Polyester film for window application and polyester film laminate for window application

Abstract

The polyester film for window attachment comprises a polyester layer (A) containing a pigment and a blue dye containing no halogen.　The invention allows a polyester film for window attachment to be provided, having no harmful effects on the environment at the time of disposal, and moreover, having excellent resistance to light.

Description

[Technical field]

[0001] The present invention relates to a polyester film for application to windows, which is applied to window glass such as automobile windows or building windows, and a polyester film laminate for application to windows. [Background technology]

[0002] Generally, films are applied to automobile windows, building windows, etc. for the purposes of privacy protection, design, sunlight adjustment, glass shatter prevention, etc. Examples of materials for such films include polyesters, which are excellent in transparency, light resistance, water resistance, heat resistance, chemical resistance, and mechanical strength, and are usually used as colored films that contain coloring materials and have a sense of transparency.

[0003] As such a film, for example, Patent Document 1 proposes a window film having a transparent first outer layer containing polyethylene terephthalate (PET), a dyed core layer containing PET and one or more dyes selected from Pigment Yellow 147, Pigment Red 177, Pigment Blue 60, Pigment Black 31, Pigment Red 149, and Pigment Red 122, and a transparent second outer layer containing PET, and having excellent resistance to fading of the colorant due to exposure to light (light resistance). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2017-509517 Summary of the Invention [Problem to be solved by the invention]

[0005] Incidentally, blue coloring materials are sometimes used as coloring materials for the above-mentioned applications, and the blue coloring materials may have halogen groups introduced into their structures in order to improve light resistance, etc. Films using coloring materials with halogen groups introduced are not preferable from the viewpoint of environmental pollution (environmental load) upon disposal, so in recent years, it has been desired to use halogen-free blue coloring materials. However, according to the investigations of the present inventors, halogen-free blue coloring materials have poor weather resistance, and colored films using such blue coloring materials have the problem that they fade when exposed to light. The present invention has been made in consideration of the above-mentioned problems of the conventional art, and an object of the present invention is to provide a polyester film for application to windows that does not adversely affect the environment when disposed of and has excellent light resistance. [Means for solving the problem]

[0006] As a result of extensive research, the inventors have discovered that by using a combination of a halogen-free blue dye and a pigment, a polyester film having excellent light resistance can be obtained without adversely affecting the environment when disposed of, and have completed the present invention as described below. That is, the present invention relates to the following [1] to

[14] . [1] A polyester film for window applications, comprising a polyester layer (A) containing a halogen-free blue dye and pigment. [2] The polyester film for window application described in [1] above, wherein the halogen-free blue dye is a halogen-free anthraquinone-based blue dye. [3] The polyester film for application to windows according to the above [2], wherein the halogen-free anthraquinone blue dye is a compound represented by the following general formula (I): [ka] (In the formula, R 1 and R 4 each independently represents a substituted or unsubstituted amino group; R 2 , R 3 , R 5 ~R8 each independently represents a hydrogen atom or a substituent; R 2 and R 3 may be bonded to each other to form a ring. [4] The polyester film for window application described in [3] above, wherein the halogen-free anthraquinone blue dye is a compound represented by the following general formula (III-a) or a compound represented by the following general formula (IV): [ka] (In the formula, X 11 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a phenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. [ka] (In the formula, X 21 ~X 24 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a phenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. [5] The polyester film for application to windows according to any one of the above [1] to [4], which has a polyester layer (B) on at least one side of the polyester layer (A). [6] The polyester film for application to windows according to any one of the above [1] to [5], wherein the ratio of the thickness of the polyester layer (B) to the thickness of the polyester layer (A) [(B) / (A)] is 0.05 to 0.5. [7] The polyester film for application to windows according to any one of the above [1] to [6], wherein the pigment is carbon black. [8] The polyester film for window application according to the above [7], wherein the content of carbon black in the polyester layer (A) is 0.001 to 1.2 mass %. [9] The polyester film for application to windows according to any one of the above [1] to [6], wherein the pigment is silica and / or alumina.

[10] The polyester film for window application according to the above [9], wherein the content (total value) of silica and / or alumina in the polyester layer (A) is 0.001 to 1.2 mass %.

[11] A polyester film laminate for window application, comprising the polyester film for window application according to any one of the above [1] to

[10] , and a hard coat layer provided on a surface of the polyester film for window application.

[12] A polyester film laminate for window application, comprising: the polyester film for window application according to any one of the above [1] to

[10] ; and an adhesive layer provided on a surface of the polyester film for window application.

[13] The polyester film laminate for window application according to the above

[11] , further comprising an adhesive layer on the side opposite to the hard coat layer of the polyester film for window application.

[14] The polyester film laminate for window application described in

[12] or

[13] above, further comprising a release film provided on the surface of the adhesive layer. Effect of the Invention

[0007] According to the present invention, it is possible to provide a polyester film for application to windows which does not adversely affect the environment when disposed of and has excellent light resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] [Polyester film for windows] The window application polyester film of the present invention has a polyester layer (A) containing a halogen-free blue dye and pigment. According to the present invention, since a halogen-free blue dye is used as a coloring material, it is possible to reduce the adverse effects on the environment when a window-applied polyester film (hereinafter, simply referred to as "polyester film") is disposed of. In addition, since a halogen-free blue dye and a pigment are used in combination, it is possible to improve the light resistance of the polyester film while suppressing the haze to a low level. The configuration of the present invention will be described in detail below.

[0009] <Polyester> The polyester used as the raw material for the polyester film of the present invention is not particularly limited, but is preferably a polycondensation polymer of a dicarboxylic acid and a diol, the dicarboxylic acid being preferably an aromatic dicarboxylic acid, and the diol being preferably an aliphatic diol. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, biphenyldicarboxylic acid, diphenylether-dicarboxylic acid, diphenylsulfone-dicarboxylic acid, diphenylketone-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. Among these, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid are preferred, and terephthalic acid is more preferred.

[0010] Examples of the aliphatic diol include aliphatic diols having a straight or branched structure such as ethylene glycol, 2-butene-1,4-diol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, methylpentanediol, and diethylene glycol; and alicyclic diols such as cyclohexanedimethanol, isosorbide, spiroglycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, norbornene dimethanol, and tricyclodecane dimethanol. Among these, ethylene glycol, neopentyl glycol, and cyclohexanedimethanol are preferred, and ethylene glycol is more preferred.

[0011] The polyester used in the present invention is preferably a polyester resin in which 50 mol % or more of the dicarboxylic acid units are structural units derived from terephthalic acid and 50 mol % or more of the diol units are structural units derived from ethylene glycol, i.e., polyethylene terephthalate, which makes the polyester resin less likely to become amorphous and has good transparency and light resistance.

[0012] When polyethylene terephthalate is used as the polyester resin, the polyester resin may be composed of polyethylene terephthalate alone, or may contain, in addition to polyethylene terephthalate, a polyester resin other than polyethylene terephthalate. In the present invention, the amount of polyethylene terephthalate in the total amount of polyester resin is preferably from 80 to 100% by mass, and more preferably from 90 to 100% by mass.

[0013] The polyethylene terephthalate used in the present invention is preferably composed only of structural units derived from terephthalic acid and ethylene glycol, but may also contain structural units derived from a bifunctional compound other than terephthalic acid and ethylene glycol. The difunctional compounds include the aromatic dicarboxylic acids and aliphatic diols other than terephthalic acid and ethylene glycol, and difunctional compounds other than aromatic dicarboxylic acids and aliphatic diols.

[0014] The bifunctional compound includes linear or branched aliphatic bifunctional compounds, and specific examples thereof include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, azelaic acid, and sebacic acid; and aliphatic hydroxycarboxylic acids such as 10-hydroxyoctadecanoyl acid, lactic acid, hydroxyacrylic acid, 2-hydroxy-2-methylpropionic acid, and hydroxybutyric acid. Also included are alicyclic difunctional compounds such as alicyclic dicarboxylic acids, for example, cyclohexanedicarboxylic acid, norbornenedicarboxylic acid, and tricyclodecanedicarboxylic acid; and alicyclic hydroxycarboxylic acids, for example, hydroxymethylcyclohexanecarboxylic acid, hydroxymethylnorbornenecarboxylic acid, and hydroxymethyltricyclodecanecarboxylic acid. Further examples include aromatic hydroxycarboxylic acids such as hydroxybenzoic acid, hydroxytoluic acid, hydroxynaphthoic acid, 3-(hydroxyphenyl)propionic acid, hydroxyphenylacetic acid, and 3-hydroxy-3-phenylpropionic acid; and aromatic diols such as bisphenol compounds and hydroquinone compounds. The content of the constitutional units derived from the bifunctional compound is preferably 20 mol % or less, and more preferably 10 mol % or less, based on the total moles of all constitutional units constituting the polyester resin.

[0015] When the polyethylene terephthalate used in the present invention contains a constituent unit derived from an aromatic dicarboxylic acid other than terephthalic acid, the aromatic dicarboxylic acid is preferably one or more selected from isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid, which are low in cost and copolymer polyester resins containing one of these are easy to produce. When polyethylene terephthalate contains structural units derived from these aromatic dicarboxylic acids, the proportion of the structural units derived from the aromatic dicarboxylic acids is preferably 1 to 20 mol %, and more preferably 1 to 10 mol %, of the dicarboxylic acid units. The intrinsic viscosity of the polyester resin used in the present invention is not particularly limited, but from the viewpoints of film formability, productivity, etc., it is preferably 0.45 to 1.0 dl / g, more preferably 0.5 to 0.9 dl / g.

[0016] The amount of polyester in the polyester film of the present invention is preferably 90% by mass or more, more preferably 95% by mass or more. When the amount of polyester is equal to or more than the lower limit, the transparency of the polyester film can be ensured.

[0017] <Halogen-free blue dye> The polyester film of the present invention contains a halogen-free blue dye in the polyester layer (A). In the present invention, since a halogen-free dye is used, it is possible to reduce the adverse effect on the environment when the polyester film is discarded. In addition, in the present invention, since a halogen-free blue dye is used in combination with a pigment described later, it is possible to obtain excellent light resistance of the polyester layer (A) while suppressing the haze of the polyester film. Although it is not clear why the use of a halogen-free blue dye in combination with a pigment improves light resistance, it is speculated that the compatibility between the halogen-free blue dye and the pigment is extremely good, and that the halogen-free blue dye and the pigment are present in close proximity to each other in the polyester layer (A), so that even though the pigment is in a low concentration, it is possible to reduce the amount of light exposure to the halogen-free blue dye while suppressing the haze of the polyester film, thereby effectively achieving light resistance.

[0018] The halogen-free blue dye used in the present invention is preferred from the viewpoint of transparency of the polyester film. Examples of halogen-free blue dyes include anthraquinone-based, azo-based and phthalocyanine-based blue dyes, with halogen-free anthraquinone-based blue dyes being preferred from the standpoint of dyeability and fastness.

[0019] The halogen-free anthraquinone blue dye used in the present invention is not particularly limited, but examples thereof include compounds represented by the following general formula (I).

[0020] [ka] (In the formula, R 1 ~R 8 are each independently a hydrogen atom or a substituent, R 2 and R 3 may be bonded to each other to form a ring.

[0021] Specifically, in the formula, R 1 ~R 8each independently represents a hydrogen atom, a nitro group, a hydroxy group, a mercapto group, a carboxyl group, a cyano group, a thiocyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted acyloxy group, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfonyloxy group, a substituted or unsubstituted alkoxycarbonyloxy group, a substituted or unsubstituted aryloxycarbonyloxy group, a substituted or unsubstituted alkoxycarbonyl group, a R represents a substituted or unsubstituted cycloalkyloxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted heterocyclic oxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic thio group, a substituted or unsubstituted alkoxysulfonyl group, a substituted or unsubstituted cycloalkyloxysulfonyl group, a substituted or unsubstituted alkenyloxysulfonyl group, a substituted or unsubstituted aryloxysulfonyl group, or a substituted or unsubstituted heterocyclic oxysulfonyl group. 2 and R 3 may be bonded to each other to form a ring.

[0022] R 1 ~R 8 The substituted or unsubstituted alkyl group includes linear or branched alkyl groups having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an i-butyl group, an n-butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, and the like.

[0023] Examples of substituted alkyl groups include hydroxy-substituted alkyl groups such as 2-hydroxyethyl and 3-hydroxyethyl groups; carboxyl-substituted alkyl groups such as carboxylmethyl and 2-carboxyethyl groups; cyano-substituted alkyl groups such as 2-cyanoethyl groups; substituted or unsubstituted amino-substituted alkyl groups such as 2-aminoethyl, 2-(N-methylamino)ethyl and 2-(N,N-dimethylamino)ethyl groups; substituted or unsubstituted carbamoyl-substituted alkyl groups such as carbamoylmethyl and N,N-dimethylcarbamoylethyl groups; substituted or unsubstituted aryl-substituted alkyl groups such as 2-phenylethyl and 2-(p-methylphenyl)ethyl groups; substituted or unsubstituted alkoxy-substituted alkyl groups such as 2-methoxyethyl and 3-methoxypropyl groups; substituted or unsubstituted aryloxy-substituted alkyl groups such as 2-phenoxyethyl and 2-(p-methylphenoxy)ethyl groups; substituted or unsubstituted acyloxy-substituted alkyl groups such as 2-acetoxyethyl groups; and cycloalkyl groups such as cyclohexyloxymethyl groups. oxy group-substituted alkyl groups; alkylthio group-substituted alkyl groups such as 2-methylthioethyl group and 3-ethylthiopropyl group; substituted or unsubstituted arylthio group-substituted alkyl groups such as phenylthiomethyl group and 2-(p-methylphenylthio)ethyl group; cycloalkylthio group-substituted alkyl groups such as cyclohexylthiomethyl group; heterocyclic thio group-substituted alkyl groups such as 2-(2-mercaptobenzothiazolyl)ethyl group; substituted or unsubstituted alkoxycarbonyl group-substituted alkyl groups such as methoxycarbonylmethyl group, 2-ethoxycarbonylethyl group and 2-(2-methoxyethoxy)carbonylethyl group; substituted or unsubstituted aryloxycarbonyl group-substituted alkyl groups such as 2-phenoxycarbonylethyl group and 2-(p-methoxyphenoxy)carbonylethyl group; cycloalkyloxycarbonyl group-substituted alkyl groups such as 2-cyclohexyloxycarbonylethyl group; carboxyl group-substituted alkyl groups such as 2-carboxyethyl group; and mercapto group-substituted alkyl groups such as 2-mercaptoethyl group.

[0024] R 1 ~R 8The substituted or unsubstituted cycloalkyl group includes those having 4 to 7 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. R 1 ~R 8 The substituted or unsubstituted alkenyl group includes linear or branched alkenyl groups having 2 to 10 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and pentenyl groups.

[0025] R 1 ~R 8 Examples of the substituted or unsubstituted aryl group include a phenyl group and a naphthyl group, and examples of the substituents thereof include a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyethyl group, a methoxyethyl group, and other substituted alkyl groups.

[0026] R 1 ~R 8 Examples of the substituted or unsubstituted heterocyclic group include a pyridyl group, a quinolyl group, a furyl group, a pyranyl group, a pyrrolyl group, an imidazolyl group, an oxazolyl group, a pyrazolyl group, a thienyl group, a thiazolyl group, an isothiazolyl group, an isoxazolyl group, a pyrimidyl group, a triazinyl group, a benzothiazolyl group, a benzoxazolyl group, and the like. Examples of the substituents thereof include a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and a substituted alkyl group such as a hydroxyethyl group or a methoxyethyl group.

[0027] R 1 ~R 8Substituents of the substituted amino group include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, 2-ethylhexyl, dodecyl, 2-hydroxyethyl, 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl, benzyl, 2-phenethyl, and tetrahydrofurfuryl groups; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and pentenyl groups; cycloalkyl groups, such as cyclopentyl and cyclohexyl groups; and substituted or unsubstituted aryl groups. and a group having as a substituent a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or a substituted alkyl group such as a hydroxyethyl group or a methoxyethyl group, specifically, a substituted or unsubstituted alkyl group such as a phenyl group, an m-methylphenyl group, a p-methoxyphenyl group, a p-cyanophenyl group, a p-carboxyphenyl group, a p-hydroxyphenyl group, a p-mercaptophenyl group, a p-(N,N-dimethylamino)phenyl group, a p-nitrophenyl group, a p-acetylphenyl group, a 1-naphthyl group, etc. Unsubstituted aryl groups; substituted or unsubstituted heterocyclic groups such as pyridyl, quinolyl, furyl, pyranyl, pyrrolyl, imidazolyl, oxazolyl, pyrazolyl, thienyl, thiazolyl, isothiazolyl, isoxazolyl, pyrimidyl, triazinyl, benzothiazolyl, and benzoxazolyl groups; substituted or unsubstituted acyl groups having 1 to 20 carbon atoms such as formyl, acetyl, propionyl, butyryl, octanoyl, benzoyl, p-methylbenzoyl, 1-naphthoyl, and thienoyl groups; methyl substituted or unsubstituted alkylsulfonyl groups having 1 to 20 carbon atoms, such as a sulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, or a 2-methoxyethylsulfonyl group; substituted or unsubstituted arylsulfonyl groups, such as a phenylsulfonyl group, a p-methylphenylsulfonyl group, a p-methoxyphenylsulfonyl group, or a 1-naphthylsulfonyl group; substituted or unsubstituted alkoxycarbonyl groups, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a benzyloxycarbonyl group;Examples of the aryloxycarbonyl group include substituted or unsubstituted aryloxycarbonyl groups such as a phenyloxycarbonyl group, a p-methylphenyloxycarbonyl group, and a 1-naphthyloxycarbonyl group; and cycloalkyloxycarbonyl groups such as a cyclohexyloxycarbonyl group and a cyclopentyloxycarbonyl group. The substituted amino group can have one or two of these substituents. The nitrogen atom of the amino group and the two substituents may combine together to form a five- or six-membered ring, and examples of the ring include a morpholine ring, a thiomorpholine ring, a piperidine ring, a piperazine ring, and rings represented by the following structures (II-a) to (II-d), and these rings can also have a substituent.

[0028] [ka] (In the above structures (II-a) to (II-d), * indicates the bond to the anthraquinone skeleton.)

[0029] R 1 ~R 8As the substituted or unsubstituted alkoxy group, examples of the unsubstituted alkoxy group include linear or branched alkoxy groups having 1 to 20 carbon atoms, specifically, methoxy group, ethoxy group, i-propoxy group, n-propoxy group, i-butoxy group, n-butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, etc., and examples of the substituted alkoxy group include those having 1 to 20 carbon atoms as the total number of carbon atoms in the substituted alkoxy group. and preferred are hydroxy-substituted alkoxy groups such as 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy, and 4-hydroxybutoxy groups; phenyl-substituted alkoxy groups such as benzyloxy and 2-phenylethoxy groups; 2-methoxyethoxy, 2-ethoxyethoxy, 2-(n)propoxyethoxy, 2-(iso)propoxyethoxy, 3-methoxypropoxy, 4-methoxybutoxy, 3-methoxybutoxy, and 2,3-dimethoxyethoxy groups. alkoxy-substituted alkoxy groups such as 2-(2-methoxyethoxy)ethoxy group, 2-(2-ethoxyethoxy)ethoxy group, 2-(2-(n)propoxyethoxy) group, 2-(2-(n)butoxyethoxy)ethoxy group, 2-{2-(2-ethylhexyloxy)ethoxy}ethoxy group, and the like; aralkyloxy-substituted alkoxy groups such as 2-phenethyloxyethoxy group, 2-benzyloxyethoxy group, and the like. alkoxy groups; acyloxy-substituted alkoxy groups such as a 2-acetyloxyethoxy group and a 2-propionyloxyethoxy group; alkoxycarbonyl-substituted alkoxy groups such as a 2-methoxycarbonylethoxy group and a 2-ethoxycarbonylethoxy group; heterocycle-substituted alkoxy groups such as a furfuryloxy group and a tetrahydrofurfuryloxy group; alkenyloxy-substituted alkoxy groups such as a 2-allyloxyethoxy group; and aryloxy-substituted alkoxy groups such as a 2-phenoxyethoxy group.

[0030] R 1 ~R 8The substituted or unsubstituted cycloalkyloxy group includes those having 4 to 7 carbon atoms, such as a cyclopentyloxy group, a cyclohexyloxy group, and a cycloheptyloxy group. R 1 ~R 8 The substituted or unsubstituted alkenyloxy group includes linear or branched alkenyloxy groups having 2 to 10 carbon atoms, such as a vinyloxy group, an allyloxy group, a propenyloxy group, a butenyloxy group, and a pentenyloxy group.

[0031] R 1 ~R 8 Examples of the substituted or unsubstituted aryloxy group include a phenoxy group and a naphthoxy group, and examples of the substituents therefor include a nitro group, a hydroxy group, a mercapto group, a carboxyl group, a cyano group, a thiocyano group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and substituted alkyl groups such as a hydroxyethyl group and a methoxyethyl group.

[0032] R 1 ~R 8 Examples of the substituted or unsubstituted heterocyclic oxy group include a pyridyloxy group, a quinolyloxy group, a furyloxy group, a pyranyloxy group, a pyrrolyloxy group, an imidazolyloxy group, an oxazolyloxy group, a pyrazolyloxy group, a thienyloxy group, a thiazolyloxy group, an isothiazolyloxy group, an isoxazolyloxy group, a pyrimidyloxy group, a triazinyloxy group, a benzothiazolyloxy group, a benzoxazolyloxy group, and the like. Examples of the substituents thereof include a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and a substituted alkyl group such as a hydroxyethyl group or a methoxyethyl group.

[0033] R 1 ~R 8Examples of the substituted or unsubstituted acyloxy group include those having 1 to 20 carbon atoms, such as an acetyloxy group, a propionyloxy group, a butyryloxy group, an octanoyloxy group, a benzoyloxy group, a p-methylbenzoyloxy group, a 1-naphthoyloxy group, and a thienoyloxy group. R 1 ~R 8 Examples of the substituted or unsubstituted alkylsulfonyloxy group include those having 1 to 20 carbon atoms, such as a methylsulfonyloxy group, an ethylsulfonyloxy group, a propylsulfonyloxy group, a butylsulfonyloxy group, a pentylsulfonyloxy group, a hexylsulfonyloxy group, a 2-ethylhexylsulfonyloxy group, an n-octylsulfonyloxy group, an n-decylsulfonyloxy group, an n-dodecylsulfonyloxy group, and a 2-methoxyethoxysulfonyloxy group.

[0034] R 1 ~R 8 Examples of the substituted or unsubstituted arylsulfonyloxy group include a phenylsulfonyloxy group, a p-methylphenylsulfonyloxy group, a p-methoxyphenylsulfonyloxy group, and a 1-naphthylsulfonyl group. R 1 ~R 8 Examples of the substituted or unsubstituted alkoxycarbonyloxy group include those having 1 to 20 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a propoxycarbonyloxy group, a butoxycarbonyloxy group, a pentyloxycarbonyloxy group, a hexyloxycarbonyloxy group, a 2-ethylhexyloxycarbonyloxy group, an n-octyloxycarbonyloxy group, an n-decyloxycarbonyloxy group, an n-dodecyloxycarbonyloxy group, and a 2-methoxyethoxycarbonyloxy group.

[0035] R 1 ~R 8 Examples of the substituted or unsubstituted aryloxycarbonyloxy group include a phenoxycarbonyloxy group, a p-methylphenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, and a 1-naphthoxycarbonyloxy group. R 1 ~R 8As the substituted or unsubstituted alkoxycarbonyl group, the unsubstituted alkoxycarbonyl group is one having a straight or branched alkoxycarbonyl group having 1 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, an n-propoxycarbonyl group, an i-butoxycarbonyl group, an n-butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, an n-octyloxycarbonyl group, an n-decyloxycarbonyl group, an Examples of the substituted alkoxycarbonyl group include a hydroxy-substituted alkoxycarbonyl group such as a 2-hydroxyethoxycarbonyl group, a 2-hydroxypropoxycarbonyl group, a 3-hydroxypropoxycarbonyl group, and a 4-hydroxybutoxycarbonyl group; a phenyl-substituted alkoxycarbonyl group such as a benzyloxycarbonyl group and a 2-phenylethoxycarbonyl group; a 2-methoxyethoxycarbonyl group; and the like. alkoxy-substituted alkoxycarbonyl groups such as 2-(2-methoxyethoxy)ethoxycarbonyl group, 2-(2-ethoxyethoxy)ethoxycarbonyl group, 2-(n)propoxyethoxycarbonyl group, 2-(iso)propoxyethoxycarbonyl group, 3-methoxypropoxycarbonyl group, 4-methoxybutoxycarbonyl group, 3-methoxybutoxycarbonyl group, 2,3-dimethoxypropoxycarbonyl group, and 2,2-dimethoxyethoxycarbonyl group; 2-(2-methoxyethoxy)ethoxycarbonyl group, 2-(2-ethoxyethoxy)ethoxycarbonyl group, 2-(2-( n) alkoxyalkoxy-substituted alkoxycarbonyl groups such as a 2-(2-(n)propoxyethoxy)ethoxycarbonyl group, a 2-{2-(2-ethylhexyloxy)ethoxy}ethoxycarbonyl group, etc.; aralkyloxy-substituted alkoxycarbonyl groups such as a 2-phenethyloxyethoxycarbonyl group, a 2-benzyloxyethoxycarbonyl group, etc.; acyloxy-substituted alkoxycarbonyl groups such as a 2-acetyloxyethoxycarbonyl group, a 2-propionyloxyethoxycarbonyl group, etc.Examples of such alkoxycarbonyl-substituted alkoxycarbonyl groups include 2-methoxycarbonylethoxycarbonyl and 2-ethoxycarbonylethoxycarbonyl groups; heterocyclic substituted alkoxycarbonyl groups such as furfuryloxycarbonyl and tetrahydrofurfuryloxycarbonyl groups; alkenyloxy-substituted alkoxycarbonyl groups such as 2-allyloxyethoxycarbonyl groups; and aryloxy-substituted alkoxycarbonyl groups such as 2-phenoxyethoxycarbonyl groups.

[0036] R 1 ~R 8 The substituted or unsubstituted cycloalkyloxycarbonyl group includes those having 4 to 7 carbon atoms, such as a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a cycloheptyloxycarbonyl group. R 1 ~R 8 The substituted or unsubstituted alkenyloxycarbonyl group includes linear or branched alkenyloxycarbonyl groups having 2 to 10 carbon atoms, such as a vinyloxycarbonyl group, an allyloxycarbonyl group, a propenyloxycarbonyl group, a butenyloxycarbonyl group, and a pentenyloxycarbonyl group.

[0037] R 1 ~R 8 Examples of the substituted or unsubstituted aryloxycarbonyl group include a phenoxycarbonyl group and a naphthoxycarbonyl group, and examples of the substituents therefor include a nitro group, a hydroxy group, a mercapto group, a carboxyl group, a cyano group, a thiocyano group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and substituted alkyl groups such as a hydroxyethyl group and a methoxyethyl group.

[0038] R 1 ~R 8Examples of the substituted or unsubstituted heterocyclic oxycarbonyl group include a pyridyloxycarbonyl group, a quinolyloxycarbonyl group, a furyloxycarbonyl group, a pyranyloxycarbonyl group, a pyrrolyloxycarbonyl group, an imidazolyloxycarbonyl group, an oxazolyloxycarbonyl group, a pyrazolyloxycarbonyl group, a thienyloxycarbonyl group, a thiazolyloxycarbonyl group, an isothiazolyloxycarbonyl group, an isoxazolyloxycarbonyl group, a pyrimidyloxycarbonyl group, a triazinyloxycarbonyl group, a benzothiazolyloxycarbonyl group, a benzoxazolyloxycarbonyl group, and the like. Examples of the substituents thereof include a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and substituted alkyl groups such as a hydroxyethyl group and a methoxyethyl group.

[0039] R 1 ~R 8Substituents of the substituted carbamoyl group include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, 2-ethylhexyl, dodecyl, 2-hydroxyethyl, 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl, benzyl, 2-phenethyl, and tetrahydrofurfuryl groups; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and pentenyl groups; cycloalkyl groups, such as cyclopentyl and cyclohexyl groups; and substituted or unsubstituted aryl groups. and the like, as a substituent, is a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or a substituted alkyl group such as a hydroxyethyl group or a methoxyethyl group. Specifically, the substituted or unsubstituted alkyl group is a phenyl group, a m-methylphenyl group, a p-methoxyphenyl group, a p-cyanophenyl group, a p-carboxyphenyl group, a p-hydroxyphenyl group, a p-mercaptophenyl group, a p-(N,N-dimethylamino)phenyl group, a p-nitrophenyl group, a p-acetylphenyl group, a 1-naphthyl group, etc. is an unsubstituted aryl group; a substituted or unsubstituted heterocyclic group such as a pyridyl group, a quinolyl group, a furyl group, a pyranyl group, a pyrrolyl group, an imidazolyl group, an oxazolyl group, a pyrazolyl group, a thienyl group, a thiazolyl group, an isothiazolyl group, an isoxazolyl group, a pyrimidyl group, a triazinyl group, a benzothiazolyl group, or a benzoxazolyl group; a substituted or unsubstituted acyl group having 1 to 20 carbon atoms such as a formyl group, an acetyl group, a propionyl group, a butyryl group, an octanoyl group, a benzoyl group, a p-methylbenzoyl group, a 1-naphthoyl group, or a thienoyl group; substituted or unsubstituted alkylsulfonyl groups having 1 to 20 carbon atoms, such as a phenylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, or a 2-methoxyethylsulfonyl group; substituted or unsubstituted arylsulfonyl groups, such as a phenylsulfonyl group, a p-methylphenylsulfonyl group, a p-methoxyphenylsulfonyl group, or a 1-naphthylsulfonyl group; substituted or unsubstituted alkoxycarbonyl groups, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a benzyloxycarbonyl group;Examples of the substituent include substituted or unsubstituted aryloxycarbonyl groups such as phenyloxycarbonyl group, p-methylphenyloxycarbonyl group, and 1-naphthyloxycarbonyl group; and cycloalkyloxycarbonyl groups such as cyclohexyloxycarbonyl group and cyclopentyloxycarbonyl group. The substituted carbamoyl group can have one or two of these substituents. The nitrogen atom of the carbamoyl group and the two substituents may be combined to form a five- or six-membered ring, and examples of the ring include a morpholine ring, a thiomorpholine ring, a piperidine ring, a piperazine ring, and rings represented by the following structures (II-a) to (II-d), and these rings can also have a substituent.

[0040] [ka] (In the above structures (II-a) to (II-d), * indicates the bond to the anthraquinone skeleton.)

[0041] R 1 ~R 8Substituents of the substituted sulfamoyl group include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, 2-ethylhexyl, dodecyl, 2-hydroxyethyl, 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl, benzyl, 2-phenethyl, and tetrahydrofurfuryl groups; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and pentenyl groups; cycloalkyl groups, such as cyclopentyl and cyclohexyl groups; and substituted or unsubstituted alkenyl groups. Aryl groups having as a substituent a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or a substituted alkyl group such as a hydroxyethyl group or a methoxyethyl group, specifically, substituted alkyl groups such as a phenyl group, an m-methylphenyl group, a p-methoxyphenyl group, a p-cyanophenyl group, a p-carboxyphenyl group, a p-hydroxyphenyl group, a p-mercaptophenyl group, a p-(N,N-dimethylamino)phenyl group, a p-nitrophenyl group, a p-acetylphenyl group, or a 1-naphthyl group. or unsubstituted aryl groups; substituted or unsubstituted heterocyclic groups such as pyridyl, quinolyl, furyl, pyranyl, pyrrolyl, imidazolyl, oxazolyl, pyrazolyl, thienyl, thiazolyl, isothiazolyl, isoxazolyl, pyrimidyl, triazinyl, benzothiazolyl, and benzoxazolyl groups; substituted or unsubstituted acyl groups having 1 to 20 carbon atoms such as formyl, acetyl, propionyl, butyryl, octanoyl, benzoyl, p-methylbenzoyl, 1-naphthoyl, and thienoyl groups; Substituted or unsubstituted alkylsulfonyl groups having 1 to 20 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, or a 2-methoxyethylsulfonyl group; substituted or unsubstituted arylsulfonyl groups, such as a phenylsulfonyl group, a p-methylphenylsulfonyl group, a p-methoxyphenylsulfonyl group, or a 1-naphthylsulfonyl group; substituted or unsubstituted alkoxycarbonyl groups, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a benzyloxycarbonyl group;Examples of the substituent include substituted or unsubstituted aryloxycarbonyl groups such as phenyloxycarbonyl group, p-methylphenyloxycarbonyl group, and 1-naphthyloxycarbonyl group; and cycloalkyloxycarbonyl groups such as cyclohexyloxycarbonyl group and cyclopentyloxycarbonyl group. The substituted sulfamoyl group can have one or two of these substituents. The nitrogen atom of the sulfamoyl group and the two substituents may be combined to form a five-membered or six-membered ring, and examples of the ring include a morpholine ring, a thiomorpholine ring, a piperidine ring, a piperazine ring, and rings represented by the following structures (II-a) to (II-d), and these rings can also have a substituent.

[0042] [ka] (In the above structures (II-a) to (II-d), * indicates the bond to the anthraquinone skeleton.)

[0043] R 1 ~R 8 Examples of the substituted or unsubstituted acyl group include substituted or unsubstituted acyl groups having 1 to 20 carbon atoms, such as a formyl group, an acetyl group, a propionyl group, a butyryl group, an octanoyl group, a benzoyl group, a p-methylbenzoyl group, a 1-naphthoyl group, and a thienoyl group.

[0044] R 1 ~R 8 The substituted or unsubstituted alkylsulfonyl group includes linear or branched alkylsulfonyl groups having 1 to 20 carbon atoms, specifically, a methylsulfonyl group, an ethylsulfonyl group, an i-propylsulfonyl group, an n-propylsulfonyl group, an i-butylsulfonyl group, an n-butylsulfonyl group, a pentylsulfonyl group, a hexylsulfonyl group, a 2-ethylhexylsulfonyl group, an n-octylsulfonyl group, an n-decylsulfonyl group, an n-dodecylsulfonyl group, etc., which may have a substituent such as a hydroxy group or an alkoxy group.

[0045] R 1 ~R8 Examples of the substituted or unsubstituted arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group, and examples of the substituents thereof include a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and a substituted alkyl group such as a hydroxyethyl group and a methoxyethyl group.

[0046] R 1 ~R 8 The substituted or unsubstituted alkylthio group includes a linear or branched alkylthio group having 1 to 20 carbon atoms, specifically, a methylthio group, an ethylthio group, an i-propylthio group, an n-propylthio group, an i-butylthio group, an n-butylthio group, a pentylthio group, a hexylthio group, a 2-ethylhexylthio group, an n-octylthio group, an n-decylthio group, an n-dodecylthio group, etc., which may have a substituent such as a hydroxy group or an alkoxy group.

[0047] R 1 ~R 8 The substituted or unsubstituted cycloalkylthio group includes those having 4 to 7 carbon atoms, such as a cyclopentylthio group, a cyclohexylthio group, and a cycloheptylthio group. R 1 ~R 8 Examples of the substituted or unsubstituted arylthio group include a phenylthio group and a naphthylthio group, and examples of the substituents thereof include a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and substituted alkyl groups such as a hydroxyethyl group and a methoxyethyl group.

[0048] R 1 ~R 8Examples of the substituted or unsubstituted heterocyclic thio group include a pyridylthio group, a quinolylthio group, a furylthio group, a pyranylthio group, a pyrrolylthio group, an imidazolylthio group, an oxazolylthio group, a pyrazolylthio group, a thienylthio group, a thiazolylthio group, an isothiazolylthio group, an isoxazolylthio group, a pyrimidylthio group, a triazinylthio group, a benzothiazolylthio group, a benzoxazolylthio group, and the like. Examples of the substituents thereof include a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and substituted alkyl groups such as a hydroxyethyl group and a methoxyethyl group.

[0049] R 1 ~R 8As the substituted or unsubstituted alkoxysulfonyl group, the unsubstituted alkoxysulfonyl group is one having a straight or branched alkoxysulfonyl group having 1 to 20 carbon atoms, specifically, a methoxysulfonyl group, an ethoxysulfonyl group, an i-propoxysulfonyl group, an n-propoxysulfonyl group, an i-butoxysulfonyl group, an n-butoxysulfonyl group, a pentyloxysulfonyl group, a hexyloxysulfonyl group, a 2-ethylhexyloxysulfonyl group, an n-octyloxysulfonyl group, an n-decyloxysulfonyl group, an n-butyl ... Examples of the substituted alkoxysulfonyl group include a hydroxy-substituted alkoxysulfonyl group, such as a 2-hydroxyethoxysulfonyl group, a 2-hydroxypropoxysulfonyl group, a 3-hydroxypropoxysulfonyl group, or a 4-hydroxybutoxysulfonyl group; a phenyl-substituted alkoxysulfonyl group, such as a benzyloxysulfonyl group or a 2-phenylethoxysulfonyl group; a 2-methoxyethoxysulfonyl group; and the like. alkoxy-substituted alkoxysulfonyl groups such as 2-(2-methoxyethoxy)ethoxysulfonyl group, 2-(2-ethoxyethoxy)ethoxysulfonyl group, 2-(n)propoxyethoxysulfonyl group, 2-(iso)propoxyethoxysulfonyl group, 3-methoxypropoxysulfonyl group, 4-methoxybutoxysulfonyl group, 3-methoxybutoxysulfonyl group, 2,3-dimethoxypropoxysulfonyl group, and 2,2-dimethoxyethoxysulfonyl group; 2-(2-methoxyethoxy)ethoxysulfonyl group, 2-(2-ethoxyethoxy)ethoxysulfonyl group, 2-(2-( n) alkoxyalkoxy-substituted alkoxycarbonyl groups such as a 2-(2-(n)propoxyethoxy)sulfonyl group, a 2-(2-(butoxyethoxy)ethoxysulfonyl group, or a 2-{2-(2-ethylhexyloxy)ethoxy}ethoxysulfonyl group; an aralkyloxy-substituted alkoxysulfonyl group such as a 2-phenethyloxyethoxysulfonyl group or a 2-benzyloxyethoxysulfonyl group; an acyloxy-substituted alkoxysulfonyl group such as a 2-acetyloxyethoxysulfonyl group or a 2-propionyloxyethoxysulfonyl group;Examples of such alkoxycarbonyl-substituted alkoxysulfonyl groups include 2-methoxycarbonylethoxysulfonyl and 2-ethoxycarbonylethoxysulfonyl groups; heterocyclic-substituted alkoxysulfonyl groups include furfuryloxysulfonyl and tetrahydrofurfuryloxysulfonyl groups; alkenyloxy-substituted alkoxysulfonyl groups include 2-allyloxyethoxysulfonyl groups; and aryloxy-substituted alkoxysulfonyl groups include 2-phenoxyethoxysulfonyl groups.

[0050] R 1 ~R 8 The substituted or unsubstituted cycloalkyloxysulfonyl group includes those having 4 to 7 carbon atoms, such as a cyclopentyloxysulfonyl group, a cyclohexyloxysulfonyl group, and a cycloheptyloxysulfonyl group. R 1 ~R 8 The substituted or unsubstituted alkenyloxysulfonyl group includes linear or branched alkenyloxysulfonyl groups having 2 to 10 carbon atoms, such as a vinyloxysulfonyl group, an allyloxysulfonyl group, a propenyloxysulfonyl group, a butenyloxysulfonyl group, and a pentenyloxysulfonyl group.

[0051] R 1 ~R 8 Examples of the substituted or unsubstituted aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group, and examples of the substituents therefor include a nitro group, a hydroxy group, a mercapto group, a carboxyl group, a cyano group, a thiocyano group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and substituted alkyl groups such as a hydroxyethyl group and a methoxyethyl group.

[0052] R 1 ~R 8Examples of the substituted or unsubstituted heterocyclic oxysulfonyl group include a pyridyloxysulfonyl group, a quinolyloxysulfonyl group, a furyloxysulfonyl group, a pyranyloxysulfonyl group, a pyrrolyloxysulfonyl group, an imidazolyloxysulfonyl group, an oxazolyloxysulfonyl group, a pyrazolyloxysulfonyl group, a thienyloxysulfonyl group, a thiazolyloxysulfonyl group, an isothiazolyloxysulfonyl group, an isoxazolyloxysulfonyl group, a pyrimidyloxysulfonyl group, a triazinyloxysulfonyl group, a benzothiazolyloxysulfonyl group, and a benzoxazolyloxysulfonyl group. Examples of the substituents thereof include a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and a substituted alkyl group such as a hydroxyethyl group or a methoxyethyl group.

[0053] Above R 1 ~R 8 Of these, R 1 and R 4 are preferably each independently a substituted or unsubstituted amino group, R 2 , R 3 , R 5 ~R 8 are each preferably independently a hydrogen atom or a substituent. Specific examples of the substituent are as described above. Also, R 2 and R 3 Examples of compounds in which the groups are bonded to each other to form a ring include compounds having a structure represented by the following general formula (III).

[0054] [ka] (In the formula, X 1 and X 4 ~X 8 are R in formula (I), 1 and R 4 ~R 8 X 9 and X 10 represents an oxygen atom, a sulfur atom, or NH, and X 11represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a phenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.

[0055] X in formula (III) 11 For the substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, and substituted or unsubstituted aryl group in R 1 ~R 8 As explained in the above. The aralkyl group in the substituted or unsubstituted aralkyl group includes an aralkyl group having 7 to 20 carbon atoms. Groups that may be substituted on the aralkyl group include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a sulfo group, and a carboxy group. Specific examples of the aralkyl group include a benzyl group, a phenethyl group, an α-methylbenzyl group, an α-methylphenylethyl group, a β-methylphenylethyl group, and a fluorenyl group.

[0056] Among the compounds represented by the above general formula (III), the compounds represented by the following general formula (III-a) are preferred. [ka] (In the formula, X 11 is as above.)

[0057] X 11 Preferably, X has 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 2 to 6 carbon atoms. 11 is preferably a substituted or unsubstituted alkyl group having 2 to 6 carbon atoms, and from the viewpoint of fastness, X 11 More preferably, it is an alkoxy-substituted alkyl group such as a 2-methoxyethyl group or a 3-methoxypropyl group.

[0058] The halogen-free anthraquinone blue dye for use in the present invention is preferably a compound represented by the following general formula (IV).

[0059] [ka] (In the formula, X 21 ~X 24 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a phenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.

[0060] X in general formula (IV) 21 ~X 24 For the substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, and substituted or unsubstituted aryl group in R 1 ~R 8 The substituted or unsubstituted aralkyl group is as described in X 11 As explained in. In the general formula (IV), X 21 ~X 24 When each is other than a hydrogen atom, it preferably has 1 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and further preferably 8 to 14 carbon atoms. Among the compounds represented by the general formula (IV), X 21 and X 23 is a hydrogen atom. From the viewpoint of fastness, the compound represented by the following formula (IV-a): 22 and X 24 More preferred are compounds in which X is selected from a phenyl group and a substituted or unsubstituted aryl group; 22 and X 24 More preferably, each is selected from the group consisting of 2,4,6-trimethylphenyl and 2,6-diethyl-4-methylphenyl.

[0061] [ka] (In the formula, X 22 and X 24 are as above.)

[0062] Furthermore, the halogen-free anthraquinone blue dye for use in the present invention is preferably a compound represented by the following general formula (V).

[0063] [ka] (In the formula, X 27 , X 28 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a phenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. Y 1 and Y 2 is a hydroxy group on one side and a nitro group (-NO2) or an amino group (-NH2) on the other side, or both are hydrogen atoms.

[0064] X in general formula (V) 27 , X 28 For the substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, and substituted or unsubstituted aryl group in R 1 ~R 8 The substituted or unsubstituted aralkyl group is as described in X 11 As explained in. X 27 and X 28 When each is other than a hydrogen atom, it preferably has 1 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and further preferably 6 to 14 carbon atoms.

[0065] Among the compounds represented by the above general formula (V), the compounds represented by the following general formulas (Va) to (Vc) are more preferable. [ka] (In the formula, X31 ~X 34 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a phenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.

[0066] X in general formulas (Va) to (Vc) 31 ~X 34 For the substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, and substituted or unsubstituted aryl group in R 1 ~R 8 The substituted or unsubstituted aralkyl group is as described in X 11 As explained in. In the general formulae (Va) to (Vc), X 31 ~X 34 When each is other than a hydrogen atom, it preferably has 1 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and further preferably 6 to 14 carbon atoms. Among the compounds represented by the general formulas (Va) to (Vc), in order to improve light resistance, the compound represented by the general formula (Va) is preferably 31 is a 4-(2-ethoxyethoxy)phenyl group, X 32 Compounds where X is a hydrogen atom 31 is a 4-hydroxyphenoxy group, X 32 is a hydrogen atom, or X 31 is a 4-methoxyphenoxy group, X 32 In the compound represented by the general formula (Vb), X is preferably a hydrogen atom. 33 Compounds in which X is a 2-hydroxyethylphenyl group, 33 Further, in the compound represented by the general formula (Vc), X is preferably a phenyl group. 34 Also preferred are compounds in which is a phenyl group. However, in the present invention, compounds other than the compound represented by general formula (I) can also be used as the halogen-free anthraquinone blue dye.

[0067] Specific examples of halogen-free anthraquinone blue dyes include Disperse Blue 3, Disperse Blue 5, Disperse Blue 14, Disperse Blue 26, Disperse Blue 28, Disperse Blue 35, Disperse Blue 334, Disperse Blue 359, Disperse Blue 60, Disperse Blue 72, Disperse Blue 73, Disperse Blue 77, Disperse Blue 214, Disperse Blue 167, Disperse Blue 54, Solvent Blue 101, Solvent Blue 102, Solvent Blue 104, Solvent Blue 122, Solvent Blue 35, Solvent Blue 36, Solvent Blue 59, Solvent Blue 63, Solvent Blue 68, Solvent Blue 78, and Solvent Blue 97. Among these, preferred compounds include dyes containing the compound represented by the above general formula (III-a), such as Disperse Blue 60. Also, preferred compounds include dyes containing the compound represented by the above general formula (IV), such as Solvent Blue 104 and Solvent Blue 97. Also, preferred compounds include dyes containing the compound represented by the above general formula (V), such as Disperse Blue 214, Disperse Blue 167 and Disperse Blue 54. The above dyes may be used alone or in combination of two or more.

[0068] The content of the halogen-free blue dye in the polyester layer (A) is preferably 0.01 to 2.0 mass%, more preferably 0.02 to 1.5 mass%, and even more preferably 0.05 to 1.0 mass%. When the content of the halogen-free blue dye is equal to or more than the lower limit, the polyester film can be provided with sufficient design. On the other hand, when the content of the halogen-free blue dye is equal to or less than the upper limit, the haze of the polyester film can be kept low.

[0069] The content of the halogen-free blue dye in the polyester film is preferably from 0.01 to 2.0% by mass, more preferably from 0.02 to 1.5% by mass, and even more preferably from 0.05 to 1.0% by mass.

[0070] <Other colorants> In the present invention, other coloring materials other than the halogen-free blue dye may be used. The other coloring materials are preferably those that dissolve in polyester and are less decomposed at the molding temperature of polyester. In terms of chemical structure, such coloring materials are preferably perinone-based, perylene-based, azomethine-based, and heterocyclic dyes. These dyes can be appropriately selected and used in combination to achieve a color tone such as a smoky tone or a brown tone. The content of other coloring materials in the polyester film is usually preferably from 0.01 to 5% by mass, and more preferably from 0.05 to 2% by mass.

[0071] <Pigments> The polyester layer (A) in the present invention contains a pigment. In the present invention, the use of the pigment makes it possible to impart light-shielding properties to the polyester film. In addition, the combined use of the pigment and the halogen-free blue dye makes it possible to reduce the haze of the polyester film, and furthermore, the light resistance of the polyester layer (A) is improved. As the pigment used in the polyester layer (A), from the viewpoint of the light-shielding property of the polyester film, black pigments and white pigments having high hiding power are preferably mentioned. In particular, by using a black pigment having high hiding power, the light-shielding property of the polyester film can be improved even in a small amount, and the haze of the polyester film can be suppressed to a low level if used in a small amount.

[0072] Examples of the pigment include organic pigments and inorganic pigments. From the viewpoint of light-shielding properties and stability, carbon-based black pigments such as carbon black and carbon nanotubes are preferred, with carbon black being more preferred.

[0073] Examples of carbon black that can be used in the present invention include furnace black, channel black, and acetylene black. The average primary particle size of the carbon black used in the present invention is preferably from 5 to 100 nm, more preferably from 10 to 50 nm, and even more preferably from 15 to 40 nm. When the average primary particle size is equal to or less than the upper limit, the haze of the film can be kept low, and the transparency of the film can be improved. On the other hand, carbon black particles may exist as aggregates formed by aggregation of fine primary particles, and when such aggregates are present in polyester and biaxially stretched, the stretching stress applied to the film also acts on the aggregates, resulting in their dispersion. When the average primary particle size is equal to or more than the lower limit, the cohesive force between the primary particles is not too strong, and the aggregates are easily dispersed by the stretching stress when the film is stretched. In the present invention, the average primary particle size refers to a particle size measured by observing carbon black particles alone or in a polyester with an electron microscope. When the particles are present as aggregates, the average primary particle size refers to the particle size of the primary particles constituting the aggregates.

[0074] Examples of the white pigment include inorganic white pigments such as inorganic oxides, barium sulfate, and calcium carbonate, and examples of the inorganic oxide include titanium oxide, zinc oxide, magnesium oxide, silica, alumina, etc. Among these, inorganic oxides are preferred, and silica and alumina are preferred, from the viewpoints of high whiteness and improved light-shielding properties.

[0075] When silica and / or alumina are used, the average particle size of silica and alumina in the polyester layer (A) is preferably 0.01 to 3 μm, more preferably 0.05 to 2 μm, and even more preferably 0.1 to 1 μm. When the average particle size of silica and alumina in the polyester layer (A) is equal to or less than the upper limit, the dispersibility in the polyester layer (A) is improved, and the haze of the polyester film is improved. When the average particle size is equal to or more than the lower limit, the light shielding property is easily ensured. The particle size can be measured in the same manner as in the case of carbon black.

[0076] The content of the pigment in the polyester layer (A) is preferably 0.001 to 1.2 mass%, more preferably 0.005 to 0.5 mass%, further preferably 0.01 to 0.3 mass%, particularly preferably 0.02 to 0.1 mass%, and particularly preferably 0.03 to 0.1 mass%. In the present invention, the pigment and the blue dye are used in combination, so that even if the amount of the pigment is small as described above, it is possible to impart light-shielding properties to the polyester film and reduce haze. In addition, the light resistance of the polyester layer (A) is also good.

[0077] The content of the pigment in the polyester film is preferably from 0.001 to 1.2% by mass, more preferably from 0.005 to 0.5% by mass, further preferably from 0.01 to 0.3% by mass, and even more preferably from 0.02 to 0.1% by mass.

[0078] <Layer configuration> The polyester film of the present invention is not particularly limited as long as it has a polyester layer (A), and may be a single layer, but it is preferable to have a polyester layer (B) on at least one side of the polyester layer (A), and it is more preferable to provide a polyester layer (B) on both sides of the polyester layer (A). By having the polyester layer (B), it is possible to suppress bleeding out of the coloring material, and further, the polyester layer (A) is protected, thereby improving durability, etc. The detailed description of the polyester used in the polyester layer (B) is the same as that of the polyester in the polyester layer (A) described above, and therefore the description is omitted. The polyester used in the polyester layer (B) may be the same as or different from the polyester used in the polyester layer (A).

[0079] It is preferable to incorporate fine particles in the polyester layer (B), which can improve the slipperiness of the surface of the polyester film. Examples of fine particles to be incorporated in the polyester layer (B) include silica, silicon oxide, calcium carbonate, kaolin, and organic polymer particles. From the viewpoints of effectively improving the slipperiness of the surface and production costs, silica is preferred. The average particle size of the fine particles in the polyester layer (B) is preferably from 0.01 to 5.0 μm, and more preferably from 0.1 to 3.0 μm. In addition, when the fine particles are powder, the average particle diameter of the fine particles can be the particle diameter (d50) at an accumulated volume fraction of 50% in the equivalent spherical distribution measured by a centrifugal sedimentation type particle size distribution measuring device (SA-CP3 type). The average particle diameter of the fine particles in the film or resin chip is determined by observing the film or resin chip using, for example, a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, "S3400N"), measuring the size of one particle from the obtained image data, and averaging the average value of 10 points (10 particles).

[0080] When the fine particles are blended in the polyester layer (B), the blending amount is preferably 0.001 to 0.5% by mass, more preferably 0.01 to 0.4% by mass, based on the total amount of the material constituting the surface layer. When the amount of the fine particles in the polyester layer (B) is within the above range, the slipping property can be improved and the haze of the polyester film can be kept low. In addition to the dyes, pigments, and fine particles described above, the polyester layer (A) and the polyester layer (B) may each contain conventionally known antioxidants, ultraviolet absorbers, heat stabilizers, lubricants, and the like, as necessary. In particular, from the viewpoint of light resistance, when a white pigment is used as the pigment, it is preferred to incorporate an ultraviolet absorber into at least one of the polyester layer (A) and the polyester layer (B), particularly into the polyester layer (A).

[0081] <Thickness> In the present invention, the thickness of the polyester layer (A) is not particularly limited, but is preferably from 5 to 50 μm, more preferably from 10 to 40 μm, and further preferably from 15 to 35 μm. In order to ensure high transparency and suppress cloudiness of the entire polyester film, it is preferable that the polyester layer (B) constituting the surface layer is as thin as possible, but from the viewpoint of preventing bleeding out of the coloring material in the polyester layer (A) which is the intermediate layer, it is preferable that it has a certain thickness. Taking these into consideration, the thickness of the polyester layer (B) is usually preferably 0.5 to 8.0 μm on one side, more preferably 1.0 to 5.0 μm.

[0082] The thickness ratio of the polyester layer (B) to the polyester layer (A) [(B) / (A)] is preferably 0.05 to 0.5. When the thickness ratio is within the above range, the transparency of the polyester film can be maintained while the bleeding out of the coloring material from the polyester layer (A) can be suppressed. From this viewpoint, the thickness ratio [(B) / (A)] is more preferably 0.07 to 0.4, and further preferably 0.08 to 0.3.

[0083] <Easy adhesion layer> The polyester film of the present invention may have an easy-adhesion layer on the outermost surface. By providing the easy-adhesion layer, it becomes easier to adhere a functional layer to the polyester film. The easy-adhesion layer is preferably provided on the surface of the polyester layer (B) opposite to the side on which the polyester layer (A) is provided. The easy-adhesion layer is formed from an easy-adhesion layer composition containing a binder resin and a crosslinking agent. When the polyester layer (B) is provided on both sides of the polyester layer (A), the easy-adhesion layer may be provided on the surfaces of both polyester layers (B), but it is sufficient that the easy-adhesion layer is provided on the surface of one of the polyester layers (B).

[0084] Examples of the binder resin include polyester resin, acrylic resin, urethane resin, polyvinyl resin such as polyvinyl alcohol, polyalkylene glycol, polyalkyleneimine, methyl cellulose, hydroxycellulose, starches, etc. Among these, it is preferable to use polyester resin, acrylic resin, or urethane resin from the viewpoint of improving adhesion to the functional layer, etc. As the crosslinking agent, various known crosslinking agents can be used, such as oxazoline compounds, melamine compounds, epoxy compounds, isocyanate compounds, carbodiimide compounds, silane coupling compounds, etc. Among these, oxazoline compounds are preferably used from the viewpoint of improving the durability and adhesion. Also, melamine compounds are preferably used from the viewpoint of improving the durability and coatability of the easy-adhesion layer.

[0085] The adhesive layer composition may contain particles for the purpose of improving blocking resistance and slippage. Specific examples of particles include silica, alumina, kaolin, calcium carbonate, organic polymer particles, and the like. Among these, silica is preferred from the viewpoint of transparency. The average particle size of the particles is preferably within a range of 0.005 to 1.0 μm, more preferably 0.01 to 0.5 μm, and even more preferably 0.01 to 0.2 μm, from the viewpoint of improving the transparency and slippage of the polyester film. The average particle size is the cumulative (weight basis) 50% (D50) value in the equivalent sphericity distribution measured using a centrifugal sedimentation type particle size distribution measuring device. The adhesive layer composition may further contain a component for promoting crosslinking, such as a crosslinking catalyst. The adhesive layer composition is preferably diluted with water, an organic solvent, or a mixture thereof, and the adhesive layer is preferably formed by coating the outermost surface of the polyester film with a diluted adhesive layer composition as a coating liquid and drying the coating. The coating may be performed by a conventional method. The thickness of the easy-adhesion layer is usually in the range of 0.003 to 1 μm, preferably 0.005 to 0.6 μm, and more preferably 0.01 to 0.4 μm. By making the thickness 0.003 μm or more, sufficient adhesion can be ensured. Also, by making the thickness 1 μm or less, deterioration of appearance and blocking are less likely to occur.

[0086] <Visible light transmittance> The visible light transmittance of the polyester film of the present invention is preferably 2 to 80%, more preferably 20 to 60%, and even more preferably 30 to 50%. If the visible light transmittance of the polyester film is equal to or greater than the lower limit, the film will have a suitable light-shielding property and will not be too dark as a window film. On the other hand, if the visible light transmittance is equal to or less than the upper limit, the film will not be too bright, which is preferable. The visible light transmittance can be adjusted to the above range by adjusting the amount of the halogen-free blue dye and pigment.

[0087] <Haze> The polyester film of the present invention has a haze of preferably 5.0% or less, more preferably 4.0% or less, and even more preferably 3.5% or less. When the haze is equal to or less than the upper limit, the view through the polyester film is less likely to become cloudy, and sufficient transparency can be ensured. The haze can be adjusted to fall within the above range by adjusting the amounts of the halogen-free blue dye and pigment.

[0088] <Manufacturing method of polyester film for window application> Next, a method for producing the window-adhesive polyester film of the present invention will be specifically described, but the method is not limited to the following production examples.

[0089] First, the dye and the pigment are added to the polyester. There is no particular restriction on the method of addition, but it is preferable to prepare a master batch of the dye or pigment and add the master batch during melt molding of the film. In addition, it is particularly preferable to use a twin-screw extruder during the melt molding in order to knead the dye and the pigment in a well-dispersed manner into the polyester.

[0090] When the polyester film for window application of the present invention has a polyester layer (A) and a polyester layer (B), the raw materials are respectively fed into a plurality of extruders, and the respective polyesters are laminated using a multi-manifold die or a feed block, and a molten sheet of a plurality of layers is extruded from a die, and the sheet is cooled and solidified by a cooling roll to obtain an unstretched sheet. In this case, in order to improve the flatness of the sheet, it is preferable to increase the adhesion between the sheet and the rotating cooling drum, and it is preferable to adopt an electrostatic application adhesion method and / or a liquid application adhesion method.

[0091] The unstretched film is then stretched in biaxial directions to be biaxially oriented. That is, the unstretched sheet is stretched in the machine direction by a roll stretching machine. The stretching temperature is usually 70 to 120°C, preferably 80 to 110°C, and the stretching ratio is usually 2.5 to 7.0 times, preferably 3.0 to 6.0 times. The film is then stretched in the transverse direction at a temperature of usually 70 to 120° C., preferably 80 to 115° C., and a stretch ratio of usually 3.0 to 7.0, preferably 3.5 to 6.0. The film is then heat-treated at a temperature of 170 to 250° C. under tension or relaxation of 30% or less to obtain a biaxially stretched film.

[0092] In the above stretching, a method of stretching in one direction in two or more stages can be used. In that case, it is preferable to perform the stretching so that the final stretching ratios in two directions are each within the above range. It is also possible to perform simultaneous biaxial stretching of the unstretched sheet so that the area stretching ratio is 10 to 40 times. Furthermore, if necessary, the sheet may be stretched again in the longitudinal and / or transverse directions before or after heat treatment.

[0093] The surface of the polyester film obtained by the above-mentioned method can be coated as necessary, and the above-mentioned easy-adhesion layer can be formed by coating. Coating can be performed in-line, off-line, or a combination of both, but in-line coating is preferable. In-line coating can use a series of processes in which a coating solution diluted mainly with water is applied at the stage where longitudinal stretching is completed, followed by drying, preheating, transverse stretching, and further heat fixing in a tenter.

[0094] [Polyester film laminate for windows] The polyester film laminate for window application of the present invention has a functional layer provided on at least one surface of the polyester film in order to impart various functions to the polyester film, and preferably has an adhesive layer provided as the functional layer. That is, the polyester film laminate for window application of the present invention preferably has a polyester film and an adhesive layer provided on the surface of the polyester film. By providing the adhesive layer in the polyester film laminate for window application, the polyester film for window application can be easily adhered to the window glass. The adhesive layer may be composed of various adhesives such as an acrylic adhesive, a polyester adhesive, a rubber adhesive, a silicone adhesive, etc., and among these, acrylic adhesives are preferred from the standpoints of adhesive strength, contamination of the adherend, and cost. The thickness of the adhesive layer is preferably 1 to 100 μm, more preferably 5 to 75 μm, and even more preferably 15 to 50 μm. When the thickness of the adhesive layer is within the above range, the strength of the adhesive layer can be sufficiently maintained while ensuring transparency. On the other hand, the polyester film used may be a single sheet, or may be configured by laminating polyester films together via an adhesive layer. In the lamination configuration, polyester films having the same color tone may be laminated together, or polyester films having different color tones may be laminated together. In this case, there is an advantage that the lineup of the obtained polyester film laminate for window application (color lineup) is increased.

[0095] In the polyester film laminate for application to windows of the present invention, a hard coat layer may be provided as a functional layer on the surface of the polyester film. By providing the hard coat layer, the surface of the polyester film can be prevented from being scratched. The hard coat layer is preferably a cured layer formed by curing a known hard coat agent. The hard coat agent is not particularly limited, but an active energy ray curable composition or the like may be used. The active energy ray means an active ray such as an ultraviolet ray or an electron beam. The hard coat agent may contain a polymerizable monomer or a polymerizable oligomer that forms a cured product upon irradiation with active energy rays, for example, at least one of a (meth)acrylate monomer or a (meth)acrylate oligomer, and more specifically, may contain a urethane (meth)acrylate, a polyester (meth)acrylate, an epoxy (meth)acrylate, a melamine (meth)acrylate, a polyfluoroalkyl (meth)acrylate, a silicone (meth)acrylate, or the like. The hard coat agent may contain additives such as a crosslinking agent, a polymerization initiator, a lubricant, a plasticizer, organic particles, inorganic particles, an antifouling agent, an antioxidant, and a catalyst, as necessary. The thickness of the hard coat layer is not particularly limited, but is, for example, in the range of 0.5 to 15 μm, and preferably 1 to 10 μm.

[0096] In the case where a hard coat layer is provided in the polyester film laminate for application to windows of the present invention, it is preferable that an adhesive layer is provided on one surface of the polyester film and a hard coat layer is provided on the other surface of the polyester film. With such a configuration, the surface of the polyester film adhered to the window glass via the adhesive layer can be prevented from being scratched by the hard coat layer. When a functional layer such as an adhesive layer or a hard coat layer is provided, the surface of the polyester film on which the functional layer is provided may be subjected to a corona discharge treatment or the above-mentioned easy-adhesion layer may be provided in order to improve adhesion. Also, when a hard coat layer is provided, it is preferable to provide the above-mentioned easy-adhesion layer on the surface of the polyester film on which the hard coat layer is provided from the viewpoint of improving adhesion.

[0097] When the polyester film laminate for window application has an adhesive layer, it may further have a release film laminated on the surface of the adhesive layer. By having the release film, the polyester film laminate for window application can protect the adhesive layer before being applied to the window glass. When applying the polyester film laminate for window application to the window glass, the release film may be peeled off and the exposed adhesive layer may be applied to the window glass. The release film may be a film whose surface has been treated with a release agent such as a silicone-based release agent, or a non-silicone-based release agent such as a long-chain alkyl resin or an olefin-based resin.

[0098] The polyester film for window application and the polyester film laminate for window application of the present invention are used by being applied to the window glass of various vehicles such as automobiles, buildings, etc. The polyester film for window application of the present invention has good light resistance and can reduce fading even after long-term use. In addition, since a halogen-free blue dye is used, there is no adverse effect on the environment when it is disposed of.

[0099] <Explanation of terms, etc.> Generally, a "sheet" is defined in JIS as a thin, flat product whose thickness is small relative to its length and width, and generally, a "film" is a thin, flat product whose thickness is extremely small relative to its length and width, and whose maximum thickness is arbitrarily limited, and which is usually supplied in the form of a roll (Japanese Industrial Standards; JIS K6900). However, the boundary between a sheet and a film is unclear, and since there is no need to distinguish between the two in the present invention, in the present invention, when it is referred to as a "film", it is intended to include a "sheet", and when it is referred to as a "sheet", it is intended to include a "film".

[0100] In addition, in this specification, when it is written "X to Y" (X and Y are any numbers), unless otherwise specified, it includes the meaning of "X or more and Y or less", as well as "preferably larger than X" or "preferably smaller than Y". In addition, when it is stated that the amount is "X or more" (X is any number), it also means that the amount is "preferably greater than X" unless otherwise specified, and when it is stated that the amount is "Y or less" (Y is any number), it also means that the amount is "preferably smaller than Y" unless otherwise specified. EXAMPLES

[0101] The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples in any way.

[0102] [Evaluation method] The polyester films obtained in the examples and comparative examples were evaluated according to the following methods. (1)Visible light transmittance The light transmittance at each wavelength was measured using a spectrophotometer SE-2000 (manufactured by Nippon Denshoku Co., Ltd.), and the visible light transmittance was calculated according to JIS-A5759.

[0103] (2) Film haze The turbidity (haze) of the polyester film was measured using a turbidity meter NDH300A (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS-K6714.

[0104] (3) Thickness of polyester film and thickness of each layer A small piece of polyester film was embedded in epoxy resin, and a section was cut out with a microtome so that the cross section in the thickness direction could be observed, and this was observed by a transmission electron microscope photograph. In the cross section, the lamination interface was observed by light and dark almost parallel to the film surface. The distance from the interface to the film surface was measured by the transmission electron microscope photograph, and the average value calculated from all the measured values ​​was taken as the thickness.

[0105] (4) Color difference (light resistance) The polyester film before the test was measured using a color difference meter (Konica Minolta, Inc. CR-410 type C light source used) and the L * ,a * ,b * was calculated. Thereafter, the polyester film was irradiated with UV light under the following conditions using a metal weather tester (KW-R5TP-A model, manufactured by Daipla Wintes Co., Ltd.). After the test, the polyester film was also subjected to the same L * ,a * ,b * Calculate the color difference ΔE before and after the test using the following formula: * ab was calculated. ΔE * ab The smaller the value, the less color change (fading) occurs due to UV light exposure, indicating superior light resistance. <Measurement conditions> Illuminance 140mW / cm2 , Irradiation time 32 hours (LIGHT (50℃, 50% RH)) Formula:ΔE * ab = [(ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2 ] 1 / 2 The above measurement conditions correspond to normal outdoor exposure for approximately 9 months.

[0106] (5) Intrinsic viscosity of polyester 1 g of polyester from which components incompatible with the polyester had been removed was precisely weighed, dissolved in 100 ml of a mixed solvent of phenol and tetrachloroethane [phenol / tetrachloroethane=50 / 50 (mass ratio)], and measured at 30°C.

[0107] (6) Average particle size of fine particles The particle size at an accumulated volume fraction of 50% in the equivalent sphericity distribution measured using a centrifugal sedimentation type particle size distribution analyzer (SA-CP3 type) manufactured by Shimadzu Corporation was used as the average particle size.

[0108] [Raw materials] <Polyester A> A polyethylene terephthalate monopolymer with an intrinsic viscosity of 0.63 dl / g.

[0109] <Polyester B> A polyethylene terephthalate monopolymer having an intrinsic viscosity of 0.61 dl / g and containing 0.6% by weight of amorphous silica particles having an average particle size of 2.3 μm.

[0110] <Polyester C> Polyester C is a polyester chipped by melt-mixing polyethylene terephthalate and a coloring material. More specifically, Polyester C is a mixture of polyethylene terephthalate and a coloring material in a ratio (mass ratio) of 90:10. The content of color materials in Polyester C is 4.5% by mass of Disperse Blue 60, 1.5% by mass of Solvent Brown 53, 0.8% by mass of carbon black (average primary particle diameter 30 nm), and also contains Solvent Red 52. The Disperse Blue 60 used in polyester C is a halogen-free anthraquinone blue dye and has the following structural formula:

[0111] [ka]

[0112] <Polyester D> Polyester D is a chip made by melt-mixing polyethylene terephthalate and a coloring material. More specifically, Polyester D is a mixture of polyethylene terephthalate and a coloring material in a ratio (mass ratio) of 85:15. The content of coloring materials in Polyester D was 7% by mass of Disperse Blue 60, 6% by mass of Solvent Brown 53, and Solvent Red 52.

[0113] <Polyester E> Polyester E is a polyester chipped by melt-mixing polyethylene terephthalate and a coloring material. More specifically, Polyester E is a mixture of polyethylene terephthalate and a coloring material in a ratio (mass ratio) of 90:10. The content of coloring materials in Polyester E is 4.5 mass% Disperse Blue 60, 1.5 mass% Solvent Brown 53, 0.6 mass% silica (average particle size 2.3 μm), and also contains Solvent Red 52.

[0114] <Polyester F> Polyester F is a polyester chipped by melt-mixing polyethylene terephthalate and a coloring material. More specifically, Polyester F is a mixture of polyethylene terephthalate and a coloring material in a ratio (mass ratio) of 90:10. The content of coloring materials in Polyester F is 4.5 mass% Disperse Blue 60, 1.5 mass% Solvent Brown 53, 0.8 mass% alumina (average particle size 0.05 μm), and also contains Solvent Red 52.

[0115] <Polyester G> Polyester G is a polyester chipped by melt-mixing polyethylene terephthalate and a coloring material. More specifically, Polyester G is a mixture of polyethylene terephthalate and a coloring material in a ratio (mass ratio) of 90:10. The colorant contents of Polyester G are 4.0% by mass of Solvent Blue 97, 2.0% by mass of Solvent Blue 104, and 0.8% by mass of carbon black (average primary particle diameter 30 nm). In addition, Solvent Red 179 and Solvent Green 3 are also contained. Solvent Blue 97 and Solvent Blue 104 used in Polyester G are halogen-free anthraquinone-based blue dyes and have the following structural formulas.

[0116] [ka] Solvent Blue 97

[0117] [ka] Solvent Blue 104

[0118] <Polyester H> A high molecular weight type ultraviolet absorber (UVA-PBT: copolymer with polybutylene terephthalate containing 30% by mass of UVA component, manufactured by Bell Polyester Products) was used.

[0119] <Polyester I> Polyester I was obtained by mixing Polyester A with 5.0% by mass of an ultraviolet absorber (Tinuvin 1577, manufactured by Tokyo Ink & Chemicals, Inc.).

[0120] [Example 1] A blend of the polyester A and C chips in a mass ratio of 95:5 was fed into the intermediate layer extruder as a resin for the polyester layer (A). Separately from this, a blend of the polyester A and B chips in a mass ratio of 78:22 was fed into the surface layer extruder as a resin for the polyester layer (B). Each extruder was a counter-rotating twin screw extruder equipped with a vent, and the resin was extruded at a melt temperature of 290°C without drying. The molten polymers were then joined together in a feed block and laminated. Next, the sheet was cooled and solidified on a cooling roll with a surface temperature set at 40° C. using an electrostatic adhesion method to obtain a laminated unstretched sheet having a two-kind three-layer structure. The obtained sheet was stretched in the machine direction at 85° C. and 3.5 times its original size. Thereafter, the film was introduced into a tenter and stretched in the transverse direction at 3.7 times at 105° C., then heat-set at 230° C., and further subjected to a 5% relaxation treatment in the transverse direction at 200° C. to produce a polyester film. The thickness of each layer of the obtained polyester film was 2 μm for the surface layer (polyester layer (B)) and 21 μm for the intermediate layer (polyester layer (A)), giving a total thickness of 25 μm. The properties of the resulting polyester film are shown in Table 1.

[0121] [Comparative Example 1] A polyester film was produced in the same manner as in Example 1, except that a blend of polyester A and D chips in a mass ratio of 96:4 was used as the resin for the intermediate layer (polyester layer (A)). The properties of this film are shown in Table 1.

[0122] [Example 2] A polyester film was produced in the same manner as in Example 1, except that the chips of polyester E were used instead of the chips of polyester C. The chips of polyester A and E were blended in a mass ratio of 94.3:5.7. The properties of this film are shown in Table 1.

[0123] [Example 3] A polyester film was produced in the same manner as in Example 1, except that the chips of polyester F were used instead of the chips of polyester C. The chips of polyester A and F were blended in a mass ratio of 94.3:5.7. The properties of this film are shown in Table 1.

[0124] [Example 4] A polyester film was produced in the same manner as in Example 1, except that a blend of the polyester A and C chips in a mass ratio of 97.5:2.5 was fed into the intermediate layer extruder as the resin for the polyester layer (A). The properties of this film are shown in Table 1.

[0125] [Example 5] A polyester film was prepared by stacking two sheets of the polyester film prepared in Example 2. The properties of this film are shown in Table 1.

[0126] [Example 6] A polyester film was produced in the same manner as in Example 1, except that a blend of the chips of polyester A and G in a mass ratio of 95:5 was fed into the extruder for the intermediate layer as the resin for the polyester layer (A). The properties of this film are shown in Table 1.

[0127] [Example 7] A polyester film was produced in the same manner as in Example 1, except that a blend of the chips of polyesters A, E and H in a mass ratio of 91.3:5.0:3.7 was fed into the extruder for the intermediate layer as the resin for the polyester layer (A). The properties of this film are shown in Table 1.

[0128] [Example 8] A polyester film was produced in the same manner as in Example 1, except that a blend of the polyester A and H chips in a mass ratio of 84:16 was fed into the surface layer extruder as the resin for the polyester layer (B). The properties of this film are shown in Table 1.

[0129] [Example 9] A polyester film was produced in the same manner as in Example 1, except that a blend of the chips of polyesters A, E and I in a mass ratio of 75.1:5.0:19.9 was fed into the extruder for the intermediate layer as the resin for the polyester layer (A). The properties of this film are shown in Table 1.

[0130] [Example 10] A polyester film was produced in the same manner as in Example 1, except that a blend of the chips of polyester B and I in a mass ratio of 22:78 was fed into the surface layer extruder as the resin for the polyester layer (B). The properties of this film are shown in Table 1.

[0131] [Table 1]

[0132] As is clear from the results in Table 1, the polyester film for application to windows of the present invention has excellent light resistance. In addition, since the polyester film for application to windows of the present invention uses a halogen-free blue dye, it has little adverse effect on the environment when it is disposed of.

[0133] In addition, in Example 1, the polyester layer (A) contained only 0.04% by mass of carbon black, so the haze value of the polyester film was suppressed to 3.2, ensuring the transparency of the film. On the other hand, compared to Comparative Example 1, even though the carbon black content was only the above-mentioned proportion, the color difference (light resistance) was improved, demonstrating that the combined use of a halogen-free blue colorant and pigment provides an effect that is durable enough for practical use. In addition, it is assumed that two or more polyester films are laminated together in Examples 2 to 6. The advantage of the laminated structure is that the color can be easily adjusted, and the lineup of polyester film laminates for window application is increased. On the other hand, when a particularly high level of light resistance is required, Example 1 or Examples 7 to 10 can be used.

Claims

1. The polyester film for window application has a polyester layer (A) containing a halogen-free blue dye and a pigment, the content of the pigment in the polyester layer (A) being 0.02 to 0.1% by mass.

2. 2. The window-applied polyester film of claim 1, wherein the halogen-free blue dye is a halogen-free anthraquinone blue dye.

3. 3. The polyester film for window application according to claim 2, wherein the halogen-free anthraquinone blue dye is a compound represented by the following general formula (I): 【Chemistry 1】 (In the formula, R 1 and R 4 each independently represents a substituted or unsubstituted amino group; R 2 , R 3 , R 5 ~R 8 each independently represents a hydrogen atom or a substituent; R 2 and R 3 may be bonded to each other to form a ring.)

4. The window-applied polyester film according to claim 3, wherein the halogen-free anthraquinone blue dye is a compound represented by the following general formula (III-a) or a compound represented by the following general formula (IV): 【Chemistry 2】 (In the formula, X 11 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a phenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. 【Chemistry 2】 (In the formula, X 21 ~X 24 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a phenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.

5. The polyester film for application to windows according to any one of claims 1 to 4, which has a polyester layer (B) on at least one side of the polyester layer (A).

6. The polyester film for window application according to any one of claims 1 to 5, wherein the ratio of the thickness of the polyester layer (B) to the thickness of the polyester layer (A) [(B) / (A)] is 0.05 to 0.

5.

7. The polyester film for window application according to any one of claims 1 to 6, wherein the pigment is carbon black.

8. The polyester film for window application according to any one of claims 1 to 6, wherein the pigment is silica and / or alumina.

9. A window-applied polyester film laminate comprising the window-applied polyester film according to any one of claims 1 to 8 and a hard coat layer provided on the surface of the window-applied polyester film.

10. A window-applied polyester film laminate comprising the window-applied polyester film according to any one of claims 1 to 8 and an adhesive layer provided on the surface of the window-applied polyester film.

11. The polyester film laminate for window application according to claim 9 , further comprising an adhesive layer on the surface of the polyester film for window application opposite to the hard coat layer.

12. The polyester film laminate for window application according to claim 10 or 11, further comprising a release film provided on a surface of the adhesive layer.

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