JP2010097062A - Long-wavelength ultraviolet ray absorbing laminated body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a long-wavelength ultraviolet ray absorbing laminated body which has drastically improved light-fastness and is suitable for various applications such as an ultraviolet ray preventing film for especially, glass as building material or a windowpane for a vehicle. <P>SOLUTION: The long-wavelength ultraviolet ray absorbing laminated body includes: a support; a long-wavelength ultraviolet ray absorbing layer formed of a resin composition containing at least one of ultraviolet ray absorbing agent A, characterized in that the maximum absorption wavelength is 350-400 nm, the half-value width is ≤55 nm, and the molar absorbance coefficient is ≥20,000 at the maximum absorption wavelength, and a resin; and a short-wavelength ultraviolet ray absorbing layer formed of a resin composition containing at least one of ultraviolet ray absorbing agent B, characterized in that the maximum absorption wavelength is ≤350 nm and the absorbance at 320 nm is ≥30% of the absorbance at the maximum absorption wavelength, and a resin, on the incident light side of the long-wavelength ultraviolet ray absorbing layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a long-wave ultraviolet absorbing laminate having significantly improved light resistance.

From the viewpoint of preventing skin cancer, preventing skin aging, or preventing photodegradation of chemical compounds and natural materials, there is an increasing need for laminates and containers containing long-wave ultraviolet absorbers or long-wave ultraviolet absorbers. Several long wave ultraviolet absorbers have been reported for both inorganic and organic systems (see Patent Documents 1 to 5).
The inorganic long-wave ultraviolet absorber is excellent in durability such as weather resistance and heat resistance, but has a low degree of freedom because the absorption wavelength is determined by the band gap of the compound, and the long wave of 320 nm to 400 nm. There is nothing that can absorb up to the ultraviolet (UV-A) region, and those that absorb long-wave ultraviolet light have absorption up to the visible region, which causes a problem of coloring.
Since the organic long-wave ultraviolet absorber has a high degree of freedom in the structural design of the absorber, it can be obtained with various absorption wavelengths by devising the structure of the absorber, but it has durability against light. However, the current situation is that practical use has not progressed.

  Patent Document 6 has a first light-resistant layer containing metal oxide particles having an ultraviolet-absorbing ability with an average particle size of 0.1 μm or less on at least one surface of a base resin film, and a surface layer of the light-resistant layer. A weather-resistant resin film is proposed in which a second light-resistant layer containing an organic ultraviolet absorber is provided. However, this proposed resin film is a multilayer of a metal particle-containing layer and an organic ultraviolet absorber-containing layer, and the long-wave ultraviolet absorption by the multilayer of the long-wave ultraviolet absorber-containing layer and the short-wave ultraviolet absorber-containing layer of the present invention. There is no disclosure or suggestion about improving light resistance in the laminate.

JP 2006-316107 A JP-A-6-145387 JP 2003-177235 A JP 2005-517787 A JP-A-7-285927 JP 2006-326971 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, an object of the present invention is to provide a long-wave ultraviolet absorbing laminate that is dramatically improved in light resistance and that is particularly suitable for various uses such as ultraviolet protection films such as glass for building materials and window glass for vehicles.

Means for solving the above-described problems are as follows. That is,
<1> a support;
Resin composition containing at least one ultraviolet absorber A having a maximum absorption wavelength of 350 nm or more and 400 nm or less, a half width of 55 nm or less, and a molar extinction coefficient at the maximum absorption wavelength of 20,000 or more, and a resin A long wave ultraviolet absorbing layer comprising:
A resin containing at least one ultraviolet absorber B having a maximum absorption wavelength of 350 nm or less and an absorbance at 320 nm of 30% or more of the absorbance at the maximum absorption wavelength on the incident light side from the long wave ultraviolet absorption layer, and a resin It is a long wave ultraviolet absorption layered product characterized by having a short wave ultraviolet absorption layer which consists of a composition.
<2> The long wave ultraviolet absorbing laminate according to the above <1>, wherein an infrared blocking layer is provided between the support and the short wave ultraviolet absorbing layer, or the support also has an infrared blocking function.
<3> Long wave ultraviolet absorption containing at least one ultraviolet absorber A having a maximum absorption wavelength of 350 nm or more and 400 nm or less, a half width of 55 nm or less, and a molar extinction coefficient at the maximum absorption wavelength of 20,000 or more. An agent-containing support;
At least one ultraviolet absorber B having a maximum absorption wavelength of 350 nm or less and an absorbance at 320 nm of 30% or more of the absorbance at the maximum absorption wavelength, and a resin, on the incident light side from the long wave ultraviolet absorber-containing support. A long-wave ultraviolet absorbing laminate comprising at least one short-wave ultraviolet absorbing layer made of a resin composition.
<4> The longwave ultraviolet absorbing laminate according to <3>, wherein an infrared blocking layer is provided between the longwave ultraviolet absorber-containing support and the shortwave ultraviolet absorbing layer.
<5> The long wave ultraviolet absorbing laminate according to any one of <1> to <4>, wherein the ultraviolet absorber A is a compound represented by the following general formula (1).
However, the general formula (1), A ₂₁ and A ₂₂ represents a hydrogen atom and atoms other than carbon atoms. Y ₂₁ and Y ₂₂ each independently represent a hydrogen atom or a monovalent substituent. However, at least one of Y ₂₁ or Y ₂₂ represents a substituent having a Hammett's substituent constant σp value of 0.2 or more. Y ₂₁ and Y ₂₂ may be bonded to each other to form a ring. (B) represents an atomic group necessary for forming a 5- or 6-membered ring together with A ₂₁ , A ₂₂ and a carbon atom.
<6> The long wave ultraviolet absorbing laminate according to any one of <1> to <5>, wherein the ultraviolet absorber B is a compound represented by the following formula (2).

  ADVANTAGE OF THE INVENTION According to this invention, various problems in the past can be solved, and the light resistance can be greatly improved. In particular, it is possible to provide a long wave ultraviolet absorbing laminate suitable for various uses such as glass for building materials and window glass for vehicles.

In the first embodiment, the long wave ultraviolet absorbing laminate of the present invention comprises a support, a long wave ultraviolet absorbing layer comprising a resin composition containing at least one ultraviolet absorber A and a resin,
It has at least one ultraviolet absorber B and a short wave ultraviolet absorbing layer made of a resin composition containing a resin on the incident light side from the long wave ultraviolet absorbing layer, and further has other layers as necessary. It becomes.

In the second embodiment, the long-wave ultraviolet absorbing laminate of the present invention has a long-wave ultraviolet absorber-containing support containing at least one ultraviolet absorber A;
On the incident light side of the long-wave ultraviolet absorber-containing support, it has at least one ultraviolet absorber B and a short-wave purple ray absorbing layer made of a resin composition containing a resin. Having a layer.

In this invention, the said ultraviolet absorber A has the characteristics that a maximum absorption wavelength is 350 nm or more and 400 nm or less, and a half value width is 55 nm or less.
The ultraviolet absorber B is characterized in that the absorbance at 320 nm is 30% or more of the absorbance at the maximum absorption wavelength, and the maximum absorption wavelength is 350 nm or less. In particular, the absorbance at 320 nm of the ultraviolet absorber B is preferably 50% or more of the absorbance at the maximum absorption wavelength.

  The ultraviolet absorber B represents one having an absorbance at 320 nm of 30% or more of the absorbance at the maximum absorption wavelength and a maximum absorption wavelength of 350 nm or less. For example, as shown in FIG. Can be classified into an ultraviolet absorber (B- (1)) having a wavelength of less than 320 nm and an ultraviolet absorber (B- (2)) having a maximum absorption wavelength of 320 nm to 350 nm. FIG. 1 shows preferred absorption spectra of the ultraviolet absorbers A and B used in the present invention.

  Those skilled in the art can easily measure the maximum absorption wavelength and the half-value width defined in the present invention. The measurement method is described in, for example, “The Fourth Edition Experimental Chemistry Course 7 Spectroscopy II” (Maruzen, 1992), pages 180 to 186, edited by the Chemical Society of Japan. Specifically, the sample is dissolved in a suitable solvent, and measurement is performed by a spectrophotometer using a cell made of quartz or glass and using two cells for sample and control. The solvent to be used is required to have no absorption in the measurement wavelength region, have a small interaction with the solute molecule, and have a very low volatility in addition to the solubility of the sample. Any solvent that satisfies the above conditions can be selected. In the present invention, measurement is performed using ethyl acetate (EtOAc) as a solvent.

The maximum absorption wavelength and half-value width of the dye in the present invention are values measured using a quartz cell having an optical path length of 10 mm by preparing a solution having a concentration of about 5 × 10 ⁻⁵ mol · dm ^{−3 using} ethyl acetate as a solvent. Is used.

  The half width of the spectrum is described in, for example, “The Fourth Edition Experimental Chemistry Course 3 Basic Operation III” (Maruzen, 1991), page 154, edited by the Chemical Society of Japan. In the above-mentioned book, the half-value width is explained with an example in which the horizontal axis is taken on the wave number scale, but the half-value width in the present invention is the value when the axis is taken on the wavelength scale, The unit is nm. Specifically, it represents the width of the absorption band that is half the absorbance at the maximum absorption wavelength, and is used as a value that represents the shape of the absorption spectrum. A spectrum with a small half-value width is a sharp spectrum, and a spectrum with a large half-value width is a broad spectrum. Ultraviolet absorbers that give a broad spectrum have absorption in a wide range from the maximum absorption wavelength to the long wave side. Therefore, in order to effectively block the long wave ultraviolet region without yellowish coloring, a spectrum with a small half-value width is used. The ultraviolet absorber which has is more preferable.

  As described in Sumida Tokita "Chemistry Seminar 9 Color Chemistry" (Maruzen, 1982), pages 154-155, the intensity of light absorption, that is, the oscillator strength, is proportional to the integral of the molar extinction coefficient. When the symmetry of the spectrum is good, the oscillator strength is proportional to the product of the absorbance at the maximum absorption wavelength and the half-value width (however, the half-value width in this case is a value centered 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 absorbers 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, it covers a wide area. Can not do it.

<Ultraviolet absorber A>
The ultraviolet absorber A is characterized in that the maximum absorption wavelength is 350 nm or more and 400 nm or less, the half width is 55 nm or less, and the molar extinction coefficient at the maximum absorption wavelength is 20,000 or more. Preferably, the maximum absorption wavelength is 360 nm or more and 385 nm or less. When this ultraviolet absorber A having a suitable maximum absorption wavelength is used in combination with the ultraviolet absorber B, there is little risk of coloring, and the UV-A region of 350 nm to 400 nm can be covered without omission. Further, the molar extinction coefficient at the maximum absorption wavelength is preferably 30,000 or more, more preferably 40,000 or more, and particularly preferably 50,000 or more. If the molar absorbance is less than 20,000, the absorption efficiency per weight of the UV absorber is deteriorated, so that a large amount of UV absorber must be used to completely absorb the UV region. This is not preferable because the working efficiency is deteriorated and the risk of bleeding out occurs. It has been found that as the molar extinction coefficient increases to 50,000 or more, the full width at half maximum becomes narrower, and as a result, the risk of coloring can be reduced. The molar extinction coefficient is based on the definition described in, for example, “New Edition Experimental Chemistry Lecture 9 Analytical Chemistry [II]” (Maruzen, 1977), page 244, edited by the Chemical Society of Japan. It can be determined together with the absorption wavelength and the half width.

  The ultraviolet absorber A may have any structure as long as this condition is satisfied. For example, triazine, benzotriazole, benzophenone, cyanine, dibenzoylmethane, cinnamic acid, p-aminobenzoic acid, benzoate, cyanoacrylate, indole, known as UV absorber structures Examples thereof include compounds, benzalmalonate series, salicylic acid series, oxalic acid anilide series, formamidine series, and benzodithiol series. Among these, indole-based and benzodithiol-based compounds, which have a relatively small half width and excellent long-wave ultraviolet absorption ability, are particularly preferable.

  Among these structures, a compound represented by the following general formula (1) is particularly preferable from the viewpoint of the maximum absorption wavelength and the small half-value width. Hereinafter, the compound represented by the following general formula (1) will be described.

However, the general formula (1), A ₂₁ and A ₂₂ represents a hydrogen atom and atoms other than carbon atoms. Y ₂₁ and Y ₂₂ each independently represent a hydrogen atom or a monovalent substituent. However, at least one of Y ₂₁ or Y ₂₂ represents a substituent having a Hammett's substituent constant σp value of 0.2 or more. Y ₂₁ and Y ₂₂ may be bonded to each other to form a ring. (B) represents an atomic group necessary for forming a 5- or 6-membered ring together with A ₂₁ , A ₂₂ and a carbon atom.

A ₂₁ and A ₂₂ each independently represent an atom other than a hydrogen atom and a carbon atom. Examples of A ₂₁ and A ₂₂ include boron, nitrogen, oxygen, fluorine, silicon, phosphorus, sulfur, and selenium atoms.

Preferred examples of A ₂₁ and A ₂₂ include nitrogen, oxygen, and sulfur. Particularly preferred is a sulfur atom. Preferred combinations are oxygen-nitrogen, nitrogen-sulfur, nitrogen-nitrogen, sulfur-sulfur combinations, and particularly preferred combinations are sulfur-sulfur combinations.

Y ₂₁ and Y ₂₂ each independently represent a hydrogen atom or a monovalent substituent. Monovalent substituents include cyano group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, nitro group, substituted or unsubstituted acyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted Substituted arylsulfonyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkyl group A substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and the like. The substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. The substituent in this case is the above monovalent substituent. Moreover, you may combine with substituents and may form a ring.

Specifically, examples of Y ₂₁ and Y ₂₂ include a cyano group, a carbamoyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms (for example, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl). A sulfamoyl group having 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (for example, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), nitro group, 1 carbon atom -20, preferably 1-12 carbon atoms, more preferably 1-8 carbon acyl groups (eg formyl, acetyl, benzoyl, trichloroacetyl), 1-20 carbon atoms, preferably 1-10 carbon atoms, more preferably Is an alkylsulfonyl group having 1 to 8 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms (for example, Methanesulfonyl, ethanesulfonyl, benzenesulfonyl, etc.), C1-20, preferably C1-10, more preferably C1-8 alkylsulfinyl groups, C6-20, preferably C6 10 arylsulfinyl groups (for example, methanesulfinyl, benzenesulfinyl), C2-C20, preferably C2-C12, more preferably C2-C8 alkoxycarbonyl groups (for example, methoxycarbonyl, ethoxycarbonyl, benzyloxy) Carbonyl), an aryloxycarbonyl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms (for example, phenoxycarbonyl), 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, More preferably, an unsubstituted alkyl group having 1 to 5 carbon atoms (for example, Til, ethyl, propyl, butyl), a substituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonyl) Methyl, acetylaminomethyl), a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (for example, phenyl, naphthyl, p-carboxyphenyl, p- Nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl, p-bromophenyl), 1-20 carbons, preferably 2-10 carbons, more preferably 4-4 carbons 6 optionally substituted heterocyclic groups (eg pyridyl, 5-methylpyridyl, thienyl, furyl, Holino, tetrahydrofurfuryl). The substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. The substituent in this case is the substituent described above. Moreover, you may combine with substituents and may form a ring.

Y ₂₁ and Y ₂₂ are preferably when at least one of Y ₂₁ and Y ₂₂ has a substituent having a Hammett's σp value of 0.2 or more.
Hammett's substituent constant σ value will be described. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp value and σm value, and these values can be found in many general books. For example, J. et al. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Areas of Chemistry”, No. 122, 96-103, 1979 (Nankodo), Chem. Rev. 1991, 91, 165-195. The substituent having Hammett's substituent constant σp value of 0.2 or more in the present invention is an electron-attracting group. The σp value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more.

Specific examples include cyano group (0.66), carboxyl group (—COOH: 0.45), alkoxycarbonyl group (—COOMe: 0.45), aryloxycarbonyl group (—COOPh: 0.44), carbamoyl. A group (—CONH ₂ : 0.36), an alkylcarbonyl group (—COMe: 0.50), an arylcarbonyl group (—COPh: 0.43), an alkylsulfonyl group (—SO ₂ Me: 0.72), or arylsulfonyl group (-SO ₂ Ph: 0.68) and the like. In the present specification, Me represents a methyl group and Ph represents a phenyl group. The values in parentheses are the σp values of typical substituents in Chem. Rev. 1991, Vol. 91, pp. 165-195.

Y ₂₁ and Y ₂₂ may be bonded to each other to form a ring. In the case of forming a ring, the σp values of Y ₂₁ and Y ₂₂ cannot be defined. However, in the present invention, it is considered that Y ₂₁ and Y ₂₂ are each substituted by a ring partial structure. The σp value in the case of formation will be defined. For example, when a 1,3-indandione ring is formed, it is considered that Y ₂₁ and Y ₂₂ are each substituted with a benzoyl group.

Preferable examples of Y ₂₁ and Y ₂₂ are each independently a cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfinyl group, sulfonyl group, or sulfamoyl group. .
Particularly preferably, at least one of Y ₂₁ and Y ₂₂ is a cyano group, and the other is an alkylcarbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, an alkylsulfonyl group, or an arylsulfonyl group. Y ₂₁ and Y ₂₂ are preferably not bonded to each other to form a ring.

(B) represents a ring formed by combining A ₂₁ , A ₂₂ and a carbon atom.
As the ring formed together with A ₂₁ , A ₂₂ and the carbon atom as (B), a 5- or 6-membered ring is preferable. Specifically, for example, pyrimidine ring, imidazolidine ring, imidazoline ring, oxazoline ring, thiazoline ring, dithiol ring and the like can be mentioned. These rings may have a monovalent substituent. In addition, a condensed ring structure may be formed together with an aromatic ring.

  Ring (B) is preferably an imidazoline ring, an oxazoline ring, a thiazoline ring, a dithiol ring, or a benzo condensed ring thereof, more preferably a benzodithiol ring, a benzoxazoline ring, a benzothiazoline ring, or a benzoimidazoline ring, Particularly preferred is a benzodithiol ring.

A preferable combination of substituents in the general formula (1) is that at least one of Y ₂₁ and Y ₂₂ is a cyano group, and the other is an alkylcarbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, an alkylsulfonyl group, or an arylsulfonyl Group, A ₂₁ and A ₂₂ are both sulfur atoms, and (B) is a combination forming a benzodithiol ring.

The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2). Next, general formula (2) will be described in detail.
However, the general formula (2), A ₃₁ and A ₃₂ each independently represent an oxygen atom, a hetero atom selected from the group consisting of nitrogen atom and sulfur atom. Y ₃₁ and Y ₃₂ each independently represent a hydrogen atom or a monovalent substituent. However, at least one of Y _{31 and} Y ₃₂ represents a substituent having a Hammett's substituent constant σp value of 0.2 or more. Y ₃₁ and Y ₃₂ may be bonded to each other to form a ring. (D) represents an atomic group necessary for forming a 5- or 6-membered ring together with a carbon atom.

A ₃₁ and A ₃₂ each independently represent a hetero atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, and preferably a sulfur atom. Preferred combinations are oxygen-nitrogen, nitrogen-sulfur, nitrogen-nitrogen, sulfur-sulfur combinations, and particularly preferred combinations are sulfur-sulfur combinations.

Y ₃₁ and Y ₃₂ each independently represent a hydrogen atom or a monovalent substituent. Examples of monovalent substituents include cyano group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, nitro group, substituted or unsubstituted acyl group, substituted or unsubstituted alkylsulfonyl group, substituted Or an unsubstituted arylsulfonyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted Examples thereof include an alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. However, at least one of Y _{31 and} Y ₃₂ represents a substituent having a Hammett's substituent constant σp value of 0.2 or more. Examples of substituents having Hammett's substituent constant σp value of 0.2 or more include cyano group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfinyl group, sulfonyl group, or sulfamoyl. Groups.

Preferably among the Y ₃₁ and Y _32, at least one of Y ₃₁ and Y ₃₂ is a cyano group and the other represents a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, a substituted or unsubstituted heteroaryl This is a case of a ring carbonyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group.

Ring (D) represents an atomic group necessary for forming a 5- or 6-membered ring containing a carbon atom.
Specific examples of the ring (D) include, for example, cycloalkanes such as cyclohexane and cyclopentane, aryls such as a benzene ring, pyridine ring, pyrrole ring, thiophene ring, thiazole ring, oxazole ring, pyrazole ring, or these benzoates. Although heterocycles, such as a condensed ring, are mentioned, More preferably, it is a benzene ring.

A preferred combination in the general formula (3) is that at least one of Y ₃₁ and Y ₃₂ is a cyano group, and the other is a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, a substituted or unsubstituted group. A heterocyclic carbonyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, A ₃₁ and A ₃₂ are both sulfur atoms, ring (D) is a benzene ring, and A ₃₁ , A ₃₂ and a combination forming a benzodithiol ring.

  The compound represented by the general formula (2) is preferably a compound represented by the following general formula (3). Next, general formula (3) will be described in detail.

However, it represents a monovalent substituent in the general formula (3), Y ₄₁ and Y ₄₂ each independently. At least one of Y _{41 and} Y ₄₂ is a cyano group, and the other is a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, a substituted or unsubstituted heterocyclic carbonyl group, a substituted or unsubstituted alkyl A sulfonyl group or a substituted or unsubstituted arylsulfonyl group.

Preferably the Y ₄₁ and Y _42, at least one of Y ₄₁ and Y ₄₂ is a cyano group, and the other is a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylcarbonyl group, or a substituted or unsubstituted hetero When it is a ring carbonyl group. Particularly preferred is when one is a cyano group and the other is a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group. It is also preferred that Y ₄₁ and Y ₄₂ do not form a ring with other atoms. More preferably, at least one of Y ₄₁ or Y ₄₂ is a cyano group, and the other is a substituted or unsubstituted alkylcarbonyl group having 3 to 18 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 7 to 18 carbon atoms. When it is.

V ₄₁ and V ₄₂ each independently represent a hydrogen atom or a monovalent substituent. Examples of monovalent substituents include halogen atoms, mercapto groups, cyano groups, carboxyl groups, phosphate groups, sulfo groups, hydroxy groups, carbamoyl groups, sulfamoyl groups, nitro groups, alkoxy groups, aryloxy groups, and acyl groups. , Acyloxy group, acylamino group, sulfonyl group, sulfinyl group, sulfonylamino group, amino group, substituted amino group, ammonium group, hydrazino group, ureido group, imide group, alkyl or arylthio group, unsubstituted or substituted alkenylthio group, alkoxy Examples include a carbonyl group, an aryloxycarbonyl group, an unsubstituted alkyl group, a substituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Specific examples of these substituents include those exemplified for Y ₄₁ and Y ₄₂ . The substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. The substituent in this case is the substituent described above. Moreover, you may combine with substituents and may form a ring.

V ₄₁ and V ₄₂ are preferably each independently a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an aryloxy group, or an acyloxy group, and particularly preferably an alkoxy group, an aryloxy group, or an acyloxy group.

A preferable combination in the general formula (3) is that at least one of Y ₄₁ and Y ₄₂ is a cyano group, and the other is a substituted or unsubstituted alkylcarbonyl group having 3 to 18 carbon atoms, or a substitution having 7 to 18 carbon atoms. Alternatively, it is an unsubstituted arylcarbonyl group, and a combination in which V ₄₁ and V ₄₂ are both an alkoxy group, an aryloxy group, or an acyloxy group.

  In the present invention, the compound represented by any one of the general formulas (1) to (3) is Journal of Chemical Crystallography, 27, 1997, page 516, right column, line 3 to page 520, right. 15th line, Liebigs Annalen der Chemie, pages 726, 106, 15th line to 109th page, 37th line, JP 49-1115, page 3 left, 7th line to 5th page left 8th line, Bioorganic & Medicinal Chemistry Letters, 7, 1997, page 652, 9th to 19th line, Journal of Organic Chemistry, 43, 1978, 2153 pages 2nd line to 12th line on the left side, JP-A-4-338759 4th page left 2nd line to 5th page left 2nd line, JP-A-3-54566 7 page left 6th to 8th page left 10th line, Synthesis, 1986, 968 page left It can be synthesized by the description, citation or similar synthesis methods in the 1st to 22nd lines.

  Specific examples of the compound represented by any one of the general formulas (1) to (3) used in the present invention are shown below, but the present invention is not limited thereto.

[Example corresponding to general formula (3)]

[Example that does not correspond to general formula (3) but corresponds to general formula (2)]

[Example that does not correspond to general formula (2) but corresponds to general formula (1)]

  Then, the compound represented by the following general formula (BI) is demonstrated.

However, in the general formula (B-1), R ^B1 , R ^B2 , R ^B3 and R ^B4 each independently represent a hydrogen atom or a monovalent substituent. R ^B5 and R ^B6 each independently represent a hydrogen atom or a monovalent substituent. X ^B1 , X ^B2 , X ^B3 and X ^B4 each independently represent a hetero atom.

In the general formula ( ^BI ), R ^B1 , R ^B2 , R ^B3 and R ^B4 each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the examples of the monovalent substituent described above in the general formula (1). The substituents may be further substituted, and when there are a plurality of substituents, they may be the same or different. Moreover, you may combine with substituents and may form a ring.

Examples of monovalent substituents for R ^B1 , R ^B2 , R ^B3 and R ^B4 include cyano group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, nitro group, substituted or unsubstituted acyl. Group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted Examples thereof include a substituted aryloxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. The substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. The substituent in this case is the above monovalent substituent. Moreover, you may combine with substituents and may form a ring.

Examples of R ^B1 , R ^B2 , R ^B3 and R ^B4 are specifically cyano groups, carbamoyl groups having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms (for example, methylcarbamoyl, ethyl). Carbamoyl, morpholinocarbonyl), sulfamoyl group having 0 to 10, preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (for example, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), nitro Group, an acyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (for example, formyl, acetyl, benzoyl, trichloroacetyl), 1 to 20 carbon atoms, preferably 1 carbon atom -10, more preferably an alkylsulfonyl group having 1 to 8 carbon atoms, an arylsulfonyl group (for example, methanesulfonyl, ethanesulfur). Nyl, benzenesulfonyl, etc.), C1-20, preferably C1-10, more preferably C1-8 alkylsulfinyl, arylsulfinyl (eg methanesulfinyl, benzenesulfinyl), C2 20, preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, Preferably an aryloxycarbonyl group having 6 to 8 carbon atoms (for example, phenoxycarbonyl), an unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms (for example, methyl, Ethyl, propyl, butyl), carbon number 1-18, preferably carbon number 1-1 0, more preferably a substituted alkyl group having 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl), 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, More preferably, it is a substituted or unsubstituted aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p- Tolyl, p-bromophenyl), an optionally substituted heterocyclic group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (for example, pyridyl, 5-methylpyridyl, thienyl). , Furyl, morpholino, tetrahydrofurfuryl). The substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. The substituent in this case is the substituent described above. Moreover, you may combine with substituents and may form a ring.

It is particularly preferable that at least one of R ^B1 , R ^B2 , R ^B3 and R ^B4 represents a substituent having a Hammett's substituent constant σp value of 0.2 or more.

R ^B1 and R ^B2 and R ^B3 and R ^B4 may be bonded to each other to form a ring. For the σp values of R ^B1 , R ^B2 , R ^B3, and R ^B4 when forming a ring, the concept described in the general formula (1) is used.

At least one of R ^B1 , R ^B2 , R ^B3 and R ^B4 represents a substituent having a Hammett's substituent constant σp value of 0.2 or more, but a pair of R ^B1 and R ^B2 or R ^B3 and R ^B4 It is preferable that either one of the groups is a substituent. More preferably, three of R ^B1 , R ^B2 , R ^B3 and R ^B4 are this substituent. Particularly preferably, R ^B1 , R ^B2 , R ^B3 and R ^B4 are all the substituents.

That is, it is more preferable that at least one of R ^B1 , R ^B2 , R ^B3 and R ^B4 is —CN, —COOR ^B8 , —CONR ^B9 R ^B10 , —COR ^B11 or —SO ₂ R ^B12 (wherein , R ^B8 , R ^B9 , R ^B10 , R ^B11 and R ^B12 each represent a hydrogen atom or a monovalent substituent. More preferred is —CN, —COOR ^B8 , —COR ^B11 or —SO ₂ R ^B12 . More preferred is -CN or -COOR ^B8 . Particularly preferred is -CN.
More preferably, at least one of R ^B1 , R ^B2 , R ^B3 and R ^B4 is an alkoxycarbonyl group having 6 or more carbon atoms. More preferably, it has 6 or more and 20 or less carbon atoms, and further preferably 6 or more and 12 or less carbon atoms. You may have a substituent in arbitrary positions on an alkoxy group. Examples of the substituent include those described above. Examples of the alkoxy group in the alkoxycarbonyl group include a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.

The combination of the combination and R ^B3 and R ^B4 and R ^B1 and R ^B2 may be any combination satisfies the conditions described above, but with the set and R ^B3 and R ^B4 and R ^B1 and R ^B2 More preferably, the sets are the same combination.

R ^B1 and R ^{B2 and} R ^B3 and R ^B4 may be bonded to each other to form a ring. As a ring to form, any of a saturated and unsaturated hydrocarbon ring and a heterocyclic ring may be sufficient. However, a dithiol ring and a dithiolane ring are not formed. For example, as a ring containing a carbon atom to which R ^B1 and R ^B2 defined in the general formula ( ^BI ) are bonded, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring Pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, oxazoline ring, thiazoline ring, pyrroline ring, pyrazolidine ring, pyrazoline ring, imidazolidine ring, imidazoline ring, piperidine ring, piperazine ring, pyran ring and the like. These may have a substituent at any position. Examples of the substituent include the examples of the monovalent substituent described above. Examples of the divalent substituent include a carbonyl group and an imino group. When there are a plurality of substituents, they may be the same or different. Moreover, it may become a condensed ring or a spiro ring by bonding with each other to form a ring.

Preferred specific examples of the combination of R ^B1 and R ^B2 or R ^B3 and R ^B4 are shown in Table 1 below, but the present invention is not limited to these. In the present specification, Et represents an ethyl group, and Bu represents a butyl group. The wavy line in the table indicates the binding site to the heterocycle in formula (BI).

R ^B5 and R ^B6 each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the examples of the monovalent substituent described above.
Among them, hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylcarbonyl group, arylcarbonyl group, nitro group, amino group, acylamino group, sulfone Amide groups, hydroxy groups, alkoxy groups, aryloxy groups, acyloxy groups, alkylsulfonyloxy groups, arylsulfonyloxy groups, sulfo groups, alkylthio groups, and arylthio groups are preferred. A hydrogen atom, a halogen atom, an amino group, an acylamino group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, and an arylthio group are more preferable. More preferred are an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an acylamino group, a carbamoyloxy group, and a carbamoylamino group. An alkoxy group, an aryloxy group, and an acyloxy group are particularly preferable. An alkoxy group having 2 or more carbon atoms is particularly preferable.

  As an alkyl group in the case of an alkoxy group, a C1-C20 alkyl group is preferable, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group etc. are mentioned. A monovalent substituent may be present at any position on the alkyl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. The alkyl group in the case of an alkoxy group is preferably an alkyl group having 3 to 20 carbon atoms. More preferably, it is a C5-C18 alkyl group. Particularly preferred is an alkyl group having 6 to 12 carbon atoms.

  In the case of an aryloxy group, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. A monovalent substituent may be present at any position on the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. The aryl group in the case of an aryloxy group is preferably an aryl group having 6 to 14 carbon atoms. More preferably, it is an aryl group having 6 to 10 carbon atoms. Particularly preferred is a phenyl group.

  The acyl group in the case of an acyloxy group is preferably an acyl group having 1 to 20 carbon atoms, and examples thereof include an acetyl group, a propionyl group, a butanoyl group, a hexanoyl group, an octanoyl group, a benzoyl group, and a naphthoyl group. A monovalent substituent may be present at any position on the acyl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. In the case of an acyloxy group, the acyl group is preferably an acyl group having 1 to 15 carbon atoms. More preferably, it is a C1-C10 acyl group. Particularly preferred is an acyl group having 4 to 8 carbon atoms.

  The alkyl group in the case of the alkoxycarbonyloxy group is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, and an octyl group. A monovalent substituent may be present at any position on the alkyl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. The alkyl group in the case of an alkoxycarbonyloxy group is preferably an alkyl group having 3 to 20 carbon atoms. More preferably, it is a C5-C18 alkyl group. Particularly preferred is an alkyl group having 6 to 12 carbon atoms.

The aryl group in the case of the aryloxycarbonyloxy group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. A monovalent substituent may be present at any position on the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. In the case of an aryloxycarbonyloxy group, the aryl group is preferably an aryl group having 6 to 14 carbon atoms. More preferably, it is an aryl group having 6 to 10 carbon atoms. Particularly preferred is a phenyl group.

  The acyl group in the case of an acylamino group is preferably an acyl group having 1 to 20 carbon atoms, and examples thereof include an acetyl group, a propionyl group, a butanoyl group, a hexanoyl group, an octanoyl group, a benzoyl group, and a naphthoyl group. A monovalent substituent may be present at any position on the acyl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Arbitrary substituents may be bonded to form a ring. In the case of an acylamino group, the acyl group is preferably an acyl group having 1 to 15 carbon atoms. More preferably, it is a C1-C10 acyl group. Particularly preferred is an acyl group having 4 to 8 carbon atoms.

  As the substituent on the nitrogen atom in the case of the carbamoyloxy group, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms are preferable. Examples thereof include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a phenyl group, and a naphthyl group. A monovalent substituent may be present at any position on the alkyl group and the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. The alkyl group and aryl group in the case of the carbamoyloxy group are preferably an alkyl group having 3 to 20 carbon atoms and an aryl group having 6 to 14 carbon atoms. More preferred are an alkyl group having 6 to 12 carbon atoms and an aryl group having 6 to 10 carbon atoms.

  As the substituent on the nitrogen atom in the case of the carbamoylamino group, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms are preferable. Examples thereof include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a phenyl group, and a naphthyl group. A monovalent substituent may be present at any position on the alkyl group and the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. The alkyl group and aryl group in the case of the carbamoylamino group are preferably an alkyl group having 3 to 20 carbon atoms and an aryl group having 6 to 14 carbon atoms. More preferred are an alkyl group having 6 to 12 carbon atoms and an aryl group having 6 to 10 carbon atoms.

R ^B5 and R ^B6 may be different from each other but are preferably the same.

Preferred specific examples of R ^B5 or R ^B6 are shown in Table 2 below, but the present invention is not limited thereto. In addition, the wavy line in a table | surface shows the coupling | bond part to the benzene ring in the said general formula (BI).

X ^B1 , X ^B2 , X ^B3 and X ^B4 each independently represent a hetero atom. Examples of the hetero atom include a boron atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, a selenium atom, and a tellurium atom. Preferably, they are a nitrogen atom, an oxygen atom, and a sulfur atom. More preferably, they are a nitrogen atom and a sulfur atom. Particularly preferred is a sulfur atom.
X ^B1 , X ^B2 , X ^B3 and X ^B4 may be different from each other, but it is more preferable that X ^B1 and X ^B2 and X ^B3 and X ^B4 each have the same combination. Are all the same. Most preferably, all represent sulfur atoms.

It is shown in the following Table 3 a preferred embodiment of the combination of X ^B1 and X ^B2 or X ^B3 and X ^B4, the present invention is not limited thereto. In the present specification, Ac represents an acetyl group. The wavy line in the table indicates the bonding site to the carbon atom to which R ^B1 and R ^B2 or R ^B3 and R ^B4 are bonded in the general formula ( ^BI ).

  The compound represented by the general formula (BI) is particularly preferably a compound represented by the following general formula (BI).

In the general formula (B-Ia), R ^Ba1 , R ^Ba2 , R ^Ba3 and R ^Ba4 represent a monovalent substituent. However, at least one of R ^Ba1 , R ^Ba2 , R ^Ba3 and R ^Ba4 is a cyano group, a C 1-20 (preferably 1-10) alkoxycarbonyl group, a C ^6-20 (preferably ^6-6 ). 10) aryloxycarbonyl group, carbamoyl group having 1 to 20 carbon atoms (preferably 1 to 10), alkylcarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10), 6 to 20 carbon atoms (preferably 6 carbon atoms) 10) an arylcarbonyl group, an alkylsulfonyl group having 1 to 20 carbon atoms (preferably 1 to 10), or an arylsulfonyl group having 6 to 20 carbon atoms (preferably 6 to 10).

Regarding the combination of (R ^Ba1 , R ^Ba2 ) and the combination of (R ^Ba3 , R ^Ba4 ), R ^Ba1 , R ^Ba2 , R ^Ba3 and R ^Ba4 are monovalent substituents in which at least one of these combinations does not form a ring. Preferably there is.
The combination of (R ^Ba1 , R ^Ba2 ) and the combination of (R ^Ba3 , R ^Ba4 ) are particularly preferably monovalent substituents that do not form a ring in this combination.
When a ring is not formed, there is an advantage that the long-wave ultraviolet absorption ability is excellent and yellowing of the compound itself can be suppressed. Further, as compared with the case of forming a ring, when no ring is formed, there is an advantage that the solubility in a solvent and the compatibility with a polymer are excellent.

  Specific examples of the monovalent substituent that does not form a ring in the present specification include a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, methyl, ethyl), and 6 to 6 carbon atoms. 20 (preferably 6 to 10) aryl group (for example, phenyl, naphthyl), cyano group, C1-C20 (preferably 1-10) alkoxycarbonyl group (for example, methoxycarbonyl), C6-C20 (preferably Are 6 to 10) aryloxycarbonyl groups (for example, phenoxycarbonyl), substituted or unsubstituted carbamoyl groups (for example, carbamoyl, N-phenylcarbamoyl, N, N-dimethyl) having 1 to 20 carbon atoms (preferably 1 to 10). Carbamoyl), an alkylcarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (eg acetyl), 6 to 20 carbon atoms ( Preferably 6 to 10) arylcarbonyl group (for example, benzoyl), nitro group, substituted or unsubstituted sulfamoyl group having 0 to 20 carbon atoms (preferably 0 to 10) (for example, sulfamoyl, N-phenylsulfamoyl) An alkylsulfonyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, methanesulfonyl), an arylsulfonyl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, benzenesulfonyl), and a 4 to 7-membered ring (Preferably a 5- to 6-membered ring) heterocyclic group (for example, pyridyl, morpholino) and the like can be mentioned. Moreover, the substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different.

However, at least one of the monovalent substituents R ^Ba1 , R ^Ba2 , R ^Ba3 and R ^Ba4 is a cyano group, an alkoxycarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10), and 6 to 20 carbon atoms. (Preferably 6-10) aryloxycarbonyl group, carbamoyl group having 1-20 carbon atoms (preferably 1-10), alkylcarbonyl group having 1-20 carbon atoms (preferably 1-10), 6-6 carbon atoms It is a 20 (preferably 6-10) arylcarbonyl group, a C1-C20 (preferably 1-10) alkylsulfonyl group, or a C6-C20 (preferably 6-10) arylsulfonyl group.

R ^1a , R ^2a , R ^3a and R ^4a are all a cyano group, an alkoxycarbonyl group having 1 to 20 carbon atoms (preferably 1 to 10), and an aryloxy group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms). Carbonyl group, C 1-20 (preferably 1-10) carbamoyl group, C 1-20 (preferably 1-10) alkylcarbonyl group, C 6-20 (preferably 6-10) aryl A substituent selected from a carbonyl group, an alkylsulfonyl group having 1 to 20 carbon atoms (preferably 1 to 10) or an arylsulfonyl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) is particularly preferable. More preferably, the combination of R ^1a and R ^2a and the combination of R ^3a and R ^4a are the same combination.

R ^Ba5 and R ^Ba6 are each an alkoxy group having 1 to 20 carbon atoms (preferably 1 to 10), an aryloxy group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), and 1 to 20 carbon atoms (preferably 1 to 1 carbon atoms). 10) an acyloxy group, an alkoxycarbonyloxy group having 1 to 20 carbon atoms (preferably 1 to 10), an aryloxycarbonyloxy group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), and 1 to 20 carbon atoms (preferably Is a carbamoyloxy group having 1 to 10), an amino group having 0 to 20 carbon atoms (preferably 0 to 10), an acylamino group having 1 to 20 carbon atoms (preferably 1 to 10), and 1 to 20 carbon atoms (preferably 1-10) represents a carbamoylamino group.

R ^Ba5 and R ^Ba6 may further have a substituent. Examples of the substituent include the monovalent substituent described above. Examples of the divalent substituent include a carbonyl group and an imino group. When there are a plurality of substituents, they may be the same or different. Moreover, it may become a condensed ring or a spiro ring by bonding with each other to form a ring.

  Although the specific example of the compound represented by either general formula (BI) or (B-Ia) used by this invention below is shown, this invention is not limited to this.

The compound represented by the general formula (BI) or (BI-Ia) can be synthesized by any method. For example, a compound in which R ^B5 and R ^B6 in the above general formula ( ^BI ) are hydroxy groups is used as a synthesis intermediate, and this is subjected to alkylation or acylation, and then synthesized by a reaction in which a desired substituent is introduced. can do.
The synthetic intermediate in which R ^B5 and R ^B6 in the general formula ( ^BI ) are hydroxy groups, for example, when X ^B1 , X ^B2 , X ^B3 and X ^B4 are all sulfur atoms, And references, for example, the reference example in the upper right row 1st line to the lower left row 1st line of page 3 of JP-A-63-225382, Liebigs Ann. Chem., 1969, Vol. 726, pages 103-109, and can be synthesized with reference to page 109, lines 5 to 12 in the literature.
In addition, the compound represented by the above general formula (BI) or (B-Ia) is disclosed in Journal of Organic Chemistry, 1990, Vol. 55, pages 5347-5350, page 5349, line 27 on the right. 1994, Volume 59, 3077-3081, page 3081, lines 11-16; Tetrahedron Letters, 1991, Volume 32, 4897-4900, page 4897, line 9 ~ 4899, page 3, line 3, 1977, 26, 2225, Table 1, Tetrahedron, 1993, volume 49, pages 3035-3042, page 3037, line 11 to line 20, and page 3040, line 22 to Line 38, Journal of the American Chemical Society, 1958, 80, 1662-1664, 1664 pages right 6-15 lines, 1995, 117, 9995-10002, 9996 12th page right to 9997th page left 46th line, JP-A-6-80672, 4th page left 43th line to 45th right line, Phosphorus, Sulfur, and Silicon, 1997, 120 & 121, 121-143 123 in literature Page 18 line-page 124 line 3, Chem. Commun., 2004, pp. 1758-1759, page 1758, left line 44-54, German Patent No. 3724852, page 4, line 46-5, page 16, line 16 100097 gazette, page 3 upper left row 3 to page 4, lower left row 4th row, Special Table Hei 5-506428 gazette page 12 lower right row 1 row to page 35 lower right row 1 row, etc. The compound can be synthesized with reference to the synthesis route of the compound having a similar structure.

For example, the exemplary compound (1) is obtained by reacting a disodium salt obtained by reacting carbon disulfide and malononitrile in the presence of sodium hydroxide with chloranil and then reacting this with 2-ethylhexanoyl chloride in the presence of a base. Can be synthesized. Illustrative compound (2) is synthesized by reacting disodium salt obtained by reacting carbon disulfide and malononitrile in the presence of sodium hydroxide with chloranil and then reacting 2-ethylhexyl bromide in the presence of a base. be able to.
Exemplified compound (11) was prepared by reacting dipotassium salt obtained by reacting carbon disulfide with ethyl cyanoacetate in the presence of potassium hydroxide with chloranil to synthesize exemplified compound (72), and 2-ethylhexanoyl It can be synthesized by reacting chloride in the presence of a base. The exemplified compound (12) can be synthesized by reacting the exemplified compound (72) with 2-ethylhexyl bromide in the presence of a base.
The exemplified compound (59) can be synthesized by reacting a dipotassium salt obtained by reacting carbon disulfide and ethyl cyanoacetate in the presence of potassium hydroxide with hexafluorobenzene.
The exemplified compound (51) can be synthesized by reacting the exemplified compound (59) with sodium dodecanethiolate.

The compounds represented by the general formula (B-I) are different from each other when R ^B1 and R ^B2 , R ^B3 and R ^B4 , X ^B1 and X ^B2 , X ^B3 and X ^B4, or R ^B5 and R ^B6 are different from each other. It can become a geometric isomer by changing the position of. Even when only one of the geometric isomers is described in the present specification, the compound represented by the general formula (BI) used in the present invention is also used for the other geometric isomers. include. Moreover, even if it is a mixture of geometric isomers in the process of synthesis or purification, only the representative structure is described in this specification. In the case of a geometric isomer mixture, the abundance ratio may be any ratio between 0: 1 and 1: 0.

  The compound represented by any one of the general formulas (1), (2), (3), (B-I) or (B-Ia) used in the present invention varies depending on the structure and the environment in which it is placed. Mutants can be taken. Although described in this specification in one of the representative forms, tautomers different from those described in this specification are also included in the compounds used in the present invention.

The compound represented by any one of the general formulas (1), (2), (3), (B-I) or (B-Ia) used in the present invention is an isotope (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O, ¹⁸ O, etc.).

  A polymer containing the structure of the compound represented by any one of the general formulas (1), (2), (3), (BI) or (B-Ia) as a UV-absorbing group in a repeating unit, It can be suitably used in the present invention. Examples of the repeating unit including the structure of the compound represented by any one of the general formulas (1), (2), (3), (BI), and (B-Ia) are shown below.

  It may be a homopolymer composed of the above repeating units or a copolymer composed of two or more kinds of repeating units. Further, it may be a copolymer containing other repeating units. Examples of other repeating units are shown below.

  As for the polymer containing the ultraviolet absorber structure in the repeating unit, JP 39-45555, line 39 to page 12, left line 38, JP-A 61-189530, page 3, upper right 8 Line 7 to page 7, lower left line 15; lower right line 3 of JP-A-62-260152; page 12, upper right line 10; upper line 1st line of JP-A 63-53544 15th page, lower right 19th line, JP-A 63-56651, page 2 upper 10th right line to page 14 lower left 3rd line, and European Patent 27242, page 4 29th line-16 It is described on page 34, line 3, page 28, line 28 to page 26, line 1 of the pamphlet of International Publication No. 2006/009451. The description of these patent documents can be referred to for the method of obtaining the polymer.

<Ultraviolet absorber B>
The ultraviolet absorbent B is characterized in that the absorbance at 320 nm is 30% or more of the absorbance at the maximum absorption wavelength. Preferably it is 50% or more. When the absorbance at 320 nm is 30% or less of the absorbance at the maximum absorption wavelength, a wavelength band that is not covered by the ultraviolet absorber A and the ultraviolet absorber B occurs between 310 nm and 330 nm. Moreover, it is preferable that the maximum absorption wavelength of the ultraviolet absorber B is 350 nm or less.

  The ultraviolet absorber B having an absorbance at 320 nm of 30% or more of the absorbance at the maximum absorption wavelength and a maximum absorption wavelength of 350 nm or less is the ultraviolet absorber B- (2) having a maximum absorption wavelength of 320 nm or less as described above, and Two types of ultraviolet absorber B- (2) having a maximum absorption wavelength of 320 nm or more and 350 nm or less are conceivable and can be appropriately selected according to the application.

  For example, the ultraviolet absorbent B- (1) is particularly preferably used when there is no element that absorbs short-wave ultraviolet rays, such as when it is kneaded into a plastic molded product or polymer. In the case of plastic molding or polymer kneading, there is no other element that absorbs short-wave ultraviolet light of 300 nm or less, so a new short-wave can be obtained by using an ultraviolet absorber B- (1) that can efficiently absorb the short-wave ultraviolet region. Without using the ultraviolet region absorption filter, the plastic molded product itself and its contents can be prevented from ultraviolet rays. Moreover, the unexpected effect that compatibility with a polymer and light fastness are improved by using in combination with the said ultraviolet absorber A is acquired.

  For example, B- (2) is particularly preferably used when there is an element that absorbs short-wave ultraviolet light, such as when it is dissolved in a film on glass or a polymer and applied to a substrate. When the ultraviolet absorber B- (2) is used, the shielding ability near 320 nm is excellent, but although it is possible to efficiently absorb the short-wave ultraviolet region of 300 nm or less, it may be difficult. Therefore, it is preferable to apply the polymer on a glass substrate that serves as a filter for shielding the short wave side. Further, the combined use of the ultraviolet absorbent A of the present invention unexpectedly improves the solubility and light fastness to a solvent (for example, ethyl acetate, methyl ethyl ketone, toluene, etc.) when using a coating film in a solvent coating system. The effect is obtained.

  The ultraviolet absorber B may have any structure as long as this condition is satisfied. For example, supervised by Shinichi Daikatsu, “Development of Polymer Additives and Environmental Measures” (CMC Publishing, 2003) Chapter 2, edited by Toray Research Center Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999) 2.3.1, and the like. For example, compounds such as triazine, benzotriazole, benzophenone, cyanine, dibenzoylmethane, cinnamic acid, acrylate, benzoate, and oxalic acid diamide known as UV absorber structures Can be mentioned. For example, Fine Chemical, May 2004 issue, pages 28-38, published by Toray Research Center, Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999), pages 96-140, Junichi Okachi Supervised “Development of Polymer Additives and Environmental Measures” (CM Publishing, 2003), pages 54-64, etc.

  Preferred are benzotriazole-based, benzophenone-based, salicylic acid-based, acrylate-based, and triazine-based compounds because of the molar extinction coefficient at 320 nm. More preferred are benzotriazole-based, benzophenone-based, and triazine-based compounds having excellent light fastness. When these preferable ultraviolet absorbers B are used in combination with the ultraviolet absorber A composed of a compound represented by any one of the above general formulas (1) to (3), (BI) or (B-Ia), coloring It is possible to absorb the ultraviolet region efficiently without any problem.

  The benzotriazole-based compound is preferably a compound having an effective absorption wavelength of about 270 to 380 nm and represented by any one of the following general formulas (IIa) and (IIb). (IIa) and (IIb) will be described in detail.

However, in the general formula (IIa), R ₁₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group.
R ₁₂ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
R ₁₃ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a —COOR ₁₄ group (where R ₁₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, Or a substituted or unsubstituted aryl group.

However, in said general formula (IIb), T represents a hydrogen atom or a substituted or unsubstituted alkyl group.
T ₁ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group.
L represents a divalent linking group or a single bond, and m represents 0 or 1.
n represents an integer of 1 to 4. When n is 1, T ₂ represents a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. When n is 2, T ₂ represents a divalent substituent, when n is 3, T ₂ represents a trivalent substituent, and when n is 4, T ₂ represents a tetravalent substituent.

-General Formula (IIa-
R ₁₁ represents a hydrogen atom, a substituted or unsubstituted alkyl, a substituted or unsubstituted cycloalkyl, or a substituted or unsubstituted aryl group.
R ₁₁ is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms. R ₁₁ is particularly preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms.

  A substituted alkyl group, a substituted cycloalkyl group, and a substituted aryl group represent an alkyl group, a cycloalkyl group, or an aryl group having a monovalent substituent at any position. Examples of monovalent substituents include halogen Atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, methyl, ethyl), 6 to 20 carbon atoms (preferably Are 6-10) aryl groups (eg phenyl, naphthyl), cyano groups, carboxyl groups, C1-C20 (preferably 1-10) alkoxycarbonyl groups (eg methoxycarbonyl), C6-C20 (preferably Is an aryloxycarbonyl group (for example, phenoxycarbonyl) having 6 to 10), a substituted or unsubstituted carbon having 0 to 20 carbon atoms (preferably 0 to 10). Moyl group (for example, carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), C1-C20 (preferably 1-10) alkylcarbonyl group (for example, acetyl), C6-C20 (preferably 6- 10) an arylcarbonyl group (for example, benzoyl), a nitro group, a substituted or unsubstituted amino group (for example, amino, dimethylamino, anilino) having a carbon number of 0 to 20 (preferably 0 to 10), a carbon number of 1 to 20 ( Preferably it is 1-10) acylamino group (for example, acetamide, ethoxycarbonylamino), C0-20 (preferably 0-10) sulfonamide group (for example, methanesulfonamide), C2-20 (preferably 2). -10) imide group (for example, succinimide, phthalimide), C1-20 (preferably 1). 10) imino group (for example, benzylideneamino), hydroxy group, C1-C20 (preferably 1-10) alkoxy group (for example, methoxy), C6-C20 (preferably 6-10) aryloxy group (For example, phenoxy), an acyloxy group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, acetoxy), an alkylsulfonyloxy group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, methanesulfonyloxy), carbon An arylsulfonyloxy group having 6 to 20 (preferably 6 to 10) arylsulfonyloxy group (for example, benzenesulfonyloxy), a sulfo group, a substituted or unsubstituted sulfamoyl group having 0 to 20 carbon atoms (preferably 0 to 10) (for example, sulfamoyl, N-phenylsulfamoyl), an alkylthio group having 1 to 20 carbon atoms (preferably 1 to 10) ( For example, methylthio), an arylthio group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms) (for example, phenylthio), an alkylsulfonyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) (for example, methanesulfonyl), and 6 to 6 carbon atoms Examples include 20 (preferably 6 to 10) arylsulfonyl groups (for example, benzenesulfonyl) and 4 to 7 membered (preferably 5 to 6 membered) heterocyclic groups (for example, pyridyl and morpholino).

R ₁₂ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ₁₂ is preferably a hydrogen atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 18 carbon atoms, or a substituted or unsubstituted group having 6 to 24 carbon atoms. An aryl group. R ₁₂ is particularly preferably a hydrogen atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.

R ₁₃ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a —COOR ₁₄ group (where R ₁₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, Or a substituted or unsubstituted aryl group. R ₁₃ is preferably a hydrogen atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, or a —COOR ₁₄ group (where R ₁₄ is A hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.

R ₁₁ and R ₁₂ may be in any position as long as they are substituted on the benzene ring, but are preferably substituted on the 2-position and 4-position of the hydroxyl group.

-General formula (IIb)-
T represents a hydrogen atom or a substituted or unsubstituted alkyl group. T is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms.
T ₁ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group. T ₁ is preferably a hydrogen atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.

-L- represents a divalent linking group or a single bond, and m represents 0 or 1.
When m is 0, it represents a case where T ₂ is directly bonded to a benzene ring without L being interposed, that is, a case where -L- represents a simple bond.
The divalent linking group -L- will be described. -L- is a divalent substituent represented by the following general formula (a).
<General formula (a)>
_{- (L 1) m1 - (} L 2) m2 - (L 3) m3 - (L 4) m4 - (L 5) m5 -
However, in said general formula (a), m1-m5 represent the integer of 0-2.
L _{1 to} L ₅ are each independently —CO—, —O—, —SO ₂ —, —SO—, —NR _L —, a substituted or unsubstituted divalent alkyl group, substituted or unsubstituted 2 Represents a valent alkenyl group or a substituted or unsubstituted divalent aryl group. R _L represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

Specific examples of _RL include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a phenyl group, and a naphthyl group. A monovalent substituent may be present at any position on the alkyl group and the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. R _L is preferably a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. More preferably, it is a substituted or unsubstituted alkyl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

That The-L-2 monovalent _{substituent, -O-CO-C 2 H} 4 -CO-O -, - O-CO-C 3 H 6 -, - NH-CO-C 3 H 6 -CO- NH -, - NH-CO- C 4 H 8 -, - CH 2 -, - C 2 H 4 -, - C 3 H 6 -, - C 4 H 8 -, - C 5 H 10 -, - C 8 H ₁₆ —, —C ₄ H ₈ —CO—O—, —C ₆ H ₄ —C ₆ H ₄ —, —NH—SO ₂ —C ₃ H ₆ — and the like are preferable.

In the general formula (IIb), n represents an integer of 1 to 4.
When n is 1, T ₂ represents a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. When n is 1, T ₂ is preferably a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.

When n is 2, T ₂ represents a divalent substituent. Specific examples of T ₂ when n is 2 include the above divalent substituents -L-. When n is 2, T ₂ is preferably —CH ₂ —, —O—CO—C ₂ H ₄ —CO—O—, —NH—CO—C ₃ H ₆ —CO—NH—.

When n is 3, T ₂ represents a trivalent substituent. The trivalent substituent will be described. The trivalent substituent is a trivalent alkyl group, a trivalent aryl group, or a substituent represented by the following general formula.
Among the trivalent substituents, a trivalent alkyl group having 1 to 8 carbon atoms, a trivalent aryl group having 6 to 14 carbon atoms, or a substituent represented by the following general formula.

When n is 4, T ₂ represents a tetravalent substituent. The tetravalent substituent will be described. The tetravalent substituent is a substituent represented by a tetravalent alkyl group or a tetravalent aryl group. Of the tetravalent substituents, a tetravalent alkyl group having 1 to 8 carbon atoms and a tetravalent aryl group having 6 to 14 carbon atoms are preferable.

In the general formula (IIb), it is particularly preferable that n is 1 or 2. That is, as a preferable combination of the general formula (IIb),
when n is 1, T is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, T ₁ is a hydrogen atom, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, An aryl group having 6 to 24 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, wherein L is —O—CO—C ₃ H ₆ —, —CH ₂ —, —C ₃ H ₆ —, —C ₅ H; ₁₀ −, —C ₈ H ₁₆ —, —NH—CO—C ₄ H ₈ — or a simple bond, and T ₂ is a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or 6 carbon atoms It is a combination of 24 to 24 substituted or unsubstituted aryl groups.
When n is 2, T is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and T ₁ is a hydrogen atom, a chlorine atom, or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms. Group, an aryl group having 6 to 24 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, L is —CH ₂ — or a simple bond, and T ₂ is —CH ₂ —, —O—CO—C. ₂ H ₄ —CO—O— or —NH—CO—C ₃ H ₆ —CO—NH—.
When n is 2, m is 0, T is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and T ₁ is a hydrogen atom, a chlorine atom, or a carbon atom having 1 to 18 carbon atoms. A substituted or unsubstituted alkyl group, an aryl group having 6 to 24 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, and T ₂ is —CH ₂ —, —O—CO—C ₂ H ₄ —CO—. A combination that is O— or —NH—CO—C ₃ H ₆ —CO—NH— is also preferable.

Representative examples of the compound represented by the general formula (IIa) or (IIb) 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-chlorobenzotriazole, 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (2'-hydroxy- 4 ' Octyloxyphenyl) benzotriazole, 2- (2′-hydroxy-3 ′-(3,4,5,6-tetrahydrophthalimidylmethyl) -5′-methylbenzyl) phenyl) benzotriazole, 2- (3 ′ -Sec-butyl-5′-t-butyl-2′-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-bis- (α, α-dimethylbenzyl) -2′-hydroxyphenyl) benzotriazole, 2- (3′-t-butyl-2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3′-t-butyl-5 ′-[ 2- (2-Ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-t-butyl-2'-hydroxy- 5 ′-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3′-t-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3′-t-butyl-2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3′-t-butyl-5 ′-[2- (2- Ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-t-butyl-2 ' -Hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-te Lamethylbutyl) -6-benzotriazol-2-ylphenol], 2- [3′-t-butyl-5 ′-(2-methoxycarbonylethyl) -2′-hydroxyphenyl] -2H-benzotriazole and polyethylene glycol 300 Transesterification product with
Wherein R = 3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2- [2′-hydroxy-3 ′-(α, α-dimethylbenzyl) -5 '-(1,1,3,3-tetramethylbutyl) -phenyl] benzotriazole; 2- [2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl) -5 ' -(Α, α-dimethylbenzyl) -phenyl] benzotriazole), and the like.

The triazine compound is preferably a compound having an effective absorption wavelength of about 270 nm to 380 nm and represented by the following general formula (III).
However, in the general formula (III), the substituents Y ₁ are independently of each other a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group. It is a group. Lf represents a divalent linking group or a single bond.
u is 1 or 2, v is 0 or 1, and r is an integer of 1 to 3, and when u is 1, Y ₂ is a hydrogen atom, a substituted or unsubstituted alkyl group, or substituted or An unsubstituted aryl group. When u is 2, Y ₂ represents a divalent substituent.

Y ₁ represents, independently of each other, a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkoxy group. Y ₁ is preferably a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, or a substituted or unsubstituted group having 1 to 18 carbon atoms. It is a substituted alkoxy group.

Lf represents a divalent linking group or a simple bond. u represents 1 or 2; r represents an integer of 1 to 3. v is 0 or 1, and when v is 0, Lf represents a simple bond.
The divalent linking group -Lf- will be described. The divalent substituent Lf is a divalent substituent represented by the following general formula (b).
<General formula (b)>
− (Lf ₁ ) _{mf 1} − (Lf ₂ ) _{mf 2} − (Lf ₃ ) _{mf 3} − (Lf ₄ ) _{mf 4} − (Lf ₅ ) _{mf 5} −
However, in the said general formula (b), mf1-mf5 represents the integer of 0-2.
Lf _{1 to} Lf ₅ each independently represent —CO—, —O—, —SO ₂ —, —SO—, —NRf _L —, a divalent substituted or unsubstituted alkyl group, divalent substituted or It represents an unsubstituted alkenyl group or a divalent substituted or unsubstituted aryl group. Rf _L represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

Specific examples of Rf _L include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a phenyl group, and a naphthyl group. A monovalent substituent may be present at any position on the alkyl group and the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Rf _L is preferably a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. More preferably, it is a substituted or unsubstituted alkyl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

That is, examples of the divalent substituent _{-Lf-, -O-CO-C 2} H 4 -CO-O -, - O-CO-C 3 H 6 -, - NH-CO-C 3 H 6 -CO -NH -, - NH-CO- C 4 H 8 -, - CH 2 -, - C 2 H 4 -, - C 3 H 6 -, - C 4 H 8 -, - C 5 H 10 -, - C ₈ H ₁₆ —, —C ₄ H ₈ —CO—O—, —C ₆ H ₄ —C ₆ H ₄ —, —NH—SO ₂ —C ₃ H ₆ — and the like are preferable.

When u is 1, Y ₂ is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. When u is 1, Y ₂ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.

When u is 2, Y ² represents a divalent substituent. Examples of the divalent substituent include the examples of the above divalent substituent -L-. Y ₂ is preferably a substituted or unsubstituted divalent alkyl group, a substituted or unsubstituted divalent alkenyl group, a substituted or unsubstituted divalent aryl group, —CH ₂ CH (OH) CH ₂ —O. _{-Y 11 -OCH 2 CH (OH)} CH 2, -CO-Y 12 -CO -, - CO-NH-Y 13 -NH-CO-, or _{- (CH 2) t -CO 2} -Y 14 -OCO - a (CH _{2) t.}
However, t is 1, 2 or 3,
Y ₁₁ represents a substituted or unsubstituted alkylene, phenylene, or -phenylene-M-phenylene- (where M represents —O—, —S—, —SO ₂ —, —CH ₂ — or C (CH ₃ ) ₂ −))
Y ₁₂ is a substituted or unsubstituted divalent alkyl group, a substituted or unsubstituted divalent alkenyl group, or a substituted or unsubstituted divalent aryl group,
Y ₁₃ is a substituted or unsubstituted divalent alkyl group, or a substituted or unsubstituted divalent aryl group,
Y ₁₄ represents a substituted or unsubstituted divalent alkyl group, or a substituted or unsubstituted divalent aryl group.

That is, when u is 2, Y ₂ is preferably a substituted or unsubstituted divalent alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted divalent aryl group having 6 to 24 carbon atoms, —CH _{2. CH (OH) CH 2 -O-} CH 2 -OCH 2 CH (OH) CH 2 -, - CH 2 CH (OH) CH 2 -O-C (CH 3) 2 -OC 8 H 16 -, or - ( _{CH 2) 2 -CO 2 -C 2} H 4 -OCO- (CH 2) 2 - is.

  Representative examples of the compound represented by the general formula (III) include 2- (4-butoxy-2-hydroxyphenyl) -4,6-di (4-butoxyphenyl) -1,3,5-triazine, 2- (4-butoxy-2-hydroxyphenyl) -4,6-di (2,4-dibutoxyphenyl) -1,3,5-triazine, 2,4-di (4-butoxy-2-hydroxyphenyl) ) -6- (4-butoxyphenyl) -1,3,5-triazine, 2,4-di (4-butoxy-2-hydroxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3 , 5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6- Bis (2,4-dimethylphenol L) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis ( 2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis ( 4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy) -3-butyloxyp Poxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl]- 4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-) Methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris (2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl) -1,3,5 -Triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-) 1-oxy) -2-hydroxy-propyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- (2-ethylhexyl) And oxy) phenyl-4,6-di (4-phenyl) phenyl-1,3,5-triazine.

As the benzophenone-based compound, a compound having an effective absorption wavelength of about 270 nm to 380 nm is preferable, and a compound represented by the following general formula (IVa) or (IVb) is preferable.
However, in the general formula (IVa), X ₁ and X ₂ are each independently a hydrogen atom, halogen atom, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted Substituted alkoxy group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, sulfonic acid group, substituted or unsubstituted alkyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, or substituted or Represents an unsubstituted amino group. s1 and s2 each independently represent an integer of 1 to 3.

In the general formula (IVb), X ₁ represents a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group, substituted or unsubstituted A substituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a sulfonic acid group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted amino group; s1 represents an integer of 1 to 3.
Lg represents a divalent substituent or a simple bond, and w represents 0 or 1.
tb represents 1 or 2, and when tb is 1, X ₃ represents a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group, Substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, sulfonic acid group, substituted or unsubstituted alkyloxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, or substituted or unsubstituted amino group Represents. When tb is 2, X ₃ represents a divalent substituent.

-General formula (IVa)-
X ₁ and X ₂ are each independently a hydrogen atom, halogen atom, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted It represents an alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a sulfonic acid group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted amino group. X ₁ and X ₂ are preferably a hydrogen atom, a chlorine atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, or a carbon number of 1 to 1 18 substituted or unsubstituted alkoxy groups, alkyloxycarbonyl groups having 2 to 18 carbon atoms, aryloxycarbonyl groups having 7 to 24 carbon atoms, sulfonic acid groups, or substituted or unsubstituted amino groups having 1 to 16 carbon atoms It is. X ₁ and X ₂ are particularly preferably a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms.

-General formula (IVb)-
tb is 1 or 2, w is 0 or 1, and s1 is an integer of 1 to 3.
Substituent X ₁ is a hydrogen atom, halogen atom, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylsulfonyl group, substituted or It represents an unsubstituted arylsulfonyl group, a sulfonic acid group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted amino group.

X ₁ is preferably a hydrogen atom, a chlorine atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, or a substitution having 1 to 18 carbon atoms. Alternatively, it is an unsubstituted alkoxy group, an alkyloxycarbonyl group having 2 to 18 carbon atoms, an aryloxycarbonyl group having 7 to 24 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms. X ₁ is particularly preferably a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms.

-Lg- represents a divalent linking group or a simple bond, and w represents an integer of 0 to 1. When w is 0, X ₃ is directly bonded to the benzene ring without Lg, that is, -Lg- represents a simple bond.
The divalent linking group -Lg- will be described. The divalent substituent Lg is a divalent substituent represented by the following general formula (c).
<General formula (c)>
− (Lg ₁ ) _{mg 1} − (Lg ₂ ) _{mg 2} − (Lg ₃ ) _{mg 3} − (Lg ₄ ) _{mg 4} − (Lg ₅ ) _{mg 5} −
However, in said general formula (c), mg1-mg5 represents the integer of 0-2.
Lg _{1 to} Lg ₅ are each independently —CO—, —O—, —SO ₂ —, —SO—, —NRg _L —, a substituted or unsubstituted divalent alkyl group, substituted or unsubstituted 2 Represents a valent alkenyl group or a substituted or unsubstituted divalent aryl group. Rg _L represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

Specific examples of Rg _L include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a phenyl group, and a naphthyl group. A monovalent substituent may be present at any position on the alkyl group and the aryl group. Examples of the monovalent substituent include the examples of the monovalent substituent described above. Rg _L is preferably a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. More preferably, it is a substituted or unsubstituted alkyl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

That is, as the divalent substituent -Lg-, -O -, - O- CO-C 2 H 4 -CO-O -, - O-C 4 H 8 -O -, - O-CO-C 3 H _{6 -, - NH-CO-} C 3 H 6 -CO-NH -, - NH-CO-C 4 H 8 -, - CH 2 -, - C 2 H 4 -, - C 3 H 6 -, - C _{4 H 8 -, - C 5} H 10 -, - C 8 H 16 -, - C 4 H 8 -CO-O -, - C 6 H 4 -C 6 H 4 -, - NH-SO 2 -C 3 H _6- and the like are preferable.

When tb is 1, X ₃ is a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylsulfonyl group A substituted or unsubstituted arylsulfonyl group, a sulfonic acid group, a substituted or unsubstituted alkyloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, or a substituted or unsubstituted amino group.
When tb is 1, X ₃ is preferably a hydrogen atom, a hydroxyl group, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, carbon A substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, an alkyloxycarbonyl group having 2 to 18 carbon atoms, an aryloxycarbonyl group having 7 to 24 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted group having 1 to 16 carbon atoms Of the amino group.
X ₃ is particularly preferably a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms.

When tb is 2, X ₃ represents a divalent substituent.
When tb is 2, specific examples of X ₃ is an example of a-L-2 monovalent substituent groups mentioned above. When tb is 2, X ₃ is preferably —CH ₂ —, —C ₄ H ₈ —, —O—C ₄ H ₈ —O—, —O—CO—C ₂ H ₄ —CO—O—, or -NH-CO-C ₃ H ₆ is -CO-NH-.

In the general formula (IVb), it is particularly preferable that tb is 1.
That is, preferred combinations of the general formula (IVb) are as follows.
Specifically, when tb is 1,
X ₁ is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms,
Lg is —O—, —O—CO—C ₂ H ₄ —CO—O—, —O—C ₄ H ₈ —O—, —O—CO—C ₃ H ₆ —, —NH—CO—C _3. H ₆ —CO—NH—, —NH—CO—C ₄ H ₈ —, —CH ₂ —, —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₅ H ₁₀ —, —C ₈ H ₁₆ —, —C ₄ H ₈ —CO—O—, —C ₆ H ₄ —C ₆ H ₄ —, or —NH—SO ₂ —C ₃ H ₆ —, or a simple bond. ,
X ₃ is a hydrogen atom, a hydroxyl group, a chlorine atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted group having 1 to 18 carbon atoms The combination which is a C2-C18 alkyloxycarbonyl group, a C7-24 aryloxycarbonyl group, a sulfonic acid group, or a C1-C16 substituted or unsubstituted amino group is preferable.

When tb is 2,
X ₁ is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a sulfonic acid group, or a substituted or unsubstituted amino group having 1 to 16 carbon atoms,
Lg is —O—, —O—CO—C ₂ H ₄ —CO—O—, —O—C ₄ H ₈ —O—, —O—CO—C ₃ H ₆ —, —NH—CO—C _3. H ₆ —CO—NH—, —NH—CO—C ₄ H ₈ —, —CH ₂ —, —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₅ H ₁₀ —, —C ₈ H ₁₆ —, —C ₄ H ₈ —CO—O—, —C ₆ H ₄ —C ₆ H ₄ —, or —NH—SO ₂ —C ₃ H ₆ —, or a simple bond. ,
X ₃ is —CH ₂ —, —C ₄ H ₈ —, —O—C ₄ H ₈ —O—, —O—CO—C ₂ H ₄ —CO—O—, or —NH—CO—C ₃ H. A combination that is _6- CO-NH- is preferred.

  Representative examples of the benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 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 trihydrate, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2-hydroxy-4 Diethylamino-2'-hexyloxycarbonylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 1,4-bis (4-benzyloxy-3-hydroxyphenoxy) butane and the like.

  The salicylic acid-based compound is preferably a compound having an effective absorption wavelength of about 290 to 330 nm, and typical examples thereof include phenyl salicylate, 4-t-butylphenyl salicylate, 4-octylphenyl salicylate, dibenzoylresorcinol, bis ( 4-t-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxysalicylate, hexadecyl 3,5-di-t-butyl-4- Hydroxy salicylate and the like can be mentioned.

  The acrylate compound is preferably a compound having an effective absorption wavelength of about 270 to 350 nm, and typical examples thereof include 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, ethyl 2-cyano-3,3- Diphenyl acrylate, isooctyl 2-cyano-3,3-diphenyl acrylate, hexadecyl 2-cyano-3- (4-methylphenyl) acrylate, methyl 2-cyano-3-methyl-3- (4-methoxyphenyl) cinnamate, butyl 2-cyano-3-methyl-3- (4-methoxyphenyl) cinnamate, methyl 2-carbomethoxy-3- (4-methoxyphenyl) cinnamate 2-cyano-3- (4-methylphenyl) acrylate, 1 , 3-Bis (2'-cyano-3,3'-diphenyl Acryloyl) oxy) -2,2-bis (((2′-cyano-3,3′-diphenylacryloyl) oxy) methyl) propane, N- (2-carbomethoxy-2-cyanovinyl) -2-methylindoline, etc. Can be mentioned.

  The oxalic acid diamide compound preferably has an effective absorption wavelength of about 250 nm to 350 nm. Typical examples thereof include 4,4′-dioctyloxyoxanilide, 2,2′-dioctyloxy-5, 5′-di-t-butyl oxanilide, 2,2′-didodecyloxy-5,5′-di-t-butyl oxanilide, 2-ethoxy-2′-ethyl oxanilide, N, N '-Bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide, 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxa Nilide etc. can be mentioned.

  The ultraviolet absorber B is particularly preferably a compound selected from the following compound group B. Compound group B is a group consisting of the following compounds (II-1) to (IV-6).

[1] Compound (II-1) represented by the general formula (IIa) 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole (II-2) 2- ( 3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole (II-3) 2- (2-hydroxy-5-t-octylphenyl) benzotriazole (II-4) 2-ethylhexyl -3- [3-t-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (II-5) 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol (II-6) 2- (2H-benzotriazol-2-yl) -3-t-butylphenol (II-7) 2- (2H-benzotria) Zol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1-3,3-tetramethylbutyl) phenol (II-8) 2- (2H-benzotriazole-2 -Yl) -3-methylphenol (II-9) 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol

[2] Compound (II-10) represented by formula (IIb) 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3- Tetramethylbutyl) phenol]

[3] Compound (III-1) represented by general formula (III) 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3 , 5-triazine (III-2) 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine (III-3) 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl-4,6-bis ( 2,4-Dimethylphenyl) -1,3,5-triazine (III-4) 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol (III- 5) Bisethylhexyloxyphenol Hydroxyphenyl triazine

[4] Compound (IV-1) represented by the above general formula (IV) Hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate (IV-2) 2,2′-hydroxy-4,4′- Dimethoxybenzophenone (IV-3) 2-hydroxy-4-methoxybenzophenone (IV-4) 1,4-bis (4-benzoyl-3-hydroxyphenoxy) butane (IV-5) 2-hydroxy-4-octoxybenzophenone (IV-6) 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (IV-7) 2,2 ′, 4,4′-tetrahydroxybenzophenone

Compound (II-1) has the following structure, and is commercially available as trade name Tinuvin 328 (manufactured by Ciba Specialty Chemicals).
Compound (II-2) has the following structure, and is commercially available as trade name Tinuvin 326 (manufactured by Ciba Specialty Chemicals).
Compound (II-3) has the following structure, and is commercially available as trade name Tinuvin 329 (manufactured by Ciba Specialty Chemicals).
Compound (II-4) has the following structure and is commercially available as trade name Tinuvin 109 (manufactured by Ciba Specialty Chemicals).
Compound (II-5) has the following structure, and is commercially available as trade name Tinuvin 171 (manufactured by Ciba Specialty Chemicals).
Compound (II-6) has the following structure, and is commercially available as trade name Tinuvin PS (manufactured by Ciba Specialty Chemicals).
Compound (II-7) has the following structure, and is commercially available as trade name Tinuvin 928 (manufactured by Ciba Specialty Chemicals).
Compound (II-8) has the following structure and is commercially available as trade name Tinuvin P (manufactured by Ciba Specialty Chemicals).
Compound (II-9) has the following structure and is commercially available as trade name Tinuvin 234 (manufactured by Ciba Specialty Chemicals).
Compound (II-10) has the following structure, and is commercially available as trade name Tinuvin 360 (manufactured by Ciba Specialty Chemicals).

Compound (III-1) has the following structure, and is commercially available as trade name Tinuvin 460 (manufactured by Ciba Specialty Chemicals).
Compound (III-2) has the following structure, and is commercially available as trade name Cyasorb UV-116 (manufactured by Cytec).
Compound (III-3) has the structure shown below and is commercially available as trade name Tinuvin 405 (manufactured by Ciba Specialty Chemicals).
Compound (III-4) has the following structure, and is commercially available as trade name Tinuvin 1577 (manufactured by Ciba Specialty Chemicals).
Compound (III-5) has the following structure, and is commercially available as trade name Tinosorb S (manufactured by Ciba Specialty Chemicals).

Compound (IV-1) has the following structure, and is commercially available as trade name Uvinul A plus (BASF).
Compound (IV-2) has the following structure, and is commercially available as trade name Uvinul 3049 (manufactured by BASF).
Compound (IV-3) has the following structure, and is commercially available as trade name Visorb 110 (manufactured by Kyodo Yakuhin Co., Ltd.).
Compound (IV-4) has the following structure, and is commercially available as trade name Seesorb 151 (manufactured by Cypro Kasei Co., Ltd.).
Compound (IV-5) has the following structure, and is commercially available as trade name Chimassorb 81 (manufactured by Ciba Specialty Chemicals).
Compound (IV-6) has the following structure, and is commercially available as trade name Uvinul MS40 (manufactured by BASF).
Compound (IV-7) has the following structure, and is commercially available as trade name Uvinul 3050 (manufactured by BASF).
Compound (IV-8) has the following structure, and is commercially available as trade name Uvinul 3039 (manufactured by BASF).

<Resin>
There is no restriction | limiting in particular as said resin, The thermoplastic resin and thermosetting resin conventionally used for manufacture of conventionally well-known various molded object, a sheet | seat, a film, etc. are mentioned.
Examples of the thermoplastic resin include polyethylene resins, polypropylene resins, acrylic resins, polystyrene resins, styrene-acrylonitrile resins, acrylonitrile-butadiene-styrene resins, polyvinyl chloride resins, polyvinylidene chloride resins, 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 Examples thereof include resin (POM), polyamide resin (PA), polycarbonate resin, polyurethane resin, and polyphenylene sulfide resin (PPS). These may be used individually by 1 type and may use 2 or more types together.
These resins are also used as thermoplastic molding materials in which natural resins contain fillers such as glass fibers, carbon fibers, semi-carbonized fibers, cellulosic fibers, glass beads, flame retardants, and the like. Moreover, conventionally used additives for resins, for example, polyolefin resin fine powder, polyolefin wax, ethylene bisamide wax, metal soap, etc. can be used alone or in combination as required.

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

There is no restriction | limiting in particular as said acrylic resin, What was synthesize | combined suitably may be used and a commercial item may be used. In the case of the synthesis, those obtained by polymerizing or copolymerizing the monomers exemplified below can be used. That is, alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, etc.); Hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; Epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether; acrylic acid and methacrylic acid Carboxy groups such as itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid or salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) Monomers having a salt of: acrylamide, methacrylamide, N-alkyl acrylamide, N-alkyl methacrylamide, N, N-dialkyl acrylamide, N, N-dialkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl Group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.), N-alkoxyacrylamide, N-alkoxymethacrylamide, N, N-dialkoxyacrylamide, N, N -Dialkoxymethacrylamide (alkoxy groups include methoxy, ethoxy, butoxy, isobutoxy, etc.), acryloylmorpholine, N-methylolacrylamide, N-methylolmethacrylamide, N-phenylacrylamido Monomers having an amide group such as N-phenylmethacrylamide; monomers of acid anhydrides such as maleic anhydride and itaconic anhydride; 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2 -Oxazoline group containing such as vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline Monomer: Methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, vinyl isocyanate, allyl isocyanate, styrene, α-methyl styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trialkoxysilane, alkyl maleic acid monoester, acrylate Kirufumaru acid monoesters, alkyl itaconic acid monoester, acrylonitrile, methacrylonitrile, vinylidene chloride, ethylene, propylene, vinyl chloride, vinyl acetate, butadiene and the like. These may be used individually by 1 type and may use 2 or more types together.
As said commercial item, for example, Dianal BR-106 (made by Mitsubishi Rayon Co., Ltd.) etc. can be used.

<First-wave long-wave ultraviolet absorbing laminate>
The long-wave ultraviolet absorbing laminate of the first embodiment has a support, a long-wave ultraviolet absorbing layer, and a short-wave ultraviolet absorbing layer on the incident light side from the long-wave ultraviolet absorbing layer, and other layers as necessary. It has.

The long wave ultraviolet absorbing laminate of the first embodiment preferably has an infrared blocking layer between the support and the short wave ultraviolet absorbing layer, or the support also has an infrared blocking function.
Here, FIGS. 2 to 4 are schematic views showing an example of the long-wave ultraviolet absorbing laminate of the first embodiment of the present invention. In FIG. 2, the short wave ultraviolet absorption layer 3, the long wave ultraviolet absorption layer 2, and the support 1 are laminated in this order from the incident light side (external light side).
In FIG. 3, the short wave ultraviolet absorption layer 3, the support 1, and the long wave ultraviolet absorption layer 2 are laminated in this order from the incident light side (external light side).
In FIG. 4, the short wave ultraviolet absorption layer 3, the infrared absorption layer 4, the support 1, and the long wave ultraviolet absorption layer 2 are laminated in this order from the incident light side (external light side).

-Support-
The support is not particularly limited in its shape, structure, size and the like, and can be appropriately selected according to the purpose. Examples of the shape include a flat plate shape, May have a single layer structure or a laminated structure, and the size can be appropriately selected according to the size of the laminated glass.
The support is preferably transparent, and the transmittance is preferably 80% or more, more preferably 90% or more.
Here, the transmittance is obtained by calculating the total light transmittance based on the content described in “Chemical Material, 4th edition 29, Polymer Materials” (Maruzen, 1992), pages 225 to 232, edited by the Chemical Society of Japan. is there.
Examples of the support include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate (PEN); polycarbonate (PC) films and polymethyl methacrylate films; polyolefin films such as polyethylene and polypropylene; polyimide films, And triacetyl cellulose (TAC) film. Among these, a polyester film is particularly preferable from the viewpoint of cost and performance.

  In the support, in order to impart an infrared absorption function, if necessary, dyes such as azo, methine, anthraquinone, quinophthalone, perylene, xanthene, coumarin, and the like; azo, phthalocyanine It is possible to add colorants such as organic pigments or inorganic pigments such as quinacridone, perylene, dioxazine, anthraquinone, and isoindoline.

  There is no restriction | limiting in particular in the thickness of the said support body, Although it can select suitably according to the objective, 125 micrometers-250 micrometers are preferable.

-Long wave ultraviolet absorption layer-
The said long wave ultraviolet absorption layer consists of a resin composition containing the at least 1 sort (s) of ultraviolet absorber A, resin, and another component.
The ultraviolet absorber A can be appropriately selected from the compounds described above. 10 mass%-50 mass% are preferable, and, as for content in the resin composition of the said ultraviolet absorber A, 20 mass%-40 mass% are more preferable.
The resin can be appropriately selected from the resins described above.
Examples of the other components include solvents; additives such as dispersants, foam inhibitors, preservatives, antifreeze agents, and surfactants.
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone, Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene S; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane and the like. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as a formation method, The said long wave ultraviolet absorption layer can be formed in accordance with a well-known method, For example, it can form suitably by the apply | coating method using the said resin composition.
Examples of the coating method include blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, U comma coating method, AKKU coating method, Examples thereof include a smoothing coating method, a micro gravure coating method, a reverse roll coating method, a four or five roll coating method, a dip coating method, a falling curtain coating method, a slide coating method, and a die coating method.
There is no restriction | limiting in particular in the thickness of the said long wave ultraviolet absorption layer, According to the objective, it can select suitably, 10 micrometers-50 micrometers are preferable, and 20 micrometers-40 micrometers are more preferable.

-Shortwave UV absorbing layer-
The shortwave ultraviolet absorbing layer is made of a resin composition containing at least one ultraviolet absorber B, a resin, and other components.
The ultraviolet absorber B can be appropriately selected from the compounds described above. 10 mass%-50 mass% are preferable, and, as for content in the resin composition of the said ultraviolet absorber B, 20 mass%-40 mass% are more preferable.
The resin can be appropriately selected from the resins described above.
Examples of the other components include solvents; additives such as dispersants, foam inhibitors, preservatives, antifreeze agents, and surfactants.

There is no restriction | limiting in particular as a formation method, The said short wave ultraviolet absorption layer can be formed in accordance with a well-known method, For example, it can form suitably by the apply | coating method using the said resin composition.
Examples of the coating method include blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, U comma coating method, AKKU coating method, Examples thereof include a smoothing coating method, a micro gravure coating method, a reverse roll coating method, a four or five roll coating method, a dip coating method, a falling curtain coating method, a slide coating method, and a die coating method.
There is no restriction | limiting in particular in the thickness of the said short wave ultraviolet absorption layer, According to the objective, it can select suitably, 10 micrometers-50 micrometers are preferable, and 20 micrometers-40 micrometers are more preferable.

-Infrared shielding layer-
The infrared blocking layer is a transparent layer made of at least one of a metal oxide and a metal having an infrared blocking function and a binder resin.
There is no restriction | limiting in particular as a metal oxide or metal which has the said infrared shielding function, According to the objective, it can select suitably. Examples thereof include doped indium oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide, and a composite system of zinc oxide, silver and zinc oxide. These may be used individually by 1 type and may use 2 or more types together.
The binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylic resin, polyester resin, polycarbonate resin, polyurethane resin, melamine resin, alkyd resin, epoxy resin, vinyl chloride resin, or ultraviolet light Examples thereof include a hard curing agent. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular in the thickness of the said infrared shielding layer, According to the objective, it can select suitably, 1.0 micrometer-5.0 micrometers are preferable.

<Second-wave long-wave ultraviolet absorbing laminate>
The long-wave ultraviolet absorbing laminate of the second embodiment has a long-wave ultraviolet absorber-containing support, and at least one short-wave violet absorption layer on the incident light side from the long-wave ultraviolet absorber-containing support, It has other layers as needed.
The long wave ultraviolet absorbing laminate of the second embodiment preferably has an infrared blocking layer between the long wave ultraviolet absorber-containing support and the short wave ultraviolet absorbing layer.
Here, FIGS. 5-6 is schematic which shows an example of the long wave ultraviolet absorption laminated body of the 2nd form of this invention. In FIG. 5, the short wave ultraviolet absorption layer 3 and the long wave ultraviolet absorber containing support 1 ′ are laminated in this order from the incident light side (external light side).
In FIG. 6, the short wave ultraviolet absorption layer 3, the infrared absorption layer 4, and the long wave ultraviolet absorber containing support 1 ′ are laminated in this order from the incident light side (external light side).

-Long wave ultraviolet absorber-containing support-
The long wave ultraviolet absorbent-containing support is the same as the support in the long wave ultraviolet absorbent laminate of the first embodiment except that it contains a long wave ultraviolet absorbent (the ultraviolet absorbent A).
The ultraviolet absorber A can be appropriately selected from those described above. The content of the ultraviolet absorber A in the support is preferably 0.2% by mass to 50% by mass, and more preferably 5.0% by mass to 10.0% by mass.
There is no restriction | limiting in particular as a method of making the said ultraviolet absorber A contain in a support body, It can select suitably according to the objective, For example, the method of melt-kneading a polyethylene terephthalate and the said ultraviolet absorber A at 200 degreeC or more, etc. Is mentioned.

-Shortwave UV absorbing layer-
It is the same as the short wave ultraviolet absorption layer in the long wave ultraviolet absorption laminate of the first embodiment.

-Infrared shielding layer-
This is the same as the infrared ray blocking layer in the long wave ultraviolet absorbing laminate of the first embodiment.

<Application>
The long wave ultraviolet absorbing laminate of the present invention has significantly improved light resistance, so it can be used in various applications where long wave ultraviolet absorption is required, but is particularly likely to be exposed to sunlight or light containing ultraviolet light. UV protection film for building materials such as general detached houses, apartment houses, office screws, stores, public facilities, factory facilities and other building openings, partitions, etc .; automobiles, buses, etc. UV protection film for window glass for various vehicles such as trucks, trains, bullet trains, airplanes, passenger planes, ships, etc., various marking plates, diffusion sheets, prism sheets, polarizing reflection sheets, optical sheets, magnetic material supports, image formation It can be widely used for a material support.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In addition, the ratio of the absorbance at 320 nm with respect to the maximum absorption wavelength, the full width at half maximum, and the maximum absorption wavelength of each ultraviolet absorber used in Examples and Comparative Examples is a concentration of 5 × 10 ⁻⁵ mol · dm ⁻³ for each ultraviolet absorber. An ethyl acetate solution was prepared, and a UV spectrum was measured using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation in a 1 cm quartz cell. From the obtained spectrum chart, the maximum absorption wavelength, the half width, and the ratio of absorbance at 320 nm to the maximum absorption wavelength were calculated.

Example 1
<Manufacture of long wave UV absorbing laminate>
-Formation of a long-wave ultraviolet absorbing layer-
The following long wave ultraviolet absorbing layer coating solution is bar coated on a polyethylene terephthalate (PET) film (Fuji Film Co., Ltd.) having a thickness of 188 μm as a support, and dried at 120 ° C. for 7 minutes to form a 30 μm thick long wave ultraviolet absorbing layer. Formed.
[Composition of long wave UV absorbing layer coating solution]
· Methyl ethyl ketone · · · 40 parts by mass · Methoxypropyl acetate · · · 10 parts by mass · Acrylic resin (Dianar BR-106, manufactured by Mitsubishi Rayon Co., Ltd.) · 10 parts by mass · UV absorber represented by the following formula A (maximum absorption wavelength 375 nm, half-value width 35 nm, molar extinction coefficient 27,300 at maximum absorption wavelength, manufactured by FUJIFILM Corporation) 2.5 parts by mass

-Formation of shortwave ultraviolet absorption layer-
The following shortwave ultraviolet absorbing layer coating solution was bar coated on the longwave ultraviolet absorbing layer provided on the support and dried at 120 ° C. for 7 minutes to form a 30 μm thick shortwave ultraviolet absorbing layer. The long wave ultraviolet absorption laminated body of Example 1 was produced by the above.
[Composition of short wave UV absorbing layer coating solution]
· Methyl ethyl ketone · · · 40 parts by mass · Methoxypropyl acetate · · · 10 parts by mass · Acrylic resin (Dianar BR-106, manufactured by Mitsubishi Rayon Co., Ltd.) · 10 parts by mass · UV absorber represented by the following formula B (Uvinul 3039, manufactured by BASF Japan Ltd., absorbance at maximum absorption wavelength 304 nm, 320 nm is 76.9% of absorbance at maximum absorption wavelength) 2.5 parts by mass

(Example 2)
-Fabrication of long-wave ultraviolet absorbing laminate-
In Example 1, a long wave ultraviolet ray was formed in the same manner as in Example 1 except that a short wave ultraviolet ray absorbing layer having a thickness of 30 μm was formed on the surface on which the long wave ultraviolet ray absorbing layer was not provided. An absorbent laminate was prepared.

(Comparative Example 1)
In Example 1, the long wave ultraviolet absorber of the comparative example 1 was produced like Example 1 except not having provided the short wave ultraviolet absorption layer.

  Next, for Examples 1 and 2 and Comparative Example 1, the transmittances at 400 nm, 420 nm, and 550 nm were measured as follows. The results are shown in Tables A to C.

<Measurement of transmittance>
Using a metal halide tester (Iwasaki Electric Co., Ltd., iSuper), the transmittance at 400 nm, 420 nm, and 550 nm after irradiation for 0 hours, 100 hours, and 200 hours at in-machine conditions of 63 ° C. and 50% RH. Measured and evaluated according to the following criteria.
[Evaluation criteria at 400 nm]
○: Increase / decrease with respect to transmittance at 0 hour is 1% or less Δ: Increase / decrease with respect to transmittance at 0 hour is 3% or less ×: Increase / decrease in transmittance at 0 hour is greater than 3%

[Evaluation criteria at 420 nm]
○: Increase / decrease with respect to transmittance at 0 hour is 1% or less Δ: Increase / decrease with respect to transmittance at 0 hour is 5% or less ×: Increase / decrease with respect to transmittance at 0 hour is greater than 5%

[Evaluation criteria at 550 nm]
○: Increase / decrease with respect to transmittance at 0 hour is 1% or less Δ: Increase / decrease with respect to transmittance at 0 hour is 5% or less ×: Increase / decrease with respect to transmittance at 0 hour is greater than 5%

  Since the light resistance of the long wave ultraviolet absorbing laminate of the present invention is drastically improved, in particular, UV protection films such as glass for building materials and window glass for vehicles, various marking plates, diffusion sheets, prism sheets, polarizing reflection sheets, etc. It is suitably used for various applications such as optical sheets, magnetic material supports, and image forming material supports.

FIG. 1 is a view showing absorption spectra of ultraviolet absorbers A and B used in the present invention. FIG. 2 is a schematic view showing an example of the long-wave ultraviolet absorbing laminate according to the first embodiment of the present invention. FIG. 3 is a schematic view showing another example of the long wave ultraviolet absorbing laminate of the first embodiment of the present invention. FIG. 4 is a schematic view showing another example of the long wave ultraviolet absorbing laminate of the first embodiment of the present invention. FIG. 5 is a schematic view showing an example of a long wave ultraviolet absorbing laminate according to the second embodiment of the present invention. FIG. 6 is a schematic view showing another example of the long wave ultraviolet absorbing laminate according to the second embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support body 1 'Long wave ultraviolet absorber containing support body 2 Long wave ultraviolet absorption layer 3 Short wave ultraviolet absorption layer 4 Infrared shielding layer 10 Long wave ultraviolet absorption laminated body

Claims (6)

A support;
Resin composition containing at least one ultraviolet absorber A having a maximum absorption wavelength of 350 nm or more and 400 nm or less, a half width of 55 nm or less, and a molar extinction coefficient at the maximum absorption wavelength of 20,000 or more, and a resin A long wave ultraviolet absorbing layer comprising:
A resin containing at least one ultraviolet absorber B having a maximum absorption wavelength of 350 nm or less and an absorbance at 320 nm of 30% or more of the absorbance at the maximum absorption wavelength on the incident light side from the long wave ultraviolet absorption layer, and a resin A long-wave ultraviolet absorbing laminate comprising a short-wave ultraviolet absorbing layer made of a composition.   The long-wave ultraviolet absorbing laminate according to claim 1, wherein an infrared blocking layer is provided between the support and the short wave ultraviolet absorbing layer, or the support has an infrared blocking function. Long wave ultraviolet absorber-containing support comprising at least one ultraviolet absorber A having a maximum absorption wavelength of 350 nm or more and 400 nm or less, a half width of 55 nm or less, and a molar extinction coefficient at the maximum absorption wavelength of 20,000 or more Body,
At least one ultraviolet absorber B having a maximum absorption wavelength of 350 nm or less and an absorbance at 320 nm of 30% or more of the absorbance at the maximum absorption wavelength, and a resin, on the incident light side from the long wave ultraviolet absorber-containing support. A long-wave ultraviolet absorbing laminate comprising at least one short-wave ultraviolet absorbing layer made of a resin composition.   The long wave ultraviolet absorption laminated body of Claim 3 which has an infrared rays shielding layer between a long wave ultraviolet absorber containing support body and a short wave ultraviolet absorption layer. The long wave ultraviolet absorption laminate according to any one of claims 1 to 4, wherein the ultraviolet absorber A is a compound represented by the following general formula (1).
However, the general formula (1), A ₂₁ and A ₂₂ represents a hydrogen atom and atoms other than carbon atoms. Y ₂₁ and Y ₂₂ each independently represent a hydrogen atom or a monovalent substituent. However, at least one of Y ₂₁ or Y ₂₂ represents a substituent having a Hammett's substituent constant σp value of 0.2 or more. Y ₂₁ and Y ₂₂ may be bonded to each other to form a ring. (B) represents an atomic group necessary for forming a 5- or 6-membered ring together with A ₂₁ , A ₂₂ and a carbon atom. The long wave ultraviolet absorption laminate according to any one of claims 1 to 5, wherein the ultraviolet absorber B is a compound represented by the following formula (2).