JPH07188473A - Agricultural material - Google Patents

Abstract

PURPOSE:To obtain a material having excellent weathering resistance, having high ultraviolet transmittance in the initial state, that is, before exposure to light rich in ultraviolet rays such as sunlight, and less deteriorated in ultraviolet transmittance even after long-term use. CONSTITUTION:This material is made of a polyolefin resin composition comprising a polyolefin resin, a hindered amine compound and an alkyl benzoate compound of the formula (wherein R' is 6-30 C alkyl).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to an agricultural material, and more particularly to an agricultural material having excellent weather resistance, high initial UV transparency, and little decrease in UV transparency even when used for a long period of time. .

[0002]

BACKGROUND OF THE INVENTION As stabilizers effective for improving the weather resistance of polyolefins, a combination of a hindered amine compound and a hydroxybenzotriazole which is an ultraviolet absorber, a combination of a hindered amine compound and an arylbenzoate compound, and the like are known. ing. However, hydroxybenzotriazole has a wavelength of 350 nm.
The polyolefin resin composition containing the hydroxybenzotriazole and the hindered amine compound has a strong absorption band in the ultraviolet region below,
The following UV transmittance is very low.

In addition, in a stabilizer in which a hindered amine compound and an aryl benzoate compound are combined,
Arylbenzoate compounds do not have an absorption band in the ultraviolet region of wavelengths of 300 nm or longer, but when exposed to ultraviolet light,
A strong absorption band appears in the ultraviolet region below 0 nm. Therefore, in the polyolefin resin composition in which the hindered amine compound and the aryl benzoate compound are blended, before exposure to the light including a large amount of ultraviolet rays such as sunlight (initial stage), it is possible to obtain a favorable ultraviolet ray of 300 nm or more. Although it shows UV transmittance, when exposed to such a large amount of UV light, the wavelength is 300 nm to 350 nm.
Ultraviolet ray transmittance in is drastically reduced.

Therefore, the polyolefin resin composition containing such a stabilizer has excellent weather resistance and 300
There is a problem in that it cannot be used for applications such as agriculture which require a high ultraviolet transmittance in the ultraviolet region of nm to 350 nm.

As a result of intensive studies to solve the above problems, the present inventors have found that a polyolefin resin composition obtained by blending two specific compounds of polyolefin has good weather resistance. Furthermore, they have found that they have good ultraviolet ray transmittance not only in the initial stage but also for a long period of time and can be suitably used for agriculture, and thus completed the present invention.

[0006]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, has good weather resistance, good initial UV transmittance, and long-term UV irradiation. It is intended to provide an agricultural material having a reduced permeability.

[0007]

SUMMARY OF THE INVENTION The agricultural material according to the present invention is characterized by comprising a polyolefin resin composition containing a polyolefin resin, a hindered amine compound and an alkylbenzoate compound represented by the following general formula [1]. There is.

[0008]

[Chemical 2]

(However, in the formula [1], R'has 6 carbon atoms.
Represents an alkyl group of ˜30. In a preferred embodiment of the present invention, the amount of the hindered amine compound is 0.01 to 2.0 parts by weight, and the amount of the alkyl benzoate compound is 0.01 to 2.0 parts by weight, based on 100 parts by weight of the polyolefin resin. It is desirable to be included in the amount of.

Agricultural materials comprising such a polyolefin resin composition are excellent in weather resistance, and have high ultraviolet transmittance at the initial stage, that is, before being exposed to light containing a large amount of ultraviolet rays such as sunlight, and thus for a long period of time. Even if it is used, there is little decrease in the ultraviolet transmittance.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The agricultural material according to the present invention will be specifically described below. [Polyolefin Resin Composition] The agricultural material according to the present invention comprises a polyolefin resin composition, and the polyolefin resin composition will be described first.

This polyolefin resin composition contains a polyolefin resin, a hindered amine compound, and an alkylbenzoate compound represented by the following general formula [1].

[0013]

[Chemical 3]

(However, in the formula [1], R'has 6 carbon atoms.
Represents an alkyl group of ˜30. ) [Polyolefin resin] As the polyolefin resin,
Specifically, for example, polyethylene, polypropylene,
Examples thereof include polybutene-1, poly-4-methylpentene-1, ethylene-propylene copolymer and the like, and polypropylene and linear low density polyethylene are preferably used.

In the case of polypropylene as the resin used at this time, the melt flow rate (MFR) measured according to ASTM D1238 at a temperature of 230 ° C. and a load of 2.16 kg is usually 0.1 to 20 g. / 10 minutes, and in the case of polyethylene, the temperature is 190 ℃
MFR is usually about 0.01 to 10 g / 10 minutes. [Hindered amine compound (H)] Specific examples of the hindered amine compound include the following (H-
1) to (H-17). (H-
1) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, (H-2) dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6 succinate -Tetramethylpiperidine polycondensate, (H-3) poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2-4-diyl]
[(2,2,6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], (H-4) tetrakis (2 , 2,6,6-Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (H-5) 2,2,6,6-tetramethyl-4-piperidylbenzoate, ( H-6) bis- (1,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, ( H-7)
Bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, (H-8) 1,1 '-(1,2-ethanediyl)
Bis (3,3,5,5-tetramethylpiperazinone), (H-
9) (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butane tetracarboxylate, (H-10) (Mixed 1,2,2, 6,6-pentamethyl-
4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (H-11) mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (H-12) Mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3,9-
[2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate,
(H-13) N, N'-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butylN- (1,2,2,6,6, -pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, (H-14) poly [[6-N-morpholyl-1,3,5-
Triazine-2-4-diyl] [(2,2,6,6-tetramethyl-4-
Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], (H-15) N, N '
-A condensate of bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, (H
-16) [N- (2,2,6,6-tetramethyl-4-piperidyl) -2
-Methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide, (H-17) 2- (3,5-di-ter
t.-Butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl).

Of these hindered amine stabilizers, the above-mentioned (H-2) to (H-4), (H-6),
The following stabilizers represented by (H-8) to (H-17) are used. (H-2) dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, (H-3) poly [[6- (1, 1,3,3-Tetramethylbutyl) imino-1,3,5-triazine-2-4-diyl]
[(2,2,6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], (H-4) tetrakis (2 , 2,6,6-Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (H-6) bis- (1,2,6,6-pentamethyl-4
-Piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, (H-8) 1,1'-
(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone) (H-9) (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1 , 2,3,4-Butane tetracarboxylate, (H-10) (Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butane tetracarboxylate Rate, (H-11) mixed {2,2,6,6
-Tetramethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2 , 3,4-Butane tetracarboxylate, (H-12) mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9 -
[2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate,
(H-13) N, N'-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butylN- (1,2,2,6,6, -pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, (H-14) poly [[6-N-morpholyl-1,3,5-
Triazine-2-4-diyl] [(2,2,6,6-tetramethyl-4-
Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], (H-15) N, N '
-A condensate of bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, (H
-16) [N- (2,2,6,6-tetramethyl-4-piperidyl) -2
-Methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide, (H-17) 2- (3,5-di-ter
t.-Butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl).

More preferably, N, N'-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butylN- (1,2,2,6, 6, -pentamethyl-4
-Piperidyl) amino] -6-chloro-1,3,5-triazine condensate, 2- (3,5-di-tert.-butyl-4-hydroxybenzyl) -2 represented by the symbol (H-17) -n-butylmalonate bis
(1,2,2,6,6-pentamethyl-4-piperidyl) and the like are used. [Alkylbenzoate Compound (A)] Above Formula [1]
And an alkyl benzoate compound (3,5-
As the alkyl ester of di-t-butyl-4-hydroxybenzoic acid, R ′ constituting the alkylbenzoate compound is a linear, branched or alicyclic alkyl group having 6 to 30 carbon atoms. The thing which is a group is mentioned.

Specifically, for example, the following (A-1) to (A-
Examples thereof include the compounds shown in 5). (A-1) Octyl-3,5-di-t-butyl-4-hydroxybenzoate, (A-2) decyl-3,5-di-t-butyl-4-hydroxybenzoate, (A-
3) Hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, (A-4) octadecyl-3,5
-Di-t-butyl-4-hydroxybenzoate, (A
-5) Cyclohexyl-3,5-di-t-butyl-4-
Hydroxybenzoate and the like.

Of these, alkylbenzoate compounds in which R'represented by the above formula [1] is a linear or branched alkyl group having 12 to 20 carbon atoms are preferable, and R'is carbon number. An alkyl benzoate compound which is a linear alkyl group of 12 to 20 is preferable,
Specifically, for example, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate represented by the above (A-3), octadecyl-3 represented by the above (A-4),
5-di-t-butyl-4-hydroxybenzoate is preferably used. More preferably, R'has 16 carbon atoms
Hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate represented by the symbol (A-3), which is an alkyl group of, is preferably used. In addition, R'is (replacement)
When an aryl benzoate compound that is an aryl group is used, it is difficult to obtain an agricultural material having excellent properties.

Specific examples of the polyolefin resin composition containing such a polyolefin resin, a hindered amine compound and an alkyl benzoate compound include the followings.

The polyolefin resin is polypropylene, and the hindered amine compound is N, N'-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butyl N- (1 , 2,2,6,6, -Pentamethyl-4
-Piperidyl) amino] -6-chloro-1,3,5-triazine condensate, wherein the alkyl benzoate compound is (A)
And a polyolefin resin composition such as hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate represented by -3).

In the polyolefin resin composition containing the above-mentioned polyolefin resin, hindered amine compound and alkyl benzoate compound, 0.01 to 2. 0 parts by weight, preferably 0.0
The amount of alkyl benzoate compound is 0.01 to 2.0 parts by weight, preferably 0.02 to 2.0 parts by weight.
It is preferably contained in an amount of 1.0 part by weight.

The total amount of the hindered amine compound and the alkyl benzoate compound is 0.02 to 4.0 parts by weight, preferably 0.04 to 2.0 parts by weight, based on 100 parts by weight of the polyolefin resin. It is desirable that the content be such that

The polyolefin resin composition contains an oxidation stabilizer, a neutralizing agent, a filler, a vulcanization accelerator, a lubricant,
An antistatic agent, an antiblocking agent, a resin plasticizer, etc. may be contained. [Manufacturing] An agricultural material comprising such a polyolefin resin composition can be manufactured using the above polyolefin resin composition according to a conventional method.

For example, 100 parts by weight of a polyolefin resin such as polypropylene is mixed with N, shown in (H-13) above.
N'-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butylN- (1,2,2,6,6, -pentamethyl-4-piperidyl) amino] -6-chloro-1, Hexadecyl-3 represented by (A-3) above in an amount of 0.01 to 2.0 parts by weight of a hindered amine compound such as a 3,5-triazine condensate.
An alkylbenzoate compound such as 5-di-t-butyl-4-hydroxybenzoate is added in an amount of 0.01 to 2.0 parts by weight, and, for example, 1 using a mixing roll, Banbury, mixer, extruder or the like. ~ 20 minutes, melt-knead at a cylinder temperature of 180 ~ 230 ℃, granulate, and then, at the same temperature as the melt-kneading temperature, sheet molding to a thickness of 0.01 ~ 2 mm with a hot press machine do it.

Such an agricultural material may be in the form of a sheet, a film or a fiber as described above, and its shape is not particularly limited. Further, such an agricultural material may be unstretched or uniaxially or biaxially stretched.

The thus-obtained agricultural material has excellent weather resistance and high UV transparency even when it is used initially and over time, that is, over a long period of time.
It is preferably used as an agricultural coating film, a greenhouse roof material, a window material and the like.

[0028]

EFFECTS OF THE INVENTION According to the present invention, the weather resistance is excellent, the ultraviolet ray transmittance is high at the initial stage, that is, before being exposed to light containing a large amount of ultraviolet rays such as sunlight, and even when used for a long period of time. Provided is an agricultural material which is less likely to have a reduced ultraviolet transparency.

[0029]

EXAMPLES Hereinafter, the agricultural material according to the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0030]

Example 1 and Comparative Examples 1-2 Polypropylene [AS
Melt flow rate (MFR) measured according to TM D 1238 at a temperature of 230 ° C and a load of 2.16 kg.
Is 1.5 g / 10 min] to 100 parts by weight, and a phenolic stabilizer tetrakis [methylene-3 (3,5-di-tert.-butyl-4-
Hydroxyphenyl) propionate] methane (manufactured by Nippon Ciba Geigy Ltd., trade name: Irganox 1010)
0.1 part by weight, 0.1 part by weight of calcium stearate and the compounds shown in Table 1 were added, and the mixture was melt-blended at 230 ° C. and pelletized using a single-screw extruder.

A press sheet having a thickness of 0.5 mm was formed from the pellets by using a press forming machine, and the weather resistance and the ultraviolet ray transmittance were evaluated. The results are shown in Table 1.

The evaluation conditions are as follows. Weather resistance: Xenon weather meter (Suga Test Instruments Co., Ltd.)
UV irradiation intensity of 4.8 mW / cm2 and rain (12 minutes out of 60 minutes) were used to irradiate the test piece with ultraviolet rays, and the tensile elongation residual rate was determined to be 50% of the initial value. And

Ultraviolet transmittance: Using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corp.), initial (before weathering test) and 100
The ultraviolet transmittance at 300 nm, 350 nm, and 380 nm after 0 hour was measured. [Compounds Used in Examples and Comparative Examples] Compound (H): Hindered amine compound "N, N'-bis (3-aminopropyl) ethylenediamine-2-
4-bis [N-butyl N- (1,2,2,6,6, -pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate (manufactured by Nippon Ciba Geigy Co., Ltd.) , Product name: Kimasorb 1
19FL) "Compound (A): Alkyl benzoate-based compound" Hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate (manufactured by Sitex, trade name:
Siasorb UV2908) "Compound (a): Arylbenzoate compound represented by the following formula [2]" 2,4-di-tert-butylphenyl-3,5-di- "
tert-butyl-4-hydroxybenzoate (manufactured by Nippon Ciba Geigy Ltd., trade name: Tinuvin 12
0) ”

[0034]

[Chemical 4]

[0035]

[Table 1]

[0036]

[Example 2 and Comparative Examples 3 to 4] Linear low density polyethylene (MFR measured at a temperature of 190 ° C and a load of 2.16 Kg)
2.5 g / 10 min) to 100 parts by weight of phenolic stabilizer n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-ter
t.-Butylphenyl) propionate (Japan Ciba Geigy
Ltd., trade name: Irganox 1076) 0.1 parts by weight, calcium stearate 0.1 parts by weight and Table 2
The compound shown in is added, and a single screw extruder is used.
Melt blended at 0 ° C and pelletized.

A press sheet having a thickness of 0.5 mm was formed from the pellets by using a press forming machine, and the weather resistance and the ultraviolet ray transmittance were evaluated. The results are shown in Table 2.

[0038]

[Table 2]

Claims (2)

[Claims] 1. An agricultural material comprising a polyolefin resin composition comprising a polyolefin resin, a hindered amine compound and an alkylbenzoate compound represented by the following general formula [1]. [Chemical 1] (However, in the formula [1], R ′ represents an alkyl group having 6 to 30 carbon atoms.) 2. The amount of the hindered amine compound is 0.01 to 2.0 parts by weight, and the amount of the alkyl benzoate compound is 0.01, based on 100 parts by weight of the polyolefin resin.
The agricultural material according to claim 1, wherein the agricultural material is contained in an amount of about 2.0 parts by weight.