JPH05117444A - Polymer composition improved in weather resistance - Google Patents

Abstract

PURPOSE:To obtain even under severe processing conditions the title compsn. which has an excellent weather resistance for a long term by compounding a polymer material with a specific triazole compd. CONSTITUTION:100 pts.wt. polymer matrial is compounded with 0.0001-5 pts.wt. benzotriazole compd. of formula I (wherein R is a group of formula II; R1 and R<2> are each R, halogen, NR4R5, or OR6; R3 is alkyl: R4, R5, and R6 are each alkyl or aryl provided that one of R4 and R5 may be H, or may combine with each other to form a ring contg. N; and X is H or halogen). Since the compd. not only improves the weather resistance of the polymer material but also has a high heat resistance in itself, it is useful as a light stabilizer for various engineering plastics as well as for general-purpose plastics.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer material composition having improved weather resistance, and more specifically, by adding a specific 2-hydroxyphenylbenzotriazole compound, the weather resistance is improved over a long period of time. An improved polymeric material composition.

[0002]

2. Description of the Related Art Polymer materials such as polyethylene, polypropylene, polyurethane, styrene resin, acrylic resin, polyvinyl chloride, etc. are deteriorated by the action of light to cause discoloration or mechanical strength. It is known that it causes deterioration and cannot withstand long-term use.

Therefore, in order to prevent the deterioration of the polymer material, various light stabilizers have been conventionally used. As these light stabilizers, hindered amine-based light stabilizers,
A benzophenone-based or benzotriazole-based ultraviolet absorber is mainly used, and in particular, a 2-hydroxyphenylbenzotriazole-based ultraviolet absorber has a large stabilizing effect and is widely used.

However, the conventionally used benzotriazole type compounds are inferior in their heat resistance,
It is unsatisfactory in practical use because it has a drawback that it is easily volatilized during the processing of the polymer material or when it is used at a high temperature or is easily extracted by water or an organic solvent.

[0005]

In view of the above situation, the present inventors have earnestly studied to obtain a novel type of light stabilizer, and as a result, a specific benzotriazole compound has excellent heat resistance. The inventors have found that a polymeric material such as a synthetic resin can be provided with long-term weather resistance even under severe processing conditions, and have reached the present invention.

That is, according to the present invention, 0.001 to 5 parts by weight of a benzotriazole compound represented by the following general formula (I) represented by the general formula (I) is added to 100 parts by weight of a polymer material. And a polymeric material composition having improved weather resistance.

[0007]

[Chemical 2]

The polymeric material composition of the present invention having the above-mentioned gist will be described in detail below.

In the above general formula (I), examples of the alkyl group represented by R ₃ , R ₄ , R ₅ and R ₆ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl and tertiary. Butyl, amyl, isoamyl, tertiary amyl, hexyl, heptyl, octyl, tertiary octyl, nonyl, decyl, dodecyl, undecyl, benzyl, α-
Examples thereof include methylbenzyl and α, α-dimethylbenzyl. The aryl group represented by R ₄ , R ₅ and R ₆ includes
Examples thereof include phenyl, tolyl, xylyl, butylphenyl, naphthyl and biphenyl. Examples of the case where R ₄ and R ₅ are bonded to each other to form a ring together with the N atom include a case where the N atom, R ₄ and R ₅ form a piperidylino group, a morpholino group or the like. The halogen atom represented by X includes fluorine, chlorine, bromine, iodine and the like.

Therefore, examples of the compound represented by the above general formula (I) include the following compounds.

[0011]

[Chemical 3] Compound No. 1

[0012]

[Chemical 4] Compound No. Two

[0013]

[Chemical 5] Compound No. Three

[0014]

[Chemical 6] Compound No. Four

[0015]

[Chemical 7] Compound No. 5

[0016]

[Chemical 8] Compound No. 6

[0017]

[Chemical 9] Compound No. 7

[0018]

[Chemical 10] Compound No. 8

[0019]

[Chemical 11] Compound No. 9

[0020]

[Chemical 12] Compound No. 10

[0021]

[Chemical 13] Compound No. 11

The compound represented by the above general formula (I) is, for example, cyanuric chloride and 2- (2'-hydroxy-3'-
It can be easily produced by a dehydrochlorination reaction with an aminophenyl) benzotriazole compound. The number of substituents for cyanuric chloride can be easily adjusted by the temperature conditions, and unreacted chlorine can be replaced later with alcohols or amines.

The synthetic method of the compound represented by the general formula (I) is shown in the following [Synthesis Example 1] to [Synthesis Example 3], but the method is not limited to this method.

[Synthesis Example 1] 2,4,6-tris- [2 '
-Hydroxy-3 '-(2H-benzotriazole-
2 "-yl) -5'-tertiary octylphenylamino]-
Synthesis of 1,3,5-triazine (Compound No.
11) 915 mg of cyanuric chloride and 12.3 g of aromatic hydrocarbon
Was dissolved in the mixture, 5.04 g of 2- (2'-hydroxy-3'-amino-5'-tertiaryoctylphenyl) benzotriazole and 1.54 g of anhydrous sodium carbonate were added, and the mixture was stirred at 170 ° C for 6 hours. After that, it was cooled to 80 ° C., 40 ml of water was added, and the aqueous layer was neutralized with 5N hydrochloric acid,
Stir for minutes. The mixture was further cooled to room temperature, and the produced crystals were filtered and washed with water. The crystals were recrystallized from a toluene / cyclohexane mixed solvent to obtain 3.8 g of a pale yellow powder (product) having a melting point of 313.5 ° C.

As a result of IR measurement of the product, 3400c
m ^-1 , 1608 cm ^-1 , 1572 cm ^-1 and 800c
Absorption was observed at m ^-1 . In addition, as a result of UV measurement, (λ
max = 325 nm, ε = 67600), (λmax = 27
Two absorptions at 4 nm, ε = 72800) were observed.
Furthermore, as a result of proton NMR measurement, 0.88 ppm (2
7H), 1.54ppm (18H), 1.93ppm
(6H), 7.29-8.11 ppm (15H), 8.
It was 84 ppm (3H) and 11.52 ppm (3H), and it was confirmed that the product was the target product.

[Synthesis Example 2] 2,4-bis- [2'-hydroxy-3 '-(2H-benzotriazol-2 "-yl) -5'-tertiary octylphenylamino] -6-chloro-1 Of 3,3,5-triazine (Compound N of Chemical formula 10
o. 8) 1.317 g of cyanuric chloride was dissolved in 81.84 g of toluene, and 2- (2′-hydroxy-3′-amino-) was dissolved therein.
5'-tertiary octylphenyl) benzotriazole 4.
835 g and 1.50 g anhydrous sodium carbonate are added,
The reaction was carried out at 70 ° C for 7 hours. The mixture was cooled to room temperature, washed with water 3 times, and the produced crystals were filtered and washed with water. This crystal was recrystallized from a mixed solvent of benzene / cyclohexane and had a melting point of 2
3.65 g of pale yellow powder (product) at 46.9 ° C. was obtained.

IR measurement result of the product: 3400c
m ^-1 , 1610 cm ^-1 , 1540 cm ^-1 and 790c
Absorption was observed at m ^-1 . In addition, as a result of UV measurement, (λ
max = 322 nm, ε = 46200), (λmax = 28
Two absorptions at 7 nm, ε = 43900) were observed.
Furthermore, as a result of proton NMR measurement, 0.84 ppm (1
8H), 1.50ppm (12H), 1.88ppm
(4H), 7.19-8.16 ppm (10H), 8.
It was 63 ppm (2H) and 11.56 ppm (2H), and it was confirmed that the product was the target product.

[Synthesis Example 3] 2,4-bis- [2'-hydroxy-3 '-(2H-benzotriazol-2 "-yl) -5'-tertiary octylphenylamino] -6- [di ( Synthesis of 2′-ethylhexyl) amino] -1,3,5-triazine (Compound No. 4 of Chemical formula 6) 5 g of cyanuric chloride was dissolved in 23 g of acetone and cooled to −5 ° C. or lower. Amine 6.
61 g was added dropwise over 10 minutes, and 1.44 g of anhydrous sodium carbonate was further added. The reaction was carried out for 3 hours while maintaining the system temperature at -5 ° C or lower. Then, at room temperature, 50 ml of water was added, and the mixture was extracted 3 times with 20 ml of chloroform. Chloroform extract obtained by this extraction operation was added to 20 ml of 1N.
After washing with an aqueous solution of sodium hydroxide, it was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the colorless liquid was washed with 10.3.
4 g was obtained.

The colorless liquid obtained by the above operation [2,4-dichloro-6-di (2-ethylhexyl) amino-1,
3,5-triazine] (2.59 g) was dissolved in an aromatic hydrocarbon solvent (21.3 g) to give 2- (2'-hydroxy-3 ').
-Amino-5'-tert-octylphenyl) benzotriazole 4.51 g and anhydrous sodium carbonate 1.39 g
Was added, and the mixture was reacted at 170 ° C. for 9 hours in a nitrogen atmosphere.
Then, it was washed with water at room temperature, and the oil layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the crude product was recrystallized from n-butyl alcohol / isopropyl alcohol to give a melting point of 1
5.44 g of pale yellow powdery crystals (product) at 80.8 ° C. were obtained.

As a result of IR measurement of the product, 3400c
m ^-1 , 1610 cm ^-1 , 1580 cm ^-1 and 800c
Absorption was observed at m ^-1 . In addition, as a result of UV measurement, (λ
max = 326 nm, ε = 44500), (λmax = 27
Two absorptions at 4 nm, ε = 53100) were observed.
Furthermore, as a result of proton NMR measurement, 0.86-1.91
ppm (64H), 3.77 ppm (4H), 7.30
-8.21 ppm (10H), 8.75 ppm (2
H), 11.61 ppm (2H), and it was confirmed that the product was the target product.

The polymer material composition of the present invention comprises a benzotriazole compound represented by the above general formula (I) as a light stabilizer added to the polymer material. 0.001 to 5 with respect to 100 parts by weight
Parts by weight, preferably 0.01 to 3 parts by weight.

Examples of the polymer material for which stability is to be improved in the present invention include high density, low density or linear low density polyethylene, polypropylene, polybutene-
1, α-olefin polymers such as poly-3-methylpentene or polyolefins such as ethylene-vinyl acetate copolymers and ethylene-propylene copolymers and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated Polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer Halogen-containing resins such as polymers, vinyl chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-cyclohexylmaleimide copolymers, vinyl chloride-cyclohexylmaleimide copolymers, petroleum resins, coumarone Resin, polystyrene, polyvinyl acetate, acrylic Resin, styrene and / or α- methylstyrene with other monomers (e.g., maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene,
Acrylonitrile, etc.) (for example, AS resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.), polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate, polytetramethylene terephthalate, etc. Polyester, polyphenylene oxide,
Polycaprolactam, polyhexamethylene adipamide and other polyamides, polycarbonates, polyacetals,
Examples thereof include thermoplastic synthetic resins such as polyphenylene sulfide, polyurethane, and fibrin-based resins and blends thereof, and thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins and unsaturated polyester resins. Furthermore, isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber,
It may be an elastomer such as styrene-butadiene copolymer rubber.

In the polymer material composition of the present invention, other general-purpose antioxidants, stabilizers and other additives can be used in combination with the compound represented by the general formula (I).

Particularly preferable examples of these additives include phenol-based, sulfur-based, phosphite-based antioxidants, and hindered amine-based light stabilizers.

Examples of the above-mentioned phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-tert-butyl-
4-hydroxyphenyl) propionate], 1,6-
Hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-sec. Tributylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid]
Glycol ester, 4,4'-butylidene bis (6-
Tert-butyl-m-cresol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-
Ethylidene bis (4-tert-butyl-6-tert-butylphenol), 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, 1,3,5-tris (3,5-di-tert-butyl-4-)
Hidoxybenzyl) isocyanurate, 1,3,5-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-
Tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tetrakis [methylene-3- (3,5-di-tert-butyl-
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-tertiary Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy) -5
Methylphenyl) propionate] and the like.

Examples of the sulfur antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Examples include β-alkyl mercaptopropionic acid esters.

Examples of the above-mentioned phosphite antioxidants include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3). -Tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, di (tridecyl) pentaerythritoldi Phosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-Methylphenyl) pentaerythritol diphos Aito, tetra (tridecyl)
Isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidene bis (2-
Tert-butyl-5-methylphenol) diphosphite,
Hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite, 9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-
Piperidyl benzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecyl succinimide,
1-[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-di-tert-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-di-tert-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) butane tetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butane tetracarboxylate, bis (1,2,2 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-tertiary 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-tetramethyl-4-piperidyl) hexamethylenediamine / Examples thereof include dibromoethane condensates.

In addition, if necessary, the polymeric material composition of the present invention contains a heavy metal deactivator, a nucleating agent, a metallic soap,
Organotin compounds, plasticizers, epoxy compounds, foaming agents, antistatic agents, flame retardants, lubricants, processing aids and the like can be included.

The compound represented by the above general formula (I) is not only excellent in the effect of improving the weather resistance of the polymer material, but also has a high degree of heat resistance, so that it is not only a general-purpose plastic but also various engineering materials. It is also useful as a light stabilizer for plastics.

The polymer material composition of the present invention can also be suitably used for applications requiring high weather resistance for a long period of time, such as agricultural materials and coating materials for automobiles. Film, fiber, tape, sheet, various molding materials,
It can be used in paints, binders for lacquers, adhesives, putties and base materials in photographic materials.

[0042]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by the following examples.

Example 1 Pellets having the following composition were extruded at 250 ° C. to prepare pellets. Then, injection molding was carried out at 250 ° C. to prepare a test piece having a thickness of 2 mm, and a weather resistance test was carried out with a sunshine weatherometer (with rain) at 83 ° C. using this test piece. The gloss ratios of the original test piece and the test piece after aging for 1500 hours were measured to determine the residual rate, and the color difference between the original test piece and the test piece after aging for 480 hours was determined. Comparative compounds 1 and 2 used in Comparative Examples
4 and 15 respectively.

The results are shown in Table 1.

[Blending] Polypropylene block copolymer 100 parts by weight Stearyl (3,5-di-tert-butyl-4-0.1 hydroxyphenyl) -propionate Tris (2,4-di-tert-butylphenyl) 0.05 phosphite Calcium stearate 0.05 Bis (2,2,6,6-tetramethyl 0.2-4-piperidyl) sebacate Sample compound (Table-1) 0.1

[0046]

[Table 1]

[0047]

[Chemical 14] Comparative compound 1

[0048]

[Chemical 15] Comparative compound 2

Example 2 0.30% by weight based on bisphenol A polycarbonate powder having an intrinsic viscosity of 0.57 (30 ° C. in dioxane)
Was added to the sample compound (Table 2) and extruded at 250 ° C. to form pellets. This pellet at 320 ℃
Was injection molded to prepare a test piece having a thickness of 2.5 mm.

This test piece was irradiated with ultraviolet rays from a high-pressure mercury lamp, and the color difference between the unirradiated test piece and the test piece after irradiation for 2 weeks was determined according to ASTM 1925.

The results are shown in Table 2.

[0052]

[Table 2]

Example 3 Polyethylene terephthalate 100 having an intrinsic viscosity of 0.72
Parts by weight, pentaerythritol tetra (3,5-di-tert-butyl-4-hydroxyphenylpropionate) 0.
1 part by weight and 1 part by weight of the sample compound (Table 3) were mixed and melt-extruded at 300 ° C to prepare a sheet on a cooling drum at 45 ° C. Next, it is stretched at a draw ratio of 3.5 times in the machine direction at a temperature of 90 ° C., stretched 3.6 times in the axial direction, and then heat set at 200 ° C. for 30 seconds to give a biaxially stretched film having a thickness of 0.125 mm. Created.

Using this film, a weather resistance test was conducted with a weatherometer. The test was carried out by measuring the change with time of the haze value of the film and determining the time until the haze value becomes twice the initial value by extrapolation.

The results are shown in Table 3.

[0056]

[Table 3]

Example 4 The following formulation was extruded at 260 ° C. to prepare pellets, and then injection-molded at 260 ° C. to prepare test pieces having a thickness of 1 mm. Using this test piece, a weather resistance test was performed with a sunshine weatherometer (without rain) at 83 ° C., and the color difference after irradiation for 400 hours was measured.

The results are shown in Table 4.

[Blending] Heat-resistant ABS resin (α-methylthrene copolymer) 100 parts by weight Magnesium stearate 0.4 Triethylene glycol bis (3-tertiary butyl 0.2-4-hydroxy-5-methylphenyl) propionate Bis (2,4-ditertiary butylphenyl) penta 0.2 Erythritol diphosphite titanium dioxide 0.5 Sample compound (Table-4) 0.5

[0060]

[Table 4]

From the results of the above-mentioned examples, it is apparent that the use of the specific benzotriazole compound of the present invention exhibits a remarkable effect as compared with the case of using the conventional benzotriazole compound.

[0062]

The polymeric material composition of the present invention has long-term weather resistance even under severe processing conditions.

Claims (1)

[Claims] 1. A polymer material containing 100 parts by weight of a benzotriazole compound represented by the following general formula (I):
A polymeric material composition having improved weather resistance, which is obtained by adding 001 to 5 parts by weight. [Chemical 1]