JP2012214385A - Compound, and resin composition and film containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound having excellent ultraviolet absorbing power and hardly bleeding out; and to provide a resin composition and a film containing the same.SOLUTION: The compound is represented by, for example, formula (3), wherein Aris a di- to deca-valent 5- to 20-membered aromatic residue, which may contain a heteroatom, and may contain a substituent; a ring bonded to Armay have a double bond at any position; Rand Rare a 1-20C divalent hydrocarbon group; Rand Rare a 1-20C monovalent hydrocarbon group; and nand nare an integer of 1 to 4.

Description

  The present invention relates to a compound that can be used as an ultraviolet absorber. Moreover, it is related with the resin composition containing this compound. Moreover, it is related with the film containing this compound.

  Conventionally, polymer materials such as polyester, polyamide, polyolefin, polyether, polystyrene cause degradation and decomposition by the action of ultraviolet rays, for example, discoloration such as yellowing occurs, mechanical strength decreases, etc. It is known that it cannot withstand long-term use. And also in the resin product which consists of these polymeric materials, the problem regarding discoloration and long-term use will arise similarly.

  Therefore, in order to prevent such degradation and decomposition of the polymer material, various ultraviolet absorbers have been conventionally studied and used together with these polymer materials. As such ultraviolet absorbers, for example, benzophenone, benzotriazole, salicylic acid, hydroquinone and the like are well known.

  However, these conventional ultraviolet absorbers themselves are inferior in heat resistance, so that there is a problem that they are deteriorated or decomposed during the processing of the polymer material or when used at a high temperature. Therefore, ultraviolet absorbers as disclosed in Patent Documents 1 to 5 have been studied. In recent years, studies such as Patent Documents 6 to 11 have been made.

JP 58-194854 A JP 59-12952 A JP 7-11231 A Japanese Patent Laid-Open No. 7-11232 JP 2009-84508 A JP 2009-96794 A JP 2009-242039 A JP 2010-59122 A JP 2010-64979 A JP 2010-64980 A JP 2010-83791 A JP 2009-242641 A JP 2010-83980 A

  On the other hand, in recent years, for example, resin molded products used as parts and casings for electronic products and optical products, magnetic tapes, photographic films, packaging films, films for electronic parts, electrical insulation films, films for laminating metal plates Further, in resin products made of the above polymer materials such as a resin film used as an optical film, it is required to further reduce defects such as scratches and foreign matters on the surface. Under such circumstances, there is a problem that the ultraviolet absorber contained in the polymer material diffuses in the polymer material at room temperature to high temperature and bleeds out to the surface.

  Further, according to the study by the present inventors, particularly when a resin film is produced, the added ultraviolet absorber is heated during the film production process, for example, in the polyester film production process, particularly in the heat setting process. Bleed out on the film surface by heating, sublimated, recrystallized and adhered on the inner wall of the film forming machine (tenter), the amount of deposits increased, the influence of wind in the film forming machine or any other impact The recrystallized UV absorber is dropped from the inner wall of the tenter by being added to the surface of the tenter and blown off by hot air to adhere to the film surface, resulting in surface defects, or recrystallized from the film surface. The UV absorber adheres to the later roll and becomes a foreign object. A problem that may become has been found to occur. The inventors of the present invention have paid attention to the need to suppress the bleed-out of the ultraviolet absorber in order to produce such a product having few surface defects and excellent quality with high efficiency. In addition, although the report which suppresses the bleed-out of a ultraviolet absorber is disclosed by patent document 12 and 13, for example, these have problems, such as being complicated as using 2 types of agents together.

  Therefore, an object of the present invention is to provide a compound that has excellent ultraviolet absorption ability and is difficult to bleed out. Moreover, it is providing the resin composition containing such a compound. Moreover, it is providing the film containing such a compound.

  Further, according to the study by the present inventors, when the molecular structure is designed to make the compound difficult to bleed out as described above, the light absorption wavelength shifts by 10 nm or more to the long wavelength side or the short wavelength side. It has been found that the absorption wavelength of the compound has an influence on the visible light region, and the resin to which the compound is added is discolored, for example, yellowing.

  Therefore, a desirable problem in the present invention is to suppress the discoloration of the resin by addition to such an extent that it has excellent ultraviolet absorption ability as described above and is difficult to bleed out and can be suitably used for optical applications. It is to provide a compound that can be used. Another object of the present invention is to provide a resin composition containing such a compound, in which discoloration is suppressed. Moreover, it is providing the film by which the discoloration containing such a compound was suppressed.

（ただし、式中、
Ａｒ^１は、２〜１０価の５〜２０員環の芳香族残基を表わす。また、該芳香族残基はヘテロ原子を含有していてもよく、置換基を有していてもよい。
Ａｒ^１に結合している環は、任意の位置に二重結合を有していてもよい。
Ｘ^ａ、Ｘ^ｂおよびＸ^ｃは、互いに独立してヘテロ原子を表わす。また、Ｘ^ａ、Ｘ^ｂおよびＸ^ｃは、置換基を有していてもよい。
Ｒ^ａ１は、炭素数１〜２０の２価の炭化水素基を表わす。
Ｒ^ｂ１は、炭素数１〜２０の１価の炭化水素基を表わす。
ｍ^１は、２〜１０の整数を表わす。
ｎ^１は、１〜４の整数を表わす。）
２．前記一般式（１）で表わされる化合物が、下記一般式（２）で表わされる化合物である、上記１に記載の化合物。

（ただし、式中、
Ａｒ^２は、前記一般式（１）のＡｒ^１と同義である。
Ｒ^ａ２は、前記一般式（１）のＲ^ａ１と同義である。
Ｒ^ｂ２は、前記一般式（１）のＲ^ｂ１と同義である。
ｍ^２は、前記一般式（１）のｍ^１と同義である。
ｎ^２は、前記一般式（１）のｎ^１と同義である。）
３．前記一般式（２）で表わされる化合物が、下記一般式（３）で表わされる化合物である、上記２に記載の化合物。

（ただし、式中、
Ａｒ^３は、２価の５〜２０員環の芳香族残基を表わす。また、該芳香族残基はヘテロ原子を含有していてもよく、置換基を有していてもよい。
Ｒ^ａ３およびＲ^ａ３’は、互に独立して、炭素数１〜２０の２価の炭化水素基を表わす。
Ｒ^ｂ３およびＲ^ｂ３’は、互いに独立して、炭素数１〜２０の１価の炭化水素基を表わす。
ｎ^３およびｎ^３’は、互に独立して、１〜４の整数を表わす。）
４．前記一般式（３）で表わされる化合物が、下記一般式（４）で表わされる化合物である、上記３に記載の化合物。

（ただし、式中、
Ｒ^ａ４およびＲ^ａ４’は、前記一般式（３）のＲ^ａ３およびＲ^ａ３’と同義である。
Ｒ^ｂ４およびＲ^ｂ４’は、前記一般式（３）のＲ^ｂ３およびＲ^ｂ３’と同義である。
ｎ^４およびｎ^４’は、前記一般式（３）のｎ^３およびｎ^３’と同義である。）
５．前記一般式（４）で表わされる化合物が、下記一般式（５）で表わされる化合物である、上記４に記載の化合物。

（ただし、式中、
Ｒ^ａ５およびＲ^ａ５’は、前記一般式（４）のＲ^ａ４およびＲ^ａ４’と同義である。
Ｒ^ｂ５およびＲ^ｂ５’は、前記一般式（４）のＲ^ｂ４およびＲ^ｂ４’と同義である。） The present invention adopts the following configuration in order to solve the above problems.
1. A compound represented by the following general formula (1).

(However, in the formula,
Ar ¹ represents a divalent to 10-valent 5- to 20-membered aromatic residue. Moreover, this aromatic residue may contain a hetero atom and may have a substituent.
The ring bonded to Ar ¹ may have a double bond at any position.
X ^a , X ^b and X ^c each independently represent a hetero atom. X ^a , X ^b and X ^c may have a substituent.
R ^a1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
R ^b1 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.
m ¹ represents an integer of 2 to 10.
n ¹ represents an integer of 1 to 4. )
2. 2. The compound according to 1 above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(However, in the formula,
Ar ² has the same meaning as Ar ^{1 in the} general formula (1).
R ^a2 is the same as defined in the ^{R a1} in formula (1).
R ^b2 is the same as defined in the ^{R b1} in formula (1).
m ² has the same meaning as m ^{1 in the} general formula (1).
n ² has the same meaning as n ^{1 in the} general formula (1). )
3. 3. The compound according to 2 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

(However, in the formula,
Ar ³ represents a divalent 5- to 20-membered aromatic residue. Moreover, this aromatic residue may contain a hetero atom and may have a substituent.
R ^a3 and R ^{a3 ′} each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms.
R ^b3 and R ^{b3 ′} each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms.
n ³ and n ^{3 ′} each independently represent an integer of 1 to 4. )
4). 4. The compound according to 3 above, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (4).

(However, in the formula,
R ^a4 and R ^{a4 ′} have the same ^meanings as R ^a3 and R ^{a3 ′ in} formula (3).
R ^b4 and R ^{b4 ′} have the same ^meanings as R ^b3 and R ^{b3 ′ in the} general formula (3).
n ⁴ and n ^{4 ′} are synonymous with n ³ and n ^{3 ′ in the} general formula (3). )
5. 5. The compound according to 4 above, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5).

(However, in the formula,
R ^a5 and R ^{a5 ′} have the same ^meanings as R ^a4 and R ^{a4 ′ in} formula (4).
R ^b5 and R ^{b5 ′} have the same ^meanings as R ^b4 and R ^{b4 ′ in the} general formula (4). )

Moreover, this invention includes the following aspects.
6). The ultraviolet absorber which consists of a compound of any one of said 1-5.
7). The resin composition containing the compound of any one of said 1-5.
8). The film containing the compound of any one of said 1-5.

  ADVANTAGE OF THE INVENTION According to this invention, the compound which is hard to bleed out and has the outstanding ultraviolet absorptivity can be provided. Moreover, the resin composition containing such a compound can be provided. Moreover, the film containing such a compound can be provided. Accordingly, surface defects due to bleeding out of the ultraviolet absorber can be suppressed in the resin product. In particular, in a resin film, it is possible to suppress bleed-out of an ultraviolet absorber and surface defects caused by sublimation and recrystallization. And the resin product in which the surface defect was suppressed can be used suitably as an electronic product, an optical product, etc., especially in a resin film as an optical film.

  Furthermore, according to a desirable aspect of the present invention, as described above, it has excellent ultraviolet absorption ability and bleed out suppression ability, and at the same time, it suppresses resin discoloration due to addition to such an extent that it can be suitably used for optical applications. In addition, it is possible to provide a resin composition containing such a compound and capable of suppressing discoloration. Moreover, the film by which the discoloration containing such a compound was suppressed can be provided. These resin products in which discoloration is suppressed have high colorlessness and can be suitably used particularly for optical products. In particular, in a resin film, it can be suitably used as an optical film.

Hereinafter, the present invention will be described in detail.
[Compound represented by general formula (1)]
The compound of the present invention is a compound represented by the following general formula (1). The compound of the present invention is a substituent having a specific structure such as an (R ^b1 —CO—O—R ^a1 —O—) group in a skeleton portion composed of a ring containing X ^a , X ^b , and X ^c and a benzene ring. Thus, a high bleed-out suppression effect is imparted while maintaining the excellent ultraviolet absorbing ability of the skeleton portion.

（ただし、式中、
Ａｒ^１は、２〜１０価の５〜２０員環の芳香族残基を表わす。また、該芳香族残基はヘテロ原子を含有していてもよく、置換基を有していてもよい。
Ａｒ^１に結合している環は、任意の位置に二重結合を有していてもよい。
Ｘ^ａ、Ｘ^ｂおよびＸ^ｃは、互いに独立してヘテロ原子を表わす。また、Ｘ^ａ、Ｘ^ｂおよびＸ^ｃは、置換基を有していてもよい。
Ｒ^ａ１は、炭素数１〜２０の２価の炭化水素基を表わす。
Ｒ^ｂ１は、炭素数１〜２０の１価の炭化水素基を表わす。
ｍ^１は、２〜１０の整数を表わす。
ｎ^１は、１〜４の整数を表わす。）

(However, in the formula,
Ar ¹ represents a divalent to 10-valent 5- to 20-membered aromatic residue. Moreover, this aromatic residue may contain a hetero atom and may have a substituent.
The ring bonded to Ar ¹ may have a double bond at any position.
X ^a , X ^b and X ^c each independently represent a hetero atom. X ^a , X ^b and X ^c may have a substituent.
R ^a1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
R ^b1 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.
m ¹ represents an integer of 2 to 10.
n ¹ represents an integer of 1 to 4. )

In General Formula (1), Ar ¹ represents a divalent to 10-valent 5- to 20-membered aromatic residue. The aromatic ring constituting Ar ¹ may be a monocyclic ring, a polycyclic ring, or a condensed ring. In the case of a single ring, Ar ¹ is preferably a 5- to 10-membered ring, and more preferably a 5- to 6-membered ring. Moreover, when it is polycyclic, what the said monocyclic thing couple | bonded is preferable. In the case of a condensed ring, Ar ¹ is preferably a 2-10 cyclic aromatic ring in which a 5-10 membered ring is condensed, and a 2-5 cyclic aromatic ring in which a 5-6 membered ring is condensed. More preferred.
Ar ¹ is preferably a divalent to hexavalent group, more preferably a divalent to tetravalent group, and even more preferably divalent from the viewpoints of cost, ease of obtaining a compound, and the like.

The aromatic residue Ar ¹ may contain a hetero atom. Examples of the hetero atom that Ar ¹ may contain include a boron atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, a selenium atom, and a tellurium atom. The hetero atom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom, more preferably a nitrogen atom or a sulfur atom, and particularly preferably a sulfur atom. When it has two or more hetero atoms, they may be the same atom or different atoms.

Ar ¹ is a 2 to 10 valent aromatic residue obtained by removing 2 to 10 hydrogen atoms from a 5 to 20-membered aromatic compound. Specific examples of such aromatic compounds include, for example, benzene, biphenyl, triphenylmethane, naphthalene, anthracene, indene, azulene, biphenylene, fluorene, phenanthrene, pyrene, triphenylene, tetraphenylene, perylene, pentacene, coronene, chrysene. Pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, furan, thiophene, oxazole, isoxazole, thiazole, Examples thereof include isothiazole, 1,2,3-oxadiazole, 1,3,4-thiadiazole and the like. The aromatic compound is preferably benzene, biphenyl, naphthalene, pyridine, or thiophene. More preferred are benzene, biphenyl and thiophene. Particularly preferred is benzene.

  The position for removing the hydrogen atom from the aromatic compound may be any location. In the case of a divalent aromatic residue, examples of the binding position of the 6-membered ring compound benzene include the 1,2-position, 1,3-position, and 1,4-position. Examples of the binding position of biphenyl include the 3,3′-position and the 4,4′-position. Examples of the bonding position in the hetero 5-membered ring compound pyrrole include the 2,3-position, 2,4-position, 2,5-position, 3,4-position, and 3,5-position. In addition, the bonding positions in the hetero 6-membered ring compound pyridine are 2, 3, 2, 4, 5, 5, 2, 6, 3, 4, 3, 5, or 3, 6 positions. Can be mentioned. In the case of a trivalent aromatic residue, for example, the bonding position of the 6-membered ring compound benzene is 1,2,3, 1,2,4, 1,2,5, or 1,3,5. Rank.

In the present invention, the aromatic residue represented by Ar ¹ is preferably an aromatic acid group which is divalent benzene and has a bonding position at the 1,3-position (meta-position). By setting it as such an aspect, discoloration of resin when a compound is added to resin can be suppressed more. Such an effect is that the compound has an (R ^b1 —O—CO—R ^a1 —O—) group in the form as shown in the general formula (1) and adopts the structure of the aromatic residue as described above. This is an effect that can be achieved.

The aromatic residue Ar ¹ may have a substituent. A monovalent substituent is mentioned as a substituent. Examples of the monovalent substituent (hereinafter referred to as R) include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear or branched alkyl group having 1 to 20 carbon atoms (for example, methyl, Ethyl), an aryl group having 6 to 20 carbon atoms (for example, phenyl, naphthyl), a cyano group, a carboxyl group, an alkoxycarbonyl group (for example, methoxycarbonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl), a substituted or unsubstituted carbamoyl group (Eg carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl group (eg acetyl), arylcarbonyl group (eg benzoyl), nitro group, substituted or unsubstituted amino group (eg amino, dimethylamino, Anilino), acylamino groups (eg aceto Imide, ethoxycarbonylamino), sulfonamide group (eg methanesulfonamide), imide group (eg succinimide, phthalimide), imino group (eg benzylideneamino), hydroxy group, alkoxy group 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 groups (eg sulfamoyl) N-phenylsulfamoyl), alkylthio group (eg methylthio), arylthio group (eg phenylthio), alkylsulfonyl group (eg methanesulfonyl), arylsulfonyl (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 R can be mentioned as an example of a substituent. Moreover, you may combine with substituents and may form a ring.
Preferred examples of the substituent include an alkyl group, an alkoxy group, and an aryl group. An alkyl group and an aryl group are more preferable, and an alkyl group is particularly preferable.

In the general formula (1), X ^a , X ^b and X ^c each independently represent a hetero atom. Examples of the hetero atom include a boron atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, a selenium atom, and a tellurium atom. A hetero atom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. More preferably, they are a nitrogen atom and an oxygen atom. By selecting these heteroatoms, the effect of improving the ultraviolet absorption ability can be enhanced, the wavelength characteristics are excellent, and the stability and heat resistance of the compound can be enhanced. It is also easy to manufacture. X ^a , X ^b and X ^c may have a substituent. For example, the nitrogen atom is selected as X ^a, when the bond between the carbon and X ^a are bonded to Ar ¹ is a single bond, the nitrogen atom is selected as X ^b, in combination with Ar ¹ When the bond between carbon and ^Xb is a single bond, or when a nitrogen atom is selected as ^Xc , the nitrogen atom appropriately has a substituent. Examples of the substituent include the examples of the monovalent substituent R described above.

The ring bonded to Ar ¹ including the above X ^a , X ^b and X ^c may have a double bond at an arbitrary position. For example, when ^a nitrogen atom is selected as X ^a , a double bond may be formed between the carbon bonded to Ar ¹ and X ^a . In the case where the nitrogen atom is selected as X ^b, between the carbon and X ^b are bonded to Ar ¹ may be a double bond.

In the general formula (1), R ^a1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. Such a hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, may contain a branched structure, or may contain a cyclic structure. Further, it may be a saturated hydrocarbon group or may have an unsaturated bond. Furthermore, you may have a substituent. As the hydrocarbon group, in particular, from the viewpoint that the effect of suppressing bleeding out can be increased, from the viewpoint of improving the effect of suppressing discoloration of the resin when added to the resin, and from the viewpoint of excellent stability, A divalent hydrocarbon group having 1 to 10 carbon atoms is preferred. Saturated and chained aliphatic hydrocarbon groups are preferred. As for carbon number, 1-6 are more preferable, and a methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group and 1,6-hexylene group are preferable. Further, the number of carbon atoms is more preferably 1 to 4, and further preferably an ethylene group, a 1,2-propylene group, and a butylene group.

In the general formula (1), R ^b1 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. Such a hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, may contain a branched structure, or may contain a cyclic structure. Further, it may be a saturated hydrocarbon group or may have an unsaturated bond. Furthermore, you may have a substituent. As the hydrocarbon group, in particular, from the viewpoint that the effect of suppressing bleeding out can be increased, from the viewpoint of improving the effect of suppressing discoloration of the resin when added to the resin, and from the viewpoint of excellent stability, A monovalent hydrocarbon group having 1 to 10 carbon atoms is preferred. Saturated and chained aliphatic hydrocarbon groups are preferred. The number of carbon atoms is more preferably 1 to 4, and a methyl group, an ethyl group, a 1,2-propyl group, a 1,3-propyl group, a 1,4-butyl group, and a 1,6-hexyl group are preferable. Furthermore, as for carbon number, 1-2 are more preferable, and a methyl group and an ethyl group are still more preferable.
In the present invention, in particular, by having a substituent having a specific structure having R ^a1 and R ^b1 at the same time, bleeding out of the compound and discoloration of the resin can be suppressed.

In the general formula (1), m ¹ represents an integer of 2 to 10. From the viewpoint of absorption wavelength and solubility, m ¹ is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 2. Moreover, the effect which suppresses discoloration of resin at the time of adding to resin can be heightened by setting it as the said range.
In the general formula (1), n ¹ represents an integer of 1 to 4. From the viewpoint that the effect of suppressing discoloration of the resin when added to the resin can be enhanced, n ¹ is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1. .

[Compound represented by formula (2)]
Furthermore, the compound represented by the general formula (1) is preferably a compound represented by the following general formula (2). By adopting such a configuration, the compound represented by the general formula (1) is further excellent in ultraviolet absorption ability while maintaining the bleed-out suppressing effect or more excellent. It can be. Further, the stability as a compound is improved, and the ultraviolet absorbing ability can be maintained over a long period of time. Furthermore, the synthesis is easy, and the cost and productivity are excellent.

（ただし、式中、
Ａｒ^２は、前記一般式（１）のＡｒ^１と同義である。
Ｒ^ａ２は、前記一般式（１）のＲ^ａ１と同義である。
Ｒ^ｂ２は、前記一般式（１）のＲ^ｂ１と同義である。
ｍ^２は、前記一般式（１）のｍ^１と同義である。
ｎ^２は、前記一般式（１）のｎ^１と同義である。）

(However, in the formula,
Ar ² has the same meaning as Ar ^{1 in the} general formula (1).
R ^a2 is the same as defined in the ^{R a1} in formula (1).
R ^b2 is the same as defined in the ^{R b1} in formula (1).
m ² has the same meaning as m ^{1 in the} general formula (1).
n ² has the same meaning as n ^{1 in the} general formula (1). )

In the general formula (2), Ar ² has the same meaning as Ar ^{1 in the} general formula (1), and the preferred embodiment and the obtained effect are also the same.
In the general formula (2), R ^a2 has the same meaning as R ^{a1 in the} general formula (1), and the preferred embodiments and the effects obtained are also the same.
In the general formula (2), R ^b2 has the same meaning as R ^{b1 in the} general formula (1), and the preferred embodiment and the obtained effects are also the same.
In the general formula (2), m ² has the same meaning as m ¹ in the general formula (1), a preferable embodiment thereof is also the same and the resulting effect.
In the general formula (2), n ² has the same meaning as n ^{1 in the} general formula (1), and the preferred embodiment and the obtained effect are also the same.

[Compound represented by the general formula (3)]
Furthermore, the compound represented by the general formula (2) is preferably a compound represented by the following general formula (3). By adopting such a configuration, the compound represented by the general formula (2) has a further excellent bleed-out suppressing effect while maintaining the ultraviolet absorbing ability or further improving these. Can be. Further, the stability as a compound is further improved, and the ultraviolet absorbing ability can be maintained for a longer period. Furthermore, synthesis is easier, and the cost and productivity are further improved.

（ただし、式中、
Ａｒ^３は、２価の５〜２０員環の芳香族残基を表わす。また、該芳香族残基はヘテロ原子を含有していてもよく、置換基を有していてもよい。
Ｒ^ａ３およびＲ^ａ３’は、互に独立して、炭素数１〜２０の２価の炭化水素基を表わす。
Ｒ^ｂ３およびＲ^ｂ３’は、互いに独立して、炭素数１〜２０の１価の炭化水素基を表わす。
ｎ^３およびｎ^３’は、互に独立して、１〜４の整数を表わす。）

(However, in the formula,
Ar ³ represents a divalent 5- to 20-membered aromatic residue. Moreover, this aromatic residue may contain a hetero atom and may have a substituent.
R ^a3 and R ^{a3 ′} each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms.
R ^b3 and R ^{b3 ′} each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms.
n ³ and n ^{3 ′} each independently represent an integer of 1 to 4. )

In the general formula (3), Ar ³ represents a divalent 5- to 20-membered aromatic residue. Here, examples of the divalent 5- to 20-membered aromatic residue include the examples described above for Ar ¹ in the general formula (1), and the preferred embodiments and the obtained effects are also the same.
The aromatic residue Ar ³ may contain a hetero atom. The aromatic residue Ar ³ may have a substituent. Examples of such an embodiment containing a hetero atom and an embodiment having a substituent include examples of an embodiment containing a hetero atom described above for Ar ¹ in the general formula (1) and an embodiment having a substituent. The same effect is obtained.

In the general formula (3), R ^a3 and R ^{a3 ′} each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms. Here, as a C1-C20 bivalent hydrocarbon group, the example mentioned above about ^Ra1 in the said General formula (1) is mentioned, A preferable aspect and the effect obtained are also the same.
In the general formula (3), R ^b3 and R ^{b3 ′} each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms. Here, as a C1-C4 monovalent hydrocarbon group, the example mentioned above about ^Rb1 in the said General formula (1) is mentioned, A preferable aspect and the effect acquired are also the same.
In the general formula (3), ^{n 3} and n ^{3 'is} mutually independently represent an integer of 1-4. Here, examples of n ³ and n ^{3 ′} include the examples described above for n ¹ in the general formula (1), and preferred embodiments and obtained effects are also the same.

[Compound represented by formula (4)]
Furthermore, the compound represented by the general formula (3) is preferably a compound represented by the following general formula (4). By adopting such a configuration, the compound represented by the general formula (3) retains the ultraviolet absorbing ability and the bleed-out suppressing effect, or further improves these, and suppresses discoloration. The effect can be further improved. Further, the stability as a compound is further improved, and the ultraviolet absorbing ability can be maintained for a longer period. Furthermore, the solubility is increased, the synthesis is easier, and the cost and productivity are further improved.

（ただし、式中、
Ｒ^ａ４およびＲ^ａ４’は、前記一般式（３）のＲ^ａ３およびＲ^ａ３’と同義である。
Ｒ^ｂ４およびＲ^ｂ４’は、前記一般式（３）のＲ^ｂ３およびＲ^ｂ３’と同義である。
ｎ^４およびｎ^４’は、前記一般式（３）のｎ^３およびｎ^３’と同義である。）

(However, in the formula,
R ^a4 and R ^{a4 ′} have the same ^meanings as R ^a3 and R ^{a3 ′ in} formula (3).
R ^b4 and R ^{b4 ′} have the same ^meanings as R ^b3 and R ^{b3 ′ in the} general formula (3).
n ⁴ and n ^{4 ′} are synonymous with n ³ and n ^{3 ′ in the} general formula (3). )

In the general formula (4), R ^a4 and R ^{a4 ′} have the same ^meanings as R ^a3 and R ^{a3 ′ in the} general formula (3), and preferred embodiments and obtained effects are also the same.
In the general formula (4), R ^b4 and R ^{b4 ′} have the same ^meanings as R ^b3 and R ^{b3 ′ in the} general formula (3), and the preferred embodiments and obtained effects are also the same.
In the general formula (4), ^{n 4} and n ^{4 ',} the general formula (3) ^{n 3} and n ^3' of the same meaning as, preferable embodiments thereof are also the same and the resulting effect.

[Compound represented by formula (5)]
Furthermore, the compound represented by the general formula (4) is preferably a compound represented by the following general formula (5). By adopting such a configuration, the compound represented by the general formula (4) retains the ultraviolet absorption ability and the bleed-out suppressing effect, or further improves these, and suppresses discoloration. The effect can be further improved. Further, the stability as a compound is further improved, and the ultraviolet absorbing ability can be maintained for a longer period. Furthermore, the reactivity is increased, the synthesis is easier, the synthesis can be performed efficiently, and the cost and productivity are further improved.

（ただし、式中、
Ｒ^ａ５およびＲ^ａ５’は、前記一般式（４）のＲ^ａ４およびＲ^ａ４’と同義である。
Ｒ^ｂ５およびＲ^ｂ５’は、前記一般式（４）のＲ^ｂ４およびＲ^ｂ４’と同義である。）

(However, in the formula,
R ^a5 and R ^{a5 ′} have the same ^meanings as R ^a4 and R ^{a4 ′ in} formula (4).
R ^b5 and R ^{b5 ′} have the same ^meanings as R ^b4 and R ^{b4 ′ in the} general formula (4). )

In the general formula (5), R ^a5 and R ^{a5 ′} have the same ^meanings as R ^a4 and R ^{a4 ′ in the} general formula (4), and preferred embodiments and effects obtained are also the same.
In the general formula (5), R ^b5 and R ^{b5 ′} have the same ^meanings as R ^b4 and R ^{b4 ′ in the} general formula (4), and preferred embodiments and obtained effects are also the same.

[Method for producing compound]
The compound represented by any one of the general formulas (1) to (5) can be synthesized by any method. For example, known patent documents and the like, for example, Examples and Comparative Examples of JP-A-57-209799, Examples and Comparative Examples of JP-A-7-11231, Examples and Comparative Examples of JP-A-2009-286717 It can be synthesized with reference to examples.

  For example, exemplary compound (1) can be synthesized by reacting an amide compound as an intermediate with acetic anhydride using 5- (2-hydroxyethoxy) anthranilic acid and isophthalic acid dichloride as starting materials. The exemplified compound (15) can be synthesized by reacting an amide compound as an intermediate with acetic anhydride using 5- (2-hydroxyethoxy) anthranilic acid and terephthalic acid dichloride as starting materials. As described above, those skilled in the art can obtain the compound of the present invention without undue trial and error by arbitrarily changing the starting material using a known synthesis method.

[Specific examples of compounds]
Specific examples of the compound represented by any one of the general formulas (1) to (5) are shown below, but the present invention is not limited thereto.

[Polymer containing compound structure]
A polymer containing the structure of the compound represented by any one of the general formulas (1) to (5) in the repeating unit can also be suitably used in the present invention. The polymer may be a homopolymer or a copolymer composed of two or more types of repeating units. Further, it may be a copolymer containing other repeating units. The polymer containing the ultraviolet absorber structure in the repeating unit is described in JP-B-1-53455, JP-A-61-189530, and European Patent 27242. The description of these patent documents can be referred to for the method of obtaining the polymer.

[Characteristics of compounds]
The compound of the present invention can be suitably used as an ultraviolet absorber by adding to the resin described later, imparting ultraviolet absorption ability to the resin, lowering the ultraviolet transmittance, and suppressing deterioration of the resin due to ultraviolet rays. Can be.

  When the compound of the present invention is seen in its light absorption characteristics, it can be seen that the absorbance of light having a wavelength of 360 nm, which is obtained by the measurement method described later, is 0.1 or more, and has an excellent ultraviolet absorbing ability. The absorbance of light having a wavelength of 360 nm is preferably 0.15 or more. At the same time, the absorbance of light with a wavelength of 390 nm is preferably 0.15 or less. Thus, the change (rise) of absorbance is steep from the ultraviolet region (near wavelength 360 nm) to the visible light region (near wavelength 390 nm). As a result, excessive light absorption in the visible light region is suppressed, and when added to the resin, discoloration due to such excessive light absorption is suppressed, in particular, yellowing is suppressed and excellent in colorlessness. From such a viewpoint, the absorbance of light having a wavelength of 390 nm is more preferably 0.1 or less, further preferably 0.05 or less, particularly preferably 0.03 or less, and ideally 0.00. In the present invention, in particular, the compound represented by the general formula (4) and preferably (5) has a sharper change in absorbance from the ultraviolet region to the visible light region, and more excessive absorption in the visible light region. Since it is suppressed, it is more excellent in colorlessness, and more excellent in the colorlessness of a resin composition using the same. Furthermore, when kneaded into a resin, deterioration due to heat or the like hardly occurs. Also by this, discoloration of the resin when added to the resin can be suppressed.

The compound of the present invention has an absorbance of light having a wavelength of 400 nm, preferably 0.05 or less, more preferably 0.03 or less, particularly preferably 0.01 or less, and ideally 0.00. . In the wavelength region of 400 to 800 nm, the absorbance at each wavelength is preferably 0.05 or less, more preferably 0.03 or less, particularly preferably 0.01 or less, and Ideally it is 00. It turns out that it is excellent in the transmittance | permeability of visible light by setting it as such an aspect. Moreover, it is excellent also in colorlessness.
Furthermore, the compound of the present invention can be obtained with high purity from its constitution.

[Use as UV absorber (resin composition)]
Since the compound of the present invention exhibits excellent compatibility with various polymer compounds, it can be suitably used as an ultraviolet absorber by blending it with a polymer material (resin). As described above, since the compound of the present invention is difficult to bleed out, the resin composition obtained by adding the compound of the present invention to a resin can obtain a resin composition with less foreign matter on the surface and excellent quality. .

Hereinafter, the aspect using the compound of this invention as a ultraviolet absorber is demonstrated. In the following, the compound of the present invention may be referred to as an ultraviolet absorber.
There is no restriction | limiting in particular as a polymeric material which comprises the resin composition of this invention, The high molecular compound which a molecular chain is easy to generate | occur | produce by an ultraviolet-ray, and the high molecular compound which does not have an ultraviolet absorptivity Furthermore, it may be a high molecular compound originally having an ultraviolet absorbing ability, and it is conceivable to further increase the ultraviolet absorbing ability. These polymer compounds may be thermoplastic resins, thermosetting resins, or uncured elastic bodies (rubber compounds).

  Examples of the thermoplastic resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyester such as PET and PEN copolymerized with isophthalic acid, polyester such as PET copolymerized with naphthalenedicarboxylic acid, Polyester / polyether or polyester / polyester segmented elastomer with polyester as hard segment and / or polyester as soft segment, polyolefin such as polyethylene, polypropylene, poly-4-methylpentene, ethylene / propylene copolymer, ethylene / Polyolefin copolymers such as vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride / ethylene copolymer , Vinyl chloride copolymer such as vinyl chloride / vinyl acetate copolymer, vinyl chloride / acrylic acid ester copolymer, polyamide such as nylon 6, nylon 11, nylon 12, nylon 66, polystyrene, AS resin, ABS resin , Various styrene resins such as MBS resin, acrylic such as poly (meth) acrylic acid ester and poly (meth) acrylamide, and others, polycarbonate, polyvinyl acetate, polyacetal, polyurethane, polyphenylene oxide, polysulfone, polyarylate, etc. be able to. Moreover, the mixture which consists of these 2 or more types can be mentioned.

  Examples of the thermosetting resin include phenol resin, melamine resin, urea resin, epoxy resin, and unsaturated polyester resin.

Examples of the uncured elastic body include natural rubber and synthetic rubber.
Among them, polyester is used in various applications because of its mechanical properties, heat resistance, and transparency, but has a drawback that it is easily deteriorated by ultraviolet rays and yellowing. For this reason, it is useful to add the compound of the present invention as an ultraviolet absorber to impart ultraviolet absorbing ability or impart durability to ultraviolet rays. In addition, since the polyester is often used for applications requiring few defects and being colorless and transparent, the application of the ultraviolet absorbent according to the present invention is useful. Thus, the ultraviolet absorber of the present invention is particularly useful for polyester.

  The amount of UV absorber added to the polymer material should be increased or decreased as appropriate in consideration of the type of polymer material and the UV absorption ability, transparency, and colorlessness required for the final product. You can choose. Moreover, the addition amount can be appropriately selected depending on the properties of the process of handling the resin composition (whether heating is performed or the like).

  The content of the ultraviolet absorber in the resin composition is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the polymer material. By making the addition amount in such a range, the effect of improving the ultraviolet absorption ability can be enhanced, and the effect of improving the bleeding out can be enhanced. Furthermore, the improvement effect of the discoloration suppression of resin by addition of an ultraviolet absorber can be heightened. When there is too little addition amount, it exists in the tendency for the effect which provides ultraviolet-absorbing ability to become low. From such a viewpoint, the addition amount is more preferably 0.05 parts by weight or more, particularly preferably 0.1 parts by weight or more with respect to 100 parts by weight of the polymer material. On the other hand, when the addition amount is too large, the effect of suppressing bleeding out tends to be low. In addition, the properties inherent to the polymer material tend to be lost. From such a viewpoint, the addition amount is more preferably 20 parts by weight or less, particularly preferably 10 parts by weight or less, with respect to 100 parts by weight of the polymer material.

  Moreover, when using a resin composition as a raw material chip | tip for manufacturing resin products, such as a resin molded product and a resin film, content of a ultraviolet absorber becomes as follows. That is, the raw material chip is used without being diluted with another resin (here, “use without dilution” is preferably 10 parts by weight or less, preferably 100 parts by weight or less with respect to 100 parts by weight of the raw material chip containing the ultraviolet absorber). Does not include the addition of other resins (raw material chips) with a small addition amount of 5 parts by weight or less.) When manufacturing resin molded products and resin films, the UV absorber in the raw material chips Content is the same as content of the ultraviolet absorber in the above-mentioned resin composition.

  On the other hand, the raw material chip is diluted with another resin (here, “diluted” means more than 10 parts by weight, preferably 50 parts by weight or more, with respect to 100 parts by weight of the raw material chip containing the UV absorber, More preferably, it means that another resin (raw material chip) is added in an addition amount of 100 parts by weight or more.) When manufacturing a resin molded product or a resin film, that is, the resin composition as a so-called master batch. When used, the content of the ultraviolet absorber in the raw material chip is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polymer material. By setting it as such a range, dilution, density | concentration adjustment, etc. become easy using this masterbatch, and a ultraviolet absorber can be disperse | distributed uniformly in manufacture of the resin product using a masterbatch. From such a viewpoint, the addition amount in this case is more preferably 2 to 70 parts by weight, particularly preferably 3 to 45 parts by weight with respect to 100 parts by weight of the polymer material.

(Production method of resin composition)
The resin composition of the present invention can be obtained by adding the compound of the present invention to the polymer material, but the addition method is not particularly limited, and a conventionally known method can be adopted. For example, a method of adding a polymer material during synthesis or polymerization, a method of adding a resin made of a polymer material to a molten resin melted in, for example, a melt extrusion process, a method of impregnating a resin product made of a polymer material, etc. Can be mentioned.

  In particular, when the polymer material is polyester, it can be added in the polyester polymerization step, for example, in the form of powder or in the form of a solution or slurry using an appropriate solvent. Moreover, the polyester once chipped can be remelted at a temperature equal to or higher than the melting point of the polyester, for example, at a temperature of 260 to 280 ° C., and added to the molten polyester. Here, the melting may be a melt extrusion process in a process for producing a polyester molded product, a melt extrusion process in a process for producing a polyester film, or a melt extrusion process in a process of producing a master batch. .

  Among these, from the viewpoint of suppressing thermal deterioration of the polymer material, it is preferable to add a compound into the molten resin and knead and mix in the melt extrusion process in the manufacturing process of the resin molded product and the resin film. . From the viewpoint of easy concentration adjustment and uniform dispersion, it is preferable to employ a master batch method.

(Use of resin composition)
As described above, the resin composition in the present invention can be used as a raw material for producing a resin product in the form of a chip, such as a resin molded product or a resin film. Examples of such resin molded products include parts and housings of electronic products and optical products, fibers, films, sheets, plates, pipes, tubes, various containers, and the like. Moreover, the resin composition in this invention can be used as a raw material chip | tip for obtaining the said resin product which has the ultraviolet absorber of this invention in chip shape.

  In addition to the ultraviolet absorber, the resin composition of the present invention includes a lubricant (wax etc.), particles (organic particles, inorganic particles, organic-inorganic composite particles, etc.), as long as the object of the present invention is not impaired. You may contain additives, such as antioxidant, an antistatic agent, a mold release agent, and a fluorescent bleaching agent. In addition, other ultraviolet absorbers (metallic ultraviolet absorbers, ultraviolet absorbers described in, for example, JP-A-7-11231, etc.) can be used in combination as long as the object of the present invention is not impaired.

(Characteristics of resin composition)
Since the ultraviolet absorber of the present invention is used, the resin composition of the present invention has an excellent ultraviolet absorbing ability, and at the same time, there is little bleeding out of the ultraviolet absorber, thereby reducing sublimates during heating. It has excellent appearance, few defects, and excellent quality.

  The resin composition of the present invention is, for example, a sublimation detected in the bleed-out property evaluation 2 of the resin composition described later, expressed as a sublimation rate based on the weight of the resin composition, and is 0.3% by weight or less. Can be suppressed. When the sublimation rate is in such a range, it indicates that there are few ultraviolet absorbers that bleed out from the resin composition, and thereby the appearance of the resin composition is excellent. Moreover, the contamination of the manufacturing process due to sublimation of the bleed-out ultraviolet absorber can be suppressed, and the defects of the resin composition resulting from the contamination can be suppressed. Furthermore, since the time required for cleaning and the like can be omitted, the productivity is excellent. From such a viewpoint, the sublimation rate is preferably 0.2% by weight or less, more preferably 0.15% by weight or less.

[Use as UV absorber (film)]
Moreover, the resin film containing a ultraviolet absorber can be obtained using the said resin composition as a raw material. In such a film, since the bleeding out of the ultraviolet absorber is suppressed, surface defects due to the bleeding out are suppressed. Moreover, since the resin film containing the ultraviolet absorber which has the preferable aspect in this invention can suppress the discoloration of resin produced when it adds to resin, it is excellent in colorlessness. A resin film excellent in colorlessness can be suitably used particularly for optical applications.

(Film production method)
The film containing the ultraviolet absorbent according to the present invention is prepared by using the above resin composition as a raw material, and a conventionally known method, for example, a method of extruding a molten resin from a die provided with a slit and cooling and solidifying the resin. It can be obtained by a method of casting a solution. In addition, when a stretchable polymer material is used, the film of the present invention is preferably stretched uniaxially or biaxially for the purpose of improving mechanical properties, heat resistance, transparency, and the like. A conventionally well-known method can be employ | adopted for this extending | stretching method, Sequential biaxial stretching method, simultaneous biaxial stretching method, inflation method etc. are mentioned. When a polymer material capable of orientation crystallization is used, orientation crystallization can be performed by such stretching and preferably subsequent heat treatment to further improve mechanical properties, heat resistance, transparency, and the like. Further, durability against ultraviolet rays can be further improved.

  Hereinafter, the production method of the film of the present invention will be described by taking as an example a case where a biaxially oriented film is obtained using a polyester having oriented crystallinity as a polymer material, which is a preferred embodiment of the present invention. Note that when other polymer materials are used, a film can be similarly produced with reference to the following description and known techniques.

  First, a masterbatch made of the resin composition described above and a polyester chip for dilution are mixed so that the concentration of the ultraviolet absorber in the obtained film is within a predetermined range, and a hot air dryer, a vacuum device, or the like is mixed. Use and dry thoroughly. Then, it is put into an extruder and melted at a temperature equal to or higher than the melting point of the polyester, for example, 260 to 320 ° C., and the molten resin is filtered through a filter to remove foreign matters, and a molten sheet is removed from a die having a slit-shaped die. Extrusion, for example, rapid cooling and solidification on a casting drum cooled to about 10 to 70 ° C. to obtain an unstretched film. Although the thickness of the unstretched film obtained here may be determined in consideration of the thickness of the film to be obtained and the stretch ratio, it is preferably 0.5 mm or more from the viewpoint of productivity.

  Next, the unstretched film is formed into a film forming machine axis direction (hereinafter, sometimes referred to as a longitudinal direction or a longitudinal direction or MD) and a direction perpendicular to the film forming machine axis direction and the thickness direction (hereinafter referred to as a horizontal direction or a width direction or TD). In some cases). Such stretching may be sequential biaxial stretching or simultaneous biaxial stretching. In the case of sequential biaxial stretching, the longitudinal direction and the transverse direction can be stretched in an arbitrary order, but from the viewpoint of productivity, longitudinal-lateral sequential biaxial stretching in which longitudinal stretching and then transverse stretching are performed is preferable. Hereinafter, a case where sequential biaxial stretching in which longitudinal stretching is performed first and then lateral stretching is employed will be described.

  First, the film is stretched in the machine direction, preferably at a temperature of 40 to 135 ° C., preferably at a magnification of 2.0 to 6.0 times, more preferably 3.0 to 4.5 times to obtain a longitudinally uniaxially stretched film. . Such longitudinal stretching can be performed by roll stretching using a conventionally known IR heater. Here, when the film to be obtained is a film having a coating layer on the surface, it is preferable to apply a coating solution for forming the coating layer to the film surface after the longitudinal stretching. As a result, the coating liquid can be dried, the reaction of components in the coating liquid can be accelerated, or the adhesion between the coating layer and the film can be improved by the heat in the subsequent transverse stretching process or heat setting process. .

  Next, the longitudinally uniaxially stretched film is led to a stenter, and stretched in the transverse direction, preferably at 95 to 145 ° C., preferably 2.0 to 6.0 times, more preferably 3.0 to 4.5 times, A biaxially stretched film is obtained. At this time, the area magnification (longitudinal stretching magnification × lateral stretching magnification) is preferably 5 to 30 times, more preferably 9 to 20 times. In the present invention, a film that is excellent in mechanical properties, heat resistance, and transparency and can be suitably used for optical applications can be obtained by adopting the above-described longitudinal stretching and transverse stretching conditions.

Subsequently, the biaxially stretched film is subjected to a heat treatment (referred to as heat setting) at a temperature not lower than the crystallization temperature of the polyester and lower than the melting point, preferably 180 to 230 ° C. for 1 to 60 seconds. Thereby, mechanical characteristics, heat resistance, and transparency can be further improved. In this way, a biaxially oriented film is obtained.
In addition, the biaxially oriented film is subjected to heat treatment in the shrinking direction by performing reheat treatment while shrinking 0 to 20% in the longitudinal direction and / or the width direction at a temperature lower by 10 to 20 ° C. than the heat treatment temperature as necessary. Adjustments can be made to reduce shrinkage.

  The content of the ultraviolet absorber in the film is preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, particularly preferably 0.3 to 2% by weight, based on the weight of the film. is there. By setting it as this range, the outstanding ultraviolet-absorbing ability can be show | played efficiently. Moreover, the improvement effect of bleeding out suppression of the ultraviolet absorber from a film can be made high. Moreover, it is excellent in transparency and can improve the colorless effect. When the content of the ultraviolet absorber is small, the effect of improving the ultraviolet absorbing ability tends to be low, while when too large, the transparency of the film tends to be lowered. Further, the improvement effect of colorless products tends to be low. Further, the amount of bleed-out and sublimation of the ultraviolet absorber tends to increase, and the degree of process contamination tends to deteriorate. Moreover, the improvement effect of the fault suppression in the film surface becomes low by it.

(Structure of the film)
The thickness of the film may be in a preferred range depending on the application, and is not particularly limited, but is preferably 1 to 500 μm, more preferably 5 to 300 μm, still more preferably 10 to 280 μm, and particularly preferably 30 to 250 μm. If the film thickness is too thin, film formation becomes difficult due to breakage or the like. For optical applications, the thickness of the film is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 25 μm or more. If the film thickness is too thin, the film is not stiff and handling such as sticking with other optical members and incorporation becomes difficult. Moreover, 300 micrometers or less are preferable, 250 micrometers or less are more preferable, 200 micrometers or less are further more preferable, and when a film thickness is too thick, since weight will increase and thereby the weight of a product will increase, it is difficult to use it suitably as a member. Moreover, when the film is thick, it tends to be inferior in transparency.

  In the film of the present invention, in addition to the ultraviolet absorber, a lubricant (wax etc.), particles (organic particles, inorganic particles, organic-inorganic composite particles, etc.), antioxidants, as long as the object of the present invention is not impaired. You may contain additives, such as an antistatic agent, a mold release agent, and a fluorescent bleaching agent. In addition, other ultraviolet absorbers (metallic ultraviolet absorbers, ultraviolet absorbers described in, for example, JP-A-7-11231, etc.) can be used in combination as long as the object of the present invention is not impaired.

  The film of the present invention may be a laminated film having at least one layer containing the ultraviolet absorbent of the present invention. As such a laminated film, when the layer containing the ultraviolet absorber of the present invention is layer A and the layer not containing it is layer B, for example, a two-layer structure of A / B, A / B / A and B / A / A three-layer structure of B can be exemplified. Further, a three-layer structure such as A / B / C and B / A / C having another layer C that does not contain the ultraviolet absorber of the present invention can be exemplified. By arranging a layer that does not contain an ultraviolet absorber on the surface layer, the effect of suppressing bleeding out of the ultraviolet absorber can be increased.

The film of the present invention may be provided with a coating layer on the surface thereof. As such a coating layer, a metal layer (for example, a layer made of Al, Au, Pt, or the like) or a metal oxide layer (for example, a layer made of SiO ₂ , TiO ₂ , ITO, IZO, or the like) obtained by an evaporation method, a sputtering method, or the like. Can be mentioned. Moreover, the metal oxide layer and resin layer (layer which consist of acryl, polyester, urethane, etc.) obtained by the apply | coating method can be mentioned. By providing the resin layer, it is possible to impart effects such as easy adhesion, easy slipping, and bleeding out prevention.

  The method of forming a coating layer by a coating method is a normal coating process, that is, a film is obtained by biaxially stretching and heat-fixing as necessary, and then applied in a process separated from the film manufacturing process. May be performed by so-called off-line coating, or may be performed by so-called in-line coating which is performed in the film manufacturing process. In-line coating makes it difficult for the film before coating to entrap soot, dust, and the like, and can increase the adhesion between the film and the coating layer. Moreover, it is preferable from a viewpoint that a coating layer can be formed with high productivity.

  As the coating method, any known coating method can be applied. For example, a roll coating method, a gravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, and a curtain coating method can be used alone or in combination.

The coating amount can be appropriately adjusted depending on the concentration and viscosity of the coating liquid to be applied, the thickness of the coating layer to be obtained, the coating method, etc. For example, 0.5 to ²⁰ g per 1 m ^{2 of the} running film, Furthermore, it becomes easy to obtain a uniform film layer by setting it as 1-10 g. The coating liquid is preferably an aqueous liquid, and more preferably used as an aqueous dispersion or emulsion. The thickness of the coating layer obtained by the coating method is preferably 0.02 to 1 μm, and the coating layer easily exhibits its function suitably. Moreover, the strength of the coating layer and the adhesion to the film can be increased. In addition, a film may be formed only on one side of a film as needed, and may be formed on both surfaces.

(Characteristics of film)
(UV absorption capacity (spectral transmittance))
Since the film of the present invention uses the ultraviolet absorbent of the present invention, it has excellent ultraviolet absorbing ability, and at the same time, there is little bleeding out of the ultraviolet absorbent, resulting in less sublimation during heating, and appearance. Excellent in quality with few surface defects.

  The film of the present invention preferably has a light transmittance of 10% or less at a wavelength of 360 nm. In such a range, it means that the ultraviolet absorbing ability is excellent. The light transmittance at a wavelength of 360 nm is more preferably 5.0% or less, and particularly preferably 1.0% or less. At the same time, the light transmittance at a wavelength of 390 nm is preferably 70% or more. In this way, when the light transmittance is abruptly changed from the ultraviolet region to the visible light region, absorption of excess light in the visible light region is suppressed, thereby suppressing discoloration and making it colorless. Excellent. From this, the light transmittance at a wavelength of 390 nm is more preferably 75% or more, further preferably 78% or more, and particularly preferably 80% or more. At the same time, the light transmittance at a wavelength of 400 nm is preferably 80% or more, more preferably 82% or more, particularly preferably 83% or more, and further excellent in colorlessness. In order to achieve such an embodiment, the compound defined by the present invention may be used as an ultraviolet absorber. Moreover, what is necessary is just to let the addition amount be the range which this invention prescribes | regulates preferably. In particular, in the present invention, a compound represented by the general formula (4), preferably the general formula (5) may be used.

  Moreover, it is preferable that the light transmittance of the film of the present invention is always 80% or more at a wavelength of 400 to 800 nm, that is, the light transmittance in the visible light region is high and transparent. The minimum value of light transmittance at a wavelength of 400 to 800 nm is more preferably 82% or more, and particularly preferably 83% or more.

  Furthermore, in the film of the present invention, the shortest wavelength at which the light transmittance is 80% or more is preferably in the range of 380 to 400 nm. When it is in such a range, it is possible to simultaneously improve the ultraviolet absorption ability and colorlessness improvement effect. If the wavelength is too short, the effect of improving ultraviolet absorption tends to be inferior, while if it is too long, the effect of improving colorlessness tends to be inferior. From such a viewpoint, it is more preferable that the shortest wavelength at which the high line transmittance is 80% or more is in the range of 385 to 395 nm.

(Haze)
The film of the present invention preferably has a haze of 3.0% or less. Thereby, it can use suitably for the use which requires transparency, such as an object for optics. From such a viewpoint, the haze is more preferably 2.5% or less, and particularly preferably 2.2% or less. Such a haze value may be within a range in which the amount of the ultraviolet absorbent of the present invention is preferably defined. Further, when the content of additives such as lubricants and particles in the film is reduced, the haze tends to be lowered.

(Transparent color b * value)
The film of the present invention preferably has a color b * value measured by a transmission method of 0.8 or less. When the color b * value is in such a range, it indicates that the colorlessness is high. Thereby, it can use suitably for the use which needs little yellowness and colorlessness, such as an optical use. The color b * value is more preferably −0.8 to 0.8. Such a color b * value can be achieved more preferably by using a compound represented by the general formula (4), preferably the general formula (5) of the present invention as an ultraviolet absorber. Further, the amount of the ultraviolet absorber added may be within the range preferably defined by the present invention.

(Bleed-out property)
The film of the present invention can suppress the haze change rate of the slide glass to 10% or less, for example, in the bleed-out property evaluation 4 described later. When the haze change rate is 10% or less, it indicates that there are few ultraviolet absorbers that bleed out from the film, and thereby surface defects of the film can be suppressed. Further, contamination of the film production process due to sublimation of the bleed-out ultraviolet absorber can be suppressed, and surface defects of the film due to such contamination can be suppressed. Furthermore, since the time required for cleaning and the like can be omitted, the productivity is excellent. From such a viewpoint, the haze change rate of the slide glass is preferably 6% or less, more preferably 4% or less.

(Use of film)
Applications of the film containing the ultraviolet absorbent of the present invention include agricultural films, packaging films, various optical films, for example, infrared absorbent protective films for flat panel displays, automobile window paste films, Examples include a film for a protective sheet of a solar cell, and can be suitably used.

Hereinafter, based on an Example, this invention is demonstrated in detail.
(1) Haze Haze was measured using a haze measuring device (trade name “NDH-2000”, manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K7361. Measurement was carried out for any five points in the sample, and the average value was obtained.

(2) Absorbance, spectral transmittance, light transmittance (absorbance of compound)
25 mg of the compound was dissolved in 100 mL of 1,1,2,2-tetrachloroethane, and 2 mL of this solution was further diluted to 100 mL with 1,1,2,2-tetrachloroethane, and then used with a Hitachi U-2800 spectrophotometer. Wavelengths of 250-410 nm were measured using a 10 mm cell. Absorbance at wavelengths of 360 nm, 390 nm, and 400 nm was determined. Moreover, the maximum value of the light absorbency in wavelength 400-800nm was calculated | required.
(Spectral transmittance of film)
Using a spectrophotometer (UV-3101PC manufactured by Shimadzu Corporation), the light transmittance at each wavelength was measured in a wavelength range of 300 to 800 nm under the conditions of a scanning speed of 200 nm, a slit width of 20 nm, and a sampling pitch of 1.0 nm. The light transmittance at wavelengths of 360 nm, 390 m, and 400 nm was determined. Moreover, the minimum value of the light transmittance was calculated | required in wavelength 400-800 nm. Further, the minimum wavelength at which the light transmittance was 80% was determined.
Further, regarding the light transmittance at a wavelength of 360 nm, a value of 10% or less was evaluated as “◯”, and a value exceeding 10% was evaluated as “x”.

(3) Colorlessness evaluation (transmission color b * value)
Measurement was performed using a color measuring instrument (trade name “SZ-Σ90” manufactured by Nippon Denshoku Industries Co., Ltd.). About three arbitrary points on a film, it measured by the transmission method and calculated | required the average value.
(Visual evaluation (unstretched film))
The end face of the roll wound up at the time of film formation was visually observed and evaluated with the following indices.
○: Yellowish end face is weak and is equivalent to the one without added UV absorber.
(Triangle | delta): The yellowishness of an end surface is a little strong.
X: The yellow end face is strong.
(Visual evaluation (stretched film))
The end face of the roll wound up at the time of film formation was visually observed and evaluated with the following indices.
○: Yellowish end face is weak and is equivalent to the one without added UV absorber.
X: The yellow end face is strong.

(4) Bleed-out evaluation [resin composition]
The bleed-out property of the resin composition was evaluated by drying the resin composition at 160 ° C. for 4 hours and then using an antimony sublimation apparatus, charging 40 g of the dried resin composition into a sealed container of the apparatus, and a temperature of 300 ° C. Then, heat treatment was performed for 4 hours under a vacuum condition of a pressure of 30 Pa, and was performed as follows. The sublimate adheres to an aluminum pan provided in the upper part of the container.
(Bleed-out evaluation 1)
In the above, the aluminum pan was visually observed and evaluated according to the following indices.
○: Sublimation adheres little.
(Triangle | delta): There is a little adhesion of a sublimate.
X: Sublimate adheres much.
(Bleed-out evaluation 2)
In the above, the sublimate adhering to the aluminum pan was collected and weighed, and the weight of the sublimate relative to the weight of the charged resin composition was determined as the sublimation rate (% by weight).

[the film]
The bleed-out property of the film was evaluated by measuring the haze change rate of the slide glass that captured the sublimate before and after the heat treatment of the film. That is, a slide glass was installed at a position of 6.5 mm above the film, and a heat treatment was performed at 230 ° C. for 15 minutes from the lower surface of the film.
(Bleed-out evaluation 3)
The slide glass after the heat treatment was visually observed and evaluated according to the following indices.
○: Less sublimate adheres and less cloudiness.
(Triangle | delta): There is little adhesion of a sublimate and there is a little cloudiness.
X: Sublimate adheres much and cloudiness is high.
(Bleed-out evaluation 4)
The haze of the slide glass before and after the heat treatment was measured, and the haze change rate of the slide glass was calculated from these values according to the following formula.
Haze change rate of slide glass (%)
= ((Slide glass haze after heating (%)-Slide glass haze before heating (%))
/ Slide glass haze before heating (%))

(5) Melting point of compound The melting point was determined by measuring with DSC (TA Instruments Co., Ltd., trade name: Thermal lyst 2100) at a sample amount of 20 mg and a heating rate of 20 ° C./min.

[Manufacture of UV absorbers]
[Example 1-1]
Example compound (1) was synthesized as follows.
(Step 1: Amidation)
5- (2-hydroxyethoxy) anthranyl in a 3000 ml four-necked flask equipped with a thermometer, stirrer, reflux condenser, dropping funnel, nitrogen gas inlet, and gas outlet connected to a hydrogen halide removal facility 140 g of acid (HEEA) was dissolved in 1690 g of methyl ethyl ketone (MEK). Next, the temperature of this solution was set to a range of 55 to 60 ° C., and 78.9 g of isophthalic acid dichloride dissolved in 369 g of MEK was added dropwise over 30 minutes. Then, it was made to react at about 80 degreeC for 12 hours, flowing nitrogen at 15 ml / min to the gaseous-phase part of a reaction flask. After the reaction, the temperature of the solution was cooled to 30 ° C. or lower, filtered, and the obtained crystal was washed with MEK.
(Process 2: Dehydration)
Place the crystal obtained above and 2300 g of acetic anhydride in a 3000 ml four-necked flask equipped with a thermometer, stirrer, reflux condenser, dropping funnel, reflux outlet and gas outlet connected to the acidic gas removal equipment. The mixture was heated to reflux for 12 hours while distilling the reflux liquid about 60 g per hour. The temperature gradually increased and eventually exceeded 130 ° C. Thereafter, the mixture was cooled to 30 ° C. or lower and filtered to obtain crystals.
This crystal and 500 g of methanol are placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, a dropping funnel, and a gas outlet connected to an acid gas removal facility for 30 minutes in the range of 50 to 60 ° C. Washed with stirring. To this, 500 g of ion-exchanged water was added dropwise, cooled to 30 ° C. or lower, filtered, and the resulting crystals were washed with methanol. The obtained crystal was dried at 60 ° C. to obtain 171 g of exemplary compound (1) (slightly yellow crystal).

[Example 1-2]
Exemplified compound (9) was obtained in the same manner as in Example 1-1 except that 177 g of 5- (4-hydroxybutoxy) anthranilic acid was used instead of 5- (2-hydroxyethoxy) anthranilic acid.

[Example 1-3]
Exemplified compound (13) was obtained in the same manner as in Example 1-1 except that 180 g of 5- (6-hydroxyhexyloxy) anthranilic acid was used instead of 5- (2-hydroxyethoxy) anthranilic acid.

[Example 1-4]
Exemplified compound (19) was obtained in the same manner as in Example 1-1 except that terephthalic acid dichloride was used instead of isophthalic acid dichloride.

[Example 1-5]
Exemplified compound (21) was obtained in the same manner as in Example 1-1 except that 107 g of 2,6-naphthalene dichloride was used instead of isophthalic dichloride.

[Example 1-6]
Exemplified compound (26) was obtained in the same manner as in Example 1-1 except that 108 g of 4,4′-biphenyl acid dichloride was used instead of isophthalic acid dichloride.

[Example 1-7]
Exemplified compound (28) was obtained in the same manner as in Example 1-1 except that 33 g of 2,5-thiophene dicarbonyl dichloride was used instead of isophthalic acid dichloride.

[Comparative Example 1-1]
86 parts by weight of anthranilic acid and 58 parts by weight of sodium carbonate were dissolved in 1200 parts by weight of water. A solution obtained by dissolving 51 parts by weight of terephthalic acid dichloride in 300 parts by weight of acetone was dropped into the above aqueous solution at room temperature, reacted for 2 hours with stirring, and further reacted for 1 hour under reflux of acetone. The obtained slurry-like reaction liquid was cooled to room temperature, and hydrochloric acid was added to make the reaction liquid acidic, followed by washing with filtered water to obtain 112 parts by weight of amide dicarboxylic acid. Next, 300 parts by weight of acetic anhydride was added to the above amide dicarboxylic acid, and the mixture was heated to reflux with stirring for 2 hours. After cooling the reaction solution to room temperature, the crystal was filtered, washed with water and methanol, and further purified by recrystallization using dimethylacetamide, and the compound represented by the following formula [Chemical Formula 11] (slightly yellowish) 85 parts by weight of white crystals were obtained.

[Comparative Example 1-2]
A compound (slightly yellowish white crystal) represented by the following formula [Chemical Formula 12] was prepared in the same manner as in Comparative Example 1-1 except that 108 parts by weight of 4-chloroanthranilic acid was used instead of anthranilic acid. Obtained.

[Comparative Example 1-3]
A compound (slightly yellowish white crystal) represented by the following formula [Chemical Formula 13] was obtained by the same method as Comparative Example 1-1 except that isophthalic acid dichloride was used instead of terephthalic acid dichloride.

  The evaluation results of the compounds obtained above are shown in Tables 6 and 7.

[Production of UV Absorber-Containing Resin Composition]
[Example 2-1]
97.5 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.65 (measured at 35 ° C. in a phenol / 1,1,2,2-tetrachloroethane mixed solvent (weight ratio 60/40) at least 3 hours at 180 ° C.) After drying, the mixture was melted at 280 ° C., 2.5 parts by weight of the UV absorber produced in Example 1-1 was added, melt-blended for 5 minutes with stirring, this was melt-extruded, and about 5 mm square The resin composition (the ultraviolet absorber concentration in the resin composition was 2.5% by weight) was obtained in the form of a chip.

[Examples 2-2 to 2-7, comparative examples 2-1 to 2-3]
Similarly to Example 2-1, a resin composition was obtained using the ultraviolet absorbers obtained in Examples 1-2 to 1-7 and Comparative Examples 1-1 to 1-3 as shown in Table 8, respectively. It was.

[Comparative Example 2-4]
A resin composition was obtained in the same manner as in Example 2-1, using only a polyethylene terephthalate chip containing no ultraviolet absorber.
The characteristics of the resin composition obtained above are shown in Tables 8 and 9.

[Production of UV absorber-containing film (unstretched)]
[Example 3-1]
40 parts by weight of the resin composition obtained in Example 2-1 (the concentration of the ultraviolet absorber in the resulting film is 1.0% by weight), and a polyerylene terephthalate chip containing no ultraviolet absorber Mix thoroughly with 60 parts by weight and a blender, dry this mixture at 160 ° C. for 3 hours, put into an extruder, melt knead at a melting temperature of 280 ° C., melt extrude, quench rapidly on a casting drum and leave it uncooled. A stretched film was obtained.

[Examples 3-2 to 3-7, Comparative examples 3-1 to 3-4]
Similarly to Example 3-1, unstretched films were obtained using the resin compositions obtained in Examples 2-2 to 2-7 and Comparative Examples 2-1 to 2-4 as shown in Table 10, respectively. It was.
The characteristics of the unstretched film obtained above are shown in Tables 10 and 11.

[Production of UV absorber-containing film (stretched)]
[Example 4-1]
20 parts by weight of the resin composition obtained in Example 2-1 (the concentration of the ultraviolet absorber in the resulting film is 0.5% by weight), and a polyerylene terephthalate chip containing no ultraviolet absorber Mix well with 80 parts by weight and blender, dry this mixture at 160 ° C. for 3 hours, put into an extruder, melt knead at a melting temperature of 280 ° C., melt extrude, quench rapidly on a casting drum and leave it uncooled. A stretched film was obtained.
Next, the obtained unstretched film was preheated at 74 to 84 ° C., supplied to a tenter, and stretched 3.4 times in the longitudinal direction and 3.6 times in the transverse direction by a simultaneous biaxial stretching machine. The obtained biaxially stretched film was heat-set at a temperature of 230 ° C. for 5 seconds to obtain a biaxially oriented polyester film having a thickness of 50 μm.

[Examples 4-2 to 4-7, comparative examples 4-1 to 4-4]
As in Example 4-1, using the resin compositions obtained in Examples 2-2 to 2-7 and Comparative Examples 2-1 to 2-4 as shown in Table 12, biaxially oriented polyester films Got.
The characteristics of the biaxially oriented polyester film obtained above are shown in Tables 12 and 13.

The compound of the present invention has an excellent ultraviolet absorbing ability, and can be imparted to such a resin by being added to the resin. Thereby, deterioration of the resin product obtained from this resin composition can be suppressed.
Moreover, since the bleed-out when the compound of this invention is added to resin is suppressed, the resin product excellent in quality can be obtained.

Claims (8)

A compound represented by the following general formula (1).

(However, in the formula,
Ar ¹ represents a divalent to 10-valent 5- to 20-membered aromatic residue. Moreover, this aromatic residue may contain a hetero atom and may have a substituent.
The ring bonded to Ar ¹ may have a double bond at any position.
X ^a , X ^b and X ^c each independently represent a hetero atom. X ^a , X ^b and X ^c may have a substituent.
R ^a1 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
R ^b1 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.
m ¹ represents an integer of 2 to 10.
n ¹ represents an integer of 1 to 4. ) The compound according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(However, in the formula,
Ar ² has the same meaning as Ar ^{1 in the} general formula (1).
R ^a2 is the same as defined in the ^{R a1} in formula (1).
R ^b2 is the same as defined in the ^{R b1} in formula (1).
m ² has the same meaning as m ^{1 in the} general formula (1).
n ² has the same meaning as n ^{1 in the} general formula (1). ) The compound according to claim 2, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

(However, in the formula,
Ar ³ represents a divalent 5- to 20-membered aromatic residue. Moreover, this aromatic residue may contain a hetero atom and may have a substituent.
R ^a3 and R ^{a3 ′} each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms.
R ^b3 and R ^{b3 ′} each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms.
n ³ and n ^{3 ′} each independently represent an integer of 1 to 4. ) The compound according to claim 3, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (4).

(However, in the formula,
R ^a4 and R ^{a4 ′} have the same ^meanings as R ^a3 and R ^{a3 ′ in} formula (3).
R ^b4 and R ^{b4 ′} have the same ^meanings as R ^b3 and R ^{b3 ′ in the} general formula (3).
n ⁴ and n ^{4 ′} are synonymous with n ³ and n ^{3 ′ in the} general formula (3). ) The compound of Claim 4 whose compound represented by the said General formula (4) is a compound represented by the following general formula (5).

(However, in the formula,
R ^a5 and R ^{a5 ′} have the same ^meanings as R ^a4 and R ^{a4 ′ in} formula (4).
R ^b5 and R ^{b5 ′} have the same ^meanings as R ^b4 and R ^{b4 ′ in the} general formula (4). )   The ultraviolet absorber which consists of a compound of any one of Claims 1-5.   The resin composition containing the compound of any one of Claims 1-5.   The film containing the compound of any one of Claims 1-5.