JP2831817B2 - Polyolefin resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyolefin-based resin composition having significantly improved colorability and weather resistance, and more particularly, to a hindered amine-based light stabilizer, a specific phenol-based antioxidant, and the like. The present invention relates to a polyolefin-based resin composition in which coloring property and weather resistance are remarkably improved by blending an oxidizing agent and an ozanilide compound or a cyanoacrylate compound.

[Problems to be solved by conventional technology and invention]

Polyolefin resins are excellent in mechanical properties, thermal properties, moldability, etc., are lightweight and relatively inexpensive, so they are widely used as various molded products, films, fibers, etc. It is known that the pigment is colored by the action of ultraviolet rays and the mechanical strength is reduced, so that it cannot withstand long-term use.

In order to prevent these harmful effects, benzophenone-based, benzotriazole-based or benzoate-based ultraviolet absorbers, hindered amine-based light stabilizers represented by polyalkylpiperidine-based compounds, nickel chelate-based quencher, etc. have been used. Used alone or in combination. In particular, hindered amine-based light stabilizers have attracted particular attention in recent years because they are non-colorable and have relatively large light stabilizing effects.

Hindered amine compounds represented by piperidine compounds are relatively excellent light stabilizers, but the effects of single use are still insufficient, so piperidine compounds and benzophenones, benzotriazoles, phenyl salicylates, etc. It has been proposed to use an ultraviolet absorber in combination, but the effect of these combined use is only additive and was not practically satisfactory.

Further, it has been proposed that a hindered amine compound is used in combination with a 3,5-di-tert-butyl-4-hydroxybenzoate compound to exhibit a synergistic stabilizing effect. To some extent. However, the combined use of a hindered amine compound and 3,5-di-tert-butyl-4-hydroxybenzoic acid ester has a major drawback in that the polyolefin resin is colored yellow, and these improvements are strongly desired. Was.

[Means for solving the problem]

In view of the above situation, the present inventors have made intensive studies to find a light stabilizer composition that significantly improves the weather resistance of a polyolefin resin and does not impart color to the resin, and as a result, a hindered amine light stabilizer It has been found that by using a specific phenolic antioxidant and an ozanilide compound or a cyanoacrylate compound together, the polyolefin resin can be stabilized for a long period without coloring, and the present invention has been achieved.

That is, the present invention relates to (a) a hindered amine-based light stabilizer of 0.05 to 100 parts by weight of a polyolefin-based resin.
10 parts by weight, (b) 3,5-di-tert-butyl-4-hydroxybenzoate compound represented by the following general formula (I)
A polyolefin-based resin obtained by adding 0.01 to 10 parts by weight, and (c) 0.01 to 10 parts by weight of an oxanilide compound represented by the following general formula (II) or a cyanoacrylate compound represented by the following general formula (III): It provides a composition.

(In the formula, R represents an alkyl group or an aryl group which may have a _{substituent, R 1, R 2, R} 3 and R ₄ are each a hydrogen atom, an alkyl group, an alkoxy group or a hydroxyl group, R ₅
And R ₆ are each a hydrogen atom, a halogen atom, a hydroxyl group,
R ₇ represents an alkyl group or an alkoxy group, and R ₇ represents an alkyl group. Hereinafter, the present invention having the above gist will be described in detail.

The hindered amine light stabilizer used in the present invention includes 1-substituted or unsubstituted-2,2,6,6-tetramethyl-4-piperidinol and 1-substituted or unsubstituted-2,
2,6,6-Tetramethyl-4-piperidylamine derivatives are preferred.

More specifically, 1-substituted or unsubstituted-2,2,6,6-
As derivatives of tetramethyl-4-piperidinol,
Esters of the piperidinol with a mono- or polyhydric carboxylic acid may be mentioned. The ester may be a partial ester containing another monohydric alcohol component or a polyester containing a polyhydric alcohol component. -Hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol and a polyester of a polycarboxylic acid.

1-substituted or unsubstituted-2,2,6,6-tetramethyl-4
-Piperidylamine derivatives include amides or imides of piperidylamine and mono- or polyvalent carboxylic acids, condensates of piperidylamine with cyanuric chloride and, if necessary, polyamines, and bis (2,2,6 , 6-tetramethyl-4-piperidylamino) alkane, and bis (2,2,6,6-tetramethyl-4-pipedidylamino) alkane with 2-substituted-4,6-dichloro-s
-Condensates with triazines or halogenoalkanes are also preferred.

Therefore, typical examples of preferred hindered amine light stabilizers are 2,2,6,6-tetramethyl-4-piperidyl benzoate, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2, 2,6,6-pentamethyl-4-piperidyl stearate, 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, tetra (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate,
Tetra (1,2,2,6,6-pentamethyl-4-piperidyl)
-1,2,3,4-butanetetracarboxylate, bis (2,2
2,6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl)・ Di (tridecyl) -1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- ｛2,3,4-tris (2,2,6,6- Tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxydiethyl] -2,4,8,
10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {2,3,4-tris (1,2,2,6,6-
Pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxydiethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1- [2- {β- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionyloxydiethyl] -2,2,6,6-tetramethyl-4-piperidyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol /
Dimethyl succinate condensate, N- (2,2,6,6-tetramethyl-4-piperidyl) -2- (2,2,6,6-tetramethyl-4-piperidylamino) isobutyric acid amide, N- (2,2,
6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane, 1,5,8,12-tetrakis [ Four,
6-bis {N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl]
-1,5,8,12-tetraazadodecane, 1,6-bis (2,2,6,6
-Tetramethyl-4-piperidylamino) hexane / 2-
Tertiary octylamino-4,6-dichloro-s-triazine condensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2-morpholino-4,6-dichloro -S-triazine condensate and 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane condensate.

The amount of the hindered amine light stabilizer to be added is 0.05 to 10, preferably 0.1 to 5 parts by weight based on 100 parts by weight of the polyolefin resin.

Further, 3,5-di-tert-butyl- represented by the general formula (I)
As the alkyl group which may have a substituent represented by R constituting 4-hydroxybenzoic acid ester, an alkyl group having 1 to 18 carbon atoms is preferable, for example, methyl,
Ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, amyl, isoamyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl,
Tertiary octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 12-hydroxystearyl, oleyl, cyclohexyl, benzyl, phenylethyl, 2-hydroxyethyl, 2,3-epoxypropyl, dimethylaminopropyl, methoxyethyl, etc. Is raised. Examples of the aryl group include a phenyl, biphenyl, naphthyl group and the like, and these may be substituted with a halogen, a hydroxyl group, an alkyl group, a cycloalkyl group and the like.

These compounds are known compounds, and are well-known methods for synthesizing 3,5-di-tert-butyl-4-hydroxybenzoate, for example, 3,5-di-tert-butyl-4-hydroxybenzoic acid, It can be easily produced by reacting a lower alkyl ester or halide with an alcohol compound or a phenol compound.

The amount of the benzoic acid ester compound to be added is 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the polyolefin resin.

Further, the substituents represented by R ₁ , R ₂ , R ₃ and R ₄ constituting the oxanilide compound represented by the general formula (II) are each a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, Dibutyl, tertiary butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, isooctyl, tertiary octyl, nonyl, decyl,
An alkyl group such as lauryl; an alkoxy group such as methoxy, ethoxy, propoxy, butoxy, allyloxy, octoxy or a hydroxyl group;

Further, as the substituents represented by R ₅ and R ₆ constituting the cyanoacrylate compound represented by the general formula (III), a hydrogen atom; a halogen atom such as chlorine and bromine; a hydroxyl group; methyl, ethyl, propyl, Alkyl groups such as butyl, hexyl, and octyl or alkoxy groups such as methoxy, ethoxy, and butoxy are exemplified.Examples of the alkyl group represented by R ₇ include methyl, ethyl, propyl, butyl, hexyl, octyl, and 2-ethylhexyl. Alkyl group.

In the composition of the present invention, at least one of the above-mentioned ogizanilide compound and the cyanoacrylate compound may be added, and the amount of these added is 10%.
0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 0 parts by weight
Parts by weight.

Examples of the polyolefin resin that can be used in the present invention include homo- or copolymers of α-olefins such as ethylene, propylene, butene, pentene, hexene, 4-methylpentene, heptene and octene;
A majority of olefins and vinyl esters such as vinyl acetate, unsaturated organic acids (including esters, salts, amides and amines) such as acrylic acid, maleic anhydride and methyl methacrylate; vinyl silanes such as vinyl trimethoxysilane Random, block or graft copolymers; or chlorination, sulfonation,
Examples thereof include those subjected to a modification treatment such as oxidation.

Specifically, low, medium or high density polyethylene, polypropylene, polybutene, ethylene-propylene random or block copolymer, ethylene-propylene-butene copolymer, ethylene-butene copolymer, ethylene-4-methylpentene copolymer Examples thereof include a polymer, a propylene-hexene copolymer, and a propylene-hexene-butene copolymer.

Particularly effective among these polymers are polypropylene, ethylene-propylene random or block copolymer, ethylene-propylene-butene copolymer,
It is a propylene-based copolymer such as a propylene-hexene-butene copolymer.

The polyolefin-based resin composition of the present invention may further comprise, if necessary, a phenolic resin other than the 3,5-di-tert-butyl-4-hydroxybenzoate compound represented by the general formula (I). An oxidizing agent, an organic phosphorus-containing compound such as an organic phosphite compound, another ultraviolet absorber, and a thioether-based antioxidant can be added to further improve the oxidation stability and light stability.

Phenolic antioxidants other than the 3,5-di-tert-butyl-4-hydroxybenzoate compound that can be used in the present invention 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], 4,4'-
Thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 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) butylic 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-di-tert-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-hydroxyethyl) -2,4,
8,10-tetraoxaspiro [5.5] undecane-bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], triethylene glycol bis [β- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionate].

The amount of the phenolic antioxidant other than these 3,5-di-tert-butyl-4-hydroxybenzoate compounds is 0.001 to 5 parts by weight per 100 parts by weight of the polyolefin resin.
Parts by weight are preferred, and more preferably 0.01 to 3 parts by weight.

Examples of the organic phosphorus-containing compound that can be used in the present invention include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tridecyl phosphite, di (tridecyl) pentaerythritol diphosphite, and distearyl. Pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-
4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4'-
n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,1
3-tris (3-tert-butyl-4-hydroxy-5-methylphenyl) butanetriphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octadecylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) fluorophosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene And phosphonites.

The amount of the organic phosphorus-containing compound to be added is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the polyolefin resin.

Other UV absorbers that can be used in the present invention include 2,4
-Dihydroxybenzophenone, 2-hydroxy-4-
2-hydroxybenzophenones such as methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzo Triazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 -Hydroxy-3-tert-butyl-5-methylphenyl) -5
Chlorobenzotriazole, 2- (2-hydroxy-5
-Tert-octylphenyl) benzotriazole, 2-
(2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 3- (3-tert-butyl-4-hydroxy 2- (2-hydroxyphenyl) benzotriazoles such as -5-benzotriazolylphenyl) propionic acid-polyethylene glycol ester; phenyl salicylate, resorcinol monobenzoate, hexadecyl-3,5-di-tert-butyl-4
Other benzoates, such as -hydroxybenzoate.

The amount of these ultraviolet absorbers added is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the polyolefin resin.

The thioether antioxidants that can be used in the present invention include thiodipropionic acid dilauryl, dimyristyl,
Β of dialkylthiodipropionates such as distearyl esters and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate)
-Alkyl mercaptopropionates.

The amount of the thioether-based antioxidant to be added is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, per 100 parts by weight of the polyolefin resin.

In addition, the polyolefin resin composition of the present invention,
Inorganic fillers such as talc, calcium carbonate, glass fiber, etc., metal soaps such as calcium stearate, calcium stearyl lactate, aluminum-p-tert-butylbenzoate, dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol, bis (4 Nucleating agents, pigments, dyes, etc., such as -tert-butylphenyl) phosphate sodium salt and 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate sodium salt, may be added as desired. .

The composition of the present invention can be molded by a conventionally known method such as injection molding, extrusion molding, or blow molding, and is not limited by the molding method or its form.

In addition, the surface properties of the composition of the present invention can be improved by subjecting the composition to a known treatment such as a low-temperature plasma treatment after molding.

〔Example〕

Next, the effect of the present invention will be specifically shown by way of examples.
The present invention is not limited at all by the following examples.

Example 1 According to the following composition, pellets were prepared by extrusion at 250 ° C. using a twin-screw extruder. Using the pellets, a test piece having a thickness of 2 mm was prepared by injection molding at 250 ° C.

This test piece was irradiated in a sunshine weatherometer at a black panel temperature of 83 ° C. to perform a weather resistance test. Further, the yellowness of the test piece when irradiated for 480 hours was measured using a Hunter colorimeter, and the color difference from that before irradiation was determined.

 Table 1 shows the results.

<Compound> Unstabilized polypropylene 100 parts by weight Calcium stearate 0.1 Tetrakis [methylene-3- (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionate] methane 0.1 bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite 0.05 tetra (2,2,6,6-tetramethyl-4-piperidyl)-
1,2,3,4-butanetetracarboxylate 0.2 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di-tert-butylphenyl 0.1 Sample compound (Table 1) 0.2 Example 2 In order to see the effect of the present invention in the polypropylene copolymer, a test piece was prepared by the same operation as in Example 1 with the following composition, and the same test as in Example 1 was performed.

 Table 2 shows the results.

<Compound> Polypropylene copolymer 100 parts by weight Calcium stearate 0.05 Stearyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 0.1 Tris (2,4-di-tert-butylphenyl) phosphite 0.05 3,9-bis [1,1-dimethyl-2- {2,3,4-tris (1,
2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxydiethyl] -2,4,8,10-
Tetraoxaspiro [5.5] undecane 0.2 2-ethoxy-4'-isodecyl oganilide 0.1 benzoate (Table 2) 0.1 [Effects of the Invention] From the results of the above examples, it is clear that the composition according to the present invention does not color the polyolefin-based resin and improves the weather resistance over a long period of time. On the other hand, when a compound other than 3,5-di-tert-butyl-4-hydroxybenzoate is used, or when an ozanilide compound or a cyanoacrylate compound is not used in combination, the coloring property and the long-term weather resistance are improved. It is clear that it cannot be improved and that the effect of the present invention is very specific.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 23/00-23/36

Claims (1)

(57) [Claims] (1) a hindered amine light stabilizer in an amount of 0.05 to 10 parts by weight, and (b) a 3,5-di-thiocyanate represented by the following general formula (I) based on 100 parts by weight of a polyolefin resin. 0.01 to 10 parts by weight of a tributyl-4-hydroxybenzoate compound and (c) 0.01 to 10 parts by weight of an ozanilide compound represented by the following general formula (II) or a cyanoacrylate compound represented by the following general formula (III) A polyolefin-based resin composition obtained by adding parts. (In the formula, R represents an alkyl group or an aryl group which may have a _{substituent, R 1, R 2, R} 3 and R ₄ are each a hydrogen atom, an alkyl group, an alkoxy group or a hydroxyl group, R ₅
And R ₆ are each a hydrogen atom, a halogen atom, a hydroxyl group,
R ₇ represents an alkyl group or an alkoxy group, and R ₇ represents an alkyl group. )