JPS59155405A - Resin composition - Google Patents

Abstract

PURPOSE:A resin composition which, when added to an organic material, gives enduring stable weather-resistance, comprising a piperidine compound and a functional group-containing polymer. CONSTITUTION:A resin composition comprising a 2,2,6,6-tetraalkyl-substituted piperidine (e.g., 4-hydroxy-2,2,6,6-tetramethylpiperidine) and a polymer having a functional group covalently bondable to the piperidine compound (e.g., ethylene/acrylic acid copolymer). This resin composition can exhibit a performance as an enduring weathering stabilizer when it is added to an organic material (e.g., olefin polymer, styrene polymer, or polyester) in an amount of about 0.02-1wt% (in terms of an ionized piperidine compound).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to resin compositions. More specifically, the present invention relates to a resin composition that is effectively used as a weathering stabilizer for organic side slopes.

2.2,6.6-titraalkyl-substituted H'-21-nodine (g), because it has a sterically hindered nitrogen atom in its structure,
It is known to have a good photostabilizing effect on organic materials. However, these piperidine compounds generally have high volatility, so it is difficult to add them to polymers, etc., or even if they can be added, they migrate to the surface of the molded product rapidly, so the effect does not last long. In the end, it was inconvenient to use it as a weathering stabilizer for polymers.

Therefore, it has been proposed to maintain the effect of the polymer as a weathering stabilizer by increasing the molecular weight of such piperidine compounds (Japanese Unexamined Patent Publication No. 5431.2/1982). This high-molecular weight product has a structure in which the piperidine compound is covalently bonded in the polymer chain, so the reaction to produce it takes a long time, and since the reaction is carried out in a solvent, The problem was that it was expensive because it required complicated operations to separate the product and recover the solvent.

The present inventor has discovered that when a polymer having acidic hydrogen atoms such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group is melt-mixed with a piverizine compound to form a resin composition, ionic bonds are easily formed therein. - It was discovered that the bonded piperidine compound has significantly improved volatility and has a lasting weathering stabilizer effect, and the present invention has now been completed.

Therefore, the present invention relates to a resin composition, which comprises 8% 2,2,6,6-tetraalkyl piperidine and a polymer having a functional group capable of ionically bonding with the piperidine compound.

As a 2,2,6,6-thitraalkyl-substituted piperidine with a sterically hindered nitrogen atom (e.g. 2,2,6,6
-Tetramethylpiperidine, 2,6-dimethyl-2゜6
-Dinitylbiperidine, 1,2,2,6.6-pentamethylpiperidine, ■-Ethyl-2.2. I'i, 6-
Tetramethylpiperidine, 2,2,3,6.6-pentamethylpiperidine, 4-hydroxy-2,2,6,6-
Tetramethylpiperidine, 4-hydroxy-2,6-dimethyl-2,6-dinitylpiperidine, 4-bitroxy-1,,2,2,6,6-pentamethylpiperidine, 1
-ethyl-4-hydroxy-2,',), , G,
6-tetramethylpiperidine, 1-butyl-4-hydroxy-2,2゜6.6-tetramethylpiperidine, 4-
Hydroxy-2,2,3,6,6-pentamethylpiperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 2,2゜4.6.6-pentamethylpiperidine, 4-acetoxy- 2L2,6.6-tetramethylpiperidine, 4-(propylcarbonyloxy)-2,2,
6,6-tetramethylpiperidine, 4-acetoxy-1
,2,2,6,6-pentamethylpiperidine, 2,2,
6.6-thitramethylpiveridone, 4-ethoxy-2,
2,6,6-tetramethylpiperidine, 4-butoxy-
2,2,6,6-tetramethylpiperidine, 4-7 enoxy 2.2,6°6-tetramethylpiperidine, 4-
Ethyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 7.7,9.9-tetramethyl-1,3
,8-) Riazaspiro[4,5':ldecane-2,4-
dione, 3-methyl-7,7,9,9-tetramethyl-
1,3,8-1 riazaspiro[4,5]]decane-2,
4-dione 3-7enyl-7.7,9.9-tetramethyl-1;3.8-)riazaspiroC4,5']decane-2,4-dione and the like are used.

As mentioned above, examples of polymers having functional groups capable of ionically bonding with these piperidine compounds include carboxyl groups,
Polymers having acidic hydrogen atoms such as sulfonic acid groups, phosphorus groups, and - groups are used, and polymers having carboxyl groups are particularly preferred.

The carboxyl group-containing polymer is generally a copolymer of α-olefin and α, β-, β-carboxylic acid, and includes ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl -α-olefins such as 1-pentene and α-, β- such as acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, hexamaric acid, methyl hydrogen maleate, methyl hydrogen fumarate, ethyl hydrogen fumarate, etc.
- unsaturated carbon dioxide in the presence of a free radical polymerization initiator such as an azo compound or a vortex oxide under high pressure and high humidity conditions, e.g., reaction conditions of about 50 to 3000 atmospheres and about 150 to 300°C. Below, α, β-, β-carboxylic acid is approximately 50 mol%
It can be obtained by direct copolymerization in the following proportions. In addition to direct copolymers, those obtained by graft copolymerization with α,β-unsaturated carbon-fin polymers can be used, and in the case of olefin polymers other than ethylene polymers, graft Copolymers are effective.

Examples of such copolymers include ethylene-acrylic hard copolymer, ethylene-Yl/-methacrylic acid copolymer, ethylene-itaconic acid copolymer, and ethylene-Yl/-1 copolymer.
Methyl hydrogen ester copolymer, ethylene-maleic copolymer, ethylene-acrylic acid-methyl methacrylate ternary copolymer, ethylene-methacrylic acid-ethyl acryl ester copolymer, ethylene-itafonic acid- Methyl methacrylate terpolymer, ethylene-methyl hydrogen maleate-
Ethyl acrylate terpolymer, ethylene-methacrylic acid-[j? Hinyl terpolymer, ethylene-acrylic @
-Vinyl alfur ternary copolymer, ethylene-propylene-acrylic acid ternary copolymer, ethylene-styrene-acrylic acid ternary copolymer, ethylene-methacrylic acid-acrylonitrile ternary copolymer, ethylene-fumaric acid -vinyl methyl ether ternary copolymer, ethylene-vinyl chloride-acrylic acid copolymer, ethylene-vinylidene chloride-acrylic acid copolymer, °ethylene-fluorinated pinino and -methacrylic acid ternary copolymerffi, ethylene-chlortri Fluoroethyl/methacrylic acid ternary copolymer, acrylic acid graft copolymer to polyethylene, methacrylic acid graft copolymer to polyurethane, acrylic acid graft copolymer to ethylene-propylene copolymer, ethylene- Methacrylic acid graft copolymer to 1-butene copolymer, methacrylic acid graft copolymer to ethylene-vinyl acetate copolymer, methacrylic acid graft copolymer to polypropylene, methacrylic acid graft copolymer to poly(1-butene) Examples include acrylic acid graft copolymers of , acrylic acid graft copolymers of poly (3-methyl-1-butene), acrylic acid and ethyl acrylate co-graft copolymers of polyethylene, and the like.

In addition to copolymers with α-olefins, examples of α,β-unsaturated carbonic acid copolymers include copolymers with styrene, such as styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, Styrene-acrylic acid-methyl methacrylate ternary copolymer, styrene-methacrylate-ethyl acrylate ternary copolymer, styrene-acrylic acid-ethyl acrylate ternary copolymer, styrene-methacrylic acid-methacrylic acid A methyl terpolymer or the like can also be used.

The amino group of the piperidine compound reacts with the hydrogen atom of the carboxyl group in these copolymers to form a quaternary nitrogen atom.
It is thought that the carboxyl group in this copolymer becomes a class ammonium salt, while the carboxyl group becomes an ionized state, and the two electrostatically intersect to form a complex. Characteristic absorption of infrared absorption spectrum of (-CoOH) (1,700 t77+ which is f7
The absorption intensity of -' decreases depending on the degree of reaction with the amine, and at the same time the ionized carboxyl group (-aOO-)
This is also supported by the fact that the citric acid strength increases at 1,550 cm-', which is the characteristic absorption band of .

The acidic hydrogen atom that ionically bonds with the amine 7 group of the piperidine compound is not limited to only a carboxyl group, but may also be an acidic hydrogen atom such as a sulfone group or a phosphoric acid group. Similarly, polymers having .

The degree of ionization is preferably within the range of 20 to 10% based on the carboxyl groups in the copolymer. If the degree of ionization is lower than this, a larger amount of resin composition will need to be added to the organic material to achieve the desired weathering stability effect, which is not only economically disadvantageous but also This is because the original properties of the organic material that is used will be impaired.

Preparation of a resin composition from a piperidine compound and a functional group-containing electropolymer can be obtained by mixing both in solution or by melt-mixing (C can be obtained more easily than by a special preparation). Although not all conditions are necessary, it is preferable to operate at a temperature of about 250° C. or lower, with care not to increase the temperature excessively.In particular, the preparation of the resin composition is carried out by mixing in the molten state. The absence of by-products in the reaction allows the use of closed melt mixers such as extruders, which is a great advantage from an industrial perspective.

The resin composition thus prepared generally contains about 0% ionized piperidine compound relative to the organic material.
．． It is added by conventional means in a proportion of 0.02 to 1% by weight to effectively exhibit its performance as a long-lasting weathering stabilizer.

Examples of the organic material to be stabilized include olefin polymers, styrene polymers, halogenated vinyl polymers,
Vinylidene halide polymers, α, β-unsaturated unsaturated carboxylic acid terminated polymers β-, β-carboxylic acid ester polymers, vinyl carboxylic ester polymers or their saponified products, epoxide polymers, polyesters, Polyamide, polyurethane, polyurea, polyphenylene oxide, polyacetal, polysulfone, polycarbonate,
Examples include phenol resins, alkyd resins, and various natural polymers, among which olefin polymers, styrene polymers, polyesters, polyamides, polyurethanes, and the like are particularly effectively stabilized.

Organic materials weather-resistant in this way can be effectively used as molded articles, such as containers, industrial and civil engineering films, for example.

Next, the present invention will be explained with reference to examples.

Example 1 Ethylene-acrylic acid copolymer (acrylic copolymer fi20
Weight %, melt index 300) 34!7 and 4
- 14 g of hydroxy-2,2,6,6-titramethylbiveridine at 150° C. in a Gravender plastograph.
, and melt-kneaded for 5 minutes. The molten mixture was taken out and crushed with a press sheet to obtain granules.
degree of ionization (xylene-isopropanol (4:1)
When dissolved by heating in a mixed solvent and using a thymol blue indicator, the ph luenesulfonic acid (statutory) was 95%, and the melt index was 87.

This ionized particulate material has a final concentration of 2000pp.
Using a 20 diameter extruder, ethylene-
The mixture was kneaded and mixed with a vinyl acetate copolymer (vinyl acetate content: 14% by weight). This mixture was formed into a press sheet with a thickness of 1 mm, and a Ducycle Sunshine Weather
After 400 hours of irradiation with a meter, the residual tensile strength (according to T Engineering SK-7113-81) was measured by a tensile test. At the same time, the press sheet was immersed in various solvents and an extraction test was conducted at 60°C for 10 hours to determine the residual rate of the piperidine compound stabilizer in the sheet according to JIS K.
-2609 microelectromechanism titration method to determine the weight percent of N in the polymer.

Example 2 In Example 1, high-density polyethylene (Mitsui Petrochemicals Hizetsukuzu 2100.7) was used instead of the ethylene-vinyl acetate copolymer, and tensile strength retention and stabilizer retention (solvent boiling point, 6 hours) were used. ) were measured.

Example 3 In Example 1, polypropylene (Mitsui Petrochemicals, T-30) was used instead of the ethylene-vinyl acetate copolymer.
0) was used, and the tensile strength residual ratio was measured in the same manner.

Comparative Example 1 In Example 1, low density polyethylene (density 0920q/cttl) was used instead of the ethylene-vinyl acetate copolymer.
, melt index 1.0)'E- and 4-hydroxy-2,2,6,6-titramethylbiperidine was used to make a pressed sheet, but this sheet was uneven and these two components It was clear that the mixing ratio was extremely uneven.

Comparative Example 2 In Example 1, the ethylene-vinyl acetate copolymer used therein was used instead of the ethylene-acrylic acid copolymer, and 4-hydroxy-2,2,6°6-titramethylpiperidine was used. A press sheet was formed from the molten mixture, and the residual rate of the stabilizer was similarly measured on this sheet.

Comparative Example 3 The tensile strength retention of the ethylene-vinyl acetate copolymer press sheet used in Example 1 was measured.

Comparative Example 4 The tensile strength retention of the high-density polyethylene press sheet used in Example 2 was measured.

Comparative Example 5 The tensile strength retention of the polyethylene press sheet used in Example 3 was measured.

The measurement results for each of the following Examples and Comparative Examples are shown in the following table.

Table Example 1 40 77 22
-//2 35 54 98 2
2//337 - - - Comparative example 22
8 18'3 -//322-'-- //422-,-- /15'13 - - -Procedure
Amendment (self-motivated) September 16, 1981 1. Indication of the case 1982 Patent Application No. 27990 2. Title of the invention: Resin composition 3. Person making the amendment Relationship with the case Patent applicant Mitsui Name Mitsui Polychemical Co., Ltd. 4, Agent Address 5 Ato Building, 1-2-7 Shiba Daimon, Minato-ku, Tokyo
Insert No. 01 Fuft Copolymer.

(2) Insert "acrylic acid graft copolymer to ethylene-vinyl acetate copolymer" after "methacrylic acid graft copolymer" on page 7, lines io to 11.

(3) On page 7, between lines 12 and 13, there is a statement that says “maleic acid graft copolymer to ethylene-vinyl acetate copolymer, acrylic 1 graft copolymer to ethylene-ethyl acrylate copolymer”
a methacrylic acid graft copolymer to an ethylene-ethyl acrylate copolymer, and a maleic acid graft copolymer to an ethylene-ethyl acrylate copolymer.

(4) Insert "before weather meter irradiation" in front of "press sheet" on page 12, line 9.

(5) “Tensile strength residual ratio and” on page 12, lines 4-3.
The tensile strength residual rate of the press sheet after weather meter irradiation and that of the press sheet before weather meter irradiation have been corrected.

(6) Corrected to "Polyethylene, J-kF polypropylene" on page 14, line 8.

(7) Page 13, lines 6 to 1o, “In Example 1,
...The press sheet and ``but'' should be corrected as follows.

"34 g of the ethylene-vinyl acetate copolymer used in Example 1 and 14 g of 4-hydroxy-2,2,6,6-titramethylpiveridine were melt-mixed to form a press sheet." (8 ) Page 12, lines 7-2 are corrected as follows.

``The ethylene-vinyl acetate copolymer used in Example 1 was directly dissolved and mixed with 4-hydroxy-2,2,6,6-titramethylpiperidine equivalent to 2000 ppm K using a prabender. From this mixture the thickness l TJ
n press sheets were molded. Regarding this press sheet, the stabilizer residual rate (extraction at 6° C. for 10 hours) was similarly measured. (9) Page 12, line 9, 16:17 JI J (i')
Insert "I'd ICli".

Claims (1)

[Scope of Claims] A resin composition comprising a 1,2,2,6,6-titraalkyl-substituted bipeinodine and a polymer having a functional group capable of ionically bonding with the piperidine compound. 2. The resin composition according to claim 1, wherein the functional group-containing polymer is an α,β-unsaturated carbonic acid copolymer. 3. Approximately 20-100% of the functional groups in the polymer are
Claim 1, which is ionically bonded to the zinc compound.
2. The resin composition according to item 2. 4. The resin composition according to claim 1, which is used as a weathering stabilizer for organic materials.