JPS5825711B2 - Yuukizairiyouyouantheizai - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel stabilizers for organic materials for protecting organic materials susceptible to decomposition by oxygen and heavy metals.

Organic materials such as hydrocarbon oils, synthetic resins, and rubber.

Decomposition and deterioration occur due to the supply of heat, light, oxygen, and other external sources of energy.

At this time, if heavy metals such as Mn, CotCu, Fe, Pb, etc. are present in the decomposition/degradation reaction system in the form of ions or complex compounds, they participate in the reaction and have a catalytic action that significantly accelerates the reaction.

But useful organic materials synthetic resins, hydrocarbon oils.

Rubber and the like are often used in situations where they are unintentionally contaminated with polymeric metals or come into contact with heavy metals.

Antioxidants to prevent these toxic effects.

Various improvements have been made by allowing additives such as light stabilizers to coexist with organic materials, but they are still insufficient.

In severe cases, the effect may be completely lost.

For example, among poly-α-olefins, polypropylene resin has been increasingly used in recent years due to its properties, and oxidative deterioration can be prevented to a large extent by combining various antioxidants. When used in coating materials, electrical insulation, printed wiring, etc., it deteriorates in a few months, reducing its mechanical strength and rendering it unusable in practice.

In addition, plating on plastics has been increasing more and more in recent years, but for example, when copper plating is applied to polypropylene,
The first layer is plated with chemical nickel.

Copper is plated on top of it.

That is, the first layer is plated with chemical nickel to prevent deterioration caused by contact between the polypropylene and the copper.

Furthermore, when coloring agents, especially pigments containing heavy metals such as phthalocyanine blue, are used to color polypropylene etc., there is a phenomenon in which the deterioration of the plastic is accelerated by the heavy metals, so there are restrictions on the use of colorants. There is.

Alternatively, when storing or using hydrocarbon oil, if it is often stored or used in direct contact with a metal container for a long period of time, heavy metal ions will dissolve from the metal wall surface, promoting decomposition and deterioration, and significantly reducing the quality. There are many cases of loss.

Various efforts have been made to neutralize these toxic effects.

For example, Japanese Patent No. 405139, Japanese Patent No. 4613
No. 69, No. 461558, '*-No. 48222
No. 2, No. 482223, No. 482222, No. 482223, No. 421211, No. 49200
There are inventions of No. 5 and No. 505061.

However, these inventions are also insufficient to give satisfactory results.

For example, N-salicylidene-N'-salicylhydrazide, a representative compound of salicylhydrazone derivatives disclosed in Japanese Patent No. 505061, which is said to have excellent effects as a copper damage inhibitor for synthetic resins, is used during resin processing. It imparts color and significantly impairs commercial value, and has a major practical drawback.

An object of the present invention is to provide an organic material composition that has an even better effect of preventing oxidative deterioration than conventional inventions, and thereby to further develop and expand the uses of conventional organic materials.

The inventors of the present invention have conducted extensive studies over a long period of time, and have found that the product does not cause coloring and has an extremely excellent copper content activation effect.

Furthermore, we have discovered an organic material stabilizer with extremely excellent dispersibility for organic materials.

In other words, it has been found that, in contrast to organic materials that are subject to significant deterioration due to the presence of heavy metals, organic materials containing the compound according to the present invention hardly deteriorate under normal conditions and provide excellent transparency.

That is, the present invention provides a stabilizer for organic materials for stabilizing organic materials against heavy metals using ~5.0 parts by weight of compounds o, ooi represented by the following general formula for 100 parts by weight of organic materials. Regarding drugs.

It represents a group represented by the general formula, R1, R2, R3, R4, R5 and R6 represent the same or different lower alkylene groups, and R7
represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a substituted group thereof.

R' represents a hydrogen atom or a group represented by the formula -C-R8, R8 is an alkyl group, an alkenyl group, an aryl group,
Cycloalkyl group, alkylaryl group.

Indicates an arylalkyl group or a substituted group thereof.

) Organic materials that require the stabilizer for organic materials according to the present invention are materials having hydrocarbon groups that are easily oxidized, and are particularly susceptible to oxidative deterioration due to the presence of heavy metal ions or heavy metals that can be used as a matrix in the pre-stage of heavy metal ions. means an organic material that can be accelerated to

More specifically, synthetic polymeric materials, naturally occurring rubbers, or hydrocarbon oils are useful as organic materials.

To be more specific, examples of synthetic polymer materials include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, polyvinyl acetate, chlorinated polyethylene, chlorinated polypropylene, polyfluorinated Vinylidene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer.

Vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer,
Vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer α-olefin polymers or ethylene-vinyl acetate copolymers, ethylene-propylene copolymers with halogen-containing synthetic resins such as coalesced and internally plasticized polyvinyl chloride, polyethylene, polypropylene polybutyne, and poly-3-methylbutene. polyolefins and their copolymers, such as polystyrene, acrylic resins, copolymers of styrene with other monomers (e.g. eva-maleic anhydride, butadiene, acrylonidonol, etc.), IJ-butadiene-styrene copolymers , acrylic ester-butadiene-styrene copolymer, methacrylic ester-butadiene-styrene copolymer or blends of these resins, block copolymers, graft copolymers, polyoxyphenylene polymers, polyoxymethylene polymers, polyethylene oxide, polypropylene oxide polymers, and epoxy resins, polyester resins, and the like.

Furthermore, rubber collected from nature includes natural rubber, which naturally also includes vulcanized rubber.

or hydrocarbon oils, such as metalworking oils, gasoline,
Examples include lubricating oil, transformer oil, heavy oil, kerosene and other processed oils, naphtha cracked oil, crude oil, and animal and vegetable oils.

Furthermore, it is possible to mention organic materials intended for paints such as lacquers.

Adding an antioxidant to the present invention increases the antioxidant properties of the present invention, so it can be used as appropriate depending on the purpose of use.

These antioxidants include phenolic antioxidants, phosphite antioxidants, amine antioxidants, sulfur antioxidants, and the like.

Among them, examples of phenolic antioxidants include 1, for example, 1-oxy-3-methyl-4-isopropylbenzene, 2,6
-di-tert-butylphenol, 2,4-di-methyl-
6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-di-tert-butyl-6-(
2'-methylcyclohexyl)phenol, alkylated phenol, 2,5-di-tert-butylhydroquinone,
3-tert-butyl-4-oxy-anisole, styrenated phenol hydroquinone monobenzyl ether, 2,
5-di-tertiary-amylhydroquinone 2,6-di-tert-butyl-4-methoxyphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol%2,6-
Di-tert-butyl-α-dimethylamino-p-cresol, 4-oxy-3,5-di-tert-butylbenzylphosphonic acid ester, such as dimethyl, diethyl or dioctadecyl ester, β-4-oxy-3°5 - Ji 3rd
Butylphenylpropionic acid and monohydric or polyhydric alcohol, such as methanol, ethanol, octadecanol,
Esters with hexanediol, nonanediol, trimethylhexanediol, thiodiethylene glycol, trimethylolethane or pentaerythritol, 6-
(4oxy-3,5-tert-butylanilino)-2゜4
-Dioctyl-thio-s-triazine, 2,4-bis(3,5-di-tert-butyl-4-oxy-phenoxy)-6-octylthio-s-triazine, N-stearoylpara-aminophenol.

4.4'-dioxydiphenyl, 4.4'-bis-(2
, 6-di-tert-butylphenol), 2゜2'-methylene-bis-(4-methyl-6-tert-butylphenol, 2.2'-methylene-bis-(4--[-F-ru6 -36th phthylphenol).

4.4'-methylene-bis-(6-tert-butyl-〇-
cresol), 4,4'-methylene-bis-(2,6-
di-tert-butylphenol), 2゜2'-di-oxy-3,3'-di(α-methylcyclohexyl)-5,
5'-dimethyl-diphenylmethane, 1,1-bis-(
4-oxy-phenyl)-cyclohexane, 4.4'-
Cyclohexylitine-bis-(2-cyclohexylphenol).

4.4'-Butylidene-bis(6-tert-butyl-m-
cresol), 2,2'-thio-bis-(4-methyl-
6-tertiary-butylphenol).

Bis-(2-oxy-3,5-di-tert-butylphenyl) sulfide, 4,4'-thio-bis-(3-methyl-6-tert-butylphenol).

4.4'-thio-bis-(6-tert.butyl-O-cresol), -bis-(3,5-di-tert.phthyl-4-
oxybenzyl)-malonic acid noesters 1, such as didodecyl ester, dioctadecyl ester and 2-dodecyl mercaftoethyl ester and p-tertiary octylphenyl ester, 1,1-bis(4-oxy-2-methyl- 5-tert-butylphenyl)-3-dodecylmercapto-butane 2-(3-methyl-4-oxy-5-
tert-butylbenzyl)-malonic acid dioctadecyl ester, 5-(3,5-dimethyl-4-oxyphenyl)-
Thioglycolic acid octadecyl ester, tris(3,
5-di-tert-butyl-4-oxybenzyl)isocyanurate), 2,6-bis-(2'-oxy-3'-tertiary)
-Butyl-5'-methylbenzyl)-4-methylphenol.

1.1.3-) Lis-(2'-methyl-4'-oxy-
5'-tertiary-butylphenyl)-butane%1゜3.5-
) Lis-(3', 5'-tert-butyl-41-
oxybenzyl)-2,4,6-1-limethylbenzene,
Tris(3,5-di-tert-butyl-4-oxyphenyl)phosphate, 4-,t-oxymethyl-1-phospha-2,6,7-1-(2,2,2)-
Octane-3(3,5-di-3j-4-oxyphenyl)-propionate, 1,3,5-tris(3,5
-di-tert-butyl-4-oxy-hydrocinnamoyl)
Hexahydro-S-) liazine, tris-3(4-hydroxy-3,5-di-tert-butylphenyl)propionyloxyethyl iris cyanurate, and the like.

Examples of phosphite-based antioxidants include diphenyldecyl phosphite, triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, and tributyl phosphite.

Dilauryl acid phosphite, dibutyl acid phosphite, tris(dinonylphenyl) phosphite, trilauryl trithiophosphite.

trilauryl phosphite, bis(neopentyl glycol) 1.4 cyclohexane dimethylene/phosphite,
distearyl penkune erythritol diphosphite,
Diisodecylpene querrythritol diphosphite, diphenyl acid phosphite, tris(lauryl-2-
thioethyl) phosphite, tris(mono-, dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, diphenyl bis(4,4'-n-butylidene bis(2-tertiary) -y
'f-5-methylphenol)]thiogetanol diphosphite, bis(octylphenyl) bis(4,
4'-n-butylidene bis(2-tert-butyl-5-methylphenol)]■.

6 hexanediol diphosphite, phenyl 4.4
'-Isopropylidene diphenol/pentaerythritol diphosphite, phenyldiisodecyl phosphite, tetratridecyl-4゜4'-n-butylidenebis(2-tert-butyl-5-methylphenol) diphophite, tetratridecyl-1, 1,3-)lis(2'-methyl-5'-tert-butyl-4'-oxyphenyl)butane diphosphite, tetra(C12-15 mixed alkyl)4,4'-isopropylidene diphenyl diphosphite, Examples include tris(4-oxy-2,5-di-tert-butylphenyl) phosphite, tris(4-oxy-3,5-di-tert-butylphenyl) phosphite, and 2-ethylhexyldiphenyl phosphite.

Examples of amine antioxidants include phenyl-1-naphthylamine, phenyl-2-naphthylamine, NjN
'-diphenyl-p-phenylenediamine, N, N'-
Di-2-naphthyl-p-phenylenediamine, N, N'
-di-tert-butyl-p-phenylenediamine% 6-
Nitoxy2゜2.4-trimethyl-1,2-dihydroquinoline 6-dozosil-2.2.4-)trimethyl-1,
Examples include 2-dihydroquinoline, mono- and di-octyliminodibenzyl, polymerized 2,2.4-)lyntyl-1,2-dihydroquinoline, and the like.

Examples of sulfur-based antioxidants include esters of β-thio-di-propionic acid, such as ethyl lauryl, stearyl, myristyl or tridecyl esters, salts of 2-mercaptopenzimitasole, such as zinc salts, diphenylthiourea. , stearyl-(3,5-dimethyl-4-
Examples include oxybenzyl)thioglycolic acid ester, thiodipropionic acid, phenothiazine, and tetrakis(β-dodecylthiopropionyloxymethyl)methane.

Light stabilizers include, for example: a) optionally substituted aryl esters of benzoic acid, such as benzoylresorcin, dibenzoylresorcin, monosalicylic acid ethylene glycol ester;
Phenyl salicylate.

p-tertiary-butylphenyl salicylate, p-salicylate
Octylphenyl, p-tert-octylphenyl salicylate, 2,4-di-tert-butylphenyl or octadecyl ester of 3,5-di-tert-butyl-4-oxybenzoic acid.

or -2-methyl-4,6-di-tert-butyl phenyl ester, bis-(4-3-7'thylbenzoyl)resorcin; b) 2-oxy-benzophenone, such as 4-oxy, 4-methoxy, 4-n-hebutoxy, 4-n-octoxy, 4-iso-decyloxy.

4-decyloxy, 4-dodecyloxy, 4-octadecyloxy, 4-oxybenzyl, 5chloro 5-benzoyl-6-oxy, 4methoxy-4'-chloro 4-
Methoxy-2'oxy, 4-methoxy-2'-carboxy, 4°2', 4'-trioxy, 2'-oxy-4
, 4'-dimethoxy, 4-methoxy-5-sulfonic acid.

4-Methoxy-5-sulfotrihydric acid, 2'-oxy-4
,4'-dimethoxy-5-sulfonic acid sodium derivative; c) 2-(2'-t +diphenyl)-benztriazole, such as 5'-methyl, 3'-tert-butyl-5-methyl, 3', 5'-tert-butyl, 3'
, 5'-cyamyl, 5'-tert-butyl.

5-chloro-3', 5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl 3', 5'-di-tert-amyl, 3'-methyl-5 '-β-methoxylponylethyl, 5-chloro-3', 5'-di-tertiary
- amyl derivatives; d) acrylates, e.g. ethyl-2
-Cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cya-3,3-diphenylacrylate, p-methoxybenzylidenemalonic acid dimethyl ester, α-methoxycarbonyl-cinnamate methyl ester, α- Cyano-β-methyl-p-methoxy-cinnamate methyl or butyl ester, N-(β-carbomethoxy-vinyl)-2-methyl-indoline; e) 1,3
-bis-(2'-oxybenzoyl)benzene, e.g. 1,3-bis-(2'-oxy-4'-hexyloxybenzoyl)benzene, ■, 2-bis-(2'-oxy-4' octyloxybenzoyl)-benzene, 1°3-bis=(2'-oxy-4'-dodecyloxybenzoyl)-benzene; f) 2,4-bis-(2'-oxyphenyl)-6-alkyl-S -) riazine, e.g. 6-ethyl or 6-undecyl derivatives; g) nickel compounds, manganese compounds 1 e.g. 2°2'
Nickel complexes of -thio-bis-(4-tertiary-octylphenol) 1, e.g., 1:1 and 1:2 complexes with other ligands, such as n-butylamine, bis-
Nickel complex of (4-tertiary octylphenyl)-sulfone.

For example, 2:1 complexes optionally with other ligands such as 2-ethyl-caproic acid, dibutylnickel dithiocarbamate, 4-oxy-3,5-di-tert-butylbenzylphosphone monoalkyl ester, e.g. nickel salts of methyl, ethyl or butyl esters, or mankan salts, nickel complexes of 2-oxy-4-methyl-phenyl-undecyl-ketoxime; h) oxalic diamides 18 e.g. 4,4'-dioctyloxyoxanily 2,2'-di-octyloxy-5,5'-di-tertiary-butyloxanilide, 2,2'-di-dodecyloxy-5,5'-di-tertiary-butyloxanilide ;
i) Others 1 For example, β-benzoyloxy 2'-oxy-chalcone-2,4,5-)lioxybutylophenone, 2,2,6,6-titramethylbiperidine, for example 2,2, Examples include 6,6tetramethyl-4-stearoyloxypiperidine, bis-(2,2,6,6-tetramethyl-4-oxypiperidine)-sebacate, and the like.

Nucleating agents include, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, and the like.

Examples of metal deactivators include oxanilide.

Dicarboxylic acid dihydrazide, dicarboxylic acid bisphenyl hydrazide, salicylic acid hydrazide.

N-Salicyloyl-N'-Salicylidenehydrazine Bis-Salicyloyl-dicarboxylic acid dihydrazide, Bis-
Acylated dicarboxylic acid dihydrazide.

Examples include salicyloyl-hydrazinotriazine, bissusa J tyroyl-hydrazine, and bis(benzylidene hydrazide) oxalate.

Others as necessary, such as plasticizers, metal soaps, epoxy stabilizers, organic chelator-5 pigments, fillers, blowing agents, etc.
Antistatic agent, antifogging agent, playout inhibitor 1 Surface treatment agent, lubricant, flame retardant, fluorescent agent.

Antifungal agents, bactericidal agents, photodegradants, nonmetallic stabilizers, epoxy resins, boric acid esters, thiourea derivatives, processing aids, mold release agents, reinforcing agents, and the like can be included.

Next, Table 1 shows examples of typical compounds shown in the above general formula.
Shown below.

Note that + in the examples represents a tertiary-butyl group.

A specific method for producing the stabilizer for organic materials of the present invention will be explained using the following representative synthesis examples.

However, the present invention is not limited to the synthesis examples listed here.

Synthesis Example 1 (Synthesis of A1.) Rice diethylene glycol monomethyl ether 150c
After adding 1 g of potassium hydroxide to C and stirring for about 30 minutes to obtain a homogeneous solution, 10 g of dicyandiamide and 5.2 g of adiponitrile were added, the temperature was raised, and the mixture was heated and stirred at 125° C. for 4 hours.

At the start of the reaction, the solution was homogeneous, but a precipitate began to separate out after about 2 hours.

After cooling, the product was collected, thoroughly washed with diethylene glycol monomethyl ether, and dried to form a white powder.
I got g.

Melting point 296-300°C Synthesis Example 2 (Synthesis of /1613.) 10 g of dicyandiamide in 50 cc of diethylene glycol monomethyl ether in which 1 g of potassium hydroxide was dissolved.
and 3,9-bis(2-cyanoethyl)-2,4,8,1
0-tetraoxaspiro[5゜5]undecane 12.8
g were mixed and reacted at 105-110°C.

After 0.5 hours, the heterogeneous mixture became a pale orange homogeneous solution, and then after 1 hour crystals began to precipitate.

After heating and stirring for 5 hours, the mixture was cooled and filtered to collect crystals, which were treated with water at 70° C. for 30 minutes, washed with alcohol, and dried to obtain white crystals 15.29.

Melting point 275℃ Synthesis example 3 Acylation of guanamines Acylation of each guanamine was synthesized by the following method.

Guanamine and 1.5 equivalents of the corresponding phenyl ester of the acid were heated and stirred at 145 to 150° C. for 5 to 7 hours in dimethylformamide as a solvent.

After cooling, crystals precipitated were filtered and washed with alcohol to obtain a product.

In cases where crystals did not precipitate even after cooling, the reaction product was poured into a large amount of water to crystallize it, and the product was obtained by filtration and washing with alcohol.

Next, the present invention will be explained with reference to examples, but the present invention is not limited in any way by these examples.

Example 1 To examine the effect of preventing deterioration of an organic composite material containing the stabilizer of the present invention due to contact with heavy metals.

A 0.5 mm thick polypropylene film containing steel powder with the following composition was heated at 180°C with a mixing roll.
Processed for 1 minute, then 5 minutes at 180℃ and 200kg/d.
It was obtained by compression molding for minutes.

Hot pack this sheet film in oven 150.5
Heat deterioration was performed in air at ℃, and the time when the material changed color or became brittle was defined as the time when deterioration started.

The results are shown in Part 2 below.

[Composition]

Unstabilized polypropylene resin 100 parts Good
rite 3114*0.20 distearylthiodipropio 0.3 nate steel mill fine powder 10 parts Stabilizer (Table 2) 0.45 (i
Example 2 In this example, the following formulation was used: 100 parts of unstabilized polypropylene resin Topa
nol CA*0.1 dilauryl thiodipropionate 0.3 stabilizer (
Table-3) 0.4(X ICI
10% in a peeling machine according to the manufacturer's phenolic antioxidant)
Dry blend for 1 minute.

At this time, fine particles with an average size of 5 microns were used as the stabilizer.

This mixture was passed through a 30 mm extruder (rotation speed 3).
A compound was prepared by extrusion at a temperature of 245° C. using a 0 rpm press.

This compound was compression molded for 5 minutes at 180° C. and 200 kg/cyA to form a sheet with a thickness of 0.5 mm.

Cut the sheet into a size of 40 x 50 mm, and
Rolled copper foil with a thickness of mm was sandwiched from above and below in a sandwich-like manner, and a load of 145 g was applied uniformly to the entire surface to make them stick together.
．． A copper foil contact heating deterioration test was conducted in a hot pack oven at 5°C in an empty air atmosphere.

The results are shown in Table 3 below.

Example 3 The effect of the stabilizer of the present invention on polyethylene, which is often used for coating copper wires, etc., was tested using the following composite material and copper powder kneaded.

In other words, the first formulation is HIZEX 5100B" 100 Togin Fine Powder 1.2 Stabilizer (Table 4) 0.3 (*
Stabilized medium-low pressure polyethylene (manufactured by Mitsui Petrochemical Co., Ltd.) was masticated using a mixing roll.
Compression molding was performed for 5 minutes at 0° C. and 200 k19/cr/l to create a sheet with a thickness of 0.5 ytm.

This sheet film is subjected to a heat deterioration test in a hot pack oven at 149° C. in an air atmosphere.

The deterioration start time indicates the time when it becomes discolored and grease-like.

The results are shown in Table 4 below.

Example 4 Organic composite materials are often used colored.

In particular, a large proportion of pigments are used.

Heavy metals are present in commonly used pigments in the form of coordination compounds, some of which accelerate the deterioration of organic materials.

Therefore, the formulation described in Example G [stabilizer (Table 5)
)) and 0.28 parts of copper phthalocyanine blue were added to 100 parts of the compound obtained by the operation, mixed, kneaded in a roll mill for 5 minutes at 180°C, and compression molded at 180°C for 5 minutes at 200 kg/d. 0.
I created a sheet for 5 minutes.

Ten test pieces (10 x 20 pieces) were heated at 160°C in an air atmosphere in a gear oven, and five of the same samples were tested.
The time when more than one sheet discolored and deteriorated was defined as the deterioration start time.

The results are shown in Table 5 below.

Example 5 The following formulation ABS resin ('Blendex 111) 100
Part Zinc stearate 0.5 Titanium dioxide 5.0 Stabilizer (
Table 6) A sheet of 0.5 is prepared according to the method of Example 1.

Next, the copper foil was adhered in the same manner as in Example 2 and heated at 180°C.
A heating test was conducted in an oven under an air atmosphere for 1 hour.

The results are shown in Table 6 below.

The symbols indicating the degree of coloring in the table have the following meanings.

++++++ (very intensely colored) ++ (slightly colored) + (pale yellowish white) Example 6 100 parts of natural rubber, 5.0 parts of zinc oxide, 1 part of stearic acid
．． An aging test is conducted on a sample containing 0 part of steel mill fine powder, 1.0 part of phenyl beta naphthylamine, and 0.5 part of stabilizer (Table 7) at 130° C. in an oxygen pressure of 760 mm.

To save time, the time when oxygen absorption occurs rapidly is defined as the deterioration start time, and empirically, the amount of oxygen absorbed is 50m1/
The time was indicated as 7.

The results are shown in Table 7 below.

Example 7 A mixture consisting of 1.0 mol of nylon 6,6 salt (hexamethylene diamine adipate), 0.01 mol of hexamethylene diamine, and 1.0% by weight of stabilizer (Synthesis Example-1) was charged into a polymerization tube. , and heated at 220°C and 1 atm for 1 hour, then raised the temperature to 285°C and lowered the pressure to L.
Gradually reduce to tnm.

Hold this for 30 minutes. The lOI was then poured into a 10 mm deep box made of 40 x 50 mm copper foil and aged by heating at 180° C. in Osin.

As a result, it was confirmed that the synthesis example in which one compound was used had a significantly lower degree of coloring and weight loss than the one in which it was not added (Reference Example-7).

EXAMPLE 8 The interaction of lubricating oil or hydraulic fluid with heavy metal surfaces in contact with a composite material has a significant effect on the degradation of the composite material.

In other words, the purpose of suppressing the catalytic action of heavy metals is to prevent their corrosivity.

One of the main bench scale methods used to measure this corrosivity is the method of MI LL-L-9236A.

In this method, the lubricant to be treated is heated to a specific temperature in the presence of a certain metal and air, and the corrosivity is determined by measuring the change in the weight of the metal.

This example was tested according to this MIL-L-9236A method.

Here, the test was conducted on copper at 260° C., and the corrosivity to metal was determined by weighing the metal specimen before and after the test.

Base material is m-bis(phenylmercapto)benzene 60%
A test was conducted by adding 0.1 part of the stabilizer (Table 8) to 100 parts of a mixture of 30% 1m-phenoxyphenyl-m-phenylmercaptophenyl sulfide and 10% bis(m-phenoxyphenyl) sulfide.

The results are shown in Table 8 below.

Example 9 The following formulation Vinyl chloride resin (Zeon 103EP) 00 DOP 48 parts Epoxidized dog bean oil 2 Brass powder
2.5 Zn-stearate 0.2Ba-
Stearate 0.6 stabilizer (Table-
9) Knead 0.5 with a mixing roll at 170°C for 5 minutes to create a sheet with a thickness of 1.0Wt7rL.

From this, a test piece with a size of 10 x 20 mm was prepared, and 19
An accelerated heating test was conducted in an oven at 0°C in an air atmosphere.

The results are shown in Table 9 below.

Note that the deterioration start time is the time when discoloration and blackening occur.

Example 10 In order to see the effect of preventing the filler from deteriorating the composition containing the stabilizer of the present invention, a 0.6 mm thick polypropylene film containing talc having the following composition was heated at 175°C with a mixing roll. Process for 5 minutes, then 18
9/cI at 0°C, 250! It was obtained by compression molding for 5 minutes under the following conditions.

Then, this sheet film was subjected to heating deterioration in air at 160.0° C. in a hot pack oven, and the time when the film changed color or became brittle was defined as the deterioration start time.

The results are shown in Table 10 below.

[Composition]

100 parts of unstabilized polypropylene resin (plo
fax 6501) Topanol CA O,I
D5TDP 0
．． 2 tarri
30 Stabilizer (Table-10)
0.5 Example 11 In order to see the effect when a filler (asbestos) is included in a composition containing the stabilizer of the present invention, a composition containing a 0.5 am thick film was prepared using the following formulation.
Create a polypropylene film.

The start time of deterioration was measured in a 160°C Gyaozin.

The results are shown in Table 11 below.

[Composition]

polypropylene 5TDP asbestos Distearylpentaerythri tall diphosphite Stabilizer (Table-11) 100 copies 0.3 0 0.1 0.3

Claims (1)

[Claims] 1 A compound represented by the following general formula is used. Stabilizer for organic materials to stabilize organic materials. general formula %formula%)