JP2010202521A - New triazine compound, method for producing the same, ultraviolet absorber including the same, and polymer composition including the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a triazine compound that has low volatility, is a liquid at a normal temperature, and is excellent in compatibility with a polymer or the like, a method for producing the same, an ultraviolet absorber including the same, and a polymer composition including the same. <P>SOLUTION: The triazine compound is represented by formula (I) (in the formula, R<SP>1</SP>represents a 1-3C straight chain or branched alkyl group, and R<SP>2</SP>represents a 4-6C straight chain or branched alkyl group). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a specific triazine compound in a liquid state at room temperature, a process for producing the compound, an ultraviolet absorber comprising the compound, and a polymer composition containing the same.

Recently, with the expansion of application fields such as synthetic polymers and the development of new applications, there is a growing demand for UV absorbers with low volatility and good compatibility.
Furthermore, in many cases where the crystal material is handled, there are problems such as dust scattering and incompatibility with synthetic polymers, and improvement is required.

As a low-volatile ultraviolet absorber, an ultraviolet absorber made of 2- (2-hydroxy-4-alkoxyphenyl) -4,6-bisaryl-1,3,5-triazine is effective for various organic materials. It is known that there is.
For example, Patent Documents 2 to 6 include 2- (2-hydroxy-4-n-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine (melting point: 84 ° C.) and the like.
However, since both are crystalline substances having a relatively high melting point, there is a drawback that dust scattering and compatibility are poor.

Moreover, as what improved compatibility, patent document 1 shows the characteristic of being easy to melt | dissolve in an organic solvent, and 2, 4- di (2, 4- dimethylphenyl) -6- (2-hydroxy-4-O). - (mixed alkyl) phenyl) -1,3,5-triazine ( "mixed alkyl" herein is an isomeric mixture of C ₈ alkyl group) (as solids) is disclosed at room temperature.
However, since this compound is solid at room temperature, it cannot be said that the compatibility is sufficiently improved.
Furthermore, since it is a mixture of alkyl isomers, there is a drawback that the composition and physical properties of the mixture are difficult to stabilize.
Further, there is no knowledge that a triazine-based compound can obtain a liquid compound at room temperature with almost a single component.
Further, the triazine-based ultraviolet absorbers currently on the market are of the -CH ₂ -R type octyl group (C ₈ ) type, all of which are solid at room temperature, and no liquid is found at room temperature.
Obtaining a triazine-based compound that is a single component and is liquid at room temperature is very important in the industrial field in terms of stability of physical properties, compatibility with synthetic polymers, prevention of dust scattering, and the like.

Japanese Patent No. 2894519 JP 2003-233161 A JP 2003-202652 A Special table 2002-524451 gazette German Patent No. 1215712 Swiss Patent No. 480091

  An object of the present invention is to provide a triazine compound which is liquid at room temperature and has low volatility and excellent compatibility with a polymer, a production method thereof, an ultraviolet absorber comprising the same, and a polymer composition containing the same. is there.

（式中、Ｒ^１は炭素数１〜３の直鎖または分岐のアルキル基、Ｒ^２は炭素数４〜６の直鎖または分岐のアルキル基であり、Ｒ^１とＲ^２の炭素数の合計が５〜９、好ましくは６〜８、とくに好ましくは７である）
で示されるトリアジン系化合物に関する。
本発明の第２は、Ｒ^１がメチル基である請求項１記載のトリアジン系化合物に関する。
本発明の第３は、請求項１または２記載のトリアジン系化合物を有効成分として含有する紫外線吸収剤に関する。
本発明の第４は、下記式

で示される２−（２，４−ジヒドロキシフェニル）−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジンと一般式（II）で示される化合物

および、一般式（III）で示される化合物

（式中、Ｒ^１は炭素数１〜３の直鎖または分岐のアルキル基、Ｒ^２は炭素数４〜６の直鎖または分岐のアルキル基でＲ^１とＲ^２の炭素数の合計が５〜９、好ましくは６〜８、とくに好ましくは７であり、ＸおよびＹは脱離基である）
よりなる群から選ばれたアルキル化剤とを反応させることを特徴とする請求項１または２記載のトリアジン系化合物の製造方法に関する。
本発明の第５は、請求項１または２記載のトリアジン系化合物を含有する高分子組成物に関する。 The first of the present invention is the general formula (I)

Wherein R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms, R ² is a linear or branched alkyl group having 4 to 6 carbon atoms, and the total number of carbon atoms of R ¹ and R ² Is 5-9, preferably 6-8, particularly preferably 7.)
It is related with the triazine type compound shown by these.
The second of the present invention relates to the triazine compound according to claim ¹ , wherein R ¹ is a methyl group.
3rd of this invention is related with the ultraviolet absorber which contains the triazine type compound of Claim 1 or 2 as an active ingredient.
The fourth of the present invention is the following formula

2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and a compound represented by the general formula (II)

And a compound represented by the general formula (III)

Wherein R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms, R ² is a linear or branched alkyl group having 4 to 6 carbon atoms, and the total number of carbon atoms of R ¹ and R ² is 5 To 9, preferably 6 to 8, particularly preferably 7, and X and Y are leaving groups)
3. The method for producing a triazine compound according to claim 1, wherein an alkylating agent selected from the group consisting of the compounds is reacted.
5th of this invention is related with the polymer composition containing the triazine type compound of Claim 1 or 2.

などを挙げることができ、２価の脱離基Ｙとしては、例えば−ＳＯ_４−などを挙げることができる。具体的には、ハロゲン化アルキル、硫酸モノアルキル、硫酸ジアルキル、アルキルトルエンスルホネート、アルキルスルホン酸などの脱離基部分である。
本発明の常温液状の低揮発性トリアジン系化合物の製造に用いるアルキル化剤としては、ハロゲン化アルキルが好ましい。
反応温度は５０〜２００℃が好ましく、特に、１００〜１５０℃が好ましい。
溶媒としては原材料を溶解または分散し、反応基質と反応しないものであればよく、その例としては、トルエン、キシレン、モノクロロベンゼン、メチルシクロヘキサン、メチルセロソルブ、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン等があり、単独または２種以上混合して使用しても良い。 In the alkylating agent represented by the general formulas (II) and (III) used in the present invention, the leaving group X is a monovalent leaving group, for example,

Examples of the divalent leaving group Y include —SO ₄ — and the like. Specifically, it is a leaving group moiety such as alkyl halide, monoalkyl sulfate, dialkyl sulfate, alkyltoluenesulfonate, and alkylsulfonic acid.
Alkyl halides are preferred as the alkylating agent used in the production of the room temperature liquid low-volatile triazine compound of the present invention.
The reaction temperature is preferably 50 to 200 ° C, particularly preferably 100 to 150 ° C.
Any solvent may be used as long as it dissolves or disperses the raw material and does not react with the reaction substrate. Examples thereof include toluene, xylene, monochlorobenzene, methylcyclohexane, methyl cellosolve, N, N-dimethylformamide, N-methyl- 2-pyrrolidone and the like may be used alone or in combination of two or more.

The triazine-based compound of the present invention can be added to a polymer, that is, a synthetic resin or synthetic rubber to form a composition that is stable against ultraviolet rays.
Examples of these synthetic resins and synthetic rubbers include polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, ethylene / propylene copolymer, polymethyl methacrylate, polyacrylonitrile, ABS, polyester, polyamide, polyimide, polyurethane, polycarbonate, polyethylene terephthalate, and acrylonitrile. -Styrene resin, unsaturated polyester, alkyd resin, thermosetting acrylic resin, epoxy resin, urea resin, melamine resin, phenol resin, SBR, NBR and the like.

When the compound of the present invention is used as the ultraviolet absorber, it is preferable to add 0.05 to 10% by weight based on the substance to be stabilized.
Moreover, when using this invention compound as this ultraviolet absorber, the compound of this invention can be used as a single compound or in mixture of 2 or more types.
Of course, it can be used in combination with any conventionally known ultraviolet absorber, antioxidant, light stabilizer and the like.

Examples of known light stabilizers that can be used in combination with the ultraviolet absorber of the present invention include bis- (2,2,6,6-tetramethylpiperidine) sebacate and bis- (1,2,2,6,6-). Pentamethylpiperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1- {2-3-[(3,5-di-tbutyl-4-hydroxyphenyl) propionyloxy] ethyl } -4- [3- (3,5-di-tbutyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9- Tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2,4-dione, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6, succinate 6-teto Methylpiperidine polycondensate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6- Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, 2- (3,5-di-tbutyl-4-hydroxybenzyl)- 2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetraxy (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4- Butanetetracarboxylate, a condensate of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4- Butanetetracarboxylic acid and 2, , 6,6-tetramethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol and And hindered amines such as 1,2,2,6,6-pentamethyl-4-piperidyl-methacrylate and 2,2,6,6-tetramethyl-4-piperidyl-methacrylate.
Also, for example, [2,2-thio-bis- (4-t-octylphenolate)]-n-butylamine-nickel (II), 4,4'-dioctyloxyoxanilide, dilaurylthiodipro Examples include compounds such as pionate, tris (2,4-di-t-butylphenyl) phosphite, and bis (nonylphenyl) pentaerythritol diphosphite.

  Examples of known ultraviolet absorbers that can be used in combination with the ultraviolet absorber of the present invention include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy. -4-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy Benzophenone UV absorbers such as -4,4'-dimethoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (2'-hydroxy-3 ', 5'-di -T-butylphenyl) -5-chlorobenzotriazole, 2- (2 ' Hydroxy-3 ', 5'-di-t-amylphenyl) -benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) -benzotriazole, 2- (2'-hydroxy-5'- t-octylphenyl) -benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- [2'-hydroxy-3 ', 5' -Bis- (α, α-dimethylbenzyl) phenyl] -benzotriazole, methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol Condensate with a molecular weight of about 300, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxy Phenyl) octyl propionate, 2- (2′-hydroxy-3′-α, α-dimethylbenzyl-5′-t-octylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -6 Benzotriazole ultraviolet absorbers such as dodecyl-4-methylphenol and 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazolylphenol], p- Salicylate-based UV absorbers such as octylphenyl salicylate, phenyl salicylate, t-butylphenyl salicylate, resorcinol monobenzoate, 3,5-di-t-butyl-4-hydroxybenzoic acid hexadecyl ester, 5-t-butyl-2-ethoxy-2 ', 2'-ethyloxanilide, 5-dihexylamino- -Cyano-2,4-pentadienenitrile, 2- (2-hydroxy-4-n-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, etc. An ultraviolet absorber is mention | raise | lifted.

  Examples of known antioxidants that can be used in combination with the ultraviolet absorber of the present invention include 2,6-di-t-butyl-4-methylphenol, 2-t-butyl-4,6-dimethylphenol, 2, Alkylphenols such as 6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,6 Alkylated hydroquinones such as -di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 4,4'-thiobis- (3 -Methyl-6-t-butylphenol), 2,2'-thiobis- (4-methyl-6-t-butylphenol), 4,4'-thiobis- (2-methyl-6-t-butylphenol) ), Thiobisphenols such as 2,2'-thiobis- (4-octylphenol), 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-ethylidene-bis -(4,6-di-t-butylphenol), 4,4'-methylene-bis- (2,6-di-t-butylphenol), 2,2'-methylene-bis- (4-methyl-6 Nonylphenol), alkylidene bisphenols such as 1,1,3-tris- (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane, and 1,3,5-trimethyl-2,4 6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris- (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3- t-butyl-5-methyl-4-hydroxyphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,3-bisbutyrate -(3-t-butyl-4-hydroxyphenyl) ethylene ester, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydro Xylphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethylene Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′- Hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, and the like.

  The ultraviolet absorber of the present invention can be used in combination with, for example, a plasticizer, an emulsifier, a lubricant, a pigment, a fluorescent brightening agent, a flame retardant, an antistatic agent and the like.

Conventional methods for producing triazine-based compounds are described in Swiss Patent No. 480091, US Pat. No. 3,268,474, Special Table No. 2002-524451, and Patent No. 2894519, etc., and are solid crystalline compounds at room temperature. On the other hand, the triazine compound of the present invention is a novel liquid compound at ordinary temperature, has low volatility characterized by the triazine compound, and is excellent as a polymer compound due to the moderate branching property of its alkyl group. It is a compatible UV absorber.
Since the ultraviolet absorber of the present invention is in a liquid state, it has good miscibility with paints, and is particularly preferably used for automobile paints.
Further, it can be mixed with a photographic material without using a solvent or with a small amount of solvent, and can be evenly mixed with a thermosetting resin which cannot be melt-mixed. When the particles remain, it is suitable as a stabilizer for photographic materials that cause scratches.
Furthermore, it can also be used as an emulsified composition effective for dyeing, and by adding it to synthetic and natural fibers, it is possible to suppress color deterioration of the substrate fibers and decolorization of the dyes.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to synthesis examples of the compound of the present invention, but these are only exemplifications of preferred embodiments, and the present invention is not limited only to these examples.

を得た。
収率は９８．４％であった。
この化合物は、−１０℃で１ヶ月保存しても、固化することはなかった。 Synthesis example 1
2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 39.7 g (0.100 mol), N, N-dimethylformamide (DMF) ) 54 mL, caustic soda 6.6 g (0.165 mol), sodium bicarbonate 15.1 g (0.180 mol) and 2-octyl bromide 42.5 g (0.220 mol) in a four-necked flask equipped with a stirrer and a condenser tube The reaction was conducted in a nitrogen stream at 125 to 130 ° C. for 12 hours.
After completion of the reaction, DMF was recovered under reduced pressure, and toluene and water were added and washed with water.
Further, water was added, 75% sulfuric acid was added until the pH of the aqueous layer reached 7, and the mixture was washed with water and again with water.
The remaining organic layer was decolorized with activated carbon, and the activated carbon was isolated, and then toluene was recovered up to 130 ° C. under a reduced pressure of 1.3 hPa to obtain a pale yellow clear liquid 2- [2-hydroxy-4- (1-methyl). -Heptyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine

Got.
The yield was 98.4%.
This compound did not solidify even when stored at −10 ° C. for 1 month.

を得た。
収率は９７．０％であった。 Synthesis example 2
In Synthesis Example 1, 3-octyl bromide was used instead of 2-octyl bromide, and the reaction and post-treatment were performed in the same manner as in Synthesis Example 1.
A pale yellow clear liquid 2- [2-hydroxy-4- (1-ethyl-hexyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine

Got.
The yield was 97.0%.

Comparative Synthesis Example 1
In Synthesis Example 1, 1-octyl bromide was used in place of 2-octyl bromide, and the reaction and post-treatment were performed in the same manner as in Synthesis Example 1.
2- [2-hydroxy-4- (n-octyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine as a pale yellow solid (melting point: 92 ° C.) Obtained.
The yield was 97.9%.

Example 1
After blending 0.5 parts by weight of the compound produced in Synthesis Example 1 with 100 parts by weight of polypropylene powder and thoroughly mixing with a mixer, a pellet was prepared by melt mixing with a cylinder temperature of 200 ° C. and a 25 mm diameter extruder. (Sample A).
The obtained pellets were compression-molded into a sheet having a thickness of 0.25 mm at 210 ° C. to prepare a test piece.
The obtained test piece was punched into a dumbbell shape corresponding to a tensile test.
Test piece to which the compound of Comparative Synthesis Example 1 was added by the same method as above (Sample B), 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine (CYTEC INDUSTRIES INC. Trade name: CYASORB UV-1164L (xylene solution) obtained by distilling off the solvent) and a non-added test piece (sample C) D) was prepared and evaluated for comparison purposes.
As is clear from the results shown in Table 1, the compound of Synthesis Example 1 is the compound of Comparative Synthesis Example 1 and 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyl). Stabilization effect superior to oxyphenyl) -1,3,5-triazine (CYTEC INDUSTRIES INC., Trade name: CYASORB UV-1164L (xylene solution)) )showed that.
These test pieces were irradiated with light at a black panel temperature of 80 ° C. using a WEL-75XS-HS-BEC type xenon sunshine long life weather meter manufactured by Suga Test Instruments Co., Ltd. Changes over time were compared.
The tensile test was conducted using a DSS-5000 type tensile tester manufactured by Shimadzu Corporation at a temperature of 23 ± 2 ° C., a relative humidity of 50 ± 5%, and a test speed of 50 ± 5.0 mm / min.
The tensile strength was determined by the following method.
[Equation 1]
Ts = S / T · W

Ts = tensile strength (kgf / mm ² )
T = sample thickness (mm)
W = width of sample (mm)
S = Maximum strength of the sample (kgf)
The results of the obtained tensile strength were as shown in Table 1.

Claims (5)

Formula (I)

Wherein R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms, R ² is a linear or branched alkyl group having 4 to 6 carbon atoms, and the total number of carbon atoms of R ¹ and R ² Is 5-9)
A triazine compound represented by the formula: The triazine compound according to claim 1, wherein R ¹ is a methyl group.   An ultraviolet absorber containing the triazine compound according to claim 1 or 2 as an active ingredient. Following formula

2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and a compound represented by the general formula (II)

And a compound represented by the general formula (III)

(Wherein R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms, R ² is a linear or branched alkyl group having 4 to 6 carbon atoms, and the total number of carbon atoms of R ¹ and R ² is 5-9, X and Y are leaving groups)
The method for producing a triazine-based compound according to claim 1 or 2, wherein an alkylating agent selected from the group consisting of the compounds is reacted.   A polymer composition containing the triazine-based compound according to claim 1.