JP3932144B2 - Triazine compound, ultraviolet absorber comprising the same, and polymer material composition containing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a specific triazine compound, an ultraviolet absorber comprising the compound, and a polymer material composition to which the ultraviolet absorber is added.
[0002]
[Prior art and problems]
It is known that polymer materials such as polyolefin, polyester, polycarbonate, and polyamide are deteriorated by the action of light, causing discoloration or a decrease in mechanical strength and cannot withstand long-term use.
[0003]
Therefore, various ultraviolet absorbers have been conventionally used to prevent deterioration of these polymer materials and to control the wavelength of transmitted light and the amount of transmitted light of a film or lens using the polymer material. As these ultraviolet absorbers, benzophenone-based, benzotriazole-based, 2,4,6-triaryltriazine-based and cyanoacrylate-based ultraviolet absorbers are known.
[0004]
The 2,4,6-triaryltriazine-based ultraviolet absorber to which the specific ultraviolet absorber of the present invention belongs is an ultraviolet absorber excellent in heat resistance. The basic structure is 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine and a compound obtained by etherification or esterification of the 4-hydroxy group. Proposed. For example, Japanese Patent Laid-Open No. 8-53427 proposes various compounds having one of aryl groups as a 2,4-dihydroxyphenyl group and a substituent at the 5-position, and etherified and esterified products thereof. . These were intended to enhance the stabilizing effect by utilizing the shift of the absorption wavelength by the substituent.
[0005]
Japanese Patent Application Laid-Open No. 61-24577 proposes a 2,4,6-triaryltriazine-based ultraviolet absorber having a structure in which a sulfonate is introduced. The solubility of the ultraviolet absorber is adjusted by the substituent.
[0006]
However, when these UV absorbers are kneaded at the time of processing of the resin, the UV absorbers are partly volatilized by being exposed to a high temperature at the time of processing, and the effectiveness is lowered. Volatilizes when used and loses its effectiveness. In addition, when adsorbed at the time of fiber dyeing, the exhaustion rate depends on the affinity to the resin, and the adsorbed UV absorber is also volatilized during long-term use or is extracted by washing and loses its effectiveness. Satisfactory long-term light resistance was not obtained. Moreover, when using for an intraocular lens etc., the ultraviolet absorber which was hard to be extracted from a safety viewpoint was desired. Therefore, there has been a demand for an ultraviolet absorber having excellent affinity for synthetic polymer materials.
[0007]
[Means for Solving the Problems]
As a result of intensive studies in view of the above situation, the present inventors have found that the specific triazine-based ultraviolet absorber represented by the following general formula (I) has a low volatility and affinity for a polymer having an aromatic ring. The present invention has been found by being excellent in the effect of imparting long-term light resistance.
[0008]
That is, this invention provides the ultraviolet absorber which is low in the volatility containing the compound represented with the following general formula (I), and is excellent in affinity with resin.
[0009]
In the formula , R ₁ is a carbonyl group, —R ₇ O—CO—OR ₈ —, —CO—O—R ₉ —O—CO— or —R ₁₀ O—CO—O—R ₁₁ —O—CO—O. -R _{12 - represents, R 7, R 8, R} 9, R 10, R 11 and _{R 12} are each an alkylene group having 1 to 8 carbon atoms, a group represented by phenylene group or the following formula (II) There, _{R 7} and _{R 8} may be a hydroxy alkylene group having 1 to 8 carbon _atoms, represents a R _2, R 3, _{R 4} and R ₅ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
[0010]
Hereinafter, the present invention having the above gist will be described in detail.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
In the above _{formulas, R 7, R 8, R 9} , R 10, R 11 and _{R 12,} in an alkylene group having 1 to 8 carbon atoms represented, for example, methylene, ethylene, trimethylene, propylene, tetramethylene 2-methyltrimethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene and octamethylene . R ₇ and R ₈ may be a hydroxyalkylene group having 1 to 8 carbon atoms such as 2-hydroxytrimethylene .
[0012]
Examples of the phenylene group represented by R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ include 1,3-phenylene and 1,4-phenylene .
[0013]
Examples of the alkyl group having 1 to 10 carbon atoms represented by R ₂ , R ₃ , R ₄ and R ₅ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl , Tertiary amyl, octyl, tertiary octyl, decyl, isodecyl and the like .
[0014]
Examples of the compound represented by the above formula (I) of the present invention include the following compound No. 1-No. 6 and the like. For example, Compound No. 1 indicates that two groups in parentheses are bonded via a carbonyl group. The same applies to other compounds.
[0015]
[Formula 4]
[0016]
[Chemical formula 5]
[0017]
[Chemical 6]
[0018]
[Chemical 7]
[0019]
[Chemical 8]
[0020]
[Chemical 9]
[0021]
The method for synthesizing the compound represented by the general formula (I) of the present invention is not particularly limited, and any of the commonly used methods for synthesizing carbonate compounds may be used. For example, Compound No. 3 reacts 2- (2,4-dihydroxyphenyl) -4,6-diphenyltriazine with diphenyl carbonate to obtain the desired product.
[0022]
Examples of the synthetic polymer material to which the ultraviolet absorbent comprising the triazine compound of the present invention is applied include, for example, high density, low density or linear low density polyethylene, polypropylene, polybutene-1, poly-3-methylpentene, and the like. Α-olefin polymers or polyolefins such as ethylene-vinyl acetate copolymers and ethylene-propylene copolymers, and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, and polyvinylidene fluoride. , Rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic ester Copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride Halogen-containing resins such as ru-cyclohexylmaleimide copolymer, vinyl chloride-cyclohexylmaleimide copolymer, petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and / or α-methylstyrene and other single quantities Copolymer (eg, AS resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.), polymethyl methacrylate, polyvinyl alcohol, and the like (eg, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) Polyvinyl formal, polyvinyl butyral, linear polyesters such as polyethylene terephthalate and polytetramethylene terephthalate, polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonate Thermosets of thermoplastic synthetic resins such as bonates, branched polycarbonates, polyacetals, polyphenylene sulfides, polyurethanes, and fiber-based resins, and blends thereof, phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polycastel resins, etc. Resins can be mentioned. Furthermore, elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber may be used. In particular, application to a resin having an aromatic ring such as aromatic polycarbonate or aromatic polyester is preferable because of excellent compatibility.
[0023]
The processing method of these resins is not particularly limited, and any resin processing method such as extrusion processing, co-extrusion processing, injection molding, blow molding, and calendar processing can be used. In addition, as applications, films, sheets, fibers and various molded products are used for automobile interior materials, exterior materials, agricultural materials, building materials, clothing, household goods, beverage bottles, packaging materials, and the like. In particular, since it is excellent in light resistance and compatibility, it is suitably used for a protective layer of a laminated film by coextrusion processing.
[0024]
The triaryl tocazine-based ultraviolet absorber having a specific structure in the present invention is usually used in an amount of 0.001 to 30 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the resin.
[0025]
Since the ultraviolet absorber of the present invention has low volatility and imparts excellent light resistance, it is particularly useful in fields requiring high light resistance such as agricultural materials and automobile paints.
[0026]
The ultraviolet absorber of the present invention can be used in combination with other general-purpose antioxidants, stabilizers and other additives as necessary.
[0027]
Particularly preferable examples of these additives include phenol-based, sulfur-based and phosphite-based antioxidants, hindered amine-based light stabilizers, and particularly 2,2,6,6-tetramethylpiperidine compounds. Hindered amine-based light stabilizers typified by are preferable because they have a synergistic effect with the compound of the present invention.
[0028]
Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6 -Hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide] 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6-tert. Butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4 '-Butylidenebis (6-tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert Tributylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3- Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 3,5-tris (3,5-ditert-butyl-4-hydroxylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2, 4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-ditert Tributyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1 , 1-Dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] And ndecane and triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].
[0029]
Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl, and β-alkyl polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include mercaptopropionic acid esters.
[0030]
Examples of the phosphite antioxidant include trisnonylphenyl phosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tris [2-tertiarybutyl-4- (3-tertiary). Butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, Distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4- Methylphenyl) pentaerythritol diphosphite, (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tertiary Butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, 2,2′-methylenebis (4 6-ditert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) octadecyl phosphite, 2,2'-methylenebis (4,6-ditertiary Butylphenyl) fluorophosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphospho 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1 , 3,2] dioxaphosphin-6-yl) oxy] ethyl) amine and the like.
[0031]
Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidylbenzoate and N- (2,2,6,6-tetramethyl-4-piperidyl) dodecyl succinic acid. Imido, 1-[(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-ditert-butyl- 4-hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, N, N′-bis (2,2 , 6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6- Pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) -di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy] ) Butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1 Dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane 1,5,8,12-tetrakis [4,6-bis {N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl ] -1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino -4,6-dichloro-s-triazine / N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2, 6,6-tetrame Til-4-piperidyl) hexamethylenediamine / dibromoethane condensate and the like.
[0032]
If necessary, the composition of the present invention includes heavy metal deactivator, nucleating agent, metal soap, organic tin compound, plasticizer, epoxy compound, foaming agent, antistatic agent, flame retardant, lubricant, processing aid. Agents and the like can be included.
[0033]
The method of applying the ultraviolet absorbent of the present invention to the organic material is not particularly limited, and the form upon addition may be a powder, an aqueous dispersion such as an emulsion or a suspension, or a solution with an organic solvent. Further, since the ultraviolet absorber of the present invention has an unsaturated bond, the ultraviolet absorber of the present invention can be used alone or as an oligomer by copolymerization with other monomers.
[0034]
Furthermore, various addition steps are possible depending on the form to be added, and when the organic material to be stabilized is a polymer material, any method of applying an ultraviolet absorber to a polymer material that is usually used may be used. For example, it may be added during processing, may be adsorbed and impregnated after processing, or may be coated with a film to which the ultraviolet absorbent of the present invention is added. In the addition method at the time of processing, a master batch blended at a high concentration may be prepared, or after granulating to suppress dust, the final blend may be kneaded. In paints, heat-sensitive recording materials, liquid crystal compositions, etc., they may be added directly or in the protective layer.
[0035]
【Example】
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not restrict | limited at all by the following example.
[0036]
Specific synthesis examples of the compound represented by the general formula (I) used in the present invention are listed below, but the present invention is not limited by the following synthesis examples.
[0037]
(Synthesis Example-1: Synthesis of Compound No. 1)
2- (2,4-dihydroxy-3-methylphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine 82.2 g (0.2 mol), diphenyl carbonate 21.4 g (0. 1 mol) and 0.2 g (0.002 mol) of sodium carbonate were added and reacted at 200 ° C. for 2 hours. After cooling, recrystallization from toluene gave 68.1 g (yield 83%) of a pale yellow powder having a melting point of 268 ° C. The obtained compound had a maximum absorption wavelength (λ _MAX ) of 340.0 nm and a molar extinction coefficient (ε) of 1.84 × 10 ⁴ .
[0038]
The resulting compound was identified by Compound No. ¹ by H ¹ -NMR. 1 was identified.
_{2.4,2.7 (-CH 3), 6.5-6.7 (} Ar-H), 7.0-7.5 (Ar-H), 8.0-8.2 (Ar-H), 8.4-8.6 (Ar-H), 13.4 (-OH)
[0039]
(Synthesis Example-2: Synthesis of Compound No. 2)
[0040]
2- (2-hydroxy-4- (2-hydroxyethoxy) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine 88.2 g (0.2 mol), diphenyl carbonate 21.4 g (0.1 mol) and 0.3 g (0.002 mol) of potassium carbonate were added, and the mixture was heated to 170 ° C. in 300 ml of an aromatic hydrocarbon solvent and reacted for 5 hours. After removing the solvent, 66.3 g (yield 73%) of a pale yellow powder having a melting point of 229 ° C. was obtained by recrystallization from dimethylformamide. The obtained compound was ε4.23 × 10 ⁴ at λ _MAX 336.4 nm.
[0041]
The resulting compound was identified by Compound No. ¹ by H ¹ -NMR. 2 was identified.
2.4,2.7 (-CH ₃ ), 4.2-4.4 (-OCH ₂ CH ₂ O-), 4.5-4.7 (-OCH ₂ CH ₂ O-), 6.5-6.7 (Ar-H), 7.0-7.5 (Ar- H), 8.0-8.2 (Ar-H), 8.4-8.6 (Ar-H), 13.4 (-OH)
[0042]
(Example-1)
Pellets were produced by extrusion at 250 ° C. according to the formulation shown in Table 1 below. Next, a test piece having a thickness of 2 mm was produced by injection molding at 250 ° C., and the yellowness was measured. The test piece was subjected to a weather resistance test using a sunshine weatherometer in a rain cycle of 18 minutes in a black panel temperature of 83 ° C. for 120 minutes. The evaluation method was based on comparison of crack generation times. The results are shown in the following Table-2.
[0043]
[Table 1]
[0044]
[Table 2]
[0045]
[Chemical Formula 10]
[0046]
Embedded image
[0047]
(Example-2)
A protective layer having a thickness of 40 μm and a base layer of 10 mm (ultraviolet rays) obtained by adding 10 parts by weight of an ultraviolet absorber (see Table 3) to 100 parts by weight of bisphenol A polycarbonate having an intrinsic viscosity of 0.57 (30 ° C. in dioxane). A test sheet was obtained by bonding bisphenol A polycarbonate not containing an absorbent) at 280 ° C. by coextrusion using a sheet die. The obtained test piece was irradiated with ultraviolet light with a high-pressure mercury lamp, and light resistance was evaluated from the color difference before irradiation and after irradiation for 2 weeks. Moreover, the presence or absence of bleeding was confirmed by surface observation after 60 ° C. × 1 week when the addition amount of the ultraviolet absorber was 20 parts by weight. The results are shown in Table-3.
[0048]
[Table 3]
[0049]
(Example-3)
30 g of an ultraviolet absorber (described in Table 4) and 30 g of a liquid finely dispersed in 1 part by weight of a nonionic surfactant (adduct of nonylphenol and ethylene oxide) and 64 parts by weight of water and an anthraquinone red dye (Resolin Red) (FB: manufactured by Bayer) 10 g of acetic acid and 0.3 g of acetic acid were dispersed in 1 liter of water as a dyeing solution, and 100 g of polyester cloth was put in a sealed container at a bath ratio of 1:10 and dyed in a 130 ° C. constant temperature bath for 30 minutes. After cooling, the sample was washed with water and reduced and washed by a conventional method to obtain a test piece. The exhaustion rate of the UV absorber was measured from the absorbance before and after the dyeing solution was dyed. In addition, a weather resistance test was performed on the obtained dyed fabric using a color difference from that before the test after 240 hours at 83 ° C. (no watering).
[0050]
The exhaustion rate was also measured when no dye was present. The results are shown in Table 4 below.
[0051]
[Table 4]
[0052]
(Example-4)
A film having a thickness of 0.1 mm was prepared by kneading with a kneading roll using the composition shown in Table 5 below. A specimen was cut from the film and subjected to a weather resistance test using a sunshine weatherometer (no rain). The results are shown in Table-6.
[0053]
[Table 5]
[0054]
[Table 6]
[0055]
(Example-5)
1 part by weight of a sample compound shown in Table 7 was added to 100 parts by weight of polyphenylene ether and dissolved in chloroform to make a 1% by weight solution, and then a cast film was prepared on a 76 mm × 26 mm glass plate. The resulting film was measured for color difference after 48 hours at 63 ° C. and 50% humidity. The results are shown in Table 7 below.
[0056]
[Table 7]
[0057]
【The invention's effect】
From the results of the above examples, it is clear that when the specific ultraviolet absorber of the present invention is used, the stabilizing effect is remarkably large compared to the case where a conventionally known triazine-based ultraviolet absorber is used. is there.

Claims (5)

A triazine compound represented by the following general formula (I).
In the formula , R ₁ is a carbonyl group, —R ₇ O—CO—OR ₈ —, —CO—O—R ₉ —O—CO— or —R ₁₀ O—CO—O—R ₁₁ —O—CO—O. -R _{12 - represents, R 7, R 8, R} 9, R 10, R 11 and _{R 12} are each an alkylene group having 1 to 8 carbon atoms, a group represented by phenylene group or the following formula (II) Yes, _{R 7} and _{R 8} may be a hydroxy alkylene group having 1 to 8 carbon _atoms, represents a R _2, R 3, _{R 4} and R ₅ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
The ultraviolet absorber which consists of a triazine type compound represented with the following general formula (I).
In the formula , R ₁ is a carbonyl group, —R ₇ O—CO—OR ₈ —, —CO—O—R ₉ —O—CO— or —R ₁₀ O—CO—O—R ₁₁ —O—CO—O. -R _{12 - represents, R 7, R 8, R} 9, R 10, R 11 and _{R 12} are each an alkylene group having 1 to 8 carbon atoms, a group represented by phenylene group or the following formula (II) There, _{R 7} and _{R 8} may be a hydroxy alkylene group having 1 to 8 carbon _atoms, represents a R _2, R 3, _{R 4} and R ₅ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
The polymeric material composition formed by adding 0.001-30 weight part of ultraviolet absorbers described in Claim 2 with respect to 100 weight part of resin. The polymer material composition according to claim 3, wherein the resin is polycarbonate. The polymer material composition according to claim 3, wherein the resin is polyester.