JP6668091B2 - UV absorber and resin member using the same - Google Patents

Description

  The present invention relates to an ultraviolet absorber added to a matrix such as a resin and a resin member using the same.

  Conventionally, the harmfulness of ultraviolet rays to resins and human bodies has been known.

  The resin member is deteriorated by the action of ultraviolet rays, causing quality deterioration such as discoloration and reduction in mechanical strength, and hindering long-term use. In order to prevent such quality deterioration or to control the wavelength of transmitted light, it is common practice to mix an inorganic or organic ultraviolet absorber in the resin member.

  Ultraviolet rays also act on the skin, causing spots, freckles, wrinkles, and skin cancer. In order to prevent such effects on the skin, it is common practice to add an inorganic or organic ultraviolet absorber to cosmetics and sunscreens.

  Inorganic UV absorbers have excellent durability, such as weather resistance and heat resistance, but have a low degree of freedom in selection because the absorption wavelength is determined by the band gap of the compound. Few can absorb light in the ultraviolet (UV-A, 315 to 400 nm) region, and those that absorb long-wave ultraviolet light absorb a large amount of light having a wavelength in the range of 400 to 500 nm (visible region), and thus are accompanied by coloring.

  On the other hand, organic UV absorbers have a high degree of freedom in the structural design of the absorber, so that various types of absorption wavelengths can be obtained by devising the structure of the absorber. Conventionally, as an organic ultraviolet absorber, a triazine-based, benzotriazole-based, benzophenone-based, cyanoacrylate-based, salicylate-based ultraviolet absorber, and the like have been known (for example, Patent Documents 1 to 4).

JP 2013-67811 A JP 2012-184168 A JP-T-2005-504047 Japanese Patent Publication No. 6-505744 PCT / JP2015 / 72284

  However, in the case of optical materials such as optical films and optical molded products, and various coating agents, in addition to exhibiting a shielding effect up to the UV-A region, the visible light absorption of the ultraviolet absorber is considered from the viewpoint of obtaining a transparent appearance. It has been desired to suppress yellowing coloring caused by the above.

  Optical materials, transparent resin members such as coating agents are desired to be transparent after molding or over time in use, and from the viewpoint of preventing opacity and deterioration of optical characteristics caused by discoloration due to ultraviolet deterioration, and Also, in the application from the viewpoint of health care for skin and the like, there is a need for a drug that efficiently absorbs light having a long wavelength of 360 to 400 nm even in UV-A. However, in order to sufficiently absorb light having a wavelength in the UV-A region of 360 to 400 nm, a conventional ultraviolet absorber has a low absorption efficiency in the wavelength region and requires a large amount of addition. Due to its characteristics, it also absorbs a large amount of light in the visible light region having a wavelength longer than about 400 nm. For example, there is a problem that the resin turns yellow when used in a resin component. On the other hand, even with an ultraviolet absorbent that sufficiently absorbs the UV-A region up to 400 nm, there is also a problem that the resin member also absorbs a large amount of light in the visible light region having a longer wavelength than around 400 nm, and the resin member turns yellow. Was.

  In addition, when the amount of the ultraviolet absorber added is large, the problem of cost or the compatibility with the matrix resin is restricted, and it becomes difficult to uniformly dissolve at a high concentration, or white turbidity is caused to increase the transparency. It may be damaged. Therefore, in applications where high transparency is required or applications where use under severe conditions is anticipated, it has been desired to sufficiently exhibit the required ultraviolet absorption performance even with a small amount of addition.

  Many conventional organic UV absorbers do not have a well-balanced three of the above-mentioned three factors: absorption of ultraviolet rays in the long wavelength region, suppression of yellowing, and high molar extinction coefficient that can be used with a small amount of addition. .

  On the other hand, when an organic ultraviolet absorber is used to heat and mold and process a resin composition containing the ultraviolet absorber, the ultraviolet absorber thermally decomposes, lowering the ultraviolet absorbing ability of the resin member, and In the case of (1), there is a possibility of impairing the transparency and further contaminating the inside of a molding and processing apparatus, and an organic ultraviolet absorber having more excellent heat resistance is required.

  The present inventors have developed an ultraviolet absorber in which a sulfur-containing group is introduced into a triazine-based ultraviolet absorption skeleton (Patent Document 5). However, in the examples, the introduction position of the sulfur-containing group to the three benzene rings bonded to the triazine skeleton was particularly excellent from the viewpoint of absorbing ultraviolet light in a long wavelength region and suppressing yellowing even with a small amount of addition. No consideration was given to things.

  The present invention has been made in view of the circumstances as described above, and efficiently absorbs ultraviolet light in a long wavelength region of 360 to 400 nm even with a small amount of addition, and obtains a resin member in which yellowing and coloring are suppressed. It is an object of the present invention to provide an ultraviolet absorber excellent in heat resistance and a resin member using the same.

  In order to solve the above problems, the ultraviolet absorber of the present invention has the following formula (I):

（式中、Ｒ^１〜Ｒ^１５はそれぞれ独立に、下記式（i）：

(Wherein, R ^{1 to} R ¹⁵ are each independently the following formula (i):

（式（i）中、Ｒ^１６は芳香族基、不飽和基、硫黄含有基、酸素含有基、リン含有基、脂環式基、及びハロゲン原子から選ばれる１価もしくは２価の基で、水素原子が置換されるか、両端の少なくともいずれかが中断されるか、又は炭素−炭素結合が中断されていてもよい炭素数１〜２０の２価の炭化水素基を示し、Ｒ^１７はｙが２以上の場合はそれぞれ独立に芳香族基、不飽和基、硫黄含有基、酸素含有基、リン含有基、脂環式基、及びハロゲン原子から選ばれる１価もしくは２価の基で、水素原子が置換されるか、両端の少なくともいずれかが中断されるか、又は炭素−炭素結合が中断されていてもよい炭素数１〜２０の２価の炭化水素基を示し、Ｒ^１８は芳香族基、不飽和基、硫黄含有基、酸素含有基、リン含有基、脂環式基、及びハロゲン原子から選ばれる１価のもしくは２価の基で、水素原子が置換されるか、基端が中断されるか、又は炭素−炭素結合が中断されていてもよい炭素数１〜２０の１価の炭化水素基、または水素原子を示す。Ｒ^１６とｙ個のＲ^１７とＲ^１８の総炭素数は６０以下である。ｘは０又は１の整数を示し、ｙは０〜３の整数を示す。）で表わされる１価の硫黄含有基、水素原子、炭素数１〜１０の炭化水素基、芳香族基、不飽和基、硫黄含有基、酸素含有基、リン含有基、脂環式基、及びハロゲン原子から選ばれる１価の基を示す。Ｒ^１〜Ｒ^５、Ｒ^６〜Ｒ^１０、及びＲ^１１〜Ｒ^１５の３つの群から選ばれるいずれか２つの群のうちの１群当たり１〜４個の基が、式（i）で表わされる１価の硫黄含有基である。）で表わされることを特徴としている。

(In the formula (i), R ¹⁶ is a monovalent or divalent group selected from an aromatic group, an unsaturated group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom; A hydrogen atom, a divalent hydrocarbon group having 1 to 20 carbon atoms which may have at least one of both ends interrupted, or an interrupted carbon-carbon bond, and R ¹⁷ is y Is 2 or more, each independently represents a monovalent or divalent group selected from an aromatic group, an unsaturated group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom; A divalent hydrocarbon group having 1 to 20 carbon atoms in which an atom is substituted, at least one of both ends is interrupted, or a carbon-carbon bond may be interrupted, and R ¹⁸ is aromatic Groups, unsaturated groups, sulfur-containing groups, oxygen-containing groups, phosphorus-containing groups, alicyclic groups, and A monovalent or divalent group selected from the group consisting of a hydrogen atom, a hydrogen atom being substituted, a base end being interrupted, or a carbon atom having 1 to 20 carbon atoms which may have an interrupted carbon-carbon bond. A total of carbon atoms of R ¹⁶ and y R ¹⁷ and R ¹⁸ is 60 or less, x is an integer of 0 or 1, and y is an integer of 0 to 3 A) a monovalent sulfur-containing group, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an aromatic group, an unsaturated group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, or an alicyclic group. And a monovalent group selected from a group and a halogen atom. R ^{1 to} R ⁵ , R ^{6 to} R ¹⁰ , and R ^{11 to} R ¹⁵ each have 1 to 4 groups per group out of any two groups selected from the three groups represented by formula (i). Is a monovalent sulfur-containing group. ).

  The resin member of the present invention contains the above-mentioned ultraviolet absorber in the resin of the matrix.

  According to the ultraviolet absorbent of the present invention, it is possible to obtain a resin member that absorbs ultraviolet light in a long wavelength region of 360 to 400 nm and suppresses yellowing and coloring due to the characteristics of the absorption peak. Further, since the molar extinction coefficient is high and the efficiency of ultraviolet absorption in a long wavelength region is high, the amount of addition to a matrix such as a resin can be reduced. Furthermore, it is excellent in heat resistance and can be applied to a high resin processing temperature.

  ADVANTAGE OF THE INVENTION According to the resin member of this invention, it is excellent in the ultraviolet absorption performance of a long wavelength region, and there is little yellowing coloring caused by an ultraviolet absorber. In addition, the transparent resin member has high transparency in addition to them.

It is an ultraviolet-visible absorption spectrum (UV chart) of Examples 1-5. 9 is an ultraviolet-visible absorption spectrum (UV chart) of Comparative Examples 1 to 5.

Hereinafter, the present invention will be described in detail.
The ultraviolet absorbent represented by the above formula (I) introduces a monovalent sulfur-containing group represented by the formula (i) into a triazine-based ultraviolet absorbing skeleton, and converts the tribenzene skeleton into three benzene rings bonded to the triazine skeleton. Are introduced into any two groups selected from three groups of R ^{1 to} R ⁵ , R ^{6 to} R ¹⁰ , and R ^{11 to} R ¹⁵ . By introducing the sulfur-containing group at this specific position, it is possible to obtain a resin member having a high molar absorption coefficient, absorbing ultraviolet rays in a long wavelength region even with a small amount of addition, and suppressing yellowing and coloring. It can also be excellent in properties.

[Substituents, etc.]
In the present invention, “a monovalent or divalent group selected from an aromatic group, an unsaturated group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom” includes a high refractive index. , A group capable of adjusting the heat resistance and compatibility with the resin, a group reacting with the resin and / or a monomer of the resin, and the like. Examples thereof include the following.
(Aromatic group)
The aromatic group contains an aromatic ring such as a benzene ring, a naphthalene ring, and an anthracene ring, and preferably has 6 to 18, and more preferably 6 to 14 carbon atoms. Examples of the monovalent or divalent aromatic group include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, and 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 4-biphenyl group, 1-naphthyl group, 2-methoxyphenyl group , 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-chlorophenyl, 2-fluorophenyl, 4-fluorophenyl, 2- Examples include a trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group.
(Unsaturated group)
The unsaturated group includes a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-oxygen double bond (a carbonyl group, an aldehyde group, a carboxyl group, etc.), a carbon-nitrogen double bond (an isocyanate group, etc.), It contains a carbon-carbon or carbon-heteroatom unsaturated bond such as a nitrogen triple bond (such as a cyano group or a cyanato group), and preferably has 1 to 10, and more preferably 1 to 8 carbon atoms. Examples of the monovalent or divalent unsaturated group include an acryloyl group, a methacryloyl group, a maleic acid monoester group, a styryl group, an allyl group, a vinyl group, an amide group, a carbamoyl group, a cyano group, an isocyanate group, and the like.
(Sulfur-containing group)
The sulfur-containing group includes a thiol group, a sulfide group, a disulfide group, a sulfonyl group, a sulfo group, a thiocarbonyl group, a thiocarbamoyl group, or a thiourea group, and preferably has 0 to 10 carbon atoms. Examples of the monovalent or divalent sulfur-containing group include thiomethoxy, thioethoxy, thio-n-propoxy, thioisopropoxy, thio-n-butoxy, thio-t-butoxy, thiophenoxy, p- Examples include a methylthiophenoxy group, a p-methoxythiophenoxy group, a thiophene group, a thiazole group, a thiol group, a sulfo group, a sulfide group, a disulfide group, a sulfonyl group, a thiocarbonyl group, and a thiourea group.
(Oxygen-containing group)
The oxygen-containing group preferably has 6 to 12 carbon atoms when it contains an aromatic or alicyclic group, and preferably has 0 to 6 carbon atoms when it contains no aromatic or alicyclic group. is there. Examples of the monovalent or divalent oxygen-containing group include hydroxy, methoxy, ethoxy, propoxy, butoxy, phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy, phenylmethoxy, phenylethoxy, and acetoxy. Groups, acetyl group, aldehyde group, carboxyl group, carbamoyl group, urea group, ether group, carbonyl group, ester group, oxazole group, morpholine group and the like.
(Phosphorus-containing group)
The phosphorus-containing group includes a phosphine group, a phosphite group, a phosphonic acid group, a phosphinic acid group, a phosphoric acid group, or a phosphoric acid ester group. 6 to 22, when it does not contain an aromatic ring group or an alicyclic group, it preferably has 0 to 6 carbon atoms. Examples of the monovalent or divalent phosphorus-containing group include a trimethylphosphine group, a tributylphosphine group, a tricyclohexylphosphine group, a triphenylphosphine group, a tolylphosphine group, a methylphosphite group, an ethylphosphite group, and a phenylphosphite group. Examples include a phosphonic acid group, a phosphinic acid group, a phosphoric acid group, and a phosphoric ester group.
(Alicyclic group)
The alicyclic group preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. Examples of the monovalent or divalent alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
(Halogen atom)
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
1. Ultraviolet absorber represented by formula (I) The ultraviolet absorber represented by formula (I) contains a trivalent skeleton containing a monovalent sulfur-containing group represented by formula (i).

In the formula (i), R ¹⁶ is a monovalent or divalent group selected from an aromatic group, an unsaturated group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom. A divalent hydrocarbon group having 1 to 20 carbon atoms, in which an atom is substituted, at least one of both ends is interrupted, or a carbon-carbon bond may be interrupted.

Examples of the divalent hydrocarbon group for R ¹⁶ include a linear or branched alkylene group, a linear or branched alkenylene group, and a linear or branched alkynylene group. Specifically, for example, methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, 1-methylethane-1,2-diyl group, butane-1,4-diyl group, butane- 1,3-diyl group, 2-methylpropane-1,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, hexane-1,6-diyl group, heptane-1, 7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-yl group, tetradecane-1,14-yl group, pentadecane-1,15-yl group, hexadecane-1,16-yl group, heptadecane-1,17-yl group, octadecane-1,18 -Yl group, nonadeca -1,19- yl group, eicosane -1,20- yl group. Among these, an alkylene group is preferable, and a linear alkylene group is more preferable.

When the divalent hydrocarbon group for R ^{16 is} the monovalent or divalent group, the hydrogen atom is substituted, the base is interrupted, or the carbon-carbon bond is interrupted. The number of divalent or divalent groups is preferably 2 or less, more preferably 1 or less, and particularly preferably 0.

  Specific examples of the monovalent or divalent aromatic group, unsaturated group, sulfur-containing group, oxygen-containing group, phosphorus-containing group, alicyclic group, and halogen atom include the above-mentioned [Substituents and the like]. The following are examples.

In the formula (i), when y is 2 or more, R ¹⁷ is independently selected from an aromatic group, an unsaturated group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom. A monovalent or divalent group is substituted with a hydrogen atom, at least one of both ends is interrupted, or a divalent carbon atom having 1 to 20 carbon atoms which may have an interrupted carbon-carbon bond. Shows a hydrogen group.

As the divalent hydrocarbon group for R ¹⁷ , those exemplified above for the divalent hydrocarbon group for R ¹⁶ can be mentioned. Among these, an alkylene group is preferable, and a linear alkylene group is more preferable.

When the divalent hydrocarbon group represented by R ^{17 is} the monovalent or divalent group, the hydrogen atom is substituted, the base is interrupted, or the carbon-carbon bond is interrupted. The number of divalent or divalent groups is preferably 2 or less, more preferably 1 or less, and particularly preferably 0.

  Specific examples of the monovalent or divalent aromatic group, unsaturated group, sulfur-containing group, oxygen-containing group, phosphorus-containing group, alicyclic group, and halogen atom include the above-mentioned [Substituents and the like]. The following are examples.

In the formula (i), R ¹⁸ is a monovalent or divalent group selected from an aromatic group, an unsaturated group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom. A monovalent hydrocarbon group having 1 to 20 carbon atoms, in which an atom may be substituted, a base end is interrupted, or a carbon-carbon bond is interrupted, or a hydrogen atom.

Examples of the monovalent hydrocarbon group represented by R ¹⁸ include a linear or branched alkyl group, a linear or branched alkenyl group, and a linear or branched alkynyl group. Specifically, for example, methyl group, ethane-1-yl group, propan-1-yl group, 1-methylethane-1-yl group, butan-1-yl group, butan-2-yl group, 2-methyl Propan-1-yl group, 2-methylpropan-2-yl group, pentan-1-yl group, pentan-2-yl group, hexane-1-yl group, heptane-1-yl group, octane-1-yl Group, nonan-1-yl group, decane-1-yl group, undecane-1-yl group, dodecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecane-1-yl group Hexadecan-1-yl group, heptadecane-1-yl group, octadecane-1-yl group, nonan-1-yl group, eicosan-1-yl group and the like. Among these, an alkyl group is preferable, and a linear alkyl group is more preferable.

When the monovalent hydrocarbon group for R ¹⁸ is the above monovalent or divalent group, the hydrogen atom is substituted, the base is interrupted, or the carbon-carbon bond is interrupted, Is preferably 2 or less, more preferably 1 or less, and particularly preferably 0.

  Specific examples of the monovalent or divalent aromatic group, unsaturated group, sulfur-containing group, oxygen-containing group, phosphorus-containing group, alicyclic group, and halogen atom include the above-mentioned [Substituents and the like]. The following are examples.

In the formula (i), x represents an integer of 0 or 1, and y represents an integer of 0 to 3, preferably 0 or 1. In the formula (i), the total carbon number of R ¹⁶ and y R ¹⁷ and R ¹⁸ is 60 or less, preferably 36 or less, more preferably 24 or less, and particularly preferably 16 or less. Among these, it is possible to obtain a resin member that absorbs ultraviolet rays in a long wavelength region and suppresses yellowing coloring even with a small amount of addition, and can be excellent in heat resistance. Then, in the monovalent sulfur-containing group represented by the formula (i), R ¹⁶ and y R ¹⁷ each include an alkylene group having 18 or less carbon atoms, and R ¹⁸ is an alkyl group having 18 or less carbon atoms. It is preferred to include. Further, it is preferable that R ¹⁶ and y R ¹⁷ and R ¹⁸ are all linear, and each of R ¹⁶ , R ¹⁷ and R ¹⁸ has 1 to 18 carbon atoms (here, x = 0 And y = 0.) Among these, an embodiment in which x = 0 and y = 0 is one of preferred embodiments.

In the formula (I), when R ^{1 to} R ¹⁵ are groups other than the monovalent sulfur-containing group represented by the formula (i), a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an aromatic group, It represents a monovalent group selected from a saturated group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom.

When R ^{1 to} R ¹⁵ are a monovalent hydrocarbon group, examples of the monovalent hydrocarbon group include a linear or branched alkyl group, a linear or branched alkenyl group, and a linear or branched alkynyl group. Is mentioned. Specifically, for example, methyl group, ethane-1-yl group, propan-1-yl group, 1-methylethane-1-yl group, butan-1-yl group, butan-2-yl group, 2-methyl Propan-1-yl group, 2-methylpropan-2-yl group, pentan-1-yl group, pentan-2-yl group, hexane-1-yl group, heptane-1-yl group, octane-1-yl Group, nonan-1-yl group, decane-1-yl group and the like. Among these, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable.

When R ^{1 to} R ¹⁵ are a monovalent group selected from an aromatic group, an unsaturated group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom, specific examples thereof include And the above-mentioned [substituents and the like].

Among these, at least ^one of R ^{1 to} R ¹⁵ other than the monovalent sulfur-containing group represented by the formula (i) is selected from an alkyl group having 1 to 4 carbon atoms, a hydroxy group, and a halogen atom. The species embodiment is one of the preferred embodiments.

In the formula (I), 1 to 4 groups per group of any two groups selected from three groups of R ^{1 to} R ⁵ , R ^{6 to} R ¹⁰ , and R ^{11 to} R ¹⁵ are represented by the following formula: It is a monovalent sulfur-containing group represented by the formula (i). The 1-4 groups in each of the two groups may be the same or different.

The position of the monovalent sulfur-containing group represented by the formula (i) in the formula (I) is not particularly limited, and examples thereof include R ³ , R ⁸ , and R ¹³ .

  The ultraviolet absorber of the formula (I) has a high solubility in a resin monomer, does not precipitate on the surface even when processed into a resin member, has high transparency, and has a wavelength region from 250 to 400 nm from its optical characteristics. Light can be sufficiently absorbed. In addition, the ultraviolet absorption effect (molar extinction coefficient) is high, and the addition of a small amount can sufficiently absorb the wavelength light, and the slope of the absorption peak at 360 to 400 nm in a chloroform solution is larger than that of a conventional ultraviolet absorber. Yellowing of the resin member can be suppressed.

  In order to efficiently absorb light having a wavelength in the range of 360 nm to 400 nm in the UV-A region, particularly in the long wavelength region, and to suppress yellowing and obtain a resin member having excellent appearance, a long wavelength region (360 to 400 nm) absorption effect is required. It is necessary to consider the yellow suppression effect and ultraviolet absorption effect.

In order to efficiently absorb light having a longer wavelength of 360 to 400 nm even in the UV-A region, the absorption peak of the maximum absorption wavelength exists in the longer wavelength region, and the larger the peak area of 360 to 400 nm is, the better. good. Therefore, it is preferable that the absorption peak of light in the 315 to 400 nm region of the 5 μM chloroform solution is at a maximum absorption wavelength (λ _max ) of 370 to 400 nm. The peak area at 360 to 400 nm in the long wavelength region is preferably 7 or more. In addition, when added to a resin member, in order to further suppress absorption in the visible region and suppress yellowing, it is not preferable that the absorption peak in the 315 to 400 nm region is too close to 400 nm. Therefore, the absorption spectrum of the 5 μM chloroform solution in the 315 to 400 nm region is preferably 390 nm or less, and the peak is better when the peak is sharp (the absolute value of the slope is larger), and the slope of the absorption peak on the longer wavelength side (absorption peak) (The absolute value of the slope of the straight line connecting the peak end of the absorption spectrum on the long wavelength side to the peak end: see FIG. 1, Example section described later) is preferably 0.003 or more. From such optical characteristics, the peak area in the visible region of 400 to 450 nm is preferably 1 or less.

Further, in order to efficiently absorb a small amount, the molar absorption coefficient of the absorption peak of above 315 to 400 nm (maximum molar extinction coefficient: epsilon _.lambda.max) is, 40000L / (mol · cm) or more.

That is, in order to efficiently absorb light having a wavelength of 360 to 400 nm in a long wavelength region and to suppress yellowing when added to a resin member, the absorption peak of light in a region of 315 to 400 nm in a 5 μM chloroform solution has a maximum absorption. The wavelength (λ _max ) is between 370 and 390 nm, the slope is 0.003 or more, the molar extinction coefficient is 40000 or more, the peak area at 360 to 400 nm is 7 or more, and the peak area at 400 to 450 nm is 1 or less. Is preferred.

Further, a compound in which an electron-withdrawing group, for example, a halogen atom is bonded to the positions of R ^{1 to} R ¹⁵ , shifts to a longer wavelength within a range where the maximum absorption peak at 315 to 400 nm is 390 nm or less from the viewpoint of yellow suppression effect. In addition, it is possible to further increase the peak area and the molar extinction coefficient in the long wavelength region (360 to 400 nm), and to increase the absorption efficiency in the long wavelength region (360 to 400 nm). Further, a compound in which a monovalent sulfur-containing group or a hydrogen atom represented by the formula (i) is bonded to the positions of R ^{1 to} R ¹⁵ has a smaller peak area at 400 to 450 nm, and further suppresses yellowing. To make things possible.

  The ultraviolet absorber of the present invention exhibits an ultraviolet absorbing ability by a triazine-based ultraviolet absorbing skeleton, has an ultraviolet absorption band around 250 to 400 nm, cuts a wavelength in an ultraviolet region, and transmits a wavelength in a visible light region. . There is a need for an ultraviolet absorber capable of absorbing up to the UV-A region (315 to 400 nm), which has an effect on the photodegradation of any organic substance, but the ultraviolet absorber of the present invention has excellent UV-absorbing ability in the UV-A region, It is also possible to efficiently cut ultraviolet rays up to a region near 400 nm. The ultraviolet absorber of the present invention in which a thioether group (i) is introduced into a triazine-based compound suppresses absorption of light having a wavelength of 400 to 450 nm (visible region), shifts significantly to longer wavelengths, and is more effective in the UV-A region. It is possible to efficiently cut off ultraviolet rays having a long wavelength near 360 to 400 nm.

  The ultraviolet absorber of the present invention can maintain the transparency of the resin when added to the resin, and since the ultraviolet absorber of the present invention has excellent heat resistance, the resin member containing the same can be subjected to heat molding. Since it is difficult to be thermally decomposed in the process of processing, a resin member which does not impair the appearance and does not reduce the ultraviolet absorbing ability and high refractive index of the resin member, and a transparent resin member which has high transparency can be obtained.

On the other hand, R ^{1 to} R ¹⁵ , polymerization of carbon-carbon double bond, vinyl group, vinyloxy group, allyl group, (meth) acryloyl group, maleoyl group, styryl group, cinnamoyl group and the like to the thioether group of formula (i) The ultraviolet absorber of the present invention represented by the formula (I) having a reactive functional group such as a hydroxyl group, a thiol group, a carboxyl group, an amino group and a silyl group, which also contains a reactive functional group and a crosslinkable functional group, (E.g., isocyanate group, epoxy group, carboxylic acid group, carbonyl group, hydroxy group, alkenyl group, alkynyl group, ether group, thioisocyanate group, thioepoxy group, thiocarboxylate group, thiocarbonyl group, thiol group) Group)), a reaction, copolymerization and molding process using a raw monomer and resin for the film and resin member containing In this case, the above-mentioned ultraviolet absorber reacts with those monomers and copolymerizes or reacts with the functional group of the resin, and is immobilized on the matrix. The function of increasing the refractive index can be maintained for a long time.

  In producing the ultraviolet absorbent represented by the formula (I), reference is made to the disclosure of Examples described later and known techniques.

2. Resin member using the ultraviolet absorbent of the present invention The resin member of the present invention contains the above-described ultraviolet absorbent of the present invention.

  The shape of the resin member of the present invention is not particularly limited, and may be any shape. However, since the resin member can be provided with a high ultraviolet absorbing ability and / or a high refractive index while maintaining transparency, the resin member is laminated. The multilayer structure is simplified, and the manufacturing process and cost can be reduced. Among them, one layer of members having a multilayer structure, a film or sheet having flexibility or flexibility, or a plate-like member having rigidity is preferable, and other optical resins such as optical molded products. Preferably, an optical lens is used.

  The resin member containing the ultraviolet absorbent of the present invention can maintain the transparency of the resin, and since the ultraviolet absorbent of the present invention has excellent heat resistance, heat molding and processing the resin member containing the same. Since it is difficult to be thermally decomposed in the process, it is possible to obtain a resin member which does not lose its appearance and does not decrease the ultraviolet absorbing ability and high refractive index of the resin member, and a transparent member which has high transparency.

Further, the transparent resin member containing the ultraviolet absorbent of the present invention represented by the formula (I) allows absorption of a wavelength in a long wavelength region while suppressing yellowing from the characteristic of the peak of the ultraviolet absorption. Further, R ^{1 to} R ¹⁵ , the resin member containing the ultraviolet absorbent of the present invention having a reactive functional group such as a thiol group, a vinyl group, or a hydroxy group in the thioether group of the formula (i) are contained in the ultraviolet absorbent. Functional groups (e.g., isocyanate group, epoxy group, carboxylic acid group, carbonyl group, hydroxy group, alkenyl group, alkynyl group, ether group, thiol group, vinyl group, hydroxy group) When reacting and molding using a raw material monomer and a resin for a film and a resin member containing an isocyanate group, a thioepoxy group, a thiocarboxylate group, a thiocarbonyl group, a thiol group, etc., the obtained resin has the above-mentioned ultraviolet absorption. The agent reacts with those monomers, functional groups of the resin, is immobilized on the matrix, without bleeding out, Ultraviolet absorption capacity of respectively, can be maintained for a long time the function of increasing index of refraction.

  The transparent resin member containing the ultraviolet absorbent of the present invention maintains transparency, and further suppresses absorption of 400 to 500 nm (visible region) from the characteristic of the ultraviolet absorbing ability of the ultraviolet absorbent. It is possible to sharply cut ultraviolet light having a long wavelength of about 360 to 400 nm. For this reason, a resin member having excellent appearance in which yellowing is suppressed is obtained.

  Although the resin member of the present invention is not particularly limited, for example, acrylic resin such as poly (methyl) acrylate, poly (ethyl) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, etc. , Polyethylene, polypropylene, polymethylpentene, polyolefin resins such as cyclic olefin polymers, polycarbonate resins, thermoplastic polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polyurethane, polythiourethane, polystyrene, polyamide, polyimide, acrylonitrile- Cellulose resins such as styrene copolymer, polyether sulfone, polysulfone, and triacetyl cellulose, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl pyrrolidone, polyvinyl chloride, and polysalt Thermoplastic resins such as vinylidene, polyetheretherketone, polyacetal, nylon, thermosetting resins such as urethane, thiourethane, urea, melamine, acrylic melamine, episulfide, epoxy, allyl, silicone, phenol, urea, and unsaturated polyester; Acrylics, for example, monofunctional or polyfunctional (meth) acrylate compounds such as acrylic acid or 2-hydroxyethyl methacrylate or methacrylate of polyhydric alcohol, diisocyanate and polyhydric alcohol and hydroxy ester of acrylic acid or methacrylic acid, etc. Polyfunctional urethane (meth) acrylate compounds synthesized from acrylate-based polyethers, polyesters, epoxies, alkyds, spiroacetals, polybutadienes, polyethers They include ultraviolet curable resins, such as thiol polyene.

Although the resin member of the present invention is not particularly limited, for example, it can be manufactured by the following methods (1) to (4).
(1) A method of applying a coating solution containing the ultraviolet absorbent and a resin or a raw material monomer of the present invention to a substrate, heating, irradiating with ultraviolet light or drying to form a film.
(2) A method of kneading and kneading the ultraviolet absorbent of the present invention with a resin or a raw material monomer, and forming and forming a film using an extruder or the like.
(3) A method of incorporating the ultraviolet absorbent of the present invention into a resin adhesive and applying the resin adhesive to a film
(4) A method of dissolving the ultraviolet absorbent of the present invention in a raw material monomer, casting the mixture in a mold or glass mold, heating, curing by ultraviolet irradiation or drying, and molding.

  Among these methods, the method of applying (1) the coating solution containing the ultraviolet absorbent of the present invention and a resin or a raw material monomer to form a film is from the viewpoint of obtaining a transparent multilayer structure, film, or sheet. It is suitable in the present invention.

  In this method, a coating solution is prepared by diluting the ultraviolet absorbent of the present invention and a resin or a raw material monomer with or without dilution in an organic solvent or an aqueous solvent, and is applied to a substrate to form a film. If necessary, drying, cooling, heating and UV irradiation are performed to improve the film strength.

  The resin is not particularly limited and, for example, a film or a member having a functional optical layer may be appropriately selected in consideration of necessary physical properties such as adhesion to a substrate and hardness. it can. Specifically, an ultraviolet curable resin, an electron beam curable resin, a thermosetting resin, a thermoplastic resin, and the like can be given. More specifically, polyester resin, acrylic resin, urethane resin, thiourethane resin, polyethylene terephthalate resin, polystyrene resin, polycarbonate resin, urea resin, melamine resin, acrylic melamine resin, epoxy resin, alkyd resin, spiro acetal resin, polybutadiene Resins, polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, modified polyvinyl resins (PVB, EV, etc.), silicone resins, polyamide resins, polyether resins, episulfide resins, nylon resins, and copolymer resins thereof.

  For a film or a member having a functional optical layer, an ultraviolet curable resin, an electron beam curable resin, a thermosetting resin, a thermoplastic resin, or the like can be used. A coating solution containing these resins is applied to a transparent substrate to form a coating film, and the coating film is subjected to a drying treatment as necessary. Then, a transparent optical layer can be formed by irradiating or heating an ultraviolet-ray or an electron beam to a coating film, and performing a hardening reaction.

  An acrylic material can be used as the ultraviolet-curable resin. As the acrylic material, for example, a monofunctional or polyfunctional (meth) acrylate compound such as acrylic acid or methacrylic acid ester, a diisocyanate and a polyhydric alcohol, and a hydroxyester of acrylic acid or methacrylic acid can be used. Polyfunctional urethane (meth) acrylate compounds can be used. In addition, other than these, a polyether resin having an acrylate-based functional group, a polyester resin, an epoxy resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiolpolyene resin, and the like can also be used.

  When using an ultraviolet curable resin, a photopolymerization initiator is added to the coating liquid. Any photopolymerization initiator may be used as long as it generates radicals when irradiated with ultraviolet rays. For example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like can be used.

  As the thermosetting resin, for example, urethane resin, thiourethane resin, melamine resin, acrylic melamine resin, urea resin, phenol resin, epoxy resin, episulfide resin and the like can be used.

  As the thermoplastic resin, urethane resin, thiourethane resin, polyethylene terephthalate resin, polystyrene resin, polycarbonate resin, polyester resin, polyethylene resin, polypropylene resin, acrylic resin, nylon resin and the like can be used.

  If necessary, a solvent for dilution may be added to the coating liquid. Examples of the solvent include aromatic hydrocarbons such as toluene, xylene, cyclohexane and cyclohexylbenzene; hydrocarbons such as n-hexane; dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, dioxane, and dioxolane. , Trioxane, tetrahydrofuran, anisole, phenetole, and other ethers; methyl isobutyl ketone, methyl butyl ketone, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone, and other ketones; Ethyl, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate, γ-butyrolact Esters and the like; methyl cellosolve, cellosolve, butyl cellosolve, cellosolve such as cellosolve acetate; alcohols such as methanol, ethanol, and isopropyl alcohol; water and the like.

  If necessary, an ultraviolet absorber such as an antifoaming agent, a leveling agent, an antioxidant, a light stabilizer, a polymerization inhibitor, a catalyst, a dye, and a pigment may be added to the coating liquid.

  The amount of the ultraviolet absorbent used in the present invention is not particularly limited in consideration of the ultraviolet absorbing ability, high refractive index, transparency, etc., depending on the purpose, but excludes volatile components such as solvents. 0.01 wt%, 0.1 wt% or more, 10 wt% or more, 30 wt% or more, or 50 wt% or more can be added to the total amount of the coating liquid.

  The prepared coating liquid is applied to the substrate by an appropriate method such as a bar coater, a gravure coater, a comma coater, a lip coater, a curtain coater, a roll coater, a blade coater, a spin coater, a reverse coater, a die coater, a spray, and dipping. be able to.

  The substrate for coating is not particularly limited, and examples thereof include a resin plate, a resin film, a resin sheet, glass, and a building material.

  When the resin member of the present invention is used as a part of a film or a member having a functional optical layer such as an antireflection film, as a base material for coating, optical properties such as transparency and refractive index of light, Further, the material can be selected in consideration of various physical properties such as impact resistance, heat resistance, and durability. Examples of such a material include, but are not particularly limited to, poly (methyl) acrylate, poly (ethyl) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, and the like. Acrylic resin, polyethylene, polypropylene, polymethylpentene, polyolefin resin such as cyclic olefin polymer, polycarbonate resin, thermoplastic polyester resin such as polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polystyrene, acrylonitrile-styrene copolymer , Polyethersulfone, polysulfone, cellulose resins such as triacetylcellulose, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyether ether ketone, polyurethane A thermoplastic resin material such as tan or soda glass, potash glass, (including ceramic) glasses such as lead glass, quartz, fluorite, and the light-transmissive inorganic material such as diamond.

  To these materials, known UV absorbers, for example, UV absorbers, infrared absorbers, high refractive index agents, plasticizers, lubricants, coloring agents, antioxidants, flame retardants and the like may be added.

  The thickness of the substrate when used as a film having a functional optical layer is not particularly limited, but is, for example, 10 nm to 200 μm. Such a base material may be a single layer or a laminate of a plurality of layers.

  Further, among the above-mentioned methods for producing the resin member of the present invention, the method of (2) kneading and kneading the ultraviolet absorbent of the present invention into a resin, and forming and forming into a film by an extruder, etc. An ultraviolet absorber can be manufactured by adding to a resin powder or pellets, heating and dissolving, and then molding.

  The resin powder or pellets are not particularly limited, but include acrylic resins such as poly (methyl) acrylate, poly (ethyl) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, and polyethylene. , Polypropylene, polymethylpentene, polyolefin resins such as cyclic olefin polymers, polycarbonate resins, thermoplastic polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polystyrene, acrylonitrile-styrene copolymer, polyether sulfone , Polysulfone, cellulose resins such as triacetyl cellulose, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinylpyrrolidone, polyvinyl chloride, polyvinylidene chloride, polyether ether ketone Emissions, polyacetal, nylon, a thermoplastic resin material such as polyurethane, and the like.

  The method of molding the resin member is not particularly limited, but an injection molding method, an extrusion molding method, a calendar molding method, a blow molding method, a compression molding method, or the like can be used. When an extruder is used, a resin member can be manufactured by a method of forming a film with an extruder, or forming a raw material with an extruder, and then stretching the film uniaxially or biaxially to form a film. .

  The heat resistance of the ultraviolet absorbent of the present invention is improved by introducing a thioether group. The 5% weight loss temperature of the ultraviolet absorbent of the present invention is 350 ° C. or more, and the softening temperature of general resin is 100 to 250 ° C. (“Plastic well understood”, supervision: Japan Plastics Industry Federation, publishing: Nippon Jitsugyo) Publisher)), it can be applied to thermosetting resins and thermoplastic resins with a molding temperature of 100 to 200 ° C, as well as thermoplastic resins that require a molding temperature of 200 to 250 ° C or higher. Become.

  When kneading, an ultraviolet absorber used for ordinary resin molding such as an infrared absorber, an ultraviolet absorber, a high refractive index agent, an antioxidant, a light stabilizer, a flame retardant, and a plasticizer may be added. .

  Further, among the above methods for producing the resin member of the present invention, in the method of (3) containing the ultraviolet absorbent of the present invention in a resin adhesive and applying the resin adhesive to a film, the resin adhesive is used as a resin adhesive. UV absorbers of the present invention using known transparent adhesives such as generally used silicone-based, urethane-based, acrylic-based, polyvinylbutyral adhesive (PVB), ethylene-vinyl acetate-based, and epoxy-based adhesives By bonding and curing the resin films with each other by using a resin adhesive having added thereto, a composite material including the resin member of the present invention can be manufactured.

  When the resin member of the present invention is used as a part of a film or a member having a functional optical layer, the film thickness is within a range capable of satisfying required physical properties such as the type of resin material, adhesion, and hardness. Although it is not particularly limited as long as it is within the range, for example, it is within the range of 10 nm to 200 μm.

  Further, among the above methods for producing the resin member of the present invention, the ultraviolet absorbent of the present invention (4) is dissolved in a raw material monomer, cast into a mold or a glass mold, heated, cured by ultraviolet irradiation or drying. In the method of molding by molding, in the case of curing by heating, a monomer for a thermosetting resin can be used, and there is no particular limitation, for example, urethane, thiourethane, epoxy, thioepoxy, melamine, silicone, phenol, urea, unsaturated polyester resin Resin raw material monomers that can be produced can be used. After dissolving the ultraviolet absorbent of the present invention in at least one of the resin raw material monomers, mixing other resin monomers necessary for resinification, casting the mixture into a mold or a glass mold, and heating the mixture according to the present invention. The resin member containing the ultraviolet absorbent can be manufactured. An acrylic material can be used as the ultraviolet-curable resin. Examples of the acrylic material include monofunctional or polyfunctional (meth) acrylate compounds such as acrylic acid, 2-hydroxyethyl methacrylate or methacrylic acid ester, diisocyanates and polyhydric alcohols, and hydroxy esters of acrylic acid or methacrylic acid. A polyfunctional urethane (meth) acrylate compound as synthesized can be used. In addition, other than these, a polyether resin having an acrylate-based functional group, a polyester resin, an epoxy resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiolpolyene resin, and the like can also be used.

  The resin member of the present invention can be used for all applications where a synthetic resin is used, and is not particularly limited, but can be particularly preferably used for applications that may be exposed to light including sunlight or ultraviolet rays. . For example, glass substitutes, glass such as window glass, daylighting glass and light source protective glass, coatings and protective agents such as metals and resins, members for light sources emitting ultraviolet rays such as fluorescent lamps and mercury lamps, and containers for foods and chemicals Alternatively, examples thereof include packaging materials, agricultural and industrial sheets, printed matter, dyed matter, dyes and pigments, display plates, indicator lights, fading inhibitors for cards, and the like.

  Among them, the resin member of the present invention, while maintaining the transparency of the matrix, ultraviolet absorbing ability, from the point that it is possible to impart a high refractive index, especially optical materials, especially films and members having a functional optical layer It is suitable for optical molded products.

  As a film or member having a functional optical layer, a single-layer film, a substrate film or a substrate, a multilayer film or a substrate with an optical layer provided with one or more optical layers according to various applications. When a plurality of optical layers are provided, the resin member of the present invention is used for at least one of the optical layers.

  Among films and members having a functional optical layer, the optical film may be a substrate film provided with a functional layer according to various uses on a substrate film, for example, various optical disk substrate protective films, reflective films , An antireflection film, an orientation film, a polarizing film, a polarizing layer protective film, a retardation film, a light diffusion film, a viewing angle improving film, an electromagnetic wave shielding film, an antiglare film, a light shielding film, and a brightness improving film.

  As a member having a functional optical layer, at least one of an antireflection layer, a hard coat layer, an antistatic layer, an adhesion stabilizing layer, a protective layer, an electromagnetic wave shielding layer, an infrared cut layer, etc. And members laminated in one layer or multiple layers.

  Further, the resin member of the present invention is suitable for a surface protective film for a solar cell. A solar cell element usually has a configuration in which an active layer serving as a solar cell is provided between a pair of substrates, but a flexible solar cell is made of a polyester material such as a gas barrier film used as a member thereof, or an organic material. In a solar cell, the active layer itself absorbs ultraviolet rays and is deteriorated, so that an ultraviolet-absorbing protective film is required. In addition, since solar cells are installed outdoors and for many years, such protective films are required to have high weather resistance. Furthermore, since a solar cell absorbs light energy and converts it into electric power, such a protective film is required to have high transparency. That is, a protective film for protecting a flexible solar cell is required to have high transparency, high ultraviolet absorbing ability, high weather resistance, and flexibility, but the resin member of the present invention is suitable for such applications. .

  Further, the resin member of the present invention can be used for optical pickup lenses, optical lenses such as camera lenses and lenticular lenses, prisms, filters, optical substrates such as touch panel substrates and light guide plates, optical fibers, and optical molded products such as information recording substrates. It can be suitably used. Optical lenses include plastic lenses, such as lens films such as Fresnel lens films and lenticular lens films, as well as miniaturized optical functional elements to improve light-condensing and light-diffusing properties, and to condense light to the light-receiving element of the image sensor. It is also suitable for a microlens array using a microlens of a small diameter of several μm used for such purposes.

  Further, the resin member of the present invention is used for a display substrate, for example, a flat panel display substrate such as a liquid crystal display, an organic EL display, a plasma display, a field emission display, and electronic paper or a liquid crystal display, a signal, and a backlight for a neon sign. It is also suitable for substrates and the like.

  When absorbing ultraviolet light of a wide range of wavelengths with a resin member such as a film, it is necessary to use a plurality of ultraviolet absorbers, add the ultraviolet absorber at a high concentration, or make the film or resin thicker. In such a case, problems tend to occur in terms of transparency and coloring. However, the triazine compound having two introduced thioether groups used in the ultraviolet absorber of the present invention has an ultraviolet absorption band in a long wavelength region of 360 to 400 nm and a short wavelength ultraviolet region of 250 to 300 nm, and has a wider range of ultraviolet absorption. And a single ultraviolet absorber can absorb ultraviolet light having a low concentration and a wide range of wavelengths.

  For example, in a light-shielding film, it is desirable to cut ultraviolet rays from 360 to 400 nm. However, a general ultraviolet absorber cuts most of the wavelength light in the range of 400 to 500 nm (visible region), so that visible light is reduced. There was a problem of fading or discoloration. However, the ultraviolet absorber of the present invention in which a thioether group (i) is introduced into a triazine-based compound suppresses absorption of light having a wavelength of 400 to 500 nm (visible region), and even at 315 to 400 nm (UV-A region). It is possible to cut out ultraviolet rays having a long wavelength of 360 to 400 nm, which is highly useful.

  Further, the ultraviolet absorber of the present invention is not only a film and a resin member, but also has the above-mentioned functions, and is required to be stabilized and functionalized by the ultraviolet absorber, for example, a dye, a pigment, a pigment, an ink, It can also be used for paints, pharmaceuticals, surface coatings, cosmetics, photographic materials, textiles, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
<Example 1>

シアヌル酸クロリド（５．００ｇ, ２７．１ｍｍｏｌ）をテトラヒドロフラン５０ｍＬに混合し、氷冷後、フェニルマグネシウムブロミド（１６％テトラヒドロフラン溶液）（３０．７５ｇ, ２７．１ｍｍｏｌ）を３０分かけて滴下した後、１時間室温で反応した。反応終了後、トルエンを加えて水洗を行い、溶媒を留去して得られた固体を洗浄することにより中間体１を固体で得た。

Cyanuric chloride (5.00 g, 27.1 mmol) was mixed with 50 mL of tetrahydrofuran, cooled with ice, and phenylmagnesium bromide (16% solution in tetrahydrofuran) (30.75 g, 27.1 mmol) was added dropwise over 30 minutes. Reacted for 1 hour at room temperature. After the completion of the reaction, toluene was added and the mixture was washed with water, and the solvent was distilled off. The obtained solid was washed to obtain Intermediate 1 as a solid.

3-Hydroxybenzenethiol (15.00 g, 118.8 mmol), bromooctane (21.79 g, 112.8 mmol), and potassium carbonate (24.60 g, 178.0 mmol) were heated and refluxed in 150 mL of acetonitrile for 6 hours. After completion of the reaction, toluene was added, and the mixture was washed with water, distilled off the solvent, and purified by column to obtain Intermediate 2 as a liquid.
Intermediate 1 (5.00 g, 22.1 mmol) was reacted with aluminum chloride (9.73 g, 73.0 mmol) in 100 mL of O-xylene at 25 ° C. for 30 minutes, and then Intermediate 2 (17.40 g, 73.0 mmol) and reacted at 80 ° C. for 8 hours. After the completion of the reaction, compound 1 was obtained by adding toluene, washing with water, distilling off the solvent, purifying with a column, and recrystallization.

FT-IR (KBr): 3064 cm ^-1 : O-H stretching vibration 1568, 845 cm ^-1 : Triazine ring stretching vibration 602 cm ^-1 : CS stretching vibration
_{^{1 H-NMR (CDCl 3 400MHz}} ): δ 0.90 (t, 6H, C H 3 (CH 2) 7 S), 1.30 (m, 16H, CH 3 (C H 2) 4 (CH 2) 3 S), 1.48 (m, 4H, CH ₃ (CH ₂ ) ₄ C H ₂ (CH ₂ ) ₂ S), 1.76 (m, 4H, CH ₃ (CH ₂ ) ₅ C H ₂ CH ₂ S), 3.02 (t, 4H , CH ₃ (CH ₂ ) ₆ C H ₂ S), 6.70 (d, 4H), 7.60 (t, 2H), 7.67 (d, 1H), 8.41 (d, 4H), (insg.13arom. C H ) , 13.27 (s, 2H, Ph-O H )
_{^{13 C-NMR (CDCl 3 400MHz}} ): δ 14.1 (C H 3 (CH 2) 7 S), 22.6 (CH 3 C H 2 (CH 2) 6 S), 29.0 (CH 3 CH 2 C H 2 (CH _{2) 5 S), 29.1 (} CH 3 (CH 2) 2 (C H 2) 3 (CH 2) 2 S), 31.5 (CH 3 (CH 2) 5 C H 2 CH 2 S), 31.8 (CH 3 (CH ₂ ) ₆ C H ₂ S), 114.3 ((HO-) C _arom C _arom C (-N) = N), 117.9, 128.8, 129.2, 129.8 ( C H _arom ), 148.5 ( C _arom -S) , 162.6 ( C _arom -OH), 178.5 (N- (C _arom ) -C = N)

<Example 2>

シアヌル酸クロリド（５．００ｇ, ２７．１ｍｍｏｌ）をテトラヒドロフラン５０ｍＬに混合し、氷冷後、ｐ−トリルマグネシウムブロミド（１９％テトラヒドロフラン溶液）（２７．８７ｇ, ２７．１ｍｍｏｌ）を３０分かけて滴下した後、１時間室温で反応した。反応終了後、トルエンを加えて水洗を行い、溶媒を留去して得られた固体を洗浄することにより中間体３を固体で得た。

Cyanuric chloride (5.00 g, 27.1 mmol) was mixed with 50 mL of tetrahydrofuran, and after cooling with ice, p-tolylmagnesium bromide (19% solution in tetrahydrofuran) (27.87 g, 27.1 mmol) was added dropwise over 30 minutes. Thereafter, the reaction was carried out at room temperature for 1 hour. After completion of the reaction, toluene was added thereto, and the mixture was washed with water. The solvent was distilled off, and the obtained solid was washed to obtain Intermediate 3 as a solid.

  Intermediate 3 (5.00 g, 20.8 mmol) was reacted with aluminum chloride (9.15 g, 68.6 mmol) in 100 mL of O-xylene at 25 ° C. for 30 minutes, and then Intermediate 2 (16.35 g, 68.6 mmol) and reacted at 80 ° C. for 8 hours. After the completion of the reaction, compound 2 was obtained by adding toluene, washing with water, distilling off the solvent, purifying the column, and recrystallization.

FT-IR (KBr): 3065cm -1: O-H stretching vibration 1570, 845cm ^-1: triazine ring stretching vibration 600 cm ^-1: CS stretching vibration
_{^{1 H-NMR (CDCl 3 400MHz}} ): δ 0.90 (t, 6H, C H 3 (CH 2) 7 S), 1.32 (m, 16H, CH 3 (C H 2) 4 (CH 2) 3 S), _{1.48 (m, 4H, CH 3} (CH 2) 4 C H 2 (CH 2) 2 S), 1.77 (m, 4H, CH 3 (CH 2) 5 C H 2 CH 2 S), 2.48 (s, 3H , C H ₃ ), 3.03 (t, 4H, CH ₃ (CH ₂ ) ₆ C H ₂ S), 6.86 (d, 4H), 7.38 (t, 2H), 8.29 (d, 4H), (insg.13arom C H ), 13.33 (s, 2H, Ph-O H )
_{^{13 C-NMR (CDCl 3 400MHz}} ): δ 14.1 (C H 3 (CH 2) 7 S), 21.8 (C H 3), 22.7 (CH 3 C H 2 (CH 2) 6 S), 28.7 (CH 3 _{CH 2 C H 2 (CH 2} ) 5 S), 29.2 (CH 3 (CH 2) 2 (C H 2) 3 (CH 2) 2 S), 31.6 (CH 3 (CH 2) 5 C H 2 CH 2 S), 31.8 (CH ₃ (CH ₂ ) ₆ C H ₂ S), 114.2 ((HO-) C _arom C _arom C (-N) = N), 117.8, 128.8, 129.9, 148.3 ( C H _arom ), 144.6 ( C _arom -S), 162.5 ( C _arom -OH), 178.5 (N- (C _arom ) -C = N)

<Example 3>

シアヌル酸クロリド（５．００ｇ, ２７．１ｍｍｏｌ）をテトラヒドロフラン５０ｍＬに混合し、氷冷後、４−クロロマグネシウムブロミド（１．０Ｍジエチルエーテル溶液）（１９．３４ｇ, ２７．１ｍｍｏｌ）を３０分かけて滴下した後、１時間室温で反応した。反応終了後、トルエンを加えて水洗を行い、溶媒を留去して得られた固体を洗浄することにより中間体４を固体で得た。

Cyanuric chloride (5.00 g, 27.1 mmol) was mixed with 50 mL of tetrahydrofuran, and after cooling with ice, 4-chloromagnesium bromide (1.0 M diethyl ether solution) (19.34 g, 27.1 mmol) was added over 30 minutes. After the addition, the reaction was carried out at room temperature for 1 hour. After the completion of the reaction, toluene was added and the mixture was washed with water, and the solvent was distilled off. The obtained solid was washed to obtain Intermediate 4 as a solid.

  Intermediate 4 (5.00 g, 19.2 mmol) was reacted with aluminum chloride (8.45 g, 63.4 mmol) in 100 mL of O-xylene at 25 ° C. for 30 minutes, and then Intermediate 2 (15.11 g, 63.4 mmol) and reacted at 80 ° C. for 8 hours. After the completion of the reaction, compound 3 was obtained by adding toluene, washing with water, distilling off the solvent, purifying the column, and recrystallization.

FT-IR (KBr): 3060cm -1: O-H stretching vibration 1560, 840 cm ^-1: triazine ring stretching vibration 600 cm ^-1: CS stretching vibration
_{^{1 H-NMR (CDCl 3 400MHz}} ): δ 0.90 (t, 6H, C H 3 (CH 2) 7 S), 1.32 (m, 16H, CH 3 (C H 2) 4 (CH 2) 3 S), 1.48 (m, 4H, CH ₃ (CH ₂ ) ₄ C H ₂ (CH ₂ ) ₂ S), 1.75 (m, 4H, CH ₃ (CH ₂ ) ₅ C H ₂ CH ₂ S), 3.03 (t, 4H _{, CH 3 (CH 2) 6} C H 2 S), 6.85 (d, 4H), 7.56 (t, 2H), 8.33 (d, 4H), (insg.13arom. C H), 13.12 (s, 2H, Ph-O H )
_{^{13 C-NMR (CDCl 3 400MHz}} ): δ 14.1 (C H 3 (CH 2) 7 S), 22.6 (CH 3 C H 2 (CH 2) 6 S), 29.0 (CH 3 CH 2 C H 2 (CH _{2) 5 S), 29.1 (} CH 3 (CH 2) 2 (C H 2) 3 (CH 2) 2 S), 31.6 (CH 3 (CH 2) 5 C H 2 CH 2 S), 31.8 (CH 3 (CH ₂ ) ₆ C H ₂ S), 114.4 ((HO-) C _arom C _arom C (-N) = N), 118.1, 128.8, 129.2, 129.8 ( C H _arom ), 149.1 ( C _arom -S) , 162.5 ( C _arom -OH), 179.4 (N- (C _arom ) -C = N)

<Example 4>

３−ヒドロキシベンゼンチオール（１５．００ｇ, １１８．８ｍｍｏｌ）、炭酸カリウム（２４．６０ｇ, １７８．０ｍｍｏｌ）をアセトニトリル１５０ｍＬに混合し、氷冷後、ヨウ化メチル（１７．７０ｇ, １２４．７ｍｍｏｌ）を３０分かけて滴下した後、１時間室温で反応した。反応終了後、トルエンを加えて、水洗、溶媒留去、カラム精製を行うことにより、中間体５を液体で得た。

3-Hydroxybenzenethiol (15.00 g, 118.8 mmol) and potassium carbonate (24.60 g, 178.0 mmol) were mixed with 150 mL of acetonitrile, and after cooling with ice, methyl iodide (17.70 g, 124.7 mmol) was added. After dropping over 30 minutes, the reaction was carried out at room temperature for 1 hour. After completion of the reaction, toluene was added, and the mixture was washed with water, evaporated, and purified by column to obtain Intermediate 5 as a liquid.

  Intermediate 1 (5.00 g, 22.1 mmol) was reacted with aluminum chloride (9.73 g, 73.0 mmol) in 100 mL of O-xylene at 25 ° C. for 30 minutes, and then Intermediate 5 (10.24 g, 73.0 mmol) and reacted at 80 ° C. for 8 hours. After the completion of the reaction, compound 4 was obtained by adding toluene, washing with water, distilling off the solvent, purifying the column, and recrystallization.

FT-IR (KBr): 3060cm -1: O-H stretching vibration 1565, 840 cm ^-1: triazine ring stretching vibration 600 cm ^-1: CS stretching vibration
¹ H-NMR (CDCl ₃ 400 MHz): δ 2.53 (s, 6H, C H ₃ ), 6.83 (d, 4H), 7.56 (t, 2H), 7.64 (d, 1H), 8.38 (d, 4H), (insg.13arom. C H ), 13.25 (s, 2H, Ph-O H )
¹³ C-NMR (CDCl ₃ 400 MHz): δ 14.6 ( C H ₃ ), 113.3 ((HO-) C _arom C _arom C (-N) = N), 117.1, 128.7, 129.2, 133.5 ( C H _arom ), 149.2 ( C _arom -S), 162.6 ( C _arom -OH), 178.5 (N- (C _arom ) -C = N)

<Example 5>

３−ヒドロキシベンゼンチオール（１５．００ｇ, １１８．８ｍｍｏｌ）、ブロモオクタデカン（３７．６１ｇ, １１２．８ｍｍｏｌ）、炭酸カリウム（２４．６０ｇ, １７８．０ｍｍｏｌ）をアセトニトリル１５０ｍＬ中で６時間加熱還流した。反応終了後、トルエンを加えて、水洗、溶媒留去、カラム精製を行うことにより、中間体６を液体で得た。

3-Hydroxybenzenethiol (15.00 g, 118.8 mmol), bromooctadecane (37.61 g, 112.8 mmol), and potassium carbonate (24.60 g, 178.0 mmol) were heated to reflux in 150 mL of acetonitrile for 6 hours. After the completion of the reaction, toluene was added, and the mixture was washed with water, distilled off the solvent, and subjected to column purification to obtain Intermediate 6 as a liquid.

  Intermediate 1 (5.00 g, 22.1 mmol) and aluminum chloride (9.73 g, 73.0 mmol) were reacted in 100 mL of O-xylene at 25 ° C. for 30 minutes, and then Intermediate 6 (27.64 g, 73.0 mmol) and reacted at 80 ° C. for 8 hours. After the completion of the reaction, compound 5 was obtained by adding toluene, washing with water, distilling off the solvent, purifying the column, and recrystallization.

FT-IR (KBr): 3055 cm ^-1 : O-H stretching vibration 1572, 850 cm ^-1 : Triazine ring stretching vibration 602 cm ^-1 : CS stretching vibration
_{^{1 H-NMR (CDCl 3 400MHz}} ): δ 0.88 (t, 6H, C H 3 (CH 2) 17 S), 1.25 (m, 28H, CH 3 (C H 2) 14 (CH 2) 3 S), 1.48 (m, 4H, CH ₃ (CH ₂ ) ₁₄ C H ₂ (CH ₂ ) ₂ S), 1.77 (m, 4H, CH ₃ (CH ₂ ) ₁₅ C H ₂ CH ₂ S), 3.02 (t, 4H , CH ₃ (CH ₂ ) ₁₆ C H ₂ S), 6.90 (d, 4H), 7.57 (t, 2H), 7.65 (d, 1H), 8.43 (d, 4H), (insg.13arom. C H ) , 13.28 (s, 2H, Ph-O H )
_{^{13 C-NMR (CDCl 3 400MHz}} ): δ 14.1 (C H 3 (CH 2) 17 S), 22.7 (CH 3 C H 2 (CH 2) 16 S), 29.2 (CH 3 CH 2 C H 2 (CH _{2) 15 S), 29.6 (} CH 3 (CH 2) 2 (C H 2) 13 (CH 2) 2 S), 31.5 (CH 3 (CH 2) 15 C H 2 CH 2 S), 31.9 (CH 3 (CH ₂ ) ₁₆ C H ₂ S), 114.3 ((HO-) C _arom C _arom C (-N) = N), 117.9, 128.8, 129.2, 129.8 ( C H _arom ), 148.5 ( C _arom -S) , 162.6 ( C _arom -OH), 178.5 (N- (C _arom ) -C = N)

<Comparative Example 1>

ヒドロキシベンゼンチオール（１５．０ｇ, １１８．８ｍｍｏｌ）、ブロモヘキサン（１８．６３ｇ, １１２．８ｍｍｏｌ）及び炭酸カリウム（２４．６ｇ, １７８．２ｍｍｏｌ）をアセトニトリル１５０ｍＬ中で６時間加熱還流した。反応終了後、トルエンを加えて、水洗、溶媒留去、カラム精製を行うことにより、中間体７を液体で得た。

Hydroxybenzenethiol (15.0 g, 118.8 mmol), bromohexane (18.63 g, 112.8 mmol) and potassium carbonate (24.6 g, 178.2 mmol) were heated to reflux in 150 mL of acetonitrile for 6 hours. After completion of the reaction, toluene was added, and the mixture was washed with water, evaporated, and purified by column to obtain Intermediate 7 as a liquid.

  2-chloro-4,6-diphenyl-1,3,5-triazine (1.92 g, 7.14 mmol) and aluminum chloride (2.37 g, 17.85 mmol) in 50 mL of O-xylene at 25 ° C. After reacting for 10 minutes, Intermediate 7 (2.00 g, 14.25 mmol) was added and reacted at 80 ° C. for 8 hours. After the completion of the reaction, compound 6 was obtained by adding toluene, washing with water, distilling off the solvent, purifying the column, and recrystallization.

FT-IR (KBr): 3064 cm ^-1 : O-H stretching vibration 1568, 846 cm ^-1 : Triazine ring stretching vibration 602 cm ^-1 : CS stretching vibration
_{^{1 H-NMR (CDCl 3 400MHz}} ): δ 0.90 (t, 3H, C H 3 (CH 2) 5 -S), 1.34 (m, 2H, CH 3 (C H 2) 2 (CH 2) 3 S) , 1.47 (quin, 2H, CH ₃ (CH ₂ ) ₂ C H ₂ (CH ₂ ) ₂ S), 1.75 (quin, 2H, CH ₃ (CH ₂ ) ₃ C H ₂ CH ₂ S), 3.03 (t, 2H, CH ₃ (CH ₂ ) ₃ CH ₂ C H ₂ S), 6.89 (d, 2H), 7.62 (m, 6H), 8.58 (d, 1H), 8.63 (m, 4H) (insg.13arom.C H ), 13.43 (s, 1H, Ph-O H )
_{^{13 C-NMR (CDCl 3 400MHz}} ): δ 14.0 (C H 3 (CH 2) 5 S), 22.5 (CH 3 C H 2 (CH 2) 4 S), 28.7 (CH 3 CH 2 C H 2 (CH _{2) 3 S), 28.8 (} CH 3 (CH 2) 2 C H 2 (CH 2) 2 S), 31.4 (CH 3 (CH 2) 3 C H 2 CH 2 S), 31.8 (CH 3 (CH 2 ) ₄ C H ₂ S), 114.3 ((HO-) C C _arom C (-N) = N), 117.9, 129.0, 129.9, 133.0 ( C H _arom ), 135.3 ( C _arom -C = N), _147.4 ( C _arom -S), 162.3 ( C _arom -OH), 171.4 (C _arom - C = N)

<Comparative Example 2>

シアヌル酸クロリド（１．９２ｇ, ７．１４ｍｍｏｌ）と中間体２（７．６６ｇ, ３２．１３ｍｍｏｌ）を１，２−ジクロロエタン５０ｍＬ中で、加熱溶解させた後氷冷し、塩化アルミニウム（０．９５ｇ,７．１４ｍｍｏｌ）を３０分かけて加えた後、７０℃、５４時間反応した。反応終了後、トルエンを加えて水洗、溶媒留去、カラム精製、再結晶を行うことにより、化合物７を得た。

Cyanuric chloride (1.92 g, 7.14 mmol) and Intermediate 2 (7.66 g, 32.13 mmol) were dissolved in 50 mL of 1,2-dichloroethane by heating, then ice-cooled, and aluminum chloride (0.95 g). , 7.14 mmol) over 30 minutes and then reacted at 70 ° C. for 54 hours. After the completion of the reaction, compound 7 was obtained by adding toluene, washing with water, distilling off the solvent, purifying the column, and recrystallization.

FT-IR (KBr): 2951cm -1: O-H stretching vibration 1570, 843cm ^-1: triazine ring stretching vibration 606 cm ^-1: CS stretching vibration
_{^{1 H-NMR (CDCl 3 400MHz}} ): δ 0.90 (t, 3H, C H 3 (CH 2) 7 S), 1.32 (m, 8H, CH 3 (C H 2) 4 (CH 2) 3 S), _{1.47 (quin, 2H, CH 3} (CH 2) 4 C H 2 (CH 2) 2 S), 1.72 (quin, 2H, CH 3 (CH 2) 5 C H 2 CH 2 S), 2.92 (t, 2H , CH ₃ (CH ₂ ) ₆ C H ₂ S), 6.70 (d, 2H), 7.72 (d, 1H), (insg.13arom.C H ), 12.99 (s, 1H, Ph-O H )
_{^{13 C-NMR (CDCl 3 400MHz}} ): δ 14.1 (C H 3 (CH 2) 7 S), 22.7 (CH 3 C H 2 (CH 2) 6 S), 28.6 (CH 3 CH 2 C H 2 (CH _{2) 5 S), 29.2 (} CH 3 (CH 2) 2 (C H 2) 3 (CH 2) 2 S), 31.5 (CH 3 (CH 2) 5 C H 2 CH 2 S), 31.9 (CH 3 (CH ₂ ) ₆ C H ₂ S), 111.8 ( C _arom C = N), 113.9, 117.7, 128.4 ( C H _arom ), 149.6 ( C _arom -S), 162.7 ( C _arom -OH), 168.2 (C _arom - C = N)

<Comparative Example 3>

<Comparative Example 4>

２−（２−ヒドロキシ−３−ｔｅｒｔ−ブチル−５−メチルフェニル）−５−クロロベンゾトリアゾール（５．００ｇ, １５．８ｍｍｏｌ）、オクタンチオール（７．６３ｇ, ５２．１ｍｍｏｌ）、炭酸カリウム（７．２０ｇ, ５２．１ｍｍｏｌ）及びヨウ化カリウム（０．１８ｇ, １．１ｍｍｏｌ）を、ＤＭＦ５０ｍＬ中で、１５０℃、２０時間反応した。反応終了後、トルエンを加えて、水洗、溶媒留去、カラム精製を行うことにより、化合物９を得た。

2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole (5.00 g, 15.8 mmol), octanethiol (7.63 g, 52.1 mmol), potassium carbonate (7 .20 g, 52.1 mmol) and potassium iodide (0.18 g, 1.1 mmol) were reacted in 50 mL of DMF at 150 ° C. for 20 hours. After completion of the reaction, compound 9 was obtained by adding toluene, washing with water, distilling off the solvent, and performing column purification.

FT-IR (KBr): 3125 cm ^-1 : O-H stretching vibration 1438, 1391 cm ^-1 : Triazole ring stretching vibration 661 cm ^-1 : CS stretching vibration
_{^{1 H-NMR (CDCl 3 400MHz}} ): δ 0.88 (t, 3H, C H 3 (CH 2) 7 S), 1.27 (m, 8H, CH 3 (C H 2) 4 (CH 2) 3 S), 1.49 (m, 11H, -Ph- OH-CH 3 -C (C H 3) 3, CH 3 (CH 2) 4 C H 2 (CH 2) 2 S), 1.75 (quin, 2H, CH 3 (CH _{2) 5 C H 2 CH 2} S), 2.38 (s, 3H, -Ph-OH-C H 3 -C (CH 3) 3), 3.03 (t, 2H, CH 3 (CH 2) 5 CH 2 C H ₂ S), 7.16 (s, 1H), 7.37 (d, 1H), 7.70 (s, 1H), 7.81 (d, 1H), 8.05 (s, 1H), (insg.5arom. C H ), 11.61 (s, 1H, -Ph-O H -CH ₃ -C (CH ₃ ) ₃ )
_{^{13 C-NMR (CDCl 3 400MHz}} ): δ 14.0 (C H 3 (CH 2) 7 S), 20.0 (-Ph-OH- C H 3 -C (CH 3) 3), 22.6 (-Ph-OH- _{CH 3 - C (CH 3)} 3), 28.7 (CH 3 (C H 2) 5 CH 2 CH 2 S), 31.9 (-Ph-OH-CH 3 -C (C H 3) 3), 33.2 (CH ₃ (CH ₂ ) ₅ C H ₂ CH ₂ S), 35.4 (CH ₃ (CH ₂ ) ₅ CH ₂ C H ₂ S), 113.6, 117.5, 119.3, 128.7, 129.3 ( C H _arom ), 141.2, 143.4 ( C _arom ), 125.4 ( C _arom -N), 128.3 (C _arom -C H ₃ ), 138.0 ( C _arom -S), 139.1 ( C _arom -C (CH ₃ ) ₃ ), 146.7 ( C _arom -OH)

<Comparative Example 5>

化合物１０は、東京化成(株)製の試薬を用いた。

As the compound 10, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used.

  The absorption effect of the ultraviolet absorber in the long wavelength region is “wavelength of the absorption peak in the 315 to 400 nm region (maximum absorption wavelength: λmax)” and “peak area of the long wavelength region (360 to 400 nm)”, and addition to the resin member The yellow suppression effect at this time is as follows: “wavelength of absorption peak in the region of 315 to 400 nm (maximum absorption wavelength: λmax)”, “absolute value of long wavelength side slope of absorption peak in the region of 315 to 400 nm”, and “400− The peak area at 450 nm "and the ultraviolet absorption efficiency are correlated with the" molar extinction coefficient ".

Absorption effect in long wavelength region (1) Wavelength of absorption peak in 315 to 400 nm region (maximum absorption wavelength: λmax)
The compounds of Examples and Comparative Examples were diluted with chloroform at 5 μM, accommodated in a 10-mm quartz cell, and the ultraviolet-visible absorption spectrum was measured using an ultraviolet-visible spectrophotometer (V-550, manufactured by JASCO Corporation) (FIGS. 1 and 2). ) And the absorption peak in the region of UV-A (315-400 nm) were read (Table 1).

  The absorption peaks of the compounds 1 to 5 (Examples 1 to 5) into which the formula (i) of the present invention is introduced are longer than the absorption peaks of the compounds 6, 8, 9, 10 (Comparative Examples 1, 3, 4, 5). The wavelength was shifted to a peak in the long wavelength region of 370 to 400 nm even in the UV-A region, and it was confirmed that light of a long wavelength was favorably absorbed.

(2) Peak area in long wavelength region (360 to 400 nm) From the absorption spectra (5 μM) of the compounds of Examples and Comparative Examples, the peak area in the long wavelength region (360 to 400 nm) (Example: FIG. 1 Example 2) ) Was calculated using an ultraviolet-visible spectrophotometer (V-550, manufactured by JASCO Corporation) (Table 1). The peak area in the long wavelength region (360 to 400 nm) of Compounds 1 to 5 (Examples 1 to 5) is the same as that of triazine-based compound 6 (Comparative Example 1) into which one phenyl containing formula (i) is introduced. (I) The area is larger than that of the triazine-based compound 8 having no substituent (Comparative Example 3) and the benzotriazole-based compounds 9 and 10 (Comparative Examples 4 and 5).

  That is, from the results of the above (1) and (2), the triazine-based compounds 1 to 5 (Examples 1 to 5) into which two phenyls containing the formula (i) are introduced have a particularly long wavelength even in UV-A. Of about 360 to 400 nm.

Yellow suppression effect (3) Wavelength of absorption peak in 315-400 nm region (maximum absorption wavelength: λmax)
Regarding the absorption peak measured in the above (1), from the viewpoint of suppressing yellowing of the resin member to which the ultraviolet absorbent is added, if the absorption peak in the 315 to 400 nm region is too close to 400 nm, the wavelength in the visible region is increased. For absorption, the absorption peak is preferably 390 nm or less. Compound 7 (Comparative Example 2) has an absorption peak (392.5 nm) of 391 nm or more, and tends to yellow the resin member, whereas Compounds 1 to 5 (Examples 1 to 5) have a peak of 360. At the same time as having an excellent ultraviolet absorption effect at around 400 nm, their maximum absorption peak is at 390 nm or less, which suppresses absorption of wavelengths in the visible region and suppresses yellowing of the added resin member.

(4) Absolute value of the slope of the absorption peak in the region of 315 to 400 nm on the long wavelength side From the absorption spectra (5 μM) of the compounds of Examples and Comparative Examples, the absorption spectrum on the long wavelength side of the absorption peak at 315 to 400 nm The point of intersection of the peak with the baseline (line where the slope of the absorption spectrum at 400 to 500 nm is 0) is taken as the peak end (Example: FIG. 1 Example 1), and the length of the absorption peak in the wavelength region of 315 to 400 nm is calculated by the following equation. The absolute value of the slope on the wavelength side was determined (Tables 1, 3).
| Long-wavelength slope of the absorption peak in the wavelength region of 315 to 400 nm | = | (absorbance at peak end-absorbance of absorption peak in wavelength region of 315 to 400 nm) / (absorption wavelength at peak end -315 to 400 nm Wavelength of the absorption peak in the wavelength region of

  When suppressing the yellow discoloration at the same time as absorbing the wavelength in the range of 360 to 400 nm, in addition to the above (3), an ultraviolet absorber having a larger (sharper) absorption peak in the visible region (from 400 nm) At the wavelengths of the above, and yellow discoloration can be suppressed. The slopes of the absorption peaks at 315 to 400 nm of Compounds 1 to 5 (of Examples 1 to 5) are as follows: triazine-based compound 6 into which one phenyl containing formula (i) is introduced (Comparative Example 1); The slope of the triazine-based compound 8 (Comparative Example 3) and the benzotriazole-based compounds 9 and 10 (Comparative Examples 4 and 5) having no substituent is larger (sharp) than 0.003 and 0.003 or more. Yes, it was confirmed that the effect of suppressing yellow discoloration was high.

(5) Peak area at 400 to 450 nm Similarly to the above (2), from the absorption spectra (5 μM) of the compounds of the examples and comparative examples, the peak area of the visible light region (400 to 450 nm) was determined to be ultraviolet-visible. It was calculated using a spectrophotometer (V-550 manufactured by JASCO Corporation) (Table 1).

  The peak area of 400 to 450 nm of the compounds 1 to 5 (Examples 1 to 5) having the optical characteristics of the above (3) and (4) is based on the triazine-based compound having three phenyls containing the formula (i). Compared to Compound 7 (Comparative Example 2), the peak area of 400 to 450 nm, which is a factor of yellow, is small (the absorption of wavelength in the visible light region is small), and it is possible to suppress yellowing when used for a resin member. It was suggested.

(6) Molar extinction coefficient The absorbance of the maximum absorption peak (maximum absorption wavelength: λ _mx ) in the wavelength region of 315 to 400 nm was read from the absorption spectra of the compounds of the examples and comparative examples, and the molar extinction coefficient (maximum mole) of the peak was read. The extinction coefficient: ε _mx ) was determined by the following equation (Tables 1 and 2).
Molar extinction coefficient: ε _mx (L / (mol · cm) =: absorbance / [c: molar concentration (mol / L) × l: cell optical path length (cm)]

  Compounds 1 to 5 (of Examples 1 to 5) are triazine-based compounds 6 (Comparative Example 1) into which one phenyl containing formula (i) is introduced, and a triazine having no substituent of formula (i) It was confirmed that the compounds had higher molar extinction coefficient than the compound 8 (Comparative Example 3) and the benzotriazole compounds 9 and 10 (Comparative Examples 4 and 5), and efficiently absorbed ultraviolet light by adding a small amount.

  That is, when these ultraviolet absorbers are added to the member to absorb ultraviolet rays in the range of 360 to 400 nm to the same extent, Compounds 1 to 5 have the above-mentioned molar extinction coefficient and peak area in the long wavelength region (360 to 400 nm). It may be large and may be less than the added amount of the compounds 6, 8, 9, and 10. Further, at that time, the peak wavelength (390 nm or less) and the inclination of Compounds 1 to 5 are large, and the peak area in the visible region of 400 nm to 450 nm can be further reduced (visible light absorption can be suppressed). Yellowing of the resin member can be suppressed.

Compound 3 in which a halogen atom is bonded at the positions of R ^{1 to} R ¹⁵ (Example 3) shifts to longer wavelengths among compounds 1 to 5 when the maximum absorption peak at 315 to 400 nm is 390 nm or less. Then, it was confirmed that the peak area (9.5 or more) and the molar extinction coefficient (55000 or more) in the long wavelength region (360 to 400 nm) were large and the absorption efficiency in the long wavelength region (360 to 400 nm) was higher.

Further, Compounds 1, 4, and 5, in which the formula (i) or a hydrogen atom is bonded to the positions of R ^{1 to} R ¹⁵ , have a peak area of 400 to 450 nm of 0.5 or less, which is smaller than compounds 1 to 5, It was confirmed that the yellow suppression effect was greater.

  On the other hand, the triazine-based compound 7 (Comparative Example 2) into which three phenyls containing the formula (i) are introduced has a peak area of 360 to 400 nm and a larger slope than that of compounds 1 to 5, but 370 to 400 nm. Since the peak of the region is 392.5 nm (391 nm or more) having a longer wavelength than compounds 1 to 5, it absorbs a large amount of light at 400 nm to 450 nm (the peak area at 400 to 450 nm is large), and the yellow suppression effect is low.

The above measurement results were evaluated based on the following criteria, and are summarized in Table 1.
[1] Long wavelength absorption effect
Wavelength of absorption peak in 315 to 400 nm region (maximum absorption wavelength: λmax)
：: 370 to 400 nm
Δ: 365 to 369 nm
×: less than 365 nm Peak area in long wavelength region (360 to 400 nm) ○: 7 or more △: 3 or more ×: less than 3
[2] Yellow suppression effect
Wavelength of absorption peak in 315 to 400 nm region (maximum absorption wavelength: λmax)
：: 390 nm or less ×: 391 nm or more
Absolute value of the slope on the long wavelength side of the absorption peak in the range of 315 to 400 nm ○: 0.003 or more △: 0.002 or more ×: less than 0.002
400-450 nm peak area ○: 1 or less △: 3 or less ×: 4 or more
[3] Ultraviolet absorption efficiency Molar extinction coefficient ○: 40000 or more △: 20,000 or more ×: less than 20,000

表１から、化合物１〜５（実施例１〜５）及び化合物７（比較例２）は、類似する式（i）を含有するフェニルを導入したトリアジン系化合物の化合物６と比較して、ＵＶ−Ａでも長波長の３６０〜４００ｎｍの長波長領域の吸収効果は高い。しかしながら、化合物７は黄色抑制効果が低く、化合物１〜５と比較して樹脂部材に添加した場合、黄色化すると示唆された。つまり、化合物１〜５は、樹脂部材に添加した場合、黄色化を抑制し、長波長領域の波長光を効率良くに吸収することができる。

From Table 1, it can be seen that Compounds 1 to 5 (Examples 1 to 5) and Compound 7 (Comparative Example 2) were compared with Compound 6 of a phenyl-introduced triazine compound containing a similar formula (i) by UV. -A also has a high absorption effect in a long wavelength region of 360 to 400 nm, which is a long wavelength. However, Compound 7 has a low yellowing inhibitory effect, suggesting that when it is added to the resin member as compared with Compounds 1 to 5, it turns yellow. That is, when the compounds 1 to 5 are added to the resin member, yellowing can be suppressed, and light having a wavelength in a long wavelength region can be efficiently absorbed.

That is, Compounds 1 to 5 (Examples 1 to 5) are good in all of the above items, and the absorption peak of light in the 315 to 400 nm region is 370 to 390 nm at the maximum absorption wavelength (λ _max ). With a slope of 0.003 or more, a molar extinction coefficient of 40000 or more, a peak area of 360 to 400 nm of 7 or more, and a peak area of 400 to 450 nm of 1 or less, compared with compounds 6 to 10 (Comparative Examples 1 to 5). Then, with a small amount of addition, it is possible to obtain a resin member that efficiently absorbs light in the long wavelength region of 360 to 400 nm and suppresses yellowing and coloring.

5% Weight Loss Temperature For the compounds of Examples and Comparative Examples, using a simultaneous thermogravimetric analyzer (TG / T6200, manufactured by SII), a temperature increase temperature: 10 ° C./min, a measurement range: 25 to 550 ° C. The temperature at which the change in weight (TG) was reduced by 5% by weight was read.

実施例１〜５の化合物は、式（i）の置換基を２つ導入することにより、式（i）の置換基のない比較例３の化合物８、ベンゾトリアゾール骨格の比較例４、５の化合物９，１０や、更には式（i）の置換基を１つ導入した比較例１の化合物６よりも５％重量減少温度が高く、耐熱性（紫外線吸収剤の熱分解による樹脂部材の紫外線吸収能、透明樹脂の透明性の低下を抑制）が向上し、２００〜２５０℃より高い成形加工温度が求められる熱可塑性樹脂に対して適用性があることを確認した。 Table 4 shows the measurement results.

The compounds of Examples 1 to 5 were prepared by introducing two substituents of the formula (i) to give the compound 8 of the comparative example 3 having no substituent of the formula (i) and the comparative examples 4 and 5 of the benzotriazole skeleton. It has a higher 5% weight loss temperature than Compounds 9 and 10 and Compound 6 of Comparative Example 1 in which one substituent of the formula (i) is introduced, and has high heat resistance (ultraviolet rays of a resin member due to thermal decomposition of an ultraviolet absorber). It has been confirmed that the resin has improved absorbability and suppresses the decrease in the transparency of the transparent resin, and is applicable to a thermoplastic resin requiring a molding temperature higher than 200 to 250 ° C.

Evaluation of Film The effect of the compatibility (transparency) of the compound of the present invention on the film and the resin member was confirmed by the following method (Table 5).

  After uniformly mixing 0.1 g of the compounds of Examples 1 to 5 and Comparative Example 2, 0.1 g of an acrylic resin, and 4 g of chloroform, chloroform was concentrated to about 2 to 3 g, and this was dropped on a slide glass, and then cooled to 45 ° C. The solvent was removed in an oven for 2 hours to produce an acrylic film having a thickness of 10 to 100 μm. Further, without adding additives, 0.1 g of acrylic resin and 4 g of chloroform were uniformly mixed, and the same operation as described above was performed to produce a film.

(1) Appearance The appearance of the film was visually observed and evaluated according to the following criteria.
：: transparent without cloudiness ×: cloudiness was observed and transparency was poor

(2) Film Thickness The film thickness was measured by using a table microscope (Miniscope TM3000 manufactured by Hitachi High-Tech Co., Ltd.) on a section obtained by cutting the film.

本発明の式（i）を含有するフェニルを２つ導入した化合物１〜５（実施例１〜５）は、式（i）を含有するフェニルを３つ導入したトリアジン系の化合物７（比較例２）と比べて、樹脂との相溶性が良好となり、黄変色がない透明なアクリルフィルムを作製することが可能であった。

Compounds 1 to 5 (Examples 1 to 5) of the present invention in which two phenyls containing formula (i) are introduced are triazine-based compounds 7 (Comparative Examples) in which three phenyls containing formula (i) are introduced. Compared with 2), the compatibility with the resin was improved, and it was possible to produce a transparent acrylic film without yellow discoloration.

Claims (7)

The following formula (I):

(Wherein, R ^{1 to} R ¹⁵ are each independently the following formula (i):

(In the formula (i), R ¹⁷ is independently selected from an aromatic group, an unsaturated group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom when y is 2 or more. The hydrogen atom is substituted, at least one of both ends is interrupted, or the carbon-carbon bond may be interrupted by a divalent group having 1 to 20 carbon atoms. A hydrocarbon group; R ¹⁸ is a monovalent or divalent group selected from an aromatic group, an unsaturated group, a sulfur-containing group, an oxygen-containing group, a phosphorus-containing group, an alicyclic group, and a halogen atom; A monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom which may be substituted with a hydrogen atom, interrupted at a base end, or interrupted at a carbon-carbon bond. the total number of carbon atoms of R ¹⁷ and R ¹⁸ is 60 or less. y monovalent represented by the indicating.) an integer of 0 to 3 A sulfur-containing group, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an aromatic group, an unsaturated group, a disulfide group, a sulfonyl group, a sulfo group, a thiocarbonyl group, a thiocarbamoyl group, a thiourea group, an oxygen-containing group, It represents a monovalent group selected from a phosphorus-containing group, an alicyclic group, and a halogen atom. R ^{1 to} R ⁵ , R ^{6 to} R ¹⁰ , and R ^{11 to} R ¹⁵ each represent a group represented by the formula (i) in which one to four groups per two groups out of any two groups are represented by the formula (i). Is a monovalent sulfur-containing group. UV absorber represented by).   The ultraviolet absorbent according to claim 1, wherein y is 0 in the monovalent sulfur-containing group represented by the formula (i). The monovalent sulfur-containing group represented by the formula (i), wherein y R ¹⁷ include an alkylene group having 18 or less carbon atoms, and R ¹⁸ includes an alkyl group having 18 or less carbon atoms. 3. The ultraviolet absorbent according to 1. The substituent other than the monovalent sulfur-containing group represented by the formula (i) among R ^{1 to} R ¹⁵ is selected from an alkyl group having 1 to 4 carbon atoms, a hydroxy group, and a halogen atom. The ultraviolet absorber according to any one of the above. A resin member containing the ultraviolet absorbent according to any one of claims 1 to 4 in a matrix resin. The resin member according to claim 5 , wherein the matrix is a transparent resin. The resin member according to claim 5, which is a film, a sheet, a plate-shaped member, or an optical resin.

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