JPH0480244A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in colorability and weathering resistance by mixing a polyolefin resin with a hindered amine light stabilizer, a specified phenolic antioxidant and an oxanilide compound or a cyanoacrylate compound. CONSTITUTION:100pts.wt. polyolefin resin is mixed with 0.05-10pts.wt. hindered amine light stabilizer, 0.01-10pts.wt. 3,3-di-tert-butyl-4-hydroxybenzoate compound of formula I and 0.01-10pts.wt. oxanilide compound of formula II or cyanoacrylate compound of formula III to obtain the title composition. In the above formulas, R is (substituted) alkyl or aryl; R1 to R4 are each H, alkyl, alkoxy or OH; R5 and R6 are each H, halogen, OH, alkyl or alkoxy; and R7 is alkyl. This composition is markedly improved in colorability and weathering resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyolefin resin composition with significantly improved coloring properties and weather resistance. Oxidant,
The present invention also relates to a polyolefin resin composition that has significantly improved colorability and weather resistance by incorporating an ogizanilide compound or a cyanoacrylate compound.

[Prior art and problems to be solved by the invention] Polyolefin resins have excellent mechanical properties, thermal properties, moldability, etc., are lightweight, and are relatively inexpensive, so they can be used in various molded products, films, Although it is widely used as fiber, it is known to be sensitive to ultraviolet rays, and is known to become colored and lose its mechanical strength due to the action of ultraviolet rays, making it unable to withstand long-term use.

To prevent these harmful effects, benzophenone-based, hensitriazole-based, or benzoate-based ultraviolet absorbers, hindered amine light stabilizers represented by polyalkylpiperidine-based compounds, and nickel chelate-based quenchers have been used. They are used alone or in combination. In particular, hindered amine light stabilizers have attracted particular attention in recent years because they are non-coloring and have a relatively large light stabilizing effect.

Hindered amine compounds, typified by piperidine compounds, are relatively hard light stabilizers, but their effects are still insufficient when used alone, so piperidine compounds, hensyphenones, hensitriazoles, phenyl salicylates, etc. Although it has been proposed to use UV absorbers in combination, the effects of these combinations are only additive and have not been practically satisfactory.

Furthermore, it has been proposed that the combined use of a 3,5-di-tert-butyl-4-hydroxybenzoic acid ester compound in a hindered amine compound exhibits a synergistic stabilizing effect, and it has been shown that the use of a 3,5-di-tert-butyl-4-hydroxybenzoic acid ester compound in combination with the hindered amine compound exhibits a synergistic stabilizing effect. The effects have appeared. However, the combined use of a hindered amine compound and 3,5-di-tert-butyl-4-hydroquine benzoate has a major drawback in that the polyolefin resin is colored yellow, and improvements to these have been strongly desired. .

[Means for resolving issues]

In view of the above-mentioned current situation, the present inventors have conducted intensive studies to find a light stabilizer composition that significantly improves the weather resistance of polyolefin resins and does not color the resins.
The present invention was achieved by discovering that polyolefin resins can be stabilized for a long period of time without being colored by using a specific phenolic antioxidant and an ogizanilide compound or a cyanoacrylate compound in combination with a hindered amine light stabilizer.

That is, in the present invention, (a) 0.0 part of the hindered amine light stabilizer is added to 100 parts by weight of the polyolefin resin.
5 to 10 parts by weight, (b) 3 represented by the following general formula (I)
, 0.01 to 10 parts by weight of a 5-di-tert-butyl-4-hydroxybenzoic acid ester compound, and (c) an ogizanilide compound represented by the following general formula (U) or a general formula (
Cyanoacrylate compound represented by I[l] 0.01
The object of the present invention is to provide a polyolefin resin composition in which 10 parts by weight is added.

(In the formula, R represents an alkyl group or an aryl group that may have a substituent, R1, R2, R3, and R2 each represent a hydrogen atom, an alkyl group, an alkoxy group, or a hydroxyl group, and R6 and R6 each represent a hydrogen atom. atom, halogen atom, hydroxyl group, alkyl group or alkoxy group, R
7 represents an alkyl group. ) Hereinafter, the present invention having the above-mentioned summary will be explained in detail.

The hindered amine derivatives used in the present invention include 1-substituted or unsubstituted-2,2,6-rotetramethyl-4-piperiditul and 1-substituted or unsubstituted-
2,2,6,6-tetramethyl-4-piperidylamine derivatives are preferred.

More specifically, 1-substituted or unsubstituted-2゜2.6.
Examples of derivatives of 6-tetramethyl-4-piperiditul include esters of the piperiditul and monohydric or polyhydric carboxylic acids, and the esters include partial esters containing other monohydric alcohol components or polyhydric alcohol components. It may be polyester, and furthermore, 1-(2hydroxyethyl)-2,2,6,6-tetramethyl-4
- It may be a polyester of piperiditul and polyhydric carboxylic acid.

Derivatives of 1-substituted or unsubstituted-2,2,6,6-tetramethyl-4-piperidylamine include amide or imide of the piperidylamine and monovalent or polyvalent carboxylic acid, and derivatives of the piperidylamine and cyanuric chloride. Condensates with polyvalent amines and bis(2,2,6,
6-tetramethyl-4-piperidylamino)alkane, and bis(2,2,6,6-tetramethyl-4piperidylamino)alkane and 2 3Em 46
-Dichloro-5-triazine or condensates with dihalogenoalkane are also preferred.

Therefore, representative examples of preferred hindered amine light stabilizers include 2,2,6.6-tetramethyl-4-piperidylbensoate, 2,2,6.6-tetramethyl-4-piperidyl stearate, 1,2゜2.6.6-bentamethyl-4-piperidyl stearate, bis(2,2,6
6-tetramethyl-4piperidyl) sebacate, bis(
I,2,2,6,6pentamethyl-4-pivridyl) sebacate, bis(c2,2,6,6-bentamethyl-4
-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxyhensyl)malonate, tetra(
2,2,6,6-tetramethyl-4-piperidyl)-1
, 2,3,4-butanetetracarboxylate, tetra(c2,2,6,6-pentamethyl-4piperidyl)
-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl4-piperidyl)・
Di(tridecyl) -C2,3゜4-butanetetracarboxylate, bis(I゜2.2,6.6-bentamethyl-4-piperidyl)di(tridecyl) -1,2,3
, 4-butanetetracarboxylate, 3,9-bis[
1, age methyl 2- (2,3,4-tris(2,2
,6,6-tetramethyl-4-piperidyloxycarbonyl)butylcarbonyloxy)ethyl] -2,4,
8,10-tetraoxaspiro(5,5)undecane,
3,9bis[l,1-dimethyl-2-(2,3,4-tris(I,2,2,6,6-bentamethyl-4-piperidyloxycarbonyl)butylcarbonyloxy)ethyl)-2,4, 8,10-tetraoxaspiro [5゜5
]Undecane, 1-C2-(β-(3,5-ditert-butyl-4-hydroxyphenyl)propionyloxy)
ethyl)-2,2,6,6-tetramethyl-4-piperidyl-β-(3,5-ditert-butyl-4-hydroxyphenyl)propionate, 1-(2-hydroxyethyl)-2,2,6 , 6-tetramethyl-4-piperiditul/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-his(2
,2,6,6-tetramethyl-4-piperidylamino)
Hexane, C5,8,12-tetrakis[46-bis(
N-(2,2,6,6-tetramethyl-4piperidyl)
Butylamino l-1,3,5-)riazin-2-yl)-1,5,8,12-tetraazadodecane, 1.6
-bis(2,2,6,6-tetramethyl4-piperidylamino)hexane/2-tertiary octylamino-46-dichloro-5-triazine condensate, 1,6-bis(2,2
,6,6-tetramethyl-4-piperidylamino)hexane/2morpholino-4,6-dichloro-5-)lyazine condensate, 1,6-bis(2,2,6,6-tetramethyl4-piperidylamino) ) Hexane/dibromoethane condensate, etc.

The amount of these hindered amine light stabilizers added is 0.05 to 10 parts by weight per 100 parts by weight of the polyolefin resin.
, preferably 0.1 to 5 parts by weight.

Furthermore, the alkyl group which may have a substituent represented by R constituting the 3,5-di-butyl-4-hydroxybenzoic acid ester represented by -formation (I) has 1 to 18 carbon atoms. Preferred are alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, nibutyl, tert-butyl, amyl, isoamyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexynyl,
Tertiary octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 12-hydroxystearyl, oleyl, cyclohexyl, hensyl, phenylethyl, 2-hydroxyethyl, 2,3-epoxypropyl, dimethylaminopropyl, methoxoethyl group, etc. can give. In addition, examples of aryl groups include:
Examples include phenyl, biphenyl, and naphthyl groups, which may be substituted with halogen, hydroxyl, alkyl, cycloalkyl, and the like.

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

The amount of these benzoic acid ester compounds 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.

In addition, the substituents represented by R1, R2, R3 and R4 constituting the ogizanilide compound represented by -formation (II) include hydrogen atoms; methyl, ethyl, propyl, isopropyl, butyl, nibutyl, tertiary butyl,
Alkyl groups such as isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, isooctyl, tertiary octyl, nonyl, decyl, lauryl; alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, allyloxy, octoxy, and hydroxyl groups.

Furthermore, the substituents represented by R3 and R6 constituting the cyanoacrylate compound represented by the -formation (III) include a hydrogen atom; a halogen atom such as chlorine or bromine; a hydroxyl group; methyl, ethyl, propyl, butyl, Alkyl groups such as hexyl and octyl, or methoxy,
Examples include alkoxy groups such as ethoxy and butoxy, and R
Examples of the alkyl group represented by 7 include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, and 2-ethylhexyl.

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

Examples of polyolefin resins that can be used in the present invention include homopolymers or copolymers of α-olefins such as ethylene, propylene, butene, pentene, hexene, 4-methylpentene, heptene, and octene;
Majority weight of olefins and random compounds such as vinyl esters such as vinyl acetate, acrylic acid, unsaturated organic acids (including esters, salts, amides and amines) such as maleic anhydride and methyl methacrylate, and vinyl silanes such as vinyltrimethoxysilane , floc, or graft copolymers; or modified polymers such as chlorination, sulfonation, and oxidation.

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

Particularly effective among these polymers are propylene copolymers such as polypropylene, ethylene-propylene random or block copolymers, ethylene-propylene-butene copolymers, and propylene-hexene-butene copolymers. be.

In addition, the polyolefin resin composition of the present invention may optionally contain phenolic antiseptics other than the 3,5-di-tert-butyl-4-hydroxybenzoic acid ester compound represented by the above-mentioned -formation (I). The oxidative stability and photostability can be further improved by adding an oxidizing agent, an organic phosphorus-containing compound such as an organic phosphite compound, another ultraviolet absorber, or a thioether antioxidant.

Phenolic antioxidants other than the 3,5-di-tert-butyl 4-hydroxybenzoate compound that can be used in the present invention include 26-di-tert-butyl-p-cresol;
26-diphenyl-4-octadecyloxyphenol,
Stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3゜5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 1,000-ocyethylene glycol bis((3,5-di-tert-butyl) propionate, 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[3,3bis(4-hydroxy-3-tert-butylphenyl)butyric acid] glycol ester, 4,4'-butylidene bis(6
-tert-butyl m-cresol), 2.2'-ethylidene bis(46-di-tert-butylphenol), 2.2"-
ethylidenebis(4-sec-butyl-6-tert-butylphenol), Ll, 3-tris(2-methyl-4hydroxy-5-tert-butylphenyl)butane, bis[2
-tert-butyl-4-methyl-6(2-hydroxy-3-
tert-butyl-5-methylhensyl) phenyl] terephthalate, 1,35-tris(2,6-dimethyl-3-hydroxy 4-tert-methylhensyl) isocyanurate,
1.3.5-) Lis(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, L3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)
-2,4,6-triethylenezene, 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(I,1-dimethyl-2hydroxyethyl")-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]
-Hydroxy-5-methylphenyl)propionate]
etc.

The amount of phenolic antioxidants other than these 3.5-di-tert-butyl-4-hydroxybenzoic acid ester compounds added is 0.0 parts by weight per 100 parts by weight of polyolefin resin.
01 to 5 parts by weight is preferable, more preferably 0.01 to 5 parts by weight.
It is 3 parts by weight.

Examples of organic phosphorus-containing compounds that can be used in the present invention include trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, di(tridecyl)pentaerythritol diphosphite, distearyl Pentaerythritol diphosphite, bis (2,4-',; tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra ( tridecyl) isopropylidene diphenol diphosphite, tetra(tridecyl)
4+4' n-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-)lis(3-tert-butyl-4
-Hydroxy-5-methylphenyl)butane triphosphite, 2,2゛-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, 2,2゛-methylenebis(4,6-di-tert-butylphenyl)octadecylphosphite phyto, 2,2'-methylenebis(4,6-di-tert-butylphenyl)fluorophosphite, and tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite.

The amount of these organic phosphorus-containing compounds added is preferably 0.001 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 ultraviolet absorbers that can be used in the present invention include 2.4
-2-hydroxybenzophenones such as 12-(2-hydroxybenzophenone), 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5.5-methylenebis(2-hydroxy-4-methoxybenzophenone). -5methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-ditert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-ditert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy 3-tert-butyl-5-methylphenyl)-5-
Chlorobenzotriazole, 2-(2-hydroxy-5
-tertiary octylphenyl)benzotriazole, 2-(
2-Hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2゛methylenebis(4-tert-octyl-6-henditriazolylphenol L3-(3-tert-butyl-4-hydroxy-5-benzotriazole) 2-(2-hydroxyphenyl)benzotriazoles such as zolylphenyl)propionic acid-polyethylene glycol ester; phenyl salicylate, resorcinol monobenzoate, hexadecyl-3,5-ditert-butyl-4
Other benzoates include -hydroxybenzoate.

The amount of these ultraviolet absorbers added is 0.01 to 5 parts by weight per 100 parts by weight of the polyolefin resin! It is preferable that
More preferably, it is 0.05 to 3 parts by weight.

The thioether antioxidants that can be used in the present invention include:
Examples include dialkyl thiodipropionates such as dilauryl, similystyl, and distearyl esters of thiodipropionic acid, and β-alkylmercaptopropionate esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate).

The amount of these thioether antioxidants 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 includes inorganic fillers such as talc, calcium carbonate, and glass fiber;
Metal soaps such as calcium stearate, calcium stearyl lactate, aluminum-p-tert-butylphenshede, dibenzylidene sorbitol, bis(4-methylbenzylidene) sorbitol, bis(4-tert-butylphenyl) phosphate sodium salt, 2. Nucleating agents such as 2'-methylenebis(4,6-di-tert-butylphenyl)phosphate sodium salt, pigments, dyes, etc. may be added as desired.

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

The surface properties of the composition of the present invention can also be improved by subjecting it to well-known treatments, such as low-temperature plasma treatment, after molding.

〔Example〕

Next, the effects of the present invention will be concretely illustrated by Examples, but the present invention is not limited in any way by the following Examples.

Example 1 The following formulation was extruded using a two-wheel extruder at 250°C to create pellets. Using this pellet, a test piece with a thickness of 2 m++ was prepared by injection molding at 250°C.

This test piece was irradiated in a sunshine weather meter with a blank panel temperature of 83°C to perform a weather resistance test.

Further, the yellowness of the test piece after 480 hours of irradiation was measured using a Hunter colorimeter, and the color difference from before irradiation was determined.

The results are shown in Table-1.

<Formulation> Unstabilized polypropylene 100 parts by weight Calcium stearate 0.1 Sample compound (Table 0.2 Table Example 2 In order to see the effect of the present invention on a polypropylene copolymer, Example 1 and A test piece was prepared using the same procedure, and a similar test was conducted.

The results are shown in Table 2.

<Formulation> Polypropylene copolymer calcium stearate Example 1 and 100 parts by weight 0.05 benzoic acid ester It is clear that it does not cause coloring and also improves weather resistance over a long period of time.In contrast, when a compound other than 3,5-di-tert-butyl-4-hydroxybenzoic acid ester is used, or when an ogizanilide compound or It is clear that coloring properties and long-term weather resistance cannot be improved unless a cyanoacrylate compound is used in combination, and it is clear that the effects of the present invention are extremely specific.

Claims (1)

[Scope of Claims] Based on 100 parts by weight of polyolefin resin, (a) 0.05 to 10 parts by weight of a hindered amine light stabilizer, (b) 3,5- expressed by the following general formula (I) Di-tert-butyl-4-hydroxybenzoic acid ester compound 0.0
1 to 10 parts by weight, and (c) 0.01 to 10 parts by weight of an ogizanilide compound represented by the following general formula (II) or a cyanoacrylate compound represented by the general formula (III). based resin composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R has a substituent represents an optional alkyl group or aryl group, R_1, R_2, R_3 and R_4
each represents a hydrogen atom, an alkyl group, an alkoxy group, or a hydroxyl group, R_5 and R_6 each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, or an alkoxy group, and R_7 represents an alkyl group. )