WO2011089968A1 - Composition absorbant la lumière ultraviolette - Google Patents

Composition absorbant la lumière ultraviolette Download PDF

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WO2011089968A1
WO2011089968A1 PCT/JP2011/050487 JP2011050487W WO2011089968A1 WO 2011089968 A1 WO2011089968 A1 WO 2011089968A1 JP 2011050487 W JP2011050487 W JP 2011050487W WO 2011089968 A1 WO2011089968 A1 WO 2011089968A1
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ultraviolet
evaluation
compound
substituent
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PCT/JP2011/050487
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Japanese (ja)
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一路 尼崎
桂三 木村
ゆきえ 渡邊
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms

Definitions

  • the present invention relates to an ultraviolet absorber composition, and more particularly to an ultraviolet absorber composition containing a novel triazine derivative.
  • ultraviolet absorbers have been imparted by sharing ultraviolet absorbers with various resins.
  • An inorganic ultraviolet absorber and an organic ultraviolet absorber may be used as the ultraviolet absorber.
  • Inorganic UV absorbers (see, for example, Patent Documents 1 to 3) have excellent durability such as weather resistance and heat resistance, but are free to be selected because the absorption wavelength is determined by the band gap of the compound. None of them absorbs the long-wave ultraviolet (UV-A) region near 400 nm, and those that absorb the long-wave ultraviolet have absorption up to the visible region and are colored.
  • the organic ultraviolet absorber since the organic ultraviolet absorber has a high degree of freedom in the structural design of the absorbent, it is possible to obtain various absorption wavelengths by devising the structure of the absorbent.
  • Patent Document 4 discloses a triazole ultraviolet absorber.
  • Patent Document 5 describes a trisaryl-s-triazine having an alkoxy group and a hydroxy group at specific positions.
  • those having a maximum absorption wavelength in the long wave ultraviolet region have poor light resistance, and the ultraviolet shielding effect decreases with time.
  • materials applied to solar cells, etc. that have been developed in recent years need to be exposed to sunlight outdoors for a long time, and it is inevitable that their properties will deteriorate due to exposure to ultraviolet rays over time. It was. Therefore, there is a need for a compound that can be used as an ultraviolet absorber that exhibits a shielding effect up to the UV-A region and has an excellent light resistance.
  • Patent Document 6 describes an ultraviolet absorber containing a triazole-based ultraviolet absorber and trisaryltriazine.
  • Japanese Unexamined Patent Publication No. 5-339033 Japanese Laid-Open Patent Publication No. 5-345639 Japanese Unexamined Patent Publication No. 6-56466 Japan Special Table 2002-524442 Japanese Patent No. 3965631 Japanese Patent No. 4379640
  • An object of the present invention is to solve the above-described problems, and to provide an ultraviolet absorbent composition having high light solubility in an organic solvent, an ultraviolet shielding effect even in a long wavelength region, and having light resistance. .
  • An object of the present invention is to provide an ultraviolet absorbent composition that is not out and that can maintain long-wave ultraviolet absorption ability for a long period of time.
  • the present inventors have shown a shielding effect in the UV-A region (315 nm to 400 nm), have excellent light resistance, and have high solubility in organic solvents.
  • the present invention was completed by finding a compound having a structure which has not been known so far and using it in combination with other ultraviolet absorbers. That is, the said subject can be achieved by the following means.
  • An ultraviolet absorbent composition comprising a compound represented by the following general formula (1) and an ultraviolet absorbent having a maximum absorption wavelength of 270 to 400 nm.
  • R 1a , R 1c and R 1e represent a hydrogen atom.
  • R 1b and R 1d each independently represent a hydrogen atom or a substituent having a positive Hammett's ⁇ p value, and at least one represents a substituent having a positive Hammett's ⁇ p value.
  • R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p each independently represent a hydrogen atom or a monovalent substituent. Moreover, you may combine with substituents and may form a ring.
  • the monovalent substituent is a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, substituted or Unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group, substituted or unsubstituted sulfamoyl group, thiocyanate group, Or a substituted or unsubstituted alkylsulfonyl group, where the substituent is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, an alkoxycarbony
  • the substituent having a positive Hammett's ⁇ p value is a group selected from COOR r , CONR s 2 , a cyano group, CF 3 , a halogen atom, a nitro group, and SO 3 M, 1] to ultraviolet absorber composition according to any one of [3] [R r, R s independently of one another, represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal. ].
  • UV absorber composition Any one of [1] to [7], wherein R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p are hydrogen atoms.
  • UV absorber composition [9] The ultraviolet absorber composition according to any one of [1] to [8], wherein pka is in the range of -5.0 to -7.0.
  • the ultraviolet absorber having a maximum absorption wavelength of 270 to 400 nm is composed of a benzotriazole compound, a benzophenone compound, a benzoxazinone compound, a cyanoacrylate compound, a benzoxazole compound, a merocyanine compound, and a triazine compound.
  • the mass ratio of the compound represented by the following general formula (1) and the ultraviolet absorber having the maximum absorption wavelength at 270 to 400 nm is 0.2: 1 to 20: 1 [1]
  • the ultraviolet absorbent composition of the present invention exhibits an ultraviolet shielding effect even in a long wavelength region and has light resistance.
  • a polymer material or the like By mixing with a polymer material or the like, not only the ultraviolet light durability can be improved, but also the decomposition of other unstable compounds can be suppressed by using the polymer material as an ultraviolet filter.
  • it is highly soluble in organic solvents, does not precipitate or bleed out, and can maintain long-wave ultraviolet absorption ability for a long period of time.
  • the ultraviolet absorbent composition of the present invention contains a compound represented by the following general formula (1) and an ultraviolet absorbent having a maximum absorption wavelength at 270 to 400 nm.
  • the compound represented by the general formula (1) is highly soluble in an organic solvent, exhibits an ultraviolet shielding effect even in a long wavelength region (for example, 315 nm to 400 nm), and has light resistance. Therefore, it can be suitably used as an ultraviolet absorber that does not precipitate or bleed out and can maintain long-wave ultraviolet absorption ability for a long period of time. Further, when used in combination with another ultraviolet absorber having a different basic skeleton, it absorbs ultraviolet rays in a wider wavelength region and has a more excellent ultraviolet shielding effect and light resistance.
  • an ultraviolet absorber composition is odorless depending on a use
  • the ultraviolet absorber composition of this invention is odorless even if it uses it in high concentration, and is excellent also in the point of odor.
  • R 1a , R 1c and R 1e each represent a hydrogen atom
  • R 1b and R 1d are independently of each other a hydrogen atom or a Hammett's ⁇ p value is positive.
  • at least one of R 1b and R 1d represents a substituent having a positive Hammett's ⁇ p value
  • the LUMO is stabilized by the electron-attracting group, so that the excitation lifetime is Shorter.
  • the symmetry of the compound structure is broken, and it has excellent light resistance and high solubility in a solvent.
  • R 1a , R 1c and R 1e represent a hydrogen atom.
  • R 1b and R 1d each independently represent a hydrogen atom or a substituent having a positive Hammett's ⁇ p value, and at least one represents a substituent having a positive Hammett's ⁇ p value.
  • R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p each independently represent a hydrogen atom or a monovalent substituent. Moreover, you may combine with substituents and may form a ring. ]
  • Examples of the monovalent substituent (hereinafter referred to as A) in the general formula (1) include, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group having 1 to 20 carbon atoms (for example, Methyl, ethyl), aryl groups having 6 to 20 carbon atoms (for example, phenyl, naphthyl), cyano groups, carboxyl groups, alkoxycarbonyl groups (for example, methoxycarbonyl), aryloxycarbonyl groups (for example, phenoxycarbonyl), substituted or unsubstituted Carbamoyl groups (eg carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl groups (eg acetyl), arylcarbonyl groups (eg benzoyl),
  • substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different.
  • the above-mentioned monovalent substituent A can be mentioned as an example of a substituent.
  • Rings formed by bonding between substituents include benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, oxadiazole And a ring, a thiazole ring, a thiadiazole ring, a furan ring, a thiophene ring, a selenophene ring, a silole ring, a gelmol ring, and a phosphole ring.
  • Examples of the monovalent substituent in the general formula (1) include a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted group.
  • R 1b and R 1d each independently represent a hydrogen atom or a substituent having a positive Hammett's ⁇ p value, and at least one represents a substituent having a positive Hammett's ⁇ p value.
  • Solvent solubility means solubility in an organic solvent such as ethyl acetate, methyl ethyl ketone, and toluene. It is preferably 10% by mass or more and 30% by mass in an organic solvent such as ethyl acetate, methyl ethyl ketone, and toluene. It is more preferable to dissolve the above.
  • ⁇ p value is a positive Hammett equation in formula (1), preferably, sigma electron withdrawing group p value of 0.1 to 1.2.
  • the electron withdrawing group having a ⁇ p value of 0.1 or more include COOR r (R r represents a hydrogen atom or a monovalent substituent), CONR s 2 (R s represents a hydrogen atom).
  • a monovalent substituent and examples thereof include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heterocyclic group having 6 to 20 carbon atoms, preferably a hydrogen atom.
  • Cyano group, halogen atom, nitro group, SO 3 M (M represents a hydrogen atom or an alkali metal), acyl group, formyl group, acyloxy group, acylthio group, alkyloxycarbonyl group, aryloxycarbonyl Group, dialkylphosphono group, diarylphosphono group, dialkylphosphinyl group, diarylphosphinyl group, phosphoryl group, alkylsulfinyl group, arylsulfinyl group, alkyl A sulfonyl group, an arylsulfonyl group, an acylthio group, a sulfamoyl group, a thiocyanate group, a thiocarbonyl group, an imino group, an imino group substituted with an N atom, a carboxy group (or a salt thereof), and substituted with at least two or more halogen atoms
  • An alkyl group (for
  • the substituent having a positive Hammett's ⁇ p value in the general formula (1) is more preferably COOR r , CONR s 2 , a cyano group, CF 3 , a halogen atom, a nitro group, or SO 3 M [R r 1 and R s each independently represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal]. Examples of the monovalent substituent include the substituent A.
  • the substituent having a positive Hammett's ⁇ p value in the general formula (1) is more preferably a COOR r or cyano group, and further preferably COOR r .
  • R r preferably represents a hydrogen atom or an alkyl group, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and still more preferably a linear or branched alkyl group having 1 to 15 carbon atoms.
  • R r is more preferably a branched alkyl group having 5 to 15 carbon atoms from the viewpoint of solubility in a solvent.
  • the branched alkyl group has a secondary carbon atom or a tertiary carbon atom, preferably contains 1 to 5 secondary carbon atoms or tertiary carbon atoms, preferably contains 1 to 3, preferably 1 or 2 It is preferable to contain it, and it is more preferable to contain 1 or 2 secondary carbon atoms and tertiary carbon atoms. Further, it preferably contains 1 to 3 asymmetric carbons.
  • R r is a branched alkyl group having 5 to 15 carbon atoms containing 1 or 2 secondary carbon atoms and tertiary carbon atoms and 1 or 2 asymmetric carbons from the viewpoint of solubility in a solvent. It is particularly preferred. This is because the symmetry of the compound structure is broken and the solubility is improved.
  • a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable from the viewpoint of ultraviolet absorbing ability.
  • Examples of the straight or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i- Mention may be made of pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl and i-octyl, preferably methyl or ethyl, particularly preferably methyl.
  • R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p represent a monovalent substituent
  • R 1h is a substituent in which the ⁇ p value in the Hammett rule is positive.
  • R 1b or R 1d and R 1h represent a substituent having a positive (preferably 0.1 to 1.2) ⁇ p value according to the Hammett rule. This is because it has excellent light resistance.
  • R 1h or R 1n is preferably each independently a hydrogen atom, COOR r , CONR s 2 , a cyano group, CF 3 , a halogen atom, a nitro group, or SO 3 M, and R 1h or R 1n is more preferably a hydrogen atom, R 1h and R 1n are more preferably hydrogen atoms, and R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p Particularly preferably represents a hydrogen atom. It is for showing the outstanding light resistance.
  • R 1b or R 1d is a substituent having a positive Hammett's ⁇ p value (preferably 0.1 to 1.2), and R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p preferably represent a hydrogen atom, and R 1b or R 1d is COOR r , CONR s 2 , a cyano group, CF 3 , a halogen atom , nitro group, in any one of SO 3 M, R 1g, R 1h, R 1i, R 1j, R 1k, R 1m, R 1n and R 1p is more preferably a hydrogen atom. It is for showing the outstanding light resistance.
  • the compound represented by the general formula (1) preferably has a pKa in the range of ⁇ 5.0 to ⁇ 7.0. Further, it is more preferably in the range of -5.2 to -6.5, particularly preferably in the range of -5.4 to -6.0.
  • Me represents a methyl group
  • Ph represents a phenyl group
  • —C 6 H 13 represents n-hexyl.
  • the compound represented by the general formula (1) is preferably contained in the ultraviolet absorber composition in an amount of 0.01% to 50% by mass, more preferably 0.1 to 10% by mass, The content is most preferably 0.3 to 3% by mass. It is because the effect of high light resistance can be obtained by setting the content of the compound represented by the general formula (1) within the above range.
  • the compound represented by the general formula (1) can take a tautomer depending on the structure and the environment in which the compound is placed. Although the present invention is described in one of the representative forms, tautomers different from those described in the present invention are also included in the compounds of the present invention.
  • the compound represented by the general formula (1) may contain an isotope (for example, 2 H, 3 H, 13 C, 15 N, 17 O, 18 O, etc.).
  • the compound represented by the general formula (1) can be synthesized by any method.
  • known patent documents and non-patent documents for example, JP-A-7-188190, JP-A-11-315072, JP-A-2001-220385, “Dye and Drug”, Vol. 40, No. 12 (1995)
  • exemplary compound (m-31) can be synthesized by reacting salicylamide, 3,5-bis (trifluoromethyl) benzoyl chloride and 2-hydroxybenzamidine hydrochloride. It can also be synthesized by reacting salicylamide, salicylic acid and 3,5-bis (trifluoromethyl) benzamidine hydrochloride.
  • the ultraviolet absorber of the present invention is represented by the general formula (1). Since the ultraviolet absorber represented by the general formula (1) of the present invention has a substituent having a positive Hammett's ⁇ p value at a specific position, LUMO is stabilized by an electron withdrawing group. It has the characteristics that the lifetime is shortened and it has excellent light resistance. Even when it is used as an ultraviolet absorber, when a known triazine compound is used, it has an adverse effect such as decomposition and yellowing when used for a long time. On the other hand, since the ultraviolet absorber represented by the general formula (1) has excellent light resistance, the effect of not decomposing and yellowing even when used for a long time can be obtained.
  • the ultraviolet absorber represented by the general formula (1) has a substituent at the m-position (R 1b and R 1d in the structural formula), the symmetry of the compound structure is broken, so that the solubility in organic solvents is improved. It has the feature of being excellent. Even when used as a UV absorber, known triazine compounds have adverse effects such as precipitation and bleeding out due to long-term use, decomposition and yellowing when used at high concentrations. On the other hand, the ultraviolet absorber represented by the general formula (1) has excellent solubility and light resistance, so that precipitation or bleed-out does not occur even when used at a high concentration. It is possible to obtain an effect that a change in hue, such as a reduction in effect or yellowing due to decomposition, hardly occurs.
  • the compound represented by the general formula (1) may be used alone or in combination of two or more having different structures.
  • a compound in which R 1b or R 1d represents a substituent having a positive Hammett's ⁇ p value and a compound in which R 1c represents a substituent having a positive Hammett's ⁇ p value can be used in combination.
  • the maximum absorption wavelength of the compound represented by the general formula (1) is not particularly limited, but is preferably 250 to 400 nm, and more preferably 280 to 380 nm.
  • the full width at half maximum is preferably 20 to 100 nm, more preferably 40 to 80 nm.
  • a person skilled in the art can easily measure the maximum absorption wavelength and the full width at half maximum defined in the present invention.
  • the measurement method is described in, for example, “The Fourth Edition Experimental Chemistry Course 7 Spectral Spectroscopy II” (Maruzen, 1992), pages 180 to 186, edited by the Chemical Society of Japan.
  • the sample is dissolved in a suitable solvent, and measurement is performed by a spectrophotometer using a cell made of quartz or glass and using two cells for sample and control.
  • the solvent to be used is required to have no absorption in the measurement wavelength region, have a small interaction with the solute molecule, and have a very low volatility in addition to the solubility of the sample. Any solvent that satisfies the above conditions can be selected.
  • measurement is performed using ethyl acetate (EtOAc) as a solvent.
  • the maximum absorption wavelength and half width of the compound in the present invention are values measured using a quartz cell having an optical path length of 10 mm by preparing a solution having a concentration of about 5 ⁇ 10 ⁇ 5 mol ⁇ dm ⁇ 3 using ethyl acetate as a solvent. Is used.
  • the half width of the spectrum is described in, for example, “The Fourth Edition Experimental Chemistry Lecture 3 Basic Operation III” (Maruzen, 1991), page 154, edited by the Chemical Society of Japan.
  • the half-value width is explained with an example in which the horizontal axis is taken on the wave number scale, but the half-value width in the present invention is the value when the axis is taken on the wavelength scale,
  • the unit is nm. Specifically, it represents the width of the absorption band that is half the absorbance at the maximum absorption wavelength, and is used as a value that represents the shape of the absorption spectrum.
  • a spectrum with a small half-value width is a sharp spectrum
  • a spectrum with a large half-value width is a broad spectrum.
  • the UV-absorbing compound that gives a broad spectrum has absorption in a wide region from the maximum absorption wavelength to the long wave side. Therefore, in order to effectively block the long wave UV region without yellowing, a spectrum with a small half-value width is used.
  • the ultraviolet absorbing compound having is preferable.
  • the intensity of light absorption ie the oscillator strength
  • the oscillator strength is proportional to the product of the absorbance at the maximum absorption wavelength and the full width at half maximum (however, the full width at half maximum is a value obtained by taking an axis on the wavelength scale). This means that when the transition moment values are the same, a compound having a spectrum with a small half width has a large absorbance at the maximum absorption wavelength.
  • Such UV-absorbing compounds have the advantage of being able to effectively shield the area around the maximum absorption wavelength with a small amount of use, but since the absorbance decreases sharply when the wavelength is slightly away from the maximum absorption wavelength, a wide range of areas can be used. It cannot be shielded.
  • the compound represented by the general formula (1) preferably has a molar extinction coefficient at the maximum absorption wavelength of 20000 or more, more preferably 30000 or more, and particularly preferably 50000 or more. If it is 20000 or more, since the absorption efficiency per mass of the ultraviolet absorber is sufficiently obtained, the amount of the ultraviolet absorber used for completely absorbing the ultraviolet region can be reduced. This is preferable from the viewpoint of preventing skin irritation and accumulation in a living body and from the point that bleeding out hardly occurs.
  • the molar extinction coefficient uses the definition described in, for example, “New Edition Experimental Chemistry Course 9 Analytical Chemistry [II]” (Maruzen, 1977), page 244, etc., edited by the Chemical Society of Japan. It can be determined together with the absorption wavelength and the half width.
  • the ultraviolet absorber is not particularly limited as long as it is an ultraviolet absorber having a maximum absorption wavelength in the range of 270 to 400 nm.
  • the benzotriazole compound, the benzophenone compound, the benzoxazinone compound, the cyanoacrylate compound, the benzoxazole It is preferable to use a compound, a merocyanine compound, a triazine compound, or any combination thereof. This is because a wide wavelength range is absorbed.
  • benzotriazole compounds, benzophenone compounds, and triazine compounds are more preferable, and triazine compounds are most preferable from the viewpoint of compatibility with the compound represented by the general formula (1) and light resistance.
  • benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-3′-t-butyl-5 ′-(2- (octyloxycarbonyl) ethyl) phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′- Dodecyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotri Sol, 2- (2′-hydroxy-5′-t-octy
  • benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4 Benzyloxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxypropoxy) benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone Hydrate, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2-hydroxy-4-diethylamino-2'-hexyloxycarbonyl Zophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 1,4-
  • benzoxazinone compounds include 2,2′-p-phenylenebis (4H-3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (6-methyl-4H— 3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (6-chloro-4H-3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (6 -Methoxy-4H-3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (6-hydroxy-4H-3,1-benzoxazin-4-one), 2,2 '-(naphthalene-) 2,6-diyl) bis (4H-3,1-benzoxazin-4-one), 2,2 ′-(naphthalene-1,4-diyl) bis (4H-3,1-benzoxazin-4-one) , 2,2 '-(thio -2,5-diyl) bis (4H-3,1-benzo
  • cyanoacrylate compounds include 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, ethyl 2-cyano-3,3-diphenyl acrylate, hexadecyl 2-cyano-3- (4-methylphenyl) acrylate , 2-cyano-3- (4-methylphenyl) acrylate, 1,3-bis (2′-cyano-3,3′-diphenylacryloyl) oxy) -2,2-bis (((2′- And cyano-3,3′-diphenylacryloyl) oxy) methyl) propane.
  • those having a maximum absorption wavelength of 270 to 400 nm can be used in the present invention.
  • benzoxazole compounds include 2,5-thiophenediyl (5-tert-butyl-1,3-benzoxazole), 2,6-di (benzoxazol-2-yl) naphthalene, 1,4-di (Benzoxazol-2-yl) naphthalene, 1,4-di (benzoxazol-2-yl) benzene, 4- (benzoxazol-2-yl) -4 '-(5-methylbenzoxazol-2-yl) And stilbene, 4,4′-bis (benzoxazol-2-yl) stilbene, 4,4′-bis (benzoxazol-2-yl) furan, and the like. Of these, those having a maximum absorption wavelength of 270 to 400 nm can be used in the present invention.
  • merocyanine compounds include 1,3-dimethyl-5- [2- (3-methyloxazolidine-2-ylidene) ethylidene] pyrimidine-2,4,6-trione, 1,3-dimethyl-5 [2- (1-Methylpyrrolidine-2-ylidene) ethylidene] pyrimidine-2,4,6-trione, 1,3-dimethyl-5- [2- (3-methylthiazolidine-2-ylidene) ethylidene] pyrimidine- 2,4,6-trione, 3-ethyl-5- [2- (3-methyloxazolidine-2-ylidene) ethylidene] -2-thioxooxazolidin-4-one, 3-ethyl-5- [2- ( 1-methylpyrrolidin-2-ylidene) ethylidene] -2-thioxooxazolidin-4-one, octyl-5-N, N-diethyla
  • compounds such as salicylic acid compounds, cyanine compounds, dibenzoylmethane compounds, cinnamic acid compounds, and benzoic acid esters may be used as long as they have a maximum absorption wavelength of 270 to 400 nm. it can.
  • Fine Chemical, May 2004 issue pages 28-38, published by Toray Research Center, Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999), pages 96-140, Jun Ohkatsu Ultraviolet absorbers described in the supervision of “Development of Polymer Additives and Environmental Countermeasures” (CMC Publishing Co., Ltd., 2003), pages 54 to 64 can be used.
  • the ultraviolet absorber having a maximum absorption wavelength of 270 to 400 nm used in the present invention the following are particularly preferable.
  • the mass ratio of the compound represented by the general formula (1) and the ultraviolet absorbent having the maximum absorption wavelength at 270 to 400 nm is 0.2: 1 to 20: 1. Is preferable, a range of 1: 1 to 10: 1 is more preferable, and a range of 2: 1 to 5: 1 is most preferable. By setting it as such a mass ratio, the more preferable ultraviolet-ray blocking effect is acquired and a bleed-out can be suppressed more effectively.
  • the ultraviolet absorbent composition of the present invention the ultraviolet absorbent having at least two different structures of the compound represented by the general formula (1) and the ultraviolet absorbent having a maximum absorption wavelength at 270 to 400 nm is used.
  • ultraviolet rays in a wide wavelength region can be absorbed.
  • the dispersion state of the ultraviolet absorber is also stabilized. Therefore, in addition to these ultraviolet absorbers, ultraviolet absorbers known in the art other than the ultraviolet absorber having a maximum absorption wavelength of 270 to 400 nm can be further added.
  • the compound represented by the general formula (1) according to the present invention and the ultraviolet absorber alone can provide a practically sufficient ultraviolet shielding effect, but the hiding power is required when more strictness is required.
  • a strong white pigment such as titanium oxide may be used in combination.
  • a small amount (0.05% by mass or less) of a colorant can be used in combination depending on the preference.
  • a fluorescent brightening agent may be used in combination.
  • the optical brightener include those commercially available, general formula [1] described in JP-A-2002-53824, and specific compound examples 1 to 35.
  • the ultraviolet absorbent composition of the present invention may be in the form of a dispersion in which the compound represented by the general formula (1) and the ultraviolet absorbent are dispersed in a dispersion medium.
  • a dispersion medium may be used, and examples thereof include water, organic solvents, resins, and resin solutions. These may be used alone or in combination.
  • organic solvent for the dispersion medium examples include hydrocarbons such as pentane, hexane, and octane, aromatics such as benzene, toluene, and xylene, ethers such as diethyl ether and methyl-t-butyl ether, methanol, ethanol, and isopropanol.
  • Alcohols such as acetone, ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl Amides such as pyrrolidone, sulfoxides such as dimethyl sulfoxide, amines such as triethylamine and tributylamine, carboxylic acids such as acetic acid and propionic acid, halogens such as methylene chloride and chloroform, tetrahydro Orchids, heterocyclic ring systems such as pyridine, and the like. These can be used in combination at any ratio.
  • thermoplastic resins examples include thermoplastic resins and thermosetting resins conventionally used in the production of various conventionally known molded articles, sheets, films and the like.
  • thermoplastic resins include polyethylene resins, polypropylene resins, poly (meth) acrylic ester resins, polystyrene resins, styrene-acrylonitrile resins, acrylonitrile-butadiene-styrene resins, polyvinyl chloride resins, Polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol resin, polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), liquid crystal polyester Resin (LCP), polyacetal resin (POM), polyamide resin (PA), polycarbonate resin, polyurethane resin, polyphenylene sulfide resin (PPS), and the like, which are one kind or
  • resins are also used as thermoplastic molding materials in which natural resins contain fillers such as glass fibers, carbon fibers, semi-carbonized fibers, cellulosic fibers, glass beads, flame retardants, and the like.
  • conventionally used additives for resins for example, polyolefin resin fine powder, polyolefin wax, ethylene bisamide wax, metal soap, etc. can be used alone or in combination as required.
  • thermosetting resin examples include epoxy resins, melamine resins, unsaturated polyester resins, and the like. These include natural resins, glass fibers, carbon fibers, semi-carbonized fibers, cellulosic fibers, glass beads, and the like. It can also be used as a thermosetting molding material containing a flame retardant.
  • dispersions can be further used in combination with a dispersant, an antifoaming agent, a preservative, an antifreezing agent, a surfactant and the like.
  • a dispersant an antifoaming agent, a preservative, an antifreezing agent, a surfactant and the like.
  • any compound may be included. Examples thereof include dyes, pigments, infrared absorbers, fragrances, polymerizable compounds, polymers, inorganic substances, metals, and the like.
  • the content of the compound represented by the general formula (1) in the dispersion and the ultraviolet absorber having the maximum absorption wavelength at 270 to 400 nm differs depending on the purpose of use and the form of use, but cannot be uniquely determined. It may be any content depending on the purpose.
  • the total content is preferably 0.001 to 30% by mass, more preferably 0.01 to 10% by mass, based on the total amount of the dispersion.
  • a high-speed stirring type disperser having a large shearing force As a device for obtaining these dispersions, a high-speed stirring type disperser having a large shearing force, a disperser that gives high-intensity ultrasonic energy, and the like can be used.
  • a colloid mill a homogenizer, a capillary emulsifying device, a liquid siren, an electromagnetic distortion ultrasonic generator, an emulsifying device having a Paulman whistle, and the like.
  • a high-speed stirring type disperser preferable for use in the present invention is a high-speed rotation (500 to 15,000 rpm) in a liquid in which a main part such as a dissolver, polytron, homomixer, homoblender, ket mill, or jet agitator is dispersed.
  • the high-speed stirring type disperser used in the present invention is also called a dissolver or a high-speed impeller disperser.
  • a saw-tooth plate is attached to a shaft that rotates at high speed.
  • a preferred example is one in which impellers that are alternately bent in the vertical direction are mounted.
  • a hydrophobic compound is dissolved in an organic solvent, one kind arbitrarily selected from a high-boiling organic substance, a water-immiscible low-boiling organic solvent, or a water-miscible organic solvent, or two or more kinds of arbitrary substances Dissolve in the multi-component mixture and then disperse in water or aqueous hydrophilic colloid in the presence of a surface active compound.
  • the mixing method of the water-insoluble phase containing the hydrophobic compound and the aqueous phase may be a so-called forward mixing method in which the water-insoluble phase is added to the aqueous phase with stirring or a reverse mixing method.
  • the ultraviolet absorbent composition of the present invention may be in the form of a solution in which the compound represented by the general formula (1) and the ultraviolet absorbent are dissolved in a liquid medium.
  • Any solvent may be used, and examples thereof include water, organic solvents, resins, and resin solutions. Examples of the organic solvent, the resin, and the resin solution include those described as the above dispersion medium. These may be used alone or in combination.
  • solutions may contain any other compound in addition.
  • examples thereof include dyes, pigments, infrared absorbers, fragrances, polymerizable compounds, polymers, inorganic substances, metals, and the like.
  • these arbitrary compounds do not necessarily need to be dissolved.
  • the contents of the compound represented by the general formula (1) and the ultraviolet absorber having the maximum absorption wavelength in the range of 270 to 400 nm in these solutions vary depending on the purpose of use and the form of use, but cannot be uniquely determined.
  • the concentration may be any depending on the purpose.
  • the total content is preferably 0.001 to 30% by mass, more preferably 0.01 to 20% by mass, based on the total amount of the solution. It is also possible to prepare a solution at a high concentration in advance and dilute it when desired.
  • the dilution solvent can be arbitrarily selected from the above-mentioned solvents.
  • the ultraviolet absorber composition of the present invention is dyes, pigments, foods, beverages, body care products, vitamins, pharmaceuticals, inks, oils, fats, waxes, surface coatings, cosmetics, photographic materials, textiles And pigments thereof, plastic materials, rubber, paints, resin compositions, polymer additives, and the like.
  • the ultraviolet absorber composition of this invention can be used conveniently for a resin composition.
  • the resin composition containing the ultraviolet absorbent composition of the present invention will be described.
  • the resin composition containing the ultraviolet absorbent composition of the present invention may contain a resin and may be formed by dissolving the resin in an arbitrary solvent.
  • the ultraviolet absorbent composition of the present invention can be contained in the resin composition by various methods. When the ultraviolet absorbent composition of the present invention is compatible with the resin composition, the ultraviolet absorbent composition of the present invention can be directly added to the resin composition.
  • the ultraviolet absorbent composition of the present invention may be dissolved in an auxiliary solvent having compatibility with the resin composition, and the solution may be added to the resin composition.
  • the ultraviolet absorbent composition of the present invention may be dispersed in a high-boiling organic solvent or polymer, and the dispersion may be added to the resin composition.
  • the boiling point of the high-boiling organic solvent is preferably 180 ° C. or higher, and more preferably 200 ° C. or higher.
  • the melting point of the high-boiling organic solvent is preferably 150 ° C. or lower, and more preferably 100 ° C. or lower.
  • Examples of the high boiling point organic solvent include phosphate ester, phosphonate ester, benzoate ester, phthalate ester, fatty acid ester, carbonate ester, amide, ether, halogenated hydrocarbon, alcohol and paraffin. Phosphate esters, phosphonate esters, phthalate esters, benzoate esters and fatty acid esters are preferred.
  • JP-A-58-209735, JP-A-63-264748, JP-A-4-1911851, JP-A-8-272058, and British Patent No. 201106017A are described. Can be helpful.
  • the resin used for the resin composition will be described.
  • the resin may be a natural or synthetic polymer.
  • polyolefins eg, polyethylene, polypropylene, polyisobutylene, poly (1-butene), poly-4-methylpentene, polyvinylcyclohexane, polystyrene, poly (p-methylstyrene), poly ( ⁇ -methylstyrene), polyisoprene, Polybutadiene, polycyclopentene, polynorbornene, etc.
  • copolymers of vinyl monomers eg ethylene / propylene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / vinylcyclohexane copolymer, ethylene / cycloolefin copolymer (eg ethylene / propylene copolymer)
  • Cycloolefin copolymers such as norbornene (C
  • Polycarbonate polyketone, polysulfone polyetherketone, phenolic resin, melamine resin, cellulose ester (eg diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polysiloxane, natural Examples thereof include polymers (for example, cellulose, rubber, gelatin and the like).
  • polystyrene resin polystyrene resin
  • acrylic polymers polystyrene resin
  • polyesters polycarbonates
  • cellulose esters are more preferred.
  • the ultraviolet absorbent composition of the present invention can contain any amount necessary for imparting desired performance. These vary depending on the compound and resin used, but the content can be determined as appropriate. As content, it is preferable that it is more than 0 mass% and 20 mass% or less in a resin composition, It is more preferable that it is more than 0 mass% and 10 mass% or less, 0.05 mass% or more and 5% mass or less More preferably it is. When the content is in the above range, a sufficient ultraviolet shielding effect can be obtained and bleeding out can be suppressed, which is preferable.
  • the resin composition may further contain optional additives such as antioxidants, light stabilizers, processing stabilizers, anti-aging agents, and compatibilizers as necessary.
  • the resin composition containing the ultraviolet absorbent composition of the present invention can be used for all applications in which a synthetic resin is used, but is particularly suitable for applications that may be exposed to sunlight or light including ultraviolet rays.
  • Specific examples include, for example, glass substitutes and surface coating materials thereof, housing, facilities, window glass for transportation equipment, coating materials for daylighting glass and light source protection glass, housing, facilities, window films for transportation equipment, housing, Inner and outer packaging materials for facilities, transportation equipment, etc., and coating films formed by the coating, alkyd resin lacquer coating and coating formed by the coating, acrylic lacquer coating and coating formed by the coating, fluorescence Light source components that emit ultraviolet rays, such as lamps and mercury lamps, precision machinery, components for electronic and electrical equipment, materials for blocking electromagnetic waves generated from various displays, containers or packaging materials for food, chemicals, chemicals, bottles, boxes, blisters , Cup, special packaging, compact disc coat, agricultural or industrial sheet or film material, printed matter, dyed matter, dyed face Anti-fading agents, protective films for polymer supports (e
  • Examples of the shape of the polymer molded product formed from this resin composition include flat membranes, powders, spherical particles, crushed particles, massive continuous bodies, fibers, tubulars, hollow fibers, granules, plates, porouss, etc. Either shape may be sufficient.
  • this resin composition contains the ultraviolet absorbent composition of the present invention, it has light resistance (fastness to ultraviolet light), causing precipitation of the ultraviolet absorbent composition and bleeding out due to long-term use. There is nothing. Moreover, since this resin composition is provided with an excellent long-wave ultraviolet absorbing ability, it can be used as an ultraviolet absorbing filter or a container, and can protect compounds that are sensitive to ultraviolet rays. For example, by molding this resin composition by any method such as extrusion molding or injection molding, it is possible to obtain a molded product (such as a container) having excellent long-wave ultraviolet absorption ability. In addition, a molded product coated with an ultraviolet absorbing film containing the ultraviolet absorbent composition of the present invention can be obtained by applying and drying a solution of the resin composition to a separately manufactured molded product.
  • the resin is preferably transparent.
  • transparent resins include cellulose esters (eg, diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate).
  • Phthalate polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene) , Polyolefin (eg, polyethylene, polypropylene, polymethylpentene), polymethyl methacrylate, syndiotactic polystyrene, Examples include resulfone, polyethersulfone, polyetherketone, polyetherimide, and polyoxyethylene.
  • cellulose ester Preferred are cellulose ester, polycarbonate, polyester, polyolefin, and acrylic resin, and more preferred are polycarbonate and polyester. More preferred is polyester, and particularly preferred is polyethylene terephthalate.
  • the polymer molded product obtained from this resin composition can also be used as a transparent support, and the transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more.
  • the packaging material containing the ultraviolet absorbent according to the present invention will be described.
  • the packaging material containing the ultraviolet absorbent according to the present invention may be a packaging material made of any kind of polymer as long as it contains the compound represented by the general formula (1).
  • thermoplastic resin, polyvinyl alcohol, polyvinyl chloride, polyester, heat shrinkable polyester, styrenic resin, polyolefin, ROMP and the like can be mentioned.
  • a resin having an inorganic vapor-deposited thin film layer may be used.
  • coated resin containing a ultraviolet absorber may be sufficient.
  • the packaging material containing the ultraviolet absorbent according to the present invention may package any foods, beverages, drugs, cosmetics, personal care products, and the like.
  • food packaging colored liquid packaging, packaging for the described liquid preparations, pharmaceutical container packaging, sterilization packaging for medical products, photographic photosensitive material packaging, photographic film packaging, UV curable ink packaging, shrink label, and the like.
  • the packaging material containing the ultraviolet absorber of the present invention may be, for example, a transparent package or a light-shielding package.
  • the packaging material containing the ultraviolet absorbent according to the present invention may have, for example, not only ultraviolet shielding properties but also other performances. Examples thereof include those having gas barrier properties, those containing an oxygen indicator, and combinations of ultraviolet absorbers and fluorescent brighteners.
  • the packaging material containing the ultraviolet absorbent according to the present invention may be produced using any method. Examples thereof include a method of forming an ink layer, a method of melt-extruding and laminating a resin containing an ultraviolet absorber, a method of coating on a base film, and a method of dispersing an ultraviolet absorber in an adhesive.
  • the container containing the ultraviolet absorbent according to the present invention will be described.
  • the container containing the ultraviolet absorbent according to the present invention may be a container made of any kind of polymer as long as it contains the compound represented by the general formula (1). Examples include thermoplastic resin containers, polyester containers, polyethylene naphthalate containers, polyethylene containers, cyclic olefin resin composition containers, plastic containers, and transparent polyamide containers.
  • it may be a paper container containing resin. It may be a glass container having an ultraviolet absorbing layer.
  • the use of the container containing the ultraviolet absorbent according to the present invention may contain any foods, beverages, drugs, cosmetics, personal care products, shampoos and the like.
  • the container containing the ultraviolet absorbent according to the present invention may have not only ultraviolet blocking properties but also other performance.
  • an antibacterial container, a flexible container, a dispenser container, a biodegradable container, etc. are mentioned.
  • the container containing the ultraviolet absorbent according to the present invention may be manufactured using any method.
  • a method using two-layer stretch blow molding, a multilayer coextrusion blow molding method, a method of forming an ultraviolet absorbing layer on the outside of a container, a method using a shrinkable film, a method using a supercritical fluid, and the like can be mentioned.
  • the coating material containing the ultraviolet absorber of the present invention may be a coating material composed of any component as long as it contains the compound represented by the general formula (1).
  • an acrylic resin system, a urethane resin system, an amino alkyd resin system, an epoxy resin system, a silicone resin system, a fluororesin system, etc. are mentioned. These resins can be arbitrarily mixed with a main agent, a curing agent, a diluent, a leveling agent, a repellant and the like.
  • acrylic urethane resin or silicon acrylic resin is selected as the transparent resin component
  • polyisocyanate is used as the curing agent
  • hydrocarbon solvents such as toluene and xylene are used as the diluent
  • Alcohol solvents such as ester solvents, isopropyl alcohol, and butyl alcohol can be used.
  • the acrylic urethane resin refers to an acrylic urethane resin obtained by reacting a methacrylic ester (typically methyl), a hydroxyethyl methacrylate copolymer and a polyisocyanate.
  • the polyisocyanate in this case includes tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and the like.
  • the transparent resin component include polymethyl methacrylate, polymethyl methacrylate styrene copolymer, polyvinyl chloride, and polyvinyl acetate.
  • a leveling agent such as an acrylic resin or a silicone resin, an anti-fogging agent such as a silicone or acrylic resin, and the like can be blended as necessary.
  • the use purpose of the paint containing the ultraviolet absorber of the present invention may be any application.
  • the coating material containing the ultraviolet absorber of the present invention is generally composed of a coating material (including a transparent resin component as a main component) and an ultraviolet absorber, but preferably a composition of 0 to 20% by mass of the ultraviolet absorber based on the resin. It is.
  • the thickness at the time of application is preferably 2 to 1000 ⁇ m, more preferably 5 to 200 ⁇ m.
  • the method of applying these paints is arbitrary, but there are a spray method, a dipping method, a roller coat method, a flow coater method, a flow coating method and the like. Drying after application varies depending on the paint components, but it is preferably performed at room temperature to 120 ° C for about 10 to 90 minutes.
  • the coating film containing the ultraviolet absorber of the present invention is a coating film containing an ultraviolet absorber made of the compound represented by the general formula (1), and is formed using the above-described coating material containing the ultraviolet absorbent of the present invention. Coating film.
  • the ink containing the ultraviolet absorbent according to the present invention will be described.
  • the ink containing the ultraviolet absorber of the present invention may be any form of ink as long as it contains the compound represented by the general formula (1). Examples thereof include dye ink, pigment ink, water-based ink, and oil-based ink. Moreover, you may use for any use. For example, screen printing ink, flexographic printing ink, gravure printing ink, lithographic offset printing ink, letterpress printing ink, UV ink, EB ink and the like can be mentioned. Further examples include inkjet ink photochromic ink, thermal transfer ink, masking ink, security ink, DNA ink, and the like.
  • any form obtained by using the ink containing the ultraviolet absorber of the present invention is also included in the present invention.
  • examples thereof include a printed material, a laminate obtained by laminating the printed material, a packaging material and container using the laminate, and an ink receiving layer.
  • the fiber containing the ultraviolet absorbent according to the present invention will be described.
  • the fiber containing the ultraviolet absorber of the present invention may be a fiber made of any kind of polymer as long as it contains the compound represented by the general formula (1). Examples thereof include polyester fiber, polyphenylene sulfide fiber, polyamide fiber, aramid fiber, polyurethane fiber, and cellulose fiber.
  • the fiber containing the ultraviolet absorber of the present invention may be produced by any method.
  • a polymer preliminarily containing the compound represented by the general formula (1) may be processed into a fiber shape.
  • a compound represented by the general formula (1) may be included in a polymer processed into a fiber shape. Processing may be performed using a solution or the like. You may process using a supercritical fluid.
  • the fiber containing the ultraviolet absorber of the present invention can be used for various applications.
  • the building material containing the ultraviolet absorber of the present invention will be described.
  • the building material containing the ultraviolet absorber of the present invention may be a building material made of any kind of polymer as long as it contains the compound represented by the general formula (1).
  • vinyl chloride type, olefin type, polyester type, polyphenylene ether type, polycarbonate type and the like can be mentioned.
  • the building material containing the ultraviolet absorber of the present invention may be produced by any method. For example, it may be formed into a desired shape using a material containing the compound represented by the general formula (1), or may be formed by laminating a material containing the compound represented by the general formula (1). Then, a coating layer using the compound represented by the general formula (1) may be formed, or a coating containing the compound represented by the general formula (1) may be applied.
  • the building material containing the ultraviolet absorber of the present invention can be used for various applications.
  • Examples thereof include a sheet-like photocurable resin, wood protective coating, a cover for a push button switch, a bonding sheet agent, a base material for building material, wallpaper, a polyester film for covering, a polyester film for covering a molded member, and a flooring.
  • the recording medium containing the ultraviolet absorber of the present invention will be described.
  • the recording medium containing the ultraviolet absorbent according to the present invention may be any one as long as it contains the compound represented by the general formula (1). Examples thereof include an ink jet recording medium, an image receiving sheet for sublimation transfer, an image recording medium, a thermal recording medium, a reversible thermal recording medium, and an optical information recording medium.
  • the image display device containing the ultraviolet absorbent according to the present invention may be any one as long as it contains the compound represented by the general formula (1).
  • an image display device using the described electrochromic element, an image display device called so-called electronic paper, a plasma display, an image display device using an organic EL element, and the like can be given.
  • the ultraviolet absorber of the present invention may be, for example, a material that forms an ultraviolet absorbing layer in a laminated structure, or a material that contains an ultraviolet absorber in a necessary member such as a circularly polarizing plate.
  • the solar cell cover including the ultraviolet absorbent according to the present invention will be described.
  • the solar cell applied in the present invention may be a solar cell comprising any type of element such as a crystalline silicon solar cell, an amorphous silicon solar cell, and a dye-sensitized solar cell.
  • a cover material is used as a protective member that imparts antifouling, impact resistance, and durability.
  • a metal oxide semiconductor that is activated by light (especially ultraviolet rays) in a dye-sensitized solar cell is used as an electrode material, the dye adsorbed as a photosensitizer deteriorates, and the photovoltaic power generation efficiency gradually increases. There is a problem of lowering, and it has been proposed to provide an ultraviolet absorbing layer.
  • the solar cell cover containing the ultraviolet absorbent according to the present invention may be made of any kind of polymer.
  • examples thereof include polyesters, thermosetting transparent resins, ⁇ -olefin polymers, polypropylene, polyether sulfone, acrylic resins, transparent fluorine-based resins and the like described in JP-A-2006-310461.
  • the solar cell cover containing the ultraviolet absorber of the present invention may be produced by any method.
  • an ultraviolet absorbing layer may be formed, a layer containing an ultraviolet absorber may be laminated, or a film made from a polymer containing an ultraviolet absorber may be contained in the filler layer resin. It may be formed.
  • the solar cell cover containing the ultraviolet absorbent according to the present invention may have any shape. Examples thereof include a film, a sheet, a laminated film, and a cover glass structure.
  • the sealing material may contain an ultraviolet absorber.
  • the glass and glass coating containing the ultraviolet absorber of the present invention will be described.
  • the glass and glass coating containing the ultraviolet absorber of the present invention may be in any form as long as it contains the compound represented by the general formula (1). Moreover, you may use for any use.
  • light source covers for lighting devices artificial leather, sports goggles, deflection lenses, hard coats for various plastic products, hard coats for pasting windows, window pasting films, high-definition anti-glare hard coat films, Antistatic hard coat film, transparent hard coat film, anti-counterfeit book described in JP-A-2002-113937, turf purpura inhibitor, resin film sheet bonding sealant, light guide, rubber coating agent , Agricultural coating materials, dyed candles, fabric rinse agent compositions, prism sheets, special protective layer transfer sheets, photo-curing resin products, floor sheets, light-shielding printing labels, oiling cups, hard coating coated articles, intermediate Transfer recording media, artificial hair, low-temperature heat-shrinkable film for labels, fishing equipment, microbeads, pre-coated metal plates, Meat film, heat shrinkable film, label for in-mold molding, projection screen, decorative sheet, hot melt adhesive, adhesive, electrodeposition coat, base coat, wood surface protection, light control material, light control film, light control glass, Examples
  • the light resistance when used as a packaging / container application can be evaluated by the method of JIS-K7105 and a method referring to this.
  • Specific examples include light transmittance of bottle body, transparency evaluation, sensory test evaluation of bottle contents after UV exposure using xenon light source, haze value evaluation after xenon lamp irradiation, haze value evaluation as halogen lamp light source , Yellowing evaluation using a blue wool scale after exposure to mercury lamp, haze value evaluation using a sunshine weather meter, visual evaluation of coloring, UV transmittance evaluation, UV blocking rate evaluation, light transmittance evaluation, ink in ink container Viscosity evaluation, light transmittance evaluation, sample in container after sun exposure, color difference ⁇ E evaluation, ultraviolet transmittance evaluation after white fluorescent light irradiation, light transmittance evaluation, color difference evaluation, light transmittance evaluation, haze value evaluation, Color tone evaluation, yellowness evaluation, light-shielding evaluation, L * a * b * whiteness evaluation using the color system color difference formula, post
  • JIS-K5400 JIS-K5600-7-5: 1999, JIS-K5600-7-6: 2002, JIS-K5600-7-7: 1999, JIS. It can be evaluated by the method of K5600-7-8: 1999, JIS-K8741 and a method referring to this.
  • Color difference ⁇ Ea * b * in the color density and CIE L * a * b * color coordinates after exposure by a xenon light resistance test machine and UVCON device and specific examples thereof include evaluation using residual gloss, xenon arc light for quartz slides on the film Absorbance evaluation after exposure using a tester, evaluation using a fluorescent lamp in wax, color density after exposure to UV lamp and color difference ⁇ Ea * b * in CIE L * a * b * color coordinates, metal weather weathering tester Hue evaluation after exposure using a glass, gloss retention evaluation after an exposure test using a metal hydride lamp, evaluation using a color difference ⁇ Ea * b * , evaluation of glossiness after exposure using a sunshine carbon arc light source, metal weather evaluation using the color difference after exposure using a weatherometer ⁇ Ea * b *, gloss retention, appearance evaluation, sunshine weatherometer Gloss retention evaluation after exposure using Ta, evaluation using color difference after exposure using a QUV weathering tester ⁇ Ea * b *, gloss retention evaluation, post
  • the light resistance when used as an ink application can be evaluated by the method of JIS-K5701-1: 2000, JIS-K7360-2, ISO105-B02 and a method referring to this. Specifically, evaluation by measurement of color density and CIE L * a * b * color coordinates after exposure using an office fluorescent lamp, a fading tester, evaluation of electrophoresis after exposure to ultraviolet rays using a xenon arc light source, Density evaluation of printed matter using a xenon fade meter, evaluation of ink removal using a 100 W chemical lamp, evaluation of dye remaining rate of an image forming site using a weather meter, evaluation of choking of printed matter using an eye super UV tester, and discoloration evaluation, xenon fade
  • evaluation using the color difference ⁇ Ea * b * in the CIE L * a * b * color coordinates evaluation of the reflectance after exposure using a carbon arc light source, and the like can be given.
  • the light resistance of the solar cell module can be evaluated by the method of JIS-C8917: 1998, JIS-C8938: 1995 and a method referring to this. Specifically, IV measurement after light exposure using a light source with a solar simulation correction filter mounted on a xenon lamp, evaluation of photovoltaic power generation efficiency after exposure using a sunshine weather meter, fade meter, Examples include color and appearance adhesion evaluation.
  • the light resistance of fibers and fiber products is JIS-L1096: 1999, JIS-A5905: 2003, JIS-L0842, JIS-K6730, JIS-K7107, DIN75.202, SAEJ1885, SN-ISO-105-B02, AS / NZS4399.
  • This method can be evaluated by the above method and a method referring to this method.
  • UV transmittance Evaluation of UV transmittance, evaluation of discoloration of blue scale after exposure using xenon light source, carbon arc light source, evaluation of UV cut rate described, evaluation of UV blocking property, change of blue scale after exposure using carbon arc light source after dry cleaning Fading evaluation, lightness index after exposure using a fadeometer, color difference ⁇ E * evaluation based on chromaticness index, tensile strength evaluation after exposure using a UV tester, sunshine weather meter, total transmittance evaluation, strength retention evaluation , UVF (UPF) evaluation, discoloration gray scale evaluation after exposure using a high-temperature fade meter, appearance evaluation after outdoor exposure, yellowness (YI) after yellow exposure, yellowness ( ⁇ YI) evaluation, regulations For example, reflectivity evaluation.
  • UPF UVF
  • the light resistance of building materials can be evaluated by the method of JIS-A1415: 1999 and a method referring to this. Specifically, surface color evaluation after exposure using a sunshine weatherometer, appearance evaluation after exposure using a carbon arc light source, appearance evaluation after exposure using an eye super UV tester, absorbance evaluation after exposure, Chromaticity after exposure, color difference evaluation, evaluation using CIE L * a * b * color difference after exposure using a metal hydride light source, evaluation using color difference ⁇ Ea * b * in color coordinates, evaluation of gloss retention, JP-A-10-44352 Gazette, Japanese Patent Application Laid-Open No.
  • the light resistance when used as a recording medium can be evaluated by the method of JIS-K7350 and a method referring to this.
  • evaluation can be performed by the method of JIS-K7103 and ISO / DIS9050 and a method based on this method. Specifically, the appearance of the polycarbonate-coated film after exposure with a UV tester, the blue scale evaluation after exposure to ultraviolet rays on artificial hair, the evaluation of the treated water contact angle for evaluation after exposure using an accelerated weathering tester, Visual evaluation of projected images projected on the projection screen after exposure using the weathering tester described in Kaikai 2005-55615, surface deterioration of the specimen after exposure using a sunshine weather meter and metal weather meter, visual inspection of changes in design Evaluation, visual visual evaluation after exposure to lighting using a metal lamp reflector Evaluation of light transmittance of bottle labels, evaluation of deterioration of polypropylene after exposure using a xenon weather meter, hard coat using a sunshine weatherometer Film degradation assessment, substrate degradation assessment, hydrophilicity assessment, scratch resistance assessment Evaluation of grayscale color difference of artificial leather after exposure using xenon lamp light source, evaluation of liquid crystal device characteristics after exposure using mercury
  • Synthesis Example 1 (Preparation of exemplary compound (m-2)) 300 g of salicylic acid was suspended in 600 mL of toluene, 258 g of thionyl chloride and 7 mL of DMF were added, and the mixture was stirred at 50 ° C. for 2 hours (Solution A). A solution A prepared by adding 900 mL of acetonitrile and 660 g of DBU (1,8-diazabiccyclo [5.4.0] undec-7-ene) to 299.0 g of salicylamide was dissolved. Was added dropwise at 5 ° C. and then stirred at room temperature for 24 hours. To this reaction solution, 300 mL of 35% hydrochloric acid was added and stirred at room temperature for 2 hours. The obtained solid was filtered and washed with water to obtain 504 g of synthetic intermediate A (yield 90%).
  • Synthesis Example 3 (Preparation of exemplary compound (m-3)) To 200.0 g of salicylamide, 800 mL of acetonitrile and 444.0 g of DBU were added and dissolved. To this solution, 303.9 g of 3- (trifluoromethyl) benzoyl chloride was added and stirred at room temperature for 24 hours. To this reaction solution, 2000 mL of water and 200 mL of hydrochloric acid were added, and the resulting solid was filtered and washed with water to obtain 428.3 g of synthetic intermediate D (yield 95%).
  • reaction mixture was extracted and separated with an aqueous ammonium chloride solution and ethyl acetate, and the resulting organic phase was washed with saturated brine and separated.
  • the organic phase thus obtained was concentrated by a rotary evaporator to obtain a residue obtained as a crude product of compound (X-2).
  • Synthesis Example 4 (Preparation of exemplary compound (m-4)) To 200.0 g of salicylamide, 800 mL of acetonitrile and 444.0 g of DBU were added and dissolved. To this solution, 255.0 g of 3-chlorobenzoyl chloride was added and stirred at room temperature for 24 hours. To this reaction solution, 2000 mL of water and 200 mL of hydrochloric acid were added, and the resulting solid was filtered and washed with water to obtain 389.9 g of synthetic intermediate F (yield 97%).
  • ⁇ Measurement method of pKa> The exemplified compound (m-1) was dissolved in acetonitrile so that the absorbance was 1, and 70% perchloric acid (acetic acid solvent) was added dropwise to this solution to change the pH. The solution absorption spectrum at that time was measured, and the ratio between the triazine free form and the proton adduct at each pH was calculated from the absorbance at ⁇ max. The pKa value was determined from the point at which the values became equal.
  • the triazine-free form represents the exemplified compound (m-1) itself, and the proton adduct represents a compound in which a proton is added to the nitrogen atom of the triazine ring of the exemplified compound (m-1).
  • exemplary compound (m-2), exemplary compound (m-3), exemplary compound (m-4), exemplary compound (m-19), exemplary compound (m-20), and exemplary compound (m-21) PKa value was determined.
  • the absorption spectrum was measured using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation.
  • the pH was measured using a pH meter meter HM60G (trade name) manufactured by Toa Denpa Kogyo.
  • the absorbance is a value measured at the maximum absorption wavelength of each compound. The results are shown in Table 1.
  • Each of the prepared films was irradiated with light for 1000 hours under the conditions of an illuminance of 90 mW / cm 2 , a temperature of 63 ° C. and a humidity of 50% with a metal halide lamp (cut about 290 nm or less) (trade name: iSuper UV Tester, manufactured by Iwasaki Electric Co., Ltd.).
  • a metal halide lamp cut about 290 nm or less
  • the haze value of the molded product was measured using a haze measuring device, and the difference from the haze value before irradiation was evaluated according to the following criteria.
  • ⁇ haze value after irradiation / haze value before irradiation ⁇ 2.0 ...
  • ⁇ Measurement method of absorption maximum wavelength The values of the absorption maximum wavelength were determined for the compounds (a-1) to (a-11). The absorption maximum wavelength was measured in an ethyl acetate solvent using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation. The results are shown in Table 3.
  • the ultraviolet absorbent compositions of the present invention (Examples 1 to 22) were free from haze change, hue change and odor as compared with Comparative Examples 1 to 3. It was also found that there was no precipitation or bleed-out, the haze value hardly changed even when irradiated with ultraviolet rays at a high temperature for a long time, long-wave ultraviolet absorbing ability could be maintained for a long time, and heat resistance was excellent.
  • the ultraviolet absorbent composition of the present invention exhibits an ultraviolet shielding effect even in a long wavelength region and has light resistance.
  • a polymer material or the like By mixing with a polymer material or the like, not only the ultraviolet light durability can be improved, but also the decomposition of other unstable compounds can be suppressed by using the polymer material as an ultraviolet filter.
  • it is highly soluble in organic solvents, does not precipitate or bleed out, and can maintain long-wave ultraviolet absorption ability for a long period of time.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Optical Filters (AREA)

Abstract

La présente invention concerne une composition absorbant la lumière ultraviolette qui est très soluble dans des solvants organiques et présente un effet de protection contre la lumière ultraviolette même dans les régions de longueurs d'onde longues, et qui est résistante à la lumière. La présente invention concerne spécifiquement une composition absorbant la lumière ultraviolette qui contient un composé représenté par la formule générale (1) et un matériau absorbant la lumière ultraviolette ayant une longueur d'onde d'absorption maximale de 270 à 400 nm. [R1a, R1c et R1e représentent des atomes d'hydrogène. R1b et R1d représentent indépendamment des atomes d'hydrogène ou des substituants ayant une valeur de Hammett σp positive, au moins l'un des deux représentant un substituant ayant une valeur de Hammett σp positive. R1g, R1h, R1i, R1j, R1k, R1m, R1n et R1p représentent indépendamment des atomes d'hydrogène ou des substituants monovalents. Les substituants peuvent se lier les uns aux autres pour former des cycles.]
PCT/JP2011/050487 2010-01-19 2011-01-13 Composition absorbant la lumière ultraviolette WO2011089968A1 (fr)

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WO2012077469A1 (fr) * 2010-12-08 2012-06-14 富士フイルム株式会社 Film de résine et son procédé de fabrication
WO2012077470A1 (fr) * 2010-12-08 2012-06-14 富士フイルム株式会社 Film de résine et module de cellule solaire

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JP5672473B2 (ja) * 2010-04-09 2015-02-18 三菱レイヨン株式会社 活性エネルギー線硬化性被覆材組成物及び積層体
JP6668091B2 (ja) * 2016-01-29 2020-03-18 ミヨシ油脂株式会社 紫外線吸収剤とそれを用いた樹脂部材
JP6642212B2 (ja) * 2016-03-31 2020-02-05 三菱ケミカル株式会社 ポリカーボネート樹脂組成物及び成形体
CN109071953B (zh) 2016-06-17 2021-05-25 东丽株式会社 树脂组合物、固化膜、固化膜的制造方法及显示装置

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JP2007298648A (ja) * 2006-04-28 2007-11-15 Konica Minolta Opto Inc セルロースエステル光学フィルム、その製造方法、それを用いた偏光板及び液晶表示装置
JP2007297469A (ja) * 2006-04-28 2007-11-15 Konica Minolta Opto Inc セルロースエステル光学フィルム、その製造方法、それを用いた偏光板及び液晶表示装置
WO2011013723A1 (fr) * 2009-07-29 2011-02-03 富士フイルム株式会社 Nouveau dérivé de triazine, absorbeur d'ultraviolets et composition de résine

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JP5613482B2 (ja) * 2009-07-29 2014-10-22 富士フイルム株式会社 新規なトリアジン誘導体、紫外線吸収剤及び樹脂組成物

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JP2007298648A (ja) * 2006-04-28 2007-11-15 Konica Minolta Opto Inc セルロースエステル光学フィルム、その製造方法、それを用いた偏光板及び液晶表示装置
JP2007297469A (ja) * 2006-04-28 2007-11-15 Konica Minolta Opto Inc セルロースエステル光学フィルム、その製造方法、それを用いた偏光板及び液晶表示装置
WO2011013723A1 (fr) * 2009-07-29 2011-02-03 富士フイルム株式会社 Nouveau dérivé de triazine, absorbeur d'ultraviolets et composition de résine

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012077469A1 (fr) * 2010-12-08 2012-06-14 富士フイルム株式会社 Film de résine et son procédé de fabrication
WO2012077470A1 (fr) * 2010-12-08 2012-06-14 富士フイルム株式会社 Film de résine et module de cellule solaire

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