JPS60115644A - Stabilized polyolefin composition - Google Patents

Abstract

PURPOSE:To improve light resistance and weatherability of polyolefins by incorporating specified formamidine compounds into the polyolefins. CONSTITUTION:100pts.wt. polyolefin is incorporated with 0.01-1pt.wt. formamidine of formula I , in which R1 is an alkyl of 1-5C; R2 is H, Cl, OH or methoxy; R3 is an alkyl of 1-9C or phenyl; R4 is H, a halogen, an alkyl of 1-5C an alkoxy of 1-4C, a carboalkoxy of 2-5C or dimethylamino; R5 is H, Cl or methoxy. By incorporating one or more compounds selected from among compounds of formulas II-VII into the aforemention, the weatherability and yellowness index can be improved. The amounts of the compounds of II-VII to be incorporated are 0.01-1pts.wt. each and in total based on 100pts.wt. polyolefin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to stabilized polyolefin compositions, and more particularly to polyolefin compositions whose light stability is significantly improved through the incorporation of specific stabilizers.

Polyolefins such as polypropylene are generally sensitive to the effects of light in the absence of stabilizers, and deteriorate due to the effects of light, causing discoloration or a decrease in mechanical strength. Products that have deteriorated in this way cannot be molded. It is known that the product cannot withstand long-term use. The reason for this is that polyolefins are activated by high-energy ultraviolet rays and undergo oxidative deterioration in the presence of oxygen.

Polyolefin has solar energy of 290-400n
Polypropylene showed the most significant deterioration at 28 m.
It is known that solar energy in the vicinity of 0 to 325 nI11 and 37 Onm accelerates deterioration.

Therefore, various ultraviolet absorbers have been conventionally used as stabilizers to prevent polyolefins from deteriorating due to sunlight and other light rays. However, such known ultraviolet absorbers themselves were not fully satisfactory in terms of absorption ability in the wavelength range of 290 to 340 nm, stability against heat and air oxidation, coloring property, and sublimation resistance.

The present inventors have conducted extensive studies to solve the above-mentioned problems with ultraviolet absorbers for polyolefins. As a result, it was found that a specific formamidine compound represented by the formula CI) described below has a significantly superior absorption ability to known ultraviolet absorbers in the wavelength range of 290 to 340 nm (see attached figure). Furthermore, the formamidine compound is
It has been found that the above-mentioned stability against hot air oxidation and associated coloration resistance and schizophrenia resistance are outstanding, and that these properties are exhibited without any problems when the compound is blended with polyolefin. .

By the way, in addition to using a UV absorber alone as a light stabilizer, it is also possible to use ◎ two types of similar UV absorbers, or ◎ a light stabilizer consisting of a UV absorber and a hindered amine compound that has been attracting attention in recent years. (hereinafter abbreviated as HALS)
It is widely used in combination. The purpose of these combinations is to obtain a photostabilizing effect due to the mutual effect and to reduce the cost of the stabilizer accordingly.

The present inventors investigated ultraviolet absorbers to be used in combination with the compound of CI), and found that a benzophenone compound represented by the formula (II) described below, a benzosalicylate compound represented by the formula [■], and a benzosalicylate compound represented by the formula ( As is clear from the attached diagram, a composition in which one or more of the benzotriazole compounds represented by IT) is used in combination with the compound represented by CI) has a wide absorption band in the wavelength range of 290 to 370 nm and a mutually It was found that it has absorption ability.

Furthermore, it has surprisingly been found that polyolefin compositions containing the above-mentioned combinations have significantly better weather resistance than known compositions.

In addition, regarding the combination of the above-mentioned compound CI) and HALS, as the latter, the formula (V), (VT) or [■]
A polyolefin composition containing any one or more of the compounds represented by the above CI) and (H'] to (I) may also be used.
The present invention was completed by discovering that it has excellent absorption capacity and weather resistance similar to the combination V).

As is clear from the description in section 2 below, an object of the present invention is to provide a polyolefin composition that is excellent in light resistance and weather resistance.

The present invention has the following main configuration (1), the following (2) and (
3) has an implementation-like configuration.

(1) To 100 parts by weight of polyolefin, the following general formula CI
) A stabilized polyolefin composition containing 0.01 to 1 part by weight of a formamidine compound represented by:

(R1 is an alkyl group having 1 to 5 carbon atoms, R2 is hydrogen, chlorine, hydroxyl group, or methoxy group, and R3 is an alkyl group having 1 to 5 carbon atoms.
-9 alkyl group or phenyl group, R4 is hydrogen, halogen, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 4 carbon atoms, carbalkoxy group having 2 to 5 carbon atoms, or dimethylamino group, ns is hydrogen, chlorine or methoxy group.

(2) 1 selected from benzophenone compounds represented by the following general formula (II), benzosalicylate compounds represented by the general formula (I[r), or benzotriazole compounds represented by the general formula (TV)] More than one species 0
．． 01 to 1 part by weight of the composition according to item (1) above.

(R5 is the same as in the above formula CI), and R6
is hydrogen, an alkyl group having 1 to 18 carbon atoms, or 7 carbon atoms
-10 phenylpolymethylene group, and R7 is hydrogen or an alkyl group having 1 to 8 carbon atoms.

(3) The above-mentioned (1) compounded with 0.01-1 parts by weight of one or more compounds selected from hindered amine compounds represented by the following general formulas (V), (Vl) and [■]
The composition described in Section.

(and R9 and R9 each have a carbon number of 1-18.1
~8 alkyl group, m and n are each O~30.1
~40 integer.

The polyolefins used in the present invention are not limited, but polyolefins with particularly remarkable stabilizing effects include polypropylene (homopolymer), propylene-ethylene-random or block copolymer, propylene-ethylene-phthene copolymer, etc. Polymers or propylene-based polymers such as propylene-hexene-phthene copolymers can be mentioned.

The stabilizer basically included in the composition of the present invention is a formamidine compound having the general formula [■] above. Specific examples include N-(p-ethoxycarbonylphenyl)-N-ethyl-No-phenylformamidine, N-(4-ethoxycarbonylphenyl)-N
'-Methyl-No-phenylformamidine), N-(
4-ethoxycarbonylphenyl-(4-methoxyphenyl)-N'-methylformamidine, N,N'-bis(4-ethoxycarbonylphenyl)-No-methylformamidine, N'-(4-dimethylaminophenyl )-N-(4-ethoxycarbonylphenyl)-No-
Methylformamidine, N-(4-ethoxycarbonylphenyl)-N'-(2-methoxyphenyl)-No
-Methylformamidine, N-(4-ethoxycarbonylphenyl)-N'-(3,4-dichlorophenyl)
-N'-Methylformamidine, N'-(4-butoxycarbonylphenyl)-N-(4-ethoxycarbonylphenyl)-N'-methylformamidine, N-(
4-butoxycarbonylphenyl)-N'-methyl-N
o-phenylformamidine, N-(3-hydroxy-4-methoxycarbonylphenyl)-N'-methyl-
N'-phenylformamidine, No-butyl-No
-Phenyl-N-(4-ethoxycarbonylphenyl)
Formamidine, N-(4-dioxycarbonylphenyl)-N'-(n-octyl)-N'-phenylformamidine, N', N'-diphenyl-N-(4-
ethoxycarbonylphenyl)formamidine, N-
(4-ethoxycarbonyl-3-me)xyphenyl)
-N'-methyl-No-phenylformamidine, N
-(4-isopropoxycarbonylphenyl)-N'-
Methyl-No-phenylformamidine, N-(4-
ethoxycarbonylphenyl)-N'-methyl-N'-
(p-ethylphenyl)formamidine and N-(2
-chloro-4-methoxycarbonylphenyl)-N'-
Methyl-No-phenylformamidine is mentioned.

The amount of the stabilizer of the formula CI) to be blended with the polyolefin is 0.000.
0.01 to 1 part by weight, preferably 0.01 to 0.5 part by weight. If it is less than 0.01 part by weight, the stabilizing effect will be insufficient, and if it exceeds 1 part by weight, the effect will not be particularly improved, which is not economical. The blending method is not limited, but usually involves mixing stabilizer powder with polyolefin powder and then forming the mixture into pellets using a pelletizer.

The composition of the present invention may contain stabilizers other than those of formulas (H) to [■] and various other known additives. These are, for example, antioxidants, clarifying agents, nucleating agents, antistatic agents, anti-static agents, anti-drop agents, pigments, peroxides, dispersants or neutralizing agents exemplified by metal soaps. The method of adding these additives also follows known methods.

In embodiment (2) of the present invention, in addition to the compound of the above formula [E], one or more compounds selected from the compounds of the above formula [: TI ] to formula (TV) are added to the polyolefin to improve weather resistance. Gender and YT (YELLOW-N
ESSINDEX) can be further adjusted. Specific examples of the compound of formula [■■] include 2-hydroxy-4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-door.
They are siloxybenzophenone, 2-hydroxy-4-stearoxybenzophenone and 2-hydroxy-4-pencytoxybenzophenone. Specific examples of the compound of formula [■] are phenyl salicylate, 4-octylphenyl salicylate, and 4-t-butyl salicylate. Specific examples of compounds of formula (TV) include 2(
2'-Hydroxy-3'-1-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2(2'-hydroxy-3',5'-di-t-butylphenyl)
-5-chlorobenzotriazole, 2(2'-hydroxy-5°-methylphenyl)benzotriazole, 2
(2'-Hydroxy-3',5'-di-t-butylphenyl)benzoi-lyazole, 2(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, °-Hydroxy-3°-cutyl-5
°-pentylphenyl)benzotriazole and 2(
2'-human 0+cy 3°, 5°-cypentylphenyl) benzotriazole, and the like.

The amount of the stabilizers of formulas (II) to [■] based on 100 parts by weight of the polyolefin is 0.01 to 1 part by weight, preferably 0.01 to 1 part by weight. O1~0
．． 5 parts by weight. The blending amount outside this range is calculated using the above formula [■
] is not suitable for the same reason as the case of the compound. The method of blending these stabilizers is also the same as in the case of the compound of formula CI).

In embodiment (3) of the present invention, weather resistance and YI can be further improved.

Specific examples of the compound of formula (V) include (2,2,Ei,
6-tetramethylpiperidyl)adipate, bis(2,
2,13,B-tetramethylpiperidyl) sebacate and bis(2,2,6,B-tetramethylpiperidyl)
such as fumarate. Specific examples of the compound represented by formula (Vl) include compounds where n8 is a methyl group and n=6 to 8. As a specific compound of the compound represented by formula [■], port 8 is a methyl group, and R9
Compounds in which m=6 and n=4 to 5 are t-octyl groups. The amount of the stabilizer of formula (V) to [■] based on 100 parts by weight of polyolefin is 0.01 to 1 part by weight, preferably 0.0
1 to 0.5 overlapping parts. Amounts outside this range are not appropriate for the same reasons as in the case of the compound of formula CI). The method of blending these stabilizers is also the same as in the case of the compound of formula [I] described above.

As mentioned above, the method for producing the composition of the present invention generally involves adding a predetermined type and amount of each stabilizer to powdered polyolefin, and using an appropriate mixer such as a Henschel mixer (trade name). It is practical to supply the mixture to an extruder, melt and knead it into pellets, and then subject the pellets to molding such as injection molding.

The present invention will be explained below with reference to Examples.

Examples 1-8. Comparative Example 1-19 Powdered propylene-ethylene block copolymer (MF
R2, 8g/10 minutes, ethylene content M8.5% by weight) 1
A predetermined amount of the stabilizer (ultraviolet absorber) and HALS and other additives according to the present invention as shown in the table below were added and mixed to 00 parts by weight, and the mixture was heated at 200°C using a 40mm diameter extruder.
pelletized. The obtained pellets were injection molded (25
0°C) to form a DuPont impact test piece and test it with a sunshine weather meter (blank panel temperature 63°C1).
The weather resistance was measured in water spray (with water spray), and the point at which cracks appeared was defined as ``deterioration''.In addition, in order to investigate the coloring properties due to hot air oxidation, - the hue of the pellets and the yellowing after light irradiation. The relationship between the stabilizer (trade name) and the chemical structure according to the present invention shown in the table below is as follows.

A.Specific formamidine compounds ■GIVSORB IJV-2, Gibauda 7C; arp
B, benzophenone compound GYASORB UV-531, manufactured by American Cyanamint Co., Ltd., with the formula (II) above, Rs = n
-Ce II7 (7) compound.

C, penzosalicylate-1-based compound ■5ALOL: Manufactured by Dow Chemical Co., in the above formula [■], R7=H.

D, benzotriazole compound @ TTNUVTN 328; manufactured by Ciba Gaiki Co., Ltd. In the above [■], to R = [EI, R7 = t-butyl (
3rd position), a compound where R7=CH3 (5th position).

E, specific hindered amine compound ■5ANOL LS-770; manufactured by Sankyo ■ with the above formula [l]
In, the compound where l11-" + Re = CR3.

(←) SANOL LSJ22LD; Manufactured by Sankyo■ In the formula (VI), n=6 to 8, +18=CH
3 compounds.

■5ANOL LS-944, made by Tamakodo■, the above formula [■]
, m=6, n=4 to 5, R8=C
H3,11s=t-octyl compound.

F, other additives (fficYAsORB UV-334e; 7 J'
J Cuff "j-ia + Oligomer-based hindered amine manufactured by Mitsu F.

Tool ti6+ IRGANOX +010; Made by Chipagaygin 1 Terakis [Methylene-3-(3,5-di-t
-butylhydroxyphenyl)propionate comethane.

Surface DMTP, Similistylthiodipropionate manufactured by Yoshitomi Pharmaceutical ■.

@Karste; Calcium stearate manufactured by Nihon Yushi ■.

Table, +1. "% based on 100 parts of resin, main resin 1
For 00-fold division

[Brief explanation of drawings]

The figure shows the ultraviolet absorber used in the present invention (concentration + 01 Wg
The relationship between absorbance of /l) and wavelength (nm) is shown. In the figure, UV-1,N-(p-ethoxycarbonylphenyl)-
N-ethyl-N-phenylformamidine UV-2
, 2-hydroxy-4-n-octoxybenzophenone UV-3, phenyl salicylate UV-4; 2(2'-1=droxy-3°-1-butyl-5°-methylphenyl)-5-chlor - Benzotriazole and above L

Claims (3)

[Claims] (1) 100 parts by weight of polyolefin, the following general formula C
A stabilized polyolefin composition comprising 0.01 to 1 part of a formamidine compound represented by I). (R, is an alkyl group having 1 to 5 carbon atoms, Rt (hydrogen, chlorine, hydroxyl group, or methoxy group, R3 is an alkyl group having 1 to 5 carbon atoms,
~9 alkyl, (or phenyl), R4 is hydrogen, halogen, alkyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms
4 alkoxy group, carbalkoxy group having 2 to 5 carbon atoms, or dimethylamino group, and R5 is hydrogen, chlorine, or methoxy group. (2) One species returned from a benzophenone compound represented by the following -tib formula [11], a benzosalicylate compound represented by general formula (m), or a benzotriazole compound represented by general formula (IV) Compound 0 below
．． Claim No. 1 (1) containing 01 to 1 part by weight
). C, B- is the same as in the above formula (1), and I'
16 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or a phenylpolymethylene group having 7 to 1 o carbon atoms, and R7 is hydrogen or an alkyl group having 1 to 8 carbon atoms. (3) The claim 1 contains 0.01 to 1 part by weight of one or more compounds selected from the following general formulas (V), CVI) and [■]. The composition according to item (1). (R8 and R9 each have 1 to 18.1 carbon atoms
~8 alkyl group, m and n are each O~30.1
~40 integer.