is more preferable, and 180 to 350 is particularly preferable. . By setting the polymerization degree within this range, the viscosity of the cellulose ester resin of the present invention is not excessively high, and the molded product of the present invention can be easily produced. It is preferable because the physical properties are in an appropriate range. The average degree of polymerization can be measured by the intrinsic viscosity method of Uda et al. {Kazuo Uda, Hideo Saito, "Journal of Textile Society," Vol. 18, No. 1, pages 105-120 (1962)}. This method is also described in detail in JP-A-9-95538.

The molecular weight distribution of cellulose acylate preferably used in the present invention is evaluated by gel permeation chromatography, and its polydispersity index Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) is small, and the molecular weight distribution is Narrow is preferred. The specific value of Mw / Mn is preferably 1.0 to 4.0, more preferably 2.0 to 3.5, and most preferably 2.3 to 3.3. preferable.
The number average molecular weight (Mn) of the cellulose ester is preferably 30,000 to 300,000, and more preferably 50,000 to 200,000.

  Further, when the low molecular component of cellulose acylate is removed, the average molecular weight (degree of polymerization) increases, but the viscosity is lower than that of normal cellulose acylate, which is useful. Cellulose acylate having a small amount of low molecular components can be obtained by removing low molecular components from cellulose acylate synthesized by a usual method. The removal of the low molecular component can be carried out by washing the cellulose acylate with an appropriate organic solvent.

  In addition, when manufacturing a cellulose acylate with few low molecular components, it is preferable to adjust the sulfuric acid catalyst amount in an acetylation reaction to 0.5-25 mass parts with respect to 100 mass parts of cellulose. When the amount of the sulfuric acid catalyst is in the above range, cellulose acylate that is preferable in terms of molecular weight distribution (uniform molecular weight distribution) can be synthesized.

[Water content of cellulose acylate]
The water content of cellulose acylate preferably used in the present invention is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly 0.7% by mass or less. In general, cellulose acylate contains water, and a water content of about 2.5 to 5% by mass is known. In order to obtain a preferable moisture content of the cellulose acylate in the present invention, it is necessary to dry the cellulose acylate, and the method is not particularly limited as long as the desired moisture content is obtained. These cellulose acylates are described in detail on pages 7 to 12 of the raw material cotton and the synthesis method in the Japan Society for Invention and Technology (public technical number 2001-1745, published on March 15, 2001, Japan Society for Invention). ing.

  The cellulose ester resin composition of the present invention can contain other resin components in combination with the cellulose ester resin. 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, polycarbonate, polyester (for example, polyethylene terephthalate, polyethylene Naphthalate, etc.), polyketone, polysulfone polyether ketone, phenol resins, melamine resins, polysiloxane, natural polymers (e.g., cellulose, rubber, gelatin, etc.), and the like.

  The resin component that can be used in combination is preferably a synthetic polymer, and more preferably a polyolefin, an acrylic polymer, or a polyester. Among these, polyethylene, polypropylene, poly (4-methylpentene), polymethyl methacrylate, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate are particularly preferable. The resin component that can be used in combination is preferably a thermoplastic resin.

In the cellulose ester resin composition of the present invention, any one of an ultraviolet absorber, a light stabilizer, an antioxidant and a plasticizer having a structure other than the compound represented by the general formula (1) is used alone as an additive. Or it is preferable to contain 2 or more types of these. Furthermore, as other additives, a heat stabilizer, a fluorescent thickening agent, a flame retardant, and the like may be appropriately contained.
Examples of the ultraviolet absorber having a structure other than the compound represented by the general formula (1) include those described above.

  As the antioxidant, it is preferable that the cellulose ester-based resin composition of the present invention further contains a phosphorus-based stabilizer from the viewpoint that the thermal stability can be improved. Phosphorous stabilizers include phosphorous acid, phosphoric acid, phosphite esters, phosphate esters, etc. Among them, phosphites, phosphonites and the like are included because they contain trivalent phosphorus and easily exhibit a discoloration suppressing effect. Phosphites 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 and the like.

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

  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.

The phosphorus stabilizer used in the present invention can be mixed and contained in two or more types, but the total content of the phosphorus stabilizer is 0.0005 with respect to 100 parts by mass of the cellulose ester resin composition. It is preferable that it is -0.3 mass part, and it is more preferable that it is 0.001-0.1 mass part. 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, with respect to 100 parts by mass of the cellulose ester resin composition, 0.05 to 3 parts by mass of the compound represented by the general formula (1) and 0.0005 to 0.3 parts by mass of the phosphorus stabilizer Preferably there is.

As an antioxidant, the cellulose ester-based resin composition of the present invention further contains a hindered phenol-based stabilizer, which stabilizes the compound represented by the general formula (1), and the cellulose ester-based 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 stabilizer is a compound known as an antioxidant and may be a commercially available one. For example, 2,6-di-t-butyl-4-methylphenol, Ciba Specialty An antioxidant manufactured by Chemicals Co., Ltd. can be mentioned.
Although the hindered phenol stabilizer used for this invention can mix and contain 2 or more types, the total content rate of a hindered phenol stabilizer is 100 mass parts of cellulose ester-type resin compositions. 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and 0.001 to 0.1 part by mass. More preferably, it is a part.

As the plasticizer, phosphoric acid ester or carboxylic acid ester can be used. Examples of phosphate esters include triphenyl phosphate (TPP) and tricresyl phosphate (TCP). Representative examples of the carboxylic acid ester include phthalic acid esters and citric acid esters. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethylhexyl phthalate (DEHP). Examples of citrate esters include triethyl O-acetylcitrate (OACTE) and tributyl O-acetylcitrate (OACTB). Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.
The addition amount of the plasticizer is preferably 0.1 to 25% by mass in the cellulose ester resin composition, more preferably 1 to 20% by mass, and more preferably 3 to 15% by mass. Further preferred.

A preferable example of the light stabilizer is a compound represented by JP2009-242641A. Specifically, the compounds described in [0081] to [0128] of JP-A-2009-242641 are preferable. The compound represented by the general formula (TS-II) described in paragraph [0082] is particularly preferable.
The addition amount of the light stabilizer is preferably 100 parts by mass of the cellulose ester-based resin composition, preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, The amount is more preferably 1 part by mass, and further preferably 0.001 to 0.5 part by mass.

There is no particular limitation on the method for preparing the cellulose ester resin composition of the present invention by mixing the compound represented by the general formula (1) and a resin component such as cellulose ester.
When the compound represented by the general formula (1) is compatible with the resin component such as cellulose ester, the compound represented by the general formula (1) is directly added to the resin component such as cellulose ester. be able to. 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) may be dissolved in an auxiliary solvent having compatibility with a resin component such as cellulose ester and the solution may be added to the resin component such as cellulose ester. The compound represented by the general formula (1) may be dispersed in a high-boiling organic solvent or polymer, and the dispersion may be added to a resin component such as a cellulose ester.
The timing of addition and mixing may be before the resin component such as cellulose ester is formed by polymerization or after it is formed by polymerization.
In addition, the cellulose ester resin composition of the present invention may be formed by dissolving a cellulose ester 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.

  The cellulose ester-based resin composition of the present invention can be used for all applications in which a synthetic resin is used, but can be particularly suitably used for applications that may be exposed to sunlight or light including ultraviolet rays. Specific examples include, for example, optical films for image display devices (polarizing plate protective films, retardation plates, optical compensation films and other supports), glass substitutes and surface coating materials, residences, facilities, and transportation equipment. Coating materials for window glass, daylighting glass and light source protection glass, window films for houses, facilities, transportation equipment, interior / exterior materials for interiors, facilities, transportation equipment, etc. , Alkyd resin lacquer paint and coating film formed by the paint, acrylic lacquer paint and paint film formed by the paint, fluorescent light, mercury lamp and other light source members, precision machinery, electronic and electrical equipment members, Materials for shielding electromagnetic waves generated from various displays, containers or packaging materials for food, chemicals, chemicals, bottles, boxes, blisters Cups, special packaging, compact disc coats, agricultural or industrial sheet or film materials, printed materials, dyeing products, anti-fading agents such as dyes and pigments, polymer supports (for example, plastic parts such as machinery and automobile parts) Protective film, printed overcoat, inkjet media coating, laminated matte, optical light film, safety glass / windshield interlayer, electrochromic / photochromic application, overlaminate film, solar control film, sun cream, shampoo, rinse, Cosmetics such as hairdressing, textile products for clothing such as sportswear, stockings, and hats, and home interior products such as textiles, curtains, carpets, and wallpaper, medical equipment such as plastic lenses, contact lenses, artificial eyes, optical filters, bags Light display fill , Mention may be made of a prism, a mirror, an optical article such as a photographic material, the mold film, decal, anti-graffiti film, tape, ink and the like stationery, indicia plate, marking and the like and the surface coating material and the like.

Next, the molded product of the present invention will be described.
The molded article of the present invention can be molded from the cellulose ester resin composition of the present invention.
As the shape of the molded article of the present invention formed from the cellulose ester resin composition, a flat membrane shape, a powder shape, a spherical particle, a crushed particle, a massive continuous body, a fiber shape, a tubular shape, a hollow fiber shape, a granular shape, a plate shape, Any shape such as a porous shape may be used, but a thickness of 0.1 μm to 25 mm, for example, a film shape, a flat film shape, a plate, from the balance between the suppression of precipitation and bleed out and the long wave ultraviolet shielding effect It is preferable that it is a shape. In the case of a film, it is preferably 20 μm to 1000 μm, and more preferably 30 μm to 250 μm.
Further, from the viewpoint of the long-wave ultraviolet shielding effect, the molded product of the present invention preferably contains 0.1 to 10.0 g / m ^{2 of the} compound represented by the general formula (1). more preferably contained 0 g / ^{m 2,} and more preferably contains 0.1-5 g / ^{m 2.} If it is this range, since an ultraviolet-ray can be cut efficiently, without coloring by ultraviolet absorber addition, it is preferable.

Since the cellulose ester-based resin composition of the present invention contains a cellulose ester-based resin, it can be made transparent, and in that case, it can be molded as an ultraviolet absorption filter or an ultraviolet absorption film.
In this case, the cellulose ester resin composition of the present invention can contain other transparent resins. Examples of other transparent resins include polycarbonate, polyamide, polyester (eg, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4. , 4'-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polyethylene, polypropylene, polymethylpentene), polymethyl methacrylate, syndiotactic polystyrene, polysulfone, polyethersulfone , Polyether ketone, polyether imide, polyoxyethylene and the like.
The molded product of the present invention obtained from the cellulose ester-based resin composition can be a transparent support, and the transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. preferable.

  The molded article of the present invention is molded from the cellulose ester resin composition and has an excellent long-wave ultraviolet absorbing ability, so that it can be used as an ultraviolet absorbing filter or a container and protects a compound that is sensitive to ultraviolet rays. You can also. For example, the molded article of the present invention can be obtained as a container or the like by molding the cellulose ester resin composition by any method such as extrusion molding or injection molding. Moreover, it can also be set as the molded article by which the ultraviolet absorber film which consists of the said cellulose ester-type resin composition was coated by apply | coating and drying the solution of the cellulose ester-type resin composition of this invention to the molded article produced separately. .

  In order to effectively utilize the long-wave ultraviolet shielding effect and transparency of the cellulose ester resin composition of the present invention, the cellulose ester resin composition of the present invention is particularly suitable for solar cell backsheets and windows. It is suitably used for applications of adhesive films, food / medical packaging films, agricultural films, optical films, and fibers.

  In the present invention, the matters described in paragraph numbers [0192] to [0230] of JP2009-209343A can be applied.

The packaging material containing the cellulose ester resin composition of the present invention will be described. The packaging material containing the cellulose ester resin composition of the present invention may be a packaging material made of any type of polymer as long as it contains the cellulose ester resin composition. For example, thermoplastic resin, polyvinyl alcohol, polyvinyl chloride, styrene resin, polyolefin, ROMP and the like can be mentioned. For example, a resin having an inorganic vapor-deposited thin film layer may be used. For example, paper coated with a resin containing a cellulose ester resin composition may be used.
The packaging material containing the cellulose ester-based resin composition of the present invention may package any foods, beverages, drugs, cosmetics, personal care products, and the like. For example, food packaging, colored liquid packaging, packaging for the described liquid preparations, pharmaceutical container packaging, sterilization packaging for medical products, photographic photosensitive material packaging, photographic film packaging, UV curable ink packaging, shrink label, and the like.

  The packaging material containing the cellulose ester resin composition of the present invention may be, for example, a transparent package or a light-shielding package.

  The packaging material containing the cellulose ester-based resin composition of the present invention has not only ultraviolet shielding properties, for example, but may also have other performances. Examples thereof include those having a gas barrier property, those having an oxygen indicator, and those in which a cellulose ester resin composition and a fluorescent brightening agent are combined.

  You may manufacture the packaging material containing the cellulose-ester-type resin composition of this invention using any method. Examples thereof include a method for forming an ink layer, a method for melt extrusion of a resin containing a cellulose ester resin composition, a method for coating on a base film, and a method for dispersing a cellulose ester resin composition in an adhesive. .

For example, a film containing the cellulose ester resin composition of the present invention can be produced by a solvent cast method. In the solvent cast method, a film is produced using a solution (dope) obtained by dissolving a cellulose ester resin composition in an organic solvent.
The organic solvent is a solvent selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. It is preferable to contain.
The ether, ketone and ester may have a cyclic structure. A compound having two or more functional groups of ether, ketone and ester (that is, —O—, —CO— and —COO—) can also be used as the organic solvent. The organic solvent may have another functional group such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more types of functional groups, the number of carbon atoms is preferably within the above-described preferable range of carbon atoms of the solvent having any functional group.

Examples of the ether having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole.
Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone.
Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.
Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.
The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The proportion of halogenated hydrocarbon hydrogen atoms substituted with halogen is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. More preferred is 40 to 60 mol%. Methylene chloride is a representative halogenated hydrocarbon. Two or more organic solvents may be mixed and used.

A cellulose ester resin composition solution can be prepared by a general method comprising treating at a temperature of 0 ° C. or higher (ordinary temperature or high temperature). The solution can be prepared by using a dope preparation method and apparatus in a normal solvent cast method. In the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly methylene chloride) as the organic solvent.
The amount of the cellulose ester-based resin composition is adjusted so as to be contained in an amount of 10 to 40% by mass in the obtained solution. The amount of the cellulose ester resin composition is more preferably 10 to 30% by mass. Arbitrary additives described later may be added to the organic solvent (main solvent).
The solution can be prepared by stirring the cellulose ester resin composition and the organic solvent at room temperature (0 to 40 ° C.). The high concentration solution may be stirred under pressure and heating conditions. Specifically, cellulose acetate and an organic solvent are placed in a pressure vessel and sealed, and stirred while heating to a temperature not lower than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil.
The heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., more preferably 80 to 110 ° C.

Each component may be coarsely mixed in advance and then placed in a container. Moreover, you may put into a container sequentially. The container needs to be configured so that it can be stirred. The container can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may utilize the raise of the vapor pressure of the solvent by heating. Or after sealing a container, you may add each component under pressure.
When heating, it is preferable to heat from the outside of the container. For example, a jacket type heating device can be used. The entire container can also be heated by providing a plate heater outside the container and piping to circulate the liquid.
It is preferable to provide a stirring blade inside the container and stir using this. The stirring blade preferably has a length that reaches the vicinity of the wall of the container. A scraping blade is preferably provided at the end of the stirring blade in order to renew the liquid film on the vessel wall.
Instruments such as a pressure gauge and a thermometer may be installed in the container. Each component is dissolved in a solvent in the container. The prepared dope is taken out of the container after cooling, or taken out and then cooled using a heat exchanger or the like.

A solution can also be prepared by a cooling dissolution method. In the cooling dissolution method, the cellulose ester resin composition can be dissolved in an organic solvent that is difficult to dissolve by a normal dissolution method. In addition, even if it is a solvent which can melt | dissolve a cellulose-ester-type resin composition with a normal melt | dissolution method, there exists an effect that a uniform solution can be obtained rapidly according to a cooling melt | dissolution method.
In the cooling dissolution method, first, a cellulose ester resin composition is gradually added to an organic solvent at room temperature while stirring.
The amount of the cellulose ester resin composition is preferably adjusted so as to be contained in the mixture in an amount of 10 to 40% by mass. The amount of the cellulose ester resin composition is more preferably 10 to 30% by mass. Furthermore, you may add arbitrary additives in a mixture.

The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). The mixture of the cellulose ester resin composition and the organic solvent is solidified by cooling.
The cooling rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The faster the cooling rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling until the final cooling temperature is reached.

Furthermore, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), the cellulose ester resin composition dissolves in the organic solvent. . The temperature may be increased by simply leaving it at room temperature or in a warm bath.
The heating rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The higher the heating rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The heating rate is a value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating until the final heating temperature is reached. .
A uniform solution is obtained as described above. If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution with the naked eye.

In the cooling dissolution method, it is desirable to use a sealed container in order to avoid moisture mixing due to condensation during cooling. In the cooling and heating operation, when the pressure is applied during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container.
In addition, according to the measurement by a differential scanning calorimeter (DSC), the 20 mass% solution which melt | dissolved cellulose acetate (acetylation degree: 60.9%, viscosity average polymerization degree: 299) in methyl acetate by the cooling dissolution method is. In the vicinity of 33 ° C., there exists a quasi-phase transition point between a sol state and a gel state, and a uniform gel state is obtained below this temperature. Therefore, this solution needs to be maintained at a temperature equal to or higher than the pseudo phase transition temperature, preferably about the gel phase transition temperature plus about 10 ° C. However, this pseudo phase transition temperature varies depending on the degree of acetylation of cellulose acetate, the degree of viscosity average polymerization, the concentration of the solution, and the organic solvent used.

A cellulose ester resin composition film is produced from the prepared cellulose ester resin composition solution (dope) by a solvent cast method. It is preferable to add a retardation increasing agent to the dope.
The dope is cast on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust the concentration of the dope before casting so that the solid content is 18 to 35%. The surface of the drum or band is preferably finished in a mirror state. The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less.

When the dope (cellulose ester resin composition solution) is cast on a band, it is dried for 10 seconds to 90 seconds, preferably 15 seconds to 90 seconds in the first half of drying before stripping, in a substantially windless manner. The process to do is performed. In the case of casting on a drum, in the first half of drying before peeling, a step of drying in a substantially windless manner for 1 second to 10 seconds, preferably 2 seconds to 5 seconds is performed. “Drying before stripping” refers to drying from when a dope is applied on a band or drum until stripping as a film. In addition, the “first half” refers to a process before half of the total time required from dope application to stripping. “Substantially no wind” means that a wind speed of 0.5 m / s or more is not detected at a distance within 200 mm from the band surface or drum surface (the wind speed is less than 0.5 m / s).
The first half of the pre-peeling drying is usually about 30 to 300 seconds on the band, but is dried for 10 to 90 seconds, preferably 15 to 90 seconds, without wind. When it is on the drum, it is usually about 5 to 30 seconds, but it is dried without wind for 1 to 10 seconds, preferably 2 to 5 seconds. The atmospheric temperature is preferably 0 ° C to 180 ° C, more preferably 40 ° C to 150 ° C. The operation of drying without wind can be carried out at any stage in the first half of the drying before peeling, but it is preferably carried out immediately after casting. When the time for drying without wind is less than 10 seconds on the band (less than 1 second on the drum), it is difficult for the additive to be uniformly distributed in the film, and when it exceeds 90 seconds (drum In the above case, if it exceeds 10 seconds), the film will be peeled off due to insufficient drying, and the surface condition of the film will deteriorate.
Drying can be performed by blowing an inert gas for a time other than drying without wind in drying before peeling. The air temperature at this time is preferably 0 ° C to 180 ° C, more preferably 40 ° C to 150 ° C.

  As for the drying method in the solvent casting method, U.S. Pat. Nos. 2,336,310, 2,367,603, 2,429,078, 2,429,297, 2,429,978, 2,607,704, 2,739,69, 2,739,070, British Patents 6,407,331, 7,36892 Nos. 45-4554, 49-5614, JP-A-60-176834, JP-A-60-203430, and JP-A-62-115035. Drying on the band or drum can be performed by blowing air or an inert gas such as nitrogen.

  The obtained film can be peeled off from the drum or band and further dried with high-temperature air whose temperature is successively changed from 100 to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

  Using the prepared cellulose ester resin composition solution (dope), two or more layers can be cast to form a film. In this case, it is preferable to produce a cellulose ester resin composition film by a solvent cast method. The dope is cast on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust the concentration of the dope before casting so that the solid content is in the range of 10 to 40%. The surface of the drum or band is preferably finished in a mirror state.

  When casting a plurality of cellulose ester resin composition liquids of two or more layers, it is possible to cast a plurality of cellulose ester resin composition solutions, provided at intervals in the direction of travel of the support. You may produce a film, casting and laminating | stacking the solution containing a cellulose-ester-type resin composition from several casting openings, respectively. For example, the methods described in JP-A-61-158414, JP-A-1-122419, and JP-A-11-198285 can be used. Moreover, it can also be formed into a film by casting the cellulose ester resin composition solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-947245, JP-A-61-104413, JP-A-61-158413, and JP-A-6-134933. The method described in each publication can be used. Further, the flow of the high-viscosity cellulose ester resin composition solution described in JP-A-56-162617 is wrapped with a low-viscosity cellulose ester resin composition solution, and the high and low-viscosity cellulose ester resin composition A method for casting a cellulose ester resin composition film in which the solution is simultaneously extruded can also be used.

Also, using two casting ports, the film formed on the support by the first casting port is peeled off, and the second casting is performed on the side that was in contact with the support surface to produce a film. You can also For example, the method described in Japanese Patent Publication No. 44-20235 can be mentioned.
As the cellulose ester resin composition solution to be cast, the same solution may be used, or different cellulose ester resin composition solutions may be used. In order to give a function to a plurality of cellulose ester resin composition layers, a cellulose ester resin composition solution corresponding to the function may be extruded from each casting port. Furthermore, the cellulose ester resin composition solution of the present invention can be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, an ultraviolet absorption layer, a polarizing layer, etc.). .

  In the conventional single-layer liquid, it is necessary to extrude a high-concentration and high-viscosity cellulose ester resin composition solution in order to obtain a necessary film thickness. In that case, the stability of the cellulose ester-based resin composition solution is poor, and solids are generated. This often causes problems such as defects and poor flatness. As a solution to this problem, by casting a plurality of cellulose ester resin composition solutions from the casting port, it is possible to extrude a highly viscous solution onto the support at the same time. In addition to producing a film-like film, the use of a concentrated cellulose ester-based resin composition solution can achieve a reduction in drying load and increase the production speed of the film. The preferred width of the film is 0.5-5 m, more preferably 0.7-3 m. The preferable winding length of a film is 300-30000m, More preferably, it is 500-10000m, More preferably, it is 1000-7000m.

  The container containing the cellulose ester resin composition of the present invention will be described. The container containing the cellulose ester resin composition of the present invention may be a container made of any type of polymer as long as it contains the cellulose ester resin composition. Examples include thermoplastic resin containers, polyester containers, polyethylene naphthalate containers, polyethylene containers, cyclic olefin resin composition containers, plastic containers, and transparent polyamide containers. For example, it may be a paper container containing resin. It may be a glass container having a cellulose ester resin layer.

  The container containing the cellulose ester-based resin composition of the present invention may be used to contain any foods, beverages, drugs, cosmetics, personal care products, shampoos and the like. Liquid fuel storage container, golf ball container, food container, liquor container, drug filling container, beverage container, oil-based food container, analytical reagent solution container, instant noodle container, light-resistant cosmetic container, pharmaceutical container, high purity Examples thereof include chemical liquid containers, liquid agent containers, ultraviolet curable ink containers, and W plastic ampules.

  The container containing the cellulose ester-based resin composition of the present invention may not only have ultraviolet blocking properties but also have other performances. For example, an antibacterial container, a flexible container, a dispenser container, a biodegradable container, etc. are mentioned.

  You may manufacture the container containing the cellulose-ester-type resin composition of this invention using any method. For example, a method using two-layer stretch blow molding, a multilayer coextrusion blow molding method, a method of forming an ultraviolet absorbing layer on the outside of a container, a method using a shrinkable film, a method using a supercritical fluid, and the like can be mentioned.

  The paint and coating film containing the cellulose ester resin composition of the present invention will be described. The coating material containing the cellulose ester resin composition of the present invention may be a coating material composed of any component as long as it contains the compound represented by the general formula (1). For example, an acrylic resin system, a urethane resin system, an amino alkyd resin system, an epoxy resin system, a silicone resin system, a fluororesin system, etc. are mentioned. These resins can be arbitrarily mixed with a main agent, a curing agent, a diluent, a leveling agent, a repellant and the like.

  For example, when acrylic urethane resin or silicon acrylic resin is selected as the transparent resin component, polyisocyanate is used as the curing agent, hydrocarbon solvents such as toluene and xylene are used as the diluent, isobutyl acetate, butyl acetate, amyl acetate, etc. Alcohol solvents such as ester solvents, isopropyl alcohol, and butyl alcohol can be used. Here, the acrylic urethane resin refers to an acrylic urethane resin obtained by reacting a methacrylic ester (typically methyl), a hydroxyethyl methacrylate copolymer and a polyisocyanate. The polyisocyanate in this case includes tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and the like. Other examples of the transparent resin component include polymethyl methacrylate, polymethyl methacrylate styrene copolymer, polyvinyl chloride, and polyvinyl acetate. Further, in addition to these components, a leveling agent such as an acrylic resin or a silicone resin, an anti-fogging agent such as a silicone or acrylic resin, and the like can be blended as necessary.

  The intended use of the paint containing the cellulose ester resin composition of the present invention may be any use. For example, ultraviolet shielding paint, ultraviolet / near infrared shielding paint, electromagnetic shielding paint, clear paint, metallic paint composition, cationic electrodeposition paint, antibacterial and lead-free cationic electrodeposition paint, powder paint, aqueous intermediate paint, aqueous Metallic paints, water-based clear paints, top coat paints used in automobiles, buildings, civil engineering products, curable paints, coating film forming compositions used for plastic materials such as automobile bumpers, metal plate paints, cured gradient paints Films, wire coating materials, automotive repair coatings, anion electrodeposition coatings, automotive coatings, painted steel sheet coatings, stainless steel coatings, lamp insecticide coatings, UV curable coatings, special antibacterial coatings, and eye strain prevention coatings , Antifogging paint, super weather resistant paint, gradient paint, photocatalyst paint, peelable paint, concrete peeling paint, anticorrosion paint, protective paint, water repellent protective paint, prevention of glass sheet scattering Paint, alkali-soluble protective paint, aqueous temporary protective paint composition, floor paint, emulsion paint, two-part aqueous paint, one-part paint, UV curable paint, electron beam curable paint composition, thermosetting Examples thereof include coating compositions, aqueous coatings for baking lacquers, powder coatings and slurry coatings, repair coatings, powder coating water dispersions, plastic coatings, and electron beam curable coatings.

  The paint containing the cellulose ester resin composition of the present invention is generally composed of a paint (including a transparent resin component as a main component) and a cellulose ester resin composition, and preferably 0 to 20 mass% of the cellulose ester resin composition. % Composition. The thickness at the time of application is preferably 2 to 1000 μm, more preferably 5 to 200 μm. The method of applying these paints is arbitrary, but there are a spray method, a dipping method, a roller coat method, a flow coater method, a flow coating method and the like. Although drying after application varies depending on the paint components, it is preferably performed at room temperature to 120 ° C. for about 10 to 90 minutes.

  The coating film containing the cellulose ester-based resin composition of the present invention is a coating film including the compound represented by the general formula (1), and is formed using a paint including the cellulose ester-based resin composition of the present invention. The coated film.

  The ink containing the cellulose ester resin composition of the present invention will be described. The ink containing the cellulose ester resin composition of the present invention may be any form of ink as long as it contains the cellulose ester resin composition. Examples thereof include dye ink, pigment ink, water-based ink, and oil-based ink. Moreover, you may use for any use. For example, screen printing ink, flexographic printing ink, gravure printing ink, lithographic offset printing ink, letterpress printing ink, UV ink, EB ink and the like can be mentioned. Examples thereof include inkjet ink photochromic ink, thermal transfer ink, masking ink, security ink, and DNA ink.

  Any form obtained by using an ink containing the cellulose ester-based resin composition of the present invention is also included in the present invention. Examples thereof include a printed material, a laminate obtained by laminating the printed material, a packaging material and container using the laminate, and an ink receiving layer.

  The fiber containing the cellulose ester resin composition of the present invention will be described. The fiber containing the cellulose ester resin composition of the present invention may be a fiber containing any kind of polymer as long as it contains the cellulose ester resin composition. Examples thereof include polyester fiber, polyphenylene sulfide fiber, polyamide fiber, aramid fiber, polyurethane fiber, and cellulose fiber.

  The fiber containing the cellulose ester resin composition of the present invention may be produced by any method. For example, a polymer preliminarily containing the compound represented by the general formula (1) may be processed into a fiber shape. For example, a compound represented by the general formula (1) may be processed with respect to a fiber processed into a fiber shape. You may process using the solution etc. which contain. You may process using a supercritical fluid.

  The fiber containing the cellulose ester resin composition of the present invention can be used for various applications. For example, clothing, lining, underwear, blankets, socks, artificial leather, insect-proof mesh sheets, construction mesh sheets, carpets, special moisture / water-proof sheets, non-woven fabrics, ultrafine fibers, sheet materials made of fibers, breathable cool clothing Waterproof sheet, flame retardant artificial suede-like structure, resin tarpaulin, film agent, exterior wall material, agricultural house, net for building materials, mesh, filter substrate, antifouling film agent, mesh fabric, land net, underwater Examples include nets, ultrafine fibers, woven fabrics, airbag fabrics, and UV-absorbing fiber products.

  The building material containing the cellulose ester resin composition of the present invention will be described. The building material containing the cellulose ester resin composition of the present invention may be a building material containing any type of polymer as long as it contains the cellulose ester resin composition. For example, vinyl chloride type, olefin type, polyester type, polyphenylene ether type, polycarbonate type and the like can be mentioned.

  The building material containing the cellulose ester resin composition of the present invention may be produced by any method. For example, it may be formed into a desired shape using a material containing the cellulose ester resin composition, or may be formed by laminating a material containing the cellulose ester resin composition, or the general formula (1) ) Or a coating layer containing the cellulose ester resin composition may be applied.

  The building material containing the cellulose ester resin composition of the present invention can be used for various applications. For example, exterior building materials, wooden structures for building materials, roofing materials for building materials, antibacterial building materials, base materials for building materials, antifouling building materials, flame retardant materials, ceramic building materials, decorative building materials, painted articles for building materials, makeup Materials, nets for building materials, moisture permeable waterproof sheets for building materials, mesh sheets for building work, film for covering materials for building materials, coating materials for building materials, adhesive compositions for building materials, civil engineering and building structures, pedestrian coating materials, Sheet-like photocurable resin, protective coating for wood, cover for pushbutton switch, bonding sheet agent, base material for building material, wallpaper, cellulose ester film for covering, cellulose ester film for covering molded parts, flooring, etc. .

  The recording medium containing the cellulose ester resin composition of the present invention will be described. The recording medium containing the cellulose ester resin composition of the present invention may be any as long as it contains the compound represented by the general formula (1). Examples thereof include an ink jet recording medium, an image receiving sheet for sublimation transfer, an image recording medium, a thermal recording medium, a reversible thermal recording medium, and an optical information recording medium.

  An image display device including the cellulose ester resin composition of the present invention will be described. The image display device containing the cellulose ester resin composition of the present invention may be any one as long as it contains the compound represented by the general formula (1). For example, an image display device using the described electrochromic element, an image display device called so-called electronic paper, a plasma display, an image display device using an organic EL element, and the like can be given. The cellulose ester-based resin composition of the present invention may be, for example, one that forms an ultraviolet absorbing layer in a laminated structure, or one that includes a cellulose ester-based resin composition in a necessary member such as a circularly polarizing plate. .

  The cover for solar cells containing the cellulose ester-type resin composition of this invention is demonstrated. The solar cell applied in the present invention may be a solar cell comprising any type of element such as a crystalline silicon solar cell, an amorphous silicon solar cell, and a dye-sensitized solar cell. In crystalline silicon solar cells and amorphous silicon solar cells, a cover material is used as a protective member that imparts antifouling, impact resistance, and durability. In addition, since a metal oxide semiconductor that is activated by light (especially ultraviolet rays) in a dye-sensitized solar cell is used as an electrode material, the dye adsorbed as a photosensitizer deteriorates, and the photovoltaic power generation efficiency gradually increases. There is a problem of lowering, and it has been proposed to provide an ultraviolet absorbing layer.

  The solar cell cover containing the cellulose ester resin composition of the present invention may contain any type of polymer. Examples include polyester, thermosetting transparent resin, α-olefin polymer, polypropylene, polyether sulfone, acrylic resin, and transparent fluororesin.

  You may manufacture the cover for solar cells containing the cellulose-ester-type resin composition of this invention by any method. For example, an ultraviolet absorbing layer may be formed, layers each containing a cellulose ester resin composition may be laminated, or the resin of the filler layer may be included in the cellulose ester resin composition. A film may be formed from the containing polymer.

  The solar cell cover containing the cellulose ester-based resin composition of the present invention may have any shape. Examples thereof include a film, a sheet, a laminated film, and a cover glass structure. The sealing material may contain a cellulose ester resin composition.

  The glass and glass film containing the cellulose ester resin composition of the present invention will be described. As long as the glass and glass film containing the cellulose-ester-type resin composition of this invention contain the compound represented by the said General formula (1), any form may be sufficient as it. Moreover, you may use for any use. For example, heat-shielding glass window glass, colored glass, UV sharp-cut glass for high-intensity light sources such as mercury lamps and metal halide lamps, frit glass, UV-shielding glass for vehicles, colored heat-ray absorbing glass, fluorescent whitening agent UV absorption Insulating glass, automotive UV heat shield glass, exterior stained glass, water repellent UV infrared absorbing glass, glass for vehicle head-up display devices, light control and heat insulation multi-layer window, UV infrared cut glass, UV cut glass, for windows UV-infrared absorbing glass, UV-blocking antifouling film for windows, translucent panel for cultivation room, UV-infrared absorbing and low-transmitting glass, low reflectance and low-transmitting glass, edgelight device, rough surface forming plate glass, laminated glass for display, conductive Glass with light-sensitive film, anti-glare glass, ultraviolet infrared absorption medium transmission glass, Window glass for privacy protection, glass for anti-fogging vehicles, glass for paving materials, glass plate with water droplet adhesion prevention and heat ray blocking properties, ultraviolet and infrared absorption bronze glass, laminated glass, glass with ID identification function, for PDP Examples include an optical filter and a skylight. The glass containing the cellulose ester resin composition of the present invention may be made by any method.

  Other examples of use include light source covers for lighting devices, artificial leather, sports goggles, deflection lenses, hard coats for various plastic products, hard coats for attaching to the outside of windows, window covering films, high-definition anti-glare hard coat films, Antistatic hard coat film, transparent hard coat film, anti-counterfeit book described in JP-A-2002-113937, turf purpura inhibitor, resin film sheet bonding sealant, light guide, rubber coating agent , Agricultural coating materials, dyed candles, fabric rinse agent compositions, prism sheets, special protective layer transfer sheets, photo-curing resin products, floor sheets, light-shielding printing labels, oiling cups, hard coating coated articles, intermediate Transfer recording media, artificial hair, low-temperature heat-shrinkable film for labels, fishing equipment, microbeads, pre-coated metal plates, thin Film, heat-shrinkable film, label for in-mold molding, projection screen, decorative sheet, hot melt adhesive, adhesive, electrodeposition coat, base coat, wood surface protection, light control material, light control film, light control glass, anti-reflection Examples include a lantern, a touch panel, a sealing agent for bonding a resin film sheet, a polycarbonate film coating, an optical fiber tape, and a solid wax.

Next, a method for evaluating the light resistance of the polymer material will be described. As a method for evaluating the light resistance of a polymer material, “Polymer Light Stabilization Technology” (CMC Co., Ltd., 2000), pages 85 to 107, “Basic and Physical Properties of High-Functional Paint” (CMC Co., Ltd.) , 2003) pages 314 to 359, "Durability of polymer materials and composite products" (CMC Corporation, 2005), "Extension of polymer material life and environmental measures" (CMC Corporation, 2000), H.C. Zweifel edition “Plastics Additives Handbook 5th Edition” (Hanser Publishers) 238-244, Katsura Tadahiko “Basic Science 2 Science of Plastic Packaging Containers” (Japan Packaging Society, 2003) Chapter 8 it can.
The evaluation for each application can be achieved by the following known evaluation method.
The deterioration of the polymer material due to light is determined according to JIS-K7105: 1981, JIS-K7101: 1981, JIS-K7102: 1981, JIS-K7219: 1998, JIS-K7350-1: 1995, JIS-K7350-2: 1995, JIS. It can be evaluated by the method of -K7350-3: 1996, JIS-K7350-4: 1996 and a method referring to this.

The light resistance when used as a packaging / container application can be evaluated by the method of JIS-K7105 and a method referring to this. Specific examples include light transmittance of bottle body, transparency evaluation, sensory test evaluation of bottle contents after UV exposure using xenon light source, haze value evaluation after xenon lamp irradiation, haze value evaluation as halogen lamp light source , Yellowness evaluation using blue wool scale after exposure to mercury lamp, haze value evaluation using sunshine weatherometer, colorability visual evaluation, UV transmittance evaluation, UV blocking rate evaluation, light transmittance evaluation, in ink container Ink viscosity evaluation, light transmittance evaluation, sample in container after sun exposure, color difference ΔE evaluation, UV transmittance evaluation after white fluorescent light irradiation, light transmittance evaluation, color difference evaluation, light transmittance evaluation, haze value evaluation , Color tone evaluation, yellowness evaluation, shading evaluation, L ^* a ^* b ^* whiteness evaluation using the color system color difference formula, post-exposure support for each wavelength after spectral separation of xenon light Color difference ΔEa ^* b ^* in samples, after UV exposure, UV absorption rate evaluation, film tensile elongation after exposure using a sunshine weather meter, antibacterial evaluation after xenon weather meter exposure, after fluorescent light irradiation Evaluation of discoloration of packaging contents, peroxide value evaluation of oil after exposure to fluorescent lamps for bottles filled with salad oil, color evaluation, evaluation of difference in absorbance after irradiation with chemical lamp, retention of surface gloss after exposure using sunshine weatherometer Rate, appearance evaluation, color difference after exposure using a sunshine weatherometer, bending strength evaluation, shading ratio evaluation, evaluation of peroxide generation in kerosene, and the like.

The long-term durability when used for paints and coatings is JIS-K5400, JIS-K5600-7-5: 1999, JIS-K5600-7-6: 2002, JIS-K5600-7-7: 1999, JIS. -K5600-7-8: It can be evaluated by the method of 1999, JIS-K8741 and a method referring to this. Color difference ΔEa ^* b ^* in the color density and CIE ^L * ^a * ^{b *} color coordinates after exposure by a xenon light resistance test machine and UVCON device and specific examples thereof include evaluation using residual gloss, xenon arc light for quartz slides on the film Absorbance evaluation after exposure using a tester, evaluation using a fluorescent lamp in wax, color density after exposure to UV lamp and color difference ΔEa ^* b ^* in CIE L ^* a ^* b ^* color coordinates, metal weather weathering tester Hue evaluation after exposure using a glass, gloss retention evaluation after an exposure test using a metal hydride lamp, evaluation using a color difference ΔEa ^* b ^* , evaluation of glossiness after exposure using a sunshine carbon arc light source, metal weather evaluation using the color difference after exposure using a weatherometer ΔEa ^* b ^*, gloss retention, appearance evaluation, sunshine weatherometer Gloss retention evaluation after exposure using Ta, evaluation using color difference after exposure using a QUV weathering tester ΔEa ^* b ^*, gloss retention evaluation, post exposure gloss retention using a sunshine weatherometer Evaluation, Appearance evaluation after exposure using sunshine weatherometer on coated plate Gloss retention after exposure using sunshine weatherometer, Evaluation of change in lightness value, Evaluation of coating deterioration after exposure to Ducycle WOM for coating Appearance evaluation, UV transmittance evaluation of coating film, UV blocking rate evaluation of coating film, time comparison evaluation with coating film gloss retention 80% using sunshine weatherometer, exposure using dew panel light control weather meter use after the rust evaluation, the strength of the concrete evaluation of painted formwork after the outdoor exposure, color difference after weathering the ΔEa ^* b ^* Evaluation, cross-cut adhesion evaluation, the surface appearance evaluation, gloss retention evaluation after weathering, yellowing after exposure using a carbon arc light source (.DELTA.YI) Evaluation, and the like.

The light resistance when used as an ink application can be evaluated by the method of JIS-K5701-1: 2000, JIS-K7360-2, ISO105-B02 and a method referring to this. Specifically, evaluation by measurement of color density and CIE L ^* a ^* b ^* color coordinates after exposure using an office fluorescent lamp, a fading tester, evaluation of electrophoresis after exposure to ultraviolet rays using a xenon arc light source, Density evaluation of printed matter using a xenon fade meter, evaluation of ink removal using a 100 W chemical lamp, evaluation of dye remaining rate of an image forming site using a weather meter, evaluation of choking of printed matter using an eye super UV tester, and discoloration evaluation, xenon fade For the printed matter after exposure to the meter, evaluation using the color difference ΔEa ^* b ^* in the CIE L ^* a ^* b ^* color coordinates, evaluation of the reflectance after exposure using a carbon arc light source, and the like can be given.

  The light resistance of the solar cell module can be evaluated by the method of JIS-C8917: 1998, JIS-C8938: 1995 and a method referring to this. Specifically, IV measurement after exposure with a light source equipped with a correction filter for solar simulation on a xenon lamp, evaluation of photovoltaic power generation efficiency, evaluation of discolored gray scale after exposure using a sunshine weatherometer and a fade meter , Color, appearance adhesion evaluation and the like.

The light resistance of the fiber and the textile product is JIS-L1096: 1999, JIS-A5905: 2003, JIS-L0842, JIS-K6730, JIS-K7107, DIN75.202, SAEJ1885, SN-ISO-105-B02, AS / NZS4399. This method can be evaluated by the above method and a method referring to this method. Evaluation of UV transmittance, evaluation of discoloration of blue scale after exposure using xenon light source, carbon arc light source, evaluation of UV cut rate described, evaluation of UV blocking property, change of blue scale after exposure using carbon arc light source after dry cleaning Fading evaluation, brightness index after exposure using a fade meter, color difference ΔE ^* evaluation based on chromaticness index, tensile strength evaluation after exposure using a UV tester, sunshine weatherometer, total transmittance evaluation, strength retention evaluation , UVF (UPF) evaluation, discoloration gray scale evaluation after exposure using a high-temperature fade meter, appearance evaluation after outdoor exposure, yellowness (YI) after yellow exposure, yellowness (ΔYI) evaluation, regulations For example, reflectivity evaluation.

The light resistance of building materials can be evaluated by the method of JIS-A1415: 1999 and a method referring to this. Specifically, surface color evaluation after exposure using a sunshine weatherometer, appearance evaluation after exposure using a carbon arc light source, appearance evaluation after exposure using an eye super UV tester, absorbance evaluation after exposure, Chromaticity after exposure, color difference evaluation, evaluation using CIE L ^* a ^* b ^* color difference after exposure using a metal hydride light source, evaluation using color difference ΔEa ^* b ^* in color coordinates, evaluation of gloss retention, Japanese Patent Laid-Open No. 10-44352 Gazette, JP-A No. 2003-111538, evaluation of haze value change after exposure using sunshine weather meter, evaluation of elongation retention using tensile tester after exposure, evaluation of UV transmittance after solvent immersion, eye super Appearance visual evaluation after exposure using UV tester, gloss rate change evaluation after QUV test, gloss retention after exposure using sunshine weatherometer Value, evaluation using black light blue fluorescent color difference after ultraviolet exposure using a lamp ΔEa ^* b ^*, adhesion retention evaluation after exposure using Kobukon accelerated tester, ultraviolet screening assessment, especially outdoor exposure (JIS- A1410) Appearance evaluation, total light transmittance evaluation, haze change evaluation, tensile shear bond strength evaluation, total light transmittance evaluation after exposure using a xenon weatherometer, haze evaluation, yellowing degree evaluation, sunshine weather Examples include yellowing degree (ΔYI) after exposure using an ohmmeter, evaluation of residual ratio of ultraviolet absorbers, and the like.

The light resistance when used as a recording medium can be evaluated by the method of JIS-K7350 and a method referring to this. Specifically, the background color difference change evaluation in the printed part after the fluorescent lamp irradiation, the image density residual rate evaluation by the exposure using the xenon weather meter, the optical reflection density change evaluation by the exposure using the xenon weather meter, the Suntest CPS light L ^* a ^* b ^* post-exposure yellowing evaluation using an amber tester, fading evaluation after exposure using a fade meter, visual discoloration evaluation after exposure using a xenon fade meter, indoor sunlight Evaluation of color density retention after exposure, evaluation of color density retention after exposure using a xenon weather meter, evaluation of C / N after exposure using a fade meter, evaluation of fog density after exposure to fluorescent light, use fluorescent light There optical reflection density evaluation after exposure, erasability evaluation, color difference Delta] E ^* evaluation after exposure using Atlas fade meter, a carbon arc fade menu Fading visually after exposure using a coater evaluation, the organic EL element color conversion characteristic retention evaluation, the organic EL display luminance measurement evaluation after exposure by a xenon discoloration tester and the like.

  As other evaluation methods, it can be evaluated by the method of JIS-K7103 and ISO / DIS9050 and a method referring to this. Specifically, the appearance of the polycarbonate-coated film after exposure with a UV tester, the blue scale evaluation after exposure to ultraviolet rays on artificial hair, the evaluation of the treated water contact angle for evaluation after exposure using an accelerated weathering tester, Visual evaluation of images projected on a projection screen after exposure using the weathering tester described in Japanese Unexamined Patent Publication No. 2005-55615, surface deterioration of the specimen after exposure using a sunshine weather meter, metal weather meter, visual inspection of changes in design Evaluation, visual visual evaluation after exposure to lighting using a metal lamp reflector Evaluation of light transmittance of bottle labels, evaluation of deterioration of polypropylene after exposure using a xenon weather meter, hard coat using a sunshine weatherometer Film degradation assessment, substrate degradation assessment, hydrophilicity assessment, scratch resistance assessment Grayscale color difference evaluation of artificial leather after exposure using a xenon lamp light source, evaluation of liquid crystal device characteristics after exposure using a mercury lamp, adhesion evaluation after exposure using a sunshine weatherometer, evaluation of the degree of purpura on the turf, xenon Post-exposure UV transmittance evaluation using an arc light source, tensile strength evaluation, concrete adhesion rate evaluation, post-exposure appearance evaluation using a sunshine weatherometer, coating film adhesion evaluation, yellow after exposure using a carbon arc light source Degree of change, adhesion evaluation, adhesion performance evaluation using an ultraviolet fade meter, insect flying suppression evaluation during lighting, yellowing degree (ΔYI) evaluation of laminated glass using an eye super UV tester, QUV irradiation, moisture resistance test Surface appearance evaluation, gloss retention evaluation, dew panel light control weather meter Color difference evaluation over time, glossiness (DI), yellowness index (YI) evaluation in the coated state of a wood substrate after exposure using a xenon weatherometer, ultraviolet ray irradiation, ultraviolet absorption evaluation after repeated darkness, ultraviolet light And dye fading color difference ΔE evaluation after exposure.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

(Synthesis example)
Synthesis example 1
(Preparation of exemplary compound (2))
To 160.0 g of salicylamide, 600 mL of acetonitrile and 355.2 g of DBU (1,8-diazabiccyclo [5.4.0] undec-7-ene) 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%).

(Synthesis of X-2)
In a three-necked flask, 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 were added at room temperature for 30 minutes. 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)
The whole composition of the compound (X-2) obtained above is put into a three-necked flask, 700 mL of ethanol and 500 mL of 1M hydrochloric acid water are added, and the reaction mixture is heated to an internal temperature of 80 ° C. 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 composition 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 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 2
(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 +)

  The compounds used in the examples were prepared using the same method as described above.

<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). In the same manner, exemplary compounds (21), (m-1), (m-2), (m-20), (m-21), (m-25), and comparative compounds "A1" and "A2" The value of pKa was determined. 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 Table 1.

[Examples 1 to 8 and Comparative Examples 1 and 2]
The cellulose triacetate resin composition solution (dope) with the following solvent composition and cellulose triacetate concentration added to the amount shown in Table 2 was further cast, and the residue was left in hot air at 100 ° C. The film was dried until the amount of the solvent reached 10% by mass, and then dried with hot air at 140 ° C. for 10 minutes to produce a film having an absorbance at the maximum absorption wavelength of 1 of the ultraviolet absorber compound. The cellulose triacetate used was one having an acetyl substitution degree of 2.86 and an average polymerization degree of 310.
Solvent composition (mass ratio): methylene chloride / methanol = 90/10
Cellulose triacetate concentration: 17.0% by mass

The produced film was exposed in an eye super UV tester W151 (manufactured by Iwasaki Electric Co., Ltd.) (exposure conditions: 90 mW / cm ² , 63 ° C., 50% relative humidity, SCHOTT color glass filter WG-320 applied). The remaining amount of the compound was measured (measured at λmax by spectral absorption measurement), and the relative value of the time until the remaining amount of the compound reached 90% before the test was shown in Table 2 as an index of light resistance.

The following compounds were used as comparative compounds.
A1: TINUVIN 1577FF
A2: CYASORB UV-1164

  The above compounds are commercially available, Example A1 is Tinuvin 1577FF manufactured by Ciba, and Example A2 is CYASORB UV-1164 manufactured by CYTEC.

[Examples 9 to 18 and Comparative Examples 3 to 5]
The following solvent composition and cellulose triacetate concentration were cast in the dope formulation shown in Table 3, dried with hot air at 100 ° C. until the residual solvent amount was 10 mass%, and then heated with hot air at 140 ° C. The film was dried for a minute. In addition, each addition amount of Table 3 is the mass% with respect to a cellulose triacetate.
Solvent composition (mass ratio): methylene chloride / methanol = 90/10
Cellulose triacetate concentration: 17.0% by mass

The comparative compounds are the following compounds.
Triphenyl phosphate (plasticizer): B1 (ultraviolet absorber) manufactured by ALDRICH: TINUVIN 928 (manufactured by Ciba Specialty Chemicals)
B2 (light stabilizer): TINUVIN 770 (manufactured by Ciba Specialty Chemicals)

  The prepared film was placed on a poster as a protective film and subjected to an outdoor exposure test. The amber color of the poster photo was visually evaluated, and the time until the amber color started to stand out was summarized in Table 4 as relative values. Further, the film after the exposure test was observed with a microscope, and the precipitation of the compound (the ultraviolet absorber A and the additive) was examined. Evaluation was made with ○ indicating no precipitation and × indicating presence of precipitation. The evaluation results are also shown in Table 4.

Of these, Comparative Example 3 could not be tested for light resistance due to precipitation.
From the above result, as above-mentioned, it turns out that the film obtained from the cellulose-ester resin composition containing the compound represented by General formula (1) of this invention has high light resistance. In addition, by comparing Examples 14 and 15 with Comparative Examples 4 and 5, the compound represented by the general formula (1) of the present invention is used in combination with other ultraviolet absorbers and light stabilizers, and thus, light resistance. It can be seen that the sex is dramatically improved. In addition, by comparing Example 12 with Comparative Example 3, the compound represented by the general formula (1) of the present invention has dramatically improved solubility with respect to the compound of Comparative Example by using a plasticizer. It can be seen that precipitation of the compound can be prevented.

Claims (9)

A cellulose ester resin composition comprising a compound represented by the following general formula (1) ( excluding a compound having a sugar residue) and a cellulose ester resin.

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or OH, and at least one of the substituents is a Hammett's σp value represents COOR ^r or CN is a positive substituent. 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} represents a water MotoHara child. R ^r represents a hydrogen atom or a monovalent substituent. ]   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, alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group, substituted or unsubstituted sulfamoyl group, thiocyanate group, Or a substituted or unsubstituted alkylsulfonyl group, and when having a substituent, the substituent is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylcarbonyl group Group, nitro group, amino group, hydroxy group, alkoxy group having 1 to 20 carbon atoms, aryloxy group Group, a sulfamoyl group, characterized in that it is a thiocyanate group, or an alkylsulfonyl group, a cellulose ester resin composition according to claim 1. At least one of the R ^1b , R ^1c, and R ^1d is COOR ^r (R ^r is a hydrogen atom or a monovalent substituent) or CN which is a substituent having a positive Hammett's σp value. Item 3. The cellulose ester resin composition according to Item 1 or 2. The cellulose ester-based resin composition according to any one of claims 1 to 3 , comprising 0.1 to 30% by mass of the compound represented by the general formula (1). The cellulose according to any one of claims 1 to 4 , wherein the cellulose ester-based resin is at least one selected from the group consisting of cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate. Ester resin composition. Furthermore, at least 1 chosen from the group which consists of a ultraviolet absorber, a light stabilizer, antioxidant, and a plasticizer is included, The cellulose-ester-type resin composition of any one of Claims 1-5 characterized by the above-mentioned. object. The molded article which consists of a cellulose-ester-type resin composition of any one of Claims 1-6 . The molded article according to claim 7 , comprising 0.1 to 10.0 g / m ^{2 of the} compound represented by the general formula (1). The molded product according to claim 7 or 8 , wherein the thickness is 20 µm to 1000 µm.