JPH04363362A - Polymeric material composition improved in light resistance - Google Patents

Abstract

PURPOSE:To obtain a stable polymeric material composition having light resistance for a long period even under severe processing conditions without yellowing by blending a polymeric material with a specific benzotriazole compound as a light stabilizer. CONSTITUTION:A polymeric material composition is obtained by blending (A) 100 pts.wt. polymeric material (e.g. propylene-based polymer, ABS resin or polyurethane) with (B) 0.001-5 pts.wt., preferably 0.01-3 pts.wt. benzotriazole compound, prepared by esterifying a 2-hydroxyphenylbenzotriazole compound with a carboxylic acid such as hydroxybenzoic acid or a hydroxyphenylalkanoic acid in a solvent such as toluene or xylene under refluxing conditions of the solvent and expressed by the formula [R<1> and R2 are H or 1-8C alkyl; R3 is H or 1-12C alkyl or arylakyl; R4 is H or halogen; (m) is 0-2] and preferably further a hindered amine-based compound, a phenolic antioxidant, a sulfur-based antioxidant, a phosphite-based antioxidant, etc.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a polymeric material composition with improved light resistance, and more specifically, by adding a specific esterified product of 2-hydroxyphenylbenzotriazole, the composition has improved light resistance for a long period of time. The present invention relates to a polymeric material composition with improved properties.

0002

[Prior Art and Problems to be Solved by the Invention] Polymer materials such as polyethylene, polypropylene, styrene resin, and polyvinyl chloride deteriorate due to the action of light, causing discoloration and a decrease in mechanical strength, resulting in long-term problems. It is known that it cannot withstand the use of

[0003] Various light stabilizers have heretofore been used to prevent the deterioration of polymeric materials. These light stabilizers include hindered amine light stabilizers,
Benzophenone-based or benzotriazole-based ultraviolet absorbers are mainly used, and in particular, 2-hydroxyphenylbenzotriazole-based ultraviolet absorbers have a great stabilizing effect and are widely used.

However, the conventionally used benzotriazole compounds themselves have a hydroxyl group at the ortho position, so they have poor heat resistance, are unstable, and have the disadvantage of yellowing during storage. .

[0005] For this reason, the unstable ortho-position hydroxyl group,
Attempts have been made to improve the yellowing of ultraviolet absorbers themselves by esterifying them with aromatic acids. (JP 51-63845, JP 51-63846, JP 58-37314) However, their photostability was still insufficient.

[0006]

[Means for Solving the Problems] In view of the above-mentioned current situation, the present inventors have made extensive studies to obtain a new type of light stabilizer for polymeric materials, and have found that the following general formula (I) It has been discovered that the compound represented by is stable, does not yellow, and can impart long-term light resistance to polymeric materials such as synthetic resins even under severe processing conditions.

The present invention has been made based on the above findings, and is based on the benzotriazole represented by the general formula (I) shown in the following chemical formula 2 (same as chemical formula 1), based on 100 parts by weight of the polymeric material. The present invention provides a polymeric material composition with improved light resistance, which contains 0.001 to 5 parts by weight of a compound.

[0008]

[Chemical formula 2] (R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
12 alkyl group or arylalkyl group, R
4 represents a hydrogen atom or a halogen atom, m is 0 to 2
shows. )

[0009] Hereinafter, the present invention having the above-mentioned summary will be explained in detail.

In the above formula, examples of the alkyl group represented by R1 and R2 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, tertiary-amyl, octyl, Examples include tri-octyl. Examples of the alkyl group represented by R3 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, tertiary amyl, octyl, tertiary octyl, decyl, dodecyl, etc. Examples of the arylalkyl group include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and the like. Examples of the halogen atom for R4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The compound represented by the above general formula (I) has 2
It can be easily synthesized by esterifying a -hydroxyphenylbenzotriazole compound with a carboxylic acid such as hydroxybenzoic acid or hydroxyphenylalkanoic acid.

Examples of the 2-hydroxyphenylbenzotriazole compound used to produce the compound represented by the above general formula (I) include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-
(2-hydroxy-5-α,α-dimethylbenzyl)benzotriazole, 2-(2-hydroxy-5-sec-butylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole ,
Examples include 2-(2-hydroxy-5-tertiary octylphenyl)benzotriazole, 2-(2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, and the like.

Further, as the carboxylic acid used for producing the compound represented by the above general formula (I), 2-
Hydroxybenzoic acid, 2-hydroxy-3-methylbenzoic acid, 2-hydroxy-5-tert-butylbenzoic acid, 2-
Hydroxy-5-tert-octylbenzoic acid, 4-hydroxy-3,5-tert-dibutylbenzoic acid, 4-hydroxy-
3-tert-butyl-5-methylbenzoic acid, 4-hydroxy-3,5-di-tertiary amylbenzoic acid, (4-hydroxy-
3,5-di-tert-butylphenyl)acetic acid, β-(4-hydroxy-3,5-tert-dibutylphenyl)propionic acid, β-(4-hydroxy-3-tert-butyl-5-methylphenyl)propion Examples include acids.

The above esterification reaction is carried out under reflux of a solvent such as toluene or xylene.

Next, the general formula (I) used in the present invention
), but the present invention is not limited by the following synthesis examples.

Synthesis Example 1 Synthesis of [2-(4-hydroxy-3,5-tert-dibutylbenzoyloxy)-4-methylphenyl]benzotriazole (compound represented by formula 3)

[0017]

[Chemical formula 3]

7.51 g of 2-(2-hydroxy-5-methylphenyl)benzotriazole, 4-hydroxy-
6.76 g of 3,5-di-tert-butylbenzoic acid, 4.6 g of phosphorous oxychloride, and 0.66 g of dimethylformamide were dissolved in 40 ml of toluene, and the mixture was reacted for 10 hours under refluxing toluene. After the reaction is complete, add 40ml of toluene.
was added, washed with water, dehydrated, and toluene was distilled off under reduced pressure. Thereafter, it was recrystallized from a normal hexane/toluene mixed solvent to obtain a white solid with a melting point of 137°C.

As a result of infrared spectroscopic analysis of the above white solid, 35
There is absorption at 60 and 1710 cm-1, and as a result of UV spectrum absorption analysis, Max: 278 nm, ε: 2
4,400, confirming that it was the target object.

By the same operation as in Synthesis Example 1 above, the following compounds (No. 2 to No. 6) were synthesized.

[0021]

[C4]

[0022]

[C5]

[0023]

[C6]

[0024]

[C7]

[0025]

[Chemical formula 8]

The present invention uses the above-mentioned specific benzotriazole compound as a light stabilizer for polymeric materials, and the amount added is not particularly limited, but is limited to 100 parts by weight of the polymeric material. It is usually 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight.

Examples of polymeric materials whose stability is to be improved in the present invention include high-density, low-density, or linear low-density polyethylene, polypropylene, and polybutene.
1. α-olefin polymers such as poly-3-methylpentene or polyolefins such as ethylene-vinyl acetate copolymers and ethylene-propylene copolymers, and their copolymers, 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 Polymers, halogen-containing resins such as vinyl chloride-acrylic ester copolymers, vinyl chloride-maleic ester copolymers, vinyl chloride-cyclohexylmaleimide copolymers, vinyl chloride-cyclohexylmaleimide copolymers, petroleum resins, coumarons resins, polystyrene, polyvinyl acetate, acrylic resins, styrene and/or α-methylstyrene and other monomers (e.g. maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene,
acrylonitrile, etc.) (e.g., AS resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.), linear chains of polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate, polytetramethylene terephthalate, etc. Polyamides such as polyester, polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, thermoplastic synthetic resins such as polycarbonate, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, cellulose resins, and blends thereof, or phenolic resins, Examples include thermosetting resins such as urea resin, melamine resin, epoxy resin, and unsaturated polyester resin. Furthermore, elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber may also be used.

In the composition of the present invention, other general-purpose additives such as antioxidants and stabilizers can be used together 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, particularly 2,2,6,6-tetra Hindered amine light stabilizers, typified by methylpiperidine compounds, are preferred because they have a synergistic effect with the compound of the present invention.

Examples of the above-mentioned phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-p-cresol,
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-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(3,5-di-tert-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-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-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 -ditert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-ditert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1, 3,5-tris[(3,5-di-tert-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-tert-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-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl thiodipropionate, and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Examples include β-alkylmercaptopropionic acid esters.

[0032] The above-mentioned phosphite-based antioxidants include, for example, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris[2-tert-butyl-4-(3 -tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol di 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 diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tetra(tridecyl)isopropylidene diphenol diphosphite phyto, tetra(tridecyl)-4,4'
-n-butylidenebis(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-
Examples include 10-phosphaphenanthrene-10-oxide.

[0033] Further, as the above-mentioned hindered amine light stabilizer, for example, 2,2,6,6-tetramethyl-4-
piperidyl benzoate, N-(2,2,6,6-tetramethyl-4-piperidyl)dodecylsuccinimide,
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-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, 1,5,8,1
2-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,
Examples include 6,6-tetramethyl-4-piperidyl)hexamethylene diamine/dibromoethane condensate.

[0034] In addition, if necessary, the composition of the present invention may contain a heavy metal deactivator, a nucleating agent, a metal soap, an organic tin compound, a plasticizer, an epoxy compound, a blowing agent, an antistatic agent, a flame retardant, and a lubricant. , processing aids, and the like.

The polymeric material stabilized according to the present invention is particularly useful in fields that require a high degree of light resistance, such as agricultural materials and automotive paints, and is particularly useful in applications such as films, fibers, tapes, and sheets. It can be used for various molding materials, paints, binders for lacquers, adhesives, putty, and base materials for photographic materials.

[0036]

[Examples] Next, the present invention will be specifically explained with reference to Examples.

Example 1 Pellets were prepared by extrusion processing at 250° C. using the following formulation. Next, injection molding was performed at 250° C. to prepare a test piece with a thickness of 2 mm, and the degree of yellowness was measured. Regarding this test piece, using a sunshine weather meter,
A light fastness test was conducted with a black panel temperature of 83° C. and a rain cycle of 18 minutes out of 120 minutes. The evaluation method was a comparison of crack generation time.

The results are shown in Table 1 below.

[Blend] Ethylene-propylene copolymer
100 parts by weight stearyl (3,
5-Ditert-butyl-4-hydroxyph 0.1
phenyl) propionate tris(2,4-di-tert-butylphenyl) phosphite 0.05 bis(2,2,6,6-tetramethyl-4-piperidyl 0.3) sebacate calcium stearate
0.05 sample compound (see Table-1)

[0040]

[0041]

[Chemical formula 9]

[0042]

[Chemical formula 10]

[0043]

[Chemical formula 11]

Example 2 Pellets were made by extrusion at 260°C using the following formulation, and then injection molded at 260°C to a thickness of 1.
A test piece of mm was prepared. Using this test piece, 83℃
A weather resistance test was conducted using a Sunshine Weatherometer (no rain), and the color difference after 400 hours of irradiation was measured.

The results are shown in Table 2 below.

[Blend] Heat-resistant ABS resin (α-methylstyrene copolymer)
100 parts by weight magnesium stearate

0.4 triethylene glycol bis(3-tert-butyl-4-hyperoxy-5-methylphenyl) propionate bis(2,4-di-tert-butylphenyl) pentaerythri 0.2 tol diphosphite titanium dioxide
0.
5-bis(2,2,6,6-tetramethyl-4-piperidyl 0.3)-1,2,3,4-tetracarboxylate sample compound (see Table 2)

[0047]

Example 3 The following formulation was kneaded on a roll at 70°C for 5 minutes,
A test piece with a thickness of 0.5 mm was prepared by pressing at ℃ for 5 minutes. Using this test piece, the residual elongation rate after irradiation for 50 hours and 100 hours was measured using a fade meter.

The results are shown in Table 3.

[Formulation] Polyurethane resin (Asahi Denka U-100)
100 parts by weight barium stearate

0.7 zinc stearate

0.32,6-di-tert-butyl-p-cresol 0.1 Adekastab LA-62*
0.3 Sample compound (see Table 3) *Hindered amine light stabilizer manufactured by Asahi Denka Kogyo

[0051]

Example 4 The following formulation was kneaded with a kneading roll to give a thickness of 0.
．． A 1 mm film was prepared. A test piece was cut from this film and subjected to a weather resistance test using a weatherometer.

The results are shown in Table 4.

[Blend] Vinyl chloride resin (degree of polymerization 1,000)
100 parts by weight dioctyl phthalate
47 Trixylenyl phosphate
3 Zinc stearate
0.8 Phosphonic acid nonylphenyl ester barium salt
0.8 Tetra(tridecyl)bisphenol A
Diphosphite 0.8 Bisphenol A diglycidyl ether
3 methylene bis (stearamide)
0.5 sorbitan monopalmitate
2bis(2,2,6,6-tetramethyl-4-piperidyl 0.5)-1,2,3,4-
Tetracarboxylate sample compound (see Table 4)

[0055]

From the results of the above examples, it is clear that when a benzotriazole compound esterified with a specific hydroxyphenyl group-containing carboxylic acid used as a light stabilizer in the present invention is used, it can be compared with a conventionally known benzotriazole compound. It is clear that not only is the stabilizing effect significantly greater than when a benzoic acid ester compound is used, but also there is no drawback of coloring the resin.

[0057]

[Effect of the invention] The polymeric material composition of the present invention is stable,
It does not yellow and has long-term light resistance even under harsh processing conditions.

Claims (1)

[Claims] Claim 1: The following formula 1 is added to 100 parts by weight of a polymeric material.
A polymeric material composition with improved light resistance, which contains 0.001 to 5 parts by weight of a benzotriazole compound represented by the general formula (I). [Formula 1] (R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
12 alkyl group or arylalkyl group, R
4 represents a hydrogen atom or a halogen atom, m is 0 to 2
shows. )