JPH0131544B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilizer for halogen-containing resins, which contains as a main component an organic phosphorus compound that is stable against hydrolysis and has excellent compatibility with halogen-containing resins. When halogen-containing resins are exposed to physical energy such as heat or light in the presence of oxygen, they undergo various changes such as dehydrohalogenation, the formation of carbonyl groups or conjugated double bonds, crosslinking, and molecular chain scission. It is known that deterioration occurs, resulting in discoloration and a decrease in mechanical strength. Conventionally, in order to suppress the deterioration of halogen-containing resins, metal soaps, organic tin stabilizers, and stabilizing aids such as antioxidants, ultraviolet absorbers, epoxy compounds, organic phosphites, and organic phosphates have been used. They have been used together. These stabilizing aids are usually used together with stabilizers for the purpose of preventing thermal discoloration in the early and mid-term stages and for photostabilization, and are expected to have a synergistic effect. The agent has thermal processability,
The drawback was that unfavorable phenomena were observed in terms of initial coloring properties, physical and chemical properties after processing, and photostabilization. For example, organic phosphites such as triphenyl phosphite, trisnonylphenyl phosphite, and diphenyl isodecyl phosphite, which are widely used as conventional stabilizing aids, are themselves susceptible to hydrolysis and require long-term storage. I can't do it,
Furthermore, if added in large amounts, there is a disadvantage that a discharge phenomenon occurs on the surface of the resin sheet.Organic phosphates such as tricresyl phosphate and tricylenyl phosphate have disadvantages such as poor thermal stability and weather resistance. It was hot. The present inventor has developed an organic phosphorus compound that does not have the drawbacks of conventional stabilizing aids such as organic phosphites and organic phosphates, that is, is stable against hydrolysis and has good compatibility with halogen-containing resins. As a result of extensive research to develop a stabilizer that is highly effective in suppressing the deterioration of halogen-containing resins, we have found that a specific organic phosphorus compound represented by the following general formula () can be suitable for this purpose. Based on this finding, the present invention has been accomplished. (However, in the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different groups, each representing a phenyl group, an alkyl-substituted phenyl group, an aralkyl group, or a cycloalkyl group, and n is 1 or 2. ) That is, the present invention provides a stabilizer for halogen-containing resins comprising an organic phosphorus compound represented by the general formula (). In the present invention, the halogen-containing resin includes:
For example, polyvinyl chloride, polyvinylidene chloride, chloroprene, copolymers of these monomers with other polymerizable monomers, chlorinated products such as chlorinated polyvinyl chloride, chlorinated polyethylene, and halogen-containing resins thereof. Examples include graftomers and blended synthetic resins based on In the above general formula () in the present invention, R ₁ , R ₂ ,
The alkyl-substituted phenyl group represented by R ₃ and R ₄ is a so-called mono- or dialkyl-substituted phenyl group in which one or two hydrogen atoms of the phenyl nucleus are substituted with an alkyl group having 1 to 10 carbon atoms. can be mentioned. Examples of alkyl groups in the alkyl-substituted phenyl group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl,
n-octyl, iso-octyl, n-nonyl, iso
-nonyl, n-decyl, iso-decyl, etc. Furthermore, examples of aralkyl groups include benzyl and phenethyl, and examples of cycloalkyl groups include cyclopentyl and cyclohexyl. The organic phosphorus compound represented by the general formula () of the present invention is, for example, a divalent hydroxy compound corresponding to R in the general formula () and this compound.
Add 0.1-2.0% Friedel-Crafts reaction catalyst, such as aluminum chloride, zinc chloride, boron trifluoride ethyl ether, then add a given equivalent of phosphorus oxychloride and heat at 70-110°C, and add a stoichiometric amount of hydrochloric acid. After the gas is generated, further in the general formula ()
At least one monohydroxy compound corresponding to R ₁ to _{R 4} is added in a predetermined equivalent amount or a slight excess amount.
It can be produced by heating reaction at 100 to 200°C. Alternatively, after mixing the monohydroxy compound and the divalent hydroxy compound corresponding to R, phosphorus oxychloride may be added and reacted. In this case, by-products are likely to be produced, but this reaction product can also be used as a stabilizer in the present invention. Further, predetermined equivalent amounts of an organic phosphorochloridate corresponding to the monohydroxy compound and a divalent hydroxy compound corresponding to R are dissolved in an aromatic solvent such as benzene or toluene, and the mixture is heated for 40 to 40 minutes in the presence of a dehydrochlorination agent such as triethylamine. It can also be produced by reacting at 80°C. Further, an organic phosphate having a lower alkyl group or phenyl group with high transesterification reactivity, a divalent hydroxy compound corresponding to R, and the monohydroxy compound are mixed in predetermined equivalent amounts in the presence of a transesterification catalyst such as potassium carbonate. 100~200
It can also be produced by transesterification at a temperature of .degree. As the stabilizer of the present invention, the organic phosphorus compound represented by the general formula () may be produced by any method, and it is most preferable if it is a pure product, but the organic phosphorus compound represented by the general formula () does not need to be a pure product. It may also be a reaction product containing a compound. The amount of the organic phosphorus compound represented by the general formula () used in the present invention is usually 0.01 to 10 parts by weight, particularly 0.1 to 10 parts by weight, based on 100 parts by weight of the halogen-containing resin.
5 parts by weight is preferred. Furthermore, the organic phosphorus compound of the present invention can be used in combination with other commonly known stabilizers, stabilizing aids, antioxidants, ultraviolet absorbers, and the like. Known stabilizers include fatty acids Zn, Ca,
Salts such as Ba, Mg, Sn, R ₂ Sn, mercaptides,
There are mercapto acid esters, etc., but the organophosphorus compound of the present invention, especially when used in combination with a Ca-Zn or Ba-Zn fatty acid salt, has extremely superior heat resistance than known organic phosphites or organic phosphates.
Provides stain resistance and weather resistance. Examples of stabilizing aids preferably used in combination include epoxy compounds, known organic phosphites, organic phosphates, and polyhydric alcohols. As shown in the examples below,
In particular, when used in combination with epoxy compounds and organic phosphites, heat resistance and weather resistance are improved, and epoxidized oils such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized rapeseed oil and bisphenol A
Epoxy compounds represented by epoxy resins such as glycidyl ether of trimethylolpropane, glycidyl ether of pentaerythritol; triphenyl phosphite, diphenyldecyl phosphite, tribenzyl phosphite, diphenyl tridecyl phosphite. Organic phosphites such as trisnonyl phenyl phosphite; zinc octylate, zinc laurate, zinc palmitate, zinc stearate, zinc oleate, zinc ricinoleate, zinc naphthenate, zinc salicylate, zinc benzoate ,
The four-way combination system of carboxylic acid zinc salt such as zinc p-tert-butylbenzoate and the organic phosphorus compound of the present invention significantly improves weather resistance. In addition, the organic phosphorus compound of the present invention can also be used as a lubricant,
It can be used in combination with additives for halogen-containing resins, such as fillers and plasticizers. The organic phosphorus compound represented by the general formula () of the present invention is stable against hydrolysis, so it can withstand long-term storage and has good compatibility with halogen-containing resins, so it can be used in an amount greater than that of ordinary phosphites. There is no discharge phenomenon on the film surface, and as a stabilizer, it has excellent early and mid-term thermal coloring prevention properties and weather resistance, and is highly effective, so the amount used can be reduced compared to the amount of regular phosphate. It can be said to be an extremely practical stabilizer for halogen-containing resins. In this way, it has excellent effects as a stabilizer, especially weather resistance, and there is no discharge phenomenon on the film surface, so it can be used in halogen-containing resin products used outdoors where weather resistance is required, such as agricultural films and irrigation. It is ideal for compounding products such as industrial hoses and window frame materials. Next, the present invention will be explained in more detail using reference examples and examples. Reference Example 1 11.0 g (0.1 M) of hydroquinone and 0.3 g of powdered aluminum chloride were mixed well and heated to 80 to 90°C.
30.7g (0.2M) of phosphorus oxychloride was added dropwise over 1 hour to react. Next, 45.4g (0.42M) of cresol was added dropwise in the same manner over 1 hour, and then the temperature was lowered to 10℃/30℃.
The temperature was increased in increments of 180°C for reaction. After cooling, 200 ml of toluene was added to dissolve the viscous reaction liquid, and the mixture was washed twice with 200 ml of water to remove aluminum chloride as a catalyst.
The solvent toluene was removed under reduced pressure and filtered to obtain compound No. 1 shown in Table 1. Reference Example 2 Compound No. 2 shown in Table 1 was produced according to Reference Example 1. Table 1 shows the properties of these compounds.

【table】

[Table] Example 45 parts by weight of dioctyl phthalate, 1.2 parts by weight of subsalt stearate, 0.8 parts by weight of calcium stearate, and the substances of the present invention shown in Table 1 were added to 100 parts by weight of polyvinyl chloride resin with a degree of polymerization of 1300. After thorough mixing, the mixture was kneaded for 5 minutes using a 6-inch roll at 160°C to produce a film with a thickness of 0.2 mm. Next, each film was heat-treated in a gear aging tester at 190°C, and the time until blackening was measured. Further, the above film was kneaded for 5 minutes with a 6-inch roll at 175°C to prepare a film with a thickness of 0.15 mm, and a weather resistance test was conducted using a sunshine weather meter. The results are shown in Table 2.

【table】

Claims (1)

[Claims] 1. General formula (However, in the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different groups, each representing a phenyl group, an alkyl-substituted phenyl group, an aralkyl group, or a cycloalkyl group, and n is 1 or 2. ) A stabilizer for halogen-containing resins consisting of an organic phosphorus compound represented by: