JPS5820993B2 - Antei Casareta Yuukizairiyouso Saibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to stabilized organic material compositions containing novel cyclohexylphenyl phosphites.

Synthetic or natural polymers such as polyolefins and polyvinyl chloride are often subjected to oxidative degradation by oxygen, resulting in a loss of quality.

Other materials such as synthetic lubricants, hydrocarbons, natural or synthetic rubbers, animal or vegetable oils are also susceptible to heating and oxidative degradation.

Such substances are also unstable to ultraviolet and visible light.

Furthermore, when heavy metals used as catalysts during polymerization and pigments containing heavy metals are used as coloring agents to color polypropylene and the like, the deterioration of plastics is accelerated by the heavy metals.

Organic materials are subject to such deterioration, resulting in discoloration, deterioration of physical properties such as tensile strength and elasticity of resins, deterioration of performance, and generation of odors, which have become major obstacles in use.

For this purpose, various stabilizers have been developed and used.

However, the effectiveness of these stabilizers varies, and some are very effective but have the disadvantage of imparting color to the product.

Although some stabilizers have relatively satisfactory effects, these stabilizers exhibit stabilizing effects over a relatively short period of time; As a result, it only shows a stabilizing effect that is not sustainable due to migration to other materials.

The present invention provides organic material compositions that are persistently stabilized and remain stable during use under a variety of conditions, including processing such as compression molding, extrusion, injection molding, spinning, and grinding, storage, and handling. There is a particular thing.

That is, the present invention provides an organic material composition stabilized with a cyclohexylphenyl phosphite represented by the following general formula (1).

[In the formula, R1, R2 and R3 are hydrogen atoms, alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, cyclohexylphenyl, cellosolve and calpitol residues, group call residues or divalent or trivalent phenol residues shows.

(-CH2+18 group is shown.

n represents an integer of 1 to 20.

] Examples of the above alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,
Tertiary butyl, amyl, neopentyl, isoamyl, hexyl, inhexyl, heptyl, octyl, inoctyl, 2-ethylhexyl, decyl, isodecyl, lauryl, tridecyl, CI2-1. Mixed alkyl, stearyl, etc. can be mentioned.

Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-methylcyclohexyl, and the like.

Examples of aryl groups include phenyl, naphthyl, and the like.

Examples of the arylalkyl group include benzyl, β-phenylethyl, γ-phenylpropyl, and β-phenylpropylnato.

Examples of alkylaryl groups include tolyl, xylyl, ethylphenyl, butylphenyl, tert-butylphenyl,
Examples include octylphenyl, isooctylphenyl, tertiary octylphenyl, nonylphenyl, and the like.

Examples of cellosolve or carpitol residues include methyl, ethyl, isopropyl, butyl, inftyl, phenylcellosolve: methyl, ethyl, isopropyl, butyl, isobutylcarpitol; triethylene glycol, monomethyl, Examples include residues such as monoethyl and monobutyl ether.

Examples of divalent or trivalent alcohol residues or phenol residues include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, phthylene gelicol, bentanediol, hexanediol, decanediol, thiodiethylene glycol, Dihydric or trihydric alcohol residues or derivatives thereof such as neopentyl glycol, cyclohexane dimetatool, phenyl dimethanol, hydrogenated bisphenol A, glycerin, trimethylol hydroxide, tris(2-hydroxyethyl) isocyanurate, etc. Can be mentioned.

Also, 2,5-di-t-butylhydroquinone, 2.5
-di-t-amylhydroquinone, 4,4'-dioxyphenyl, 4,4'-bis(2,6-di-t-butylphenol), 2,2'-methylenebis(4-methyl-6
-1-butylphenol), 2,2'-methylenebis(
4-ethyl-6-t-butylphenol), 4-47-
Methylenebis(6-1-butyl-0-cresol), 4
, 4'-methylenebis(2,6-di-t-butylphenol), bisphenol A, 2,2'-di-oxy-3
-3'-di(α-methylcyclohexyl)-5,5'-
dimethyl-diphenylmethane, ], ]1-bis-4-,
t-xy-phenyl)cyclohexane, 4,4'-cyclohexylidenebis(2-cyclohexylphenol), 4,4'-butylidenebis(6-t-butyl-m-
cresol), 2,2'-thiobis-(4-methyl-6
-1-butylphenol), 4゜4'-thiobis-(3
-methyl-6-t-butylphenol), 4,4'-thiobis-(6-1-butyl-0-cresol), tris(3,5-di-t-7'thyl-4-oxybenzyl)insia Nurate, 2,6-bis(2'-oxy-3'-
t-Butyl-5'-methylbenzyl)4-methylphenol, 1.1.3-tris(2'-methyl-4'-oxy-5'-1-butylphenyl)-butane, 1,3,5
-Tris(3/, 5/-di-t-butyl-4'-oxybenzyl)2,4.6-)limethylbenzene, bisphenol S, and other divalent or trivalent phenol residues.

Examples of the average formula of phosphites represented by the general formula according to the present invention include the compounds shown in Table 1 below.

Next, a simple method for producing the compounds shown in Table 1 above (synthesis example)
As described below, this production method is merely an example, and the organic phosphite compound of the present invention can be produced by methods other than these, and the present invention is not limited in any way by these production methods. It's not a thing.

Synthesis Example 1 /164 Synthesis 24.8.9 (0.08 mol) of triphenyl phosphite, 9.69 (0.04 mol) of hydrogenated bisphenol A and 0.034 g of potassium carbonate were heated at 130°C. 3
The mixture was stirred while blowing in N2 gas.

Next, dephenolization was performed under reduced pressure at a maximum temperature of 160° C./3 mHg, and 7.5 g (99.6%) of phenol was distilled out.

4-hydroxymethyl-1-phospha-
2,6,7-Dryoxabicyclo(2,2,2)octane 13.1. ! 9 (0.08 mol) and 14.1.9 (0
, 08 mol) of O-cyclohexylphenol and 0.08 mol).
Add 054g of potassium carbonate and heat with N2 at 130℃ for 3 hours.
I stirred it under gas blowing.

Next, dephenolization was performed under reduced pressure at a maximum of 160°G/3ymxHg, and 14.6g (96.9%) of phenol was distilled off.

The product was a white powdery solid with a melting point of 73-80°C.

P content Experimental value 6.15% Calculated value 6.20% Synthesis example 2 Synthesis of A13 3.6: 1 (0,117 mol) of triphenyl phosphite, 36.1,9 (0.15 mol) of water Bisphenol-A, 8.7!11 (0.05 mol) of 0-cyclohexylphenol and 0.081. ! ? of potassium carbonate was stirred at 130°C for 3 hours while blowing N2 gas.

Next, dephenolization was performed under reduced pressure at a maximum temperature of 160° C. for 3 hours, and 28.2 g (85.5%) of phenol was distilled out.

The product was a pale yellow powdery solid with a melting point of 62-69°C.

P content Experimental value 7.55% Calculated value 7.51% The organic phosphite compound represented by the general formula (1) according to the present invention is generally 0.0 parts by weight per 100 parts by weight of the organic material.
1-10 parts by weight are added.

Organic materials to be stabilized against thermal oxidative degradation in the present invention include synthetic polymeric substances, rubbers which can be obtained from nature,
Alternatively, hydrocarbon oils are useful.

To be more specific, examples of synthetic polymer materials include polyvinyl chloride, polyvinyl fluoride, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene chloride, polyvinyl acetate, chlorinated polyethylene, chlorinated polypropylene. , brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride) L/-7' propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride- Isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, 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 - Halogen-containing synthetic resins such as methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-3-methylbutene, or ethylene - Polyolefins such as vinyl acetate copolymers, ethylene-propylene copolymers and their copolymers, polystyrene, acrylic resins, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.) acrylonitrile-butadiene-styrene copolymer, acrylic ester-butadiene-styrene copolymer, methacrylic ester-butadiene-styrene copolymer, or blends, block copolymers, graft copolymers of these resins, etc. , polyoxyphenylene polymer, polyoxymethylene polymer, polyethylene oxide, polypropylene oxide polymer, epichlorohydrin polymer, epichlorohydrin-ethylene oxide copolymer, epoxy resin, polyester resin, and polyvinyl butyral resin.

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, heavy oil such as kerosene, naphtha cracked oil, crude oil, and animal and vegetable oils.

Furthermore, organic materials intended for coatings such as lacquers may be mentioned.

By using the various additives shown below in the organic material composition of the present invention, its effects can be significantly increased, or
It imparts new properties and increases the usefulness of organic materials.

That is, examples of the phenolic antioxidants used as these additives include 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-tert-butylphenol,
2゜4-di-methyl-6-tert-butylphenol, 2
, 6-tert-butyl-4-methylphenol, 2.
4-di-methyl-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-tert-amylhydroquinone, 2゜6-di-tert-butyl-4-methoxyphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, 2,6-di-tert-butyl- 2-Dimethylamine-p-cresol, 4-oxy-3°5-di-tert-butylbenzylphosphonic acid ester, such as dimethyl, diethyl or dioctadecyl ester, β-4-
Oxy-3,5-tert-butylphenylpropionic acid and a monohydric or polyhydric alcohol, such as methanol, ethanol, octadecanol, hexanediol, nonanediol, trimethylhexanediol, thiodiethylene glycol, trimethylolethane, tris(2 -Hydroxyethyl)in cyanurate or ester with pentaerythritol, 6-(4-oxy-3,5-tert-butylanilino)-2,4-dioctyl-thio s-triazine, 2,4-bis(3, 5-G tertiary butyl-4
-oxy-phenoxy)-6-octylthio-s-triazine, N-stearoylparaminphenol, 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-ethyl-6-tertiary
・butylphenol), 4,4'-methylene-bis-
(6-tert-butyl-o-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)-cyclo+ -))-, 4,4'-cyclohexylidene-bis-(2-cyclohexylphenol), 4,4'-butylidene-bis(6-tert-butyl-m-cresol)
, 2,2'-thio-bis-(4-methyl-6-tert-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-0-cresol), bis-(3゜5-thio-tert-butyl-4-
oxybenzyl)-malonic acid, such as didodecyl ester, dioctadecyl ester and 2-dodecyl-mercapto-ethyl ester and p-tertiary octylphenyl ester 1,1-bis(4-oxy-2-methyl-5- tertiary-butylphenyl)-3-dodecylmercapto-butane, 2-(3-methyl-4-oxy-5-tertiary-butylbenzyl)-malonic acid dioctadecyl ester, s (3t 5 yl methyl-4-oxy phenyl)-thioglycolic acid octadecyl ester, tris(3,5-di-tert-butyl-4-oxybenzyl)in cyanurate, 2,6-bis-(2'-oxy-3'
-tertiary-phthyl-5'-methylbenzyl)-4-methylphenol, 1,1,3-tris-(2'-methyl-4
'-oxy-57-tert-butylphenyl)-butane,
1.3,5~tris-(3/, 5/-di-tert.butyl-4'-oxybenzyl)-2,4,6-1-limethylbenzene, tris(3,5-di-tert.-butyl-4'-oxybenzyl)-2,4,6-1-limethylbenzene, Butyl-4
-oxyphenyl)phosphate, 1,3°5-tris(3,5-di-tert-butyl-4-oxy-hydrocinnamoyl)hexahydro-s-triazine, tris(3
, 5-di-tert-butyl-4-oxyphenylpropionyloxyethyl) isocyanurate.

Examples of phosphite antioxidants include diphenyldecyl phosphite and triphenyl phosphite.
Triro-nonylphenyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tributyl phosphite, dilauryl acid phosphite, dibutyl acid phosphite, tris(dinonylphenyl] phosphite, trilauryl trithiophosphite phyto, trilauryl phosphite, bis(neopentyl glycol) 1,4 cyclohexane dimethylene phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, diphenyl acid phosphite, tris(lauryl-2-thioethyl) Phosphite, tris(mono, dimixed nonylphenyl) phosphite, hydrogenated-4,4'-
Isopropylidene diphenol polyphosphite diphenyl bis(4,4' to n-butylidene bis(2-tertiary)
butyl-5-methylphenol)] thiogetanol diphosphite, bis(octylphenyl) bis(4,
4'-n-butyrythene bis(2-tert-butyl-5-methylphenol):) I, 6 hexanediol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite, phenyl diisodecyl phosphite Siphite, tetratridecyl-4,
4'-n-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, tetratridecyl-1
゜1.3-Tris(2/-methyl-5'-tert-butyl-
4'-oxyphenyl)butane diphosphite, Tecitra (C1□-15 mixed alkyl) 4,4'-isopropylidene diphenyl diphosphite, tris(4-oxy-2,5-di-tert-butylphenyl) phosphite, Examples include tris(4-oxy-3,5-di-3'7'f-ruphenyl) phosphite, 2-ethyl; hexyldiphenyl phosphite.

Examples of amine antioxidants include phenyl-1-naphthylamine, phenyl-2-naphthylamine, N, N
'-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-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, mono- and di-octyliminodi4benzyl, polymerization 2 ,2,4-4limethyl-1
, 2-dihydroquinoline, etc.

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

Light stabilizers include, for example, optionally substituted aryl esters of benzoic acid, 2-oxy-benzophenones, 2-(2'-oxyphenyl)-benzotriazoles, acrylates, 1,3-bis- (2'-oxybenzoyl)-benzenes, 2,4-bis-(2'
Examples include -oxyphenyl)-6-alkyl-α-triazines, nickel compounds, manganese compounds, oxalic acid diamides, and piperidines.

Examples of metal deactivators include oxanilide, dicarboxylic acid dihydrazide, dicarboxylic acid bis-phenyl hydrazide, salicylic acid hydrazide, N-salicyloyl-
N'-Salicylidenehydrazine, Bis-Salicyloyl-
Dicarboxylic acid dihydrazide, bis-acylated dicarboxylic acid dihydrazide, salicyloyl-hydrazinotriazine, bis-salicyloyl-hydrazine, bis(benziritine hydrazide) oxalate, 3-salicyloylamino-1
Examples include 2.4-triazole, N,N'-bis(salicyloyl)thiodipropionic acid bishydrazide, and the like.

Examples of the nucleating agent include 4-tert-butylbenzoic acid, adipic acid, and diphenylacetic acid.

In general, metal soaps can be used as stabilizers for synthetic resins, but in this case, some are often used alone, such as organotin stabilizers and lead soaps, but cadmium, barium, zinc, calcium, magnesium, etc. Metal soaps such as strontium, sodium, and potassium are often used in combination of two or more of these.

For example, Cd-Ba. act-Ba-Zn, Ba-
Zn, Ca-Zn.

Ca Mg, Ca Mg-Zn, Ca-Ba-organotin, Zn-8r, Cd-Ba-pb, Ca
-8r.

Many combinations are adopted depending on the purpose of use, such as Z n -N a and Z n -.

Furthermore, the rigidity of synthetic resin molded products such as polyolefin,
Fillers, especially talc, to improve dimensional stability etc.
Effects can be seen when melamine, dicyandiamide compounds, etc. are added when asbestos, calcium carbonate, carbon black, etc. are added, or when they are not added.

Others as necessary, such as plasticizers, epoxy stabilizers,
Organic chelators, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, heat retardants, fluorescent agents, antifungal agents, bactericidal agents, photodegradants, non-containing agents. Metal stabilizers, borate esters, thiourea derivatives, processing aids, mold release agents, reinforcing agents, and the like can be included.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 In order to examine the stabilizing effect of the polypropylene composition containing the organic phosphite according to the present invention, samples were prepared with the following formulation, and the time at which they began to deteriorate due to oxygen absorption (160°C) was measured.

The results are shown in Table 2.

Blend> Polypropylene 100 parts Organic phosphite (Table 2) 0.3 Ca-stearate 0.3 Prepare data, 210℃, 50kg/cI! , The color of the material was measured after 10 minutes.

Note that the deterioration of ABS resin due to heat is accompanied by a change in color from white to light yellow, yellow, deep yellow, and brown in sequence, regardless of the presence or absence of a stabilizer.

In this example, this was divided into 10 levels and compared.

That is, 1 represents white and 10 represents brown.

The results are shown in Table 3. <Formulation> Unstabilized ABS resin 100 parts Ca-stearate 1.0 Organic phosphite (Table 3) 0.5 Example 2 Containing the organic phosphite according to the present invention In order to examine the stabilizing effect of an acrylonitrile-butadiene-styrene copolymer (ABS resin) composition consisting of In order to examine the stabilizing effect of the polyvinyl chloride resin composition made of polyvinyl chloride, a sheet with a thickness of 1 mm was prepared by calender roll method and hot press processing using the following formulation, and a heat stabilization test was conducted in a gear open at 180 ° C. I did this.

The results are shown in Table 4. Blend> Polyvinyl chloride resin 100 parts Dioctyl phthalate 50 Zn-Octoate 0.5Ba-
Nonylphenate 1.0 Organic phosphite (Table 4) 1.5 Example 4 Polypropylene oxide (average molecular weight 3,000) 1
00 parts were mixed with 0.2 parts of the phosphite compounds listed in Table 5, and the degree of coloration after heating at 160° C. for 1 hour was measured.

The results are shown in Table 5. Example 5 In order to examine the effect of the organic phosphite according to the present invention on ethylene-vinyl acetate copolymer, a sample was prepared with the following formulation and the thermal stability and initial coloring property were measured in a gear oven at 190°C. did.

The results are shown in Table 6.

Blend> Ethylene-vinyl acetate copolymer 100 parts dilauryl thiodipropionate 061BHT
0.2 parts of O,1 phosphite (Table 7) Example 6 0.2 parts of the phosphite compound listed in Table 8 was added to 100 parts of (po')(2,6-dimethyl-1,4-phenylene oxide).
5 parts were added, processed in a laboratory mixer, and subsequently pressed at 300°C to produce a 1-hole test sheet.

This sheet was heated at 225° C. for 30 minutes in heated air F, and the discoloration of the polyphenylene oxide was measured.

The results are shown in Table 8.

Example 7 100 parts of polycarbonate resin powder are mixed with 0.05 parts of phosphite compounds listed in Table 9, processed in a laboratory mixing apparatus and subsequently pressed at 260° C. to form a 1 mm test sheet. do.

The degree of discoloration of the polycarbonate resin composition when this sheet was heated at 225° C. for 30 minutes in heated air was measured.

The results are shown in Table 8. Example 8 In order to examine the effect of the combined use of other additives in the composition of the present invention, the same test as in Example 1 was conducted using the following formulation.

The results are shown in Table 9. <Blend> Polyvinyl chloride resin 100 parts Dioctyl phthalate 5゜Ca-stearate 0.7 Zn-stearate
0.3 phosphite (Table 1 411)
0.3 Other additives (Table 10) 0.3 Example 9 The performance of the phosphite compounds according to the invention in mineral oil was tested.

Phosphite compounds per 100ml of mineral oil (Table 11)
0.15g was dissolved and the method of Example 2 was followed.

However, the temperature was set at 150°C.

Claims (1)

Claims: 1. A stabilized organic material composition comprising an organic phosphite compound represented by the following general formula CI). [In the formula, R1, R2 and R3 are hydrogen atoms, alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, cyclohexylphenyl, cellosolve and calpitol residues, group call residues or divalent or trivalent phenol residues shows. Indicates a group selected from +CH2+10. n represents an integer of 1 to 20. ]