JP5798727B2 - Polymer, polymer composition, ultraviolet absorber, paint and resin molded product - Google Patents

Description

  The present invention relates to a novel polymer having a triazine compound as a structural unit, a polymer composition using the polymer, an ultraviolet absorber, a paint, and a resin molded product.

Conventionally, ultraviolet absorbers have been imparted by sharing ultraviolet absorbers with various resins. An inorganic ultraviolet absorber and an organic ultraviolet absorber may be used as the ultraviolet absorber. 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. There is no such thing that can absorb up to 400 nm in the long wave ultraviolet (UV-A) region, and those that absorb long wave ultraviolet light have absorption up to the visible region and are colored.
On the other hand, since the organic ultraviolet absorber has a high degree of freedom in the structural design of the absorbent, various absorption wavelengths can be obtained 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, those having a maximum absorption wavelength in the long wave ultraviolet region have poor light resistance, and the ultraviolet shielding effect decreases with time.
In addition, since these organic ultraviolet absorbers are low molecular compounds, their compatibility with high molecular compounds such as resins is limited. For example, these organic ultraviolet absorbers are added at a high concentration in order to obtain a high ultraviolet shielding effect. In some cases, there is a problem that precipitation of the ultraviolet absorber and bleeding out due to long-term use occur.
Patent Document 6 describes a triazine UV absorber as a crosslinking agent for a polymer network. Patent Document 7 describes a UV absorber composition containing a hydroxyphenyltriazine compound.

  Furthermore, materials applied to solar cells, etc. that have been developed in recent years need to be exposed to sunlight outdoors for a long time, and it is inevitable that their properties will deteriorate due to exposure to ultraviolet rays over time. It was. For this reason, there is a need for a compound that can be used as an ultraviolet absorber that exhibits a shielding effect up to the UV-A region and has an excellent light resistance.

JP-A-5-339033 JP-A-5-345639 JP-A-6-56466 Special Table 2002-524442 Japanese Patent No. 3965631 JP 2005-510611 A JP 2005-532273 A

  The object of the present invention is to have excellent light resistance and high compatibility with the resin, and when added to the resin, it effectively suppresses deterioration of the resin due to long-term light exposure and its own bleed-out. It is an object of the present invention to provide a polymer useful as an ultraviolet absorber capable of achieving the above. Moreover, it is providing the polymer composition, ultraviolet absorber, coating material, and resin molding using this polymer.

  The inventors of the present invention have intensively studied to achieve the above object, and as a result, a polymer using a triazine compound having a specific structure as a monomer has excellent light resistance and a resin. The present inventors have found that it has high compatibility and have completed the present invention.

＜２＞
＜１＞に記載の重合体を含むことを特徴とする高分子組成物。
＜３＞
＜１＞に記載の重合体を含むことを特徴とする紫外線吸収剤。
＜４＞
＜３＞に記載の紫外線吸収剤を含むことを特徴とする塗料。
＜５＞
下記例示化合物（１）〜（５）のいずれかで表される単量体に由来する構造単位を有する重合体と、
アクリル樹脂、メタクリル樹脂、アクリルアミド樹脂、ポリスチレン樹脂、ポリエチレン樹脂、ポリエチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、及びポリカーボネート樹脂から選択される少なくとも１種とを含有する樹脂組成物。

＜６＞
＜５＞に記載の樹脂組成物を含むことを特徴とする塗布フィルム。
＜７＞
＜５＞に記載の樹脂組成物を含むことを特徴とする樹脂成形物。
本発明は、前記＜１＞〜＜７＞に係る発明であるが、以下、それ以外の事項（例えば、下記〔１〕〜〔９〕）についても記載している。
〔１〕
一般式（１）で表される単量体に由来する構造単位を有することを特徴とする重合体。

［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、置換基のうち少なくとも１つは、ハメット則のσｐ値が正である置換基を表す。また置換基同士で結合して環を形成しても良い。Ｒ^１ｆ、Ｒ^１ｇ、Ｒ^１ｈ、Ｒ^１ｉ、Ｒ^１ｊ、Ｒ^１ｋ、Ｒ^１ｍ、Ｒ^１ｎ及びＲ^１ｐは、互いに独立して、水素原子又は１価の置換基を表す。また置換基同士で結合して環を形成しても良い。Ｒ^１ａ〜Ｒ^１ｐの少なくとも１つは、重合性基を有する。］
〔２〕
Ｒ^１ａ、Ｒ^１ｂ、Ｒ^１ｃ、Ｒ^１ｄ及びＲ^１ｅのいずれか少なくとも１つがＣＯＯＲ^１ｑであることを特徴とする〔１〕に記載の重合体［Ｒ^１ｑは、重合性基を有する置換基を表す。］。
〔３〕
Ｒ^１ｃがＣＯＯＲ^１ｑであることを特徴とする〔２〕に記載の重合体。
〔４〕
Ｒ^１ｑの重合性基が、アクリル基又はメタクリル基であることを特徴とする〔２〕又は〔３〕に記載の重合体。
〔５〕
Ｒ^１ｆがＯＨであることを特徴とする〔１〕〜〔４〕のいずれか一項に記載の重合体。
〔６〕
〔１〕〜〔５〕のいずれか一項に記載の重合体を含むことを特徴とする高分子組成物。
〔７〕
〔１〕〜〔５〕のいずれか一項に記載の重合体を含むことを特徴とする紫外線吸収剤。
〔８〕
〔７〕に記載の紫外線吸収剤を含むことを特徴とする塗料。
〔９〕
〔７〕に記載の紫外線吸収剤を含むことを特徴とする樹脂成形物。 The object of the present invention has been achieved by the following method.
<1>
A polymer having a structural unit derived from a monomer represented by any one of the following exemplary compounds (1) to (5) .

< 2 >
A polymer composition comprising the polymer according to <1 > .
< 3 >
The ultraviolet absorber characterized by including the polymer as described in <1 > .
< 4 >
The coating material characterized by including the ultraviolet absorber as described in < 3 >.
< 5 >
A polymer having a structural unit derived from a monomer represented by any of the following exemplary compounds (1) to (5) ;
A resin composition comprising at least one selected from an acrylic resin, a methacrylic resin, an acrylamide resin, a polystyrene resin, a polyethylene resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, and a polycarbonate resin.

< 6 >
The coating film characterized by including the resin composition as described in < 5> .
< 7 >
< 5> The resin molding characterized by including the resin composition as described in.
The present invention is an invention according to the above <1> to < 7 >, but other matters (for example, the following [1] to [9]) are also described below.
[1]
A polymer having a structural unit derived from a monomer represented by the general formula (1).

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or OH, and at least one of the substituents has a Hammett's σp value Represents a substituent which is positive. Moreover, you may combine with substituents and may form a ring. R ^1f , 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. At least one of R ^{1a to} R ^1p has a polymerizable group. ]
[2]
The polymer according to [1], wherein at least one of R ^1a , R ^1b , R ^1c , R ^1d and R ^1e is COOR ^1q [R ^1q represents a substituent having a polymerizable group. Represent. ].
[3]
The polymer according to [2], wherein R ^1c is COOR ^1q .
[4]
The polymer according to [2] or [3], wherein the polymerizable group of R ^1q is an acryl group or a methacryl group.
[5]
R ^1f is OH, The polymer according to any one of [1] to [4].
[6]
A polymer composition comprising the polymer according to any one of [1] to [5].
[7]
An ultraviolet absorber comprising the polymer according to any one of [1] to [5].
[8]
[7] A paint comprising the ultraviolet absorbent described in [7].
[9]
[7] A resin molded product comprising the ultraviolet absorbent according to [7].

  According to the present invention, it has excellent light resistance and high compatibility with the resin, and when added to the resin, it effectively suppresses deterioration of the resin due to long-term light exposure and its own bleed-out. Thus, it is possible to provide a polymer useful as an ultraviolet absorber. Further, by using the polymer, it is possible to provide a polymer composition, an ultraviolet absorber, a paint, and a resin molded product having high light stability.

Hereinafter, the present invention will be described in detail.
First, Hammett's substituent constant σp value and polymerizable group used in the present specification will be described.

(Hammett's substituent constant σp value)
Hammett's rule is a method described in 1935 in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, but this means that it is limited to only a substituent having a value known in the literature, which can be found in the above-mentioned book. Needless to say, even if the value is unknown, it includes a substituent that would be included in the range when measured based on Hammett's rule. Although the compound concerning this invention is not a benzene derivative, (sigma) p value is used as a scale which shows the electronic effect of a substituent irrespective of a substitution position. In the present invention, the σp value will be used in this sense.

(Polymerizable group)
In the present invention, the polymerizable group means a substituent capable of polymerizing a polymerizable component by light irradiation, radiation irradiation, heating, use of a radical initiator, or the like. In the case of using radical polymerization, examples of the polymerizable group include functional groups having an unsaturated bond such as an acryl group, a methacryl group, an acryloyl group, a methacryloyl group, an acrylamide group, a methacrylamide group, a styryl group, and a vinyl group. . When cationic polymerization is used, examples of the polymerizable group include an oxirane group and an oxetane group. A radical polymerizable group is preferable in that the dark reaction does not proceed.

[Monomer represented by general formula (1)]
The present invention is a polymer having a structural unit derived from a monomer represented by the following general formula (1).

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or OH, and at least one of the substituents has a Hammett's σp value Represents a substituent which is positive. Moreover, you may combine with substituents and may form a ring. R ^1f , 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. At least one of R ^{1a to} R ^1p has a polymerizable group. ]

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 rule σp value Represents a substituent that 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.
In addition, at least one of R ^1a , R ^1c , and R ^1e preferably represents a substituent having a positive Hammett's σp value, and R ^1c represents a substituent having a positive Hammett's σp value. Is more preferable.
More preferably, R ^1c is a substituent having a positive Hammett's σp value, and R ^1a , R ^1b , R ^1d , and R ^1e represent a hydrogen atom.
When R ^1c represents a substituent having a positive Hammett's σp value, LUMO is stabilized by the electron-attracting group, which is preferable because the excitation lifetime is shortened and the light resistance is improved.

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

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

Examples of the monovalent substituent in the general formula (1) include a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted. Substituted carbamoyl group, substituted or unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, OR ^U (R ^u represents a hydrogen atom or a monovalent substituent), substituted or An unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted sulfamoyl group, a thiocyanate group, or a substituted or unsubstituted alkylsulfonyl group is preferable, OR ^U , an alkyl group, An amide group is more preferable, and OR ^U and an alkyl group are more preferable.
R ^u represents a hydrogen atom or a monovalent substituent, and examples of the monovalent substituent include the substituent A. Among them, it is preferable to represent a linear or branched alkyl group having 1 to 20 carbon atoms. A linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, and examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, 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 substituent σp value is a positive Hammett equation in formula (1), preferably, sigma _p value of the electron-withdrawing group 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), 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, alkyloxy Carbonyl group, aryloxycarbonyl group, dialkylphosphono group, diarylphosphono group, dialkylphosphinyl group, diarylphosphinyl group, phosphoryl group, alkylsulfinyl group, arylsulfinyl group, acylthio group, sulfamoyl group, thiocyanate group, Thiocarbonyl group, imino group, imino group substituted with N atom, carboxy group (or salt thereof), at least two or more An alkyl group substituted with halogen atoms (e.g., CF _3), at least two or more alkoxy groups substituted with halogen atom, at least two aryloxy groups substituted with halogen atom, acylamino group, at least two An alkylamino group substituted with the above halogen atoms, an alkylthio group substituted with at least two or more halogen atoms, an aryl group substituted with another electron withdrawing group having a σ _p value of 0.2 or more, hetero Examples thereof include a ring group, a halogen atom, an azo group, and a selenocyanate group. 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 solubility.
R ^r represents 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 group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl. Group, n-pentyl group, i-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, t-hexyl group, n-octyl group, t-octyl group, i-octyl group. The methyl group is preferably an ethyl group, and particularly preferably a methyl group.

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

In addition, when R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e have a polymerizable group, the number of polymerizable groups is not particularly limited, but is preferably one, and R ^1a , R ^1b , R 1 It is preferable that ^1c , R ^1d or R ^1e is COOR ^1q (R ^1q represents a substituent having a polymerizable group). Of these, R ^1c is more preferably COOR ^1q . This is because the electron withdrawing group improves light resistance and improves compatibility with the resin.
The polymerizable group for R ^1q is not particularly limited, but is preferably a radical polymerization reactive group.

  As a radically polymerizable reactive group, the structure represented by the following general formula (a4-1) is preferable.

In the general formula (a4-1), R ^{41 to} R ⁴³ each independently represents a hydrogen atom, an alkyl group, or an aryl group. In General Formula (a4-1), Y ⁴ represents a single bond, or a group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. It represents a divalent linking group selected from the above. Specific examples of comprising the combination Y ⁴ below. In the following examples, the left side is bonded to the main chain, and the right side is bonded to the ethylenically unsaturated bond.

L19: -CO-NH-divalent aliphatic group -O-CO-
L20: -CO-divalent aliphatic group -O-CO-
L23: -CO-O-divalent aliphatic group -O-CO-
L24: -Divalent aliphatic group -O-CO-
L25: -CO-NH-divalent aromatic group -O-CO-
L26: -CO-divalent aromatic group -O-CO-
L27: -Divalent aromatic group -O-CO-
L28: -CO-O-divalent aliphatic group -CO-O-divalent aliphatic group -O-CO-
L29: -CO-O-divalent aliphatic group -O-CO-divalent aliphatic group -O-CO-
L30: -CO-O-divalent aromatic group -CO-O-divalent aliphatic group -O-CO-
L31: -CO-O-divalent aromatic group -O-CO-divalent aliphatic group -O-CO-
L32: -CO-O-divalent aliphatic group -CO-O-divalent aromatic group -O-CO-
L33: -CO-O-divalent aliphatic group -O-CO-divalent aromatic group -O-CO-
L34: -CO-O-divalent aromatic group -CO-O-divalent aromatic group -O-CO-
L35: -CO-O-divalent aromatic group -O-CO-divalent aromatic group -O-CO-
L36: -CO-O-divalent aromatic group -O-CO-NH-divalent aliphatic group -O-CO-
L37: -CO-O-divalent aliphatic group -O-CO-NH-divalent aliphatic group -O-CO-
L38: -CO-NH-divalent aliphatic group -O-CO-NH-divalent aliphatic group -O-CO-
The divalent aliphatic group is preferably an aliphatic group having 1 to 6 carbon atoms, and more preferably an aliphatic group having 1 to 4 carbon atoms. As the divalent aromatic group, phenylene and naphthylene are preferable, and phenylene is preferable. As the radical polymerizable reactive group, among the above-mentioned groups, an acryl group, a methacryl group, or an acrylamide group is preferable, and an acryl group or a methacryl group is more preferable.

In the present invention, when R ^1f , R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ^1n, and R ^1p represent a monovalent substituent, R ^1f , R ^1g , R ^1h , More preferably, at least one of R ¹ⁱ , R ^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 at least one of R ^1j represents a substituent having a positive Hammett's σp value (preferably 0.1 to 1.2), and R ^1h is a positive Hammett's σp value. It is more preferable to represent the substituent which is. 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, R ^1f is preferably OH in order to expand the absorption region to the long wavelength region and increase the effect of shielding ultraviolet rays by increasing ε. R ^1h or R ¹ⁿ is independently a hydrogen atom, COOR ^r , CONR ^s ₂ , CN, CF ₃ , halogen atom, NO ₂ , or SO ₃ M (M represents a hydrogen atom or an alkali metal). R ^1h or R ¹ⁿ is more preferably a hydrogen atom, R ^1h and R ¹ⁿ are more preferably a hydrogen atom, and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R 1 It is particularly preferable that ^1k , R ^1m , R ¹ⁿ and R ^1p represent a hydrogen atom. It is for showing the outstanding light resistance.

In the present invention, at least one of R ^{1a to} R ^1p has a polymerizable group.
Although the number of the polymerizable groups which the monomer represented by the general formula (1) has is not particularly limited, it is preferably 1 to 3, and more preferably 1.
Also, R ^1c or R ^1h is, preferably contains a polymerizable group in which one polymerizable group, among them R ^1c are, and more preferably contains either a polymerizable group polymerizable group.

Specific examples of the monomer represented by the general formula (1) are shown below, but the present invention is not limited thereto.

  The monomer represented by the general formula (1) can take a tautomer depending on the structure and the environment in which the monomer 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 monomer 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 monomer represented by the general formula (1) can be synthesized by any method.
For example, known patent documents and non-patent documents, for example, JP-A-7-188190, JP-A-11-315072, JP-A-2001-220385, “Dye and Drug”, Vol. 40, No. 12 (1995) Can be synthesized with reference to pages 325-339.

(Polymer)
The polymer of the present invention has a structural unit derived from the monomer represented by the general formula (1). Moreover, other polymerizable monomers other than the monomer represented by the general formula (1), a polymerizable oligomer, and a polymerizable polymer can be included as a copolymerization component. In addition, the monomer represented by the said General formula (1) may use only 1 type, and may use 2 or more types together.

  The polymer of the present invention has a mass average molecular weight of preferably 10,000 to 500,000, more preferably 20,000 to 300,000, and still more preferably 50,000 to 200,000. In addition, when a copolymer component is included, depending on the copolymer component included, random copolymer, alternating copolymer, block copolymer, graft copolymer, etc. can be used in any sequence, and a linear polymer Alternatively, a three-dimensional crosslinked structure having a crosslinking point may be formed.

  The mass ratio of the monomer represented by the general formula (1) to be used and the other copolymer component is the type of the copolymer component and the type of resin to which the polymer is added as an ultraviolet absorber. It is appropriately selected depending on. Usually, from the viewpoint of the effect as an ultraviolet absorber and the compatibility with the resin to be added, the amount of the other copolymer component used is 5 with respect to 100 parts by mass of the monomer represented by the general formula (1). -2000 mass parts is preferable, and 10-500 mass parts is more preferable.

  The polymerizable monomer as the copolymer component is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate) , 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethyl) Styrene, p-methoxystyrene, etc.), fluorine-containing vinyl ethers, vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, cinnamic acid vinyl) ), Unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, Nt-butylacrylamide, N-cyclohexylacrylamide, etc.), Examples include methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

  In the present invention, a polymerizable monomer having an ultraviolet absorbing residue such as a benzophenone group, a benzotriazole group, or a cyanoacrylate group can be suitably used. For example, as an acrylic monomer having a benzotriazole group, RUVA- 93 (trade name) (2- (2′-hydroxy-5′methacryloxyethylphenyl) -2H-benzotriazole, manufactured by Otsuka Chemical Co., Ltd.).

  The polymerizable oligomer or polymerizable polymer as the copolymer component is not particularly limited, and is generally selected from, for example, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate, and butadiene. A homopolymer or copolymer formed from at least one selected monomer can be mentioned, and specifically, polystyrene, polybutadiene, poly-2hydroxyethyl (meth) acrylate, polymethyl (meth) acrylate, Examples thereof include poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acrylate, and copolymers thereof.

In the polymerization of the polymer of the present invention, for example, a polymerization initiator may be used as an additive.
As the polymerization initiator, an appropriate polymerization initiator is used in accordance with the polymerization method (anionic polymerization, cationic polymerization, radical polymerization, etc.). Of these, a radical polymerization initiator is preferred. The radical polymerization initiator is not particularly limited, and may be a so-called thermal polymerization initiator or photopolymerization initiator. Specifically, α-diketones such as benzyl and diacetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, thioxanthone, 2,4-diethylthioxanthone, thioxanthone- Thioxanthones such as 4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone, benzophenones such as 4,4′-bis (diethylamino) benzophenone, Michler's ketones, acetophenone, 2- (4-toluenesulfonyl) Oxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α &apos; -dimethoxyacetoxybenzophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxy Acetophenones such as cetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Quinones such as anthraquinone and 1,4-naphthoquinone, phenacyl chloride, halogen compounds such as trihalomethylphenylsulfone, tris (trihalomethyl) -s-triazine, acylphosphine oxides, di-t-butyl peroxide, etc. Examples of the thermal polymerization initiator include azobisisobutyronitrile and benzoyl peroxide. In addition, Irgacure-184, 261, 369, 500, 651, 907 (manufactured by Ciba Specialty Chemicals), Darocur-1173, 1116, 2959, 1664, 4043 (Ciba Specialty) Commercial products such as Chemicals) can also be used.

(Polymer composition)
The polymer composition of the present invention contains the polymer of the present invention and is particularly suitable for stabilizing organic materials against damage by light, oxygen or heat. Among these, the polymer composition of the present invention can be suitably used as a light stabilizer, particularly an ultraviolet absorber.

[Ultraviolet absorber]
Hereinafter, the ultraviolet absorber containing the polymer of the present invention will be described.

The ultraviolet absorber of the present invention has a structural unit derived from the monomer represented by the general formula (1). Since the monomer represented by the general formula (1) has a substituent having a positive Hammett's σp value at a specific position, LUMO is stabilized by an electron-attracting group, so that the excitation lifetime is short. It has the feature of having excellent light resistance. When a known triazine-based compound is used as an ultraviolet absorber, it has an adverse effect such as decomposition and yellowing when used for a long time.
In contrast, since the monomer represented by the general formula (1) of the present invention has excellent light resistance, the ultraviolet absorber of the present invention having a structural unit derived from the monomer is used for a long time. Even if it does, the effect that it does not decompose and does not yellow.

The ultraviolet absorber of the present invention may be used alone or in combination of two or more.
Any use form of the ultraviolet absorber of the present invention may be used. For example, a liquid dispersion, a solution, a resin composition, etc. are mentioned.
Although the maximum absorption wavelength of the ultraviolet absorber of this invention is not specifically limited, Preferably it is 250-400 nm, More preferably, it is 280-380 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 to 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.

The maximum absorption wavelength and the half width of the compound in the present invention are values 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. Is used.

  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 ultraviolet absorber 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, since the absorption efficiency per mass of the ultraviolet absorber is sufficiently obtained, the amount of the ultraviolet absorber used for completely absorbing the ultraviolet region 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 ultraviolet absorber of the present invention (hereinafter sometimes simply referred to as “ultraviolet absorber”) can also be used in the form of a dispersion in which the ultraviolet absorber is dispersed in a dispersion medium. Hereinafter, the ultraviolet absorbent dispersion containing the ultraviolet absorbent of the present invention will be described.
Any medium may be used for dispersing the ultraviolet absorbent according to the present invention. For example, water, an organic solvent, a resin, a resin solution, and the like can be given. These may be used alone or in combination.

  Examples of the organic solvent for the dispersion medium used in the present invention include hydrocarbons such as pentane, hexane and octane, aromatics such as benzene, toluene and xylene, ethers such as diethyl ether and methyl t-butyl ether, Alcohols such as methanol, ethanol and isopropanol, esters such as acetone, ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethyl Amides such as acetamide and N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide, amines such as triethylamine and tributylamine, carboxylic acids such as acetic acid and propionic acid, halogens such as methylene chloride and chloroform Tetrahydrofuran, heterocyclic ring system, such as pyridine, and the like. These can be used in combination at any ratio.

  Examples of the dispersion medium resin used in the present invention include thermoplastic resins and thermosetting resins conventionally used in the production of various conventionally known molded articles, sheets, films and the like. Examples of thermoplastic resins include polyethylene resins, polypropylene resins, poly (meth) acrylic ester resins, polystyrene resins, styrene-acrylonitrile resins, acrylonitrile-butadiene-styrene resins, polyvinyl chloride resins, Polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol resin, polyacrylamide, polyethylene terephthalate resin (PET), polyethylene naphthalate resin (PEN) , Polybutylene terephthalate resin (PBT), liquid crystal polyester resin (LCP), polyacetal resin (POM), polyamide resin (PA), polycarbonate resin, polyurethane resin, and polyphenylene sulfide Id resin (PPS) and the like, which are used as one or more polymer blends or polymer alloy. These resins are also used as thermoplastic molding materials in which natural resins contain fillers such as glass fibers, carbon fibers, semi-carbonized fibers, cellulosic fibers, glass beads, flame retardants, and the like. Moreover, conventionally used additives for resins, for example, polyolefin resin fine powder, polyolefin wax, ethylene bisamide wax, metal soap, etc. can be used alone or in combination as required.

  Examples of the thermosetting resin include epoxy resins, melamine resins, unsaturated polyester resins, and the like. These include natural resins, glass fibers, carbon fibers, semi-carbonized fibers, cellulosic fibers, glass beads, and the like. It can also be used as a thermosetting molding material containing a flame retardant.

  In the dispersion containing the ultraviolet absorber, a dispersant, an antifoaming agent, a preservative, an antifreezing agent, a surfactant and the like can be used in combination. In addition, any compound may be included. Examples thereof include dyes, pigments, infrared absorbers, fragrances, polymerizable compounds, polymers, inorganic substances, metals, and the like.

  As a device for obtaining a dispersion containing the ultraviolet absorbent according to the present invention, a high-speed stirring disperser having a large shearing force, a disperser giving high-intensity ultrasonic energy, or the like can be used. Specifically, there are a colloid mill, a homogenizer, a capillary emulsifying device, a liquid siren, an electromagnetic distortion ultrasonic generator, an emulsifying device having a Paulman whistle, and the like. A high-speed stirring type disperser preferable for use in the present invention is a high-speed rotation (500 to 15,000 rpm) in a liquid in which a main part that performs a dispersing action, such as a dissolver, polytron, homomixer, homoblender, caddy mill, jet agitator. Preferably, it is a disperser of the type of 2,000 to 4,000 rpm. The high-speed agitation type disperser used in the present invention is also called a dissolver or a high-speed impeller disperser. As described in Japanese Patent Application Laid-Open No. 55-129136, a saw-tooth plate is attached to a shaft that rotates at high speed. A preferred example is one in which impellers that are alternately bent in the vertical direction are mounted.

  In preparing an emulsified dispersion comprising a hydrophobic compound, various processes can be followed. For example, when a hydrophobic compound is dissolved in an organic solvent, one kind arbitrarily selected from a high-boiling organic substance, a water-immiscible low-boiling organic solvent, or a water-miscible organic solvent, or two or more kinds of arbitrary substances Dissolve in the multi-component mixture and then disperse in water or aqueous hydrophilic colloid in the presence of a surface active compound. The mixing method of the water-insoluble phase containing the hydrophobic compound and the aqueous phase may be a so-called forward mixing method in which the water-insoluble phase is added to the aqueous phase with stirring or a reverse mixing method.

Moreover, the ultraviolet absorber of this invention can be used also in the state of the solution melt | dissolved in the liquid medium. Hereinafter, the ultraviolet absorbent solution containing the ultraviolet absorbent of the present invention will be described.
Any liquid may be used for dissolving the ultraviolet absorbent according to the present invention. For example, water, an organic solvent, a resin, a resin solution, and the like can be given. Examples of the organic solvent, the resin, and the resin solution include those described as the above dispersion medium. These may be used alone or in combination.

  The solution of the ultraviolet absorber of the present invention may contain any other compound in addition. Examples thereof include dyes, pigments, infrared absorbers, fragrances, polymerizable compounds, polymers, inorganic substances, metals, and the like. Except for the ultraviolet absorbent according to the present invention, it may not necessarily be dissolved.

  The content of the ultraviolet absorber in the solution containing the ultraviolet absorber of the present invention varies depending on the purpose of use and the form of use and cannot be uniquely determined, but may be any concentration depending on the purpose of use. Preferably it is 0.001-30 mass% with respect to the whole quantity of a solution, More preferably, it is 0.01-10 mass%. It is also possible to prepare a solution at a high concentration in advance and dilute it when desired. The dilution solvent can be arbitrarily selected from the above-mentioned solvents.

What is stabilized by the ultraviolet absorber of the present invention includes dyes, pigments, foods, beverages, body care products, vitamins, pharmaceuticals, inks, oils, fats, waxes, surface coatings, cosmetics, photographic materials, textiles and the like Examples thereof include pigments, plastic materials, rubber, paints, resin compositions, and polymer additives.
When the ultraviolet absorbent according to the present invention is used, the mode thereof may be any method. Although the ultraviolet absorber of the present invention may be used alone or as a composition, it is preferably used as a composition. Especially, it is preferable that it is resin compositions, such as a coating material or a resin molding containing the ultraviolet absorber of this invention.
Hereinafter, the resin composition containing the ultraviolet absorbent according to the present invention will be described.

(Resin composition)
The resin composition containing the ultraviolet absorbent according to the present invention contains a resin. The resin composition containing the ultraviolet absorbent according to the present invention may be formed by dissolving a resin in an arbitrary solvent.

  The ultraviolet absorber of the present invention can be contained in the resin composition by various methods. When the ultraviolet absorbent of the present invention has compatibility with the resin composition, the ultraviolet absorbent of the present invention can be directly added to the resin composition. The ultraviolet absorbent of the present invention may be dissolved in an auxiliary solvent having compatibility with the resin composition, and the solution may be added to the resin composition. The ultraviolet absorbent of the present invention may be dispersed in a high-boiling organic solvent or polymer, and the dispersion may be added to the resin composition.

(High boiling point organic solvent)
The boiling point of the high-boiling organic solvent is preferably 180 ° C. or higher, and more preferably 200 ° C. or higher. The melting point of the high-boiling organic solvent is preferably 150 ° C. or lower, and more preferably 100 ° C. or lower. 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.
As for the method of adding the ultraviolet absorber of the present invention, JP-A-58-209735, JP-A-63-264748, JP-A-4-1911851, JP-A-8-272058, and British Patent No. 201616017A are described. Can be helpful.

(resin)
The resin used for the resin composition will be described. The resin may be 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, Sobutylene / isoprene copolymer, ethylene / vinyl cyclohexene copolymer, ethylene / alkyl acrylate copolymer, ethylene / alkyl methacrylate copolymer, etc.), acrylic polymer (eg, polymethacrylate, polyacrylate, polyacrylamide, polyacrylonitrile, etc.), polyvinyl chloride, poly Vinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride / vinyl acetate copolymer, polyether (eg, polyalkylene glycol, polyethylene oxide, polypropylene oxide, etc.), polyacetal (eg, polyoxymethylene), polyamide, polyimide, polyurethane, Polyurea, polyester (for example, polyethylene terephthalate, polyethylene naphthalate, etc. , Polycarbonate, polyketone, polysulfone polyetherketone, phenolic resin, melamine resin, cellulose ester (eg diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polysiloxane, natural Examples thereof include polymers (for example, cellulose, rubber, gelatin and the like).

The resin used in the present invention is preferably a synthetic polymer, more preferably a polyolefin, an acrylic polymer, polyester, polycarbonate, or cellulose ester. Among these, polyethylene, polypropylene, poly (4-methylpentene), polymethyl methacrylate, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and triacetyl cellulose are particularly preferable.
The resin used in the present invention is preferably a thermoplastic resin.

  The ultraviolet absorbent according to the present invention can contain any amount necessary for imparting desired performance. These vary depending on the compound and resin used, but the content can be determined as appropriate. As content, it is preferable that it is more than 0 mass% and 20 mass% or less in a resin composition, It is more preferable that it is more than 0 mass% and 10 mass% or less, 0.05 mass% or more and 5% mass or less More preferably it is. When the content is in the above range, a sufficient ultraviolet shielding effect can be obtained and bleeding out can be suppressed, which is preferable.

  In addition to the above-described polymer substance and UV stabilizer, the resin composition appropriately contains optional additives such as an antioxidant, a light stabilizer, a processing stabilizer, an anti-aging agent, and a compatibilizer as necessary. May be.

The resin composition containing the ultraviolet absorbent according to the present invention can be used for all uses in which a synthetic resin is used, but can be particularly suitably used for an application that may be exposed to sunlight or light containing ultraviolet rays. . Specific examples include, for example, glass substitutes and surface coating materials thereof, housing, facilities, window glass for transportation equipment, coating materials for daylighting glass and light source protection glass, housing, facilities, window films for transportation equipment, housing, Inner and outer packaging materials for facilities, transportation equipment, etc., and coating films formed by the coating, alkyd resin lacquer coating and coating formed by the coating, acrylic lacquer coating and coating formed by the coating, fluorescence Light source components that emit ultraviolet rays, such as lamps and mercury lamps, precision machinery, components for electronic and electrical equipment, materials for blocking electromagnetic waves generated from various displays, containers or packaging materials for food, chemicals, chemicals, bottles, boxes, blisters , Cup, special packaging, compact disc coat, agricultural or industrial sheet or film material, printed matter, dyed matter, dyed face Anti-fading agents, protective films for polymer supports (eg for plastic parts such as machinery and automotive parts), printed overcoats, inkjet media coatings, laminated matte, optical light films, safety glass / windshields Intermediate layers, electrochromic / photochromic applications, overlaminate films, solar heat control films, sunscreen creams, shampoos, rinses, hairdressing cosmetics, sportswear, stockings, hats and other clothing textiles and fibers, curtains, carpets, Home interior items such as wallpaper, plastic lenses, contact lenses, medical devices such as artificial eyes, optical filters, backlight display films, prisms, mirrors, optical materials such as photographic materials, mold films, transfer stickers, graffiti prevention Film, tape, ink, etc. Bogu, sign plate, and a marking device such as a surface coating material or the like.

  Examples of the shape of the polymer molded product formed from the resin composition include flat membranes, powders, spherical particles, crushed particles, massive continuous bodies, fibers, tubulars, hollow fibers, granules, plates, porouss, etc. Either shape may be sufficient.

  Since the resin composition contains the ultraviolet absorber of the present invention, it has excellent light resistance (fastness to ultraviolet light), and precipitation of the ultraviolet absorber and bleeding out due to long-term use may occur. Absent. In addition, since the resin composition has an excellent long-wave ultraviolet absorbing ability, it can be used as an ultraviolet absorbing filter or a container, and can protect compounds that are sensitive to ultraviolet rays. For example, a molded product (such as a container) containing the ultraviolet absorbent of the present invention can be obtained by molding the resin composition by any method such as extrusion molding or injection molding. In addition, a molded product coated with the ultraviolet absorbing film containing the ultraviolet absorbent of the present invention can be obtained by applying and drying the solution of the resin composition to a separately manufactured molded product.

  When the resin composition is used as an ultraviolet absorption filter or an ultraviolet absorption film, the resin composition is preferably transparent. Examples of transparent resins include cellulose esters (eg, diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). Phthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene) , Polyolefins (eg, polyethylene, polypropylene, polymethylpentene), polymethyl methacrylate, syndiotactic polystyrene, Risuruhon, polyether sulfone, polyether ketone, polyether imides, polyoxyethylene, and the like. Preferred are cellulose ester, polycarbonate, polyester, polyolefin, and acrylic resin, and more preferred are polycarbonate and polyester. More preferred is polyester, and particularly preferred is polyethylene terephthalate. The polymer molded product obtained from the resin composition can also be used as a transparent support, and the transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more.

  In the present invention, two or more kinds of ultraviolet absorbers having different structures may be used in combination. Moreover, you may use together the ultraviolet absorber of this invention, 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. As the ultraviolet absorber having a structure other than the general formula (1) constituting the ultraviolet absorber of the present invention, any one can be used, triazine, benzotriazole, benzophenone, merocyanine, cyanine, di Examples include compounds such as benzoylmethane, cinnamic acid, cyanoacrylate, and benzoate. 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 benzoxazinone compounds. The ultraviolet absorber having a structure other than the general formula (1) is described in detail in paragraph numbers [0117] to [0121] of JP-A-2008-273950, and the material described in the publication is the present invention. It can also be applied.

  As described above, in the present invention, it is preferable to use a combination of the ultraviolet absorbent of the present invention and a benzoxazinone compound. Since the compound represented by the general formula (1) has excellent light resistance even in the long wavelength region, it has the effect of preventing deterioration of the benzoxazinone that can be shielded to a longer wavelength region, together with the benzoxazinone-based compound. Use is preferable because the shielding effect can be sustained for a long time up to a longer wavelength region.

  In the present invention, a sufficient ultraviolet shielding effect can be obtained practically only with the ultraviolet absorber of the present invention, but when more strictness is required, a white pigment having a strong hiding power, such as titanium oxide, is used in combination. Also good. 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.

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

  The structures of the monomers used in the examples and comparative examples are shown below.

(Synthesis of Exemplary Compound (1))
300 g of salicylic acid was suspended in 600 mL of toluene, 258 g of thionyl chloride and 7 mL of DMF were added, and the mixture was stirred at 50 ° C. for 2 hours (Solution A). A solution A prepared by adding 900 mL of acetonitrile and 660 g of DBU (1,8-diazabiccyclo [5.4.0] undec-7-ene) to 299.0 g of salicylamide was dissolved. Was added dropwise at 5 ° C. and then stirred at room temperature for 24 hours. To this reaction solution, 300 mL of 35% hydrochloric acid was added and stirred at room temperature for 2 hours. The obtained solid was filtered and washed with water to obtain 504 g of synthetic intermediate A (yield 90%).

  1400 mL of toluene and 10.5 g of p-toluenesulfonic acid monohydrate were added to 140 g of the synthetic intermediate A, and the mixture was stirred at 150 ° C. for 6 hours. After cooling to 60 ° C., 14 mL of triethylamine was added to the reaction solution and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 122 g of synthetic intermediate B (yield 94%).

  To 401 g of terephthalonitrile, 8000 mL of methanol and 309 g of 28% sodium methoxide methanol solution were added and stirred at room temperature for 3 hours. To this reaction solution, 428 g of ammonium chloride was added and stirred at room temperature for 24 hours. The reaction solution was concentrated with a rotary evaporator, and the resulting solid was washed with methanol and ethyl acetate and recrystallized with water to obtain 310 g of synthetic intermediate C (yield 55%).

  To 42 g of synthetic intermediate C, 1000 mL of methanol and 44 g of 28% sodium methoxide methanol solution were added. 50 g of synthetic intermediate B was added to this suspension at room temperature, and the mixture was stirred at room temperature for 2 hours and at 60 ° C. for 2 hours. To this reaction solution, 2 mL of 35% hydrochloric acid was added, and the resulting solid was washed with methanol and water to obtain 74 g of synthetic intermediate D (yield 96%).

  200 g of 3,5,5-trimethyl-1-hexanol and 13 g of sulfuric acid were added to 25 g of the synthetic intermediate D and stirred for 16 hours under reflux conditions. After cooling to room temperature, the obtained solid was washed with methanol and water to obtain 32 g of synthetic intermediate E (yield 91%).

  500 mL of ethanol and 400 mL of a 10% potassium hydroxide ethanol solution and 100 mL of water were added to 10.0 g of the synthetic intermediate E, and the mixture was stirred at room temperature for 24 hours. 60 mL of 35% hydrochloric acid was added, and the obtained solid was washed with methanol and water to obtain 7.1 g of synthetic intermediate F (yield 94%).

  Synthetic intermediate F5.0 g, 5.1 g of 2-hydroxyethyl methacrylate and 0.5 g of 4-dimethylaminopyridine were added to 20 mL of methylene chloride, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide was added at 0 ° C. 3.2 g of hydrochloride was added. The solution was stirred at room temperature for 24 hours. Methanol was added to the reaction solution, and the resulting solid was washed with methanol and water to obtain 6.2 g of exemplary compound (1) (yield 96%).

(Synthesis of Exemplary Compound (2))
Synthetic intermediate F5.0 g, 5.0 g of 2-hydroxyethyl acrylate and 0.5 g of 4-dimethylaminopyridine were added to 20 mL of methylene chloride, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide was added at 0 ° C. 3.2 g of hydrochloride was added. The solution was stirred at room temperature for 24 hours. Methanol was added to the reaction solution, and the resulting solid was washed with methanol and water to obtain 6.1 g of Exemplified Compound (2) (yield 97%).

(Synthesis of Exemplary Compound (3))
Synthetic intermediate F5.0 g, N- (2-hydroxyethyl) acrylamide 5.0 g and 4-dimethylaminopyridine 0.5 g were added to 20 mL of methylene chloride, and 1-ethyl-3- (3-dimethyl) was added at 0 ° C. Aminopropyl) carbodiimide hydrochloride 3.2 g was added. The solution was stirred at room temperature for 24 hours. Methanol was added to the reaction solution, and the resulting solid was washed with methanol and water to obtain 6.0 g of exemplary compound (3) (yield 95%).

(Synthesis of Exemplary Compound (4))
Exemplified Compound (4) was synthesized in the same manner as Exemplified Compound (1) except that isophthalonitrile was used instead of terephthalonitrile.

(Synthesis of Exemplified Compound (5))
Synthetic intermediate D 5.0 g, 2-bromoethyl methacrylate 2.6 g, and potassium carbonate 1.9 g were added to 20 mL of dimethylacetamide and stirred at 80 ° C. for 7 hours. After cooling the reaction solution, the solid obtained by adding methanol was washed with methanol and water to obtain 5.8 g of Exemplified Compound (5) (yield 89%).

(Synthesis of polymer (1))
In a glass flask equipped with a cooler, a nitrogen introducing tube, a thermometer, a dropping funnel and a stirrer, a mixture of 30 g of exemplary compound (1), 70 g of methyl methacrylate and 2.8 g of azobisisobutyronitrile was added. The solution was gradually added dropwise to 100 g of dimethylformamide heated to 0 ° C. and then kept at the same temperature for 4 hours. The obtained reaction solution was poured into a large excess of methanol, and the precipitated solid was collected by filtration and vacuum dried at 40 ° C. for 15 hours to obtain 98 g of a slightly yellow powdery polymer. This product had a mass average molecular weight of 31,000 by GPC analysis based on standard polystyrene. Further, from the ¹ H-NMR analysis and the absorbance at the maximum absorption wavelength, the polymer is a copolymer of Exemplified Compound (1) and methyl methacrylate, and Exemplified Compound (1) is contained in 30% by mass in the copolymer composition. It was.

(Synthesis of polymer (2))
In a glass flask equipped with a cooler, a nitrogen introducing tube, a thermometer, a dropping funnel and a stirrer, a mixture of 30 g of exemplary compound (2), 70 g of methyl acrylate and 2.8 g of azobisisobutyronitrile was added. The solution was gradually added dropwise to 100 g of dimethylformamide heated to 0 ° C. and then kept at the same temperature for 4 hours. The obtained reaction solution was poured into a large excess of methanol, and the precipitated solid was collected by filtration and vacuum dried at 40 ° C. for 15 hours to obtain 69 g of a slightly yellow powdery polymer. This product had a mass average molecular weight of 86,000 by GPC analysis based on standard polystyrene. Further, from the ¹ H-NMR analysis and the absorbance at the maximum absorption wavelength, the polymer is a copolymer of Exemplified Compound (2) and methyl acrylate, and Exemplified Compound (2) is contained in a copolymer composition at 30% by mass. It was.

(Synthesis of polymer (3))
In a glass flask equipped with a cooler, a nitrogen inlet tube, a thermometer, a dropping funnel and a stirrer, a mixture of 30 g of Exemplified Compound (3), 70 g of acrylamide and 2.8 g of azobisisobutyronitrile was heated to 120 ° C. The solution was gradually added dropwise to 100 g of heated dimethylformamide and then kept at the same temperature for 4 hours. The obtained reaction liquid was poured into a large excess of methanol, and the precipitated solid was collected by filtration and vacuum dried at 40 ° C. for 15 hours to obtain 72 g of a slightly yellow powdery polymer. This product had a mass average molecular weight of 124,000 by GPC analysis based on standard polystyrene. Further, from the ¹ H-NMR analysis and the absorbance at the maximum absorption wavelength, the polymer was a copolymer of Exemplified Compound (3) and acrylamide, and Exemplified Compound (3) was contained by 30% by mass in the copolymer composition.

(Synthesis of polymer (4))
In a glass flask equipped with a cooler, a nitrogen inlet tube, a thermometer, a dropping funnel and a stirrer, a mixture of 30 g of Exemplified Compound (3), 70 g of RUVA-93 and 2.8 g of azobisisobutyronitrile, The solution was gradually added dropwise to 100 g of dimethylformamide heated to 120 ° C. and then kept at the same temperature for 4 hours. The obtained reaction solution was poured into a large excess of methanol, and the precipitated solid was collected by filtration and vacuum dried at 40 ° C. for 15 hours to obtain 61 g of a slightly yellow powdery polymer. This product had a mass average molecular weight of 47,000 by GPC analysis based on standard polystyrene. Further, from the ¹ H-NMR analysis and the absorbance at the maximum absorption wavelength, the polymer is a copolymer of Exemplified Compound (3) and RUVA-93, and Exemplified Compound (3) is contained in 30% by mass in the copolymer composition. It was.

(Synthesis of polymer (5))
30 g of Exemplified Compound (1) and 2.8 g of benzoyl peroxide were added to a benzene solution in which 70 g of polybutadiene was dissolved in a glass flask equipped with a condenser, a nitrogen inlet tube, a thermometer, a dropping funnel and a stirrer. Polymerization was carried out at 0 ° C. After drying the solid obtained from this reaction solution, the homopolymer of homopolybutadiene and exemplary compound (1) was removed by extraction to obtain a graft copolymer of polybutadiene and exemplary compound (1). This product had a mass average molecular weight of 36,000 by GPC analysis based on standard polystyrene.

(Synthesis of polymer (6))
In a glass flask equipped with a cooler, a nitrogen inlet tube, a thermometer, a dropping funnel and a stirrer, a mixture of 30 g of Exemplified Compound (4), 70 g of methyl methacrylate and 2.8 g of azobisisobutyronitrile was added. The solution was gradually added dropwise to 100 g of dimethylformamide heated to 0 ° C. and then kept at the same temperature for 4 hours. The obtained reaction solution was poured into a large excess of methanol, and the precipitated solid was collected by filtration and vacuum dried at 40 ° C. for 15 hours to obtain 77 g of a slightly yellow powdery polymer. This product had a mass average molecular weight of 159,000 by GPC analysis based on standard polystyrene. Further, from the ¹ H-NMR analysis and the absorbance at the maximum absorption wavelength, the polymer is a copolymer of Exemplified Compound (4) and methyl methacrylate, and Exemplified Compound (4) is contained in 30% by mass in the copolymer composition. It was.

(Synthesis of polymer (7))
In a glass flask equipped with a condenser, a nitrogen inlet tube, a thermometer, a dropping funnel and a stirrer, a mixture of 30 g of Exemplified Compound (5), 70 g of methyl methacrylate and 2.8 g of azobisisobutyronitrile was added. The solution was gradually added dropwise to 100 g of dimethylformamide heated to 0 ° C. and then kept at the same temperature for 4 hours. The obtained reaction solution was poured into a large excess of methanol, and the precipitated solid was collected by filtration and vacuum dried at 40 ° C. for 15 hours to obtain 85 g of a slightly yellow powdery polymer. This product had a mass average molecular weight of 253,000 by GPC analysis based on standard polystyrene. Further, from the ¹ H-NMR analysis and the absorbance at the maximum absorption wavelength, the polymer is a copolymer of Exemplified Compound (5) and methyl methacrylate, and Exemplified Compound (5) is contained in 30% by mass in the copolymer composition. It was.

(Synthesis of polymer (8))
A glass flask equipped with a cooler, a nitrogen inlet tube, a thermometer, a dropping funnel and a stirrer, and a mixture comprising 30 g of RUVA-93 (manufactured by Otsuka Chemical), 70 g of methyl methacrylate and 2.8 g of azobisisobutyronitrile. Was gradually added dropwise to 100 g of dimethylformamide heated to 120 ° C., and then kept at the same temperature for 4 hours. The obtained reaction liquid was poured into a large excess of methanol, and the precipitated solid was collected by filtration and vacuum dried at 40 ° C. for 15 hours to obtain 64 g of a slightly yellow powdery polymer. This product had a mass average molecular weight of 91,000 by GPC analysis based on standard polystyrene. Further, from the ¹ H-NMR analysis and the absorbance at the maximum absorption wavelength, the polymer was a copolymer of RUVA-93 and methyl methacrylate, and RUVA-93 was contained by 30% by mass in the copolymer composition.

Example 1: (Preparation of coating film (1))
After thoroughly mixing 30 parts of the polymer (1) obtained above and 100 parts of a 20% methylene chloride solution of a methacrylic resin (trade name: Dianal BR80, manufactured by Mitsubishi Rayon Co., Ltd.), a 100 μm polyethylene terephthalate film The film was coated with a bar coater so that the dry film thickness was 10 μm, and dried at 100 ° C. for 10 minutes.

Example 2: (Preparation of coated film (2))
After thoroughly mixing 30 parts of the polymer (2) obtained above and 100 parts of a 20% methylene chloride solution of an acrylic resin (Mitsubishi Rayon Co., Ltd.), a dry film thickness of 10 μm is formed on a 100 μm polyethylene terephthalate film. Then, it was coated with a bar coater and dried at 100 ° C. for 10 minutes.

Example 3: (Production of coated film (3))
After thoroughly mixing 30 parts of the polymer (3) obtained above and 100 parts of a 20% methylene chloride solution of acrylamide resin (manufactured by Mitsubishi Rayon Co., Ltd.), a dry film thickness of 10 μm was formed on a 100 μm polyethylene terephthalate film. Then, it was coated with a bar coater and dried at 100 ° C. for 10 minutes.

Example 4: (Preparation of coated film (4))
After thoroughly mixing 30 parts of the polymer (4) obtained above and 100 parts of a 20% polystyrene methylene chloride solution, a 100 μm polyethylene terephthalate film was dried with a bar coater to a dry film thickness of 10 μm. It was applied and dried at 100 ° C. for 10 minutes.

Example 5: (Preparation of coated film (5))
After 30 parts of the polymer (1) obtained above and 100 parts of a 20% polyethylene methylene chloride solution were mixed well, a 100 μm polyethylene terephthalate film was mixed with a bar coater so that the dry film thickness was 10 μm. It was applied and dried at 100 ° C. for 10 minutes.

Example 6: (Preparation of coated film (6))
1 part of the polymer (5) obtained above was dissolved in 100 parts of methylene chloride, and applied to a 100 μm polyethylene terephthalate film with a bar coater so that the dry film thickness was 10 μm. Dried for minutes.

Example 7: (Preparation of coating film (7))
After thoroughly mixing 30 parts of the polymer (6) obtained above and 100 parts of a 20% methylene chloride solution of a methacrylic resin (trade name: Dianal BR80, manufactured by Mitsubishi Rayon Co., Ltd.), a 100 μm polyethylene terephthalate film The film was coated with a bar coater so that the dry film thickness was 10 μm, and dried at 100 ° C. for 10 minutes.

Example 8: (Preparation of coated film (8))
After thoroughly mixing 30 parts of the polymer (7) obtained above and 100 parts of a 20% methylene chloride solution of a methacrylic resin (trade name: Dianal BR80, manufactured by Mitsubishi Rayon Co., Ltd.), a 100 μm polyethylene terephthalate film The film was coated with a bar coater so that the dry film thickness was 10 μm, and dried at 100 ° C. for 10 minutes.

Comparative Example 1: (Production of coated film (9))
After thoroughly mixing 30 parts of the polymer (8) obtained above and 100 parts of a 20% methylene chloride solution of a methacrylic resin (trade name: Dianal BR80, manufactured by Mitsubishi Rayon Co., Ltd.), a 100 μm polyethylene terephthalate film The film was coated with a bar coater so that the dry film thickness was 10 μm, and dried at 100 ° C. for 10 minutes.

Comparative Example 2: (Production of coated film (10))
After thoroughly mixing 1 part of the comparative compound (2) and 100 parts of a 20% methylene chloride solution of a methacrylic resin (trade name: Dianal BR80, manufactured by Mitsubishi Rayon Co., Ltd.), a dry film thickness is formed on a 100 μm polyethylene terephthalate film. The film was coated with a bar coater so as to have a thickness of 10 μm, and dried at 100 ° C. for 10 minutes.

Comparative Example 3: (Production of coated film (11))
Dissolve only base polymer (methacrylic resin) in solvent and apply (comparative example)
Only 100 parts of a 20% methylene chloride solution of methacrylic resin (trade name: Dianal BR80, manufactured by Mitsubishi Rayon Co., Ltd.) is coated on a 100 μm polyethylene terephthalate film with a bar coater so that the dry film thickness is 10 μm. And dried at 100 ° C. for 10 minutes.

<Evaluation test>
About each produced film, a metal halide lamp (about 290 nm or less in the presence of a cut filter) (trade name: iSuper UV Tester, manufactured by Iwasaki Electric Co., Ltd.), illuminance of 90 mW / cm ² , relative temperature of 63 ° C., humidity of 50%, 1000 hours Irradiated with light.
The film was visually observed before and after irradiation, and the stain (bleed out) and hue change on the film surface were evaluated.
Surface contamination: ○ indicates no change in hue, Δ indicates slightly colored, and × indicates large coloring.
Hue change: ◯ indicates no hue change, Δ indicates slight coloration, and x indicates large coloration.
The results are shown in Table 1.

Example 9: (Production of resin molded product (1))
10 parts of the polymer (1) obtained above and 10 parts of methacrylic resin (trade name: Acrypet VH-001, manufactured by Mitsubishi Rayon Co., Ltd.) were extruded at 260 ° C. to produce pellets.
Next, 1 part of the pellet obtained above was added to 10 parts of methacrylic resin (trade name: Acrypet VH-001, manufactured by Mitsubishi Rayon Co., Ltd.), kneaded, injection molded at 260 ° C., and 2 mm thick A film was prepared.

Example 10: (Preparation of resin molded product (2))
10 parts of the polymer (2) obtained above and 10 parts of methacrylic resin (trade name: Acrypet VH-001, manufactured by Mitsubishi Rayon Co., Ltd.) were extruded at 260 ° C. to produce pellets.
Next, 1 part of the pellets obtained above was added to 10 parts of methacrylic resin, kneaded, and injection molded at 260 ° C. to produce a 2 mm thick film.

Example 11: (Production of resin molded product (3))
10 parts of the polymer (3) obtained above and 10 parts of a polyethylene terephthalate resin (trade name: Unipet RT543, manufactured by Nihon Unipet) were extruded at 280 ° C. to produce pellets.
Next, 1 part of the pellet obtained above was added to 10 parts of polyethylene terephthalate resin, kneaded, and extruded at 280 ° C. to produce a film having a thickness of 2 mm.

Example 12: (Production of resin molded product (4))
10 parts of the polymer (4) obtained above and 10 parts of a polycarbonate resin (trade name: Panlite L-1250Y, manufactured by Teijin Chemicals) were extruded at 300 ° C. to produce pellets.
Subsequently, 1 part of the pellets obtained above was added to 10 parts of the polycarbonate resin, kneaded, and injection molded at 300 ° C. to produce a film having a thickness of 2 mm.

Example 13: (Production of resin molded product (5))
10 parts of the polymer (1) obtained above and 10 parts of polyethylene naphthalate resin (trade name: Teonex TN8065S, manufactured by Teijin) were extruded at 260 ° C. to produce pellets.
Next, 1 part of the pellets obtained above was added to 10 parts of polyethylene naphthalate resin, kneaded, and injection molded at 260 ° C. to produce a 2 mm thick film.

Example 14: (Production of resin molded product (6))
10 parts of the polymer (7) obtained above and 10 parts of methacrylic resin (trade name: Acrypet VH-001, manufactured by Mitsubishi Rayon Co., Ltd.) were extruded at 260 ° C. to produce pellets.
Next, 1 part of the pellet obtained above was added to 10 parts of methacrylic resin (trade name: Acrypet VH-001, manufactured by Mitsubishi Rayon Co., Ltd.), kneaded, injection molded at 260 ° C., and 2 mm thick A film was prepared.

Comparative Example 4: (Production of resin molded product (7))
10 parts of the polymer (8) obtained above and 10 parts of methacrylic resin (trade name: Acrypet VH-001, manufactured by Mitsubishi Rayon Co., Ltd.) were extruded at 260 ° C. to produce pellets.
Next, 1 part of the pellet obtained above was added to 10 parts of methacrylic resin (trade name: Acrypet VH-001, manufactured by Mitsubishi Rayon Co., Ltd.), kneaded, injection molded at 260 ° C., and 2 mm thick A film was prepared.

Comparative Example 5: (Production of resin molded product (8))
One part of the comparative compound (2) and 30 parts of methacrylic resin (trade name: Acrypet VH-001, manufactured by Mitsubishi Rayon Co., Ltd.) were extruded at 260 ° C. to produce pellets.
Next, 1 part of the pellet obtained above was added to 10 parts of methacrylic resin (trade name: Acrypet VH-001, manufactured by Mitsubishi Rayon Co., Ltd.), kneaded, injection molded at 260 ° C., and 2 mm thick A film was prepared.

Comparative Example 6: (Production of resin molded product (9))
Methacrylic resin (trade name: Acrypet VH-001, manufactured by Mitsubishi Rayon Co., Ltd.) was injection-molded at 260 ° C. to produce a film having a thickness of 2 mm.

<Evaluation test>
About each produced film, a metal halide lamp (about 290 nm or less in the presence of a cut filter) (trade name: iSuper UV Tester, manufactured by Iwasaki Electric Co., Ltd.), illuminance of 90 mW / cm ² , relative temperature of 63 ° C., humidity of 50%, 1000 hours Irradiated with light.

[Visual film]
The film was visually observed before and after irradiation, and the contamination (bleed out) on the film surface was evaluated.
Surface contamination: ○ indicates no change in hue, Δ indicates slightly colored, and × indicates large coloring.

[Change in breaking strength]
After irradiation, using a strograph VE10D (manufactured by Toyo Seiki), a tensile test was performed to measure the breaking strength. The difference from the breaking strength before irradiation was evaluated according to the following criteria, and changes in breaking strength are listed in Table 2. did.
○: Post-irradiation breaking strength value / pre-irradiation breaking strength value X100 ≧ 80 ... very good Δ: 80> Post-irradiation breaking strength value / pre-irradiation breaking strength value X100 ≧ 50 ... Good x: 50> Post-irradiation breaking strength value / irradiation Pre-breaking strength value X100 ... Poor

[Light resistance]
Each molded film was irradiated with a metal halide lamp (in the presence of a cut filter of about 290 nm or less) (trade name: iSuper UV Tester, manufactured by Iwasaki Electric Co., Ltd.) under the conditions of an illuminance of 90 mW / cm ² , a temperature of 63 ° C., and a relative humidity of 50%. did. The residual amount of each compound was measured.
The evaluation was made as follows and shown in Table 2 below.
Each film sheet was evaluated for the time taken for the shielding rate to reach 5% after light irradiation at a wavelength where the shielding rate before light irradiation was 1%. When the time taken when the film of the resin molded product (6) was tested was 1, it was evaluated according to the following criteria and listed in Table 2 as light resistance.
◎: 4 or more ○: 2 or more and less than 4 △: 1 or more and less than 2 ×: 0.1 or more and less than 1

Claims (7)

A polymer having a structural unit derived from a monomer represented by any one of the following exemplary compounds (1) to (5) .

A polymer composition comprising the polymer according to claim 1 . An ultraviolet absorber comprising the polymer according to claim 1 . A paint comprising the ultraviolet absorber according to claim 3 . A polymer having a structural unit derived from a monomer represented by any of the following exemplary compounds (1) to (5) ;
A resin composition comprising at least one selected from an acrylic resin, a methacrylic resin, an acrylamide resin, a polystyrene resin, a polyethylene resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, and a polycarbonate resin.

A coated film comprising the resin composition according to claim 5 . A resin molded product comprising the resin composition according to claim 5 .