JPS6312903B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilizer for halogen-containing resins. Generally, halogen-containing resins deteriorate when used under conditions where they are exposed to heat, light, air, etc. It is known that various stabilizers and stabilizing aids are added to prevent this. It is also known that these stabilizers and stabilizing aids can be used in combination in various ways so as to exhibit a synergistic effect. Such known stabilizers include metal soaps and organic tin compounds, and stabilizing aids include antioxidants, ultraviolet absorbers, epoxy compounds, organic phosphites, organic phosphates, and polyhydric alcohols. These stabilizing aids are usually used with stabilizers for the purpose of preventing thermal coloring in the early and middle stages and for light stabilization, and are expected to have a mutual effect. Auxiliary agents have the disadvantage of causing unfavorable phenomena in terms of heat processability, initial coloring, photostabilization, and physical and chemical properties after processing. For example, organic phosphites such as triphenyl phosphite and diphenyldecyl phosphite, which are widely used as conventional stabilizing aids, are themselves susceptible to hydrolysis and cannot be stored for long periods of time. It has the disadvantage that a phenomenon of discharge onto the surface occurs, and organic phosphates such as tricresyl phosphate and tricylenyl phosphate have disadvantages such as poor thermal stability and weather resistance. The present inventors have developed an organic phosphorus compound that does not have the drawbacks of conventional stabilizing aids such as organic phosphites and organic phosphates, that is, it is stable against hydrolysis, has good compatibility with halogen-containing resins. As a result of extensive research in order to develop a stabilizer that is highly effective in suppressing the deterioration of The present invention was completed by obtaining an organic phosphorus compound with good photostabilizing ability. For example, in the case of weather-resistant vinyl chloride resin compositions, which are used as agricultural materials, in conventional formulations, plasticizers are added to 100 parts by weight of the resin in order to improve weather resistance.
A synergistic effect has been obtained using 40 to 50 parts by weight of tricresyl phosphate and 3 parts by weight or less of a composite metal soap stabilizer and 2 to 5 parts by weight of an epoxy polymer. This is also true. However, unless the amount added is increased, weather resistance cannot be achieved to a practical level, which may lead to disadvantages such as deterioration of physical properties. In contrast, the organic phosphorus compound of the present invention has a
A small addition amount of ~5 parts by weight, preferably 0.5 to 1.0 parts by weight provides a vinyl chloride resin composition with excellent weather resistance. That is, the present invention is based on the general formula [] (However, in the formula, at least one of R ₁ R ₂ R ₃ R ₄ is hydrogen, and the others are the same or different C ₄ to _{C 18} alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, alkosyl alkyl groups. group, aryloxyalkyl group, polyoxyalkylenealkyl group, polyoxyalkylenearyl group, C ₁ - C ₁₈
is an aralkyl group such as an alkyl-substituted aryl group or a benzylphenylethyl group, X is a polyhydric alcohol residue, a polyphenol residue, or a polyoxyalkylene polyhydric alcohol residue, and m and n are 1 to
It is an integer of 3, and m+n≧2. ) The present invention provides a stabilizer for halogen-containing resins comprising an organic phosphorus compound represented by: In the present invention, after polymerization of halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, chloroprene, copolymers of these monomers and other polymerizable monomers, chlorinated polyvinyl chloride, chlorinated polyethylene, etc. Examples include chlorinated resins, graftomers mainly composed of halogen-containing resins, and synthetic resins obtained by blending these halogen-containing resins. Further, the organic phosphorus compound represented by the general formula [] of the present invention will be described in detail. Examples of the alkyl group of R ₁ R ₂ R ₃ R ₄ include butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, octyl, 2-ethylhexylisooctyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, and octadecyl. I can do it. As a cycloalkyl group, cyclopentyl,
Examples include cyclohexyl. The alkenyl group is oleyl, the aryl group is phenyl, and examples of the alkylaryl group are cresyl, xylyl, ethyl phenyl, propylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, t-butylphenyl,
Isoamyl phenyl, hexyl phenyl, cyclohexyl phenyl, octylphenyl, 2-ethylhexyl phenyl, nonylphenyl, decylphenyl, paracumyl phenyl and the like can be mentioned. Examples of the arylalkyl group include benzyl, 2-methylbenzyl, phenylethyl, phenylpropyl, phenylisopropyl, phenylbutyl, phenylisobutyl, phenylt-butyl, phenylcyclohexyl, and the like. Examples of further substituted alkylaryl and arylalkyl groups include 3.5-
Di-t-butyl-4-hydroxyphenyl, 2.6
-di-t-butyl-P-cresol, methylbenzyl, ethylbenzyl, propylbenzyl, isopropylbenzyl, butylbenzyl, isobutylbenzyl, t-butylbenzyl, cyclohexylbenzyl, methylphenylethyl, isopropylphenylethyl, methylphenyl isopropyl,
Examples include ethyl phenyl isopropyl and t-butylphenyl isopropyl. Examples of alkoxyalkyl and aryloxyalkyl groups include methoxyethyl, ethoxyethyl, propoxyethyl, isopropoxyethyl,
Butoxyethyl, isobutoxyethyl, t-butoxyethyl, amyloxyethyl, hexoxyethyl, cyclohexoxyethyl, heptoxyethyl, octoxyethyl, 2-ethylhexoxyethyl, desiloxyethyl, dodecyloxyethyl,
Phenoxyethyl, benzyloxyethyl, methoxypropyl, ethoxypropyl, butoxypropyl, t-butoxypropyl, cyclohexoxypropyl, 2-ethylhexoxypropyl, octoxypropyl, methoxybutyl, 3-methoxybutyl, butoxybutyl, t-butoxybutyl ,
Cyclohexoxybutyl, octoxybutyl, 2
-ethylhexoxybutyl, phenoxybutyl,
Benzyloxybutyl, methoxycyclohexyl, ethoxycyclohexyl, butoxycyclohexyl, t-butoxycyclohexyl, methoxyphenyl, ethoxyphenyl, propoxyphenyl, isopropoxyphenyl, butoxyphenyl, isobutoxyphenyl, t-butoxyphenyl, hexoxyphenyl , cyclohexoxyphenyl, octoxyphenyl, 2-ethylhexoxyphenyl, etc., and polyoxyalkylene alkyl groups and polyoxyalkylene aryl groups include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl, etc. Ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, diethylene glycol monocyclohexyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monooctyl ether, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol monononyl ether, diethylene glycol monodecyl ether , diethylene glycol monoisodecyether, diethylene glycol monododecyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol monophenyl ethyl ether, diethylene glycol methyl benzyl ether, diethylene glycol monoisopropyl benzine ether, diethylene glycol monophenyl isopropyl ether, triethylene glycol monomethyl ether , triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, triethylene glycol monooctyl ether, triethylene glycol mono-2-ethylhexyl ether, triethylene glycol monocyclohexyl ether, triethylene glycol monobenzyl ether, triethylene glycol monophenyl ether , dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monocyclohexyl ether, dipropylene glycol monobenzyl ether, dipropylene glycol monophenyl ether, dibutylene glycol methyl ether, dibutylene glycol Examples include monoethyl ether, dibutylene glycol monobutyl ether, and dibutylene glycol monophenyl ether. Examples of polyhydric alcohols and polyhydric phenols of general formula butylene glycol, octylene glycol, isooctylene glycol, neopentylene glycol, 1,3,5-hydroxybenzyltriol, trimethylolpropane, glycerin, pentaerythritol, bisphenol A,
2.2'-bis(4-hydroxy-3-t-butylphenyl)propane, methylenebis(P-cresol), methylenebis(2.6-di-t-butylphenol), 4.4'-thiobisphenol, 4.4'-thiobis(4- Examples include methyl-6-t-butylphenol). Examples of polyoxyalkylene polyhydric alcohols include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, dipentylene glycol, and the like. Furthermore, the organic phosphorus compound of the present invention can be used in combination with other generally known stabilizers, stabilizing aids, organic phosphites, organic phosphates, antioxidants, epoxy compounds, ultraviolet absorbers, and the like. Known stabilizers include fatty acids Cd.Zn.Ca.Ba.Mg.Sn.
There are salts such as R ₂ Sn, mercaptides, mercapto acid esters, etc., but the organophosphorus compound of the present invention is very superior to known organic phosphites or organic phosphates, especially when used in combination with Ca.Zn or Ba-Zn fatty acid salts. Provides heat resistance, stain resistance and weather resistance. In addition, the organic phosphorus compound of the present invention can be used as a lubricant,
It can be used in combination with additives normally used for halogen-containing resins, such as fillers and plasticizers. Next, a synthesis example of the organic phosphorus compound represented by the above general formula [] of the present invention will be shown. However, the present invention is not limited to these synthesis examples. Further, representative compounds are shown in Table 1. Synthesis example 1 Bisphenol A 22.8gr (0.1mol), powdered potassium carbonate 0.05gr and diphenyl phosphate 50gr (0.2gr)
mol), heated and stirred at 155-160°C for 2 hours, removed by-product phenol under reduced pressure, cooled to 80°C, and filtered to obtain the compound No. 1 in Table 1. The recovery rate of phenol was 98.7%.

【table】

【table】

[Table] The present invention will be explained in more detail with reference to Examples below. Note that parts in this example indicate parts by weight. However, the present invention is not limited to the following examples. Example 1 100 parts of polyvinyl chloride resin with a degree of polymerization of 1300, 45 parts of dioctyl phthalate, 1 part of liquid epoxy resin,
Add 1.2 parts of Zn stearate, 0.8 parts of Ca stearate, and the organic phosphorus compound shown in Table 2, mix thoroughly, and knead for 5 minutes with a 6-inch roll at 160°C.
A film with a thickness of 0.2 m/m was produced. Next, each film was heat-treated at 190° C. in a gear aging tester, and the time until blackening was measured. Also, knead the above film with a 6-inch roll at 175℃ for 5 minutes,
A film with a thickness of 0.15 m/m was prepared and subjected to a weather resistance test using a Sunshine Weatherometer. The results are shown in Table 2.

[Table] Huaito

[Table] 〓No.5
Example 2 100 parts of polyvinyl chloride resin with a degree of polymerization of 1300, 30 parts of dioctyl phthalate, 2 parts of epoxidized soybean oil,
2 parts of Ba-Zn stabilizer The organic phosphorus compounds shown in Table 3 were thoroughly mixed and kneaded for 5 minutes using an 8-inch roll at 160°C to produce a film with a thickness of 0.2 m/m. Next, each film was heat-treated in a Gear aging tester at 180°C, and the change in color tone and time until blackening were measured. On the other hand, 160℃, 15Kg/cm ² , 15
A press plate with a thickness of 5 m/m was produced under the conditions of
Colored surface transparent and in constant temperature and humidity chamber at 60℃ and 90% humidity
The forced eruption phenomenon was observed for 30 days. The results are shown in Table 3.

[Table] Example 3 100 parts of a commercially available polyvinyl chloride resin with a degree of polymerization of 800, 15 parts of an acrylonitrile-butidiene-styrene terpolymer as a reinforcing agent, 2 parts of an organotin stabilizer, and the organic phosphorus compound shown in Table 1 above. and 0.5 part of a conventional organic phosphite were thoroughly mixed and kneaded for 5 minutes using a 6-inch roll at 165°C to produce a film with a thickness of 0.3 m/m. Next, for each film, 190
Heat treatment was performed in a gear aging tester at ℃, and the time until coloration and blackening was measured. The results are shown in Table 4.

[Table] Suphaite

【table】

Claims (1)

[Claims] 1. A stabilizer for halogen-containing resins, characterized by comprising a compound represented by the general formula [] (However, in the formula, at least one or more of R ₁ , R ₂ , R ₃ , and R ₄ is hydrogen, and the others are the same or different, C ₄
~ _C18 alkyl group, alkenyl group, cycloalkyl group, aryl group, alkoxyalkyl group, aryloxyalkyl group, polyoxyalkylenealkyl group, polyoxyalkylenearyl group
C1 _{- C18} alkyl-substituted aryl group, benzyl,
an aralkyl group such as phenylethyl, X is a polyhydric alcohol residue, a polyphenol residue, a polyoxyalkylene polyhydric alcohol residue, m,
n is an integer of 1 to 3, and m+n≧2. )